Addition Reactions to Alkenes

Addition of Hydrogen Halides to Alkenes.

General Reaction R2C=CR2 + HX R2HC-CR2X

H X
Slow H + X H
H H + C C
C C + H H Nucleophile C C
H H H
H H (base)
H
HH
Electrophile Electrophile Fast
Nucleophile (acid) (acid)
(weak base) Reactivity parallels acid strength. The
alkene is a very weak base so you need
Order of reactivity = HI > HBr > HCl > HF Why? a very strong acid to get a reaction.

Unsymmetrical alkene

Why?

Sec. 10 - alkenes/alkynes 1
 Markovnikov’s Rule
In the ionic addition of an unsymmetrical reagent to a double bond, the positive
portion of the adding reagent attaches itself to a carbon atom to the double bond as
to yield the more stable carbocation as an intermediate (You already knew this from
SN1 reactions. The most stable carbocation intermediate forms)

or
Hydrogen becomes
attached to the carbon
atom of the double
bond with the greater
number of hydrogens

Sec. 10 - alkenes/alkynes 2
 Examples
sp3 Br
H3C H +
H
H Br H3C +
C C C CH2CH3
CH3 C C H3C
H3C sp2 electrophile H sp3
(acid) H3C sp2 H3C major product
CH3
nucleophile
(weak base)
bottom
Br
H H
CH3 CH3
CH3
+ +
(S)
H Br

(R) diastereomers
CH3 top CH3
CH3
CH3
top Br
(R)
+
(R)
CH3
bottom

Sec. 10 - alkenes/alkynes 3
 Examples
H3C
I – Cl
C CH2
H3 C
nucleophile electrophile
(weak base) (acid)

no water

H3C H2SO4
cold concentrated
C CH2
H3 C H O

O S OH very weak base

poor nucleophile
O
weak bond
HSO4¯ great leaving group

Sec. 10 - alkenes/alkynes 4
 Examples

hydration
water present O
H3C
dilute H2SO4 O S OH
C CH2
H3 C O O
H
O S OH H2O - weak base
H or poor nucleophile but better
+ O than HSO4¯ also in greater concentration
O H
H

H2O

Sec. 10 - alkenes/alkynes 5
 What is the difference between hydration, elimination of alcohols and substitution
reactions with alcohols, they all seem the same?

OH concentrated + OH2
H3C
H2SO4 -H2O H3C + E1
H3C C CH3 H3C C CH3 C CH2
C CH3
dehydration -H+
CH3 CH3 H3C H3C
cold
H3C OSO3H
concentrated H3C cold add
C CH2 H2SO4 +

C CH3 HSO4¯ H3C C CH3 H2O

H3C heat
H3C CH3
dilute
H3C H2SO4 H3C H3C
heat + H2O +

C CH2 C CH3 -H+ C CH3

H2O
hydration H3C H3C + HSO4¯
H3C OH -H+
SN1 hydration
concentrated H3C C CH3
H3C
H3C H2SO4 +
C CH3 CH3
C CH2
NaBr H3C NaBr Br
H3C SN1
Don’t forget anytime H3C C CH3
a carbocation is formed
rearrangement of the carbon Sec. 10 - alkenes/alkynes 6
skeleton can occur
CH3
 Anti-Markovnikov addition
The hydrogen atom becomes attached to the carbon atom with the fewer hydrogen atoms
This is a free radical reaction not an ionic reaction. You do not have to memorize the
statement above if you understand the mechanism.
HBr
CH3CH=CH2 CH3CH2CH2Br
Mechanism ROOR
a peroxide

H3C CH CH2
RO OR 2 RO RO H Br ROH + Br

propagation
H3C CH CH2 Br H Br H C
3 CH2 CH2 Br + Br
2° most stable than 1°
same as carbocations

Br H

C C H
Br H H
C C H
H H C
CH3
2°
H
H
Sec. 10 - alkenes/alkynes 7
 Addition of Bromine and Chlorine to Alkenes
Addition produces vicinal dihalides

Sec. 10 - alkenes/alkynes 8
 Mechanism
Br δ−
electrophile +
(acid) Br Br
Br δ+ R R
R R R C C R + Br
C C C C
R R R nucleophile R
R
nucleophile (base) Br
R
(base) bromonium ion
intermediate anti addition
forms trans products
electrophile
(acid)

Br δ−
polarized
Br δ+ Br +
Br
R R
R R C C
C C R R
R R

not true diagrams of orbitals

but okay for our needs
Sec. 10 - alkenes/alkynes 9
 Example

Br2
CCl4
(solvent)
+ enantiomer
trans-1,2-dibromocyclohexane

Unsymmetrical Alkene
weaker bond stronger
δ+ bond
Br H3C
H3C Br
H3C 3° H H3C
C CH2 + Br – Br C C + Br
1° C C
H3C δ+ H H
H3C Br H

3° carbon can bear more of the positive charge.

Sec. 10 - alkenes/alkynes 10
Bromonium Ion

Sec. 10 - alkenes/alkynes 11
 Halohydrin Formation (halogen + alcohol)

Br – Br

H2O
(solvent)

Major product

+
OH
Br2 Na OH

H2O H2O
Br

Sec. 10 - alkenes/alkynes 12
Sec. 10 - alkenes/alkynes 13
 Oxidation States of Carbon
A reaction of an organic molecule usually corresponds to increasing its hydrogen
content or decreasing its oxygen content.
O [O] O
[O] [O]
RCH3 RCH2OH R C H R C OH
[H] [H] [H] Highest
Lowest Oxidation
Oxidation State
State OH [O] O
R CH R R C R
[H]
Oxidation → broad definition → a reaction that increases its content of any element
more electronegative than carbon
[O]
CH3 CH2Cl
[H]

How to figure out the oxidation state of a carbon atom

a bond to hydrogen or anything less electronegative than carbon is electron donating → -1
a bond to nitrogen, oxygen or anything more electronegative than carbon is electron withdrawing → +1
a bond to a carbon H H → 0
H O C O
H C C OH
H C H
H H
H
Sec. 10 - alkenes/alkynes 14
OS = oxidation state
 Oxidation States of Carbon
H H H H H O
H H
H2/Pd KMnO4
C C H C C H H C C OH H C C OH
H H
Reduction H H H H Oxidation H

LEO goes GER – Loss of Electrons Oxidation, Gain of Electrons Reduction

Oxidation Alkenes: Syn 1,2-dihydroxylation

Sec. 10 - alkenes/alkynes 15
 Mechanism

one oxygen
acts like an
electrophile
(acid) the other oxygen
acts like an Syn addition causes cleavage without
nucleophile (same side) altering stereochemistry
(base)

COLD

Sec. 10 - alkenes/alkynes 16
 Example
O

O Os
O
• OsO4, ether
O
H
2) Na2SO3
H
intermediate
(if you remember this
you know the answer)

Oxidative Cleavage of Alkenes (KMnO4 or K2Cr2O7)

Bond
Cleavage

Sec. 10 - alkenes/alkynes 17
 Mechanism
can’t break C-C bonds
O O 4 electron transfer no further oxidation
O O
OS = +7 Mn
Mn OS = +5
O O
O O cleavage
O O
+ C
C
H C C CH3 H3C CH3
H CH3
H3CH2C C(CH3)2 H3C CH3 OS = +1 OS = +2
OS = 0 OS = 0 OS = +1 further
OS =-1 O Mn O
oxidation of +
carbon while
O OS = +3
manganese is
Ox reduced In an acidic solution
C Mn2+ will be the final
HO CH3 manganese product

OS = +3 In a basic solution Mn(IV)O2

is formed not MnO3¯ and is
Ox Ox the final manganese
product

no further formic acid decomposition Do not need to know just

oxidation for interest
formaldehyde carbonic acid

Sec. 10 - alkenes/alkynes 18
 Example
1) KMnO4/NaOH
heat Ox
2) H3O+

intermediate

Ozonolysis of Alkenes
Ozone is in a class of compounds called 1,3-dipole reagents. They are so called
because good neutral resonance forms cannot be written for them.
+ + + + + O
R2C N N RC N O R N N N R2C N
R
Diazo Nitrile oxide Azides Nitrones

Sec. 10 - alkenes/alkynes 19
 Ozonolysis of Alkenes
+ +
O 1,3-dipolar
O O O O
O O addition
O O + reaction

O
O O O reverse
+ 1,3-dipolar O O 1,3-dipolar CH3
addition (CH3)C CH3
addition (CH3)3C
C C C O
+ C C(CH3)3
(CH3)C CH3 H C(CH3)3 H O
C C O
H C(CH3)3 ozonide
not stable

1,3-dipolar (CH3)C O CH3

C C This form is favoured because of the formation of
addition
stronger C-O bonds as opposed to weak O-O bonds
H O O C(CH3)3
ozinide
more stable

reductive work up
same products as oxidative H2O2 Zn, H2O or Zn, CH3COOH
work up
KMnO4 or K2Cr2O7

O O O O
(CH3)3C OH + CH3 C C(CH3) (CH3)3C H + CH3 C C(CH3)

a carboxylic acid a ketone an aldehyde a ketone

Sec. 10 - alkenes/alkynes 20
 Examples
H
1) O3, CH2Cl2, -78°C

2) Zn/HOAc

Could also use

1) O3, CH2Cl2, -78°C 1) KMnO4/NaOH
H
heat
2) H2O2 2) H3O+

What is A?

OO
1) O3, CH2Cl2, -78°C H
A +
2) Zn/HOAc O O
O O
OO
H

1) O3, CH2Cl2, -78°C OH

A + OO
2) H2O2
O O
O O
OO
OH

Sec. 10 - alkenes/alkynes 21
 Addition of Bromine and Chlorine to Alkynes
Addition of halogen to alkynes can occur once or twice depending on
how many equivalents of the halogen are added
Addition of one equivalent usually proceeds to give the trans dihalide

Sec. 10 - alkenes/alkynes 22
 Addition of Hydrogen Halides to Alkynes
Addition of hydrogen halides occurs once or twice depending on how
many molar equivalent of hydrogen halide are added
Both additions are Markovnikov and give gem-halides

HBr can be generated by reaction of acetyl bromide and alumina

Anti-Markovnikov addition of HBr occurs in the presence of peroxide

Sec. 10 - alkenes/alkynes 23
 Oxidative Cleavage of Alkynes

Reaction of alkynes with ozone or basic potassium permanganate

both lead to formation of carboxylic acids

Sec. 10 - alkenes/alkynes 24
Not covered

Not covered

Sec. 10 - alkenes/alkynes 25
 H 2 O2

Not covered Not covered

Sec. 10 - alkenes/alkynes 26