Alkenes and Alkynes I:

Properties and Synthesis.

Elimination Reactions
of Alkyl Halides

1
1. Introduction
❖ Alkenes
● Hydrocarbons containing C=C
● Old name: olefins

CH2OH

Vitamin A
H3C

H3C

H H
Cholesterol
HO 2
 ❖ Alkynes
● Hydrocarbons containing C≡C
● Common name: acetylenes
H
N O I Cl
C
O C O
Cl
F3C C Cl
C
Cl

Efavirenz Haloprogin
(antiviral, AIDS therapeutic) (antifungal, antiseptic)
3
2. The (E) - (Z) System for
Designating Alkene Diastereomers
❖ Cis-Trans System
● Useful for 1,2-disubstituted alkenes
● Examples:
H Br
(1) Cl vs Cl
Br H
H H
trans -1-Bromo- cis -1-Bromo-
2-chloroethene 2-chloroethene
4
● Examples
H
(2) vs
H
H H
trans -3-Hexene cis -3-Hexene

Br
(3) Br Br vs
Br
trans -1,3- cis -1,3-
Dibromopropene Dibromopropene
5
❖ (E) - (Z) System
● Difficulties encountered for
trisubstituted and tetrasubstituted
alkenes

CH3
e.g. Cl cis or trans?
Br
H
Cl is cis to CH3
and trans to Br
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❖ The Cahn-Ingold-Prelog (E) - (Z)
Convention

● The system is based on the atomic

number of the attached atom

● The higher the atomic number, the

higher the priority

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❖ The Cahn-Ingold-Prelog (E) - (Z) Convention
● (E) configuration – the highest priority
groups are on the opposite side of the
double bond
⧫ “E ” stands for “entgegen”; it means
“opposite” in German
● (Z) configuration – the highest priority
groups are on the same side of the double
bond
⧫ “Z ” stands for “zusammer”; it means
“together” in German

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● Examples
CH3
Cl 1
2 Br
H

On carbon 2: Priority of Br > C

On carbon 1: Priority of Cl > H
⇒ highest priority groups
are Br (on carbon 2)
and Cl (on carbon 1)
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● Examples CH3
Cl
Br
H
⇒ (E )-2-Bromo-1-chloropropene

Br
Cl
CH3
H
⇒ (Z )-2-Bromo-1-chloropropene
10
 ● Other examples

H (E )-1,2-Dichloroethene
(1) Cl [or trans-1,2-Dichloroethene]
2
1 Cl
H C1: Cl > H
C2: Cl > H

2 (Z )-1-Bromo-1,2-dichloroethene
Cl
(2) 1 Cl
Br C1: Br > Cl
C2: Cl > H
11
 ● Other examples

Br
3 1
4
(3) 2
5
7
8 6 (Z )-3-Bromo-4-tert-butyl-3-octene

C3: Br > C
t n
C4: Bu > Bu

12
3. Relative Stabilities of Alkenes
❖ Cis and trans alkenes do not have the
same stability
crowding

R R H R
C C C C
H H R H

Less stable More stable

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3A. Heat of Reaction

Pt
C C + H H C C
H H

❖ Heat of hydrogenation
● ∆H° ≃ -120 kJ/mol

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 + H2

7 kJ/mol
+ H2
ΔH° = -127 kJ/mol
Enthalpy

5 kJ/mol + H2

ΔH° = -120 kJ/mol

ΔH° = -115 kJ/mol

≈ ≈ ≈

15
3B. Overall Relative Stabilities of
Alkenes
❖ The greater the number of attached
alkyl groups (i.e., the more highly
substituted the carbon atoms of the
double bond), the greater the alkene’s
stability.

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 ❖ Relative Stabilities of Alkenes

R R R R R H R H R R R H H H
> > > > > >
R R R H R H H R H H H H H H
tetra- tri- di- mono- un-
substituted substituted substituted substituted substituted

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❖ Examples of stabilities of alkenes

(1) >

(2) >

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4. Cycloalkenes
❖ Cycloalkenes containing 5 carbon atoms
or fewer exist only in the cis form

cyclopropene cyclobutene cyclopentene

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❖ Trans – cyclohexene and trans –
cycloheptene have a very short lifetime
and have not been isolated

cyclohexene Hypothetical
trans - cyclohexene
(too strained to exist at r.t.)

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❖ Trans – cyclooctene has been isolated
and is chiral and exists as a pair of
enantiomers

cis - cyclooctene trans - cyclooctenes

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5. Synthesis of Alkenes via
Elimination Reactions
❖ Dehydrohalogenation of Alkyl Halides
H
H H H H
base
C C
H -HX
X H H
H

❖ Dehydration of Alcohols
H
H H +
H , heat H H
C C
H OH -HOH H H
H
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6B. Zaitsev’s Rule
❖ Examples of dehydrohalogenations
where only a single elimination product
is possible
EtONa
(1) o
(79%)
Br EtOH, 55 C

EtONa
(2) o
(91%)
Br EtOH, 55 C

t -BuOK
(3) ( )
Br ( ) (85%)
n o
t -BuOH, 40 C n
23
 H
❖ Rate = k H3C C CH3 EtO
Br (2nd order overall)
⇒ bimolecular

a
̶ H
a b
B H H
2-methyl-2-butene

Br
b
̶ H
2-methyl-1-butene
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 ⊖
❖ When a small base is used (e.g. EtO or
⊖
HO ) the major product will be the
more highly substituted alkene (the
more stable alkene)
❖ Examples:
a b
H H NaOEt
(1) +
EtOH
70oC
Br 69% 31%
(eliminate Ha) (eliminate Hb)
Br KOEt
(2) + +
EtOH
51% 18% 31%

69% 25
❖ Zaitsev’s Rule
● In elimination reactions, the more
highly substituted alkene product
predominates
❖ Stability of alkenes
Me Me Me Me Me H
C C > C C > C C
Me Me Me H H Me

Me Me Me H
> C C > C C
H H H H 26
6C. Formation of the Less Substituted
Alkene Using a Bulky Base
❖ Hofmann’s Rule
● Most elimination reactions follow
Zaitsev’s rule in which the most stable
alkenes are the major products.
However, under some circumstances,
the major elimination product is the
less substituted, less stable alkene

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 ● Case 1: using a bulky base
EtO CH3CH CHCH3 (80%)
+
(small) CH3CH2CH CH2 (20%)

CH3CH2CHCH3
Br t CH3CH CHCH3 (30%)
BuO
+
(bulky) CH3CH2CH CH2 (70%)
EtO⊖
(small base)
H H H H tBuO⊖

H C C C C H (bulky base)
H H Br H 28
 ● Case 2: with a bulky group next
to the leaving halide
less crowded β-H

Me H Br H Me H
EtO
H3C C C C C H H3C C C C CH2
Me H Me H Me H Me

(mainly)
more crowded β-H

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❖ Zaitsev Rule vs. Hofmann Rule

● Examples
a b
H H
(1) +

Br a b
(eliminate H ) (eliminate H )
o
NaOEt, EtOH, 70 C 69% 31%
t t o
KO Bu, BuOH, 75 C 28% 72%

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 ● Examples

b
H Br a
H
(2) +

a b
(eliminate H ) (eliminate H )
o
NaOEt, EtOH, 70 C 91% 9%
t t o
KO Bu, BuOH, 75 C 7% 93%

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7. Acid-Catalyzed Dehydration of
Alcohols
❖ Most alcohols undergo dehydration
(lose a molecule of water) to form an
alkene when heated with a strong acid

HA
C C C C + H2O
heat
H OH

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❖ The temperature and concentration of
acid required to dehydrate an alcohol
depend on the structure of the alcohol
substrate
● Primary alcohols are the most difficult to
dehydrate. Dehydration of ethanol, for
example, requires concentrated sulfuric
acid and a temperature of 180°C
H H conc. H 2SO4 H H
H C C H C C + H2O
o
180 C H H
H OH
Ethanol (a 1o alcohol)
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 ● Secondary alcohols usually dehydrate
under milder conditions. Cyclohexanol, for
example, dehydrates in 85% phosphoric
acid at 165–170°C

OH
85% H3PO4
+ H2O
o
165-170 C

Cyclohexanol Cyclohexene
(80%)

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 ● Tertiary alcohols are usually so easily
dehydrated that extremely mild conditions
can be used. tert-Butyl alcohol, for
example, dehydrates in 20% aqueous
sulfuric acid at a temperature of 85°C

CH3 CH2
20% H2SO4
H3C C OH + H2O
o
CH3 85 C H3C CH3

tert-Butyl alcohol 2-Methylpropene

(84%)
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● The relative ease with which alcohols
will undergo dehydration is in the
following order:

R R H
R C OH > R C OH > R C OH
R H H
o o o
3 alcohol 2 alcohol 1 alcohol

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9. The Acidity of Terminal Alkynes
Acetylenic hydrogen
sp sp2 sp3
H H H H
H C C H C C H C C H
H H H H
pKa = 25 pKa = 44 pKa = 50

❖ Relative basicity of the conjugate base

CH3CH2 > CH2 CH > CH CH

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 ❖ Comparison of acidity and basicity of 1st
row elements of the Periodic Table
● Relative acidity
H OH > H OR > H C CR > H NH2 > H CH CH2 > H CH2CH3

pKa 15.7 16-17 25 38 44 50

● Relative basicity
OH < OR < C CR < NH2 < CH CH2 < CH2CH3

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10. Synthesis of Alkynes by
Elimination Reactions
❖ Synthesis of Alkynes by
Dehydrohalogenation of Vicinal
Dihalides

H H
NaNH2
C C C C
heat
Br Br

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❖ Mechanism

H
H H
NH2
R
R C C R R
E2
Br Br Br

NH2

R R

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❖ Examples
Br
H NaNH2
(1)
heat
H Br (78%)

Br H
Ph Br2 Ph
(2)
Ph CCl4 Ph NaNH2
H Br
heat

Ph Ph

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❖ Synthesis of Alkynes by
Dehydrohalogenation of Geminal
Dihalides
O PCl5 Cl Cl

R CH3 o R CH3
0 C
gem-dichloride

1. NaNH2 (3 equiv.), heat

2. HA

Ph H
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11. Replacement of the Acetylenic
Hydrogen Atom of Terminal
Alkynes
❖ The acetylide anion can be prepared by

NaNH2
R H R Na + NH3
liq. NH3

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❖ Acetylide anions are useful
intermediates for the synthesis of other
alkynes

R R' X R R' + X

O
ONLY GOOD FOR 1 R’

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 Ph H
❖ Examples
NaNH2
liq. NH3
I
Ph Na

CH3 I
H

SN 2 E2

Ph CH3 Ph H
+ +
NaI
+
I 45
13. Hydrogenation of Alkenes
H2
H H
Pt, Pd or Ni
C C C C
solvent
heat and pressure

H2
H H
Pt, Pd or Ni
C C C C
solvent
heat and pressure H H

❖ Hydrogenation is an example of addition

reaction
46
❖ Examples
H
H2
H
Rh(PPh 3)3Cl

H
H2
Pd/C
H

47
14. Hydrogenation: The Function
of the Catalyst
❖ Hydrogenation of an alkene is an
exothermic reaction
● ∆H° ≃ -120 kJ/mol
hydrogenation
R CH CH R R CH2 CH2 R
+ H2 + heat

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49
14A. Syn and Anti Additions
❖ An addition that places the parts of the
reagent on the same side (or face) of
the reactant is called syn addition
syn
C C + X Y C C
addition
X Y

Pt
C C + H H C C
H H

Catalytic hydrogenation is a syn addition.

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❖ An anti addition places parts of the
adding reagent on opposite faces of the
reactant

Y
anti
C C + X Y C C
addition
X

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