DIKTAT MATA KULIAH

K I M I A O R G AN I K

:
Drs. Adiwarna

Disusun oleh

JURUSAN TEKNIK KIMIA FAKULTAS TEKNIK

UNIVERSITAS MUHAMMADIYAH JAKARTA
2008
1

DAFTAR ISI
TINJUAN MATAKULIAH
MODUL 1

: TEORI DASAR TENTANG ATOM DAN IKATAN ATOM

Latihan
Rangkuman
Tes formatif

MODUL 2

: JENIS-JENIS IKATAN KIMIA

Latihan
Rangkuman
Tes formatif

MODUL 3

: KONSEP DASAR SENYAWA ORGANIK

Latihan
Rangkuman
Tes formatif

MODUL 4

|: JENIS-JENIS REAKSI DALAM SENYAWA ORGANIK

Latihan
Rangkuman
Tes formatif

MODUL 5

: JENIS-JENIS SENYAWA ORGANIK

Latihan
Rangkuman
Tes formatif

MODUL 6

: TEORI TENTANG STEREO KIMIA

Latihan
Rangkuman
Tes formatif

MODUL 7

: PUSAT CHIRAL
Latihan
Rangkuman
Tes formatif

MODUL 8

: KARBOHIDRAT
Latihan
Rangkuman
Tes formatif

MODUL 9

: ASAM AMINO DAN PROTEIN

Latihan
Rangkuman
Tes formatif

MODUL 10

: TRIGLISERIDA
Latihan
Rangkuman
Tes formatif

MODUL 11

: ALKALOID
Latihan
Rangkuman
Tes formatif

MODUL 12

: TERPENOID
Latihan
Rangkuman
Tes formatif

MODUL 13

: STEROID DAN SAPONIN

Latihan
Rangkuman
Tes formatif

MODUL 14

: ASAM NUKLEAT
Latihan
Rangkuman
Tes formatif

MODUL 15

: FLAVONOID DAN QUINONOID

Latihan
Rangkuman
Tes formatif

MODUL 16

: POLIMER
Latihan
Rangkuman
Tes formatif

KUNCI JAWABAN TES FORMATIF

DAFTAR PUSTAKA
KAMUS UMUM

TINJAUAN MATAKULIAH
Mata kuliah kimia organik merupakan matakuliah MKDU yang diajarkan pada semester
II. Diharapkan setelah mengikuti matakuliah ini mahasiswa dapat memahami tentang konfigurasi
elektron dalam atom dan molekul, proses terjadinya ikatan kimia, sehingga dengan demikian
mengetahui sifat keelektronegatifan, muatan formal, momen dipol, sifat keasaman dan kebasaan
menurut bronsted Lowry dan Lewis.
Setelah mengetahui dasar-dasar pembentukan ikatan mahasiswa harus tahu tentang
berbagai gugus fungsi pada senyawa organik, bermacam-macam reaksi organik, struktur senyawa
organik, permberian nama senyawa organik, dan kelompok sennyawa organik.
Mata kuliah kimia organik meerupakan matakuliah wajib bagi mahasiswa yang mengikuti
program S1 Teknik Kimia Fakultas Teknik Universitas Muhammadiyah jakarta. Setelah mengikuti
matakkuliah ini mahasiswa diharapkan mampu :
1.
Mengetahui konsep dasar tentang atom dan molekul serta proses terjadinya ikatan kimia.
2.
Mengetahui sifat-sifat kimia akibat terjadinya ikatan kimia dan gugus fungsi pada senyawa
organik.
3.
Mengetahui struktur dan pemberian nama bermacam-macam senyawa organik dan
sintesanya.
4.
Bisa membedakan senyawa organik dengan senyawa anorganik.
5.
Mengenal tentang isomer, kiralitas berbagai senyawa organik serta bisa menentukan sifat
optis aktisnnya.
6.
Mengetahui bermacam-macam struktur senyawa karbohidrat, memberi nama, dan bisa
mengidentifikasi dengan reagen khusus.
7.
Mengetahui jenis-jenis struktur asam amino, pembentukan ikatan peptida menjadi protein,
serta bisa mensintesa asam amino dan protein..
8.
Mengetahui struktur ester trigliserida, bisa membedakan kelompok trigliserida, dan
mengenal biosintesa asam-asam lemak.
9.
Mengenal struktur dan bisa memeberi nama senyawa bahan alam yakni terpenoid, steroid,
alkaloid, flavonoid, quinonoid, saponin; dan bisa mensintesanya.
10.
Mengenal susunan struktur asam nukleat, bisa memberi nama, dan bisa menistesa.
11.
Menngenal struktur dan nama beberapa jenis-jenis polimer serta bisa mensintesanya.
Matakuliah kimia organik ini mempunyai bobot 3 sks dengan kode KIM008 terdiri dari 16 modul
Sebagai berikut :
MODUL 1
MODUL 2
MODUL 3
MODUL 4
MODUL 5
MODUL 6
MODUL 7
MODUL 8
MODUL 9
MODUL 10
MODUL 11
MODUL 12
MODUL 13
MODUL 14
MODUL 15
MODUL 16

: Teori dasar tentang atom dan ikatan atom.

: Jenis-jenis ikatan kimia.
: Konsep dasar senyawa organik.
: Jenis-jenis reaksi dalam senyawa organik
: Jenis-jenis senyawa organik.
: Teori tentang stereo kimia
: Pusat chiral
: Karbohidrat
: Asam amino dan protein.
: Trigliserida
: Alkaloid
: Terpenoid
: Steroid dan saponin
: Asam nukleat
: Flavonoid dan quinonoid
: Polimer
4

MODUL I
I.
TEORI DASAR TENTANG ATOM DAN IKATAN ATOM
Konfigurasi Elektron dalam Atom
Menurut Mendelejev electron dalam suatu atom akan mengisi orbital mulai dari tingkat
energi terendah terlebih dahulu dari orbital 1s, 2s; 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d;

Tti
ng
kat
en
erg
i

Tingkat energi tertinggi

5f
6p
6s
4d
5s
4p
3d
4s
3p
3s
2p
2s
1s
Tingkat energi terendah
Orbital s maksimum terisi 2 elektron, orbital p maksimum terisi maksimum 6 elektron, orbital d
maksimum terisi 10 elektron, orbital f maksimum terisi maksimum 14 elektron.
Orbital s berbentuk lingkaran, orbital p berbentuk ellip yang tersusun dalam tiga dimensi, orbital d
berbentuk ellip yang lebih lonjong yang tersusun dalam lima dimensi, dan orbital f berbentuk
sangat lonjung yang tersusun dalam 7 dimensi

Orbital s

Orbital p
Orbital d

Orbital d

Orbital f

Contoh orbital s adalah atom hindrogen yang mempunyai 1 elektron ( biru ) dan 1 proton
(merah).

Konfigurasi elektron dalam molekul

Susunan tingkat energi dasar dalam suatu atom dapat dijelaskan dengan teori orbital atom dan
tingkat energinya. Ada tiga prinsip yang harus dipenuhi dalam pengisian electron pada suatu
orbital atom :
1. Electron mengisi orbital tingkat energi terendah terlebih dahulu.( prinsip Aufbau)
2. Hanya maksimum dua electron menempati suatu orbital dengan spin yang berlawanan
arah. (prinsip ekslusi Pauli).
3. Pengisian electron pada orbital bertingkat energi sama harus terisi satu-satu electron
terlebih dahulu ( Aturan Hund).
Orbital molekul
Bila dua atau lebih atom bergabung membentuk molekul unsur atau senyawa maka orbital
electron molekul adalah merupakan gabungan dari orbital electron atom-atom penyusun
molekul tersebut.
Contoh 1. orbital molekul H2
1s

1s
H

H2

Contoh 2. Orbital molekul C2

2p

2p

2p

2p
s

s
C

s
C2

Hibrida molekul
Bila dua electron dari dua atom bergabung membentuk ikatan maka akan terbentuk
hibrida orbital. Bentuk hibrid orbital tergantung kepada asal orbital electron pembentuk
ikatan, jika kedua electron tidak berpasangan dari dua atom berasal dari orbital s maka
akan terbewntuk hibrid orbital s-s, jika dua electron tidak berpasangan dari dua atom
berasal dari orbital s dan p maka akan terbewntuk hibrid orbital s-p, jika dua electron
tidak berpasangan dari dua atom berasal dari orbital s dan d maka akan terbewntuk huibrid
orbital s-d jika dua electron tidak berpasangan dari dua atom berasal dari orbital s dan f
maka akan terbewntuk huibrid orbital s-f, jika dua electron tidak berpasangan dari dua
atom berasal dari orbital p dan d maka akan terbewntuk huibrid orbital p-d, jika dua
electron tidak berpasangan dari dua atom berasal dari orbital p dan f maka akan
terbewntuk huibrid orbital p-f jika dua electron tidak berpasangan dari dua atom berasal
dari orbital d dan f maka akan terbewntuk huibrid orbital d-f jika dua electron tidak
berpasangan dari dua atom berasal dari orbital d dan d maka akan terbewntuk huibrid
orbital d-d jika dua electron tidak berpasangan dari dua atom berasal dari orbital f dan f
maka akan terbewntuk huibrid orbital f-f. jika electron tidak berpasangan dari dua atom
6

berasal dari orbital 3s dan 3p maka akan terbewntuk huibrid orbital sp 3, jika electron tidak
berpasangan dari dua atom berasal dari orbital 2s dan 2p maka akan terbewntuk huibrid
orbital sp2.
MODUL II
II.

JENIS-JENIS IKATAN KIMIA

Teori tentang ikatan kimia
Ikatan kimia antar atom-atom bisa terjadi apabila electron kulit terluar dari suatu atom ada
yang tidak berpasangan. Suatu atom bisa berikatan dengan beberapa atom lain jika atom
tersebut mempunyai banyak elekton terluar (valensi) tak berpasangan. Contohnya CH4.

2p
2p

2p
H

s
C

CH4
Sebelum membentuk molekul CH4 pada mulanya jika ikatan terjadi antara atom karbon
dalam keadaan dasar dengan atom hindrogen hanya akan terbentuk molekul CH2, namun
karbon sendiri bisa mengalami eksitasi dari keadaan dasar.

2p

+
H

2p

2p

s
C

s
CH2

2p
2p

2p
H

2s

2s

1s

2s

2s

1s

1s

1s
+ 1s
1s
1s
4H

1s

C
Ground state

2p

C
Exited state

CH4

Jenis-jenis ikatan kimia

Ikatan ion
Ikatan ion terjadi dalam suatu molekul jika molekul tersebut mengalami polarisasi muatan
elektrostatik. Hal ini terjadi pada molekul yang terdiri dari atom-atom elektropositif dan
atom elektronegatif membentuk molekul polar. Molekul polar apabila dilarutkan dalam
pelarut polar maka jarak atom elektropositif dan elektronegatif menjadi lebih jauh,
sehingga dengan demikian akan terjadi polarisasi muatan elektrostatik, dimana electron
terkuar dari atom elektro positif beredar pada inti atom elektronegatif sehingga atom
elektropoasitif akan kekurangan electron dan kelebihan proton keadaan seperti ini
membentuk mnuatan positif, sebaliknya atom elektronegatif akan menarik satu electron
at6om elektropositif yang beredar pada inti atom elektronegatif sehingga terbentuklah
muatan negative akibat atom elektronegatif kelebihan electron seperti reaksi berikut :
11

Na8OH + H2O

10

Na(H2O)2+ + 9OH-

Atom Natrium yang mempunyai 11 elektron dan 11 proton, pada molekul Na(H 2O)2+
Elektron atom Natrium hanya 10 elektron yang mengitari orbit inti atom Natrium sehingga
atom natrium kekurangan 1 elektron sehingga menjadi bermuatan (+) sedangkan atom
oksigen yang mempunyai 8 elektron pada molekul OH- atom oksigen mempunyai 9
elektron sehingga bermuatan (-). Senyawa organic kebannyakan tidak ada yang berikatan
polar tetapi hanya berikatan semi polar.
Ikatan kovalen
Ikatan kovalen adalah pemasangan electron tunggal dua atom atau lebih membentuk
molekul tanpa terjadinya polarisasi electron. Kedua electron yang berpasangan dari dua
atom berotasi mengitari inti dari masing-masing atom penyusunnya. Contohnya molekul
CH4. :

H
.

C.

4 H.

C H
H

Ikatan hydrogen
Ikatan hydrogen adalah ikatan atom hydrogen dalam molekul senyawa asam Lewis dengan
atom-atom elektronegatif dalam dasa Lewis. Ikatan hydrogen terjadi apabila electron dari
atom hydrogen dalam suatu molekul beredarar pada orbit electron atom. Ikatan hydrogen
8

dikenal dari sifat air yang mempunyai titik didih lebih tinggi dari molekul lain seperti H 2S
dan CH4, air dengan berat molekul 18 mempunyai titik didih 100 oC sedangkan H2S
dengan berat molekul 34 mempunyai titik didih 25 oC dan C2H6 dengan berat molekul 30
mempunyai titik didih 25 oC -5 C
ikatan vanderwalls
London force
Bentuk-bentuk hibrida molekul
Hibridisasi adalah penggabungan electron yang tidak berpasangan dalam orbital suatu
atom dengan electron yang tak berpasangan dari atom lain. Orbital yang terbentuk dari
hibridisasi ini disebut hybrid orbital. Hybrida orbital bisa berbentuk s-s, s-p, s-d, s-f, p-p,
p-d, p-f, d-d, d-f, atau f-f tergantung kepada asal orbital electron dari masing-masing atom.
Hibrida molekul terjadi dari penggabungan electron tak berpasangan pada orbital dalam
suatu molekul dari atom-atom penyusunnya. Bentuk hibrida molekul pada senyawa
organic adalah sp3, sp2, dan sp. Sp3 ada pada senyawa alkana, sp2 ada pada senyawa
alkena, dan sp ada pada senyawa alkuna.
Hibridisasi sp3 pada molekul alkana berarti 1 dari 4 elektron orbital S hydrogen masuk ke
orbital 2S dan 3 elektron orbital S dari hydrogen masuk ke 3 orbital P atom karbon.
2p

2p

2p
H

2s

1s

2s

1s
+ 1s
1s
1s
4H

1s

C
Ground state

2p

C
Exited state

2s

2s

1s

1s

CH4

Hibridisasi sp2 pada molekul alkena berarti 1 dari 3 elektron orbital S hydrogen masuk ke
orbital 2S dan 3 elektron orbital S dari hydrogen masuk ke 3 orbital P dari atom karbon.
2p

2p

2p
H

2s

2s

1s

1s

2p

2p

2p
H

1s
+ 1s
1s
1s
4H

2s

2s

1s

C
C
1s

Ground state
Exited state
-CH3
Hibridisasi sp3 pada molekul alkana berarti 1 dari 4 elektron orbital S hydrogen masuk ke
orbital 2S dan 3 elektron orbital S dari hydrogen masuk ke 3 orbital P dari atom karbon.
2p

2p
9

H
2s

1s
C
Ground state

1s
+ 1s
1s

2s

1s
4H

1s
C
Exited state

2s

2s

1s

1s
-CH2

Polarisasi dan elektronegatifitas.

Dari sekiian banyak molekul senyawa organic hanay sedikit sekalli yang ditemukan
berupa senyawa dipolar. Akan tetapi kebanyakan molekul senyawa organic adalah polar.
Hal ini menunjukan meskipun tidak bisa mengikuti muatan formal atom-atom, namun
distribusi electron pada ikatan atom-atom tertentu adalah merupakan bentuk yang tidak
simetris. Elektron-elektron Dallam atom tidak berpasangan secara sama oleh kedua inti
atom.
Sehinngga dengan demikian ikatan kimia pada atom-atom sangat ditentukan oleh kondisi
atau situasi apakah yang terbentuk ikatan kovalen atau ionic. Belum ada penjelasan
terperinci mengenai konsep ikatan kovalen polar, akan tetapi diperkirakan ikatan yang
terjadi merupakan kelanjutan dari kemungkinan antara ikatan kovalen sempurna dengan
distribusi elektron yang simetris atau sebaliknya, dan ikatan ionic sempurna atau
sebaliknnya. Sebagai contohhnya ikatan -C-C- pada etana adalahh simetris, oleh karena itu
merupakan ikatan kovalen sempurna, dua electron yang berikatan dipasangkan bersama
antara kedua atom karbon yang setara. Sebaliknya ikatan pada Na-Cl adalah murni ionic
dan terbentuk gaya tarik medan elektrostatik
antara ion Natrium yang bermuatan positif
S
dengan ion klorida yang bermuatan negative.
i

f
a

t
-C:C; -C :Cl
; Na+:ClPada ikatan -C-Cl kemungkinan besar terjadi penarikan electron agak kuat oleh suatu
atom dari pada atom lainnya.
i
Perbedaan kepolaran atom-atom
yang berikatan mengakibatkan terjadinnya
o
elektronegatifitas.
n

Tabel 1. . Elektronegatifitas dari beberapa jenis unsur

Unsur elektronegatifitasi unsur elektronegatifitas
k
H
2.2
Mg
1.3
Li
1.0
Al
1.6
Be
1.6
Si
1.9
B
2.0
P
2.2
C
2.5
S
2.6
N
3.0
Cl
3.1
O
3.4
Br
3.0
F
4.0
I
2.6
Na
1.0
F
4

10

Unsur yang mempunyai elektronegatifitas diatas 2.5 dinyatakan dinyatakan lebih

elektronegatif sedangkan unsur yang mempunyai elektronegatifitas dibawah 2.5
dinyatakan sebagai unsur elektropositif.
Dari table diatas terlihat bahwa antara atom karbon dan hydrogen mempunyai
elektronegatifitas hamper sama maka iakatan C-H adalah ikatan non polar. Unsur-unsur
yang berada pada sebelah kanan table atom berkala seperti oksigen, florin, dan klorin
adalah lebih elektronegatif dibandingkan dengan karbon, sehinga jika atom karbon
berikatan dengan atom diatas akan menarik electron lebih kuat kearahnya dari pada atom
karbon. Sehingga bila atom karbon berikatan dengan salah satu atom ini, maka terbetuklah
ikatan terpolarisasi, sehingga dalam penggambarannya electron tertarik kearah atom
elektronegatif ini dari pada atom karbon. Atom karbon akan menjadi bermuatan parsil
positif yang dilambangkan dengan () dan atom elektronegatif akan menjadi bermuatan
parsil negative yang dilambangkan dengan (). Sebagai contoh molekul H3C-Cl berikut :
H2,2
H2,2-C2,5
H2,2

Cl-3,1

Arah pada tanda panah digunakan untuk menunjukkan arah kepolaran. Berdasarkan
konvensi kimia electron bergerah menuju arah panah. Ekor dari panah adalah atom yang
kekurangan muatan electron dan kepala dari panah adalah atom yang kelebihan muatan
electron. Unsur-unsur yang berada sebelah kiri table atom berkala adalah unsure-unsur
elektropositif dari ppada karbon dan kurang kuat menarik electron.

Electron orbitals
Electrons orbit atoms in clouds of distinct shapes and sizes. The electron clouds are layered one
inside the other into units called shells (think nested Russian dolls), with the electrons occupying
the smallest, innermost shell having the lowest energy state and the electrons in the largest,
outermost shell having the highest energy state. The higher the energy state, the more potential
energy the electron has, just like a rock at the top of a hill has more potential energy than a rock
at the bottom of a valley. These concepts will be important in understanding later concepts like
optical activity of chiral compounds as well as many interesting things outside the realm of
organic chemistry (like how lasers work).

Wave nature of electrons

Electrons behave as particles but also as waves. (Work by Albert Einstein and others revealed that
in fact, light and all matter behaves with this dual nature, and it is most clearly observed in the
tiniest particles.) One of the results of this observation is that electrons are not just in simple orbit
around the nucleus as we imagine the moon to circle the earth, but instead occupy space as if they
were a wave on the surface of a sphere.
If you jump a jumprope you could imagine that the wave in the rope is in its fundamental
frequency. The high and low points fall right in the middle, and the places where the rope doesn't
move much (the nodes) occur only at the two ends. If you shake the rope fast enough in a rythmic
11

way, using more energy than you would just jumping rope, you might be able to make the rope
vibrate with a wavelength shorter than the fundamental. You them might see that the rope has
more than one place along its length where it vibrates from its highest spot to its lowest spot.
Furthermore, you'll see that there is one or more places (or nodes) along its length where the rope
seems to move very little, if at all.
Or consider stringed musical instruments. The sound made by these instruments comes from the
different ways, or modes the strings can vibrate. We can refer to these different patterns or modes
of vibrations as linear harmonics. Going from there, we can recognize that a drum makes sound
by vibrations that occur across the 2-dimensional surface of the drumhead. Extending this now
into three dimensions, we think of the electron as vibrating across a 3-dimensional sphere, and the
patterns or modes of vibration are referred to as spherical harmonics. The mathematical analysis
of spherical harmonics were worked out by the French mathematician Legendre long before
anyone started to think about the shapes of electron orbitals. The algebraic expressions he
developed, known as Legendre polynomials, describe the three dimension shapes of electron
orbitals in much the same way that the expression x2+y2 = z describes a circle (or, for that matter,
a drumhead). Many organic chemists need never actually work with these equations, but it helps
to understand where the pictures we use to think about the shapes of these orbitals come from.

Electron shells
Each different shell is subdivided into one or more orbitals, which also have different energy
levels, although the energy difference between orbitals is less than the energy difference between
shells.
Longer wavelengths have less energy; the s orbital has the longest wavelength allowed for an
electron orbiting a nucleus and this orbital is observed to have the lowest energy.
Each shell in an orbital has a characteristic shape, and are named by a letter. They are: s, p, d, and
f.
As one progresses up through the shells (represented by the principle quantum number n) more
types of orbitals become possible.

S orbital
The s orbital is the orbital lowest in energy and is spherical in shape. Electrons in this orbital are
in their fundamental frequency.

P orbital
The next lowest-energy orbital is the p orbital. Its shape is often described as like that of a
dumbbell. There are three p-orbitals each oriented along one of the 3-dimensional coordinates x, y
or z.

12

These three different p orbitals can be referred to as the px, py, and pz.
The s and p orbitals are important for understanding most of organic chemistry as these are the
orbitals that are occupied by the type of atoms that are most common in organic compounds.

D orbital

There are 5 types of d orbitals. Three of them are roughly X-shaped, as shown here, and might be
viewed as being shaped like a crossed pair of dumbbells . They are referred to as dxy, dxz, and dyz.
Like the p-orbitals, these three d orbitals have a node at the origin of the coordinate system where
the three axes all come together. Unlike the p orbitals, however, these three d orbitals are not
oriented along the x, y, or z axes, but instead are oriented in between them. The dxy orbital, for
instance, lies in the xy plane, but the lobes of the orbital point out in between the x and y axes.

F orbital and beyond

There are 7 kinds of F orbitals, but we will not discuss their shapes here. F orbitals are filled in the
elements of the lanthanide and actinide series, although electrons in these orbitals rarely come into
play in organometallic reactions involving these elements.

Konfigurasi elektron dalam molekul

Susunan tingkat energi dasar dalam suatu atom dapat dijelaskan dengan teori orbital atom dan
tingkat energinya. Ada tiga prinsip yang harus dipenuhi dalam pengisian electron pada suatu
orbital atom :

1. Electron mengisi orbital tingkat energi terendah terlebih dahulu.( prinsip

Aufbau)
2. Hanya maksimum dua electron menempati suatu orbital dengan spin yang
berlawanan arah. (prinsip ekslusi Pauli).

13

3. Pengisian electron pada orbital bertingkat energi sama harus terisi satusatu electron terlebih dahulu ( Aturan Hund).

Orbital molekul
Bila dua atau lebih atom bergabung membentuk molekul unsur atau senyawa maka orbital
electron molekul adalah merupakan gabungan dari orbital electron atom-atom penyusun
molekul tersebut.
Contoh 1. orbital molekul H2

1s

1s
H

H2

Contoh 2. Orbital molekul C2

2p

2p

2p

2p
s

s
C

s
C2

Hibrida molekul
Bila dua electron dari dua atom bergabung membentuk ikatan maka akan terbentuk
hibrida orbital. Bentuk hibrid orbital tergantung kepada asal orbital electron pembentuk
ikatan, jika kedua electron tidak berpasangan dari dua atom berasal dari orbital s maka
akan terbewntuk hibrid orbital s-s, jika dua electron tidak berpasangan dari dua atom
berasal dari orbital s dan p maka akan terbentuk hibrid orbital s-p, jika dua electron tidak
berpasangan dari dua atom berasal dari orbital s dan d maka akan terbewntuk huibrid
orbital s-d jika dua electron tidak berpasangan dari dua atom berasal dari orbital s dan f
maka akan terbewntuk huibrid orbital s-f, jika dua electron tidak berpasangan dari dua
atom berasal dari orbital p dan d maka akan terbewntuk huibrid orbital p-d, jika dua
electron tidak berpasangan dari dua atom berasal dari orbital p dan f maka akan
14

terbewntuk huibrid orbital p-f jika dua electron tidak berpasangan dari dua atom berasal
dari orbital d dan f maka akan terbewntuk huibrid orbital d-f jika dua electron tidak
berpasangan dari dua atom berasal dari orbital d dan d maka akan terbewntuk huibrid
orbital d-d jika dua electron tidak berpasangan dari dua atom berasal dari orbital f dan f
maka akan terbewntuk huibrid orbital f-f. jika electron tidak berpasangan dari dua atom
berasal dari orbital 3s dan 3p maka akan terbewntuk huibrid orbital sp 3, jika electron tidak
berpasangan dari dua atom berasal dari orbital 2s dan 2p maka akan terbewntuk huibrid
orbital sp2.
Teori tentang ikatan kimia
Ikatan kimia antar atom-atom bisa terjadi apabila electron kulit terluar dari suatu atom ada
yang tidak berpasangan. Suatu atom bisa berikatan dengan beberapa atom lain jika atom
tersebut mempunyai banyak elekton terluar (valensi) tak berpasangan. Contohnya CH4.

2p
2p

2p
H

s
C

s
CH4

Sebelum membentuk molekul CH4 pada mulanya jika ikatan terjadi antara atom karbon
dalam keadaan dasar dengan atom hindrogen hanya akan terbentuk molekul CH2, namun
karbon sendiri bisa mengalami eksitasi dari keadaan dasar.

2p

+
H

2s
1s
15

2p

2p
2s

2s

1s
CH2

2p
2p

2p

2p
H

2s

2s

1s

1s
+ 1s
1s
1s
4H

1s

C
Ground state

C
Exited state

2s

2s

1s

1s

CH4

Jenis-jenis ikatan kimia

Ikatan ion
Ikatan ion terjadi dalam suatu molekul jika molekul tersebut mengalami polarisasi muatan
elektrostatik. Hal ini terjadi pada molekul yang terdiri dari atom-atom elektropositif dan
atom elektronegatif membentuk molekul polar. Molekul polar apabila dilarutkan dalam
pelarut polar maka jarak atom elektropositif dan elektronegatif menjadi lebih jauh,
sehingga dengan demikian akan terjadi polarisasi muatan elektrostatik, dimana electron
terkuar dari atom elektro positif beredar pada inti atom elektronegatif sehingga atom
elektropoasitif akan kekurangan electron dan kelebihan proton keadaan seperti ini
membentuk mnuatan positif, sebaliknya atom elektronegatif akan menarik satu electron
at6om elektropositif yang beredar pada inti atom elektronegatif sehingga terbentuklah
muatan negative akibat atom elektronegatif kelebihan electron seperti reaksi berikut :
11

Na8OH + H2O

10

Na(H2O)2+ + 9OH-

Atom Natrium yang mempunyai 11 elektron dan 11 proton, pada molekul Na(H 2O)2+
Elektron atom Natrium hanya 10 elektron yang mengitari orbit inti atom Natrium sehingga
atom natrium kekurangan 1 elektron sehingga menjadi bermuatan (+) sedangkan atom
oksigen yang mempunyai 8 elektron pada molekul OH- atom oksigen mempunyai 9
elektron sehingga bermuatan (-). Senyawa organic kebannyakan tidak ada yang berikatan
polar tetapi hanya berikatan semi polar.
Ikatan kovalen
16

Ikatan kovalen adalah pemasangan electron tunggal dua atom atau lebih membentuk
molekul tanpa terjadinya polarisasi electron. Kedua electron yang berpasangan dari dua
atom berotasi mengitari inti dari masing-masing atom penyusunnya. Contohnya molekul
CH4. :

H
.

C.

H.

C H
H

Muatan Formal.
Cara penentuan muatan elektrostatik secara teoritis dapat ditentukan dengan cara
pendekatan muatan formal. Pada cara ini nilai muatan formal dihitung berdasarkan jumlah
electron kulit terluar dalam suatu atom dikurangi dengan jumlah electron kulit terluar
dalam atom berikatan atau jumlah electron kulit terluar
Jumlah electron
Mf = kulit terluar dalam

jumlah electron

kulit terluar dalam.

Atom bebas

atom berikatan

Jumlah electron

jumlah electron

Mf = kulit terluar dalam

Atom bebas

kulit terluar dalam

jumlah elektron

kulit terluar bebas

atom berikatan

Momen dipole
Bila masing-masing ikatan dalam suatu molekul polar memebentuk momen, maka
ikatan keseluruhan dalam molekul sering kali jadi polar. Kepolarann total ini bersal dari
penjumlahan kepolaran semua ikatan dan kontribusi pasangan electron bebas dalam
suatu molekul. Ukuran besaran keseluruhan kepolaran dari masing ikatan dalam molekul
ini disebut moment dipole. Kita bisa menggambarkan moment dipole dengan cara
berikut, misalkan ada suatu pusat grafitasi ari seluruh muatan positif dalam suatu
molekul, misalkan juga dalam molekul tersebut ada pusat grafitasi muatan negative. Jika
kedua pusat grafitasi muatan ini tak berimpitan maka molekul tersebut mempunyai
muatan listrik yang tak simetris dan mempunyai muatan total.. Moment dipole

17

(didefinisikan sebagai besaran unit muatan listrik (e) dikali jarak (d) antar pusat
muatan yang dinyatakan dalam satuan debye (D)

e ) x ( d ) x ( 10 18 ) = Debye
e = muatan listrik dalam satuan elektrostatik ( esu) = 4,8 x 10-10 esu
d = jarak antar muatan listrik statis dalam sentimeter
sebagai contoh jika satu proton dan satu electron ( e = 4.8 x 10

-10

esu ) dipisahkan satu sama

lainnya sejarak 1 Ao (10-8 cm) , maka didapatkan nilai sebagai berikut :

= ( 4.8 x 10 -10 esu ) (10-8 cm ) (1018) = 4,8 D
Secara percobaan akan relative lebih mudah mengukur moment dipole seperti nilainya
tercantum dalam table berikut :
Tabel 1. Nilai moment dipole dari beberapa senyawa kimia
senyawa Moment dipole Senyawa

Moment dipole

NaCl
CH3Cl
H2O

( D)
9,00
1,87
1,85

H3C-CH3
C6H6
BF3

(D)
0,00
0,00
0,00

H3COH

1,70

H2C=N+ =N-

1,50

NH3

1,47

H3C-N+=O

3,46

OH4C
CCl4

0,00
0,00

Dari table 1 diatas terlihat bahwa NaCl mempunyai nilai moment dipole yang luar biasa
besarnnya karena senyawwa ini bersifat ion. Nitrometana H3CNO2 mempunyai nilai moment
dipole cukup besar, karena senyawa ini mempunyai muatan formal pada dua atomnya.
Konsep dasar asam basa

18

Pengertian asam secara kimia menurut konsep bronsted-Lowry adalah suatu molekul yang
dapat melepaskan proton ( H+ ), sedangkan basa adalah suatu molekul menerima proton
( H+ ). Keasaman adalah kemampuan suatu senyawa melepaskan proton dan kebasaan
adalah kemampuan suatu senyawa untuk menerima proton. Menurut Lewis asam adalah
senyawa yang mempunyai orbital electron terluar yang kosong untuk ditempati oleh
pasangan electron bebas dari suatu molekul senyawa lain, sedangkan basa adalah suatu
molekul yang mempunyai pasangan electron bebas yang bisa didonorkan orbital electron
terluar yang kosong dari molekul lainnya.

MODUL III
III.

KONSEP DASAR SENYAWA ORGANIK

Gugus fungsi senyawa organic

Penggolongan senyawa organic didasarkan atas reaktifitas dari gugus yang terdapat dalam
susunan molekul senyawa organic. Pusat reaksi senyawa organic berada pada gugus fungsi
tersebut. Ada senyawa organic yang mempunyai mono gugus fungsi dan ada pula yang
poli gugus fungsi. Gugus fungsi adalah merupakan bahagian dari molekul besar senyawa
organic. Ia tersusun dari atom atau gugus atom-atom yang menentukan karakteristik dari
kereaktifan kimia senyawa. Jika suatu senyawa hanya mempunyai satu gugus fungsi maka
senyawa itu disebut mono gugus fungsi. Jika suatu senyawa mempunyai banyak gugus
fungsi disebut poli gugus fungsi. Jenis-jenis gugus fungsi senyawa organic yang telah
diketahui
Tabel 2. Prefixed substituents are ordered alphabetically (excluding any modifiers such as di-, tri-,
etc.), e.g. chlorofluoromethane, not fluorochloromethane. If there are multiple functional groups
of the same type, either prefixed or suffixed, the position numbers are ordered numerically (thus
ethane-1,2-diol, not ethane-2,1-diol.) The N position indicator for amines and amides comes
before "1", e.g. CH3CH(CH3)CH2NH(CH3) is N,2-dimethylpropanamine.
Priority

Functional group

Cations
e.g. Ammonium

Carboxylic acids

Formula

Prefix

Suffix

NH4

-onioammonio-

-onium
-ammonium

COOH

carboxy-

-oic acid*

19

Thiocarboxylic acids
Selenocarboxylic acids
Sulfonic acids
Sulfinic acids
Sulfenic acids

COSH
COSeH
SO3H
SO2H
SOH

thiocarboxyselenocarboxysulfosulfinosulfeno-

-thioic acid*
-selenoic acid*
-sulfonic acid
-sulfinic acid
-sulfenic acid

Carboxylic acid derivatives

Esters
Acyl halides
Amides
Imides
Amidines

COOR
COX
CONH2
CON=C<
C(=NH)NH2

R-oxycarbonylhalidealcanoylcarbamoyl-imidoamidino-

-R-oate
-oyl halide*
-amide*
-imide*
-amidine*

Nitriles
Isocyanides

CN
NC

cyanoisocyano-

-nitrile*
isocyanide

Aldehydes
Thioaldehydes

CHO
CHS

formylthioformyl-

-al*
-thial*

Ketones
Thioketones

>CO
>CS

oxothiono-

-one
-thione

Alcohols
Thiols
Selenols
Tellurols

OH
SH
SeH
TeH

hydroxysulfanylselanyltellanyl-

-ol
-thiol
-selenol
-tellurol

Hydroperoxides

OOH

hydroperoxy-

-hydroperoxide

Amines
Imines
Hydrazines

NH2
=NH
NHNH2

aminoiminohydrazino-

-amine
-imine
-hydrazine

10

Ethers
Thioethers
Selenoethers

O
S
Se

-oxy-thio-seleno-

11

Peroxides
Disulfides

OO
SS

-peroxy-disulfanyl20

*Note: These suffixes, in which the carbon atom is counted as part of the preceding chain, are the most commonly
used. See individual functional group articles for more details.

Tabel 3. Jenis-jenis gugus fungsi senyawa organic yang telah dikenal

No Jenis senyawa

Akhiran nama

1
2
3
4
5
6
7

-ana
-ena
-una

8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25

Gugus fungsi Contoh

senyawa
Alkana
R-CH3
Alkena
C=C
Alkuna
C C
Halide alkana
RX
Alkanol
ROH
Alkoksi alkana
ROR
Alkanal
R-C=O
H
Alkanon
R-C=O
R
Alkil alkanoat
R-C=O
OR
Alkanoat
R-C=O
OH
Alkanoil halide
R-C=O
X
Alkanoil amida
R-C=O
NH2
Alkil amina
RCH2NH2
Alkil sianida
RCH2-C N
Alkil nitrit
RCH2NO2
Alkil sulfide
RCH2SH
Alkil Sulfoksi alkana R-SO-R
Dialkil Sulfonat
R-SO2-R
Alkil logam
RCH2M
Alkanoailsulfat
R-C=O
OSO3H
Alkanoail sianida
R-C=O
OCN
Alkanoail halide
R-C=O
OX
Alkanoail amida
R-C=O
ONH2
Alkanoilsianida
R-C=O
CN
Alkil karbamat
R-C=S
SH
21

-ol
-oksi -ana
-al
-on
-il -oat
-oat
-oil -ida
-oil amida
-il -amina
-il sianida
-il nitrat
-il sulfida
-il sulfoksana
-il
-il logam
-oail sulfat
-oail sianida
-oail halida
-oail amida
-oil sianidda
-il karbamat

26
27
28

diAlkil disulfida
Dialkil sulfida
Dithiokarbonat

29

Alkilsulfonat

30

Alkil sulfinat

31
32
33

Dialkilsulfat
Alkil posfat
Alkanoil posfit

34

Alkanoail posfat

35

Alkil posfat

R-S-S-R
R-S-R
RO-C=S
SH
O
R-O-S-OH
O
R-O-S=O
OH
R-O-SO2-OR
R-PO3H2
R-C=O
OPO3H2
R-C=O
PO4H2
ROPO2H

-il disulfida
-il sulfida
-il thiokarbonat
Il sulfonat
-il sulfinat
-il sulfat
-il posfit
-il posfat
Posfo alakanoat

Organic Chemistry/Overview of Functional Groups

The number of known organic compounds is quite large. In fact, there are many times more
organic compounds known than all the other (inorganic) compounds discovered so far, about 7
million organic compounds in total. Fortunately, organic chemicals consist of a relatively few
similar parts, combined in different ways, that allow us to predict how a compound we have never
seen before may react, by comparing how other molecules containing the same types of parts are
known to react.
These parts of organic molecules are called functional groups. The identification of functional
groups and the ability to predict reactivity based on functional group properties is one of the
cornerstones of organic chemistry.
Functional groups are specific atoms, ions, or groups of atoms having consistent properties. A
functional group makes up part of a larger molecule.
For example, -OH, the hydroxy group that characterizes alcohols, is an oxygen with a hydrogen
attached. It could be found on any number of different molecules.
Just as elements have distinctive properties, functional groups have characteristic chemistries.
An -OH group on one molecule will tend to react similarly, although perhaps not identically, to an
-OH on another molecule.
Organic reactions usually take place at the functional group, so learning about the reactivities
of functional groups will prepare you to understand many other things about organic chemistry.

Memorizing Functional Groups

Don't deceive yourself and think that you can simply skim over the functional groups and move
on. As you proceed through the text, the writing will be in terms of functional groups. It will be
assumed that the student is familiar with most of the ones in the tables below. It's simply
impossible to discuss chemistry without knowing the "lingo". It's like trying to learn French
without first learning the meaning of some of the words.
22

One of the easiest ways to learn functional groups is by making flash cards. Get a pack of index
cards and write the name of the functional group on one side, and draw its chemical representation
on the other.
For now, a list of the most important ones you should know is provided here. Your initial set of
cards should include, at the very least: Alkene, Alkyne, Alkyl halide (or Haloalkane), Alcohol,
Aldehyde, Ketone, Carboxylic Acid, Acyl Chloride (or Acid Chloride), Ester, Ether, Amine,
Sulfide, and Thiol. After you've learned all these, add a couple more cards and learn those. Then
add a few more and learn those. Every functional group below is eventually discussed at one point
or another in the book. But the above list will give you what you need to continue on.
And don't just memorize say, the names of the structures. To test yourself, try going through your
cards and looking at the names and then drawing their structure on a sheet of paper. Then try
going through and looking at the structures and naming them. Once you have the minimal list
above memorized backwards and forwards, you're ready to move on. But don't stop learning the
groups. If you choose to move on without learning the "lingo", then you're not going to
understand the language of the chapters to come. Again, using the French analogy, it's like trying
to ignore learning the vocabulary and then picking up a novel in French and expecting to be able
to read it.

Functional groups containing ...

In organic chemistry functional groups are submolecular structural motifs, characterized by
specific elemental composition and connectivity, that confer reactivity upon the molecule that
contains them.
Common functional groups include:
Chemical
class

Group

Formula

Acyl halide

Haloformy
l

RCOX

Hydroxyl

ROH

Alcohol

Graphical
Formula

Prefix

Suffix

haloformyl-

-oyl halide

Example

Acetyl chloride
(Ethanoyl chloride)

hydroxy-

-ol
Methanol

23

Aldehyde Aldehyde

RCHO

oxo-

-al
:Acetaldehyde
(Ethanal)

Alkane

Alkyl

RHn

alkyl-

-ane
Methane

Alkene

Alkenyl

R2C=CR2

alkenyl-

-ene
Ethylene
(Ethene)

Alkyne

Amide

Alkynyl

RCCR'

Carboxami
RCONR2
de

alkynyl-

-yne

carboxamid
o-

-amide

amino-

-amine

Acetylene
(Ethyne)

Acetamide
(Ethanamide)

Amines
Primary
amine

Secondary
amine

RNH2

Methylamine
(Methanamine)
R2NH

amino-

-amine
Dimethylamine

24

Tertiary
amine

R3N

amino-

-amine
Trimethylamine

4
ammonium
ion

Azo
Azo
compound (Diimide)

R4N+

ammonio-

-ammonium
Choline

RN2R'

azo-

-diazene
Methyl orange

Toluene
derivative

Carbonate

Benzyl

RCH2C6H5
RBn

benzyl-

Carbonate
ROCOOR
ester

1(substituent)tol
uene

alkyl
carbonate

Carboxylat Carboxylat
e
e

RCOO

carboxy-

-oate

Carboxylic
Carboxyl
acid

RCOOH

carboxy-

-oic acid

Sodium acetate
(Sodium ethanoate)

Acetic acid
(Ethanoic acid)

Cyanate

ROCN

Thiocyanat
e

RSCN

Ether

Ether

ROR'

Ester

Ester

RCOOR'

Cyanates

Benzyl bromide
(1-Bromotoluene)

cyanato-

alkyl cyanate

thiocyanato
alkyl
thiocyanate
alkoxy-

alkyl alkyl
ether

Diethyl ether
(Ethoxyethane)

-oate
Ethyl butyrate
25

(Ethyl butanoate)
Haloalkane

Halo

Hydroperox
ide (see Hydropero
organic
xy
peroxide)

RX

ROOH

halo-

alkyl halide

hydroperox
alkyl
yhydroperoxide

Primary
RC(=NH)R'
ketimine

imino-

-imine

Secondary
RC(=NR)R'
ketimine

imino-

-imine

Primary
RC(=NH)H
aldimine

imino-

-imine

Secondary
RC(=NR')H
aldimine

imino-

-imine

Chloroethane
(Ethyl chloride)

Methyl ethyl
ketone peroxide

Imine

Isocyanide Isocyanide

alkyl
isocyanide
alkyl
isocyanate

RNC

isocyano-

Isocyanate

RNCO

isocyanato-

Isothiocya
nate

RNCS

isothiocyan
alkyl
atoisothiocyanate

Ketone

Ketone

RCOR'

keto-, oxo-

-one

Nitrile

Nitrile

RCN

cyano-

alkanenitrile
alkyl cyanide

Isocyanates

Nitro
compound

Nitro

RNO2

Allyl
isothiocyanate

Methyl ethyl
ketone
(Butanone)

Benzonitrile
(Phenyl cyanide)

nitroNitromethane
26

Nitroso
compound

Nitroso

Peroxide

Peroxy

ROOR

peroxy-

alkyl peroxide

Benzene
derivative

Phenyl

RC6H5

phenyl-

-benzene

RNO

nitrosoNitrosobenzene

Di-tert-butyl
peroxide

Cumene
(2-phenylpropane)
Phosphine Phosphino

R3P

phosphino-

-phosphane

Phosphodie
HOPO(OR)
Phosphate
ster
2

phosphoric
di(substituent)
acid
hydrogenphosp
di(substitue
hate
nt) ester

Phosphonic
Phosphono
acid

RP(=O)
(OH)2

phosphono-

Phosphate Phosphate

ROP(=O)
(OH)2

phospho-

substituent
phosphonic
acid

Methylpropylphosp
hane
DNA

Benzylphosphonic
acid

Glyceraldehyde 3phosphate

4-pyridyl
(pyridin-4yl)
Pyridine
derivative

Pyridyl

3-pyridyl
(pyridin-3yl)

RC5H4N

-pyridine
Nicotine

2-pyridyl
(pyridin-2yl)
Sulfide

di(substituent)
sulfide

RSR'

27

Dimethyl sulfide

Sulfone

Sulfonyl

RSO2R'

sulfonyl-

Sulfonic
acid

Sulfo

RSO3H

sulfo-

Sulfoxide

Sulfinyl

RSOR'

sulfinyl-

di(substituent)
sulfone
Dimethyl sulfone
(Methylsulfonylmet
hane)
substituent
sulfonic acid

Benzenesulfonic
acid

di(substituent)
sulfoxide
Diphenyl sulfoxide

Thiol

Sulfhydryl

mercapto-,
sulfanyl-

RSH

-thiol

Ethanethiol
(Ethyl mercaptan)

Note: The table above is adapted from the Functional Groups table on Wikipedia.
Combining the names of functional groups with the names of the parent alkanes generates a
powerful systematic nomenclature for naming w:organic compounds.
The non-hydrogen atoms of functional groups are always associated with each by covalent bonds,
as well as with the rest of the molecule. When the group of atoms is associated with the rest of the
molecule primarily by ionic forces, the group is referred to more properly as a polyatomic ion or
complex ion. And all of these are called radicals, by a meaning of the term radical that predates
the free radical.
The first carbon after the carbon that attaches to the functional group is called the alpha carbon.
Retrieved from
"http://en.wikibooks.org/wiki/Organic_Chemistry/Overview_of_Functional_Groups"

MODUL IV
IV.

JENIS-JENIS REAKSI DALAM SENYAWA ORGANIK

Jenis-jenis reaksi pada senyawa organic

a. Reaksi addisi
28

b. C = C + H2

CH CH

b. Reaksi substitusi
RX + OH-

ROH + X-

c. Reaksi eliminasi
RCHX-CH3

RCH=CH2 + HX

d. Reaksi oksidasi
RCH2OH + KMnO4

RC =O
H

e. Reaksi reduksi
RCN + LiAlH4

RCH2NH2

f. Reaksi penataan ulang (rearrangement)

H3C-H2C-CH=CH-CH=CH2

H3C-H2C=CH-CH=CH-CH3

Pada dasarnya jenis-jenis reaksi pada senyawa organic ada 3 ienis yakni reaksi polar, reaksi
radikal, dan reaksi perisiklik.
Kecepatan dan mekanisme reaksi senyawa organic
Energi ikatan pada senyawa organic

MODUL V
V.

JENIS-JENIS SENYAWA ORGANIK

Alkana
29

Rumus umum senyawa alkana adalah CnH2n+2

Pemberian nama senyawa organic dengan dua standar :
1. IUPAC
2. Trivial :
a. Nama dagang
b. Nama sumber
c. Nama local
d Nama penemu
Pemberian nama pada deret homolog senyawa alkana dengan dua cara yaitu :
IUPAC ( International Union Pure and Applied Chemistry )
Rantai molekul lurus
Tata nama senyawa homolog hidrokarbon pada senyawa organic rantai lurus menurut IUPAC
adalah berdasarkan jumlah atom karbonnya sebagai berikut :
Senyawa
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202
C200H402

Nama
Metana
Etana
Propane
Butane
Pentane
Heksana
Heptana
Oktana
Nonana
Dekana
Undekana
Dodekana
Tridekana
Tetradekana
Pentadekana
Heksadekana
Heptadekana
Oktadekana
Nonadekana
Eikosana
Heneikosana
Dokosana
Trikosana
Tetrakosana
Pentakosana
Heksakosana
Heptakosana
Oktakosana
Nonakosana
Triakontana
Hentriakontana
Dotriakontana
Tritriakontana
Hektana
Dohektana

Senyawa
C34H44
C35H46
C36H48
C37H50
C38H52
C39H54
C40H56
C41H58
C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110
C55H112
C56H114
C57H116
C58H118
C59H120
C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802
C500H1002

Nama
tetratriakontana
pentatriakontana
heksatriakontana
heptatriakontana
oktatriakontana
nonatriakontana
Tetrakontana
hentetrakontana
Dotetrakontana
Tritetrakontana
tetratetrakontana
pentatetrakontana
heksatetrakontana
heptatetrakontana
oktatetrakontana
nonatetrakontana
Pentakontana
Henpentakontana
dopentakontana
tripentakontana
tetrapentakontana
pentapentakontana
heksapentakontana
heptapentakontana
Oktapentakontana
nonapentakontana
Heksa kontana
HenHeksa kontana
doHeksa kontana
triHeksa kontana
tetraHeksa kontana
pentaHeksa kontana
heksaHeksa kontana
Tetrahektana
Pentahektana

30

Senyawa
C67H136
C68H138
C69H140
C70H142
C71H144
C72H146
C73H148
C74H150
C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176
C88H178
C89H180
C90H182
C91H184
C92H186
C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402
C800H1602

Nama
heptaHeksa kontana
oktaHeksa kontana
nonaHeksa kontana
Heptakontana
henHeptakontana
DoHeptakontana
triHeptakontana
tetraHeptakontana
pentaHeptakontana
heksaHeptakontana
heptaHeptakontana
oktaHeptakontana
nonaHeptakontana
Oktakontana
henOktakontana
doOktakontana
triOktakontana
tetraOktakontana
pentaOktakontana
heksaOktakontana
heptaOktakontana
oktaOktakontana
nonaOktakontana
Nonakontana
henNonakontana
doNonakontana
triNonakontana
tetraNonakontana
pentaNonakontana
heksaNonakontana
HeptaNonakontana
oktaNonakontana
nonaNonakontana
Heptahektana
Oktahektana

C300H6002
C1000H2002
C2000H4002
C3000H6002

Trihektana
kiliana
Dilianatana
Triliana

C600H12002
C400H8002
C500H10002
C600H1202

Heksahektana
Tetraliana
Penliaana
Heksaliana

C900H1802
C700H14002
C800H16002
C900H18002

Nonahektana
Heptaliana
Oktaliana
Nonaliana

Rantai molekul bercabang

Untuk rantai molekul bercabang harus dipenuhi kaidah rantai lurus dan rantai lingkar.
Rantai molekul lurus bercabang lurus
Untuk pemberian nama senyawa hidrokarbon berantai molekul lurus bercabang didasarkan
pada aturan berikut :
a. rantai dasar ditentukan berdasarkan rantai molekul terpanjang.
14

CH3-CH2

CH3-(CH2)2
7

CH3

10

11

15

16

17

18

19

20

CH2-CH2-CH2-CH2-CH2-CH2-CH3

12

13

H3C-CH2-CH-CH2-CH - CH-CH2-CH2-CH-CH-CH3
1

(CH2)5-CH3

CH2CH3

CH3

7 isobutil, 9 propil, 10 etil, 11 metil, 13 isopropil eikosana

Tulisan berwarna biru menunjukkan rantai utama sedangkan tulisan berwarna merah
menunjukkan substituen.
b. Penomoran atom karbon pada hidrokarbon dimulai pada gugus tersubstitusi yang paling
dekat ke ujung rantai.
c. Bila ada beberapa gugus yang sama tersubstitusi pada rantai utama maka dinamai dengan
awalan di, tri dan seterusnya. Contoh

11 10

H3C-CH2-CH-CH2-CH2-CH-CH2-CH2-CH2-CH-CH3
CH3
CH3
2,6, 9 trimetil undekana

CH3

d. Urutan gugus tersubstitusi dimulai dari gugus berurutan dimulai berdasrkan abjad atau
nomor urut gugus yang paling dekat ke awal rantai
11 10

H3C-CH2-CH-CH2-CH2-CH-CH2-CH2-CH2-CH-CH3
CH3

CH3

CH3
31

2,6, 9 trimetil undekana

Rantai molekul lurus bercabang lingkar
H3C-CH2-CH-CH2-CH2-CH-CH2-CH2-CH2

Nonil sikloheksana
rantai molekul lingkar bercabang lingkar

Rantai molekul lingkar terkondensasi.

Rantai lingkar
a. Siklo propana

b. Siklo butana

e. Siklo pentana

f. Siklo heksana

g. Siklo oktana

32

IUPAC nomenclature of organic chemistry

From Wikipedia, the free encyclopedia
Jump to: navigation, search
The IUPAC nomenclature of organic chemistry is a systematic method of naming organic
chemical compounds as recommended[1] by the International Union of Pure and Applied
Chemistry (IUPAC). Ideally, every organic compound should have a name from which an
unambiguous structural formula can be drawn. There is also an IUPAC nomenclature of inorganic
chemistry. See also phanes nomenclature of highly complex cyclic molecules.
The main idea of IUPAC nomenclature is that every compound has one and only one name, and
every name corresponds to only one structure of molecules (i.e. a one-one relationship), thereby
reducing ambiguity.
For ordinary communication, to spare a tedious description, the official IUPAC naming
recommendations are not always followed in practice except when it is necessary to give a
concise definition to a compound, or when the IUPAC name is simpler (viz. ethanol against ethyl
alcohol). Otherwise the common or trivial name may be used, often derived from the source of the
compound (See Sec 14. below)

Basic principles
In chemistry, a number of prefixes, suffixes and infixes are used to describe the type and position
of functional groups in the compound.
The steps to naming an organic compound are:
1. Identify the parent hydrocarbon chain (The longest continuous chain of carbon atoms)
2. Identify the functional group, if any (If more than one, use the one with highest
precedence as shown here)
1. Identify the position of the functional group in the chain.
2. Number the carbon atoms in the parent chain. The functional group should end up
the least number possible (as there are two ways of numberingright to left and
left to right). The number (in Arabic numerals, i.e. 1, 2, 3....) is written before the
name of the functional group suffix (such as -ol, -one, -al, etc.). If the group is a
group that can only exist at the end of any given chain (such as the carboxylic acid
and aldehyde groups), it need not be numbered.
NOTE: If there are no functional groups, number in both directions, find the
numbers of the side-chains (the carbon chains that are not in the parent chain) in
both directions. The end result should be such that the first number should be the
least possible. In the event of the first numbers being the same for two methods of
numbering, the sum of the numbers of the side chains should be made the least
possible; for example, 2,2,5-trimethylhexane (2 + 2 + 5 = 9) is preferred over
2,5,5-trimethylhexane (2 + 5 + 5 = 12), as they both start with '2', but the sum of
the numbers of the former is less.
3. Identify the side-chains and number them. Side chains are the carbon chains that are not in
the parent chain, but are branched off from it.
If there is more than one of the same type of side-chain, add the prefix (di-, tri-, etc.)
before it. The numbers for that type of side chain will be grouped in ascending order and
33

4.

5.

6.

7.

written before the name of the side-chain. If there are two side-chains with the same alpha
carbon, the number will be written twice. Example: 2,2,3-trimethyl...
Identify the remaining functional groups, if any, and name them by the name of their ions
(Such as hydroxy for -OH, oxy for =O , oxyalkane for O-R, etc.).
Different side-chains and functional groups will be grouped together in alphabetical order.
(The prefixes di-, tri-, etc. are not taken into consideration for grouping alphabetically. For
example, ethyl comes before dihydroxy or dimethyl, as the "e" in "ethyl" precedes the "h"
in "hydroxy" and the "m" in "dimethyl" alphabetically. The "di" is not considered in both
cases.) In the case of there being both side chains and secondary functional groups, they
should be written mixed together in one group rather than in two separate groups.
Identify double/triple bonds. Number them with the number of the carbon atom at the head
of the bond (i.e the carbon atom with the lesser number that it is attached to). For example
a double bond between carbon atoms 3 and 4 is numbered as 3-ene. Multiple bonds of one
type (double/triple) are named with a prefix (di-, tri-, etc.). If both types of bonds exist,
then use "ene" before "yne" e.g. "6 13 diene 19 yne"If all bonds are single, use "ane"
without any numbers or prefixes.
Arrange everything like this: Group of side chains and secondary functional groups with
numbers made in step 3 + prefix of parent hydrocarbon chain (eth, meth) + double/triple
bonds with numbers (or "ane") + primary functional group suffix with numbers.
Wherever it says "with numbers", it is understood that between the word and the numbers,
you use the prefix(di-, tri-)
Add punctuation:
1. Put commas between numbers (2 5 5 becomes 2,5,5)
2. Put a hyphen between a number and a letter (2 5 5 trimethylhexane becomes 2,5,5trimethylhexane)
3. Successive words are merged into one word (trimethyl hexane becomes
trimethylhexane)
NOTE: IUPAC uses one-word names throughout. This is why all parts are
connected.

The finalized name should look like this:

#,#-di<side chain>-#-<secondary functional group><-#-<side chain>-#,#,#-tri<secondary
functional group><parent chain suffix><If all bonds are single bonds, use "ane">-#,#di<double bonds>-#-<triple bonds>-#-<primary functional group>
NOTE: # is used for a number. The group secondary functional groups and side chains may not
look the same as shown here, as the side chains and secondary functional groups are arranged
alphabetically. The di- and tri- have been used just to show their usage. (di- after #,#, tri- after
#,#,# , etc.)
Example:
Here is a sample molecule with the parent carbons numbered:

34

For simplicity, here is an image of the same molecule, where the hydrogens in the parent chain are
removed and the carbons are shown by their numbers:

Now, we go by the steps:

1. The parent hydrocarbon chain has 23 carbons. It is called tricos-.
2. The functional groups with the highest precedence are the two ketone groups.
1. The groups are on carbon atoms 3 & 9. As there are two, we write 3,9-dione.
2. The numbering of the molecule is based on the ketone groups. when numbering
from left to right, the ketone groups get numbered 3 and 9.when numbering from
right to left, the ketone groups get numbered 15 and 21. The sum of 3 & 9 (12) is
less than the sum of 15 & 21 (36). Therefore, the numbering is done left to right,
and the ketones are numbered 3 & 9.
3. The side chains are: an ethyl- at carbon 4, an ethyl- at carbon 8, and a butyl- at carbon 12.
NOTE:The -O-CH3 at carbon atom 15 is not a side chain, but it is a methoxy functional
group
o
o

There are two ethyl- groups, so they are combined to create, 4,8-diethyl.
The side chains shall be grouped like this: 12-butyl-4,8-diethyl. (But this is not the
final grouping, as functional groups may be added in between.)
2. The secondary functional groups are: a hydroxy- at carbon 5, a chloro- at carbon 11, a
methoxy- at carbon 15, and a bromo- at carbon 18. Grouped with the side chains, we get
18-bromo-12-butyl-11-chloro-4,8-diethyl-5-hydroxy-15-methoxy
3. There are two double bonds: one between carbons 6 & 7, and one between carbons 13 &
14. They will be called 6,13-diene. There is one triple bond between carbon atoms 19 &
20. It will be called 19-yne
4. The arrangement(with punctuation) is: 18-bromo-12-butyl-11-chloro-4,8-diethyl-5hydroxy-15-methoxytricos-6,13-diene-19-yne-3,9-dione
The final name is 18-bromo-12-butyl-11-chloro-4,8-diethyl-5-hydroxy-15-methoxytricos-6,13diene-19-yne-3,9-dione.

Alkanes
Main article: Alkanes
Straight-chain alkanes take the suffix "-ane" and are prefixed depending on the number of carbon
atoms in the chain, following standard rules. The first few are:

35

Numb
er of
1
carbo
ns

Prefix

10 11

12

13

14

15

20

30

Met Et Pro Bu Pen He Hep Oc No De Unde Dode Tride Tetrade Pentad Eico Triaco
h
h p t t
x t
t n c c
c
c
c
ec
s
nt

For example, the simplest alkane is CH4 methane, and the nine-carbon alkane CH3(CH2)7CH3 is
named nonane. The names of the first four alkanes were derived from methanol, ether, propionic
acid and butyric acid, respectively. The rest are named with a Greek numeric prefix, with the
exceptions of nonane which has a Latin prefix, and undecane and tridecane which have mixedlanguage prefixes.
Cyclic alkanes are simply prefixed with "cyclo-", for example C4H8 is cyclobutane and C6H12 is
cyclohexane.

Branched alkanes are named as a straight-chain alkane with attached alkyl groups. They are
prefixed with a number indicating the carbon the group is attached to, counting from the end of
the alkane chain. For example, (CH3)2CHCH3, commonly known as isobutane, is treated as a
propane chain with a methyl group bonded to the middle (2) carbon, and given the systematic
name 2-methylpropane. However, although the name 2-methylpropane COULD be used, it is
easier and more logical to call it simply methylpropane - the methyl group could not possible
occur on any of the other cabon atoms (that would lengthen the chain and result in butane, not
propane) and therefore the use of the number "2" is not necessary.
If there is ambiguity in the position of the substituent, depending on which end of the alkane chain
is counted as "1", then numbering is chosen so that the smallest number is used. For example,
(CH3)2CHCH2CH3 (isopentane) is named 2-methylbutane, not 3-methylbutane.

36

If there are multiple side-branches of the same size alkyl group, their positions are separated by
commas and the group prefixed with di-, tri-, tetra-, etc., depending on the number of branches
(e.g. C(CH3)4 2,2-dimethylpropane). If there are different groups, they are added in alphabetical
order, separated by commas or hyphens: 3-ethyl-4-methylhexane. The longest possible main
alkane chain is used; therefore 3-ethyl-4-methylhexane instead of 2,3-diethylpentane, even though
these describe equivalent structures. The di-, tri- etc. prefixes are ignored for the purpose of
alphabetical ordering of side chains (e.g. 3-ethyl-2,4-dimethylpentane, not 2,4-dimethyl-3ethylpentane).

Alkenes and Alkynes

Main articles: Alkenes and Alkynes

Alkenes are named for their parent alkane chain with the suffix "-ene" and an infixed number
indicating the position of the double-bonded carbon in the chain: CH2=CHCH2CH3 is but-1-ene.
Multiple double bonds take the form -diene, -triene, etc., with the size prefix of the chain taking
an extra "a": CH2=CHCH=CH2 is buta-1,3-diene. Simple cis and trans isomers are indicated with
a prefixed cis- or trans-: cis-but-2-ene, trans-but-2-ene. More complex geometric isomerisations
are described using the Cahn Ingold Prelog priority rules.

Alkynes are named using the same system, with the suffix "-yne" indicating a triple bond: ethyne
(acetylene), propyne (methylacetylene).

37

Functional Groups
Table of Functional groups
Alk is the prefix of the group (Meth, Eth, Prop, etc.)

Family

IUPAC
Structure
nomenclature

IUPAC nomenclature for cyclic

parent chains (if different from
straight chains)

Common
nomenclature

Alkyl
groups

Alkyl

Alkyl

Halogens

R
halogen

Halo'alkane

Alkyl halide

Alcohols

ROH

Alkanol

Alkyl alcohol

Amines

RNH2

Alkanamine

Alkyl amine

Carboxylic
acids

(Alk + 1)anoic
acid

Cycloalkanecarboxylic acid

Aldehydes

Alkanal

Cycloalkanecarboxaldehyde

Ketones

Alkanone

Alk(1)yl Alk(2)yl
ketone

Alkanethiol

(Alk +
1)anamide

Cycloalkanecarboxamide

Thiols

Amides

RSH

38

Ethers

R1O
R2

Esters

alkoxyalkane

Alk(1)yl Alk(2)yl
ether

Alk(1)yl
Alk(2)aneoate

Alk(1)yl Cycloalk(2)anecarboxylate

Alk(1)yl (Alk + 1)
(2)anoate

Alcohols
Main article: Alcohols

Alcohols (R-OH) take the suffix "-ol" with an infix numerical bonding position: CH3CH2CH2OH
is propan-1-ol. The suffixes -diol, -triol, -tetraol, etc., are used for multiple -OH groups: Ethylene
glycol CH2OHCH2OH is ethane-1,2-diol.

If higher precedence functional groups are present (see order of precedence, below), the
prefix "hydroxy" is used with the bonding position: CH3CHOHCOOH is 2hydroxypropanoic acid.

Halogens (Alkyl Halides)

Main article: Halogens

Halogen functional groups are prefixed with the bonding position and take the form fluoro-,
chloro-, bromo-, iodo-, etc., depending on the halogen. Multiple groups are dichloro-, trichloro-,
etc, and dissimilar groups are ordered alphabetically as before. For example, CHCl3 (chloroform)
is trichloromethane. The anesthetic Halothane (CF3CHBrCl) is 2-bromo-2-chloro-1,1,139

trifluoroethane.

[edit] Ketones
Main article: Ketones

In general ketones (R-CO-R) take the suffix "-one" (pronounced own, not won) with an infix
position number: CH3CH2CH2COCH3 is pentan-2-one. if a higher precedence suffix is in use, the
prefix "oxo-" is used: CH3CH2CH2COCH2CHO is 3-oxohexanal.

Aldehydes
Main article: Aldehydes

Aldehydes (R-CHO) take the suffix "-al".If other functional groups are present, the chain is
numbered such that the aldehyde carbon is in the "1" position.
If a prefix form is required, "oxo-" is used (as for ketones), with the position number indicating
the end of a chain: CHOCH2COOH is 3-oxopropanoic acid. If the carbon in the carbonyl group
cannot be included in the attached chain (for instance in the case of cyclic aldehydes), the prefix
"formyl-" or the suffix "-carbaldehyde" is used: C6H11CHO is cyclohexanecarbaldehyde. If a
aldehyde is attached to a benzene and is the main functional group, the suffix becomes
benzaldehyde.

Carboxylic acids
Main article: Carboxylic acids

40

In general carboxylic acids are named with the suffix -oic acid (etymologically a back-formation
from benzoic acid). As for aldehydes, they take the "1" position on the parent chain, but do not
have their position number indicated. For example, CH3CH2CH2CH2COOH (valeric acid) is
named pentanoic acid. For common carboxylic acids some traditional names such as acetic acid
are in such widespread use they are considered retained IUPAC names, although "systematic"
names such as ethanoic acid are also acceptable. For carboxylic acids attached to a benzene ring
such as Ph-COOH, these are named as benzoic acid or its derivatives.
If there are multiple carboxyl groups on the same parent chain, the suffix "-carboxylic acid" can
be used (as -dicarboxylic acid, -tricarboxylic acid, etc.). In these cases, the carbon in the carboxyl
group does not count as being part of the main alkane chain. The same is true for the prefix form,
"carboxyl-". Citric acid is one example; it is named 2-hydroxypropane- 1,2,3-tricarboxylic acid,
rather than 2-carboxy, 2-hydroxypentanedioic acid.

Ethers
Main article: Ethers

Ethers (R-O-R) consist of an oxygen atom between the two attached carbon chains. The shorter of
the two chains becomes the first part of the name with the -ane suffix changed to -oxy, and the
longer alkane chain become the suffix of the name of the ether. Thus CH3OCH3 is
methoxymethane, and CH3OCH2CH3 is methoxyethane (not ethoxymethane). If the oxygen is not
attached to the end of the main alkane chain, then the whole shorter alkyl-plus-ether group is
treated as a side-chain and prefixed with its bonding position on the main chain. Thus
CH3OCH(CH3)2 is 2-methoxypropane.

Esters
Main article: Esters

41

Esters (R-CO-O-R') are named as alkyl derivatives of carboxylic acids. The alkyl (R') group is
named first. The R-CO-O part is then named as a separate word based on the carboxylic acid
name, with the ending changed from -oic acid to -oate. For example, CH3CH2CH2CH2COOCH3 is
methyl pentanoate, and (CH3)2CHCH2CH2COOCH2CH3 is ethyl 4-methylpentanoate. For esters
such as ethyl acetate (CH3COOCH2CH3), ethyl formate (HCOOCH2CH3) or dimethyl phthalate
that are based on common acids, IUPAC recommends use of these established names, called
retained names. The -oate changes to -ate. Some simple examples, named both ways, are shown
in the figure above.

If the alkyl group is not attached at the end of the chain, the bond position to the ester group is
infixed before "-yl": CH3CH2CH(CH3)OOCCH2CH3 may be called but-2-yl propanoate or but-2yl propionate.

Amines and Amides

Main articles: Amine and Amide

Amines (R-NH2) are named for the attached alkane chain with the suffix "-amine" (e.g. CH3NH2
methanamine). If necessary, the bonding position is infixed: CH3CH2CH2NH2 propan-1-amine,
CH3CHNH2CH3 propan-2-amine. The prefix form is "amino-".
For secondary amines (of the form R-NH-R), the longest carbon chain attached to the nitrogen
atom becomes the primary name of the amine; the other chain is prefixed as an alkyl group with
location prefix given as an italic N: CH3NHCH2CH3 is N-methylethanamine. Tertiary amines (RNR-R) are treated similarly: CH3CH2N(CH3)CH2CH2CH3 is N-ethyl-N-methylpropanamine.
Again, the substituent groups are ordered alphabetically.

42

Amides (R-CO-NH2) take the suffix "-amide". There is no prefix form, and no location number is
required since they always terminate a carbon chain, e.g. CH3CONH2 (acetamide) is named
ethanamide.
Secondary and tertiary amides are treated similarly to the case of amines: alkane chains bonded to
the nitrogen atom are treated as substituents with the location prefix N: HCON(CH3)2 is N,Ndimethylmethanamide.

] Cyclic compounds

Cycloalkanes and aromatic compounds can be treated as the main parent chain of the compound,
in which case the position of substituents are numbered around the ring structure. For example,
the three isomers of xylene CH3C6H4CH3, commonly the ortho-, meta-, and para- forms, are 1,2dimethylbenzene, 1,3-dimethylbenzene, and 1,4-dimethylbenzene. The cyclic structures can also
be treated as functional groups themselves, in which case they take the prefix "cycloalkyl-" (e.g.
"cyclohexyl-") or for benzene, "phenyl-".
The IUPAC nomenclature scheme becomes rapidly more elaborate for more complex cyclic
structures, with notation for compounds containing conjoined rings, and many common names
such as phenol, furan, indole, etc. being accepted as base names for compounds derived from
them.

Order of precedence of groups

When compounds contain more than one functional group, the order of precedence determines
which groups are named with prefix or suffix forms. The highest precedence group takes the
suffix, with all others taking the prefix form. However, double and triple bonds only take suffix
form (-en and -yn) and are used with other suffixes.

43

Common nomenclature - trivial names

Common nomenclature is an older system of naming organic compounds. Instead of using the
prefixes for the carbon skeleton above, another system is used. The pattern can be seen below.
Number of Prefix as in new Common name for
carbons
system
alcohol

Common name for

aldehyde

Common name
for acid

Meth

Methyl alcohol
(wood alcohol)

Eth

Ethyl alcohol (grain

Acetaldehyde
alcohol)

Acetic acid

Prop

Propyl alcohol

Propionaldehyde

Propionic acid

But

Butyl alcohol

Butyraldehyde

Butyric acid

Pent

Amyl alcohol

Valeraldehyde

Valeric acid

Hex

Caproaldehyde

Caproic acid

Hept

Enanthyl alcohol

Enanthaldehyde

Enanthoic acid

Oct

Capryl alcohol

Caprylaldehyde

Caprylic acid

Non

Pelargonaldehyde

Pelargonic acid

10

Dec

Capric alcohol

Capraldehyde

Capric acid

12

Dodec

Lauryl alcohol

Lauraldehyde

Lauric acid

14

Tetradec

Myristaldehyde

Myristic acid

16

Hexadec

Cetyl alcohol

Palmitaldehyde

Palmitic acid

44

Formaldehyde

Formic acid

17

Heptadec

Margaric acid

18

Octadec

Stearyl alcohol

Stearaldehyde

Stearic acid

20

Icos

Arachidyl alcohol

Arachidic acid

22

Docos

Behenyl alcohol

Behenic acid

24

Tetracos

Lignoceryl alcohol

Lignoceric acid

26

Hexacos

Cerotinyl alcohol

Cerotinic acid

28

Octacos

Montanyl alcohol

Montanic acid

30

Triacont

Melissyl alcohol

Melissic acid

Ketones
Common names for ketones can be derived by naming the two alkyl or aryl groups bonded to the
carbonyl group as separate words followed by the word ketone.

Acetone
Acetophenone
Benzophenone
Ethyl isopropyl ketone
Diethyl ketone

The first three of the names shown above are still considered to be acceptable IUPAC names.

Aldehydes
The common name for an aldehyde is derived from the common name of the corresponding
carboxylic acid by dropping the word acid and changing the suffix from -ic or -oic to -aldehyde.

Formaldehyde
Acetaldehyde

45

Ions
The IUPAC nomenclature also provides rules for naming ions.

Hydron
Hydron is a generic term for hydrogen cation; protons, deuterons and tritons are all hydrons.

Parent hydride cations

Simple cations formed by adding a hydron to a hydride of a halogen, chalcogen or nitrogenfamily element are named by adding the suffix "-onium" to the element's root: H4N+ is
ammonium, H3O+ is oxonium, and H2F+ is fluoronium. Ammonium was adopted instead of
nitronium, which commonly refers to NO2+.
If the cationic center of the hydride is not a halogen, chalcogen or nitrogen-family element then
the suffix "-ium" is added to the name of the neutral hydride after dropping any final 'e'. H5C+ is
methanium, HO-O+H2 is dioxidanium (HO-OH is dioxidane), and H2N-N+H3 is diazanium (H2NNH2 is diazane).

Cations and substitution

The above cations except for methanium are not, strictly speaking, organic, since they do not
contain carbon. However, many organic cations are obtained by substituting another element or
some functional group for a hydrogen.
The name of each substitution is prefixed to the hydride cation name. If many substitutions by the
same functional group occur, then the number is indicated by prefixing with "di-", "tri-" as with
halogenation. (CH3)3O+ is trimethyloxonium. CH3F3N+ is trifluoromethylammonium.

Nama trivial ( nama lain )

Nama trivial adalah penamaan senyawa hidrokarbon tidak dengan sistematika seperti pada
aturan pemberian nama menurut IUPAC, tetapi dengan nama tertentu seperti :
a. nama dagang
b. nama lokal
c. nama penemu
d. nama sumber
Sintesa alkana
H2O

a. RX + Na
b. C = C + H2
c. R-CH2X+ B2H6

R-R + NaX
CH CH
(RCH2 CH2)3-B+ H2O2
46

RCH2 CH2OH

alkana

OH-

H2O
d. R-CH = CH2 + Hg(OCOCH3)2

R-CH = CH2

+ NaBH4

R-CH = CH3

25 C
OH HgOCOCH3
e. R-X + Mg

RMgX + H2O

OH

RH + MgXOH

Alkena
Pemberian nama
a. Alkena alifatik
aa. senyawa Alkena alifatik mempunyai struktur molekul terbuka seperti berikut :
R-CH = CH2
Tabel 5. Nama alkena alifatik sesuai dengan deret homolog alkana, akhiran nama ana diganti
dengan ena. Contoh
Senyawa
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202
C200H402
C300H6002

Nama
Metena
Etena
Propene
Butene
Pentene
Heksena
Heptena
Oktena
Nonena
Dekena
Undekena
Dodekena
Tridekena
Tetradekena
Pentadekena
Heksadekena
Heptadekena
Oktadekena
Nonadekena
Eikosena
Heneikosena
Dokosena
Trikosena
Tetrakosena
Pentakosena
Heksakosena
Heptakosena
Oktakosena
Nonakosena
Triakontena
Hentriakontena
Dotriakontena
Tritriakontena
Hektena
Dohektena
Trihektena

Senyawa
C34H44
C35H46
C36H48
C37H50
C38H52
C39H54
C40H56
C41H58
C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110
C55H112
C56H114
C57H116
C58H118
C59H120
C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802
C500H1002
C600H12002

Nama
tetratriakontena
pentatriakontena
heksatriakontena
heptatriakontena
oktatriakontena
nonatriakontena
Tetrakontena
hentetrakontena
Dotetrakontena
Tritetrakontena
tetratetrakontena
pentatetrakontena
heksatetrakontena
heptatetrakontena
Oktatetrakontena
nonatetrakontena
Pentakontena
Henpentakontena
dopentakontena
tripentakontena
tetrapentakontena
pentapentakontena
heksapentakontena
heptapentakontena
Oktapentakontena
nonapentakontena
Heksa kontena
HenHeksa kontena
doHeksa kontena
triHeksa kontena
tetraHeksa kontena
pentaHeksa kontena
heksaHeksa kontena
Tetrahektena
Pentahektena
Heksahektena

47

Senyawa
C67H136
C68H138
C69H140
C70H142
C71H144
C72H146
C73H148
C74H150
C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176
C88H178
C89H180
C90H182
C91H184
C92H186
C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402
C800H1602
C900H1802

Nama
heptaHeksa kontena
oktaHeksa kontena
nonaHeksa kontena
Heptakontena
henHeptakontena
DoHeptakontena
triHeptakontena
tetraHeptakontena
pentaHeptakontena
heksaHeptakontena
heptaHeptakontena
oktaHeptakontena
nonaHeptakontena
Oktakontena
henOktakontena
doOktakontena
triOktakontena
tetraOktakontena
pentaOktakontena
heksaOktakontena
heptaOktakontena
oktaOktakontena
nonaOktakontena
Nonakontena
henNonakontena
doNonakontena
triNonakontena
tetraNonakontena
pentaNonakontena
heksaNonakontena
HeptaNonakontena
oktaNonakontena
nonaNonakontena
Heptahektena
Oktahektena
Nonahektena

C1000H2002
C2000H4002
C3000H6002

Kiliena
Dilianatena
Trilina

C400H8002
C500H10002
C600H1202

Tetraliena
Pentaliena
Heksaliena

C700H14002
C800H16002
C900H18002

Heptaliena
Oktaliena
Nonaliena

CH3-CH2-CH2-CH = CH2
Pentena
b. alkapoliena
Nama senyawa alkapoliena alifatik disesuaikan dengan nama homolog alkana, akhiran ana
diganti menjadi poliena tergantung banyaknya gugus ena yang terdapat dalam senyawa
tersebut contoh :
1

10

CH2=CH-CH=CH-CH2-CH=CH-CH2-CH = CH2
1,3,6,9 dekatetraena
Pada senyawa ini Karenna ada 4 gugus ena maka namanya mendapat akhiran tetraena
c.Alkena siklik

Siklopropena

siklobutadiena

siklopentena

Alkenes are aliphatic hydrocarbons containing carbon-carbon double bond and general formula
CnH2n.

Naming Alkenes
Alkenes are named as if they were alkanes, but the "-ane" suffix is changed to "-ene". If the
alkene contains only one double bond and that double bond is terminal (the double bond is at one
end of the molecule or another) then it is not necessary to place any number in front of the name.
butane: C4H10 (CH3CH2CH2CH3)
butene: C4H8 (CH2=CHCH2CH3)
If the double bond is not terminal (if it is on a carbon somewhere in the center of the chain) then
the carbons should be numbered in such a way as to give the first of the two double-bonded
carbons the lowest possible number, and that number should precede the "ene" suffix with a dash,
as shown below.
correct: pent-2-ene (CH3CH=CHCH2CH3)
incorrect: pent-3-ene (CH3CH2CH=CHCH3)
48

The second one is incorrect because flipping the formula horizontally results in a lower number
for the alkene.
If there is more than one double bond in an alkene, all of the bonds should be numbered in the
name of the molecule - even terminal double bonds. The numbers should go from lowest to
highest, and be separated from one another by a comma. The IUPAC numerical prefixes are used
to indicate the number of double bonds.
octa-2,4-diene: CH3CH=CHCH=CHCH2CH2CH3
deca-1,5-diene: CH2=CHCH2CH2CH=CHCH2CH2CH2CH3
Note that the numbering of "2-4" above yields a molecule with two double bonds separated by
just one single bond. Double bonds in such a condition are called "conjugated", and they represent
an enhanced stability of conformation, so they are energetically favored as reactants in many
situations and combinations.

EZ Notation
Earlier in stereochemistry, we discussed cis/trans notation where cis- means same side and transmeans opposite side. Alkenes can present a unique problem, however in that the cis/trans notation
sometimes breaks down. The first thing to keep in mind is that alkenes are planar and there's no
rotation of the bonds, as we'll discuss later. So when a substituent is on one side of the doublebond, it stays on that side.

cis-but-2-ene and trans-but-2-ene

The above example is pretty straight-forward. On the left, we have two methyl groups on the
same side, so it's cis-but-2-ene. And on the right, we have them on opposite sides, so we have
trans-but-2-ene. So in this situation, the cis/trans notation works and, in fact, these are the correct
names.

(Z)-3-methylpent-2-ene and (E)-3-methylpent-2-ene

49

From the example above, how would you use cis and trans? Which is the same side and which is
the opposite side? Whenever an alkene has 3 or 4 differing substituents, one must use the what's
called the EZ nomenclature, coming from the German words, Entgegen (opposite) and Zusammen
(same).

E: Entgegen, opposite sides of double bond

Z: Zusammen, same sides (zame zides) of double bond
Let's begin with (Z)-3-methylpent-2-ene. We begin by dividing our alkene into left and right
halves. On each side, we assign a substituent as being either a high priority or low priority
substituent. The priority is based on the atomic number of the substituents. So on the left side,
hydrogen is the lowest priority because its atomic number is 1 and carbon is higher because its
atomic number is 6.
On the right side, we have carbon substituents on both the top and bottom, so we go out to the
next bond. On to the top, there's another carbon, but on the bottom, a hydrogen. So the top gets
high priority and the bottom gets low priority.
Because the high priorities from both sides are on the same side, they are Zusammen (as a
mnemonic, think 'Zame Zide').
Now let's look at (E)-3-methylpent-2-ene. On the left, we have the same substituents on the same
sides, so the priorities are the same as in the Zusammen version. However, the substituents are
reversed on the right side with the high priority substituent on the bottom and the low priority
substituent on the top. Because the High and Low priorities are opposite on the left and right,
these are Entgegen, or opposite.
The system takes a little getting used to and it's usually easier to name an alkene than it is to write
one out given its name. But with a little practice, you'll find that it's quite easy.

Comparison of E-Z with cis-trans

(Z)-but-2-ene

(E)-but-2-ene

cis-but-2-ene

trans-but-2-ene

To a certain extent, the Z configuration can be regarded as the cis- isomer and the E as the transisomers. This correspondence is exact only if the two carbon atoms are identically substituted.
In general, cis-trans should only be used if each double-bonded carbon atom has a hydrogen atom
(i.e. R-CH=CH-R').
50

IUPAC Gold book on cis-trans notation.

IUPAC Gold book on E-Z notation.

Properties
Alkenes are molecules with carbons bonded to hydrogens which contain at least two sp2
hybridized carbon atoms. That is, to say, at least one carbon-to-carbon double bond, where the
carbon atoms, in addition to an electron pair shared in a sigma () bond, share one pair of
electrons in a pi () bond between them.
The general formula for an aliphatic alkene is: CnH2n -- e.g. C2H4 or C3H6

Diastereomerism
Restricted rotation
Because of the characteristics of pi-bonds, alkenes have very limited rotation around the double
bonds between two atoms. In order for the alkene structure to rotate the pi-bond would first have
to be broken - which would require about 60 or 70 kcal of energy. For this reason alkenes have
different chemical properties based on which side of the bond each atom is located.
For example, but-2-ene exists as two diastereomers:

(Z)-but-2-ene

(E)-But-2-ene

cis-but-2-ene

trans-but-2-ene

Relative stability
Observing the reaction of the addition of hydrogen to 1-butene, (Z)-2-butene, and (E)-2-butene,
we can see that all of the products are butane. The difference between the reactions is that each
reaction has a different energy: -30.3 kcal/mol for 1-butene, -28.6 kcal/mol for (Z)-2-butene and
-27.6 kcal/mol for (E)-2-butene. This illustrates that there are differences in the stabilities of the
three species of butene isomers, due to the difference in how much energy can be released by
reducing them.
The relative stability of alkenes may be estimated based on the following concepts:

An internal alkene (the double bond not on the terminal carbon) is more stable than a
terminal alkene (the double bond is on a terminal carbon).
51

Internal alkenes are more stable than terminal alkenes because they are connected to more carbons
on the chain. Since a terminal alkene is located at the end of the chain, the double bond is only
connected to one carbon, and is called primary (1). Primary carbons are the least stable. In the
middle of a chain, a double bond could be connected to two carbons. This is called secondary
(2). The most stable would be quaternary (4).

In general, the more and the bulkier the alkyl groups on a sp2-hybridized carbon in the
alkene, the more stable that alkene is.

A trans double bond is more stable than a cis double bond.

Reactions
Preparation
There are several methods for creating alcohols.[1] Some of these methods, such as the Wittig
reaction, we'll only describe briefly in this chapter and instead, cover them in more detail later in
the book. For now, it's enough to know that they are ways of creating alkenes.

Dehydrohalogenation of Haloalkanes

Synthesis of alkene by dehydrohalogenation

Dehydrohalogenation is a very common method for creating alkenes. It uses the E2 elimination
mechanism that we'll discuss in detail at the end of this chapter. The base used is generally a
strong base such as KOH (potassium hydroxide) or NaOCH3 (sodium methoxide). The haloalkane
must have a hydrogen and halide 180 from each other on neighboring carbons. If there is no
hydrogen 180 from the halogen on a neighboring carbon, the reaction will not take place.

Dehalogenation of Vicinal Dibromides

Synthesis of alkene via debromination of vicinal dihalides using Sodium Iodide

Synthesis of alkene via debromination of vicinal dihalides using Zinc

52

The dehalogenation of vicinal dihalides (halides on two neighboring carbons, think "vicinity") is
another method for synthesizing alkenes. The reaction can take place using either sodium iodide
in a solution of acetone, or it can be performed using zinc dust in a solution of either heated
ethanol or acetic acid.
This reaction can also be performed with magnesium in ether, though the mechanism is different
as this actually produces, as an intermediate, a Grignard reagent that reacts with itself and and
causes an elimination, resulting in the alkene.

Dehydration of alcohols

Synthesis of alkene by dehydration of an alcohol

When an alcohol is treated with a strong acid, for example H2SO4, it is converted into an alkene.
The mechanism of this reaction is fairly straight-forward. A lone pair from the alcohol's oxygen
attacks a proton (H+) from the acid. This create a hydronium ion which easily leaves the carbon,
creating a carbocation. The acid, now deficient a proton, and the carbocation wanting to stabilize
and get a bond, a hydrogen from an adjacent bond leaves, without its electron, and the adjacent
carbons form a pi bond, creating the alkene.
The underlying mechanism is the E1 mechanism which is described below.

Wittig Reaction

Synthesis of alkene via Wittig reaction

Markovnikov's Rule
Before we continue discussing reactions, we need to take a detour and discuss a subject that's very
important in Alkene reactions, "Markovnikov's Rule." This is a simple rule stated by the Russian
Vladmir Markovnikov in 1869, as he was showing the orientation of addition of HBr to alkenes.
His rule states:"When an unsymmetrical alkene reacts with a hydrogen halide to give an alkyl
halide, the hydrogen adds to the carbon of the alkene that has the greater number of hydrogen
substituents, and the halogen to the carbon of the alkene with the fewer number of hydrogen
substituents" (This rule is often compared to the phrase: "The rich get richer and the poor get
poorer." Aka, the Carbon with the most Hydrogens gets another Hydrogen and the one with the
least Hydrogens gets the halogen)
This means that the nucleophile of the electophile-nucleophile pair is bonded to the position most
stable for a carbocation, or partial positive charge in the case of a transition state.
53

Examples
CH2 = CH CH3 + H Br > CH3 CHBr CH3 Here the Br attaches to the middle carbon
over the terminal carbon, because of Markovnikov's rule, and this is called a Markovnikov
product.

Markovnikov product
The product of a reaction that follows Markovnikov's rule is called a Markovnikov product. in

Markovnikov addition
Markovnikov addition is an addition reaction which follows Markovnikov's rule, producing a
Markovnikov product.

Anti-Markovnikov addition
Certain reactions produce the opposite of the Markovnikov product, yielding what is called antiMarkovnikov product. That is, hydrogen ends up on the more substituted carbon of the double
bond. The hydroboration/oxidation reaction that we'll discuss shortly, is an example of this, as are
reactions that are conducted in peroxides.
A modernized version of Markovnikov's rule often explains the "anti-Markovnikov" behavior.
The original Markovnikov rule predicts that the hydrogen (an electrophile) being added across a
double bond will end up on the carbon with more hydrogens. Generalizing to all electrophiles, it
is really the electrophile which ends up on the carbon with the greatest number of hydrogens.
Usually hydrogen plays the role of the electrophile; however, hydrogen can also act as an
nucleophile in some reactions. The following expansion of Markovnikov's rule is more versitile:
"When an alkene undergoes electrophilic addition, the electrophile adds to the carbon with the
greatest number of hydrogen substituents. The nucleophile adds to the more highly substituated
carbon."
Or more simply:
"The species that adds first adds to the carbon with the greatest number of hydrogens."
The fact that some reactions reliably produce anti-Markovnikov products is actually a powerful
tool in organic chemistry. For example, in the reactions we discuss below, we'll show two
different ways of creating alcohols from alkenes: Oxymercuration-Reduction and
Hydroboration/Oxidation. Oxymercuration produces a Markovnikov product while Hydroboration
produces an anti-Markovnikov product. This gives the organic chemist a choice in products
without having to be stuck with a single product that might not be the most desired.

Why it works
Markovnikov's rule works because of the stability of carbocation intermediates. Experiments tend
to reveal that carbocations are planar molecules, with a carbon that has three substituents at 120
to each other and a vacant p orbital that is perpendicular to it in the 3rd plane. The p orbital
extends above and below the trisubstituent plane.
54

This leads to a stabilizing effect called hyperconjugation. Hyperconjugation is what happens when
there is an unfilled (antibonding or vacant) C-C orbital and a filled C-H bond orbital next to
each other. The result is that the filled C-H orbital interacts with the unfilled C-C orbital and
stabilizes the molecule. The more highly substituted the molecule, the more chances there are for
hyperconjugation and thus the more stable the molecule is.
Another stabilizing effect is an inductive effect.

Exceptions to the Rule

There are a few exceptions to the Markovnikov rule, and these are of tremendous importance to
organic synthesis.
1. HBr in Hydrogen Peroxide: Due to formation of free radicals, and the mechanism in which
it reacts, the alkyl free radical forms at the middle atom, where it is most stable, and a
hydrogen attaches itself here. Note here hydrogen addition is the second step, unlike in the
above example.

Addition reactions
Hydroboration
Hydroboration is a very useful reaction in Alkenes, not as an end product so much as an
intermediate product for further reactions. The primary one we'll discuss below is the
Hydroboration/Oxidation reaction which is actually an a hydroboration reaction followed by a
completely separate oxidation reaction.

Hydroboration mechanism
The addition of BH3 is a concerted reaction in that several bonds are broken and formed at the
same time. Hydroboration happens in what's called syn-addition because the boron and one of its
hydrogens attach to the same side of the alkene at the same time. As you can see from the
transition state in the center of the image, this produces a sort of box between the two alkene
carbons and the boron and its hydrogen. In the final step, the boron, along with its other two
hydrogens, remains attached to one carbon and the other hydrogen attaches to the adjacent carbon.
This description is fairly adequate, however, the reaction actually continues to happen and the
-BH2 continue to react with other alkenes giving an R2BH and then again, until you end up with a
complex of the boron atom attached to 3 alkyl groups, or R3B.
This trialkyl-boron complex is then used in other reactions to produce various products.
55

B2H6 complex

BH3-THF complex

Borane, in reality, is not stable as BH3. Boron, in this configuration has only 6 electrons and wants
8, so in its natural state it actually creates the B2H6 complex shown on the left.
Furthermore, instead of using B2H6 itself, BH3 is often used in a complex with tetrahydrofuran
(THF) as shown in the image on the right.In either situation, the result of the reactions are the
same.

Hydroboration/Oxidation
[2]

Hydroboration/Oxidation reaction
Hydroboration/Oxidation is a 2 part reaction. The first step is the above described hydroboration.
After this step, the trialkyl-boron complex is oxidized with hydrogen peroxide (H2O2) in a basic
solution. The result is an alcohol.
As mentioned in the discussion of Markovnikov's rule, Hydroboration produces an antimarkovnikov product in that the hydrogen attaches to the most substituted side of the alkene
instead of the least substituted side.

Oxymercuration/Reduction
[2]

Oxymercuration/Reduction of 1-propene
Another useful method for creating alcohols from alkenes, is Oxymercuration/Reduction. Like the
Hydroboration/Reduction, this too is a two-step process. In the first step, the alkene is reacted
with mercury acetate in water and THF. In the second step, the mercury is reduced by the addition
of sodium borohydride.
56

Unlike Hydroboration/Oxidation, this reaction, as can be seen in the image above, follows
Markovnikov's rule. The hydrogen is added to the least substituted side and the hydroxyl group is
added to the most substituted side.

Hydroboration/Oxidation of 1-propene
By way of comparison, here's the same reaction using the Hydroboration/Oxidation reaction.
Here, the hydrogen ends up on the most substituted side and the hydroxyl group on the least
substituted side, in an anti-Markovnikov product.

Catalytic addition of hydrogen

Catalytic hydrogenation of alkenes produce the corresponding alkanes. The reaction is carried out
under pressure in the presence of a metallic catalyst. Common industrial catalysts are based on
platinum, nickel or palladium, but for laboratory syntheses, Raney's nickel (an alloy of nickel and
aluminium) is often employed.
The catalytic hydrogenation of ethylene to yield ethane proceeds thusly:
CH2=CH2 + H2 + catalyst CH3-CH3

Electrophilic addition
Most addition reactions to alkenes follow the mechanism of electrophilic addition. An example is
the Prins reaction, where the electrophile is a carbonyl group.
Halogenation
Addition of elementary bromine or chlorine to alkenes yield vicinal dibromo- and
dichloroalkanes, respectively.
The decoloration of a solution of bromine in water is an analytical test for the presence of alkenes:
CH2=CH2 + Br2 BrCH2-CH2Br
The reaction works because the high electron density at the double bond causes a temporary shift
of electrons in the Br-Br bond causing a temporary induced dipole. This makes the Br closest to
the double bond slightly positive and therefore an electrophile.
Hydrohalogenation
Addition of hydrohalic acids like HCl or HBr to alkenes yield the corresponding haloalkanes.
an example of this type of reaction: CH3CH=CH2 + HBr CH3-CHBr-CH3

57

If the two carbon atoms at the double bond are linked to a different number of hydrogen atoms,
the halogen is found preferentially at the carbon with less hydrogen substituents (Markovnikov's
rule).
Addition of a carbene or carbenoid yields the corresponding cyclopropane

Oxidation
Alkenes are oxidized with a large number of oxidizing agents. In the presence of oxygen, alkenes
burn with a bright flame to carbon dioxide and water. Catalytic oxidation with oxygen or the
reaction with percarboxylic acids yields epoxides.
Reaction with ozone in ozonolysis leads to the breaking of the double bond, yielding two
aldehydes or ketones: R1-CH=CH-R2 + O3 R1-CHO + R2-CHO + H2O
This reaction can be used to determine the position of a double bond in an unknown alkene.

Polymerization
Polymerization of alkenes is an economically important reaction which yields polymers of high
industrial value, such as the plastics polyethylene and polypropylene. Polymerization can either
proceed via a free-radical or an ionic mechanism.

Substitution and Elimination Reaction Mechanisms

Nucleophilic Substitution Reactions
Nucleophilic substitution reactions (SN1 and SN2) are very closely related to the E1 and E2
elimination reactions, discussed later in this section, and it is generally a good idea to learn the
reactions together, as there are parallels in reaction mechanism, preferred substrates, and the
reactions sometimes compete with each other.
It's important to understand that substitution and elimination reactions are not associated with a
specific compound or mixture so much as they're a representation of how certain reactions take
place. At times, combinations of these mechanisms may occur together in the same reaction or
may compete against each other, with influences such as solvent or nucleophile choice being the
determining factor as to which reaction will dominate.

58

Note
In the notation SN1 and SN2,
S stands for substitution (something takes the place of something
else)
N: stands for nucleophilic (a nucleophile displaces another
nucleophile)
1: stands for unimolecular (the concentration of only one kind of
molecule determines the rate of the reaction)
2: stands for bimolecular (the concentration of two types of
molecules determine the rate of the reaction)
In nucleophilic substitution, a nucleophile attacks a molecule and takes the place of another
nucleophile, which then leaves. The nucleophile that leaves is called the leaving group.
Nucleophilic substitutions require
1. a nucleophile (such as a Lewis base)
2. an electrophile with a leaving group
A leaving group is a charged or neutral moiety (group) which breaks free.

SN1 vs SN2
One of the main differences between SN1 and SN2 is that the SN1 reaction is a 2-step reaction,
initiated by disassociation of the leaving group. The SN2 reaction, on the other hand, is a 1-step
reaction where the attacking nucleophile, because of its higher affinity for and stronger bonding
with the carbon, forces the leaving group to leave. These two things happen in a single step.
These two different mechanisms explain the difference in reaction rates between SN1 and SN2
reactions. SN1 reactions are dependent on the leaving group disassociating itself from the carbon.
It is the rate-limiting step and thus, the reaction rate is a first-order reaction whose rate depends
solely on that step.
Rate = k[RX]
Alternatively, in SN2 reactions, the single step of the nucleophile coming together with the
reactant from the opposite side of the leaving group, is the key to its rate. Because of this, the rate
is dependent on both the concentration of the nucleophile as well as the concentration of the
reactant. The higher these two concentrations, the more frequent the collisions. Thus the reaction
rate is a second-order reaction:
Rate = k[Nu:][RX] (where Nu: is the attacking nucleophile)

SN2 Reactions
There are primarily 3 things that affect whether an SN2 reaction will take place or not. The most
important is structure. That is whether the alkyl halide is on a methyl, primary, secondary, or
59

tertiary carbon. The other two components that determine whether an SN2 reaction will take place
or not, are the nucleophilicity of the nucleophile and the solvent used in the reaction.

Reactivity Due to Structure of SN2

CH3X > RCH2X > R2CHX >> R3CX
The structure of the alkyl halide has a great effect on mechanism. CH3X & RCH2X are the
preferred structures for SN2. R2CHX can undergo the SN2 under the proper conditions (see below),
and R3CX rarely, if ever, is involved in SN2 reactions.

SN2 nucleophilic substitution of bromine with a generic nucleophile

The reaction takes place by the nucleophile attacking from the opposite side of the bromine atom.
Notice that the other 3 bonds are all pointed away from the bromine and towards the attacking
nucleophile. When these 3 bonds are hydrogen bonds, there's very little steric hinderance of the
approaching nucleophile. However, as the number of R groups increases, so does the steric
hinderance, making it more difficult for the nucleophile to get close enough to the -carbon, to
expel the bromine atom. In fact, tertiary carbons (R3CX) are so sterically hindered as to prevent
the SN2 mechanim from taking place at all.
In the case of this example, a secondary -carbon, there is still a great deal of steric hinderance
and and whether the SN2 mechanism will happen will depend entirely on what the nucleophile and
solvent are. SN2 reactions are preferred for methyl halides and primary halides.
Another important point to keep in mind, and this can be seen clearly in the example above,
during an SN2 reaction, the molecule undergoes an inversion. The bonds attached to the -carbon
are pushed away as the nucleophile approaches. During the transition state, these bonds become
planar with the carbon and, as the bromine leaves and the nucleophile bonds to the -carbon, the
other bonds fold back away from the nucleophile. This is particularly important in chiral or prochiral molecules, where an R configuration will be converted into an S configuration and vice
versa. As you'll see below, this is in contrast to the results of SN1 reactions.
Examples:
OH- + CH3Cl HOCH3 + ClOH- is the nucleophile, Cl is the electrophile, HOCH3 is the product, and Cl- is the leaving group.
60

or,
Na+I- + CH3-Br I-CH3 + Na+BrThe above reaction, taking place in acetone as the solvent, sodium and iodide disassociate almost
completely in the acetone, leaving the iodide ions free to attack the CH-Br molecules. The
negatively charged iodide ion, a nucleophile, attacks the methyl bromide molecule, forcing off the
negatively charged bromide ion and taking its place. The bromide ion is the leaving group.
Nucleophilicity
Nucleophilicity is the rate at which a nucleophile displaces the leaving group in a reaction.
Generally, nucleophilicity is stronger, the larger, more polarizable, and/or the less stable the
nucleophile. No specific number or unit of measure is used. All other things being equal,
nucleophiles are generally compared to each other in terms of relative reactivity. For example, a
particular strong nucleophile might have a relative reactivity of 10,000 that of a particular weak
nucleophile. These relationships are generalities as things like solvent and substrate can affect the
relative rates, but they are generally good guidelines for which species make the best
nucleophiles.
All nucleophiles are Lewis bases. In SN2 reactions, the preferred nucleophile is a strong
nucleophile that is a weak base. Examples of these are N3-, RS-, I-, Br-, and CN-.
Alternatively, a strong nucleophile that's also a strong base can also work. However, as mentioned
earlier in the text, sometimes reaction mechanisms compete and in the case of a strong
nucleophile that's a strong base, the SN2 mechanism will compete with the E2 mechanism.
Examples of strong nucleophiles that are also strong bases, include RO- and OH-.

List of descending nucleophilicities

I- > Br- > Cl- >> F- > -SeH > -OH > H2O

Leaving Group
Leaving group is the group on the substrate that leaves. In the case of an alkyl halide, this is the
halide ion that leaves the carbon atom when the nucleophile attacks. The tendency of the
nucleophile to leave is

61

Relative Reactivity of Leaving Groups

I- > Br- > Cl- >> FFluoride ions are very poor leaving groups because they bond very strongly and are very rarely
used in alkyl halide substitution reactions. Reactivity of a leaving group is related to its basicity
with stronger bases being poorer leaving groups.
Solvent
The solvent can play an important role in SN2 reactions, particularly in SN2 involving secondary
alkyl halide substrates, where it can be the determining factor in mechanism. Solvent can also
have a great effect on reaction rate of SN2 reactions.
The SN2 mechanism is preferred when the solvent is an aprotic, polar solvent. That is, a solvent
that is polar, but without a polar hydrogen. Polar, protic solvents would include water, alcohols,
and generally, solvents with polar NH or OH bonds. Good aprotic, polar solvents are HMPA,
CH3CN, DMSO, and DMF.
A polar solvent is preferred because it better allows the dissociation of the halide from the alkyl
group. A protic solvent with a polar hydrogen, however, forms a 'cage' of hydrogen-bonded
solvent around the nucleophile, hindering its approach to the substrate.

Relative Reactivity of Solvents

HMPA > CH3CN > DMF > DMSO >> H2O

SN1 Reactions
The SN1 mechanism is very different from the SN2 mechanism. In some of its preferences, its
exactly the opposite and, in some cases, the results of the reaction can be significantly different.
Like the SN2 mechanism, structure plays an important role in the SN1 mechanism. The role of
structure in the SN1 mechanism, however, is quite different and because of this, the reactivity of
structures is more or less reversed.

Reactivity Due to Structure of SN1

CH3X < RCH2X << R2CHX < R3CX
The SN1 mechanism is preferred for tertiary alkyl halides and, depending on the solvent, may be
preferred in secondary alkyl halides. The SN1 mechanism does not operate on primary alkyl
62

halides or methyl halides. To understand why this is so, let's take a look at how the SN1
mechanism works.

SN1 nucleophilic substitution of a generic halide with a water molecule to produce an alcohol.
At the top of the diagram, the first step is the spontaneous dissociation of the halide from the alkyl
halide. Unlike the SN2 mechanism, where the attacking nucleophile causes the halide to leave, the
SN1 mechanism depends on the ability of the halide to leave on its own. This requires certain
conditions. In particular, the stability of the carbocation is crucial to the ability of the halide to
leave. Since we know tertiary carbocations are the most stable, they are the best candidates for the
SN1 mechanism. And with appropriate conditions, secondary carbocations will also operate by the
SN1 mechanism. Primary and methyl carbocations however, are not stable enough to allow this
mechanism to happen.
Once the halide has dissociated, the water acts as a nucleophile to bond to the carbocation. In
theSN2 reactions, there is an inversion caused by the nucleophile attacking from the opposite side
while the halide is still bonded to the carbon. In the SN1 mechanism, since the halide has left, and
the bonds off of the -carbon have become planar, the water molecule is free to attack from either
side. This results in, primarily, a racemic mixture. In the final step, one of the hydrogens of the
bonded water molecule is attacked by another water molecule, leaving an alcohol.
Note: Racemic mixtures imply entirely equal amounts of mixture, however this is rarely the case
in SN1. There is a slight tendency towards attack from the opposite side of the halide. This is the
result some steric hinderence from the leaving halide which is sometimes close enough to the
leaving side to block the nucleophile's approach from that side.
Solvent
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Like the SN2 mechanism, the SN1 is affected by solvent as well. As with structure, however, the
reasons differ. In the SN1 mechanism, a polar, protic solvent is used. The polarity of the solvent is
associated with the dielectric constant of the solvent and solutions with high dielectric constants
are better able to support separated ions in solution. In SN2 reactions, we were concerned about
polar hydrogen atoms "caging" our nucleophile. This still happens with a polar protic solvent in
SN1 reactions, so why don't we worry about it? You have to keep in mind the mechanism of the
reaction. The first step, and more importantly, the rate-limiting step, of the SN1 reaction, is the
ability to create a stable carbocation by getting the halide anion to leave. With a polar protic
solvent, just as with a polar aprotic solvent,we're creating a stable cation, however it's the polar
hydrogens that stabilize the halide anion and make it better able to leave. Improving the ratelimiting step is always the goal. The "caging" of the nucleophile is unrelated to the rate-limiting
step and even in its "caged" state, the second step, the attack of the nucleophile, is so much faster
than the first step, that the "caging" can simply be ignored.

Summary
SN1, SN2, E1, and E2, are all reaction mechanisms, not reactions themselves. They are
mechanisms used by a number of different reactions. Usually in organic chemistry, the goal is to
synthesize a product. In cases where you have possibly competing mechanisms, and this is
particular the case where an SN1 and an E1 reaction are competing, the dominating mechanism is
going to decide what your product is, so knowing the mechanisms and which conditions favor one
over the other, will determine your product.
In other cases, knowing the mechanism allows you to set up an environment favorable to that
mechanism. This can mean the difference between having your product in a few minutes, or
sometime around the next ice age.
So when you're designing a synthesis for a product, you need to consider, I want to get product Y,
so what are my options to get to Y? Once you know your options and you've decided on a
reaction, then you need to consider the mechanism of the reaction and ask yourself, how do I
create conditions that are going to make this happen correctly and happen quickly?

Elimination Reactions
Nucleophilic substitution reactions and Elimination reactions share a lot of common
characteristics, on top of which, the E1 and SN1 as well as E2 and SN2 reactions can sometimes
compete and, since their products are different, it's important to understand them both. Without
understanding both kinds of mechanisms, it would be difficult to get the product you desire from a
reaction.
In addition, the SN1 and SN2 reactions will be referenced quite a bit by way of comparison and
contrast, so it's probably best to read that section first and then continue here.
Elimination reactions are the mechanisms for creating alkene products from haloalkane reactants.
E1 and E2 elimination, unlike SN1 and SN2 substitution, mechanisms do not occur with methyl
halides because the reaction creates a double bond between two carbon atoms and methylhalides
have only one carbon.

64

Note
In the notation E1 and E2,
E stands for elimination
1: stands for unimolecular (the concentration of only one kind of
molecule determines the rate of the reaction)
2: stands for bimolecular (the concentration of two types of
molecules determine the rate of the reaction)

E1 vs E2
Reaction rates
E1 and E2 are two different pathways to creating alkenes from haloalkanes. As with SN1 and SN2
reactions, one of the key differences is in the reaction rate, as it provides great insight into the
mechanisms.
E1 reactions, like SN1 reactions are 2-step reactions. Also like SN1 reactions, the rate-limiting step
is the dissociation of the halide from its alkane, making it a first-order reaction, depending on the
concentration of the haloalkane, with a reaction rate of:
Rate = k[RX]
On the other hand, E2 reactions, like SN2 reactions are 1-step reactions. And again, as with SN2
reactions, the rate limiting step is the ability of a nucleophile to attach to the alkane and displace
the halide. Thus it is a second-order reaction that depends on the concentrations of both the
nucleophile and haloalkane, with a reaction rate of:
Rate = k[Nu:][RX] (where Nu: is the attacking nucleophile)
Zaitsev's Rule
Zaitsev's rule (sometimes spelled "Saytzeff") states that in an elimination reaction, when multiple
products are possible, the most stable alkene is the major product. That is to say, the most highly
substituted alkene (the alkene with the most non-hydrogen substituents), is the major product.
Both E1 and E2 reactions produce a mixture of products, when possible, but generally follow
Zaitsev's rule. We'll see below why E1 reactions follow Zaitsev's rule more reliably and tend to
produce a purer product.

65

Dehydrohalogenation reaction of (S)-2-bromo-3-methylbutane

The above image represents two possible pathways for the dehydrohalogenation of (S)-2-bromo3-methylbutane. The two potential products are 2-methylbut-2-ene and 3-methylbut-1-ene. The
images on the right are simplified drawings of the molecular product shown in the images in the
center.
As you can see on the left, the bromine is on the second carbon and in an E1 or E2 reaction, the
hydrogen could be removed from either the 1st or the 3rd carbon. Zaitsev's rule says that the
hydrogen will be removed predominantly from the 3rd carbon. In reality, there will be a mixture,
but most of the product will be 2-methylbut-2-ene by the E1 mechanism. By the E2 reaction, as
we'll see later, this might not necessarily be the case.

E2
Reactivity Due to Structure of E2
RCH2X > R2CHX >> R3CX
The E2 mechanism is concerted and higly stereospecific, because it can occur only when the H
and the leaving group X are in an anti-coplanar position. That is, in a Newman projection, the H
and X must be 180, or in the anti-configuration. This behaviour stems from the best overlap of
the 2p orbitals of the adjacent carbons when the pi bond has to be formed. If the H and the leaving
group cannot be brought into this position due to the structure of the molecule, the E2 mechanism
will not take place.
66

Mechanism of E2 elimination. Note the anti-coplanarity of the X-C-C-H atoms

Therefore, only molecules having accessible H-X anti-coplanar conformations can react via this
route. Furthermore, the E2 mechanism will operate contrary to Zaitsev's rule if the only anticoplanar hydrogen from the leaving group results in the least stable alkene. A good example of
how this can happen is by looking at how cyclohexane and cyclohexene derivatives might operate
in E2 conditions.

E2 with preferential elimination

Let's look at the example above. The reactant we're using is 1-chloro-2-isopropylcyclohexane.
The drawing at the top left is one conformation and the drawing below is after a ring flip. In the
center are Newman projections of both conformations and the drawings on the right, the products.
If we assume we're treating the 1-chloro-2-isopropylcyclohexane with a strong base, for example
CH3CH2O- (ethanolate), the mechanism that dominates is E2. There are 3 hydrogens off of the
carbons adjacent to our chlorinated carbon. The red and the green ones are two of them. The third
would be hard to show but is attached to the same carbon as the red hydrogen, angled a little
down from the plane and towards the viewer. The red hydrogen is the only hydrogen that's 180
from the chlorine atom, so it's the only one eligible for the E2 mechanism. Because of this, the
product is going to be only 3-isopropylcylcohex-1-ene. Notice how this is contrary to Zaitsev's
rule which says the most substituted alkene is preferred. By his rule, 1-isopropylcyclohexene
should be our primary product, as that would leave the most substituted alkene. However it simply
can't be produced because of the steric hindrance.
The images below shows the molecule after a ring flip. In this conformation, no product is
possible. As you can see from the Newman projection, there are no hydrogens 180 from the
chlorine atom.
67

So it's important, when considering the E2 mechanism, to understand the geometry of the
molecule. Sometimes the geometry can be used to your advantage to preferentially get a single
product. Other times it will prevent you from getting the product you want, and you'll need to
consider a different mechanism to get your product.
Note: Often the word periplanar is used instead of coplanar. Coplanar implies precisely 180
degree separation and "peri-", from Greek for "near", implies near 180 degrees. Periplanar may
actually be more accurate. In the case of the 1-chloro-3-isopropylcyclohexane example, because
of molecular forces, the chlorine atom is actually slightly less than 180 degrees from both the
hydrogen and the isopropyl group, so in this case, periplanar might be a more correct term.

E1

E1 elimination of an alkyl halide by a base

The E1 mechanism begins with the dissociation of the leaving group from an alkyl, producing a
carbocation on the alkyl group and a leaving anion. This is the same way the SN1 reaction begins,
so the same thing that helps initiate that step in SN1 reactions, help initiate the step in E1
reactions. More specifically, secondary and tertiary carbocations are preferred because they're
more stable than primary carbocations. The choice of solvent is the same as SN1 as well; a polar
protic solvent is preferred because the polar aspect stabilizes the carbocation and the protic aspect
stabilizes the anion.
What makes the difference between whether the reaction takes the SN1 or E1 pathway then, must
depend on the second step; the action of the nucleophile. In SN1 reactions, a strong nucleophile
that's a weak base is preferred. The nucleophile will then attack and bond to the carbocation. In
E1 reactions, a strong nucleophile is still preferred. The difference is that a strong nucleophile
that's also a strong base, causes the nucleophile to attack the hydrogen at the -carbon instead of
the -carbocation. The nucleophile/base then extracts the hydrogen causing the bonding electrons
to fall in and produce a pi bond with the carbocation.
e. Alkena aromatik
Menurut kaidah Huckel senyawa alkena menjadi aromatic apabila mempunyai jumlah electron
4n+2 dengan struktur senyawa lingkar, dimana n adalah bilangan bulat dari 0,1 , 2, 3, 4,
5, dst. Setiap ikatan ganda karbon C=C mempunyai dua electron

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Siklo heksa triena (benzen)

Pada senyawa sikloheksatriena ini ada 3 x 2 = 6 elektron
Teori aromatisitas didasarkan pada sifat benzene yang mengikuti postulat Huckel berikut :
1. Benzen adalah senyawa lingkar terkonyugasi dengan rumus C6H6.
2. Benzen biasanya tidak stabil. Panas hidrogenasinya adalah 36 kcal/mole lebih kecil dari
pada panas hidrogenasi triena normal.
3. Benzen adalah molekul simetris, berupa bidang datar, dan merupakan heksagonal, semua
ikatan -C-C-C- adalah 120o, dan panjang semua ikatan C-C- adalah 1,39 Ao
4. Benzen bisa mengalami reaksi substitusi yang mengikuti konyugasi lingkar, dari pada
reaksi addisi elektrofilik yang mengakibatkan putusnya konyugasi ikatan .
5. Benzen memenuhi teori hibrida resonansi yang strukturnya merupakan peralihan antara
dua bentuk struktur menurut Kekule.

Siklo heksa triena (benzen)

Benzen ( Fisher )

Benzen ( Dewar ) Benzen (Ladenburg )

6. Ikatan pada benzen dapat lagi dengan menggunakan teori orbital molekul. Enam orbital p
bergabung membentuk enem orbital molekul benzene dengan resultante delokalisasi
electron melelui sistim konyugasi.
.

69

After understanding the usefulness of unsaturated compound, or conjugated system, we hope to

explore the unique structure of aromatic compounds, including why benzene should not be called
1,3,5-cyclohexatriene because it is more stable than a typical triene, and seemingly unreactive.
Called "aromatic" initially because of its fragrance, aromaticity now refers to the stability of
compounds that are considered aromatic, not only benzene. Any cyclic compound with 4n+2 pi
electrons in the system is aromatic. The stability of aromatic compounds arises because all
bonding orbitals are filled and low in energy.

History of Aromatics
Early in the 19th century, advances in equipment, technique and communications resulted in
chemists discovering and experimenting with novel chemical compounds. In the course of their
investigations they stumbled across a different kind of stable compound with the molecular
formula of C6H6. Unable to visualize what such a compound might look like, the scientists
invented all sorts of models for carbon-to-carbon bonding -- many of which were not entirely
stable -- in order to fit what they had observed to what they expected the C6H6 compound to look
like.
Benzene (which is the name that was given to the aromatic compound C6H6) is probably the most
common and industrially important aromatic compound in wide use today. It was discovered in
1825 by Michael Faraday, and its commercial production from coal tar (and, later on, other
natural sources) began in earnest about twenty-five years later. The structure of benzene emerged
during the 1860s, the result of contributions from several chemists, most famously that of Kekul.
Scientists of the time did not have the benefit of understanding that electrons are capable of
delocalization, so that all carbon atoms could share the same -bond electron configuration
equally. Huckel was the first to apply the new theory of quantum mechanics to clearly separating
and electrons. He went on to develop a theory of electron bonding for benzene, which was
the first to explain the electronic origins of aromaticity.

Benzene Structure
Benzene is a hexagonal ring of six carbon atoms connected to each other through one p-orbital per
carbon. Its chemical formula is C6H6, and its structure is a hexagonal ring of carbons sharing
symmetrical bonds, with all six hydrogen atoms protruding outwards from the carbon ring, but in
the same plane as the ring. The p-orbital system contains 6 electrons, and one way to distribute the
electrons yields the following structure:

However, another resonance form of benzene is possible, where the single bonds of the first
structure are replaced with double bonds, and the double bonds with single bonds. These two
resonance forms are co-dominant in benzene. (Other forms, such as a structure with a bond
connecting opposite carbons, are possible but negligible.) Thus, each bond in benzene has been
experimentally shown to be of equal length and strength, and each is accounted as approximately
a "1.5" bond instead of either a single or double bond alone.
Electron density is shared between carbons, in effect yielding neither a single nor a double bond,
but a sort of one-and-a-half bond between each of the six carbons. Benzene has a density of
negative charge both above and below the plane formed by the ring structure. Although benzene is
70

very stable and does not tend to react energetically with most substances, electrophilic compounds
may be attracted to this localized electron density and such substances may form a bond with the
aromatic benzene ring.
An electron delocalisation ring can be used to show in a single picture both dominant resonance
forms of benzene:

Benzene Properties
Benzene is a colorless, flammable liquid with a sweet aroma and carcinogenic effects. The
aromatic properties of benzene make it far different from other alkenes in many ways.

Benzene Reactions
Main article: Aromatic reactions
Unlike alkenes, aromatic compounds such as benzene undergo substitution reactions instead of
addition reactions. The most common reaction for benzene to undergo is electrophilic aromatic
substitution (EAS), although in a few special cases, it can undergo nucleophilic aromatic
substitution.

Benzene Health Effects

In the body, benzene is metabolized, and benzene exposure may have quite serious health effects.
Breathing in very high levels of benzene can result in death, while somewhat lower (but still high)
levels can cause drowsiness, dizziness, rapid heart rate, headaches, tremors, confusion, and
unconsciousness. Eating or drinking foods containing high levels of benzene can cause vomiting,
irritation of the stomach, dizziness, sleepiness, convulsions, rapid heart rate, and even death.
The major effect of benzene from chronic (long-term) exposure is to the blood. Benzene damages
the bone marrow and can cause a decrease in red blood cells, leading to anemia. It can also cause
excessive bleeding and depress the immune system, increasing the chance of infection. Some
women who breathed high levels of benzene for many months had irregular menstrual periods and
a decrease in the size of their ovaries. It is not known whether benzene exposure affects the
developing fetus in pregnant women or fertility in men, however animal studies have shown low
birth weights, delayed bone formation, and bone marrow damage when pregnant animals breathed
benzene.
The US Department of Health and Human Services (DHHS) also classifies benzene as a human
carcinogen. Long-term exposure to high levels of benzene in the air can cause leukemia, a
potentially fatal cancer of the blood-forming organs. In particular, Acute Myeloid Leukemia
(AML) may be caused by benzene.

Aromaticity
Aromaticity in organic chemistry does not refer to whether or not a molecule triggers a sensory
response from olfactory organs (whether it "smells"), but rather refers to the arrangement of
71

electron bonds in a cyclic molecule. Many molecules that have a strong odor (such as diatomic
chlorine Cl2) are not aromatic in structure -- odor has little to do with chemical aromaticity. It was
the case, however, that many of the earliest-known examples of aromatic compounds had
distinctively pleasant smells. This property led to the term "aromatic" for this class of compounds,
and hence the property of having enhanced stability due to delocalized electrons came to be called
"aromaticity".

Definition
Aromaticity is a chemical property in which a conjugated ring of unsaturated bonds, lone pairs, or
empty orbitals exhibit a stabilization stronger than would be expected by the stabilization of
conjugation alone. It can also be considered a manifestation of cyclic delocalization and of
resonance.
This is usually considered to be because electrons are free to cycle around circular arrangements
of atoms, which are alternately single- and double-bonded to one another. These bonds may be
seen as a hybrid of a single bond and a double bond, each bond in the ring identical to every other.
This commonly-seen model of aromatic rings was developed by Kekul. The model for benzene
consists of two resonance forms, which corresponds to the double and single bonds' switching
positions. Benzene is a more stable molecule than would be expected of cyclohexatriene, which is
a theoretical molecule.

Theory
By convention, the double-headed arrow indicates that two structures are simply hypothetical,
since neither can be said to be an accurate representation of the actual compound. The actual
molecule is best represented by a hybrid (average) of most likely structures, called resonance
forms. A carbon-carbon double bond is shorter in length than a carbon-carbon single bond, but
aromatic compounds are perfectly geometrical (that is, not lop-sided) because all the carboncarbon bonds have the same length. The actual distance between atoms inside an aromatic
molecule is intermediate between that of a single and that of a double bond.
A better representation than Lewis drawings of double and single bonds is that of the circular
bond (Armstrong's inner cycle), in which the electron density is evenly distributed through a
bond above and below the ring. This model more correctly represents the location of electron
density within the aromatic molecule's overall structure. The single bonds are sigma () bonds
formed with electrons positioned "in line" between the carbon atoms' nuclei. Double bonds
consist of one "in line" bond and another non-linearly arranged bond -- a -bond. The -bonds
are formed from the overlap of atomic p-orbitals simultaneously above and below the plane of the
ring formed by the "in line" -bonds.
Since they are out of the plane of the atoms, orbitals can interact with each other freely, and
thereby they become delocalized. This means that, instead of being tied to one particular atom of
carbon, each electron can be shared by all the carbon atoms in an aromatic ring. Thus, there are
72

not enough electrons to form double bonds on all the carbon atoms, but the "extra" electrons
strengthen all of the bonds of the ring equally.

Characteristics
An aromatic compound contains a set of covalently-bound atoms with specific characteristics:
1. A delocalized conjugated pi system, most commonly an arrangement of alternating single
and double bonds
2. Coplanar structure, with all the contributing atoms in the same plane
3. Contributing atoms arranged in one or more rings
4. A number of pi delocalized electrons that is even, but not a multiple of 4. (This is known
as Hckel's rule. Permissible numbers of electrons include 6, 10, 14, and so on)
5. Special reactivity in organic reactions such as electrophilic aromatic substitution and
nucleophilic aromatic substitution
Whereas benzene is aromatic (6 electrons, from 3 double bonds), cyclobutadiene is not, since the
number of delocalized electrons is 4, which is not satisfied by any n integer value. The
cyclobutadienide (2) ion, however, is aromatic (6 electrons). An atom in an aromatic system can
have other electrons that are not part of the system, and are therefore ignored for the 4n + 2 rule.
In furan, the oxygen atom is sp2 hybridized. One lone pair is in the system and the other in the
plane of the ring (analogous to C-H bond on the other positions). There are 6 electrons, so furan
is aromatic.
Aromatic molecules typically display enhanced chemical stability, compared to similar nonaromatic molecules. The circulating (that is, delocalized) electrons in an aromatic molecule
generate significant local magnetic fields that can be detected by NMR techniques. NMR
experiments show that protons on the aromatic ring are shifted substantially further down-field
than those on aliphatic carbons. Planar monocyclic molecules containing 4n electrons are called
anti-aromatic and are, in general, destabilized. Molecules that could be anti-aromatic will tend to
alter their electronic or conformational structure to avoid this situation, thereby becoming merely
non-aromatic.
Aromatic molecules are able to interact with each other in so-called - stacking: the systems
form two parallel rings overlap in a "face-to-face" orientation. Aromatic molecules are also able to
interact with each other in an "edge-to-face" orientation: the slight positive charge of the
substituents on the ring atoms of one molecule are attracted to the slight negative charge of the
aromatic system on another molecule.

Monosubstituted Benzenes
Benzene is a very important basic structure which is useful for analysis and synthesis in most
aspects of organic chemistry. The benzene ring itself is not the most interesting or useful feature
of the molecule; which substitutents and where they are placed on the ring can be considered the
most critical aspect of benzene chemistry in general.
73

Effects of Different Substituents

Depending on the type of substituent, atoms or groups of atoms may serve to make the benzene
ring either more reactive or less reactive. If the atom or group makes the ring more reactive, it is
called activating, and if less, then it is called deactivating.
Generally, the terms activating and deactivating are in terms of the reactions that fall into the
category of Electrophilic Aromatic Substitution (EAS). These are the most common forms of
reactions with aromatic rings. Aromatic rings can undergo other types of reactions, however, and
in the case of Nucleophilic Aromatic Substitution, the activating and deactivating nature of
substituents on the rings is reversed. In EAS, a hydroxyl groups is strongly activating, but in
Nucleophilic Aromatic Substitution, a hydroxyl group is strongly deactivating. But since EAS is
the most common reaction with aromatic rings, when discussing activation and deactivation, it's
normally done in terms of the EAS.
In addition to activating or deactivating, all groups and/or substituent atoms on a benzene ring are
directing. An atom or group may encourage additional atoms or groups to add or not to add to
certain other carbons in relation to the carbon connected to the directing group. This concept will
be further discussed in the next chapter, but when memorizing the groups below it is helpful to
also memorize whether it is O (ortho), M (meta) or P (para)-directing.
Another factor that heavily influences direction, however, is steric hindrance. If, for example, you
have a tert-butyl substituent on the ring, despite the fact that it is ortho/para directing, the ortho
positions will be largely blocked by the tert-butyl group and thus nearly all the product would be
para.

Activating Substituents
Activating substituents make benzene either slightly more reactive or very much more reactive,
depending on the group or atom in question. In general, if one of the major heteroatoms (nitrogen
or oxygen) is directly attached to the carbon ring then the result is probably activation. This is
merely a rule of thumb, and many exceptions exist, so it is best to memorize the groups listed
below instead of counting on a quick and dirty rule of thumb.
Group

Strength

Directing

-NH2, -NHR, -NRR

very strong ortho/para

-OH, -O-

very strong ortho/para

-NHCOCH3, -NHCOR strong

ortho/para

-OCH3, -OR

strong

ortho/para

-CH3, -C2H5, -R

weak

ortho/para

-C6H5

very weak

ortho/para

74

Deactivating Substituents
A deactivating group is a functional group attached to a benzene molecule that removes electron
density from the benzene ring, making electrophilic aromatic substitution reactions slower and
more difficult than they would be on benzene alone. As discussed above for activating groups,
deactivating groups may also determine the positions (relative to themselves) on the benzene ring
where substitutions take place, so each deactivating group is listed below along with its directing
characteristic.
Group

Strength

Directing

-NO2

very strong meta

-NR3+

very strong meta

-CF3, CCl3

very strong meta

-CN

strong

meta

-SO3H

strong

meta

-CO2H, -CO2R strong

meta

-COH, -COR

strong

meta

-F

weak

ortho/para

-Cl

weak

ortho/para

-Br

weak

ortho/para

Activation vs. Deactivation and ortho/para vs. meta directing

So why are some substituents activating or deactivating? Why are some meta directing and others
ortho/para directing? From the above tables, it seems pretty clear there's a relationship.
There are primarily two effects that substituents impart on the ring that affect these features:
1. Resonance effects
2. Inductive effects

Resonance Effects
Let's first look at resonance effects. Resonance effects are the ability or inability of a substituent
to provide electrons to the ring and enhance its resonance stability. To see this, we must first get a
basic understanding of the mechanism of Electrophilic Aromatic Subsitution. We'll discuss EAS
in more detail in the next section, but some basics are called for here.

75

As you can see in the image above, the electrophile is attacked by pi electrons in the ring. The
same carbon is now bonded to both the hydrogen that was bonded to it and the electrophile. This
in turn creates a carbocation on the adjacent carbon, making the ring non-aromatic. But aromatic
rings like to remain aromatic. The nucleophile which was previously bonded to the electrophile
now attacks the hydrogen, abstracting it from the ring and allowing the pi-bond to re-form and
returning the ring to its aromatic nature.
As we've seen before in some other reactions, when a carbocation is created as an intermediate,
stability of that carbocation is crucial to the reaction. This is the case in Electrophilic Aromatic
Subsitution as well.
So what is the effect of substituents on the ring?

76

Let's look at the situation above. In this case we have Phenol, a benzene ring with an -OH
(hydroxyl) group attached. When we nitrate the ring with nitric acid in sulfuric acid (a reaction
we'll discuss in the next section), a nitro group is attached to the benzene ring.
There are 3 possible places for the nitro group to attach: An ortho, meta, or para position. To
understand the stability of the carbocation, we need to look at the resonance structures for a given
attack and see what the results are.
The first resonance structure of the ortho attack results in a positive charge on the carbon with the
hydroxyl group. This happens to be the most stable of the 3 resonance structures for an ortho
attack because the two negative electron pairs in the oxygen act to stabilize the positive charge on
the carbon. The other two resonance forms leave a carbon with a hydrogen attached, to hold the
positive charge. Hydrogen can do nothing to stabilize the charge and thus, these are less stable
forms.
In the para attack situation, notice that the second resonance form also puts a positive charge on
the carbon with the hydroxyl group. This provides for stability just as it does in the case of an
ortho attack and thus, the middle resonance form is very stable.
Finally, in the meta attack situation, all of the resonance forms result in a positive charge on a
carbon with only a hydrogen attached. None of these is stable, and thus, meta attack with a
hydroxyl group attached, is a very small percentage of the product.
So the electron pairs in the oxygen act to stabilize the ortho and para attacks.

Inductive Effects
Now let's look at the inductive effects of deactivating substituents. Let's imagine that, instead of a
hydroxyl group, we instead have a carbonyl group attached to the ring in its place. When a
carbonyl is attached, the ring is bonded to a carbon which in turn, is double-bonded to an oxygen,
the double-bonded oxygen is withdrawing electrons and this inductive effect is felt on the ring,
strongly deactivating its pi-bond nature and putting a positive dipole on the carbon. Looking at the
resonance structures, this carbon, which already has some positive nature is now given the added
resonance of a positive charge, in the case of ortho and para attacks. Positive plus positive equals
more positive and thus, less stable. There's no negative charge or negative electron pair to
stabilize this positive charge.
So in this case, not only is the entire ring less activated, but the ortho and para attacks result in
much more unstable carbocation resonance forms. Hence, meta is the preferred position, but the
overall reaction is less active than plain benzene.

Halides as the Exception

Notice that in the list of activating vs. deactivating substituents, the activating ones are all
ortho/para directing. In the deactivating substituents, all but the halides, are meta directing. Why
are halides an exception?
Halides are more electronegative than carbon and thus they put a positive dipole on the carbon
they're attached to and thus deactivate the ring. But halides also have a bunch of electrons in their
outer shell to share with the ring, making the resonance structures with ortho and para attacks
77

relatively more stable than the meta attack resonance forms. This means that, though halides do
deactivate the ring to some extent, they are still ortho/para directing.

Detailed Effects of Substituents

We've discussed some generalities about the effects of substituents and even some specifics about
certain ones, but let's look more closely at the substituents and try to understand the details of
what makes them activating vs. deactivating.
-NH2, -NHR, and -NRR are all very strongly activating. Though nitrogen is more electronegative
than carbon, its ability to share a pair of electrons greatly outweighs its electron withdrawing
effect.
-OH and -O- is similar in that it is even more electronegative than nitrogen, but it has two pairs of
electrons to share, which also greatly outweighs its electon withdrawing effect.
-NHCOCH3 and -NHCOR are also strongly activating, but the inductive effect of the doublebonded oxygen acts to make the nitrogen more electron withdrawing, so they're not quite as
activating as the other -N subsituents above.
-OCH3 and -OR are also still strongly activating, but less so, because the electron density is shared
on both sides of the oxygen.
-CH3 and -R in general provide some electron density sharing, but not nearly as much as a pair of
electrons. Thus their effect is only weakly felt.
For deactivating groups we have:
-NO2, or nitro and -NR3+. The nitro group is very strongly deactivating because of its resonance
structure. The nitro group has two resonance forms: O=N+-O- and O--N+=O. Both of these forms
leave a full positive charge on the nitrogen making it completely unable to help stabilize the
positive carbocation intermediate. The same applies to -NR3+.
-CF3 and -CCl3 both have an inductive electronegative effect of 3 halides, but with no electrons to
share with the ring, leaving them also very strongly deactivating.
-CN has a triple bond between the carbon and nitrogen with a resonance form of a double bond
between the carbon and nitrogen and a positive charge on the carbon, meaning that between the
electronegativity of the nitrogen and positively charged carbon in the resonance form, it
destabilizes the carbocation and offer no electrons to the ring.
-SO3, -COR, -CO2R - all of these have electronegative oxygens giving the carbon a positive
partial charge and providing no electrons for stability on the ring.
-F, -Cl, -Br, all have a similar effect. They are electronegative and deactivate the ring, but have
electrons to share that, to some degree, makes up for it, allowing the ortho/para direction. But to
understand their effects better, you need to look at them in terms of their placement on the
periodic chart. Florine is the most electronegative element and it's very small and thus very close
to the hydrogen it's bonded to. This gives its electromagnetic influence a stronger deactivating
character. Chlorine is less electronegative, but it's also larger and thus further away from the
carbon, making it harder for it to share its electrons. And so on.
78

Polysubstituted Benzenes
Unsubstituted benzene is seldom encountered in nature or in the laboratory, and you will find in
your studies that most often benzene rings are found as parts of other, more complicated
molecules. In order for benzene to react in most situations, it gains or loses some functionality
dependent on which functional groups are attached. Although the simplest case is to work with
benzene that has only one functional group, it is also essential to understand the interactions and
competitions between multiple functional groups attached to the same benzene ring.
When there is more than one substituent present on a benzene ring the spatial relationship betwen
groups becomes important, which is why the arene substitution patterns ortho, meta and para
were devised. For example three isomers exist for the molecule cresol because the methyl group
and the hydroxyl group can be placed either next to each other (ortho), one position removed from
each other (meta) or two positions removed from each other (para). Where each group attaches is
most often a function of which order they were attached in, due to the activating/deactivating and
directing activities of previously attached groups.

Competition Between Functional Groups

When a ring has more than one functional group, the effects of the groups are combined and their
total effect must be taken into account. In general, effects are summed. For example, toluene
(methylbenzene) is weakly activated. But p-nitrotoluene has both a methyl group and a nitro
group. The methyl group is weakly activating and the nitro is pretty strongly deactivating, so
overall, the group is very deactivated. In terms of direction, however, both substitutents agree on
the direction. The methyl group is ortho/para directing. The nitro group occupies the para
position, so the methyl will now want just ortho direction. The nitro group is meta directing. The
positions meta to the nitro are also ortho to the methyl, so this works out and further substituents
will be almost entirely in the positions ortho to the methyl group.
If two functional groups disagree on direction, the more activating group is the one that controls
direction. That is, if you had m-nitrotoluene, most of your product would tend to be ortho/para to
the toluene and not meta to the nitro, despite the nitro having a stronger influence on overall
activation.

Naming Conventions
When a benzene ring has more than one substituent group attached, the location of all of the
groups not directly attached to carbon number one must be explicitly declared. This is done by
79

listing the number of the carbon atom where the group is attached, followed by a hyphen and the
group's name. The carbon atoms of the benzene ring should be numbered in order of previously
established precedence, i.e., a bromine would take precedence over a nitro group, which itself
would take precedence over an alcohol or alkane group. The names of the groups should be listed
in alphabetical order, i.e. "2-methyl-5-nitrobenzaldehyde."
.
Sintesa alkena
H2O

a. RCH2CH2X + KOH
b. RCHOH-CH3 + H2SO4

RCH=CH2
RCH=CH2

c. RCHXCH2X + Zn

RCH=CH2
H2O

d. R-CH = CH2 + Hg(OCOCH3)2

R-CH = CH2 + NaBH4

25 C
OH HgOCOCH3
o

R-CH = CH3
OH

Alkuna
Pemberian nama alkuna berdasarkan nama homolog alkana dimana akhiran ana diganti dengan
una. Contohnya
HC

CH etuna

Alkuna alifatik
RC
Senyawa
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44

Nama
Metuna
Etuna
Propane
Butane
Pentane
Heksana
Heptana
Oktana
Nonana
Dekana
Undekana
Dodekana
Tridekana
Tetradekana
Pentadekana
Heksadekana
Heptadekana
Oktadekana
Nonadekana
Eikosana
Heneikosana

Senyawa
C34H44
C35H46
C36H48
C37H50
C38H52
C39H54
C40H56
C41H58
C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110

CH

Nama
tetratriakontana
pentatriakontana
heksatriakontana
heptatriakontana
oktatriakontana
nonatriakontana
Tetrakontana
hentetrakontana
Dotetrakontana
Tritetrakontana
tetratetrakontana
pentatetrakontana
heksatetrakontana
heptatetrakontana
oktatetrakontana
nonatetrakontana
Pentakontana
Henpentakontana
dopentakontana
tripentakontana
tetrapentakontana

80

Senyawa
C67H136
C68H138
C69H140
C70H142
C71H144
C72H146
C73H148
C74H150
C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176

Nama
heptaHeksa kontana
oktaHeksa kontana
nonaHeksa kontana
Heptakontana
henHeptakontana
DoHeptakontana
triHeptakontana
tetraHeptakontana
pentaHeptakontana
heksaHeptakontana
heptaHeptakontana
oktaHeptakontana
nonaHeptakontana
Oktakontana
henOktakontana
doOktakontana
triOktakontana
tetraOktakontana
pentaOktakontana
heksaOktakontana
heptaOktakontana

C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202
C200H402
C300H6002
C1000H2002
C2000H4002
C3000H6002

Dokosana
Trikosana
Tetrakosana
Pentakosana
Heksakosana
Heptakosana
Oktakosana
Nonakosana
Triakontana
Hentriakontana
Dotriakontana
Tritriakontana
Hektana
Dohektana
Trihektana
kiliana
Dilianatana
Triliana

C55H112
C56H114
C57H116
C58H118
C59H120
C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802
C500H1002
C600H12002
C400H8002
C500H10002
C600H1202

pentapentakontana
heksapentakontana
heptapentakontana
Oktapentakontana
nonapentakontana
Heksa kontana
HenHeksa kontana
doHeksa kontana
triHeksa kontana
tetraHeksa kontana
pentaHeksa kontana
heksaHeksa kontana
Tetrahektana
Pentahektana
Heksahektana
Tetraliana
Penliaana
Heksaliana

C88H178
C89H180
C90H182
C91H184
C92H186
C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402
C800H1602
C900H1802
C700H14002
C800H16002
C900H18002

oktaOktakontana
nonaOktakontana
Nonakontana
henNonakontana
doNonakontana
triNonakontana
tetraNonakontana
pentaNonakontana
heksaNonakontana
HeptaNonakontana
oktaNonakontana
nonaNonakontana
Heptahektana
Oktahektana
Nonahektana
Heptaliana
Oktaliana
Nonaliana

Alkapoliuna
R(C CH)n
Contohnya :
HC

CH-HC CH
Butadiuna

Sintesa Alkuna
sintesa alkuna dalam Industri
a. CH4 + 3H2
b. CH4 + O2
c. CaC2 + H2O

HC
HC

CH
CH
HC

CH + Ca(OH)2

Sintesa alkuna di laboratorium

a. RCHXCH2X + KNH2
b. RCX2CH2X + Zn

RHC

RHC
CH

CH

The triple carbon bonds is formed in alkenes, due to the absence of hydrogens, thus allowing
carbon bonds to become stronger, due to the nucleus central force which pulls in nearby atoms
<< Alkenes |Alkynes| Dienes >>
Alkynes are hydrocarbons containing carbon-carbon triple bond. They exhibit neither geometric
nor optical isomerism. The simplest alkyne is ethyne (HCCH), commonly known as acetylene, as
shown at right.

81

Multiple Bonds Between Carbon Atoms

As you know from studying alkenes, atoms do not always bond with only one pair of electrons. In
alkenes (as well in other organic and inorganic molecules) pairs of atoms can share between
themselves more than just a single pair of electrons. Alkynes take this sharing a step further than
alkenes, sharing three electron pairs between carbons instead of just two.

Two Bonds
As you should know already, carbon is generally found in a tetravalent state - it forms four
covalent bonds with other atoms. As you know from the section on alkenes, all four bonds are not
necessarily to different atoms, because carbon atoms can double-bond to one another. What this
does is create the appearance of only being bound to three other atoms, but in actuality four bonds
exist.
Alkenes are molecules that consist of carbon and hydrogen atoms where one or more pairs of
carbon atoms participate in a double bond, which consists of one sigma () and one pi () bond.
Alkynes are also molecules consisting of carbon and hydrogen atoms, but instead of forming a
double bond with only one sigma () and one pi () bond, the alkyne has at least one pair of
carbon atoms who have a and two bonds -- a triple bond.
The carbon-carbon triple bond, then, is a bond in which the carbon atoms share an s and two p
orbitals to form just one and two bonds between them. This results in a linear molecule with a
bond angle of about 180 . Since we know that double bonds are shorter than single covalent
bonds, it would be logical to predict that the triple bond would be shorter still, and this is, in fact,
the case. The triple bonds length, 1.20, is shorter than that of ethane and ethenes 1.54 and 1.34
angstroms, respectively, but the difference between the triple and double bonds is slightly less
than the difference between the single and double bonds.
The chemistry is very similar to alkenes in that both are formed by elimination reactions, and the
major chemical reactions that alkynes undergo are addition type reactions.

Index Of Hydrogen Deficiency

If we compare the general molecular formulas for the Alkane, Alkene, and Alkyne families as well
as the Cycloalkane and cycloalkene families we see the following relationship:
Family

Molecular Formula

Alkane

CnH2n+2

Alkene

CnH2n

Cycloalkane CnH2n
Alkyne

CnH2n-2

Cycloalkene CnH2n-2
We see that for a ring structure or a double bond there is a difference of two hydrogens compared
to the alkane structure with the same number of carbons. If there is a ring + double bond
(cycloalkene) or a triple bond (alkyne) then the difference is four hydrogens compared to the
alkane with the same number of carbons. We say that the Index of Hydrogen Deficiency is equal
82

to the number of pairs of Hydrogens that must be taken away from the alkane to get the same
molecular formula of the compound under investigation. Every -bond in the molecule increases
the index by one. Any ring structure increases the index by one. Here is a list of possibilities:
Per molecule

Index of Hydrogen Deficiency

One double bond

1 ring

1 double bond and 1 ring

2 double bonds

1 triple bond

1 triple bond + 1 double bond

3 double bonds

2 double bonds + 1 ring

2 triple bonds

4 double bonds

Just remember that double bonds have 1 bond, triple bonds have 2 bonds and each bond is
an index of 1. We can use the index and the molecular formula to identify possibilities as to the
exact nature of the molecule. For example, determine the molecular formula and speculate on
what kind of Pi bonding and/or ring structure the molecules would have if the Index was given to
be 3 and it is a 6 carbon hydrocarbon.
Identify the Alkane molecular formula for six carbons. For n = 6 we would have CnH2n+2. That
would be C6H14.
Since an index of 3 means that there are 3 pairs(2) of hydrogen atoms less in the compound
compared with the alkane we determined in step 1, then we would have C6H14-6 or C6H8.
In speculating as to what the bonding and structure could be with an index of 3 that could mean:

o
o
o

Three double bonds in a non-cyclic structure like hexatriene

Two double bonds in a ring structure like a cyclohexadiene
One triple bond and one double bond in a non-cyclic structure

Clearly the answer cannot be determined from the formula alone, but the formula will give
important clues as to a molecule's structure.

Cycloalkynes
Cycloalkynes are seldom encountered, and are not stable in small rings due to angle strain.
Cyclooctyne has been isolated, but is very reactive, and will polymerize with itself quickly.
Cyclononyne is the smallest stable cycloalkyne.
Benzyne is another cycloalkyne that has been proposed as an intermediate for eliminationaddition reactions of benzene.
83

Preparation
In order to synthesize alkynes, one generally starts with a vicinal or geminal dihalide (an alkane
with two halogen atoms attached either next to one another or across from one another). Adding
sodium amide (NaNH2) removes the halogens with regiochemistry subject to Zaitsev's Rule,
resulting in a carbon-carbon triple bond due to the loss of both halogens as well as two hydrogen
atoms from the starting molecule. This is called a double dehydrohalogenation.

Dehydrogenation of an alkane or alkene

Dehalogenation of a tetrahaloalkane
Dehydrohalogenation of a dihaloalkane
Through Kolbe's Electrolysis
The starting compound is a salt already containing a carbon-carbon double bond. One such
compound is maleic acid. Mechanism is similar to that of formation of ethane using kolbe's
electrolysis.
CH-COONa
|
CH-COONa
At Anode:
CH-COO||
CH-COO-

(sodium maleate) (maleic acid)

At cathode:
2Na+ + 2e- -> 2Na
2Na + H20 -> 2NaOH + H2

-2e- ->
CH-COO*
||
->
-2CO2
CH-COO*
(free radical formation)

->

CH*
||
CH*

->

CH
|||
CH

In this manner, alkyne is obtained at anode, while NaOH is formed at cathode and hydrogen gas is
liberated.
Vicinal dihalides may be converted into alkynes by using extreme conditions such as sodium
amide NaNH2 typically at 150C or molten/fused potassium hydroxide KOH typically at 200C.

From Calcium carbide

Calcium carbide is the compound CaC2, which consists of calcium ions (Ca2+) and acetylide ions,
C22-. It is synthesized from lime and coke in the following reaction:
CaO + 3C CaC2 + CO
This reaction is very endothermic and requires a temperature of 2000o C. For this reason it is
produced in an electrical arc furnace.
84

Calcium carbide may formally be considered a derivative of acetylene, an extremely weak acid
(though not as weak as ammonia). The double deprotonation means that the carbide ion has very
high energy. Instant hydrolysis occurs when water is added to calcium carbide, yielding acetylene
gas.

From alkyl or aryl halides

Properties
Physical properties
Most alkynes are less dense than water (they float on top of water), but there are a few
exceptions.

Chemical properties
Liquid alkynes are non-polar solvents, immiscible with water. Alkynes are, however, more polar
than alkanes or alkenes, as a result of the electron density near the triple bond.
Alkynes with a low ratio of hydrogen atoms to carbon atoms are highly combustible. Carboncarbon triple bonds are highly reactive and easily broken or converted to double or single bonds.
Triple bonds store large amounts of chemical energy and thus are highly exothermic when broken.
The heat released can cause rapid expansion, so care must be taken when working with alkynes
such as acetylene.
One synthetically important property of terminal alkynes is the acidity of their protons. Whereas
the protons in alkanes have pKa's around 60 and alkene protons have pKa's in the mid-40's,
terminal alkynes have pKa's of about 25. Substitution of the alkyne can reduce the pKa of the
alkyne even further; for example, PhCCH has a pKa around 23, and Me3SiCCH has a pKa around
19. The acidity of alkynes allows them easily to be deprotonated by sufficiently strong bases, such
as butyllithium BuLi or the amide ion NH2-. More acidic alkynes such as PhCCH can even be
deprotonated by alkoxide bases under the right conditions.

Reactions
Alkynes can be hydrated into either a ketone or an aldehyde form. A (Markovnikov) ketone can be
created from an alkyne using a solution of aqueous sulfuric acid (H2O/H2SO4) and HgSO4,
whereas the anti-Markovnikov aldehyde product requires different reagents and is a multi-step
process.

Oxidative Cleavage of Alkynes

Hydrohalogenation of Alkynes
Alkynes react very quickly and to completion with hydrogen halides. Addition is anti, and follows
the Markovnikov Rule.

85

RCCH + H-Br (1 equiv) --> RCBr=CH2

RCCH + H-Br (2 equivs) --> RCBr2CH3
Adding a halide acid such as HCl or HBr to an alkyne can create a geminal dihalide via a
Markovnikov process, but adding HBr in the presence of peroxides results in the AntiMarkovnikov alkenyl bromide product.

Halogenation of Alkynes
Adding diatomic halogen molecules such as Br2 or Cl2 results in 1,2-dihaloalkene, or, if the
halogen is added in excess, a 1,1,2,2-tetrahaloalkane.
Adding H2O along with the diatomic halide results in a halohydrin addition and an -halo ketone.

Combustion
Alkynes burn in air with a sooty, yellow flame, like alkanes. Alkenes also burn yellow, while
alkanes burn with blue flames. Acetylene burns with large amounts of heat, and is used in
oxyacetylene torches for welding metals together, for example, in the superstructures of
skyscrapers.
2 C2H2 + 5 O2 --> 4 CO2 + 2 H2O

Reduction
Alkynes can be hydrogenated by adding H2 with a metallic catalyst, such as palladium-carbon or
platinum or nickel, which results in a both of the alkyne carbons becoming fully saturated. If
Lindlar's catalyst is used instead, the alkyne hydrogenates to a Z enantiomer alkene, and if an
alkali metal in an ammonia solution is used for hydrogenating the alkyne, an E enantiomer alkene
is the result.

Complete Hydrogenation of Alkynes

As mentioned above, alkynes are reduced to alkanes in the presence of an active metal catalyst,
such as Pt, Pd, Rh, or Ni in the presence of heat and pressure.
RCCR' + 2 H2 (Pt cat.)--> RCH2CH2R'

Syn-Hydrogenation of an Alkyne
There are two kinds of addition type reactions where a -bond is broken and atoms are added to
the molecule. If the atoms are added on the same side of the molecule then the addition is said to
be a "syn" addition. If the added atoms are added on opposite sides of the molecule then the
addition is said to be an "anti" addition. Hydrogen atoms can be added to an alkyne on a one mole
86

to one mole ratio to get an alkene where the hydrogen atoms have been added on the same side of
the molecule. Isotopic identification allows chemists to determine when this syn-hydrogenation
has occurred.
As mentioned above, alkynes can be reduced to cis-alkenes by hydrogen in the presence of
Lindlar Pd, i.e. palladium doped with CaSO4 or BaSO4.
RCCR + H2 cis-RCH=CHR

Anti-Hydrogenation of an Alkyne
In regards to the syn-hydrogenation, anti is hydrogenation when one hydrogen is added from the
top of the pi bond and the other is added from the bottom.

Anion formation
Because of the acidity of the protons of terminal alkynes, they are easily converted into alkynyl
anions in high yield by strong bases.
Examples
RCCH + NaNH2 -> RCCNa + NH3 C4H9Li + RCCH -> C4H10 +RCCLi
Alkynes are stronger bases than water, and acetylene (ethyne) is produced in a science classroom
reaction of calcium carbide with water.
CaC2 + 2 H20 --> Ca(OH)2 + C2H2
Alkynyl anions are useful in lengthening carbon chains. They react by nucleophilic substitution
with alkyl halides.
R-Cl + R'CCNa --> RCCR' + NaCl
The product of this reaction can be reduced to an alkane with hydrogen and a platinum or rhodium
catalyst, or an alkene with Lindlar palladium.
Alkil halide
5.4.1. Pemberian nama alkyl halida
Senyawa
CH4
C2H6
C3H8

Nama
Metil halida
Etil halida
Propil halida

Senyawa
C34H44
C35H46
C36H48

Nama
tetratriakontana
pentatriakontana
heksatriakontana

87

Senyawa
C67H136
C68H138
C69H140

Nama
heptaHeksa kontana
oktaHeksa kontana
nonaHeksa kontana

C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202
C200H402
C300H6002
C1000H2002
C2000H4002
C3000H6002

Butil halida
Pentil halida
Heksana
Heptana
Oktana
Nonana
Dekana
Undekana
Dodekana
Tridekana
Tetradekana
Pentadekana
Heksadekana
Heptadekana
Oktadekana
Nonadekana
Eikosana
Heneikosana
Dokosana
Trikosana
Tetrakosana
Pentakosana
Heksakosana
Heptakosana
Oktakosana
Nonakosana
Triakontana
Hentriakontana
Dotriakontana
Tritriakontana
Hektana
Dohektana
Trihektana
kiliana
Dilianatana
Triliana

C37H50
C38H52
C39H54
C40H56
C41H58
C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110
C55H112
C56H114
C57H116
C58H118
C59H120
C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802
C500H1002
C600H12002
C400H8002
C500H10002
C600H1202

heptatriakontana
oktatriakontana
nonatriakontana
Tetrakontana
hentetrakontana
Dotetrakontana
Tritetrakontana
tetratetrakontana
pentatetrakontana
heksatetrakontana
heptatetrakontana
oktatetrakontana
nonatetrakontana
Pentakontana
Henpentakontana
dopentakontana
tripentakontana
tetrapentakontana
pentapentakontana
heksapentakontana
heptapentakontana
Oktapentakontana
nonapentakontana
Heksa kontana
HenHeksa kontana
doHeksa kontana
triHeksa kontana
tetraHeksa kontana
pentaHeksa kontana
heksaHeksa kontana
Tetrahektana
Pentahektana
Heksahektana
Tetraliana
Penliaana
Heksaliana

C70H142
C71H144
C72H146
C73H148
C74H150
C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176
C88H178
C89H180
C90H182
C91H184
C92H186
C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402
C800H1602
C900H1802
C700H14002
C800H16002
C900H18002

5.4.2. Sintesa alkyl halida

a. C6H5CH3 + X2
b. (CH3)3CCH3 + X2

C6H5CH2X
(CH3)3CCH2X

c. R-CH2CH2OH + NaX + H2SO4

d. R-CH2CH2OH + HX
e. R-CH2CH2OH + SOX2
f. R-CH2CH2OH + PX3
g. RHC=CH2 + HX

R-CH2CH2X

R-CH2CH2X
R-CH2CH2X
R-CH2CH2X
R-CH2CH2X
88

Heptakontana
henHeptakontana
DoHeptakontana
triHeptakontana
tetraHeptakontana
pentaHeptakontana
heksaHeptakontana
heptaHeptakontana
oktaHeptakontana
nonaHeptakontana
Oktakontana
henOktakontana
doOktakontana
triOktakontana
tetraOktakontana
pentaOktakontana
heksaOktakontana
heptaOktakontana
oktaOktakontana
nonaOktakontana
Nonakontana
henNonakontana
doNonakontana
triNonakontana
tetraNonakontana
pentaNonakontana
heksaNonakontana
HeptaNonakontana
oktaNonakontana
nonaNonakontana
Heptahektana
Oktahektana
Nonahektana
Heptaliana
Oktaliana
Nonaliana

5.4.2. Reaksi-reaksi alkyl halide

Alkanol
Pemberian nama
Senyawa
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202
C200H402
C300H6002
C1000H2002
C2000H4002
C3000H6002

Nama
Metana
Etana
Propane
Butane
Pentane
Heksana
Heptana
Oktana
Nonana
Dekana
Undekana
Dodekana
Tridekana
Tetradekana
Pentadekana
Heksadekana
Heptadekana
Oktadekana
Nonadekana
Eikosana
Heneikosana
Dokosana
Trikosana
Tetrakosana
Pentakosana
Heksakosana
Heptakosana
Oktakosana
Nonakosana
Triakontana
Hentriakontana
Dotriakontana
Tritriakontana
Hektana
Dohektana
Trihektana
kiliana
Dilianatana
Triliana

Senyawa
C34H44
C35H46
C36H48
C37H50
C38H52
C39H54
C40H56
C41H58
C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110
C55H112
C56H114
C57H116
C58H118
C59H120
C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802
C500H1002
C600H12002
C400H8002
C500H10002
C600H1202

Nama
tetratriakontana
pentatriakontana
heksatriakontana
heptatriakontana
oktatriakontana
nonatriakontana
Tetrakontana
hentetrakontana
Dotetrakontana
Tritetrakontana
tetratetrakontana
pentatetrakontana
heksatetrakontana
heptatetrakontana
oktatetrakontana
nonatetrakontana
Pentakontana
Henpentakontana
dopentakontana
tripentakontana
tetrapentakontana
pentapentakontana
heksapentakontana
heptapentakontana
Oktapentakontana
nonapentakontana
Heksa kontana
HenHeksa kontana
doHeksa kontana
triHeksa kontana
tetraHeksa kontana
pentaHeksa kontana
heksaHeksa kontana
Tetrahektana
Pentahektana
Heksahektana
Tetraliana
Penliaana
Heksaliana

Senyawa
C67H136
C68H138
C69H140
C70H142
C71H144
C72H146
C73H148
C74H150
C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176
C88H178
C89H180
C90H182
C91H184
C92H186
C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402
C800H1602
C900H1802
C700H14002
C800H16002
C900H18002

Nama
heptaHeksa kontana
oktaHeksa kontana
nonaHeksa kontana
Heptakontana
henHeptakontana
DoHeptakontana
triHeptakontana
tetraHeptakontana
pentaHeptakontana
heksaHeptakontana
heptaHeptakontana
oktaHeptakontana
nonaHeptakontana
Oktakontana
henOktakontana
doOktakontana
triOktakontana
tetraOktakontana
pentaOktakontana
heksaOktakontana
heptaOktakontana
oktaOktakontana
nonaOktakontana
Nonakontana
henNonakontana
doNonakontana
triNonakontana
tetraNonakontana
pentaNonakontana
heksaNonakontana
HeptaNonakontana
oktaNonakontana
nonaNonakontana
Heptahektana
Oktahektana
Nonahektana
Heptaliana
Oktaliana
Nonaliana

Sintesa alkanol
a. RX + OHb. C = C + H2O

c. R-CH = CH2 + B2H6

ROH + XCH COH

(RCH2 CH2)3-B+ H2O2

89

RCH2 CH2OH

OHH2O
d. R-CH = CH2 + Hg(OCOCH3)2
R
e. RMgX + R-C= O

R-CH = CH2 + NaBH4

R-CH-CH3
25 oC
OH HgOCOCH3
OH
R
R
RCH2OMgX + H2O
RCH2OH + MgXOH

Reaksi-reaksi alkanol
Alkoksi alkana
Senyawa
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202
C200H402
C300H6002
C1000H2002
C2000H4002
C3000H6002

Nama
Metoksialkana
Etoksialkana
Propoksialkana
Butoksialkana
Pentane
Heksana
Heptana
Oktana
Nonana
Dekana
Undekana
Dodekana
Tridekana
Tetradekana
Pentadekana
Heksadekana
Heptadekana
Oktadekana
Nonadekana
Eikosana
Heneikosana
Dokosana
Trikosana
Tetrakosana
Pentakosana
Heksakosana
Heptakosana
Oktakosana
Nonakosana
Triakontana
Hentriakontana
Dotriakontana
Tritriakontana
Hektana
Dohektana
Trihektana
kiliana
Dilianatana
Triliana

Senyawa
C34H44
C35H46
C36H48
C37H50
C38H52
C39H54
C40H56
C41H58
C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110
C55H112
C56H114
C57H116
C58H118
C59H120
C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802
C500H1002
C600H12002
C400H8002
C500H10002
C600H1202

Nama
tetratriakontana
pentatriakontana
heksatriakontana
heptatriakontana
oktatriakontana
nonatriakontana
Tetrakontana
hentetrakontana
Dotetrakontana
Tritetrakontana
tetratetrakontana
pentatetrakontana
heksatetrakontana
heptatetrakontana
oktatetrakontana
nonatetrakontana
Pentakontana
Henpentakontana
dopentakontana
tripentakontana
tetrapentakontana
pentapentakontana
heksapentakontana
heptapentakontana
Oktapentakontana
nonapentakontana
Heksa kontana
HenHeksa kontana
doHeksa kontana
triHeksa kontana
tetraHeksa kontana
pentaHeksa kontana
heksaHeksa kontana
Tetrahektana
Pentahektana
Heksahektana
Tetraliana
Penliaana
Heksaliana

Pemberian nama
90

Senyawa
C67H136
C68H138
C69H140
C70H142
C71H144
C72H146
C73H148
C74H150
C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176
C88H178
C89H180
C90H182
C91H184
C92H186
C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402
C800H1602
C900H1802
C700H14002
C800H16002
C900H18002

Nama
heptaHeksa kontana
oktaHeksa kontana
nonaHeksa kontana
Heptakontana
henHeptakontana
DoHeptakontana
triHeptakontana
tetraHeptakontana
pentaHeptakontana
heksaHeptakontana
heptaHeptakontana
oktaHeptakontana
nonaHeptakontana
Oktakontana
henOktakontana
doOktakontana
triOktakontana
tetraOktakontana
pentaOktakontana
heksaOktakontana
heptaOktakontana
oktaOktakontana
nonaOktakontana
Nonakontana
henNonakontana
doNonakontana
triNonakontana
tetraNonakontana
pentaNonakontana
heksaNonakontana
HeptaNonakontana
oktaNonakontana
nonaNonakontana
Heptahektana
Oktahektana
Nonahektana
Heptaliana
Oktaliana
Nonaliana

Nama senyawa alkoksi alkana adalah nama homolog alkana, dimana nama alkana sebelum
atom oksigen akhiran nama alkana diganti dengan akhiran oksi dan nama homolog alkana
sesudah atom oksigen sesuai dengan homolog alkananya.
Contoh
H3C-CH2-CH2-O-CH2-CH3
Etoksi propana
Sintesa
a. H3C-CH2OH + H2SO4
b. (H3C)2-CHCl + Ag2O
c. R-O-Na + RCl

H3C-CH2-O-H2C-CH3
. (H3C)2-CH-O-CH-(H3C)2
R-O-R + NaCl

BF3
d. C7H13OH + CH2N2

C7H13OCH3 + N2

e. C6H5OH + CH2N2

C6H5OCH3 + N2

f. R-CH = CH2 + Hg(OCOCF3)2 + ROH

R-CH - CH2 + NaBH4

OR
HgOCOCF3

Alkanal
5.7.1. Pemberian nama alkanal
Nama alkanal berasal dari homolog alkana dengan mengganti akhiran a dengan al
Senyawa
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44

Nama
Metanal
Etanal
Propanal
Butanal
Pentanal
Heksana
Heptana
Oktana
Nonana
Dekana
Undekana
Dodekana
Tridekana
Tetradekana
Pentadekana
Heksadekana
Heptadekana
Oktadekana
Nonadekana
Eikosana
Heneikosana

Senyawa
C34H44
C35H46
C36H48
C37H50
C38H52
C39H54
C40H56
C41H58
C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110

Nama
tetratriakontana
pentatriakontana
heksatriakontana
heptatriakontana
oktatriakontana
nonatriakontana
Tetrakontana
hentetrakontana
Dotetrakontana
Tritetrakontana
tetratetrakontana
pentatetrakontana
heksatetrakontana
heptatetrakontana
oktatetrakontana
nonatetrakontana
Pentakontana
Henpentakontana
dopentakontana
tripentakontana
tetrapentakontana

91

Senyawa
C67H136
C68H138
C69H140
C70H142
C71H144
C72H146
C73H148
C74H150
C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176

Nama
heptaHeksa kontana
oktaHeksa kontana
nonaHeksa kontana
Heptakontana
henHeptakontana
DoHeptakontana
triHeptakontana
tetraHeptakontana
pentaHeptakontana
heksaHeptakontana
heptaHeptakontana
oktaHeptakontana
nonaHeptakontana
Oktakontana
henOktakontana
doOktakontana
triOktakontana
tetraOktakontana
pentaOktakontana
heksaOktakontana
heptaOktakontana

C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202
C200H402
C300H6002
C1000H2002
C2000H4002
C3000H6002

Dokosana
Trikosana
Tetrakosana
Pentakosana
Heksakosana
Heptakosana
Oktakosana
Nonakosana
Triakontana
Hentriakontana
Dotriakontana
Tritriakontana
Hektana
Dohektana
Trihektana
kiliana
Dilianatana
Triliana

C55H112
C56H114
C57H116
C58H118
C59H120
C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802
C500H1002
C600H12002
C400H8002
C500H10002
C600H1202

pentapentakontana
heksapentakontana
heptapentakontana
Oktapentakontana
nonapentakontana
Heksa kontana
HenHeksa kontana
doHeksa kontana
triHeksa kontana
tetraHeksa kontana
pentaHeksa kontana
heksaHeksa kontana
Tetrahektana
Pentahektana
Heksahektana
Tetraliana
Penliaana
Heksaliana

C88H178
C89H180
C90H182
C91H184
C92H186
C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402
C800H1602
C900H1802
C700H14002
C800H16002
C900H18002

oktaOktakontana
nonaOktakontana
Nonakontana
henNonakontana
doNonakontana
triNonakontana
tetraNonakontana
pentaNonakontana
heksaNonakontana
HeptaNonakontana
oktaNonakontana
nonaNonakontana
Heptahektana
Oktahektana
Nonahektana
Heptaliana
Oktaliana
Nonaliana

5.7.2. Sintesa alkanal

a. RCH2OH + KMnO4

RC =O
H

O
b. H3C-(CH2)6I + CH3 - S - CH3
c. Ar-CH3 + Cl2

Ar-CH-Cl2

H3C- (CH2)5 C =O + H3C-S-CH3

H
+ H2O

d. RCOCl + LiAl{(CH3)3CO}3)2H

ArCHO
R-CHO

+ LiCl +

Al{(CH3)3CO}3)2

HCl, AlCl3
e. C6H5(CH3)2 + CO

p-(CH3)2CHC6H4CHO
CuCl

5.7.3. Reaksi-reaksi alkanal

Alkanon
Pemberian nama alkanon
Nama alkanon berasal dari homolog alkana dengan mengganti akhiran a dengan on
Senyawa
CH4
C2H6
C3H8
C4H10
C5H12
C6H14

Nama
Metanal
Etanal
Propanon
Butanon
Pentanon
Heksana

Senyawa
C34H44
C35H46
C36H48
C37H50
C38H52
C39H54

Nama
tetratriakontana
pentatriakontana
heksatriakontana
heptatriakontana
oktatriakontana
nonatriakontana

92

Senyawa
C67H136
C68H138
C69H140
C70H142
C71H144
C72H146

Nama
heptaHeksa kontana
oktaHeksa kontana
nonaHeksa kontana
Heptakontana
henHeptakontana
DoHeptakontana

C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202
C200H402
C300H6002
C1000H2002
C2000H4002
C3000H6002

Heptana
Oktana
Nonana
Dekana
Undekana
Dodekana
Tridekana
Tetradekana
Pentadekana
Heksadekana
Heptadekana
Oktadekana
Nonadekana
Eikosana
Heneikosana
Dokosana
Trikosana
Tetrakosana
Pentakosana
Heksakosana
Heptakosana
Oktakosana
Nonakosana
Triakontana
Hentriakontana
Dotriakontana
Tritriakontana
Hektana
Dohektana
Trihektana
kiliana
Dilianatana
Triliana

C40H56
C41H58
C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110
C55H112
C56H114
C57H116
C58H118
C59H120
C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802
C500H1002
C600H12002
C400H8002
C500H10002
C600H1202

Tetrakontana
hentetrakontana
Dotetrakontana
Tritetrakontana
tetratetrakontana
pentatetrakontana
heksatetrakontana
heptatetrakontana
oktatetrakontana
nonatetrakontana
Pentakontana
Henpentakontana
dopentakontana
tripentakontana
tetrapentakontana
pentapentakontana
heksapentakontana
heptapentakontana
Oktapentakontana
nonapentakontana
Heksa kontana
HenHeksa kontana
doHeksa kontana
triHeksa kontana
tetraHeksa kontana
pentaHeksa kontana
heksaHeksa kontana
Tetrahektana
Pentahektana
Heksahektana
Tetraliana
Penliaana
Heksaliana

C73H148
C74H150
C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176
C88H178
C89H180
C90H182
C91H184
C92H186
C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402
C800H1602
C900H1802
C700H14002
C800H16002
C900H18002

triHeptakontana
tetraHeptakontana
pentaHeptakontana
heksaHeptakontana
heptaHeptakontana
oktaHeptakontana
nonaHeptakontana
Oktakontana
henOktakontana
doOktakontana
triOktakontana
tetraOktakontana
pentaOktakontana
heksaOktakontana
heptaOktakontana
oktaOktakontana
nonaOktakontana
Nonakontana
henNonakontana
doNonakontana
triNonakontana
tetraNonakontana
pentaNonakontana
heksaNonakontana
HeptaNonakontana
oktaNonakontana
nonaNonakontana
Heptahektana
Oktahektana
Nonahektana
Heptaliana
Oktaliana
Nonaliana

Sintesa alkanon
a. R2CHOH + KMnO4 + 8 H+

R2C=O + Mn+2 + 4H2O + K+

AlCl3

b ArH + RCOCl

ArCOR + HCl
O

c. R-ClC = O + H2C=CHR

(R-C-CH2 CHCl)

O
RCCH=CHR

O
d. R-ClC = O + R2Cd
e. HOOC(CH2)nCOOH + BaO
CH3

R-C-R

+ CdCl2
(CH2)n

CH3

C=O + BaCO3 + H2O

CH3

93

O
f.
CrO3
+ B2H6
H3O+

5.8.3. Reaksi-reaksi alkanon

Alkanoat
Senyawa
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202
C200H402
C300H6002
C1000H2002
C2000H4002
C3000H6002

Nama
Metanoat
Etanoat
Propanoat
Butanoat
Pentanoat
Heksanoat
Heptanoat
Oktanoat
Nonanoat
Dekanoat
Undekana
Dodekana
Tridekana
Tetradekana
Pentadekana
Heksadekana
Heptadekana
Oktadekana
Nonadekana
Eikosana
Heneikosana
Dokosana
Trikosana
Tetrakosana
Pentakosana
Heksakosana
Heptakosana
Oktakosana
Nonakosana
Triakontana
Hentriakontana
Dotriakontana
Tritriakontana
Hektana
Dohektana
Trihektana
kiliana
Dilianatana
Triliana

Senyawa
C34H44
C35H46
C36H48
C37H50
C38H52
C39H54
C40H56
C41H58
C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110
C55H112
C56H114
C57H116
C58H118
C59H120
C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802
C500H1002
C600H12002
C400H8002
C500H10002
C600H1202

Nama
tetratriakontana
pentatriakontana
heksatriakontana
heptatriakontana
oktatriakontana
nonatriakontana
Tetrakontana
hentetrakontana
Dotetrakontana
Tritetrakontana
tetratetrakontana
pentatetrakontana
heksatetrakontana
heptatetrakontana
oktatetrakontana
nonatetrakontana
Pentakontana
Henpentakontana
dopentakontana
tripentakontana
tetrapentakontana
pentapentakontana
heksapentakontana
heptapentakontana
Oktapentakontana
nonapentakontana
Heksa kontana
HenHeksa kontana
doHeksa kontana
triHeksa kontana
tetraHeksa kontana
pentaHeksa kontana
heksaHeksa kontana
Tetrahektana
Pentahektana
Heksahektana
Tetraliana
Penliaana
Heksaliana

94

Senyawa
C67H136
C68H138
C69H140
C70H142
C71H144
C72H146
C73H148
C74H150
C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176
C88H178
C89H180
C90H182
C91H184
C92H186
C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402
C800H1602
C900H1802
C700H14002
C800H16002
C900H18002

Nama
heptaHeksa kontana
oktaHeksa kontana
nonaHeksa kontana
Heptakontana
henHeptakontana
DoHeptakontana
triHeptakontana
tetraHeptakontana
pentaHeptakontana
heksaHeptakontana
heptaHeptakontana
oktaHeptakontana
nonaHeptakontana
Oktakontana
henOktakontana
doOktakontana
triOktakontana
tetraOktakontana
pentaOktakontana
heksaOktakontana
heptaOktakontana
oktaOktakontana
nonaOktakontana
Nonakontana
henNonakontana
doNonakontana
triNonakontana
tetraNonakontana
pentaNonakontana
heksaNonakontana
HeptaNonakontana
oktaNonakontana
nonaNonakontana
Heptahektana
Oktahektana
Nonahektana
Heptaliana
Oktaliana
Nonaliana

a. RCOH + (O)
b. C = C + H2O
c. R-CH = CH2 + B2H6

RCOOH
-CH CHOH- + (O)
(RCH2 CH2)3-B+ H2O2

-CH-COOH
RCH2 CH2OH
OH-

H2O
d. R-CH = CH2 + Hg(OCOCH3)2

R-CH = CH2 + NaBH4

25 C
OH HgOCOCH3
o

R-CH = CH3
OH

Alkil alkanoat
a. RCOOH + R OHb. C = C + H2O
c. R-CH = CH2 + B2H6

RCOOR + HOH
-CH CHOH
(RCH2 CH2)3-B+ H2O2

RCH2 CH2OH
OH-

H2O
d. R-CH = CH2 + Hg(OCOCH3)2
25 oC

R-CH = CH2 + NaBH4

OH HgOCOCH3

R-CH = CH3
OH

Alkanoil halide
a. RCOOH + XOH
b. C = C + H2O
c. R-CH = CH2 + B2H6

RCOOX
-CH CHOH
(RCH2 CH2)3-B+ H2O2

RCH2 CH2OH
OH-

H2O
d. R-CH = CH2 + Hg(OCOCH3)2

R-CH = CH2 + NaBH4

25 C
OH HgOCOCH3
o

R-CH = CH3
OH

Alkil amina
Senyawa amina adalah merupakan turunan hidrokarbon yang mempunyai gugus
amina pada salah satu atau beberapa atom karbonnya dalam rantai molekul hidrokarbon.
Amina digolongkan menjadi amina primer RNH2, amina sekunder R2NH, dan amina tersier
R3N yang ditentukan oleh derajad substuitusi atom nitrogennya Pemberina nama IUPAC dari
senyawa amino didasrkan pada nama homolog induk alkil alkananya kemudian ditambah
dengan amina dibelakangnya
Amina alifatik
Senyawa
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18

Nama
Metil amiana
Etetil amina
Propane
Butane
Pentane
Heksana
Heptana
Oktana

Senyawa
C34H44
C35H46
C36H48
C37H50
C38H52
C39H54
C40H56
C41H58

Nama
tetratriakontana
pentatriakontana
heksatriakontana
heptatriakontana
oktatriakontana
nonatriakontana
Tetrakontana
hentetrakontana

95

Senyawa
C67H136
C68H138
C69H140
C70H142
C71H144
C72H146
C73H148
C74H150

Nama
heptaHeksa kontana
oktaHeksa kontana
nonaHeksa kontana
Heptakontana
henHeptakontana
DoHeptakontana
triHeptakontana
tetraHeptakontana

C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202
C200H402
C300H6002
C1000H2002
C2000H4002
C3000H6002

Nonana
Dekana
Undekana
Dodekana
Tridekana
Tetradekana
Pentadekana
Heksadekana
Heptadekana
Oktadekana
Nonadekana
Eikosana
Heneikosana
Dokosana
Trikosana
Tetrakosana
Pentakosana
Heksakosana
Heptakosana
Oktakosana
Nonakosana
Triakontana
Hentriakontana
Dotriakontana
Tritriakontana
Hektana
Dohektana
Trihektana
kiliana
Dilianatana
Triliana

C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110
C55H112
C56H114
C57H116
C58H118
C59H120
C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802
C500H1002
C600H12002
C400H8002
C500H10002
C600H1202

Dotetrakontana
Tritetrakontana
tetratetrakontana
pentatetrakontana
heksatetrakontana
heptatetrakontana
oktatetrakontana
nonatetrakontana
Pentakontana
Henpentakontana
dopentakontana
tripentakontana
tetrapentakontana
pentapentakontana
heksapentakontana
heptapentakontana
Oktapentakontana
nonapentakontana
Heksa kontana
HenHeksa kontana
doHeksa kontana
triHeksa kontana
tetraHeksa kontana
pentaHeksa kontana
heksaHeksa kontana
Tetrahektana
Pentahektana
Heksahektana
Tetraliana
Penliaana
Heksaliana

C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176
C88H178
C89H180
C90H182
C91H184
C92H186
C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402
C800H1602
C900H1802
C700H14002
C800H16002
C900H18002

pentaHeptakontana
heksaHeptakontana
heptaHeptakontana
oktaHeptakontana
nonaHeptakontana
Oktakontana
henOktakontana
doOktakontana
triOktakontana
tetraOktakontana
pentaOktakontana
heksaOktakontana
heptaOktakontana
oktaOktakontana
nonaOktakontana
Nonakontana
henNonakontana
doNonakontana
triNonakontana
tetraNonakontana
pentaNonakontana
heksaNonakontana
HeptaNonakontana
oktaNonakontana
nonaNonakontana
Heptahektana
Oktahektana
Nonahektana
Heptaliana
Oktaliana
Nonaliana

Amina alisiklik
Sikloamina
Sintesa amina
a. RX + NH3
b. RX + RNH2
c. RX

+ RRNH

d. RX

+ RRRN

e. RX + NaN3
f. RX + NaCN
h. C6H5NO2 + Zn + HCl

RNH3 X- + NaOH
RRNH2X + NaOH

R NH2 + NaX + H2O

RRNH + NaX + H2O

RRRNHX + NaOH
RRRNX + NaOH
RN3 + LiAlH4
RCN + LiAlH4

RRRRN + NaOH + H2O

H2O
ether

RNH2

H2O
ether

RNH2

C6H5NH2

96

RRRN + NaX

i. RCN + LiAlH4

RCH2NH2

j. RCONR2 + LiAlH4

RCH2NHR2

NOH

NH2

k.
+ H2NOH

C2H5OH
Na
sikloheksilhidroksiamin

Sikloheksanon

sikloheksilamin

H2/Ni
l. CH3COH + NH3

CH3CH2NH2

m. RCONH2 + Br2 + 4 KOH

RNH2 + K2CO3 + 2 KBr + 2 H2O

Alkil sulfide
Senyawa
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C24H50
C25H52
C26H54
C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202

Nama
Metana
Etana
Propane
Butane
Pentane
Heksana
Heptana
Oktana
Nonana
Dekana
Undekana
Dodekana
Tridekana
Tetradekana
Pentadekana
Heksadekana
Heptadekana
Oktadekana
Nonadekana
Eikosana
Heneikosana
Dokosana
Trikosana
Tetrakosana
Pentakosana
Heksakosana
Heptakosana
Oktakosana
Nonakosana
Triakontana
Hentriakontana
Dotriakontana
Tritriakontana
Hektana

Senyawa
C34H44
C35H46
C36H48
C37H50
C38H52
C39H54
C40H56
C41H58
C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110
C55H112
C56H114
C57H116
C58H118
C59H120
C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802

Nama
tetratriakontana
pentatriakontana
heksatriakontana
heptatriakontana
oktatriakontana
nonatriakontana
Tetrakontana
hentetrakontana
Dotetrakontana
Tritetrakontana
tetratetrakontana
pentatetrakontana
heksatetrakontana
heptatetrakontana
oktatetrakontana
nonatetrakontana
Pentakontana
Henpentakontana
dopentakontana
tripentakontana
tetrapentakontana
pentapentakontana
heksapentakontana
heptapentakontana
Oktapentakontana
nonapentakontana
Heksa kontana
HenHeksa kontana
doHeksa kontana
triHeksa kontana
tetraHeksa kontana
pentaHeksa kontana
heksaHeksa kontana
Tetrahektana

97

Senyawa
C67H136
C68H138
C69H140
C70H142
C71H144
C72H146
C73H148
C74H150
C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176
C88H178
C89H180
C90H182
C91H184
C92H186
C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402

Nama
heptaHeksa kontana
oktaHeksa kontana
nonaHeksa kontana
Heptakontana
henHeptakontana
DoHeptakontana
triHeptakontana
tetraHeptakontana
pentaHeptakontana
heksaHeptakontana
heptaHeptakontana
oktaHeptakontana
nonaHeptakontana
Oktakontana
henOktakontana
doOktakontana
triOktakontana
tetraOktakontana
pentaOktakontana
heksaOktakontana
heptaOktakontana
oktaOktakontana
nonaOktakontana
Nonakontana
henNonakontana
doNonakontana
triNonakontana
tetraNonakontana
pentaNonakontana
heksaNonakontana
HeptaNonakontana
oktaNonakontana
nonaNonakontana
Heptahektana

C200H402
C300H6002
C1000H2002
C2000H4002
C3000H6002

Dohektana
Trihektana
kiliana
Dilianatana
Triliana

C500H1002
C600H12002
C400H8002
C500H10002
C600H1202

Pentahektana
Heksahektana
Tetraliana
Penliaana
Heksaliana

C800H1602
C900H1802
C700H14002
C800H16002
C900H18002

Oktahektana
Nonahektana
Heptaliana
Oktaliana
Nonaliana

H2O

a. RX + H2S
b. C = C + H2O
c. R-CH = CH2 + B2H6

RSH + HX
-CH CHOH
(RCH2 CH2)3-B+ H2O2

RCH2 CH2OH
OH-

H2O
d. R-CH = CH2 + Hg(OCOCH3)2

R-CH = CH2 + NaBH4

25 C
OH HgOCOCH3
o

R-CH = CH3
OH

Alkil fosfat adalah senyawa organic yang mengandung gugus posfat dengan rumus umum
sebagai berikut :

R-PO3H2
Senyawa
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C24H50
C25H52
C26H54

Nama
Metana
Etana
Propane
Butane
Pentane
Heksana
Heptana
Oktana
Nonana
Dekana
Undekana
Dodekana
Tridekana
Tetradekana
Pentadekana
Heksadekana
Heptadekana
Oktadekana
Nonadekana
Eikosana
Heneikosana
Dokosana
Trikosana
Tetrakosana
Pentakosana
Heksakosana

Senyawa
C34H44
C35H46
C36H48
C37H50
C38H52
C39H54
C40H56
C41H58
C42H60
C43H62
C44H64
C45H66
C46H68
C47H70
C48H72
C49H74
C50H102
C51H104
C52H106
C53H108
C54H110
C55H112
C56H114
C57H116
C58H118
C59H120

Nama
tetratriakontana
pentatriakontana
heksatriakontana
heptatriakontana
oktatriakontana
nonatriakontana
Tetrakontana
hentetrakontana
Dotetrakontana
Tritetrakontana
tetratetrakontana
pentatetrakontana
heksatetrakontana
heptatetrakontana
oktatetrakontana
nonatetrakontana
Pentakontana
Henpentakontana
dopentakontana
tripentakontana
tetrapentakontana
pentapentakontana
heksapentakontana
heptapentakontana
Oktapentakontana
nonapentakontana

98

Senyawa
C67H136
C68H138
C69H140
C70H142
C71H144
C72H146
C73H148
C74H150
C75H152
C76H154
C77H156
C78H158
C79H160
C80H162
C81H164
C82H166
C83H168
C84H170
C85H172
C86H174
C87H176
C88H178
C89H180
C90H182
C91H184
C92H186

Nama
heptaHeksa kontana
oktaHeksa kontana
nonaHeksa kontana
Heptakontana
henHeptakontana
DoHeptakontana
triHeptakontana
tetraHeptakontana
pentaHeptakontana
heksaHeptakontana
heptaHeptakontana
oktaHeptakontana
nonaHeptakontana
Oktakontana
henOktakontana
doOktakontana
triOktakontana
tetraOktakontana
pentaOktakontana
heksaOktakontana
heptaOktakontana
oktaOktakontana
nonaOktakontana
Nonakontana
henNonakontana
doNonakontana

C27H56
C28H58
C29H60
C30H62
C31H64
C32H66
C33H68
C100H202
C200H402
C300H6002
C1000H2002
C2000H4002
C3000H6002

Heptakosana
Oktakosana
Nonakosana
Triakontana
Hentriakontana
Dotriakontana
Tritriakontana
Hektana
Dohektana
Trihektana
kiliana
Dilianatana
Triliana

C60H122
C61H124
C62H126
C63H128
C64H130
C65H132
C66H134
C400H802
C500H1002
C600H12002
C400H8002
C500H10002
C600H1202

Heksa kontana
HenHeksa kontana
doHeksa kontana
triHeksa kontana
tetraHeksa kontana
pentaHeksa kontana
heksaHeksa kontana
Tetrahektana
Pentahektana
Heksahektana
Tetraliana
Penliaana
Heksaliana

C93H188
C94H190
C95H192
C96H194
C97H196
C98H198
C99H200
C700H1402
C800H1602
C900H1802
C700H14002
C800H16002
C900H18002

triNonakontana
tetraNonakontana
pentaNonakontana
heksaNonakontana
HeptaNonakontana
oktaNonakontana
nonaNonakontana
Heptahektana
Oktahektana
Nonahektana
Heptaliana
Oktaliana
Nonaliana

Biasanya senyawa alkyl posfat terdapat dalam molekul DNA dan RNA.

Organometallics is the branch of chemical science studying the chemistry of molecules that have
direct carbon-metal bonds. (Dec 30, 2005)

s ,d, p blocks

Main group organometallic chemistry

Alkali and akaline earths organometallic

Li, Na, K organyls

Be organyls
Mg organyls

Aluminium group
Silicon group

Si organyls
Ga organyls
99

Pb, Sb, Sn, Hg

Transition-metal organometallic chemistry

The organometallic chemistry of the transition elements is quite different from the main-group
ones due to the availability for bonding of the n d orbitals with consequent ability for the central
atom to change geometry and expand the octet.
Crystal field theory

Single -bonding
1. M-alkyl
-elimination

-acceptor bonding
alkene complexes

CO complexes
1. *d
2. d *
These interactions are synergicin increading the M-CO bond strength. In fact, the second
interaction, as known as pi backbonding increases the available electron density on the CO.
The partial filling of the * orbital leads to a weakened C-O triple bond, as showed from the
stretching frequencies (in cm-1) of CO free and in M/CO complexes.
Free CO
V(CO)6
Ni(CO)4
Cr(CO)6

2143
1976
2057
2000

Arene complexes
100

Carbenes and carbynes compounds

Fischer carbenes
By treatment of a CO complex with a strong nucleophile

Schrock carbenes

Catalysis by organometallic compounds

Metathesis
Richard Schrock(MIT, USA) and Robert Grubbs (CalTech, USA) received 2005 Nobel prize for
their work on the subject. Metathesis is the exchange of the termination between two alkenes [1]

It occurs via the carbene species nowaday known as Schrock's carbenes

1. ^ Grubbs, Olefin metathesis, Tetrahedron

Ziegler-Natta polymerisation
Ziegler-Natta catalyst Ziegler in the 40's worked on the oligomerisation of ethylene by aluminium
alkyls via the reaction HAl-R + CH2=CH2 -> HAl-CH2CH2-R

101

Enantioselective hydrogenation
Wilkinson's

Hydroformylation
Hydroformylation Hydroformylation is the process that transforms an alkene into an aldehyde by
reaction with CO.
The catalyst is a hydridocarbonyl complex, HCO(CO)5

Fischer-Tropsch synthesis
Fischer-Tropsch synthesis is the heterogeneously-catalysed formation of hydrocarbons (alkanes
and alkenes) from CO and hydrogen (synthesis gas). It can be seen as the inverse of synthesis gas
102

preparation (although this is usually from methane and lighter hydrocarbons). It is the heart of the
gas-to-liquids processes developed commercially by big petrochemical firms in the 90's.

Organometallics in living systems

The only example of a biological molecule containing direct carbon-metal bonds is cobalamin, as
known as vitamin B12

MODUL VI.
VI.

TEORI TENTANG STEREO KIMIA

Reaksi inversi Walden

Pada tahun 1896 seorang ahli kimia Jerman yang bernama Paul Walden menemukan
peralihan bentuk isomer dari bentuk enasiomer asam malat (+) menjadi bentuk asam malat
(-), perubahan bentuk enansiomer ini terjadi melalui sederet siklus reaksi substitusi
sederhana. Bila bentuk isomer asam malat (-) direaksikan dengan PCl 5 maka akan
terbentuk isomer asam klorosuksinat (+). Bila asam khloro suksinat (+) direaksikan
dengan Ag2O, maka akan terbentuk asam malat (+). Bila asam malat (+) direaksikan
dengan PCl5 dalam eter akan terbentuk isomer asam klorosuksinat (-). Selanjutnya bila
asam kloro suksinat (-) direaksikan dengan Ag2O dalam air akan terbentuk asam malat (-).

OH
HO2C-CH2-CH-CO2H PCl5

Cl
HO2C-CH2-CH-CO2H
103

Asam malat (-)

[ a]D = - 2,3

asam klorosuksinat (+)

Ag2O H2O

Ag2O H2O

Cl

OH

HO2C-CH2-CH-CO2H PCl5

HO2C-CH2-CH-CO2H

asam klorosuksinat (+)

Asam malat (-)

[ a]D = - 2,3

Stereokimia dan reaksi substitusi nukleofilik

Sekalipun pada reaksi inverse Walden di atas terjadi perubahan konfigurasi yang berlangsung
dalam suatu siklus reaksi, namun tahap-tahap detil dari reaksi tersebut belum bisa diketahui.
Akan tetapi pada tahun 1920an Joseph Kenyon dan Henry Philips melalui sederet pengujian
yang dirancang untuk menentukan stereokimia dari reaksi substitusi, menemukan bahwa
adanya gugus asam karboksilat pada perlakuan Walden membuat masalah jadi rumit, oleh
karena itu dia melakukan reaksi yang lebih sederhana. Diantara sekian banyak pengujiannya
dia meneliti peralihan dua isomer 1fenil2propanol dengan reaksi sebagai berikut :

OH

O-Tos

-CH-CH-CH3

-CH-CH-CH3
-

fenil-2propanol [a]D = 33o

[a]D = 31,1o
O

HOH2O

O-C-CH3

O
O- C-CH3

CH3 O

-CH-CH-CH3

-CH-CH-O-C-CH3

104

[a]D = 7o

[a]D = -7o

CH3

CH3

-CH2CH-O-Tos

-CH2-CH-OH

[a]D = 31,0o

[a]D = 33,2o

Kinetika Reaksi substitusi nukleofilik

Para ahli kimia telah sepakat bahwa secara kualitatif suatu reaksi ditentukan oleh reaksi yang
lambat. Kecepatan pada saat bahan baku bereaksi memebntuk produk disebut kecepatan
reaksi, yang besarnanya dapat diukur. Penentuan kecepatan rreaksi dan ketergantungan
kecepatan reaksi terhadap konsentrasi reagen merupakan cara yang bisa digunakan untuk
menentukan mekanisme reaksi. Dari reaksi substitusi nukleofilik berikut :
H- + CH3Br ------------- HO-CH3 + BrKecepatan reaksi = kecepatan hilangnya konsentrasi bahan baku
= k x [RX] x [HO-]
Dimana k = konstanta kecepatan reaksi
[RX] = konsentrasi CH3Br
[HO-] = konsentrasi HOReaksi SN1
Reaksi SN1 berati reaksi ini adalah reaksi substusi nukleofilik Orde satu.
Reaksi SN2
Reaksi SN2 erati reaksi ini adalah reaksi substusi nukleofilik Orde dua.
Kinetika reaksi substitusi elekrofilik
Senyawa optis aktif
105

Beberapa model enansiomer

MODUL VII
VII.

PUSAT CHIRAL

Campuran rasemat
Senyawa stereo isomer
Proyeksi struktur molekul organic
Stereoisomers are properly named using the Cahn-Ingold-Prelog (CIP) priority rules to decide
which parts of the molecule to consider first.
The rules have evolved to cover many situations, but the basic rules are:
1. Consider the first atom of each part of the molecule. An atom with higher atomic number
has higher priority. (e.g. I > Cl > C > H)
2. If the first atom of two groups is the same, consider the second atom(s) in the same way as
the first. (e.g. -C(CH3)3 > -CH(CH3)2 > -CH2CH3 > -CH3). If this does not assign priority,
consider the next atoms until there is a difference.
Realize that when you do this it will mean that sometimes groups with higher total weights will
have lower priority because of a lower weight of the atom that connects them.

[edit] R & S Notation

R- and S- notation use the CIP priority rules for the assignment of the absolute configuration
around a stereocenter.
First, assign priority to each atom surrounding the stereocenter.
Priority is based on atomic number.
Second, point the lowest priority atom away from you. Follow the direction of the remaining 3
priorities from lowest to highest.
A counterclockwise direction is an S (latin: sinister) configuration. A clockwise direction is an R
(latin: rectus) configuration.

Direction of the travel 1-2-3 dictates configuration

106

[edit] E-Z notation

The R-/S- notation is valid only for the the absolute configuration of a center having single bonds
only. In the case of a double bond, the traditional cis/trans nomenclature system is not sufficiently
accurate and the E-/Z- is currently preferred.
The basis is again the CIP priority rules.
See main discussion: E-Z notation
Retrieved from "http://en.wikibooks.org/wiki/Organic_Chemistry/Chirality/RS_notational_system"
Subject: Organic Chemistry
MODUL VIII
VIII.

KARBOHIDRAT

Klassifikasi karbohidrat
Karbohidrat adalah suatu molekul senyawa organic dengan rumus umum C n(H2O)n, jumlah
atom karbon sama dengan jumlah molekul air dimana nilai n adalah bilangan bulat lebih
besar dari tiga. Karbohidrat yang paling sederhana adalah 2,3 dihidroksi propanal (gliseral
dehid).
Secara garis besarnya kelompok karbohidrat adalah aldosa dan ketosa. Aldosa yaitu
karbohdrat yang mempunyai gugus alkanal, sedangkan ketosa adalah aldehid yang
mempunyai gugus alkanon.
konfigurasi karbohidrat
Konfigurasi karbohidrat ada 2 macam :
a. Aldosa
aa. aldotriosa
Struktur yang paling sederhana dari aldosa adalah gliseral dehid dengan 1 atom C optis
aktif (puat Chiral). Gliseral dehid mempunyai dua bentuk enasiomer yakni D-Gliseral
dehid dan L-gliseraldehid.

C
H

O
H
OH

CH2OH
D-Gliseraldehid

C
HO

H
H

CH2OH
L-Gliseraldehid
107

ab. aldotetrosa
Aldotetroasa adalah bentuk dari aldosa dengan 4 atom karbon yang mempunyai 4 bentuk
isomes optis aktif sebagai berikut :

O
H

O
H

O
H

OH

HO

OH

OH

HO

OH

CH2OH

CH2OH

O
H

C
H

OH

HO

CH2OH

CH2OH

Struktur dari Aldopentosa adalah sebagai berikut :

Aldopentoasa adalah bentuk dari aldosa dengan 5 atom karbon yang mempunyai 8 bentuk
isomes optis aktif sebagai berikut :
O
C

O
H

H
OH

H
OH

OH

OH

OH

OH

OH

H
CH2OH

OH
CH2OH

D Ribose

O
C

OH

L ribose

D Xylose

H
OH

HO

OH

OH

OH HO

D Lyxose

HO

H
CH2OH

OH
CH2OH

OH

L Xylose

OH

L Lyxose

H
H

OH OH
H
CH2OH
CH2OH

O
H

C
H

H
OH
H

OH HO
H
CH2OH
CH2OH

D Arabinose

L Arabinose

Struktur dari Aldoheksosa yang mempunyai 6 atom C dan 16 isomer optis aktif sebagai
berikut :
O
O
O
O
C H
C H
C H
C
H
108

OH

HO

HO

OH

OH

HO

HO

OH

OH

HO

HO

OH

HO

CH2OH

CH2OH

D Allosa
C

OH

OH

HO

CH2OH

L Allosa

O
H

CH2OH

D Talosa

O
H

L Talosa

O
H

O
H

OH

HO

HO

OH

OH

HO

HO

OH

HO

OH

OH HO

OH

OH

HO

CH2OH
D Gulosa

CH2OH
L Gulosa

O
H

HO

OH

HO

HO

H
CH2OH
L Glukosa
O

C
H

HO

CH2OH
D Mannosa

O
H

CH2OH
L Mannosa

O
H

OH

HO

OH HO

OH

HO

OH

HO

CH2OH

OH

OH

HO

D Idosa
O

109

OH

CH2OH

D Glukosa

O
H

CH2OH
L Idosa
O

OH

HO

HO

HO

OH

OH

OH

HO

HO

OH

OH

HO

OH

HO

OH

HO

CH2OH
D Galaktosa

CH2OH
L Galaktosa

CH2OH
D Altrosa

CH2OH
L Altrosa

Struktur dari Ketotetrosa yang mempunyai 4 atom C dengan 2 isomer sebagai berikut :
CH2OH

CH2OH

O
H

OH

O
HO

CH2OH

H
CH2OH

Struktur dari Ketopentosa yang mempunyai 5 atom C dengan 4 isomer optis aktif sebagai
berikut :

CH2OH

CH2OH

CH2OH

CH2OH

OH

HO

OH

HO

OH

HO

HO

OH

CH2OH

CH2OH

CH2OH

CH2OH

Struktur dari Ketoheksosa yang mempunyai 6 atom C dengan 8 isomer optis aktif sebagai berikut
CH2OH

CH2OH

OH

HO

OH

HO

HO
HO
110

CH2OH

CH2OH

H
H

H
H

OH
OH

OH

HO

OH

CH2OH

CH2OH

CH2OH

CH2OH

CH2OH

CH2OH

HO

H
CH2OH

CH2OH

OH

HO

HO

HO

OH

OH HO

OH

OH

HO

CH2OH

CH2OH

OH

HO

CH2OH

CH2OH

Bentuk lingkar senyawa saccharida

Bentuk lingkar pada senyawa saccharida terjadi bila atom C1 bergabung dengan gugus
hidroksil pada atom C4 atau C5 sehingga terjadi bentuk senyawa lingkar furannosida atau
pirannosida seperti berikut :

CH2OH
OH

OH

CH2OH

CH2OH

OH

H
H
H

OH

OH

poli saccharida.
H
O

CH2OH
H
OH

OH
H

O
H
111

MODUL IX
IX.

ASAM AMINO DAN PROTEIN

Klassifikasi asam amino

9.1.1. Asam amino netral
Nama

Ringkasan

BM

Struktur

Alanin

Ala (A)

89

H3C-CH-COOH
NH2

6.0

Asparagin Asn (N)

132

H3N- C-CH2-CH-COOH
O
NH2

5.4

Cysteine

121

HS-CH2-CH-COOH
NH2

5.0

Glutamine Gln (Q)

146

H3C- C-CH2-CH2CH-COOH
O
NH2

5.7

Glycine

75

CH2-COOH
NH2

6.0

Isoleusin Ile (I)

131

H3C-CH2-CH(CH3)-CH-COOH
NH2

6.0

Leusin

131

(H3C)2CH-CH2-CH-COOH
NH2

6.0

Methionine Met(M)

149

H3C-S-CH2-CH2-CH-COOH
NH2

5.7

Phenylalanine Phe (F)

165

C6H5-H2C-CH-COOH
NH2

Proline

115

H2C-CH-COOH
NH2

Cys

Gly (G)

Leu (L)

Pro (P)

Titik isoelektrik

112

5.5

6.3

Serine

Ser (S)

105

HO-H2C-CH-COOH
NH2

Threonine Thr (T)

119

H3C-CHOHCH-COOH
NH2

Trypthophan Trp (W)

204

5.7

6.0

CH2-CH-COOH
NH2

5.9

N
Tyrosine

Tyr (Y)

181

p-OH-C6H4H2C-CH-COOH
NH2

Valine

Val (V)117

(H3C)2CH-CH-COOH
NH2

5.7

6.0

9.1.2. Asam amino basa

Aspartic

Asp (D)

133

HOOC-CH2-CH-COOH
NH2

3.0

Glutamic Glu (E)

147

HOOC-CH2 -H2C-CH-COOH
NH2

3.2

Arginine Arg

174

H2N- C-NH-(H2C)3-CH-COOH
NH
NH2

6.0

Histidine his (H)

155

H2C-CH-COOH
NH2

6.0

H2N- (H2C)4-CH-COOH
NH2

6.0

9.1.3. Asam amino basa

N
Lysine

Lys (K)

146

10.2. sintesa asam amino

10.2.1. sintesa asam amino dengan pereaksi posfohalida
R-CHOH-COOH + PBr3 ------ RCHBr-COOH + NH3 ------ RCHNH2-COOH + HBr
10.2.2. sintesa asam amino dengan asam sianida dalam suasana asam
113

RCHO + HCN + H3O+ + NH4Cl---------------------- RCHNH2-COOH

10.2.3. sintesa asam amino dengan alkanonoat
RCOCOOH + NH3 + NaBH4 ------------------- RCHNH2COOH + H2O
10.4. sintesa asam amino dengan dietil asetamidomalonat
H3CCONHCH(CO2C2H5)2 + RX + H3O+ + NaOC2H5 ---------------- H2NRCHCOOH
10.3. Ikatan peptide
ikatan peptide adalah ikatan yang terjadi akibat reaksi dehidrolisa gugus -NH2 dan -COOH dari
beberapa asam amino membentuk molekul protein sebagai berikut :
R-CHNH2-COOH + RCHNHH-COOH ----------- R-CHNH2-CO-NH-COOH + H-O-H
CH
R
Blocking Gugus -NH2 Pada asam amino dari reaksi sintesa protein
{(H3C)3COCO}2O
Ditert-butil dikarbonat
Blocking Gugus -COOH Pada asam amino dari reaksi sintesa protein
a. H3COH
b. PhCH2OH
10.4. Struktur protein
struktur protein tersusun dari ikatan peptida primer, sekunder, tertier, dan kuartener membentuk
rantai helik seperti jalinan talitemali
contoh protein angiotensin II yang terdapat dalam plasma darah
H2N-D-R-V-Y-I-H-P-F-COOH

Klassifikasi protein berdasarkan konformasinya

Protein
sumber
Fibrous protein
Kolagen
jaringan penghubung, urat
keratin
rambut, kulit, kuku, tanduk
Elastin
jaringan penghubung elastis
Potein globuler
Insulin
hormone kontrol metabolisme glukosa
Lysozyme
enzim hidrolitik
Ribonuklease
enzim control sintesa RNA
Albumin
protein menggumpal oleh panas
Immunoglobulin
immune respon
Myoglobulin
oksigen transport
Klassifikasi protein konyugasi ( protein yang mengandung senyawa selain asam amino seperti
karbohidrat, ester gliserida, asam nukleat,
Protein
non asam amino
nonasam amino (%)
114

a. Glycoprotein
-Globulin
Karboksipeptidase
Interferon
b. Lipoprotein

karbohidrat
karbohidrat
karbohidrat

10
17
20

Plasma -lipoprotein lemak, kolesterol

c. Nucleoprotein

80

Ribosomal protein
RNA
Virus tembakau
RNA
d. Posfoprotein
Casein

60
5

ester posfat
e. Metallo protein

Ferritin
Hemoglobin

FeO

23

Fe

0.3

Struktur insulin
21 asama amino rantai I
H2N-G-I-V-E-Q-C-C-T-S-I-C-S-L-Y-Q-L-E-N-Y-C-N-OH
30 asam amino rantai II
H2N-F-V-N-E-H-L-C-G-S-H-L-V-E-A-L-Y-L-V-C-G-E-R-G-F-F-Y-Y-P-L-Y-OH
MODUL X.
ESTER TRIGLISERIDA(lipid)
Ester gliserida adalah senyawa molekul organic yang didapatkan dialam dipisahkan dari
sel dan jaringan biota dengan cara ekstraksi dengan pelarut organic non polar. Lipid biasanya
terdiri dari atom karbon yang banyak dalam strukturnya yang larut dalam pelarut organic non
polar dan tak larut dalam air. Lipid lebih ditentukan oleh sifat fisikanya dari pada sifat
kelarutannya sebagaimana halnya dengan karbohidrat dan protein. Ester gliserida tersusun dari
gliserol atau alkanol berberat molekul besar dengan asam lemak.
Ester gliserida dapat digolongkan menjadi 2 golongan besar yakni lipid kompleks seperti
lemak dan lilin yang mengandung ikatan ester dan dapat dihidrolisa menjadi molekul kecil, dan
lipid sederhana yang tidak dapat dihidrolisa seperti kolesterol dan steroid lainnya. Struktur ester
gliserida adalah sebagai berikut :
CH2-O-CO-R
CH-O-CO-R
CH2-O-CO-R
Berdasarkan konfigurasi ikatan asam lemak pada gliserol ada 4 konfigurasi yaitu :
CH2-O-CO-R
CH-O-CO-R
CH2-O-CO-R
Lurus
CH2-O-CO-R
RO-CO-C-H
CH2-O-CO-R
Garpu
R-OC-O-CH2
CH-O-CO-R
CH2-O-CO-R
115

Kursi
CH2-O-CO-R
CH-O-CO-R
R-OC-O-CH2
topi
Jika lipid dihidrolisa akan terurai menjadi gliserol dan asam-asam lemak
CH2-O-CO-R
CH-O-CO-R
CH2-O-CO-R
Ester gliserida

CH2OH
RCOOH
+ 3H3O+ ------------------ CH-OH + RCOOH
CH2OH
RCOOH
gliserol
asam lemak

11. 1. Klassifikasi ester gliserida

a. minyak adalah asam lemak tak jenuh dan jenuh berikatan dengan gliserol membentuk ester
CH2-O-CO-R
CH-O-CO-R
CH2-O-CO-(HC=CH)nR
b. lemak adalah asam lemak jenuh dengan gliserol membentuk ester
CH2-O-CO-R
CH-O-CO-R
CH2-O-CO-R
c. posfolipid adalah asam lemak dan senyawa basa posfolipid membentuk ester
- L Lecitin (kuning telor)
CH2-O-CO-R
R-COO-C-H
CH2-O-PO3-CH2-CH2-N+(CH3)3
- cephalin (otak)
CH2-O-CO-R
R-COO-C-H
CH2-O-PO3-CH2-CH2-N+H3
- sphingosin
CH2-OH
CH-NH2
CH-OH
CH=CH(CH2)12CH3
- sphingomyelin

CH2-OPO3-CH2-CH2-N+(CH3)3
CH-NH-CO-(CH2)16-24-CH3
CH-OH
CH=CH(CH2)12CH3
116

d. malam adalah asam lemak berberat molekul besar dengan alkanol berberat molekul besar
CH3(CH2)20-24-COO-(CH2)27CH3
Lilin lebah
Jenis-jenis asam lemak
Nama
struktur
MP (oC)
Asam lamak jenuh
Laurat
H3C-(CH2)10-COOH
44
Mirisitat
H3C-(CH2)12-COOH
58
Palmitat
H3C-(CH2)14-COOH
63
Stearat
H3C-(CH2)16-COOH
70
Arachidat
H3C-(CH2)18-COOH
75
Asam lemak tak jenuh
Palmitoleat
H3C-(CH2)5HC=CH-(CH2)7-COOH
32
Oleat
H3C-(CH2)7HC=CH-(CH2)7-COOH
4
Richinoleat H3C-(CH2)5CHOH-CH2-HC=CH-(CH2)7-COOH (cis)
5
Linoleat
H3C-(CH2)3-(CH2-HC=CH)2-(CH2)7-COOH (cis,cis)
-5
Linolenat
H3C-(CH2-HC=CH-)3-(CH2)7-COOH (cis,cis,cis)
-11
Arachidonat H3C-(CH2)4-(CH2-HC=CH)4-(CH2)2-COOH (cis4x)
-50

Komposis (%) asam lemak pada berbagai sumber bahan alami

Asam lemak jenuh
asam lamak tak jenuh
Sumber
L
M
P
S
O
R
Li
Hewan
Lemak babi
1
25
15
50
6
1
Butter
2
10
25
10
25
5
Lemak manusia
1
3
25
8
46
10
Lemak ikan paus
8
12
3
35
10
Tumbuhan
Kelapa
50
18
8
2
6
1
Jagung
1
10
4
35
45
Zaitun
1
5
5
80
7
Kacang tanah
7
5
60
20
Biji bunga matahari
5
3
20
20
Biji jarak
1
8
85
Reaksi sintesa ester gliserida
a. RCOOH + OHCH2-CHOH-CH2OH
b. Reaksi biosintesa
H3CO-S-synthetase + HOOC-CH2CO-S-ACP

Lin
50
4

ROOCH2-CHCOOR-CH2COOR
H3C-CH-C-CO-S-ACPCOOH

H3C-CO-CH2-CO-S-ACP + CO2
117

Asetoasetil ACP (acyl carrier protein)

Biosintesa lipid
H3C-CO-SCoA
Asetil CoA
ACP transferase
Asetil CoAcarboksilase
HS-ACP
CO2
H3C-CO-SACP
KetoACP transferase

HOOC-CH2-CO-SCoA
Malonil CoA
ACP transferase, HSACP

H3C-CO-SSynthetase

HOOC-CH2-CO-SACP

Keto ACP synthetase

H3C-CO-CH2-CO-SACP

CO2

HSCoA

NADPH, H+

H3C-HOH-CH2-CO-SACP
Enoyl ACP dehidrase
H3C-CH=CH-CO-SACP
NADPH

H3C-CH2-CH2-CO-SACP

MODUL XI
ALKALOID

118

berulang

Struktur kimia dari efedrin, sebuah alkaloid phenethylamine

Alkaloid adalah senyawa alami kimia yang mengandung atom nitrogen dasar [1] Nama ini berasal
dari kata basa dan digunakan untuk menggambarkan setiap basa nitrogen yang mengandung dan
senyawa organik dengan satu atau lebih dari fitur berikut:. Senyawa heterosiklik yang
mengandung nitrogen, dengan pH alkali dan tindakan fisiologis yang ditandai pada fisiologi
hewan [kutipan diperlukan]. Namun, ada pengecualian untuk masing-masing kriteria. Alkaloid
dihasilkan oleh berbagai macam organisme, termasuk bakteri, jamur, tumbuhan, dan hewan dan
merupakan bagian dari kelompok produk alami (juga disebut metabolit sekunder). Banyak
alkaloid dapat dimurnikan dari ekstrak mentah oleh ekstraksi asam-basa. Banyak alkaloid yang
beracun bagi organisme lain.
Mereka sering memiliki efek farmakologis dan digunakan sebagai obat, seperti narkoba, atau
dalam ritual entheogenic. Contohnya adalah anestesi lokal dan kokain stimulan, kafein stimulan,
nikotin, morfin analgesik, atau kina obat antimalaria. Alkaloid yang paling memiliki rasa pahit.

Caffeine, a Purine alkaloid

Struktur kimia Vinblastine, sebuah alkaloid Chemotheraputic terisolasi dari Madagaskar

periwinkle

119

Alkaloid classifications
Klasifikasi dari alkaloid adalah kompleks dan dapat dipandu oleh seperangkat aturan yang
mempertimbangkan struktur dan fitur kimia lainnya dari molekul alkaloid, asal biologisnya, serta
asal biogenetis mana dikenal [2] [3]. Sebagai contoh, di mana jalur biosintesis alkaloid yang tidak
diketahui, dapat dikelompokkan berdasarkan kemiripan struktur dengan senyawa yang diketahui,
termasuk non-nitrogen senyawa, atau dengan organisme (s) dari yang alkaloid yang diisolasi. [3]

Pyridine group: piperine, coniine, trigonelline, arecoline, arecaidine, guvacine, cytisine, lobeline,
nicotine, anabasine, sparteine, pelletierine.
Pyrrolidine group: hygrine, cuscohygrine, nicotine
Tropane group: atropine, cocaine, ecgonine, scopolamine, catuabine
Indolizine group: senecionine, swainsonine
Quinoline group: quinine, quinidine, dihydroquinine, dihydroquinidine, strychnine, brucine,
veratrine, cevadine
Isoquinoline group: opium alkaloids (papaverine, narcotine, narceine), pancratistatin,
sanguinarine, hydrastine, berberine, emetine, berbamine, oxyacanthine
Phenanthrene alkaloids: opium alkaloids (morphine, codeine, thebaine, oripavine)
Phenethylamine group: mescaline, ephedrine, dopamine
Indole group:
Tryptamines: serotonin, DMT, 5-MeO-DMT, bufotenine, psilocybin
Ergolines (the ergot alkaloids): ergine, ergotamine, lysergic acid
Beta-carbolines: harmine, harmaline, tetrahydroharmine
Yohimbans: reserpine, yohimbine
Vinca alkaloids: vinblastine, vincristine
Kratom (Mitragyna speciosa) alkaloids: mitragynine, 7-hydroxymitragynine
Tabernanthe iboga alkaloids: ibogaine, voacangine, coronaridine
Strychnos nux-vomica alkaloids: strychnine, brucine
Purine group:
Xanthines: caffeine, theobromine, theophylline
Terpenoid group:
Aconitum alkaloids: aconitine
Steroid alkaloids (containing a steroid skeleton in a nitrogen containing structure):
Solanum (e.g. potato and tomato) alkaloids (solanidine, solanine, chaconine)
Veratrum alkaloids (veratramine, cyclopamine, cycloposine, jervine, muldamine)[4]
Fire Salamander alkaloids (samandarin)
Others: conessine
Quaternary ammonium compounds: muscarine, choline, neurine
Miscellaneous: capsaicin, cynarin, phytolaccine, phytolaccotoxin

MODUL XII
TERPENOID
Terpenoid adalah senyawa organic yang terdiri dari rantai isoprena mulai dari 10 dengan kelipatan
5 atom karbon dikenal dengan nama minyak atsiri yang terdapat dalam berbagai jenis rempahrempah seperti jahe, cengkeh, kapulaga, pala, kunyit, sereh, mint, dll
Klassifikasi terpenoid
120

a. monoterpen adalah gabaungan 2 molekul isoprena

konfigurasi isoprena pada monoterpen ada 4 kombinasi :

belakang
depan
Isoprena
Belakang belakang

Belakang depan

Depan belakang

Depan depan

b. sesquiterpen
c. diterpen
d. sesterterpen
e. triterpen
f. tetraterpen
g. pentaterpen

3 molekul isoprene
4 molekul isoprene
5 molekul isoprene
6 molekul isoprene
8 molekul isoprene
10 molekul isoprene

jumlah atom C = 15
jumlah atom C = 20
jumlah atom C = 25
jumlah atom C = 30
jumlah atom C = 40
jumlah atom C = 50

Reaksi sintesa terpenoid

OPP +
IPP

OPP

OPP

DAPP
CH2OH

H2O

CH2OPP

Geraniol

GPP

CH2OPP
121

CH2OPP
+
GeraniolPP

nerolPP

limonen
CH2OPP

CH2OPP
+

GPP

IPP
CH2OPP + -:OPP

CH2OPP
Farnesol piroposfat
H2O/H+
CH2OH
Farnesol
CH2OPP
Farnesol piroposfat
+
CH2OPP
Farnesol piroposfat

pinen

carvone

squalena

camphor
122

Caryophyllene

MODUL XIII
STEROID

Steroid
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the chemical family of lipids. For the performance-enhancing substance, see
Anabolic steroid.

IUPAC recommended ring lettering (left) and atom numbering (right) of the steroid skeleton.[1][2]
The four rings A-D form a sterane core.

Stick model of the steroid lanosterol. The total number of carbons (30) reflects its triterpenoid
origin.
.
Sebuah steroid merupakan lipid terpenoid dicirikan oleh inti sterane dan kelompok fungsional
tambahan. Inti adalah struktur karbon dari empat cincin leburan: tiga cincin sikloheksana dan satu
cincin cyclopentane. Steroid bervariasi oleh kelompok-kelompok fungsional yang melekat pada
cincin ini dan keadaan oksidasi dari cincin.
Ratusan steroid yang berbeda ditemukan pada tumbuhan, hewan, dan jamur. Semua steroid yang
dibuat dalam sel baik dari lanosterol sterol (hewan dan jamur) atau cycloartenol (tanaman).
Kedua, lanosterol dan cycloartenol, berasal dari siklisasi dari squalene triterpene. [3]
123

Sterol adalah bentuk khusus dari steroid, dengan kelompok hidroksil pada atom C-3 dan kerangka
berasal dari kolestan [2] Kolesterol adalah salah satu sterol yang paling dikenal..
Klasifikasi
Taksonomi Fungsional
Beberapa kategori umum dari steroid:
Hewan steroid
o steroid Serangga
Ecdysteroids seperti ecdysterone
o Vertebrata steroid
steroid hormon
steroid Seks adalah subset dari hormon seks yang menghasilkan perbedaan seks atau reproduksi
dukungan. Mereka termasuk androgen, estrogen, dan progestagens.
Kortikosteroid meliputi glukokortikoid dan mineralokortikoid. Glukokortikoid mengatur
banyak aspek metabolisme dan fungsi kekebalan tubuh, sedangkan mineralokortikoid membantu
mempertahankan volume darah dan mengontrol ekskresi ginjal elektrolit. Kebanyakan medis
'steroid' obat kortikosteroid.
Anabolic steroids adalah kelas steroid yang berinteraksi dengan reseptor androgen untuk
meningkatkan otot dan sintesis tulang. Ada steroid anabolik alami dan sintetis. Dalam bahasa
populer, kata "steroid" biasanya mengacu pada steroid anabolik.
Kolesterol, yang memodulasi fluiditas membran sel dan merupakan konstituen utama dari plak
terlibat dalam aterosklerosis.
Tanaman steroid
o Phytosterols
o Brassinosteroids
Jamur steroid
o ergosterol
struktural
Hal ini juga memungkinkan untuk mengklasifikasikan steroid berdasarkan komposisi kimianya.
Salah satu contoh betapa MESH melakukan klasifikasi ini tersedia di katalog MESH Wikipedia.
Contoh dari klasifikasi ini meliputi:
Class

Examples

Number of carbon atoms

Cholstanes cholesterol

27

Cholanes

cholic acid

24

Pregnanes

progesterone 21

Androstanes testosterone 19
Estranes

estradiol

18

Gonane (or steroid nucleus) is the hypothetic parent (17-carbon tetracyclic) hydrocarbon molecule
without any alkyl sidechains.[4]

Metabolism
Steroid meliputi estrogen, kortisol, progesteron, dan testosteron. Estrogen dan progesteron yang
dibuat terutama di ovarium dan plasenta selama kehamilan, dan testosteron di testis. Testosteron
juga diubah menjadi estrogen untuk mengatur pasokan masing-masing, dalam tubuh baik wanita
124

dan pria. Neuron tertentu dan glia pada sistem saraf pusat (SSP) mengekspresikan enzim yang
diperlukan untuk sintesis lokal neurosteroids pregnane, baik de novo atau dari sumber perifer
yang diturunkan. Tingkat membatasi langkah sintesis steroid adalah konversi kolesterol menjadi
pregnenolon, yang terjadi di dalam mitokondria
New! Click the words above to edit and view alternate tra

Sederhana versi dari bagian akhir jalur sintesis steroid, dimana isopentenil intermediet pirofosfat
(IPP) dan pirofosfat dimethylallyl (DMAPP) bentuk geranyl pirofosfat (GPP), squalene dan,
akhirnya, lanosterol, steroid pertama dalam jalur. Beberapa intermediet dihilangkan untuk
kejelasan.
Metabolisme steroid adalah set lengkap reaksi kimia dalam organisme yang memproduksi,
memodifikasi dan mengkonsumsi steroid. Jalur metabolik meliputi:
steroid sintesis - pembuatan steroid dari prekursor sederhana
steroidogenesis - yang interkonversi dari berbagai jenis steroid
steroid degradasi.

Steroid biosynthesis
Biosintesis steroid merupakan jalur metabolisme yang menghasilkan steroid anabolik dari
prekursor sederhana. Jalur ini dilakukan dengan cara yang berbeda pada hewan daripada di
banyak organisme lain, membuat jalur target umum untuk antibiotik dan obat anti infeksi. Selain
itu, metabolisme steroid pada manusia merupakan target dari obat penurun kolesterol seperti
statin.
Dimulai di jalur mevalonate pada manusia, dengan Asetil-KoA sebagai blok bangunan yang
membentuk DMAPP dan IPP [6]. Dalam langkah-langkah berikut, DMAPP dan IPP bentuk
lanosterol, steroid pertama. Modifikasi lebih lanjut milik steroidogenesis berhasil
125

Mevalonate pathway

Mevalonate pathway
Main article: Mevalonate pathway
The mevalonate pathway or HMG-CoA reductase pathway starts with and ends with
dimethylallyl pyrophosphate (DMAPP) and isopentenyl pyrophosphate (IPP).
Peraturan dan umpan balik
Beberapa enzim kunci dapat diaktifkan melalui regulasi transkripsi DNA pada aktivasi SREBP
(Sterol Peraturan Elemen-Binding Protein-1 dan -2). Sensor intraseluler mendeteksi kadar
kolesterol rendah dan merangsang produksi endogen oleh jalur HMG-CoA, serta meningkatkan
penyerapan lipoprotein dengan up-mengatur reseptor LDL. Peraturan jalur ini juga dicapai dengan
mengendalikan laju terjemahan dari mRNA, degradasi reduktase dan fosforilasi

Farmakologi
Sejumlah obat menargetkan jalur mevalonate:
Statin (digunakan untuk kadar kolesterol tinggi)
Bifosfonat (digunakan dalam pengobatan berbagai penyakit degeneratif tulang)
Tanaman dan bakteri
Pada tumbuhan dan bakteri, jalur non-mevalonate menggunakan piruvat dan gliseraldehida 3fosfat sebagai substrat. [7] [8]
DMAPP untuk lanosterol
Pirofosfat dan isopentenil pirofosfat dimethylallyl menyumbangkan unit isoprena, yang dirakit
dan dimodifikasi untuk terpene bentuk dan isoprenoidnya [8], yang adalah kelas besar lipid yang
mencakup karotenoid, dan membentuk kelas terbesar produk tanaman alami. [9]
Di sini, unit isoprena bergabung bersama untuk membuat squalene dan kemudian dilipat dan
dibentuk menjadi satu set cincin untuk membuat lanosterol [10]. Lanosterol kemudian dapat
diubah menjadi steroid lain seperti kolesterol dan ergosterol. [10] [11]
126

Human Steroidogenesis
steroidogenesis
Steroidogenesis adalah proses dimana bentuk yang diinginkan dari steroid yang dihasilkan oleh
transformasi steroid lainnya (Pembentukan steroid; umumnya mengacu pada sintesis biologis
hormon steroid, tetapi tidak untuk produksi senyawa tersebut di laboratorium kimia). Jalur dari
steroidogenesis dapat berbeda dari organisme ke organisme, namun jalur dari steroidogenesis
manusia diperlihatkan pada gambar.
Produk dari steroidogenesis meliputi:
127

 androgen
o testosteron
estrogen dan progesteron
corticoids
o kortisol
o aldosteron

Elimination
Steroid terutama dioksidasi oleh sitokrom P450 oksidase enzim, seperti CYP3A4. Reaksi-reaksi
memperkenalkan oksigen ke dalam cincin steroid dan memungkinkan struktur untuk dipecah oleh
enzim lainnya, untuk membentuk asam empedu sebagai produk akhir. [12] Asam empedu
kemudian dapat dieliminasi melalui sekresi dari hati dalam empedu. [13] ekspresi gen ini oksidase
dapat diregulasi oleh PXR sensor steroid ketika ada konsentrasi darah tinggi steroid [14]
MODUL XIV
|FLAVONOID
Jump to: navigation, search

Molecular structure of the flavone backbone (2-phenyl-1,4-benzopyrone)

Isoflavan structure

Neoflavonoids structure
128

Flavonoid (atau bioflavonoid), juga yang dikenal sebagai vitamin P dan Citrin [1], adalah kelas
metabolit sekunder tanaman. Menurut tata nama IUPAC, [2] mereka dapat diklasifikasikan
menjadi:
flavonoid, berasal dari 2-phenylchromen-4-satu (2-fenil-1 ,4-benzopyrone) struktur (contoh:
quercetin, rutin).
isoflavonoid, berasal dari 3-phenylchromen-4-satu (3-fenil-1 ,4-benzopyrone) struktur
neoflavonoids, berasal dari 4-phenylcoumarine (4-fenil-1 ,2-benzopyrone) struktur.
Tiga kelas flavonoid di atas adalah semua keton yang mengandung senyawa, dan dengan
demikian, flavonoid dan flavonol. Kelas ini adalah yang pertama yang akan disebut
"bioflavonoid." Para flavonoid Ketentuan dan bioflavonoid juga telah lebih longgar digunakan
untuk menggambarkan senyawa polihidroksi non-keton polifenol yang lebih khusus disebut
flavonoid, flavan-3-OLS, atau katekin (catechin meskipun sebenarnya subkelompok flavonoid).

Biosynthesis
Main article: Flavonoid biosynthesis

Biological roles
Flavonoid tersebar luas pada tanaman memenuhi banyak fungsi.
Flavonoid adalah pigmen tumbuhan yang paling penting untuk pewarnaan bunga menghasilkan
pigmentasi kuning atau merah / biru di kelopak. Warna-warna itu adalah tujuan untuk menarik
hewan penyerbuk.
Flavonoid disekresikan oleh akar tanaman inang mereka rhizobia membantu dalam tahap infeksi
hubungan simbiosis dengan kacang-kacangan seperti kacang polong, kacang-kacangan, semanggi,
dan kedelai. Hidup rhizobia dalam tanah dapat merasakan flavonoid dan ini memicu sekresi faktor
Nod, yang pada gilirannya diakui oleh tanaman inang dan dapat menyebabkan akar rambut
deformasi dan tanggapan selular beberapa seperti fluks ion dan pembentukan bintil akar .
Mereka juga melindungi tanaman dari serangan mikroba, jamur [3] dan serangga.

Biological activity
Flavonoid (khususnya flavonoid seperti katekin) adalah "kelompok yang paling umum dari
senyawa polifenol dalam makanan manusia dan ditemukan ubiquitously pada tanaman" [4].
Flavonol, bioflavonoid asli seperti quercetin, juga ditemukan ubiquitously, tetapi lebih rendah
kuantitas. Kedua set senyawa memiliki bukti kesehatan modulasi efek pada hewan yang
memakannya.
Distribusi luas flavonoid, berbagai mereka dan toksisitas relatif rendah dibandingkan dengan
senyawa tanaman aktif (alkaloid misalnya) berarti bahwa banyak hewan, termasuk manusia,
menelan jumlah yang signifikan dalam diet mereka. Flavonoid telah disebut sebagai "pengubah
respon biologi alami" karena bukti eksperimental yang kuat kemampuan melekat mereka untuk
memodifikasi reaksi tubuh terhadap alergen, virus, dan karsinogen. Mereka menunjukkan antialergi, anti-inflamasi [5], anti-mikroba [6] dan aktivitas anti-kanker
New! Click the words above to edit and view alternate translations. Di

129

Antioxidant activity
Flavonoid (baik flavonol dan flavanol) yang paling sering dikenal karena aktivitas antioksidan
secara in vitro.
Konsumen dan produsen makanan telah menjadi tertarik pada flavonoid untuk properti yang
mungkin mereka obat, terutama peran putatif mereka dalam pencegahan kanker dan penyakit
kardiovaskular. Meskipun bukti fisiologis belum dibentuk, efek menguntungkan dari buah,
sayuran, dan teh atau bahkan anggur merah telah dikaitkan dengan senyawa flavonoid daripada
nutrisi yang dikenal dan vitamin. [8]
Atau, penelitian yang dilakukan di Linus Pauling Institute dan dievaluasi oleh Otoritas Keamanan
Makanan Eropa menunjukkan bahwa, setelah asupan makanan, flavonoid sendiri yang sedikit atau
tidak ada nilai antioksidan langsung [9] [10]. Seperti kondisi tubuh tidak seperti kondisi tabung
reaksi terkontrol , flavonoid dan polifenol lainnya yang kurang diserap (kurang dari 5%), dengan
sebagian besar dari apa yang diserap dengan cepat dimetabolisme dan dikeluarkan. Peningkatan
kapasitas antioksidan darah terlihat setelah konsumsi makanan kaya flavonoid tidak disebabkan
langsung oleh flavonoid sendiri, tetapi yang paling mungkin adalah karena tingkat asam urat
meningkat yang dihasilkan dari metabolisme flavonoid [11] Menurut Frei., "Kami sekarang dapat
mengikuti aktivitas flavonoid dalam tubuh, dan satu hal yang jelas adalah bahwa tubuh melihat
mereka sebagai senyawa asing dan sedang berusaha untuk menyingkirkan mereka. "

Other health benefits

Cancer
Proses bersiap-siap untuk menyingkirkan senyawa yang tidak diinginkan menyebabkan apa yang
disebut enzim fase II yang juga membantu untuk menghilangkan mutagen dan karsinogen, dan
karena itu mungkin nilai dalam pencegahan kanker. Flavonoid dapat menginduksi mekanisme
yang membantu membunuh sel kanker dan menghambat invasi tumor "[11] UCLA kanker peneliti
telah menemukan bahwa peserta studi yang makan makanan yang mengandung flavonoid tertentu
tampaknya dilindungi dari mengembangkan kanker paru-paru. Dr Zuo-Feng Zhang, dari. UCLA
Jonsson Cancer Center dan profesor kesehatan masyarakat dan epidemiologi di UCLA School of
Public Health mengatakan flavonoid yang tampaknya menjadi catechin termasuk paling protektif,
ditemukan di stroberi dan teh hijau dan hitam; kaempferol, ditemukan di brussel sprouts dan apel
;. dan quercetin, yang ditemukan dalam kacang-kacangan, bawang dan apel [12]
Penelitian mereka juga menunjukkan bahwa hanya sejumlah kecil flavonoid yang diperlukan
untuk melihat manfaat medis. Mengambil suplemen makanan besar tidak memberikan manfaat
ekstra dan dapat menimbulkan beberapa risiko. [11]
Diarrhea
Sebuah studi yang dilakukan di Rumah Sakit Anak & Research Center Oakland, bekerja sama
dengan para ilmuwan di Heinrich Heine University di Jerman, telah menunjukkan bahwa
epikatekin, quercetin dan luteolin dapat menghambat perkembangan cairan yang mengakibatkan
diare dengan menargetkan fibrosis Cl transmembran konduktansi usus kistik regulator -.
transportasi menghambat cAMP-merangsang sekresi Cl-dalam usus [13]
[sunting] agen menstabilkan kapiler
Bioflavonoid seperti rutin, monoxerutin, diosmin, troxerutin dan hidrosmin memiliki norma
vasoprotective.

130

Important flavonoids
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newly available information, and remove this template when finished. Please see the talk
page for more information. (October 2009)

Quercetin
Main article: quercetin

Quercetin
Quercetin adalah flavonoid dan, untuk lebih spesifik, sebuah flavonol. Ini adalah bentuk aglikon
dari sejumlah glikosida flavonoid lainnya, seperti rutin dan quercitrin, ditemukan dalam jeruk,
soba buah dan bawang. Quercetin membentuk quercitrin glikosida dan rutin bersama dengan
rhamnosa dan rutinose, masing-masing. Hal ini juga dapat membantu untuk mencegah beberapa
jenis kanker, namun saat ini ada penelitian lebih dibutuhkan di daerah ini.

Epicatechin

Epicatechin (EC)
Epikatekin meningkatkan aliran darah dan dengan demikian tampaknya baik untuk kesehatan
jantung. Kakao, bahan utama coklat hitam, berisi jumlah yang relatif tinggi epikatekin dan telah
ditemukan memiliki hampir dua kali kandungan antioksidan dari anggur merah dan sampai tiga
kali lipat dari teh hijau dalam in-vitro tes. [14] [15] namun dalam tes yang diuraikan di atas
sekarang muncul efek antioksidan bermanfaat minimal sebagai antioksidan dengan cepat
dikeluarkan dari tubuh.

Important dietary sources

This article may need to be updated. Please update this article to reflect recent events or
newly available information, and remove this template when finished. Please see the talk
page for more information. (October 2009)
Sumber yang baik dari flavonoid termasuk buah jeruk semua, berry, ginkgo biloba, bawang [16]
[17], peterseli [18], (bawang merah terutama [19]) pulsa [20], teh (teh terutama putih dan hijau),
131

merah anggur, seabuckthorn, dan cokelat gelap (dengan kandungan kakao dari tujuh puluh persen
atau lebih besar).

Citrus

Berbagai flavonoid yang ditemukan dalam buah jeruk, termasuk jeruk.

Bioflavonoid jeruk hesperidin meliputi (a glikosida dari hesperetin flavanon), quercitrin, rutin
(dua glikosida flavonol dari quercetin), dan tangeritin flavon. Selain memiliki aktivitas
antioksidan dan kemampuan untuk meningkatkan tingkat intraseluler vitamin C, rutin dan
hesperidin memberi efek menguntungkan pada permeabilitas kapiler dan aliran darah. Mereka
juga menunjukkan beberapa manfaat anti alergi dan anti-inflamasi dari quercetin. Quercetin juga
dapat menghambat reverse transcriptase, bagian dari proses replikasi retrovirus [21] Relevansi
terapi inhibisi ini belum ditetapkan.. Hydroxyethylrutosides (DIA) telah digunakan dalam
pengobatan permeabilitas kapiler, mudah memar, wasir, dan varises

Tea
This section does not cite any references or sources.
Please help improve this article by adding citations to reliable sources. Unsourced material may be
challenged and removed. (October 2009)

Bai Hao Yinzhen from Fuding in Fujian Province, widely considered[citation needed] the best grade of
white tea
Flavonoid teh hijau adalah senyawa antioksidan kuat, berperan untuk mengurangi kejadian kanker
dan penyakit jantung. Flavonoid utama dalam teh hijau adalah kaempferol dan catechin (katekin,
epikatekin, epikatekin galat (ECG), dan epigallocatechin gallate (EGCG)).
Dalam memproduksi teh seperti teh oolong dan teh hitam, daun yang diizinkan untuk
mengoksidasi, di mana enzim hadir dalam teh mengubah beberapa atau semua katekin untuk
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molekul yang lebih besar [kutipan diperlukan]. Namun, teh hijau diproduksi dengan dikukus daun
segar-potong, yang inactivates enzim, dan oksidasi tidak signifikan terjadi. Teh putih adalah yang
paling diproses dari teh dan ditampilkan [kutipan diperlukan] untuk menyajikan jumlah tertinggi
katekin diketahui terjadi di sinensis kamelia.

Wine
See also: Phenolic compounds in wine
Kulit anggur mengandung sejumlah besar flavonoid serta polifenol lainnya [22]. Kedua merah
dan anggur putih mengandung flavonoid, namun sejak anggur merah diproduksi oleh fermentasi
dalam kehadiran kulit anggur, anggur merah telah diamati mengandung kadar flavonoid, dan
polyphenolic lain seperti resveratrol

Dark chocolate
Flavonoid ada secara alami dalam kakao, tetapi karena mereka dapat menjadi pahit, mereka sering
dihapus dari coklat, bahkan berbagai gelap [23]. Sementara flavonoid yang hadir dalam coklat
susu, penelitian telah menunjukkan bahwa mereka tidak mudah diambil oleh tubuh;. mereka juga
tidak mudah diambil ketika coklat gelap dikonsumsi bersama susu [24]

Subgroups
Lebih dari 5000 flavonoid alami telah ditandai dari berbagai tanaman. Mereka telah
diklasifikasikan menurut struktur kimianya, dan biasanya dibagi lagi menjadi sub kelompok
berikut (untuk lebih lanjut membaca lihat [25]):

Flavones
Flavones are divided into four groups:[26]
Group

Flavone

Skeleton
Description

2-phenylchromen4-one

Examples
Function
al groups
32,3
hy dro dih
xyl ydr
o

133

Structural formula

Luteolin,
Apigenin,
Tangeritin

Flavonol
or
3-hydroxyflavone

3-hydroxy-2phenylchromen-4one

Flavanone

2,3-dihydro-2phenylchromen-4one

Hesperetin
Naringenin
Eriodictyol
Homoeriod

Flavanonol
or
3-Hydroxyflavanone
or
2,3-dihydroflavonol

3-hydroxy-2,3dihydro-2phenylchromen-4one

Taxifolin (o
Dihydroqu
n),
Dihydroka
rol

[edit] Isoflavones
Isoflavon menggunakan kerangka 3-phenylchromen-4-satu (tanpa substitusi gugus hidroksil pada
karbon pada posisi 2).
Contoh: genistein, daidzein, Glycitein

Flavan-3-ols, Flavan-4-ols, Flavan-3,4-diols, and proanthocyanidins

Flavan structure
Turunan dari flavan.
Skeleton

Name
Flavan-3-ol

134

Flavan-4-ol

Flavan-3,4-diol (leucoanthocyanidin)
Flavan-3-ols (also known as flavanols) and Proanthocyanidins
Flavan-3-ols use the 2-phenyl-3,4-dihydro-2H-chromen-3-ol skeleton.
Catechins (Catechin (C), Gallocatechin (GC), Catechin 3-gallate (Cg), Gallocatechin 3-gallate
(GCg)), Epicatechins (Epicatechin (EC), Epigallocatechin (EGC), Epicatechin 3-gallate (ECg),
Epigallocatechin 3-gallate (EGCg))
Proanthocyanidins are dimers, trimers, oligomers, or polymers of the flavanols.

Anthocyanidins

Flavylium skeleton of anthocyanidins

Anthocyanidins
Anthocyanidins adalah aglycones dari anthocyanin. Anthocyanidins menggunakan flavylium (2phenylchromenylium) ion kerangka
Contoh: cyanidin, delphinidin, Malvidin, pelargonidin, peonidin, Petunidin

Availability through microorganisms

Beberapa artikel penelitian terbaru menunjukkan produksi efisien molekul flavonoid dari rekayasa
genetik mikroorganisme [27] [28] [29]
MODUL XV
SENYAWA HETEROSIKLIK DAN ASAM NUKLEAT
Senyawa heterosiklik dari senyawa pyrimidin dan purin
Senyawa heterosiklik adalah senyawa organik berbentuk lingar yang tersusun dari 2 atom atau
lebih. Salah satu dari senyawa heterosiklik itu adalah asam nukleat. Asam nukleat terdiri dari dua
macam cincin lingkar yang berbeda yaitu pirimidina dan purin. Primidina adalah senyawwa
lingkar cincin enam yang dua dari anggota cincinnya adalah atom nitrogen selebihnya adalah
atom karbon yang mempunyai struktur seperti berikut :
N
N
135

H
pirimidin
Dan senyawa purin terdiri penggabungan dua senyawa lingkar yang terdiri dari cincin lima dan
enam yang empat dari anggota cincinnya adalah atom nitrogen selebihnya atom karbon dengan
struktur sebagai berikut :
N

N
H
purin
Atom Hidrogen H merupakan pusat reaksi dari baik basa purin maupun basa pirimidin
Asam nukleat dan nukleotida.
Asam nukleat terdiri dari tiga kompenen yakni gugus basa nukleat ( adenin, guanin cytosin, uracil,
thymin), gugus karbohidrat (ribosa dan deoksi ribosa), dan gugus posfat ( mono, di, tri dan
seterusnya). Secara garis besarnya asam nukleat terdiri dari asam ribosa nukleat (RNA) dan asam
deoksi ribosa nukleat, kedua asam nukleat ini berfungsi memberikan informasi genetik kepada sel
makhluk hidup. Penandaan DNA pada suatu sel ditentukan oleh semua informasi dari sel induk,
menegndalikan pertumbuhan suatu sel dan pembelahan sel., serta perintah biosintesa dari enzim,
dan protein-protein lainnya yang diperlukan untuk semua peran sel.
Seperti protein asam nukleat adalah polimer, enzim katalis hidrolisa yang memecah asam
nukleat menjadi gugus-gugus penyusunnyya yang disebut nulkeotida. Selanjutnya setiap
nukleotida dapat dipecah oleh enzim katalis hidrolisa menghasilkan nukleosida dan asam posfat
H3PO4, dan setiap nukleosida dapat dipecah oleh enzim katalis hidrolisa menjadi senyawa
pentosa sederhana dan senyawa heterosiklik purin dan pirimidin
Asam nukleat + H2O
Posfat
Gula
Basa nukleat
Enzim
Nukleotida
H2O
Enzim
H3PO4
+
Gula
Basa nukleat
Nukleosida
H3O+
Gula + basa nukleat
Komponen gula dalam asam ribosa nukleat adalah ribose dan komponen gula dalam deoksiribosa
nukleat adalah 2-deoksiribosa. Nama deoksi berasal dari atom oksigen pada posisi 2 hilang dari
molekul ribose, tanda pada angka 2 menunjukan posisi atom oksigen dalam molekul gula
nukleotida. Dan nama tanpa tanda menunjukkan posisi atom oksigen pada basa amina cincin
heterosiklik.
CH2OH

OH
H
H

CH2OH

OH

H
H

H
136

H
H

OH

OH

OH

Ribosa

2 deoksiribosa

Ada dua macam senyawa purin yang taerdapat pada asam nukleat yakni Adenin dan guanine
dengan struktur sebagai berikut

NH2

N
H

N
H

Adenin
Guanin
Ada 3 macam senyawa pirimidin yang terdapat pada asam nukleat yakni :
NH2

O
N

O
NH

NH

Cytosin

Uracil

Thymin

Struktur DNA
NH2

N
H2PO3CH2

OH
Adenosin 5 posfat

N
H2PO3CH2

OH
OH
Guanosin 5 posfat

NH2

O
N

H3C
137

CH2OH

CH2OH

H
H

H
OH

OH

H
OH

Ribosa

2 deoksiribosa

NH2

NH2
N

Adenin
CH2OH

Guanin
OH

CH2OH

OH

H
H
OH
Ribosa

OH

OH
2-deoksiribos

Struktur 2 DNA
posfat
Deoksiribosa

posfat
Deoksiribosa

posfat
Deoksiribosa

posfat
Deoksiribosa

posfat
Deoksiribosa

posfat
138

Deoksiribosa

posfat
Deoksiribosa

posfat

Struktur 2 strand DNA

posfat
Deoksiribosa

posfat
A

posfat
Deoksiribosa

posfat
G

posfat
Deoksiribosa

Deoksiribosa
posfat

posfat

Sintesa DNA

MODUL XV
X.

Deoksiribosa
posfat

posfat
Deoksiribosa

Deoksiribosa
posfat

posfat
Deoksiribosa

Deoksiribosa
posfat

posfat
Deoksiribosa

Deoksiribosa
posfat

posfat
Deoksiribosa

Deoksiribosa

SENYAWA HETEROSIKLIK DAN ASAM NUKLEAT

139

Deoksiribosa
posfat

Senyawa heterosiklik dari senyawa pyrimidin dan purin

Senyawa heterosiklik adalah senyawa organik berbentuk lingar yang tersusun dari 2 atom
atau lebih. Salah satu dari senyawa heterosiklik itu adalah asam nukleat. Asam nukleat
terdiri dari dua macam cincin lingkar yang berbeda yaitu pirimidina dan purin. Primidina
adalah senyawwa lingkar cincin enam yang dua dari anggota cincinnya adalah atom
nitrogen selebihnya adalah atom karbon yang mempunyai struktur seperti berikut :

N
H
Dan senyawa purin terdiri penggabungan dua senyawa lingkar yang terdiri dari cincin lima
dan enam yang empat dari anggota cincinnya adalah atom nitrogen selebihnya atom
karbon dengan struktur sebagai berikut :

N
H

Atom Hidrogen H merupakan pusat reaksi dari baik basa purin maupun basa
pirimidin
Asam nukleat dan nukleotida.
Asam nukleat terdiri dari tiga kompenen yakni gugus basa nukleat ( adenin, guanin
cytosin, uracil, thymin), gugus karbohidrat (ribosa dan deoksi ribosa), dan gugus posfat
( mono, di, tri dan seterusnya). Secara garis besarnya asam nukleat terdiri dari asam ribosa
nukleat (RNA) dan asam deoksi ribosa nukleat, kedua asam nukleat ini berfungsi
memberikan informasi genetik kepada sel makhluk hidup. Penandaan DNA pada suatu sel
140

ditentukan oleh semua informasi dari sel induk, menegndalikan pertumbuhan suatu sel dan
pembelahan sel., serta perintah biosintesa dari enzim, dan protein-protein lainnya yang
diperlukan untuk semua peran sel.
Seperti protein asam nukleat adalah polimer, enzim katalis hidrolisa yang
memecah asam nukleat menjadi gugus-gugus penyusunnyya yang disebut nulkeotida.
Selanjutnya setiap nukleotida dapat dipecah oleh enzim katalis hidrolisa menghasilkan
nukleosida dan asam posfat H3PO4, dan setiap nukleosida dapat dipecah oleh enzim
katalis hidrolisa menjadi senyawa pentosa sederhana dan senyawa heterosiklik purin dan
pirimidin
Asam nukleat

Posfat

gula

Basa nukleat

Nukleotida
H2O
Enzim

H3PO4

gula

Basa amina

Nukleosida

H3O+

Gula + amina heterosiklik

Komponen gula dalam asam ribosa nukleat adalah ribose dan komponen gula dalam
deoksiribosa nukleat adalah 2-deoksiribosa. Nama deoksi berasal dari atom oksigen pada
posisi 2 hilang dari molekul ribose, tanda pada angka 2 menunjukan posisi atom oksigen
dalam molekul gula nukleotida. Dan nama tanpa tanda menunjukkan posisi atom oksigen
pada basa amina cincin heterosiklik.

CH2OH

OH

CH2OH

OH

H
H

H
141

OH

OH

OH

Ribosa

H
2 deoksiribosa

Ada dua macam senyawa purin yang taerdapat pada asam nukleat yakni Adenin dan
guanine dengan struktur sebagai berikut :

NH2

NH2
N

N
H

Adenin

Guanin

Ada 3 macam senyawa pirimidin yang terdapat pada asam nukleat yakni :
NH2

O
H3C

N
H
Cytosin

H
Uracil

H
Thymin

Struktur DNA
NH2

N
142

NH2
N

H2PO3CH2

H2PO3CH2

H
OH

OH

H
OH

Ribosa

2 deoksiribos

NH2

O
H3C

H
CH2OH

CH2OH

H
H

H
OH

OH

H
OH

Ribosa

2 deoksiribosa

NH2

N
143

NH2
N

Adenin

Guanin

CH2OH

OH

CH2OH

OH

H
H

H
OH

OH

H
OH

Ribosa

H
2 deoksiibosa

NH2

O
H3C

H
Cytosin

CH2OH

H
Uracil

OH

H
Thymin

CH2OH

CH2OH

H
H

H
OH

OH

OH
OH

Ribosa

2 deoksiribosa

Sintesa DNA
XI.

POLIMER
Polimer adalah senyawa organic bermolekul besar yang teridiri dari unit molekul
monomer yang berulang. Banyaknya pengulangan pada molekul monomer menunjukkan
derajad polimerisasi dari molekul polimer tersebut. Makin banyak unit monomer pada
144

suatu molekul polimer maka sifat kimianya makin inert. Berdasarkan proses
pembentukanknya secara garis besar polimer dibagi menjadi polimer alami dan polimer
sintetik. Polimer alami adalah protein yang terdiri dari unit monomer asam-asam amino,
pati yang terdiri dari unit monomer heksosa, asam nukleat yang terdiri dari unit monomer
basa nukleat, ribose, dan fosfat. Polimer sintetik adalah polimer yang dibuat dibuat dalam
proses industri kimia, seperti polietilena, polipropilena, polistirena, polivinilklorida, nilon,
polyester, serat akrilat, poliepoksi, resin fwenolat, resin urea formal dehid, dan lain-lain.
Polimer bisa terbentuk melalui proses reaksi addisi dan melalui reaksi kondensasi. Contoh
reaksi polimerisasi addisi adalah sebagai berikut :

C6H5-C--O-O--C-C6H5

2 C6H5-C-Oo = Ino

Ino + H2C=CH2

In-H2C=CH2o

Klassifikasi polimer
Polimer Sintetik dapat digolongkan berdasarkan metode sintesa atau pun bisa juga tahap
pembentukan rantai polimer atau tahap pembentukan polimer. Kategori ini mencakup
banayak hal dan memerlukan kegunaan yang berbeda. Tahap pembentukan rantai polimer
disebut polimer addisi dengan istilah lain dihasilkan dengan polimerisasi reaksi berantai
yang inisiatornya teraddisi ke ikatan ganda karbon-karbon untuk menghasilkan senyawa
intermediet yang reakstif. Polimer terbentuk dari banyyaknya monomer yang teraddisi ke
ujung rantai yang reaktif dari rantai yang terbentuk. Inisiator bisa bermula baik anion,
kation, atau radikal, dan polimer yang dihasilkan dengan cara begini hanya mempunyai
atom-atom karbon pada rantai utama. Polietilen dihasilkan dengan reaksi inisiasi
polimerisasi etilen dengan tahap pembentukan polimer sebagai berikut :

Ino + H2C=CH2

In-H2C-CH2o + H2C=CH2

In-H2C-CH2-H2C-CH2o + H2C=CH2
CH2o + H2C=CH2

In-H2C-CH2-H2C-CH2-H2C-

In-H2C-CH2-H2C-CH2-H2C-CH2-H2C-CH2o
Polietilen

Tahap pembentukan polimer yang disebut dengan pertumbuhan polimer kondensasi yang
terbentuk dengan proses polimerisasi dimana tahap pembentukan ikatan terjadi pada reaksi
145

polar. Reaksi terjadi pada antara dua gugus fungsi molekul, dan sertiap ikatan dalam
polimer terbentuk secara bebas dari yang lainnnya. Polimer biasanya dihasilkan dari dua
monomer yang salling berikatan dan biasanya mempynyai atom lainnya yang teraddisi ke
atom karbon pada rantai utama. Nilon adalah merupakan suatu polimer poliamida yang
terbentuk dari reaksi asam dikarboksilat dan senyawa diamina. Dengan tahap pertumbuhan
sebagai berikut :
H2N-(CH2)6-NH2 + HOOC-(CH2)6-COOH
-NH-(CH2)6-NH-CO-(CH2)6-CO- + H2O
Nilon 66
Reaksi polimerisasi radikal, kationik dan anionic
Beberapa polimer alkena berberat molekul rendah mengalami reaksi polimerisasi yang cepat
ketika berkontak dengan sejumlah inisiator radikal. Polietilen adalah salah satu molekul
polimer berantai pertama yang dibuat diindustri secara komersil yang sederhana yang telah
diproduksi semenjak tahun 1943. Produksi tahunan untuk polimer ini dengan volume produksi
hampir 12 juta ton. Reaksi polimerisasi propilena biasanya berlangsung pada tekanan 1000
3000 atm dan suhu tinggi 100 250 oC. Dengan katalis radikal benzoil peroksida, jumlah unit
monomer bisa dari beberapa ratus sampai beberapa ribu unit rantai monomer. Semua reaksi
radikal berantai berlangsung dalam tiga macam tahap reaksi yakni tahap inisiasi, tahap
propagasi, dan tahap terminasi.
Inisiasi bermula ketika terbentuk sejumlah radikal yang dibentuk oleh katalis. Salah satu
dari radikal ini teraddisi ke molekul etilena membentuk rantai karbon radikal baru,
polimerisasi berlangsung terus menerus.
Ino + H2C=CH2

In-H2C-CH2o + H2C=CH2

In-H2C-CH2-H2C-CH2o + H2C=CH2
CH2o + H2C=CH2

In-H2C-CH2-H2C-CH2-H2C-

In-H2C-CH2-H2C-CH2-H2C-CH2-H2C-CH2o
Polietilen

Reaksi polimerisasi polipropilena terjadi dalam lima tahap berikut :

Tahap 1 ( inisiasi )
O

C6H5-C--O-O--C-C6H5

2 C6H5-C-Oo = Ino
146

Tahap 2
Ino + H3C-HC=CH2

In-HC-CH2o
H3C

Tahap 3 ( propagasi )
In-HC-CH2o + H3C-HC=CH2

In-HC-CH2-CH-CH2o

H3C

H3C

In- -H2C-CH2-HC-CH2o + n H3C-H2C=CH2

H3C

H3C
In-(HC-CH2-)n-HC-CH2o

H3C

H3C

H3C

Tahap 4 (Quenching)
In- (HC-CH2-)nHC-CH2o + In-(HC-CH2-)n-HC-CH2o
H3C

H3C

H3C

H3C

In-H2C-CH2-HC-CH2-CH2-CH-n(CH2-HC-)-In
H3C

H3C

H3C

H3C

Tahap 5 ( terminasi )
In- (HC-CH2-)nHC-CH2o + In-(HC-CH2-)m-HC-CH2o
H3C

H3C

H3C

H3C

-(H2C-CH2-)n-HC-CH2-CH2-CH-n(CH2-HC-)mH3C

H3C

H3C

H3C

Reaksi polimerisasi kationik

Senyawa turunan monomer alkena tertentu dapat dipolimerisasi dengan mekanisme reaksi
polimerisasi kationik, dan juga dengan mekanisme reaksi radikal. Reaksi polimerisasi kationik
terjadi dengan jalur reaksi berantai dan memmerlukan proton yang kuat atau asam Lewis
sebagai inisiator. Reaksi berantai ini terjadi melalui reaksi addisi elektrofilik dari karbokation
intermediet ke ikatan ganda karbon-karbon dari unit monomer lainnya
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Tahap 1 (inisiasi)
H+ + S-HC=CH2

HC-CH3
S

Tahap 2 ( propagasi )

H3C-CH-CH2-CH+

HC-CH3 + SHC=CH2
S

H3C-CH-H2C-CH+ + n S-H2C=CH2
S

(H3C-CH-)n-H2C-CH+

Tahap 4 (Quenching)
(H3C-CH+-)n + OH.

(-CH2-CH-)n + H2O

Tahap 5 ( terminasi )
I

(-+CH-CH3)n-

- H+

(-CH-CH2-)n

-(H2C-CH2-)n-HC-CH2-CH2-CH-n(CH2-HC-)H3C

H3C

H3C

H3C

Dimana Nu = inisiator nukleofilik, S = substituen gugus penarik electron

Reaksi polimerisasi anionic
Monomer alkena yang mengandung substituen gugus penarik electron dapat dipoolimerisasi
dengan katalis anionic. Reaksi berantai dapat terjadi dimana tahap yang paling menentukan
reaksi adalah tahap addisi nukleofil dari anion ke monomer tak jenuh. Contohnya
H2C=CH + Nu:-

Nu-CH2-CH:- + H2C=CH
148

Nu-CH2CH-H2C-CH:-

- (-CH2-CH-)nS
Tahap 1 (inisiasi)
Nu:- + S-HC=CH2

:HC-CH2-Nu
S

Tahap 2 ( propagasi )

:HC-CH2 -Nu + SHC=CH2

-:HC-CH2-CH2-CH-Nu

:HC-CH2-HC-CH2-Nu + n S-H2C=CH2
S

-:(-HC-CH2-)n-HC-CH2-Nu

Tahap 4 (Quenching)
-

:(HC-CH2-)n + H+

(-CH2-CH-)n + H2O

Tahap 5 ( terminasi )
Nu:- (-CH-CH2-)n S

Nu:-

(-CH-CH2-)n
S

Monomer akrinlonitril (H2C=CHCN), methyl methakrilat (H2C=C(CH3)COOCH3, dan stirena

(H2C=CHC6H5) semuanya dapat mengalami reaksi polimerisasi anionic, meskipun diperlukan
radikal sebagai inisiator polimerisasi untuk produksi skala komersil.
149

Salah satu contoh yang paling menarik dari reaksi polimerisasi anionic adalah super glue satu
tetesnya mempunyai daya rekat 2000 lb. Super glue adalah salah satu contoh produk yangpaling
sederhana dari rekasi polimerisasi anionic dari bahan murni metal a-sianokrilat. Karena ikatan
ganda karbon mempunyai dua gugus penarik electron, sehingga reaksi addisi anionic dapat
berlangsung dengan mudah dan cepat. Dengan adanya sediit air atau basa pada permukaan bahan
sudah cukup untuk memulai reaksi polimerisasi sianokrilat dan selanjutnya terjadi penggabungan
antar molekul monomer. Kulit adalah sumber yang terbaik dari inisiator dasar yang diperlukan,
dan banyak orang menemukan jarinya lengket setelah menyentuh super glue.
CN
H2C=C-COOCH3
siano akrilat

CN
+ -OH

HO-CH2-C:COOCH3
CN
-CH2-C
COOCH3
Super glue

Stereokimia dari polimer

Secara garis besarnta polimer mempunyai tiga bentuk stereokimia

Isotactic
H3C H H3C

H3C

H H3C

H3C H

Syndiotactic
H3C H

H3C

H3C

H H3C

150

H3C

Atactic
H3C H

CH3

H H3C

H H

CH3 H H3C

Polimerisasi diena ( karet alam dan karet sintetis )

kopolimer
Polimer nilon
Polimer poli uretahn
hubungna Struktur dan kimia polimer
hubungan Struktur dan sifat fisika polimer
Klassifikasi polimer sinthetik berdasarkan sifat fisikanya yang dapat digunakan untuk
menetukan hubungan sifat fisika dengan struktur polimer. Pada dasarnya penggolongan
polimer berdasarkan sifat fisikanya dapat digolongkan menjadi empat golongan bedar
yakni
a. thermoplastic.
Menurut kebanyakan orang mengira polimer adalah thermoplastic sebagai plastic.
Polimer ini keras pada suhu kamar dan lunak dan meleleh bila dipanaskan.
Thermoplastik ini bisa dibuat menjadi mainan anak-anak, alat tidur, telefon, atau beriburibu jenis produk lainnya. Karena thermopalstik tidak mempunyai ikatan silang, maka
masing-masing molekul dapat bergeser satu sama lainnya bila dipanaskan. Beberapa
produk polimer thermoplastic seperti polimetilmetakrilat, yang digunakan sebagai pleksi
glass adalah amorf, sedangkan yang lainnya seperti nilon dan poli etilen adalah kristal.
b. Fiber.
Fiber adalah serat tipis yang dihasilkan dari ekstruding dan pelelehan polimer melalui
lobang yang halus pada pemintalan serat, kemudian serat didinginkan dan dipintal.
Pengaliran menyebabkan polimer ini mempunyai oreantasi bentuk kristal sepanjang
gulunngan fiber, proses ini mengakibatkan penguatan batas kekuatan tarik polimer.
Beberapa jenis produk polimer yang tergolong semi kristal adalah nilon, dacron, dan poli
etilen.
c. Elastomer
Elastomer adalah polimet yang bersifat amorf mempunyai kemampuan memanjang dan
mengkerut menjadi bentuk awalnya kembali. Polimer-polimer ini dapat membentuk
ikatan silang untuk mencegah pergeseran antar molekul antara stu sama lainnya. Ranntai
molekulnya tak beraturan untuk mencegah pembentukan kristal yang kaku. Bila ditarik
rantai lurus yang tersusun secara random akan menjadi melar sesuai dengan arah tarikan
Gaya Van der Waals yang bekerja terlalu lemah dan sedikit sekali terjadi yang bisa
mempertahankan oreantasi ini, akan tetapi dengan adanya elastomer akan sulit
membentuk kumparan yang tersusun secara random bila dilakukan penarikan. Karet
alam adalah salah satu contoh elastomer. Karet alam mempunyai rantai yang panjang
dan terjadi ikatan silang secara elektrostatik, akan tetapi dengan geometri tak beraturan
sulit untuk terjadinya bentuk kristal. Sebaliknya Getta percha adalah polimer kristalin
yang tinggi bukan elastomer.
d. Resin thermosetting.
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Resin thermosetting adalah polimer yang banyak berikatan silang dan memadat sampai
menjadi keras, berupa massa yang tak larut bila dipanaskan. Balelit adalah salah satu
contoh resin thermosetting yang pertama kali diproduksi tahun 1907 oleh Leo
Baekeland, yang telah banyak diperdagangkan dalam waktu yang lama dari pada
polimer sintetik lainnya. Bakelit banyak sekali digunakan dalam bentuk cairan kental
untuk perekat, pelapis, dan bahkan dipakai untuk keperluan suhu tinggi seperti ujung
peluru kendali. Secara kimia bakelit adalah resin fenolik yang dihasilkan dari reaksi
fenol dan formal dehid. Pada saat pemanasan molekul air dibebaskan, terbentuklah
beberapa ikatan silang, dan polimer berubah menjadi bentuk yang paling stabil yakni
berupa massa seperti bebatuan. Ikatan silang pada bakelit dan bahan thermosetting
lainnya adalah bentuk tiga dimensi dan sangan rumit, sehingga tidak bisa digambarkan
bentuk rantai polimernya. Bakelit adalah molekul yang sangat besar sekali.

OH

OH
H+
+ H-C=O
H

Fenol

HO

formal dehid

OH

OH

OH

OH

Resin fenol formal dehid ( bakelit )

Daftar pustaka :
1. John Mc. Murry Organic chemistry Brooks/cole Publ. Co. 1984.
2. L. F. Fhiser Organic Chemistry Mazen Co. Ltd 1957
3. R.T. Morrison and N. Boyd. Organic chemistry 3rd ed Prentice Hall Publ. Co. 1978.
4. T. A. Geissman Principles of organic chemistry 3rd ed 1968 W.H. Freeman and
Company. (pp 1 - 886)
152

5. R. F. Brown Organic Cemistry 1975, Wadworth Publ. Co. (pp 1 995)

6. H. Meislich et al. Organic Chemistry Schaums outlineseries 1977.
7. "http://en.wikibooks.org/wiki/Organic_Chemistry/Overview_of_Functional_Groups"

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