Module on Preparation and Reaction of Alkenes Organic Chemistry

ALKENES

PREPARATION OF ALKENES

1. Dehydrohalogenation of alkyl halides.

Ease of dehydrohalogenation
alcohol
— C—C— + KOH —C=C— + KX + H2O of alkyl halides
3° > 2 °> 1°
H X

Examples:
KOH (alc)
CH3CH2CH2CH2Cl CH3CH2CH=CH2
n-Butyl chloride 1-Butene

KOH (alc)
CH3CH2CHClCH3 CH3CH=CHCH3 + CH3CH2CH=CH2
sec-Butyl chloride 2- Butene 1-Butene
80% 20%

2. Dehydration of alcohols.
acid
—C—C— —C=C— + H2O Ease of dehydration of alcohols
165-180oC Alkenes 3° > 2 °> 1°
H OH
Alcohols

Examples:

H H H H
acid
H—C— C—H H— C=C—H + H2O
Ethylene
H OH
Ethyl alcohol

acid
CH3CH2CH2CH2OH CH3CH2CH=CH2 + CH3CH=CHCH3
n- Butyl alcohol 1- Butene 2-Butene
Chief Product

acid
CH3CH2 —CH—CH3 CH3CH=CHCH3 + CH3CH2CH=CH2
| 2-Butene 1- Butene
OH Chief Product
sec-Butyl alcohol

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DEHYDROHALOGENATION OF ALKYL HALIDE

 1,2 elimination (loss of β – hydrogen)

Saytzeff Rule: In dehydrohalogenation, the preferred product is the alkene

that has the greater no. of alkyl groups attached to the doubly bonded carbon
atom. The more stable the alkene is, the faster it is formed.

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

1, 2 elimination

— C— C — + :B C=C + h: B + :W

Substrate base alkene protonated leaving group

Base

Kinetics of Dehydrohalogenation: Duality of mechanism

As ordinarily carried out, with a concentrated solution of a strong base,
dehydrohalogenation follows second order kinetics (E 2). That is the rate of alkene
formation depends upon the concentration of two substances: the alkyl halide and the
base. This second order kinetics is observed for all class of alkyl halide.

Rate = k [RX] [: B]

E2 mechanism (bimolecular elimination)

X
|
-
—C— C— → : X + C = C + H:B

H
:B

Base pulls a proton away from the carbon; simultaneously a halide ion departs
and the double bond forms, the halogen takes the electron pair behind to form the
double bond.

E1 mechanism (unimolecular elimination)

P a g e | 2The rate of elimination depends upon the concentration of the alkyl

halide and is independent on the concentration of the base.
Rate = k [RX]

Steps:

X
| + |
1. —C—C :X + —C—C (slow)
| |
H H
a carbocation

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+ |
2. — C — C — C=C + H:B
(fast)
H
:B

1. Substrate undergoes slow heterolysis to form halide ion and a carbocation.

2. The carbocation rapidly loses a proton to the base and forms the alkene
 The more concentrated the base, the more E2 is favored over E1

DEHYDRATION OF ALCOHOL

Steps:

1. Protonation of alcohol
2. The protonated alcohol undergo heterolysis to form carbocation and water
3. Carbocation loses and proton to the base to yield alkene.

1)
—C—C— + H:B —C—C— + :B
+
H OH H OH2

2)
—C— C— —C—C— + H2 O
+
+
H OH2 H

3) | | \ /
C—C— C=C + H: B
| + / \
H

:B

3. Dehalogenation of vicinal dihalides

—C—C— + Zn —C=C— + ZnX2

X X

Example:
Zn
CH3CHBrCHBrCH3 CH3CH=CHCH3
2,3- Dibromobutane 2- Butene

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4.Reduction of alkynes

R R
H
2 \ /
Lindlar catalyst C= C syn or cis
R—C ≡ C—R / \
An alkyne H H

Na or LiNH3 R H
\ /
C=C anti or trans
/ \

H R

REACTIONS OF ALKENES

Addition Reaction

—C=C— + YZ —C—C—

Y Z

Electrophilic Addition

The general mechanism of electrophilic addition in alkenes is shown in the

following equations:

a.) X — Y X+ + Y– ionization of the adding reagent

Electrophile nucleophile

\ / | |
b.) C = C X + —C—C— attack of the electrophile
+
/ \ |
Y
carbocation

| | | |
–
c.) —C—C— :Y —C—C— attack of the nucleophile
| + | |
X X Y

In equation a, the heterolytic cleavage of the X-Y bond results in the

formation of the nucleophile and electrophile. The electrophile then attacks the
double bond (equation b) and uses the pair of pi electrons to form a sigma bond
with one of the carbon atoms. The specie that results (enclosed in a rectangle),
the intermediate of the reaction, is called a carbocation. A carbocation is an
intermediate that contains a positively charged carbon atom (with only six
electrons in its valence shell). The carbocation is then attacked by nucleophile
which offers a pair of electrons to form the other sigma bond.

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1. Addition of hydrogen. Catalytic hydrogenation

Pt, Pd, or Ni
—C=C— + H2 —C—C

H H
Example:
H NI
CH3CH=CH2 2, CH3CH2CH3
Propene Propane
(Propylene)

2. Addition of halogens.

| | | |
—C=C— + X2 — C— C— X2 = Cl2 , Br2
| |
X X
Example:
Br in CCl
CH3CH=CH2 2 4 CH3CHBrCH2Br
Propene 1,2- dibromopropane
(Propylene) (propylene bromide)

3. Addition of hydrogen halides.

—C=C— + HX —C—C HX = HCl, HBr, HI

H X

Examples:
HI
CH3CH=CH2 CH3CHICH3
Propene 2-Iodopropane
(Isopropyl iodide)

no peroxides
CH3CHBrCH3 Markovnikov addition
2-Bromopropane
HBr
CH3CH=CH2 (Isopropyl bromide)
peroxides
CH3CH2CH2Br Anti-Markovnikov addition
1-Bromopropane
(n-Propyl bromide)

Markovnikov’s Rule:

In hydrohalogenation of an alkene or alkyne, the hydrogen atom of HX becomes

bonded to the carbon atom that had the greatest number of hydrogen atoms in the
starting alkene or alkyne.

4. Addition of sulfuric acid

| | | |
—C=C— + H2SO4 — C— C—
| |
H OSO3H

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conc. H SO
Example: CH3CH=CH2 2 4 CH3CHCH3
Propene |
OSO3H
Isopropyl hydrogen sulfate

5. Addition of water. Hydration

| | | |
H+
—C=C— + HOH —C—C—

H OH

Example:
H O, H+
CH3CH=CH2 2 CH3CHCH3
Propene |
OH
Isopropyl alcohol
(2-Propanol)

6. Halohydrin formation

| | | |
—C=C— + X2 + H2O —C—C— + HX X2= Cl2, Br2
| |
X OH

Example:
Cl , H O
CH3CH=CH2 2 2 CH3CH—CH2
Propylene | |
(Propene) OH Cl
Propylene chlorohydrin
(1-Chloro 2-propanol)

7. Oxymercuration-demercuration.

\ / | | | |
NaBH
C=C + Hg(OAc)2 + H2O —C—C— 4 —C —C—
/ \ | | | |
Mercuric acetate OH HgOAc OH H
Markovnikov
Addition

Examples:

CH3 CH3
| |
CH3 —C —CH=CH2 Hg(OAc)2, H2O NaBH
4 CH3—C—CH—CH3
| | |
CH3 CH3 OH
3,3-Dimethyl-1-butene 3,3-Dimethyl-2-butanol
No rearrangement

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8. Hydroboration-oxidation

\ / | | | |
H O , OH
C=C + (BH3)2 —C—C— 2 2 —C—C— + B(OH)3
/ \ Diborane
H B H OH
/ \ Anti-Markovnikov
Alkylborane orientation

Examples:

(BH ) H O , OH
32 2 2 CH3 H syn-Addition

CH3 H OH
1-Methylcyclopentene trans-2-Mehtyl-1-cyclopentanol

CH3 CH3
| |
(BH ) H O , OH
CH3 —C —CH=CH2 32 2 2 CH3 —C —CH2 —CH2OH

CH3 No rearrangement CH3

3,3-Dimethyl-1-butene 3, 3-Dimethyl-1-butanol

9. Polymerization
Polymerization – joining together of many small molecules to form very large molecule

Example:

heat pressure
nCH2=CH2 —CH2—CH2—CH2—CH2 or (—CH2—CH2—CH2—) n
polyethylene-plastic material in packaging
O , heat
nCH2=CHCl 2 —CH2—CH—CH2—CH—CH2—CH
Or
Cl Cl Cl

(—CH2—CH—) n
|
Cl polyvinyl chloride

10. Epoxidation

| | | |
—C=C— + C6H5CO2OH —C—C— + C6H5COOH
Peroxybenzoic \ /
Acid O

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11. Hydoxyation- Glycol formation

—C=C— + KMnO4 or HCO2OH —C—C—

| |
OH OH

Ex.

KMnO or HCO OH
CH3CH=CH2 4 2 CH3CH—CH2
Peroxy formic acid | |
(Mixture of hydrogen peroxide OH OH
and formic acid) 1, 2 propane diol (propylene glycol)

Oxidation of an Alkene by KMnO4 is stereoselective in that it involves syn addition of –

OH groups to the double bond

 Oxidation by permanganate is the basis of a very useful analytical test known as

the Baeyer’s test.
 Permanganate gives syn addition and peroxy acids give anti addition.

Substitution Reactions

12. Halogenation. Allylic substitution

| | | | | |
heat
H—C—C=C— + X2 X—C—C—C— X2 = Cl2, Br2
Low
concentration

Examples:
Cl , 600°C
CH3CH=CH2 2 Cl—CH2CH=CH2
Propylene Allyl chloride
(Propene) (3-chloro-1-propene)

Cleavage Reactions

13. Ozonolysis (Cleavage by Ozone)

| | \ O / | | Used to
H O, Zn
—C=C— + O3 —C C— 2 —C=O + O=C— determine
\ / structure
Ozone O—O Aldehydes and Ketones

Ozonide

Examples:

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H H
| |
O H O, Zn
CH3CH2CH=CH2 3 2 CH3CH2C=O + O=CH
1-Butene

CH3 CH3 H
| | |
O H O, Zn
H3—C=CH2 3 2 CH3C=O + O=CH
Isobutylene

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