Pertemuan 11: ALKENA

Tatanama
Sifat Fisik dan
Kimia
Sumber dan
Kegunaan
Reaksi-Reaksi
Alkena
Latihan dan
Tugas 1
 Alkena

Rumus umum CnH2n dimana n = 2,3, 4,

Alkena disebut juga olefin
Alkena merupakan salah satu hidrokarbon tak
jenuh selain alkuna dan cincin benzen.
Hidrokarbon tak jenuh = hidrokarbon yg
masih dapat bereaksi dengan hidrogen.
Hidrokarbon dapat berbentuk ikatan rangkap

dua (C=C), kedua atom C dlm hibridisasi sp2,

ikatan rangkap tiga (sp), dan cincin benzen.
Hidrokarbon tak jenuh/alkena dalam kehidupan

berhub. dg senyawa lipid atau lemak.

Ikatan rangkap dua pd alkena terdiri dari ikt sigma
dan ikt phi
Hidrokarbon tak jenuh dg cincin benzen &
turunannya ditemukan pd struktur protein dan
asam nukleat.
Adanya ikatan rangkap pada molekul alkena
menyebabkan alkena lebih reaktif dibandingkan
senyawa alkana.
H
H sp
2

sp2 C C C 3H
sp
H
H H
Tata nama alkena
CH2 = CH2 etena atau etilen
CH3 - CH = CH2 propena atau propilen
CH3-CH2-CH2-CH = CH-CH3 2-heksena
CH2 = CH CH = CH2 1.3-butadiena
CH3 CH CH = CH2 3-metil 1-butena
CH3

Etena banyak digunakan sbg bahan baku industri;

etanol, polimer polietilen, etilen oksida dsb.
Etena dapat dibuat dari etana dg pemanasan suhu 800oC
dg katalis Pt
Etena juga digunakan sbg hormon pematangan buah spt;
pisang & tomat
Propena digunakan sbg bahan baku polimer polipropilen
Ttd alkena selain dipengaruhi oleh jml atom C-nya
juga ditentukan oleh bentuk isomer geometriknya.
Senyawa alkena sedikit lebih polar dari syw alkana,
karena adanya ikatan rangkap dg elektron
menyebabkan terjadinya pemisahan muatan
siklopentena sikloheksa-1,4-diena siklookta-1,3,5,7-tetraena
 Ethylene
Double bond = 1 sigma bond + 1 pi bond
8
 Senyawa alkena selain mempunyai isomer kerangka,
juga dapat mempunyai isomer geometris, misalnya
senyawa butena.
CH 3

CH 2 = CH-CH 2 CH 3 CH 2 = C - CH 3 CH 3 -CH = CH -CH 3

1-butena 2-metilpropena 2-butena

ttd = -6oC ttd= -7oC

CH3 H
CH3 CH3
C C
C C
H CH3
H H

cis-2-butena trans-2-butena
ttd = 3,7oC ttd = 0,9oC
10
 CH3
1 CH3 4
1 1
CH3
4 2 4 2
2

1-metillsikloheksena 1,4-sikloheksadiena 1,5-dimetilsiklopentena

(Sikloheksa-1,4-diena)

CH2OH

Retinol (Vitamin A)

CH 3 CH 3

H3C
CH 3 -CH-CH 2 -CH 2 -CH=C-CH 3
CH 3
2,6 dimetil 2 heptena 3,4 dimetilsiklopentena
 E-Z Nomenclature
Gunakan aturan Cahn-Ingold-Prelog untuk
menentukan urutan prioritas gugus-gugus
yang terikat pada atom C ikatan rangkap.

Jika gugus-gugus yang berprioritas lebih tinggi

berada pada sisi yang sama, diberi nama Z
(zusammen).

Jika gugus-gugus yang berprioritas lebih tinggi

berada pada sisi yang berlawanan, diberi
nama E (entgegen).
 Example, E-Z

1 1 2 Cl
1
H3C Cl H CH CH3
C C C C
H CH2 H
2 1 2
2
2Z 5E

3,7-dichloro-(2Z , 5E)-2,5-octadiene
3,7-dichloro-(2Z, 5E)-octa-2,5-diene
 Cl Br

F H
Cl > F Br > H
(Z)-2-Bromo-1-chloro-1-fluoroethene

H3C H
Cl H

F Br F CH3
Cl > F Br > H F > CH3 CH3 > H
(E)-2-Bromo-1-chloro-1-fluoroethene (Z)-2-fluorobutene
 Reactions of Alkene
Reaksi Adisi oleh asam halida (HX):
Alkena + HX Alkil Halida
 MARKOVNIKOFF RULE
ANOTHER WAY TO STATE THE RULE

When the reaction forms the carbocation intermediate,

the most highly substituted carbocation is favored :
tertiary > seconday > primary.

least methyl carbocation + CH3

favored
primary carbocation R CH2
+
secondary carbocation R CH R
+
most tertiary carbocation
favored R
(lowest energy) C
R R
+
THE BEST CARBOCATION FORMS FASTEST
CH3 primary

CH3-CH-CH2
slower
+
CH3
faster
CH3-C-CH3
+
tertiary low
energy

CH3

CH3-C=CH2

+ H 3O + CH3 CH3

major CH3-C-CH3 CH3-CH-CH2-Cl

Cl minor
Conclusion: If more than one carbocation
intermediate is possible, the reaction will
proceed predominantly via the pathway
that involves the lowest energy intermediate.
CARBOCATION STABILITY
 CARBOCATION STABILITY
AN EXPLANATION

H
.. HYPERCONJUGATION
+ R electrons in an adjacent
C C C-H s bond help to stabilize
the positive charge of the
H R carbocation by proximity
(overlap)
H
lowest highest
energy R energy

R C
+ R
< R CH R < R CH2 < CH3
+ + +
tertiary secondary primary methyl
THE STRUCTURE OF THE CARBOCATION
IS THE MOST IMPORTANT FACTOR, NOT
THE NUMBER OF HYDROGENS.

WE NOW KNOW MORE THAN

MARKOVNIKOFF DID !
 EXAMINATION OF THE CARBOCATIONS
REVEALS THE ANSWER

CH CH CH3 secondary,
no resonance

+
CH CH CH3
(+)
H
+
(+) CH CH CH3

(+) H secondary,
with resonance
BETTER
CH CH CH3
CH CH CH3 H Cl
Cl H
Major Product Minor Product
 SCOPE OF
THE ADDITION OF HX
HCl, HBr AND HI REACT THE SAME WAY
(same mechanism and same regioselectivity)

major minor

conc CH3 CH2Cl

+HCl +
Cl H

conc CH3 CH2Br

+HBr +
Br H

conc CH3 CH2I

+ HI +
I H
Markovnikoff
product

HF REACTS ONLY UNDER SPECIAL CONDITIONS

 SCOPE OF THE REACTION
..
- ..
: X:
.. :X :
slow
C C C C C C
step 1 + step 2
H H
+
H
HCl usually adds, but often requires heating

HBr and HI add readily at room temperature.

HBr adds differently if peroxides are present - discussed later

HF is difficult, but will add with special solvents

to give moderate yields.

(polyhydrogenfluoride -pyridine-tetrahydrofuran at 0 o C)
 ADDITION OF OTHER HX (H2O and H2SO4)

H2O and H2SO4 can also add depending on the conditions

major minor

conc CH3 CH2OSO3H

+
+ H2SO4
OSO3H H

CH3 CH2OH
H2SO4
+ H2O +
OH H

This is covered on the next set of slides.

WHAT HAPPENS IN A SYMMETRICAL ALKENE?
(symmetrical = similar substitution at both carbons)

each carbon would form

a secondary carbocation

CH3CH2-CH=CH-CH3 each carbon has

one hydrogen

2-pentene each carbon has

conc
one alkyl group
HCl

CH3CH2-CH2-CH-CH3 + CH3CH2-CH-CH2-CH3

Cl Cl
50/50

2-chloropentane 3-chloropentane
ANTI-MARKOVNIKOFF ADDITION
HBr - Peroxides
ANOMALOUS BEHAVIOR OF HBr ADDITION
R
+ HBr

ADDITION OF HBr PRESENTS AN ENIGMA

It does not always follow the

Markovnikoff Rule.

HBr Only
This is a special case which occurs
with only HBr, and not with HCl or HI.
 ADDITION OF HBr
sometimes ... conc.
HBr Markovnikoff
Addition
CH2 CH3
Br
sometimes ... conc.
HBr
CH2 CH2Br
H
Anti-Markovnikoff
Addition

Addition of HBr presents an enigma, sometimes

you get the Markovnikoff product, and sometimes
you dont...... WHY ?
 The presence of oxygen or peroxides causes HBr
addition to proceed in anti-Markovnikoff fashion.
peroxides
CH3CH3CH3CH2 CH CH2 + HBr
present

CH3CH3CH3CH2 CH CH2
H Br

When oxygen is prevented from reaching either the

HBr or the alkene the reaction yields primarily the
Markovnikoff product.
no
CH3CH3CH3CH2 CH CH2 + HBr
peroxides

CH3CH3CH3CH2 CH CH2
Br H
 REVIEW

IONIC MECHANISM

WITH THIS MECHANISM THE

MARKOVNIKOFF PRODUCT
IS OBTAINED
 IONIC MECHANISM FOLLOWS
MARKOVNIKOFF
RULE

-
Br
R R R Br
C C C C C C
+ H
H
+
H O H
H

ionic
the most stable intermediates
carbocation is
formed
 INITIATION

FORMATION AND REACTIONS

OF RADICALS
IN ADDTION TO PROCEEDING
BY AN IONIC MECHANISM,
ADDITION OF HBr CAN ALSO
PROCEED BY A RADICAL MECHANISM

... radical intermediate

:..
A Radicals, also called
free radicals have
at least one unpaired
electron in the
They are often valence shell.
formed by a
homolytic
cleavage of an A ..A 2 A.
unstable bond.
weak bond
STABILITY OF CARBON RADICAL INTERMEDIATES
Radicals are electron-deficient, just like carbocations,
and have the same stability order.

R R
lowest highest
R C R < R C H < R CH2 < CH3
energy energy

tertiary secondary primary methyl

and they are stabilized by resonance and / or hyperconjugation.

()
()
() CH2 () CH2 etc.

() ()
 RADICAL REACTIONS NEED AN INITIATOR
An initiator is a compound that easily forms radicals.

R O O R Peroxides are
heat or
a common type
weak ultraviolet of initiator.
bond light

R O.
the O-O bond
2 is easily broken

Peroxides are formed when air (O2) gets into solutions.

O2
R-H R-O-O-R and R-O-O-H
 SOME RADICAL PROCESSES
Abstraction of a Hydrogen atom Arrow with a single
barb = movement
.. .. or a single electron
R. + H..Br
.. : R H + :Br.
..

Addition to a double bond

secondary
.
X. + H2C.. CH R X CH2 CH R

Recombination
The radical ends up
at the more substituted
R . + . R R R position.

Dissociation
R R R . + . R ( = 2 R. )
 FREE-RADICAL
MECHANISM
INITIATION Gives an anti-
.. .. ..
R O 2 R O . Markovnikoff
.. O
.. R ..
product
.. .. .. ..
R O . .. :
.. + H Br R O
.. H +
:Br.
..

PROPAGATION

Br .
.
+ H2C CH R Br CH2 CH R

. HBr Only
Br CH2 CH R + H Br
H
Br CH2 CH R + Br .
critical step

TERMINATION Br
. Br .
Br CH2 CH R + Br CH2 CH R
.
2 Br CH2 CH R Br CH2 CH CH CH2 Br
R R
 WHY ANTI -MARKOVNIKOFF ?
Anti-
FREE RADICAL Br CH2 CH R
2
Markovnikov
Br adds first .
+H . FAVORED
.. Br CH2 CH R
secondary
.. .
:Br + H2C CH R
.
CH2 CH R
primary
Br

IONIC +
CH2 CH R
H adds first
primary
H
H2C CH R
+ secondary
H CH2 CH R
H+ FAVORED
-
+ Br

CH3 CH R

Br Markovnikov
 HF, HCl and HI

These reagents do not undergo

HBr Only
free radical addition.

When HF, HCl and HI add, you always

obtain the Markovnikoff product.
The unique nature of HBr relates to the energetics of
making and breaking bonds in the propagation step.
critical step H
.C + H-X C + .X + DH
break H-X make C-H

The reaction step is fast (exothermic) for H-Br, but is

difficult for H-F or H-Cl. Compare these bond energies.
BOND ENERGIES ( Kcal/mole )
break H-X make C-H energy difference DH
H-F +135 C-H -99 + 36
unfavored
H-Cl +103 + 4

H-Br +87 - 12 favored

H-I +71 - 28 **
** HI is favored by energetics, but the products are easily re-
versed due to the weak (unstable) C-I bond (52 Kcal/mole).
Prediksikan Produk Mayor dari reaksi berikut!

1. + HBr ...................................

2. H2O2
+ HBr ...................................