Alkenes CnH2n “unsaturated” hydrocarbons

H H
C2H4 ethylene C C
H H
Functional group = carbon-carbon double bond

sp2 hybridization => flat, 120o bond angles

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)

C=C are called “vinyl” carbons

If either vinyl carbon is bonded to two equivalent groups,

then no geometric isomerism exists.

CH3CH=CHCH3 CH3CH2CH=CH2
yes no

CH3
(CH3)2C=CHCH3 CH3CH=CCH2CH3
no yes
Confusion about the use of cis- and trans-. According to
IUPAC rules it refers to the parent chain.

H3 C CH2CH3
C C “cis-”
H CH3

H3 C Cl
????????
C C
H Br
E/Z system is now recommended by IUPAC for the
designation of geometric isomerism.
1. Use the sequence rules to assign the higher priority * to
the two groups attached to each vinyl carbon.
2. * * *

*
(Z)- “zusammen” (E)- “entgegen”
together opposite
 * *
H3 C CH2CH3
C C (Z)-
H CH3

*
H3 C Cl
C C (E)-
H Br
*
Nomenclature, alkenes:
1. Parent chain = longest continuous carbon chain that
contains the C=C.
alkane => change –ane to –ene
prefix a locant for the carbon-carbon double bond using
the principle of lower number.
2. Etc.
3. If a geometric isomer, use E/Z (or cis/trans) to indicate
which isomer it is.
 * *
H3 C CH2CH3
C C
(Z)-3-methyl-2-pentene
H CH3
(3-methyl-cis-2-pentene)

*
H3 C Cl
C C (E)-1-bromo-1-chloropropene
H Br
*
 CH3
CH3CH2 CHCH2CH3
\ /
C=C 3-ethyl-5-methyl-3-heptene
/ \
CH3CH2 H (not a geometric isomer)
-ol takes precedence over –ene

CH2=CHCH2-OH 2-propen-1-ol

CH3CHCH=CH2 3-buten-2-ol
OH
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. dehydrohalogenation of alkyl halides

2. dehydration of alcohols

3. dehalogenation of vicinal dihalide

4. (later)
3. 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.
1. dehydrohalogenation of alkyl halides

| | | |
— C — C — + KOH(alc.)  —C=C— + KX + H2O
| |
H X

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

b) no rearragement 
c) may yield mixtures 
d) Saytzeff orientation
e) element effect
f) isotope effect
g) rate = k [RX] [KOH]
h) Mechanism = E2
rate = k [RX] [KOH] => both RX & KOH in RDS

R-I > R-Br > R-Cl “element effect”

=> C—X broken in RDS

R-H > R-D “isotope effect”

=> C—H broken in RDS

 Concerted reaction: both the C—X and C—H bonds are

broken in the rate determining step.
 Mechanism = elimination, bimolecular E2

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

H
base:

One step! “Concerted” reaction.

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

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

n-butyl bromide 1-butene

CH3CH2CHCH3 + KOH(alc)  CH3CH2CH=CH2

Br 1-butene 19%
sec-butyl bromide +
CH3CH=CHCH3
2-butene 81%
Problem 8.6. What akyl halide (if any) would yield each of the following
pure alkenes upon dehydrohalogenation by strong base?

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

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

note: CH3CH2CH2CHCH3 would yield a mixture! 

X

2-pentene  KOH(alc) + CH3CH2CHCH2CH3

X

2-methyl-2-butene  KOH(alc) + NONE!

 KOH(alc) CH3
????????? CH3CH CCH3 PURE!

2-methyl-2-butene

CH3 KOH(alc) CH3 CH3

CH3CHCHCH3 H2C CHCHCH3 + CH3CH CCH3
X

CH3 KOH(alc) CH3 CH3

CH3CH2CCH3 CH3CH2C CH2 + CH3CH CCH3
X

No alkyl halide will yield 2-methyl-2-butene as the only product of dehydrohalogenation

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
Elimination, unimolecular E1

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

b) rearragement possible 
c) may yield mixtures 
d) Saytzeff orientation
e) element effect
f) no isotope effect
g) rate = k [RW]
E1:
Rate = k [RW] => only RW involved in RDS

R-I > R-Br > R-Cl “element effect” =>

C—X is broken in RDS

R-H  R-D no “isotope effect” =>

C—H is not broken in the RDS
Elimination, unimolecular E1

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

b) rearragement possible “
c) may yield mixtures
d) Saytzeff orientation
e) element effect C—W broken in RDS
f) no isotope effect C—H not broken in RDS
g) rate = k [RW] only R-W in RDS
alkyl halide + base  substitution or elimination?

X
C C
H SN2

:Z
E2
R-X + base  ????????
1) If strong, conc. base:
CH3 > 1o => SN2  R-Z 
3o > 2o => E2  alkene(s)
2) If weak, dilute base:
3o > 2o > 1o => SN1 and E1  R-Z + alkene(s) 
3) If KOH(alc.)
3o > 2o > 1o => E2  alkene(s) 
 SN2
CH3CH2CH2-Br + NaOCH3  CH3CH2CH2-O-CH3
1o

CH3 E2 CH3
CH3CCH3 + NaOCH3  CH3C=CH2 + HOCH3
Br
3o
E2
CH3CH2CH2-Br + KOH(alc)  CH3CH=CH2
 CH3 CH3
CH3CHCHCH3 + dilute OH-  CH3CCH2CH3 SN1
Br OH
 CH3
+ CH3C=CHCH2 E1
CH3
CH3CHCHCH3 CH3
 + CH2=CCH2CH3 E1

 [1,2-H]

CH3
CH3CCH2CH3

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
note: reaction #3 for alcohols!
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

rearrangement!  + 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.
Syntheses, alkenes:

1. dehydrohalogenation of alkyl halides

E2
2. dehydration of alcohols
E1
3. dehalogenation of vicinal dihalide

4. (later)
 H+
R-OH

KOH
R-X Alkene
(alc.)

Zn

vicinal
dihalide
Alkyl halides:
nomenclature
syntheses:
1. from alcohols
a) HX b) PX3
2. halogenation of certain alkanes
3.
4.
5. halide exchange for iodide
reactions:
1. nucleophilic substitution
2. dehydrohalgenation
3. formation of Grignard reagent
4. reduction
Alcohols:
nomenclature
syntheses
later
reactions
1. HX
2. PX3
3. dehydration
4. as acids
5. ester formation
6. oxidation