Kimia Organik

Hidrokarbon (C & H ) Senyawa Heteroatom

alkohol R OH
alifatik aromatik
alkana R O R'
eter
O
C C
aldehida R C H
O
alkena
keton R C R'
C C O
Asam karboksilat R C OH
alkuna
O
C C ester R C OR'
R NH2
Senyawa siklis amina
O
amida R C NH2

1
Senyawa Turunan Alkana
 Isomer

Struktural Geometri Optik

Posisi Gugus fungsi H Cl * Enansiomer

Cl
and
H * Diastereoisomer
OH OH H H
* Senyawa meso
and and Cl Cl
OH or
O H
CH3
or or H3C
CHO H and
H
and and CH3
O
H
CH3

3
 ISOMER STRUKTUR
1. ISOMER KERANGKA
Isomer struktur yang terjadi karena perbedaan panjang
rantai C /rangkanya
Contoh : n-butana dan 2-metilpropana
CH 3

H 3C C CH 3 dan CH 3 CH 2 CH 2 CH 3
H
Is o -b u ta n a B u ta n a
( 2 -m e t ilp r o p a n a )

2. SOMER POSISI
Isomer struktur yang terjadi karena perbedaan posisi /
Kedudukan gugus fungsi pada senyawa-senyawa segolongan
Contoh : 1-butanol dengan 2-butanol
NH 2

CH 3 CHCH 3 dan CH 3 CH 2 CH 2 -NH 2

1 2 3 3 2 1
 lanjut

3. ISOMER FUNGSI

Isomer struktur yang terjadi karena perbedaan jenis

gugus fungsi
pada senyawa-senyawa turunan alkana

Alcohol dan eter : CnH2n+2O

Aldehid dan keton : CnH2nO
Asam karboksilat dan ester : CnH2nO2
Alkena dan sikloalkana : CnH2n
Alkuna dan alkadiena : CnH2n-2
 ISOMER RUANG
1. Isomer Cis, Trans
Isomer ruang yang terjadi karena perbedaan
atom/gugus yang terikat pada atom C ikatan rangkap
dua
Syarat punya isomer cis-trans :
1) mengandung C ikatan rangkap dua (-C=C-)
2) masing-masing C ikatan rangkap mengikat gugus /
atom yang berbeda (Mr-nya)

CIS ( gugus / atom sejenis terletak sepihak)

TRANS ( gugus / atom sejenis terletak berseberangan

Dept. Kimia FMIPA-UI 6

 LANJUT

CH3
• CIS
H

H
• TRANS

CH3
 Sequence Rules: Arti E,Z

• Senyawa yg tidak masuk dlm “cis”

or “trans”
– Substituent pada C1 berbeda
dgn C2
– We need to define “similarity” in
a precise way to distinguish the
two stereoisomers
• Cis, trans tatanama hanya belaku
ikatan rangkap yg mempunyai dua
substituen

Dept. Kimia FMIPA-UI 8

 Urutan Prioritas: Aturan Cahn-Ingold-Prelog

• Atom diurutkan sesuai dgn prioritanya.

• Atom yg mempunyai nomor atom besar diberikan prioritas
utama. Br > Cl > O > N > C > H

Senyawa ini mempunyai gugus dgn

prioritas (E-Gugusnya berlawanan):

(E )-2-bromo-2-chloro-propene

Dept. Kimia FMIPA-UI 9

 lanjut

2. ISOMER OPTIS
Isomer ruang yang terjadi karena perbedaan
letak atom / gugus yang terikat pada atom C
kiral
/ atom C asimetris ( atom C kiral : atom C yang
ke-4 tangannya mengikat gugus / atom yang
berbeda) sehingga dapat memutar bidang
cahaya yang terpolarisai
• Jumlah isomer optic = 2n , n = jumlah atom C
kiral
 Isomer Optik
E n a n s io m e r: S u a tu p a s a n g a n s e n y a w a y a n g m e ru p a k a n b e n d a d a n b a y a n g a n c e rm in
D ia s te r e o m e r :S u a tu p a s a n g a n s e n y a w a y a n g b u k a n m e r u a k a n b e n d a d a n b a y a n g a n
c e rm in .
O O O
O
C H C H
C H H C
H C OH HO C H
H C OH HO C H
HO C H H C OH
H C OH HO C H
CH 2 OH CH 2 OH
CH 2 OH CH 2 OH
(c ) (d )
(a ) (b )
P a sa n g a n E n a n sio m e r P a s a n g a n E n a n s io m e r
(e ry tro sa ) (th re o s a )

(a ) d a n (c ), (a ) d a n (d ), (b ) d a n (c ), (b ) d a n (d ) a d a la h d ia ste re o m e r

COOH COOH
COOH COOH
H C OH HO C H
H C OH HO C H

HO C H H C OH H C OH HO C H

COOH COOH COOH COOH

(c) (d)
(a) (b)

Pasangan enansiomer Senyawa Meso

11
 JENIS-JENIS REAKSI PADA SENYAWA KARBON

1. REAKSI SUBSTITUSI
2. REAKSI ADISI
3. REAKSI ELIMINASI
4. REAKSI KONDENSASI
5. REAKSI OKSIDASI
6. REAKSI POLIMERISASI
REAKSI SUBSTITUSI
REAKSI ADISI
REAKSI ELIMINASI
REAKSI KONDENSASI
REAKSI OKSIDASI
Edexcel organic reaction mechanisms
Click a box below to go to the mechanism Click here
for advice

Homolytic
Free Radical Substitution

Free Radical Addition

Heterolytic
Electrophilic Addition

Nucleophilic Substitution S N2 S N1

Electrophilic Substitution Nitration Br2 Alkylation Acylation

Nucleophilic Addition
Free radical substitution
chlorination of methane
i.e. homolytic breaking of covalent bonds

Overall reaction equation

CH4 + Cl2 CH3Cl + HCl

Conditions

ultra violet light

excess methane to reduce further substitution
Free radical substitution mechanism
ultra-violet
Cl Cl Cl Cl initiation step

H3C H Cl H3C H Cl two propagation steps

H3C Cl Cl H3C Cl Cl

H3C Cl H3C Cl termination step

minor
H3C CH3 H3C CH3 termination step
Further free radical substitutions
Overall reaction equations

CH3Cl + Cl2 CH2Cl2 + HCl

CH2Cl2 + Cl2 CHCl3 + HCl

CHCl3 + Cl2 CCl4 + HCl

Conditions ultra-violet light

excess chlorine
Free radical addition
addition polymerisation of ethene

i.e. homolytic breaking of covalent bonds

Overall reaction equation

n H2C=CH2 [ CH2CH2 ]n
ethene polyethene

Conditions

free radical source

(a species that generates free radicals
that allow the polymerisation of ethene molecules)
Free radical addition mechanism
R R R R initiation step

H2C CH2 R H2C CH2 R

H2C CH2 H2C CH2R H2C CH2 CH2CH2R

chain propagation steps

Addition of H2C=CH2 repeats the same way until:

R(CH2)nCH2 H2C(CH2)mR

termination step R(CH2)nCH2 CH2(CH2)mR

polyethene
Electrophilic addition
bromine with propene mechanism
CH3CH=CH2 + Br2 CH3CHBrCH2Br
1,2-dibromopropane

hydrogen bromide with but-2-ene mechanism

CH3CH=CHCH3 + HBr CH3CH2CHBrCH3

2-bromobutane
Electrophilic addition mechanism
bromine with propene reaction equation

H H

C C
H H carbocation
CH3 H
CH3 C C H
+ +
Br
Br
H H
Br
- Br -
Br CH3 C C H

Br Br Br

1,2-dibromopropane
Electrophilic addition mechanism
hydrogen bromide with trans but-2-ene
H CH3 reaction equation

C C
H H carbocation
CH3 H
CH3 C C CH3
+ +
H
H
Br H H
- Br -
CH3 C C CH3

Br H

2-bromobutane
Nucleophilic substitution

hydroxide ion with bromoethane mechanism

CH3CH2Br + OH- (aqueous) CH3CH2OH + Br-

ethanol

hydroxide ion with 2-bromo,2-methylpropane

mechanism

(CH3)3CBr + OH- (aqueous) (CH3)3COH + Br-

2-methylpropan-2-ol
Nucleophilic substitution mechanism
hydroxide ion with bromoethane (SN2)

H H
+ -
CH3 C Br OH
CH3 C

H
H Br-

OH - ethanol

SN2
reaction equation

S (substitution) N(nucleophilic)
2(species reacting
in the slowest step)
Nucleophilic substitution mechanism
OH- ion with 2-bromo,2-methylpropane (SN1)

Br- Br-
CH3 CH3 CH3
+ -
CH3 C Br CH3 C+ CH3 C OH

CH3 CH3 CH3

2-methylpropan-2-ol
OH -
SN1 reaction equation

S (substitution) N(nucleophilic)
1(species reacting
in the slowest step)
Nucleophilic substitution
cyanide ion with iodoethane
mechanism

CH3CH2I (ethanol) + CN-(aq) CH3CH2CN + I-

propanenitrile

cyanide ion with 2-bromo,2-methylpropane

mechanism
(CH3)3CBr (ethanol) + CN- (aqueous)

(CH3)3CCN + Br-

2,2-dimethylpropanenitrile
Nucleophilic substitution mechanism
cyanide ion with iodoethane (SN2)

H H
+ -
CH3 C I CN
CH3 C

H I -
H

CN - propanenitrile

SN2

S (substitution) N(nucleophilic)
2(species reacting
in the slowest step)

reaction equation
Nucleophilic substitution mechanism
CN- ion with 2-bromo,2-methylpropane (SN1)

Br- Br-
CH3 CH3 CH3
+ -
CH3 C Br CH3 C+ CH3 C CN

CH3 CH3 CH3

SN1 CN - 2,2-dimethyl
propanenitrile

S (substitution) N(nucleophilic)
1(species reacting
in the slowest step)

reaction equation
Nucleophilic Addition
addition of hydrogen cyanide to carbonyls
to form hydroxynitriles

RCOR + HCN RC(OH)(CN)R

RCHO + HCN RCH(OH)CN

Conditions / Reagents

NaCN (aq) and H2SO4(aq) supplies H+

supplies the CN- nucleophile

Room temperature and pressure

Nucleophilic Addition Mechanism

hydrogen cyanide with propanone

CH3COCH3 + HCN CH3C(OH)(CN)CH3

NaCN (aq) is a source of cyanide ions C N

- H+ from H2SO4 (aq)

O H+
+ O O H
CH3 C

CH3 CH3 C CN CH3 C CN

CH3 CH3
CN

2-hydroxy-2-methylpropanenitrile
 Addisi Elektrofilik HX pd Alkena
• mekanisme reaksi : addisi elektrofilk
• Serangan elektrofil (HBr) pada ikatan  alkena.
• Menghasilkan carbocation dan ion bromida
• KarboKation adalah electrophile, bereaksi dgn
nukleofilik ion bromide

Dept. Kimia FMIPA-UI 35

 Mechanistic Regiospecificity dalam Reaksi Addisi

• Jika adisi melibatkan

intermedit ion karbonium :
– Maka ada dua cara untuk
mengadisi.
– Cara yg menghasilkan
pusat ion yg mempunyai
substituen banyak adalah
yg mempunyai energi yg
rendah.
– Gugus alkil menstabilkan
ion karbonium.

Dept. Kimia FMIPA-UI 36

 Mechanism of Electrophilic Addition: Rearrangements of
Carbocations

• Karbonium ion mengalami

rearranggement struktur
• Terjadi pergeseran H- 1,2 dan
alkyl-1,2.
• Menjadi karbonium ion yg
paling stabil.

Dept. Kimia FMIPA-UI 37

 Carbocation Structure and Stability

• Ion Karbonium adalah planar dan karbon tiga koordinat

dikelilingi oleh 6 elektron dalam orbital sp2 .
• orbital keempat adalah p-orbital yg kosong.
• Kestabilan ion karbonium diukur dgn energi yg dibutuhkan utk
membentuk R-X.
• Kestabilan ion karbonium : 3º > 2º > 1º > +CH3

Dept. Kimia FMIPA-UI 38

 Contoh Addisi Electrophilic
• Addisi hydrogen bromide
pada 2-Methyl-propena
• H-Br mentransfer proton ke
C=C
• Menghasilkan intermediate
karbonium ion yg palinh stabil
• Bromida masuk ke karbonium
ion.

Dept. Kimia FMIPA-UI 39