3 Alkenes Elimination Reactions

Organic Chemistry
ABCT2423
Structure and Preparation of Alkenes:

Elimination Reactions
Dr. Chau Ming SO

Office: Y843
Email: bccmso@polyu.edu.hk
1
Handout for “ALKENES”
IUPAC Nomenclature of Alkenes

Stereochemical Notation
The Cahn-Ingold-Prelog (CIP) System
Substituent Effects on Alkene Stability
Cycloalkenes
Preparation of Alkenes: -Elimination Reactions
Dehydrogenation
Dehydration of Alcohols
Dehydrohalogenation of Alkyl Halides
2
H2C CHCH2CH3 1-Butene or

But-1-ene
(1) Find the longest continuous chain that

includes the double bond.
(2) Replace the -ane ending of the unbranched
alkane having the same number of carbons with -
ene.
(3) Number the chain in the direction that gives
the lowest number to the doubly bonded carbon.
3
H2C CHCHCH2Br
CH3
(4) If a substituent is present, identify its
position by number. The double bond takes
precedence over alkyl groups and halogens
when the chain is numbered.
The compound shown above is
4-bromo-3-methyl-1-butene.
(or 4-bromo-3-methylbut-1-ene) 4
H2C CHCHCH2OH
CH3
(5) If a substituent is present, identify
its position by number. Hydroxyl groups
take precedence over the double bond
when the chain is numbered.
The compound shown above is
2-methyl-3-buten-1-ol.
(or 2-methyl-but-3-en-1-ol) 5
Cycloalkene Nomenclature
Cyclohexene
(1) Replace the -ane ending of the

cycloalkane having the same number of
carbons with -ene.
6
Cycloalkene Nomenclature
3 2
4 1
CH3
6-Ethyl-1-methylcyclohexene
5 6
CH2CH3
(1) Replace the -ane ending of the cycloalkane

having the same number of carbons with -ene.
(2) Number through the double bond in the
direction that gives the lower number to the
first-appearing substituent. 7

Cycloalkenes
Dehydrogenation
8
cis (identical or trans (identical or

analogous substituents analogous substituents
on same side) on opposite sides)
9
CH3(CH2)6CH2 CH2(CH2)6CO2H
C C Oleic acid
H H oleic acid has a
substituents are identical or analogous cis double bond
Cl Br
cis and trans are ambiguous when
C C analogies are not obvious
H F
10
The E-Z Notational System
E : higher ranked substituents on opposite sides

Z : higher ranked substituents on same side
higher lower higher higher
C C C C
lower higher lower lower
E Z 11

Cycloalkenes
Dehydrogenation
12
(1) Higher atomic number outranks lower

atomic number
Br > F Cl > H
higher Br Cl higher
C C
lower F H lower
(Z )-1-Bromo-2-chloro-1-fluoroethene
13
(2) When two atoms are identical, compare the

atoms attached to them on the basis of their
atomic numbers. Precedence is established
at the first point of difference.
—CH2CH3 outranks —CH3
—C(C,H,H) —C(H,H,H)
14
(3) Work outward from the point of attachment,

comparing all the atoms attached to a
particular atom before proceeding further
along the chain.
—CH(CH3)2 outranks —CH2CH2OH
—C(C,C,H) —C(C,H,H)
15

Cycloalkenes
Dehydrogenation
16
Electronic
Disubstituted alkenes are more stable
than monosubstituted alkenes
Alkyl groups stabilize double bonds more than H.
Steric
trans alkenes are more stable than cis alkenes
cis alkenes are destabilized by van der Waals strain
17
Heats of
Combustion of C4H8
Isomers
2717 kJ/mol + 6O2
2710 kJ/mol
2707 kJ/mol
2700 kJ/mol
4CO2 + 8H2O
18
cis and trans-2-Butene
• van der Waals strain due to crowding of cis-
methyl groups
19

Cycloalkenes
Dehydrogenation
20
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.
21
Stereoisomeric Cycloalkenes
• cis-cyclooctene and trans-cyclooctene

are stereoisomers.
• cis-cyclooctene is 39 kJ/mol more stable
than trans-cyclooctene.
H H
H H
cis-Cyclooctene trans-Cyclooctene 22
Stereoisomeric Cycloalkenes
• cis stereoisomer is more stable than trans

through C11 cycloalkenes.
• cis and trans-cyclododecene (12 carbons)
are approximately equal in stability.
When there are more than 12 carbons
• in the ring, trans-cycloalkenes are more stable
than cis.
• The ring is large enough so the cycloalkene
behaves much like a noncyclic one.
23

Cycloalkenes
Dehydrogenation
24
Preparation of Alkenes:
-Elimination Reactions
1. Dehydrogenation of alkanes:
X = H; Y = H
2. Dehydration of alcohols:
X = H; Y = OH
3. Dehydrohalogenation of alkyl halides:
X = H; Y = Br, etc.
X C C Y C C + X Y
 25

Cycloalkenes
Dehydrogenation
26
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
27

Cycloalkenes
Dehydrogenation
28
H2SO4
CH3CH2OH H2C CH2 + H2O
160 °C
H2SO4
OH + H2O
140 °C
(79-87%)
CH3 H3C
H2SO4
H3C C OH C CH2 + H2O
heat
CH3 H3C
(82%)
29
R'
Relative tertiary:
R OH
Reactivity
C most reactive
R"
R'
R C OH
R C OH primary:
least reactive
H 30
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.
31
Regioselectivity (Zaitsev’s 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
two protons on this  carbon
three protons on this  carbon
only one proton on this  carbon
32
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.
33
Dehydration of tert-Butyl Alcohol (E1)
CH3 H3C
H2SO4
H3C C OH C CH2 + H2O
heat
CH3 H3C
34
Dehydration of tert-Butyl Alcohol
(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
35
tert-Butyloxonium ion
(Mechanism)
Step 2: Dissociation of tert-butyloxonium ion
to carbocation H
+
(CH3)3C O :
H
Because rate-determining
step is unimolecular, this slow, unimolecular
is called the E1 mechanism.
H
+ + :O:
(CH3)3C
36
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 37
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
- rearrange (from less stable to more stable)

38
Carbocations
39
40
Dehydration of Primary Alcohols (E2)
H2SO4
CH3CH2OH H2C CH2 + H2O
160 °C
• avoids carbocation because primary

carbocations are too unstable
• oxonium ion loses water and a proton in a

bimolecular step
41
Dehydration of Primary Alcohols
(Mechanism)
Step 1: Proton transfer from acid to ethanol
H
..
CH3CH2 O : + H O +
..
H
H
fast, bimolecular
H H
+
CH3CH2 O : + :O:
H H
42
Ethyloxonium ion
Dehydration of Primary Alcohols
(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
slow, bimolecular
H H
+
:O H + H2C CH2 + :O:
Because rate-determining step is bimolecular,
H H 43
this is called the E2 mechanism.
Rearrangements in Alcohol Dehydration
OH
H3PO4, heat
+ +
3% 64% 33%
44
Rearrangement Involves
Alkyl Group Migration
CH3 • Carbocation can lose a
proton as shown;
CH3 C CHCH3
+
CH3 • or it can undergo a
methyl migration.
3% • CH3 group migrates

with its pair of
electrons to adjacent
positively charged
carbon.
45
CH3 CH3
97% +
CH3 C CHCH3 CH3 C CHCH3
+
CH3 tertiary CH3
carbocation;
more stable
3%
46
47
Another Rearrangement
CH3CH2CH2CH2OH
H3PO4, heat
CH3CH2CH CH2 + CH3CH CHCH3

12% mixture of cis (32%)
and trans-2-butene (56%)
48
Rearrangement Involves Hydride Shift
H • Oxonium ion can lose

+
CH3CH2CH2CH2 O: water and a proton
H (from C-2) to give
1-butene;
• Doesn't give a
carbocation directly
because primary
carbocations are too
CH3CH2CH CH2 unstable.
49
H
+
CH3CH2CH2CH2 O: CH3CH2CHCH3
+
H
• Hydrogen migrates
with its pair of
electrons from C-2 to
C-1 as water is lost;
• Carbocation formed by
CH3CH2CH CH2
hydride shift is
secondary.
50
H
+
CH3CH2CH2CH2 O: CH3CH2CHCH3
+
H
CH3CH2CH CH2 CH3CH CHCH3

mixture of cis
and trans-2-butene51
H
+
CH3CH2CHCH2 O:
H
H
H
+
CH3CH2CHCH2 + : O:
H
H 52
53

Cycloalkenes
Dehydrogenation
54
Dehydrohalogenation
a useful method for the preparation of alkenes
NaOCH2CH3
Cl
ethanol, 55 °C
(100 %)
likewise, NaOCH3 in methanol, or KOH in ethanol
55
Dehydrohalogenation
• When the alkyl halide is primary, potassium

tert-butoxide in dimethyl sulfoxide is the
base/solvent system that is normally used.
KOC(CH3)3
CH3(CH2)15CH2CH2Cl
dimethyl sulfoxide
CH3(CH2)15CH CH2
(86%)
56
Regioselectivity
KOCH2CH3
+
Br ethanol, 70°C
29 % 71 %
more highly substituted double

bond predominates
57
Stereoselectivity
KOCH2CH3
ethanol
Br
(23%) (77%)
more stable configuration

of double bond predominates
58
Stereoselectivity
Br
KOCH2CH3
ethanol
(85%) (15%)
more stable configuration

of double bond predominates 59
Alkenes
1. Able to name the alkenes from a given compounds.

2. Understanding the stereochemical notation and
the Cahn-Ingold-Prelog (CIP) system.
3. Understanding the substituent effects on alkene
stability.
4. Understanding the stability of the alkenes’
carbocation intermediates and the rearrangement
reactions.
5. Able to apply the appropriate -elimination
reactions to prepare alkenes.
60

3 Alkenes Elimination Reactions

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Organic Chemistry

Structure and Preparation of Alkenes:

Dr. Chau Ming SO

IUPAC Nomenclature of Alkenes

H2C CHCH2CH3 1-Butene or

(1) Find the longest continuous chain that

(1) Replace the -ane ending of the

(1) Replace the -ane ending of the cycloalkane

IUPAC Nomenclature of Alkenes

cis (identical or trans (identical or

E : higher ranked substituents on opposite sides

higher lower higher higher

lower higher lower lower

IUPAC Nomenclature of Alkenes

(1) Higher atomic number outranks lower

(2) When two atoms are identical, compare the

—CH2CH3 outranks —CH3

(3) Work outward from the point of attachment,

—CH(CH3)2 outranks —CH2CH2OH

IUPAC Nomenclature of Alkenes

2717 kJ/mol + 6O2

IUPAC Nomenclature of Alkenes

• Cyclopropene and cyclobutene have angle strain.

• Larger cycloalkenes, such as cyclopentene

• cis-cyclooctene and trans-cyclooctene

• cis stereoisomer is more stable than trans

IUPAC Nomenclature of Alkenes

IUPAC Nomenclature of Alkenes

• limited to industrial syntheses of ethylene,

• important economically, but rarely used in

IUPAC Nomenclature of Alkenes

• A reaction that can proceed in more than

• A stereoselective reaction is one in which

Carbocations are intermediates in the acid-catalyzed

- react with nucleophiles

- lose a -proton to form an alkene

- rearrange (from less stable to more stable)

• avoids carbocation because primary

• oxonium ion loses water and a proton in a

3% • CH3 group migrates

CH3CH2CH CH2 + CH3CH CHCH3

H • Oxonium ion can lose

CH3CH2CH CH2 CH3CH CHCH3

IUPAC Nomenclature of Alkenes

a useful method for the preparation of alkenes

likewise, NaOCH3 in methanol, or KOH in ethanol

• When the alkyl halide is primary, potassium

more highly substituted double

more stable configuration

more stable configuration

1. Able to name the alkenes from a given compounds.

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