ALKENES

Alkenes
CnH2n “unsaturated” hydrocarbons

C2H4 ethylene
H H
Functional group = carbon-carbon double bond
C C
sp2 hybridization => flat, 120o bond angles
H H
σ bond & π bond => H2C=CH2

No rotation about double bond!

C3H6 propylene CH3CH=CH2

C4H8 butylenes CH3CH2CH=CH2

α-butylene
1-butene

CH3
CH3CH=CHCH3 CH3C=CH2
β-butylene isobutylene
2-butene 2-methylpropene
there are two 2-butenes:

H H H CH3
C C C C
H3C CH3 H3C H
cis-2-butene trans-2-butene

“geometric isomers” (diastereomers)

Physical properties:
non-polar or weakly polar
no hydrogen bonding
relatively low mp/bp ~ alkanes
water insoluble

Importance:
common group in biological molecules
starting material for synthesis of many plastics
Syntheses, alkenes
1. Dehalogenation of vicinal dihalides

| | | |
—C—C— + Zn  —C=C— + ZnX2
| |
X X

eg.
CH3CH2CHCH2 + Zn  CH3CH2CH=CH2 + ZnBr2
Br Br
Not generally useful as vicinal dihalides are usually made
from alkenes. May be used to “protect” a carbon-carbon
double bond.
2. Dehydrohalogenation of alkyl halides

| | | |
—C—C— + KOH(alc.)  —C=C— + KX + H 2O
| |
H X

a) RX: 3o > 2o > 1o

b) no rearrangement
c) may yield mixtures
d) Mechanism = E2
 Mechanism = elimination, bimolecular E2

W
RDS
C C C C + H:base + :W

H
base:

One step
CH3CHCH3 + KOH(alc)  CH3CH=CH2
Br
isopropyl bromide

CH3CH2CH2CH2-Br + KOH(alc)  CH3CH2CH=CH2

n-butyl bromide

CH3CH2CHCH3 + KOH(alc)  CH3CH2CH=CH2

Br 1-butene 19%
sec-butyl bromide +
CH3CH=CHCH3
2-butene 81%
Problem: What akyl halide (if any) would yield each of the following pure
alkenes upon dehydrohalogenation by strong base?

CH3 CH3
CH3CCH3 or CH3CHCH2-X + KOH(alc) → isobutylene
X

CH3CH2CH2CH2CH2-X + KOH(alc) → 1-pentene

CH3CH2CHCH2CH3 + KOH(alc) → 2-pentene

X

KOH(alc) + ? → 2-methyl-2-butene
Saytzeff orientation:
Ease of formation of alkenes:
R2C=CR2 > R2C=CHR > R2C=CH2, RCH=CHR > RCH=CH2 > CH2=CH2

Stability of alkenes:
R2C=CR2 > R2C=CHR > R2C=CH2, RCH=CHR > RCH=CH2 > CH2=CH2

CH3CH2CHCH3 + KOH(alc)  CH3CH2CH=CH2 RCH=CH2

Br 1-butene 19%
sec-butyl bromide +
CH3CH=CHCH3 RCH=CHR
2-butene 81%
 KOH (alc)
CH3CH2CH2CHBrCH3  CH3CH2CH=CHCH3 + CH3CH2CH2CH=CH2
71% 29%

CH3 CH3 CH3

CH3CH2CCH3 + KOH(alc)  CH3CH=CCH3 + CH3CH2C=CH2
Br 71% 29%

CH3 CH3 CH3

CH3CHCHCH3 + KOH(alc)  CH2=CHCHCH3 + CH3CH=CCH3
Br major product
Order of reactivity in E2: 3o > 2o > 1o

CH3CH2-X  CH2=CH2 3 adj. H’s

CH3CHCH3  CH3CH=CH2 6 adj. H’s & more stable

X alkene

CH3 CH3
CH3CCH3  CH=CCH3 9 adj. H’s & most stable
X alkene
Elimination unimolecular E1

RDS
1) C C C C + :W
H W H

-H
2) C C C C
H
2. dehydration of alcohols:

| | | |
— C — C — acid, heat  — C = C — + H2O
| |
H OH

a) ROH: 3o > 2o > 1o

b) acid is a catalyst
c) rearrangements are possible
d) mixtures are possible
e) Saytzeff
f) mechanism is E1
Mechanism for dehydration of an alcohol = E1

1) C C + H C C
H OH H OH2

RDS
2) C C C C + H2O
H OH2 H

3) C C C C + H
H
CH3CH2-OH + 95% H2SO4, 170oC  CH2=CH2

CH3 CH3
CH3CCH3 + 20% H2SO4, 85-90oC  CH3C=CH2
OH

CH3CH2CHCH3 + 60% H2SO4, 100oC  CH3CH=CHCH3

OH
+ CH3CH2CH=CH2

CH3CH2CH2CH2-OH + H+, 140oC  CH3CH2CH=CH2

+ CH3CH=CHCH3
Synthesis of 1-butene from 1-butanol:

CH3CH2CH2CH2-OH + HBr  CH3CH2CH2CH2-Br

SN2 E2  KOH(alc)

CH3CH2CH=CH2
only!
To avoid the rearrangement in the dehydration of the alcohol the alcohol is first
converted into an alkyl halide.
3. Witting Reaction
Aldehydes and ketones react with phosphorus ylides to yield
alkenes and triphenyl phosphine oxide

Example
Reaction mechanism

Ylide Aldehyde Betain Betain Isomer

Alkene Triphenylphosphine
Oxaphopsphetane
Oxide
Brain Games
 Chemical properties
Reactivity of C=C
• Electrons in pi bond are loosely held.
• Electrophiles are attracted to the pi electrons.
• Carbocation intermediate forms.
• Nucleophile adds to the carbocation.
• Net result is addition to the double bond.
 1. Hydrogenation
Addition of hydrogen in the presence of catalysts
 Alkenes shows addition reaction
Electrophilic Addition
• Step 1: Pi electrons attack the electrophile.
E
+
C C + E C C +

• Step 2: Nucleophile attacks the carbocation.

E E Nuc
_
C C + + Nuc: C C

=>
 Free Radical Initiation
• Initiation
heat
R O O R R O + O R

• Propagation

R O + H Br R O H + Br

• Termination

R-O. + Br. R-O-Br

 1. Addition of halides
Protonation of double bond yields the most stable
carbocation. Positive charge goes to the carbon
that was not/least protonated.
CH3
CH3 C CH CH3
CH3 +
H
CH3 C CH CH3 _
+ Br
H Br X CH3
CH3 C CH CH3
+
H
Mechanism

CH3 CH3
_
CH3 C CH CH3 CH3 C CH CH3 + Br
+
H
H Br

CH3 CH3
CH3 C CH CH3 CH3 C CH CH3
+
H Br H
_
Br
 Markovnikov and Anti-
Markovnikov additions
Anti-Markovnikov
additions
CH3
CH3 C CH CH3
CH3 xide Br
E p-o
CH3 C CH CH3 + Br CH3
CH3 C CH CH3
Br
Markovnikov additions
2. Hydration of Alkenes
+ H OH
H
C C + H2O C C
alkene
alcohol

 Reverse of dehydration of alcohol

 Use very dilute solutions of H2SO4 or H3PO4 to
drive equilibrium toward hydration.
Mechanism for Hydration
H
H
+ +
C C + H O H C C + H2O

H
+
H H O H
+
C C + H2O C C

H
+ H
H O H H O
+
C C + H2O C C + H3O
Oxidative cleavage of Alkenes

1. Alkene reacts with a peroxyacid to form an epoxide (also

called oxirane).
O O O
C C + R C O O H C C + R C O H

Mechanism OH
C C
+ H O
H3O OH
O H
O
C C C C C C
O
H2O H H H2O
Cleavage with MnO4-

H CH3
H CH3 KMnO4
C C H3C C C CH3
CH3 CH3 (warm, conc.)
OH OH

H CH3
H3C C + C CH3
O O

OH
H3C C
O
Ozonolysis

O
H CH3 O3 H CH3
C C C C
CH3 CH3 O O
H3C CH3
Ozonide

H O
(CH3)2S CH3
C O O C + CH3 S CH3
H3C CH3
DMSO