Chapter 11: Alkenes

C C Double bond

Names: ending ane ene

For example: ethene, propene, butene, etc.

Naming follows the rules for hydrocarbons

(functional groups override these rules):
General guidelines:
Rings have priority, regardless of the presence of
multiple bonds.
If there are no rings: the longest chain has priority,
regardless of the presence of multiple bonds.
 Names in the absence of rings
1. Find longest chain. If it contains both Csp2
carbons  alkene. If not  alkenylalkane (see 8.)

An octene

2. Number the chain with C C close to terminus

1
2 A 3-octene or oct-3-ene (only
3
the first of the two Csp2
8
7
6
5
carbons is listed by a #)
4

3. Name and # substituents, in alphabetical order

4-Ethyl-3-methyl-3-octene
 Names in the presence of rings

4. Find largest ring. If it contains both Csp2 carbons

 cycloalkene. If not  alkenylcycloalkane (see 8.)

1
2 Double bond carbons
are C 1 C 2 by definition.
3 Label in such a way as to
CH3 give substituents lowest
possible numbering
3-Methylcyclohexene
 5. Stereoisomers: R
cis trans
R R
R
Cis or trans applies only to 1,2-disubstituted ethenes.
6. For tri- and tetrasubstituted alkenes: E, Z
naming. Use R,S priority rules at each sp2-carbon separately, to
find yhe higher priority group at each end.

1 Respective higher priority groups on:

2 Opposite sides: E
3 Same side: Z

8 6
7 5 4
E-4-Ethyl-3-methyl-3-octene

Colloquial terms: double bond position

R R
CH2 Terminal Internal
R R
7. OH ( > SH) > ene

8. Substituents with double bond: Alkenyl

CH2 CH Ethenyl (vinyl)
CH2 CH CH2 2-Propenyl (allyl)
 Remember the basic guidelines:

Longest chain rules Ring rules

Longest chain
containing double Functional group rules
bond rules
9. Exocyclic alkenes: Alkylidenecycloalkanes

Methylidenecyclohexane
(Methylenecyclohexane)
Structure Of The Double Bond
Two components: the -bond and the -bond

Electron rich
The Sigma Bond
The Pi Bond

Ethene
 Orbital Energies

 Bond is
relatively weak

Ethene
How Weak Is The Pi Bond?

Ea = 65 kcal mol−1
Typical C-C bond
strength ~88 kcal mol−1
(Table 3-2)
Bond Strengths In Alkenes

Unusually strong because C uses sp2 hybrids

 Alkenyl Hydrogens Are
Relatively Acidic
C C pKa ~ 44 Compare CH3CH2H
pKa ~ 50
H

sp2 Has 33% s character.

C C
In contrast:
H
sp3 has 25% s
character

Net effect: relatively e-withdrawing

Therefore, in principle:
R H H
C C + CH3Li RCH C + CH4
H H Li

Problems: regio-, stereoselectivity.

Better via alkenyl organometallics:
H H
CH2 C + Li CH2 C Useful:
Br Li React
with
R H R H carbonyls
C C + Mg C C
H Br H MgBr
Stereospecific
 Relative Stability Of
Alkenes
Measure heat of hydrogenation ΔHHydrogenation of
isomers, e.g., butene
ΔH (kcal mol−1)
cat.
+ H2 −30.3
cat.
+ H2 −28.6

cat.
+ H2 −27.6

Relative stability: Internal > terminal trans > cis

 H
Why? 1. Hyperconjugation
C C
C
2. Steric hindrance (strain)

Cis is less stable than

trans because of
steric hindrance

General order of stability:

CH2 CH2 < RCH CH2 < RCH CHR cis
< RCH CHR trans < tri < tetrasubstituted
 Synthesis of Alkenes
E revisited. Best: E2 on RX. Regioselectivity?
CH3
CH3 CH3CH2O−Na+, H3C CH3 H2C
CH3CH2OH
CH3CH2 C CH3 C C + C CH2
Small H 70% CH3 H3C 30%
X base More stable Less stable

Saytzev-Rule
Non-bulky base
leads to more
stable internal Alexander

double bond.
M. Saytzev
(1841–1910)
 Saytzev’s Rule: The
Transition State

The transition
states begin
to look like
product
double bond.
 Hofmann Rule
Bulky base leads to less stable terminal double bond
August Wilhelm
von Hofmann
Large (1818–1892)

base
Elimination Is Stereoselective
Recall: Stereoselectivity is the preferential
formation of one stereoisomer over possible
others. Here: cis or trans product?
Yes, but not completely.
Br
Na+−OCH3
+ +
CH3OH
Non-bulky 51% 18% 31%
base: Saytzev Mainly trans

Dominant
rotamer Gauche,
minor
rotamer
 Elimination Is Stereospecific
Recall:
Stereospecificity is
the selective
conversion of one
stereoisomer of
starting material to
one of the product.
Here: One
diastereomer of

C* C *
H X
gives only E
alkene, the other
gives only Z.
Alkenes From ROH By Dehydration
Acid, Δ
C C C C + HOH
Dehydration
H OH Carbocations: Can be messy!
Limited synthetic utility.

Rprim OH + H2SO4 conc., goes by E2, requires heat:

+ H Δ
+ CH2 CH2 O + HSO4 −
:

:
CH3CH2OH + H
H
:

H
CH2 CH2 + H2O + H2SO4
:
:

Rsec, Rtert OH + H+ : E1 + rearrangements

 Relative Reactivity
R = primary < secondary < tertiary

E2 on oxonium ion

E1

E1
Major Problem: Rearrangements

CH3 OH
H3C H
H2SO4, Δ
CH3C CH2 CCH3 C C
−HOH
H3C CH2CH3
H H
54%
CH3
+ CH3CCH CHCH3 + other isomers
H
8%