Addition Reactions to Alkenes

Addition of Hydrogen Halides to Alkenes.
General Reaction R2C=CR2 + HX R2HC-CR2X H C
+

H H

C

C

H H

Slow + H
+

H H

X H

C

X C C

H H

H Electrophile Nucleophile (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. Electrophile (acid)

H

Nucleophile H (base) H Fast

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
H3C C H3C C CH3 H

H Br electrophile (acid)

+

H3C

+

sp3 H C H CH3

Br H3C C CH2CH3 sp3 major product H3C

sp2

C H3C sp2

nucleophile (weak base)
CH3

bottom
H H
+

H Br
CH3

+

CH3

Br CH3 (S) (R) diastereomers CH3 CH3 Br (R) (R) CH3

top

CH3

top

+

bottom Sec. 10 - alkenes/alkynes 3

Examples
H3C C H3 C CH2 I – Cl

nucleophile electrophile (acid) (weak base) no water

H3C C H3 C CH2

H2SO4 cold concentrated
H O O S O OH

very weak base poor nucleophile

weak bond HSO4¯ great leaving group

Sec. 10 - alkenes/alkynes

4

Examples
hydration water present H3C C H3 C H O H
+

O O S O OH

CH2
H

dilute H2SO4
O O S O OH

or H

H2O - weak base poor nucleophile but better than HSO4¯ also in greater concentration

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 H3C C CH3 H3C C H3C H3C C H3C CH2 CH2 CH3 dehydration
cold concentrated H2SO4 dilute H2SO4 heat

concentrated H2SO4

+

OH2 C CH3 CH3

H3C

-H2O H3C C H3C
cold

+

E1 CH3 -H+

H3C C H3C add H2O
heat

CH2

H3C C H3C H3C C H3C H3C C H3C

OSO3H H3C C CH3 CH3 H3C H2O -H+ CH3

+

CH3 HSO4¯

+

CH3

hydration concentrated H2SO4

H2O -H+ OH H3C C CH3 NaBr SN1
H3C

+

C

CH3

H3C + HSO4¯ SN1 hydration

H3C C H3C CH2

+

CH3

NaBr

Br C CH3 CH3
6

Don’t forget anytime a carbocation is formed rearrangement of the carbon skeleton can occur

Sec. 10 - alkenes/alkynes

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 CH3CH2CH2Br CH3CH=CH2 ROOR Mechanism
a peroxide

RO OR
H3C CH

2 RO
Br H

RO H Br H C 3

Br

ROH + Br

H3C

CH

CH2

CH2

CH2

CH2

Br + Br

propagation

2° most stable than 1° same as carbocations
Br C H C C H H

Br
H

H

C

C

H CH3

H


H

H
7

Sec. 10 - alkenes/alkynes

Addition of Bromine and Chlorine to Alkenes
Addition produces vicinal dihalides

Sec. 10 - alkenes/alkynes

8

Mechanism
electrophile (acid)

Br

δ−

Br δ+ C C R R R R C

Br C R + R
bromonium ion intermediate electrophile (acid)

+

Br Br
nucleophile (base)

R R

R R C C Br

R R

nucleophile (base)

anti addition forms trans products

Br polarized Br

δ− δ+

Br + R R R C C R R

Br

R R

C

C

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 δ+ stronger bond

H3C C H3C CH2 + Br – Br

H3C 3° C H3C δ+

Br C 1°

H H

+ Br

H3C

H3C C C

Br H H

Br

3° carbon can bear more of the positive charge.

Sec. 10 - alkenes/alkynes

10

Bromonium Ion

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11

Halohydrin Formation (halogen + alcohol)
Br – Br H2O (solvent)

Major product OH
+

Br2 H2O

Na OH 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.
RCH3 Lowest Oxidation State [O] [H] RCH2OH [O] [H] O R C H [O] [H] O R C OH Highest Oxidation State

OH R CH R

[O] [H]

O R C

R

Oxidation → broad definition → a reaction that increases its content of any element more electronegative than carbon
CH3
[O] [H]

CH2Cl

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 H H a bond to a carbon → 0

H

O

C

O

H

C H

C H

OH

H

C H

H

OS = oxidation state

Sec. 10 - alkenes/alkynes

14

Oxidation States of Carbon
H C H C H H H H2/Pd H C H H C H H H H C H H C H OH KMnO4 Oxidation H H C H O C OH

Reduction

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 nucleophile (base)

Syn addition (same side)

causes cleavage without altering stereochemistry

COLD
Sec. 10 - alkenes/alkynes 16

Example
O O • OsO4, ether Os O 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
O OS = +7 O
Mn

O O H H3C

O
Mn

O O C

4 electron transfer O C CH3 CH3 +

can’t break C-C bonds no further oxidation O C H3C CH3 OS = +2 +
O
Mn

OS = +5 cleavage

O C

H3CH2C OS =-1

C(CH3)2 OS = 0

CH3 H OS = +1

OS = 0

OS = +1

Ox

further oxidation of carbon while manganese is reduced

O

O C CH3

OS = +3
In an acidic solution Mn2+ will be the final manganese product In a basic solution Mn(IV)O2 is formed not MnO3¯ and is the final manganese product Do not need to know just for interest

HO

OS = +3 Ox Ox decomposition carbonic acid
Sec. 10 - alkenes/alkynes

no further oxidation

formic acid formaldehyde

18

Example
1) KMnO4/NaOH heat 2) H3O+ intermediate Ox

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.
+ + R2C N N Diazo + RC N O Nitrile oxide + R N N N Azides O + R2C N R Nitrones

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19

Ozonolysis of Alkenes
+ O O O O + O O O + O O 1,3-dipolar addition reaction

O

O

O

+
(CH3)C H CH3

1,3-dipolar addition (CH3)C
H

O

O O C CH3 C(CH3)3

C

reverse 1,3-dipolar addition (CH3)3C
H

CH3 C O O

+ C C(CH3)3
O

C

C

C(CH3)3 (CH3)C H O C C O O

ozonide not stable
CH3 C(CH3)3

1,3-dipolar addition

This form is favoured because of the formation of stronger C-O bonds as opposed to weak O-O bonds

ozinide more stable

same products as KMnO4 or K2Cr2O7

oxidative work up
O

reductive work up
H2O2 Zn, H2O or Zn, CH3COOH

O CH3 C C(CH3)

O (CH3)3C H

O

(CH3)3C OH +

+

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

H

What is A?
OO

A

1) O3, CH2Cl2, -78°C 2) Zn/HOAc 1) O3, CH2Cl2, -78°C 2) H2O2
O O O O

+
O O

H

OO H

A

+
O O

OH

OO 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

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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

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Not covered Not covered

Sec. 10 - alkenes/alkynes

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H 2 O2

Not covered

Not covered

Sec. 10 - alkenes/alkynes

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