General

Organic Chemistry
Two credits
Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Reference Book: Organic Chemistry: A Brief Course,

by Robert C. Atkins and Francis A. Carey
Third Edition

Instructor: Rabih O. Al-Kaysi, PhD.

 Lecture 6

Chapter 4

Alkenes & Alkynes

Relative Stabilities of Alkenes
 Double
Doublebonds
bondsare
areclassified
classifiedaccording
accordingto
to
the
thenumber
numberof
ofcarbons
carbonsattached
attachedtotothem.
them.

R H
C C monosubstituted
H H

R H R R' R H
C C C C C C
R' H H H H R'

disubstituted disubstituted disubstituted

Double
Doublebonds
bondsare
areclassified
classifiedaccording
accordingto
to
the
thenumber
numberof
ofcarbons
carbonsattached
attachedtotothem.
them.

R R" R R"
C C C C
R' H R' R"'

trisubstituted tetrasubstituted
 Substituent
Substituenteffects
effectson
onalkene
alkenestability
stability

Steric

trans alkenes are more stable than cis alkenes

 Problem
Problem

Give the structure or make a molecular model of

the most stable C6H12 alkene.

H3C CH3

C C
H3C CH3
 Substituent
Substituenteffects
effectson
onalkene
alkenestability
stability

Steric effects
trans alkenes are more stable than cis alkenes

cis alkenes are destabilized by van der Waals

strain
 cis and trans-2-Butene
van der Waals strain
due to crowding of
cis-methyl groups

cis-2-butene trans-2-butene
 cis
cisand
andtrans-2-butene
trans-2-butene

van der Waals strain

due to crowding of
cis-methyl groups

cis-2-butene trans-2-butene
Cycloalkenes
 Cycloalkenes
Cycloalkenes

Cyclopropene and cyclobutene have angle

strain.
Larger cycloalkenes, such as cyclopentene
and cyclohexene, can incorporate a double
bond into the ring with little or no angle strain.

Unstable and strained

Preparation of Alkenes:
Elimination Reactions
 -Elimination
-EliminationReactions
Reactions

•dehydrogenation of alkanes:
 H; Y = H
•dehydration of alcohols:
 H; Y = OH
•dehydrohalogenation of alkyl halides:
 H; Y = Br, etc.

H C C Y C C + H Y
 
 Dehydrogenation
Dehydrogenation

• limited to industrial syntheses of ethylene,

propene, 1,3-butadiene, and styrene
• important economically, but rarely used in
laboratory-scale syntheses

750°C
CH3CH3 H2C CH2 + H2

750°C
CH3CH2CH3 H2C CHCH3 + H2
Dehydration of Alcohols
 Dehydration
Dehydrationof
ofAlcohols
Alcohols
H2SO4
CH3CH2OH H2C CH2 + H2O
160°C

H2SO4
OH + H2O
140°C
(79-87%)
CH3
H3C
H3C C OH H2SO4 + H2O
C CH2
heat
CH3 H3C
(82%)
 R'
Relative tertiary:
Reactivity R C OH most reactive
R"
R'

R C OH

R C OH primary:
least reactive
H
Regioselectivity in Alcohol Dehydration:
The Zaitsev Rule
 Regioselectivity
Regioselectivity

H2SO4
HO +
80°C
10 % 90 %

• A reaction that can proceed in more than

one direction, but in which one direction
predominates, is said to be regioselective.
regioselective
 Regioselectivity
Regioselectivity

CH3 CH3 CH3

H3PO4
OH +
heat
84 % 16 %

• A reaction that can proceed in more than

one direction, but in which one direction
predominates, is said to be regioselective.
regioselective
 The
TheZaitsev
ZaitsevRule
Rule

• When elimination can occur in more than one

direction, the principal alkene is the one formed
by loss of H from the  carbon having the
fewest hydrogens.

R OH

R C C CH2R

H CH3

three protons on this  carbon

 The
TheZaitsev
ZaitsevRule
Rule

• When elimination can occur in more than one

direction, the principal alkene is the one formed
by loss of H from the  carbon having the
fewest hydrogens.

R OH

R C C CH2R

H CH3

two protons on this  carbon

 The
TheZaitsev
ZaitsevRule
Rule

• When elimination can occur in more than one

direction, the principal alkene is the one formed
by loss of H from the  carbon having the
fewest hydrogens.

R OH

R C C CH2R

H CH3

only one proton on this  carbon

 The
TheZaitsev
ZaitsevRule
Rule

• When elimination can occur in more than one

direction, the principal alkene is the one formed
by loss of H from the  carbon having the
fewest hydrogens.

R OH R CH2R

R C C CH2R C C

H CH3 R CH3

only one proton on this  carbon

 The
The Zaitsev
Zaitsev Rule
Rule

Zaitsev Rule states that the elimination

reaction yields the more highly substituted
alkene as the major product.

The more stable alkene product

predominates.
 Stereoselectivity
in
Alcohol Dehydration
 Stereoselectivity
Stereoselectivity

H2SO4
+
heat
OH (25%) (75%)

• A stereoselective reaction is one in which

a single starting material can yield two or more
stereoisomeric products, but gives one of them
in greater amounts than any other.
 The Mechanism of the
Acid-Catalyzed Dehydration of
Alcohols
 AA connecting
connecting point...
point...
• The dehydration of alcohols and the reaction
of alcohols with hydrogen halides share the
following common features:
• 1) Both reactions are promoted by acids
• 2) The relative reactivity decreases in the
order tertiary > secondary > primary
These similarities suggest that carbocations
are intermediates in the acid-catalyzed
dehydration of alcohols, just as they are in
the reaction of alcohols with hydrogen halides.
 Dehydration
Dehydration of
of tert-Butyl
tert-Butyl Alcohol
Alcohol

CH3 H3C
H2SO4
H3C C OH C CH2 + H2O
heat
CH3 H3C

•first two steps of mechanism are identical to

those for the reaction of tert-butyl alcohol with
hydrogen halides
 Mechanism

Step 1: Proton transfer to tert-butyl alcohol

H
..
(CH3)3C O : + H O ..
+
H
H
fast, bimolecular
H H
+
(CH3)3C O : + :O:

H H
tert-Butyloxonium ion
 Mechanism

Step 2: Dissociation of tert-butyloxonium ion

to carbocation
H
+
(CH3)3C O :

H
slow, unimolecular

(CH3)3C + + :O:

tert-Butyl cation H
 Mechanism

Step 3: Deprotonation of tert-butyl cation.

H

H3C H + :O:

+C CH2 H
H3C
fast, bimolecular
H3C H
+
C CH2 + H O:
H3C H
 Carbocations
Carbocations

are intermediates in the acid-catalyzed

dehydration of tertiary and secondary alcohols

Carbocations can:
•react with nucleophiles
•lose a -proton to form an alkene
(Called an E1 mechanism)
 Dehydration
Dehydrationof
ofprimary
primaryalcohols
alcohols

H2SO4
CH3CH2OH H2C CH2 + H2O
160°C

•A different mechanism from 3 o or 2 o alcohols

•avoids carbocation because primary
carbocations are too unstable
•oxonium ion loses water and a proton in a
bimolecular step
 Mechanism
Step 1: Proton transfer from acid to ethanol
H
..
CH3CH2 O : + H O
..
H
H
Just for general knowledge, will not be tested on
fast, bimolecular
H H
+
CH3CH2 O : + :O:

H H
Ethyloxonium ion
 Mechanism
Step 2: Oxonium ion loses both a proton and
a water molecule in the same step.
H H
+
: O : + H CH2 CH2 O :

H H
Just for general knowledge, will not be tested on
slow, bimolecular
H H
+
:O H + H2C CH2 + :O:

H H
 Mechanism
Step 2: Oxonium ion loses both a proton and
a water molecule in the same step.
H H
+
: O : + H CH2 CH2 O :

H
Because rate-determining H
step is bimolecular, thisbimolecular
slow,
H is called the E2 mechanism. H
+
:O H + H2C CH2 + :O:

H Just for general knowledge, will not be tested

H on
 Rearrangements in Alcohol
Dehydration

Sometimes the alkene product does not

have the same carbon skeleton as the
starting alcohol.
Example
Example
OH

H3PO4, heat

+ +

3% 64% 33%
 Rearrangement
Rearrangementinvolves
involvesalkyl
alkylgroup
groupmigration
migration

CH3 • carbocation can

lose a proton as
CH3 C CHCH3
+ shown
CH3 • or it can undergo a
methyl migration
3%
• CH3 group migrates
with its pair of
electrons to
adjacent positively
charged carbon
 Rearrangement
Rearrangementinvolves
involvesalkyl
alkylgroup
groupmigration
migration

CH3 CH3
97% +
CH3 C CHCH3 CH3 C CHCH3
+
CH3 CH3

• tertiary carbocation;
3%
more stable
 Rearrangement
Rearrangementinvolves
involvesalkyl
alkylgroup
groupmigration
migration

CH3 CH3
97% +
CH3 C CHCH3 CH3 C CHCH3
+
CH3 CH3

3%