Chapter 8 Alkenes and

alkynes I.
Properties and synthesis
8.1 Introduction
Alkenes are hydrocarbons whose
molecules contain the carbon-carbon
H
H
Ethene or
double
C
C bond.
H
ethylene
H

Hydrocarbons whose molecules contain

or
or ethyne
HC
CH
the carbon-carbon
triple acetylene
bond are
called
alkynes.

8.2 Nomenclature of alkenes and

cycloalkenes
H2C

C
H

CH3

H2C

CH3

CH3

IUPAC: Propene
common; Propylene

IUPAC: 2-MethylPropene
Common; Isobutylene

Cyclohexane

-ane-ene

Cyclohexene

The IUPAC rules for naming

alkenes are similar in many
respects to those for naming
alkanes
1. Selecting the longest chain that
contains the double bond
2. Number the chain
1
H2C

CHCH2CH3

3 2

1-Butene
(not 3-butene)

1 2 3 4 5 6
CH3CH=CHCH2CH2CH3
6 5
4 3 2 1
2-Hexene
(not 4-hexene)

3. Indicate the locations of

the substituent groups
CH3

CH3
H3C

CHCH2CH3

3 4

CH3

CH3C=CHCH2CHCH3
1 2 3 4
5 6

2-Methyl-2-pentene
(not 4-Methyl-3-pentene)

2,5-Dimethyl-2-hexene
(not 2,5-Dimethyl-4-hexene)

CH3
H3C

C
H

CHCH2C

3 4

CH3

5 6
CH3
5,5-Dimethyl-2-hexene
(not 2,2-Dimethyl-4-hexene)

CH3CH=CHCH2Cl
4 3
2 1
1-Chloro-2-butene
(not 4-chloro-2-butene)

4. Number substituted cycloalkenes in

the way that gives the carbon atoms of
the double bond the 1- and 2positions and that also gives the
substituent groups the lower numbers
at the first point of difference
1
2

1
2
3

4
1-Methylcyclopentene (1- 3,5-Dimethylcyclohexene (3,5-
(not 2-methylcyclopentene)
(not 4,6-Dimethylcyclohexene)

5. Two frequently encountered

alkenyl groups are the vinyl
group and the allyl group.
H2C

C
H

H2C

C
H

CH2

H3C

HC

C
H2

The vinyl group ( The ally group ( The Propylene group (

Br

CH2Cl

CH2Br

IUPAC: Bromoethene IUPAC: 3-Chloropropene IUPAC: 3-Bromopropene

Common; vinyl bromide Common; allyl chloride
Common; allyl bromide
(

(
(

6. Designate the geometry of a

double bond of a disubstituted
alkene with the prefixes cisand transCl

Cl

Cl

Cl

cis-1,2-Dichloroethene
Br

trans-1,2-Dichloroethene
Cl

How to do?
H

8.2A The ( E )-( Z ) System for

designation alkene
diastereomers
Higher priority

Br

Higher priority

Cl

Br

Cl

Higher priority
(Z)-2-Bromo-1-chloro-1-floroethene

Higher priority
CH3

H3C

CH3

(E)-2-Bromo-1-chloro-1-floroethene

Higher priority

H3C

H
H

CH3

Higher priority
(Z)-2-Butene
(cis)-2-Butene

(E)-2-Butene
(trans)-2-Butene

Higher priority
Cl

Cl

Cl

Br

H
H

Cl

Br

Cl

Cl

Br

(E)-1-Bromo-1,2-dichloroethene
(cis)-2-Bromo-1,2-dichloroethene

(Z)-1-Bromo-1,2-dichloroethene
(trans)-2-Bromo-1,2-dichloroethene

(HHH)
Higher priority H3C
CH3
CH3CH2

CH3

CH3

CH2CH3

(CHH)
(E)-3-Methyl-2-pentene
(cis)-3-Methyl-2-pentene

H3C

CH2CH3

CH3

(Z)-3-Methyl-2-pentene
(trans)-3-Methyl-2-pentene

8.3 Nomenclature of
alkynes
8.3A IUPAC Nomenclature
Unbranched alkynes, for example,
are named by replacing the ane of
the name of the corresponding
alkane with the ending yne. The
chain is numbered in order to give
the carbon atoms of the triple bond
the lower possible numbers.

CH2Cl

CH2Cl

IUPAC: Ethyne
IUPAC: 3-Chloropropyne IUPAC: 1-Chloro-2-butyne
Common; acetylene
(3-
(1--2-
(

Acetylenic hydrogen

A terminal alkyne
H3C

C:

The propynide ion

8.4

Physical properties of
alkenes and alkynes
8.5 Hydrogenation of alkenes
H2C

CH2

H2

H2C

CH

CH3

Ni, Pd or Pt
25oC
H2

CH3CH3
CH3CH2CH3

an addition reaction
Reduction (
Catalytic hydrogenation (

8.6 Hydrogenation: The function

of the catalyst
R

HC

CH

Ni, Pd or Pt

R + H2

25 C

HC

CH

Catalytic hydrogenation (
No cat

PE

Cat

G(1)

G(1)

G(2)

G(2)
R HC

CH R + H2
o

-1

= - 30kcal mol

Reaction coordinate

CH2

CH2

Catalytic hydrogen and Syn-addition

H

+ H2
Surface of metal
catalyst
H

H
C

H
H

H
H

H
H

8.6A Syn and anti additions

A Syn addition
+

Y
X

An anti addition
+

Y
X

8.7A Syn addition of

hydrogen: Synthesis of cisalkenes
NaBH
Ni(OCOCH3)2

CH3CH2OH
H2

H2

Ni2B (P-2)

Syn addition H3C

Ni2B (P-2)

Syn addition

Pd/CaCO3, quinoline
(Lindlar's catalyst)

CH3
H

H3C
H

CH3
H

8.7B Anti addition of hydrogen:

Synthesis of trans-alkenes
anti addition
1, Li, CH3CH2NH2
2, NH4Cl, -78oC

H3C

CH3

(E)-2-Butene

Na / NH3 (l)
anti addition

H3C
H

H
CH3

(E)-2-Butene

8.9 Relative stabilities of

alkenes
8.9A Heats of hydrogenation
H3C

CH3 H C
3

Potential energy

CH3CH2CH=CH2 + H2
H

+ H2

+ H2

CH3

Ho = -30.3 kcal mol-1

Ho = -28.6 kcal mol-1
Ho = -27.6 kcal mol-1

CH3CH2CH2CH3

CH3CH2CH2CH3

CH3CH2CH2CH3

The order of stabilities;

H3C
H

H3C

CH3

CH3CH2CH=CH2
CH3

8.9B Relative stabilities from

heats of combustion
H3C

CH3 H C
3

Potential energy

CH3CH2CH=CH2 + O2
+ O2

+ O2

CH3

Ho = -649.8 kcal mol-1

Ho = -648.1 kcal mol-1
Ho = -647.1 kcal mol-1

CO2 + H2O

CO2 + H2O

CO2 + H2O

The order of stabilities;

H3C
H

H3C

CH3

CH3CH2CH=CH2
CH3

8.9C Overall relative stabilities

of alkenes
The order of stabilities;
R
R

R
R

R
R

H
R

R
R

RCH=CH2
R

CH2=CH2

8.10 Cycloalkenes
The rings of cycloalkenes containing five
carbon atoms or fewer exist only in the cis
form. Therefore, fewer exist in the trans
form because of the ring strain.
H

Cyclopropene

H
H

Cyclobutene

Cyclopentene

Cyclohexene

Cis- and trans-Cycloalkenes

H

cis-Cyclohexene
H

trans-Cyclohexene

H
H
H

cis-Cyclooctene

trans-Cyclooctene

8.11 Synthesis of alkenes via

elimination reactions
Dehydrohalogenation of alkyl halides;
H

Base; KOH/CH3CH2OH
X

+ HX

Or CH3CH2ONa/CH3CH2OH

Dehydration of alcohols
H

H+

, heat
-H2O

OH

+ H2O

Debromination of vic-Dibromides
Br

Zn, CH3CO2H
Br

+ ZnBr2

8.12 Dehydrohalogenation of
alkyl halides
Dehydrohalogenation of alkyl halides;

Base :

Base; KOH/CH3CH2OH
X

Elimination
1,2-Elimination

Or CH3CH2ONa/CH3CH2OH
E2 reaction mechanism

+ HX

8.12A E2 reactions: The

orientation of the double bond in
the product. Zaltsevs Rule
(
CH3

CH3CH=C

Base :

H
H

H3CH2C

CH3
CH3
Br

Elimination
1,2-Elimination

CH3CH2ONa/CH3CH2OH
70oC
E2 reaction mechanism

CH3

2-Methyl-2-butene
(69%)
(more stable)
CH3

CH3CH2C=CH2
2-Methyl-1-butene
(31%)
(less stable)

----

CH3CH2CHBrCH3

CH3CH2ONa/CH3CH2OH

CH3CH=CHCH3 + CH3CH2CH=CH2
minor
major

CH3

CH3CH2CCH3

CH3

CH3CH2ONa/CH3CH2OH

Cl

CH3CH=C(CH3)2 + CH3CH2C=CH2
minor
major

8.12B An exception to Zaitsev's Rule;

CH3
CH3

CH3CH2CCH3
Br

CH3CCH3
OK
CH3

CH3CCH3

CH3

CH3CH=C(CH3)2 + CH3CH2C=CH2
major
minor

OH

The large tert-butoxide ion appears to have difficulty removing one

of the internal (2o) hydrogen atoms because of great crowding at that site
in the transition state. It removes one of the more exposed (1o) hydrogen
atoms of the methyl group instead.
Hofmann rule----the less substituted alkene

8.12C The stereochemistry of

E2 reactions:
-

Base :

Base :

Elimination
1,2-Elimination
Anti-Elimination

Elimination
1,2-Elimination
Syn-Elimination

H3C

CH2(CH3)2

H3C

CH(CH3)2

Cl

Cl

H
H3C
CH(CH3)2
H

H3C
CH(CH3)2
Cl

H
Cl

H
H3C
CH(CH3)2
H
H

CH3CH2ONa

H3C

(78%)
H

CH(CH3)2
CH3CH2OH
H
H
Cl

H3C
CH(CH3)2

(22%)

Cl
H

H3C
CH(CH3)2
Cl

H3C H

less stable

more stable

CH(CH3)2

H
H
H3C

H
Cl
H
H3C H

CH3CH2ONa

less stable

CH(CH3)2

CH3CH2OH

H
H

(100%)

CH(CH3)2

H3C H

(0%)

CH(CH3)2

8.13 Dehydration of
alcohols
H+, H2SO4, H3PO4

OH

+ H2O

heat

1. The experimental conditions----temperature

and acid concentration
CH3CH2OH

concd, H2SO4
180oC
OH

CH2=CH2 + H2O

+ H2O

85% H3PO4
165-170oC

(CH3)3COH
tert-Butyl alcohol

20% H2SO4
85oC

(80%)
H2C

C(CH3)3

+ H2O

2-Methylpropene
84%

Ease of Dehydration
R
R

C
R

R
OH

OH

tertiary alcohol ( Secondary alcohol

3o Alcohol
2o Alcohol

OH

Primary alcohol
1o Alcohol

8.13A Mechanism of alcohol

dehydration: An E1 reaction
CH3
H3C

OH

H2SO4 or H3PO4

E1
CH3

tert-Butyl alcohol (
3o Alcohol

2-Methylpropene
or isobutene

H2 O

E1 reaction

CH3
H3C

H2SO4 or H3PO4

OH

H3C

C+

Rate-Limiting
Slow

CH3

Fast
CH2

H+

Step 1
fast

C
CH3

Step 3
Step 2

CH3

H3C

Slow

fast

CH3

- H2O

OH

H lose hydrogen

Carbocation

tert-Butyl alcohol (
3o Alcohol

H3C

CH3

C+
CH2

Carbocation

Ease of dehydration for E1 reaction

R
R

R
OH

OH

CH3
3o

CH3

Primary alcohol
1o Alcohol

CH3

C+

2o

1o

Tertiary C+
Secondary C+
(

OH

CH3

CH3

C+

tertiary alcohol ( Secondary alcohol

3o Alcohol
2o Alcohol

CH3

Primary C+

The relative stability of carbocations

(Most stable)

CH3+

methyl cation

(least stable)

8.15 Carbocation stability and

the occurrence of molecular
rearrangements (

H3C

CH3 CH3

CH3

CH3
CHCH3

85% H3PO4
E1 reaction

CH3 OH

3,3-Dimethyl-2-butanol
(3,3-
3o Alcohol

H3C

CCH3

+ H3C

C
H

C=CH2

CH3

2,3-Dimethyl-2-butene
(major product)

3,3-Dimethyl-1-butene
(minor product)

CH3

CH3
H3C

CHCH3

CH3

85% H3PO4
E1 reaction

H3C

+ H3 C

CCH3

CH3

CH3

C
H

C=CH2

CH3

OH

3,3-Dimethyl-2-butanol
(3,3-
3o Alcohol

2,3-Dimethyl-2-butene
(major product)

3,3-Dimethyl-1-butene
(minor product)

H+

CH3
H3C

-H2O
CHCH3

CH3 H OH

+
Protonated alcohol

CH3

CH3
H3C

CHCH3

H3C

CHCH3
CH3

CH3

2o C+

3o C+

The type of rearrengement

CH3
CH3

methanide migration CH3- CH3

+
H3C
C
CHCH3
CHCH3
+

H
C

3o C+

2o C+

3o C+

CH3

CH3

H3C

2o C+

hydride migration (H-) CH3

CHCH3

H3C

CH2CH3

CH3

CH3
H3C

C
CH3

methanide migration CH3- CH3

+
H3C
C
CH2CH3
CH2
+

1o C+

3o C+

CH3

OH
CHCH3

H+

CH3

acid

CH3

1,2-Dimethylcyclohexene

Rearrengement mechanism (E1 reaction)

CH3

CH3

OH

CH3

OH2

lose -H2O

H+
CHCH3

acid

2o Carbocation

lose - H
CH3

3 Carbocation

CHCH3

CHCH3

CH3

- H+

CH3
CH3

1,2-Dimethylcyclohexene

8.16 Alkenes by
debromination of vicinal
dibromides
C

X= Cl, Br

A vic-dihalide
(-
X
C

C
X

A gem-dihalide
(-

H
H3C

Br

Br

NaI

CH3

acetone

H3C

Br

CH3

+ I2 + 2NaBr

Zn
H

Br

A gem-dibromo
(-

CH3COOH

CH2

+ ZnBr2

8.17 Summary of methods

for the preparation of
alkenes
1. Dehydrohalogenation of alkyl halides
CH3CH2CHCH3
Br

CH3CH2CHCH3
Br

CH3CH2ONa
CH3CH2OH
(CH3)3CONa
(CH3)3COH

CH3CH=CHCH3 + CH3CH2CH=CH2
(cis and trans, 81%)
(19%)
CH3CH=CHCH3 + CH3CH2CH=CH2
(cis and trans, 47%)
(53%)

2. Dehydration of alcohols
1. Dehydration of alcohol-----Acid as a catalyst
CH3CH2CHCH3
OH

CH3

CH3CH2CCH3
OH

cocd H2SO4
o

180 C

CH3CH=CHCH3 + CH3CH2CH=CH2
(cis and trans, 70%)
(30%)

CH3

CH3

20% H2SO4 or H3PO4

CH3CH=CCH3 + CH3CH2C=CH2
o
85 C
(20%)
(80%)

3. Dehalogenation of vicdibromides

CH3CHCHCH3
Br Br

Zn, CH3COOH

CH3CH=CHCH3
(cis and trans)

4. Hydrogenlation of
alkynes
H2

H3C

CH3

Ni2B
H

Syn addition
H3C

CH3
H3C

Li or Na
NH3, RNH2

CH3

anti addition

8.18 Synthesis of alkynes by

elimination reaction
NH2H
R

C
H

-HBr

C
H

Br2

Br

Br

H
R

NaNH2
-HBr

C
Br

CH3CH2CH=CH2

Br2

CH3CH2CHBrCH2Br

NaNH2
o

110-160 C

CH3CH2

CH

Cl

PCl5
Cl

0 oC
(-POCl3)

Methyl Cyclohexyl
Ketone (

1, 3NaNH2
2, H+

A gem-dichloride
70-80%

Cyclohexylacetylene
(

8.19 The Acidity of terminal

alkynes
The hydrogen atoms of ethyne are
considerably more acidic than those of
ethene or ethane
H

pKa = 25

pKa = 44

pKa = 50

Relative acidity;
HC

C: -

CH2=CH:

CH3CH2 :-

Relative Basicity;
CH3CH2 :-

CH2=CH:-

HC

C: -

Relative Acidity
H2 O

ROH

pKa; 15.7

HC

16-17

CR

25

NH3

CH2=CH2

38

44

CH3CH3

50

Relative Basicity;
OH-

RO-

HC

CR

NH2-

CH2=CH:-

CH3CH2 :-

Conjugate acid) (Conjugate base)

8.20 Replacement of the

acetylenic hydrogen atom of
terminal alkynes

Sodium ethynide and other sodium

alkynides can be prepared by treating
terminal alkynes with sodium amide
(NaNH2) in liquid ammonia
H

H3C

H +

NaNH2

H + NaNH2

NH3 (l)

NH3 (l)

HC

H3C

CNa + NH3
CNa + NH3

It applied synthesis (SN2)

RC

CNa

Sodium alkynide

Br

RCH2
Primary alkyl halide

RC

Br

CCH2R

+ NaBr

R
C: -

SN2

SN 2

RC

H
H

an inversion of configration

+
Sodium ethynide
HC

CNa

H3CH2CC

CNa

Sodium butynide

SN2

Br
HCH2
Methyl bromide

CH3CH2

CCH3 + NaBr

Propyne

Br

S N2

ethyl bromide

CH3CH2

CCH2CH3

3-Hexyne
75%

H2
Ni2B ( P - 2)

H3CH2C

CH2CH3

H3CH2C
H3CC

C: -

Br

H3C
H

R-

Z-3-Hexene
(Cis-3-Hexene)
CH2CH3

SN2

H3CC

CH3
H

an inversion of configration
S-

8.21 Other metal acetylides

Ethyne and terminal alkynes also form metal
derivatives with silver and copper (I) ions
R

CH

CH

+ Cu(NH3)2+ + OH+ Ag(NH3)2

+ OH

H2O
H2O

CCu

+ H2O + 2NH3

CAg

+ H2O + 2NH3

Cu(NH3)2+ + OHR

No reaction

Ag(NH3)2+ + OH-

No reaction

As a method for separating

terminal alkynes from alkynes
that have an internal triple bond
H3C

H3C

CH

CH3

Ag(NH3)2+ + OHor Cu(NH3)2+ + OH-

No precipitate
R
R

CCu

CAg

or

Homework; 8.22, 8.24, 8.25,

8.29, 8.30
Happy New Year!
Good luck for you final
organic chemistry test!