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Lecture - 8

Organic Chemistry Topic Addition Reactions Electrophilic Addition Reactions Nuceophilic Addition Reactions

Reactivity of C=C
Electrons in pi bond are loosely held. Electrophiles are attracted to the pi electrons. Reaction can be :
Ionic- Polar medium Free radical- non polar medium

Ionic: Carbocation intermediate forms.s Nucleophile adds to the carbocation. Net result is addition to the double bond. =>
Chapter 8 2

Electrophilic Addition
Step 1: Pi electrons attack the electrophile.
E C C + E
+

C +

Step 2: Nucleophile attacks the carbocation.


E C C+ + _ Nuc: E Nuc C C

Bond Broken -1 & ! Sigma Formed 2 sigma Chapter 8

=>
3

Types of Additions

=>
Chapter 8 4

Hydrogenation
Alkene + H2 Alkane Catalyst required, usually Pt, Pd, or Ni. Finely divided metal, heterogeneous Syn addition

=>
Chapter 8 5

Addition of Halogens
Cl2, Br2, and sometimes I2 add to a double bond to form a vicinal dibromide. Anti addition, so reaction is stereospecific.
Br C C + Br2 C C Br
=>

Chapter 8

Mechanism for Halogenation


Pi electrons attack the bromine molecule. A bromide ion splits off. Intermediate is a cyclic bromonium ion.
Br C C

C C

+ Br

Br

+ Br

=>

Chapter 8

Mechanism (2)
Halide ion approaches from side opposite the three-membered ring.
Br Br C C C C Br Br

=>
Chapter 8 8

Examples of Stereospecificity

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Chapter 8

Test for Unsaturation


Add Br2 in CCl4 (dark, red-brown color) to an alkene in the presence of light. The color quickly disappears as the bromine adds to the double bond. Decolorizing bromine is the chemical test for the presence of a double bond.
=>
Chapter 8 10

Formation of Halohydrin
If a halogen is added in the presence of water, a halohydrin is formed. Water is the nucleophile, instead of halide. Product is Markovnikov and anti.
Br C C H2O Br C C H O H

Br C C H H2O
Chapter 8 11

+ H3O
=>

Regiospecificity
The most highly substituted carbon has the most positive charge, so nucleophile attacks there.

=>
Chapter 8 12

Addition of HX (1)
Protonation of double bond yields the most stable carbocation. Positive charge goes to the carbon that was not protonated.
CH3 CH3 CH3 C CH CH3 H Br CH3 C CH CH3 + H

X
Chapter 8

+ Br CH3 CH3 C CH CH3 + H

=>
13

Addition of HX (2)
CH3 CH3 C CH CH3 H Br CH3 CH3 C CH CH3 + H + Br _

CH3 CH3 C CH CH3 + H _ Br

CH3 CH3 C CH CH3 Br H


=>

Chapter 8

14

Regiospecificity
Markovnikovs Rule: The proton of an acid adds to the carbon in the double bond that already has the most Hs. Rich get richer. More general Markovnikovs Rule: In an electrophilic addition to an alkene, the electrophile adds in such a way as to form the most stable intermediate. HCl, HBr, and HI add to alkenes to form Markovnikov products. =>
Chapter 8 15

Free-Radical Addition of HBr


In the presence of peroxides, HBr adds to an alkene to form the anti-Markovnikov product. Only HBr has the right bond energy. HCl bond is too strong. HI bond tends to break heterolytically to form ions. =>
Chapter 8 16

Free Radical Initiation


Peroxide O-O bond breaks easily to form free radicals.
R O O R
heat

R O

O R

Hydrogen is abstracted from HBr.

R O

+ H Br

R O H

+ Br

=>
Chapter 8

Electrophile

17

Propagation Steps
Bromine adds to the double bond.
Br
+

C C

C C Br

Hydrogen is abstracted from HBr.

C C Br

H Br

C C Br H
Chapter 8

Br

Electrophile =>

18

Anti-Markovnikov ??
CH3 CH3 C CH CH3

CH3 CH3 C CH CH3 + Br

Br

CH3 CH3 C CH CH3 Br

Tertiary radical is more stable, so that intermediate forms faster. =>


Chapter 8 19

Hydration of Alkenes
H C C alkene + H2O
+

H OH C C alcohol

Reverse of dehydration of alcohol Use very dilute solutions of H2SO4 or H3PO4 to drive equilibrium toward hydration. =>
Chapter 8 20

Mechanism for Hydration


H H C C + + H O H + C C + H2O

+ C C

H + H O H + H2O C C

H + H O H C C + H2O

H H O C C + H3O +
=>

Chapter 8

21

Orientation for Hydration


Markovnikov product is formed.
CH3 H CH3 CH3 C CH CH3 + H2O + H
H2O

CH3 C CH CH3 + H O+ H
CH3 CH3 C CH CH3 +O H H H H2O
Chapter 8

CH3 CH3 C CH CH3 H O H

=>
22

Epoxidation
Alkene reacts with a peroxyacid to form an epoxide (also called oxirane). Usual reagent is peroxybenzoic acid.
O C C + R C O O H O C C O + R C O H
=>

Chapter 8

23

Mechanism
One-step concerted reaction. Several bonds break and form simultaneously.
C

O O

C O C +

O
H

C O

H O

=>
Chapter 8 24

Epoxide Stereochemistry
Since there is no opportunity for rotation around the double-bonded carbons, cis or trans stereochemistry is maintained.
O H CH3 C C H CH3 Ph C O O H H CH3 O C C H CH3
=>

Chapter 8

25

Opening the Epoxide Ring


Acid catalyzed. Water attacks the protonated epoxide. Trans diol is formed.
H3O O C C
+

OH C C O

H O C C

OH C C O

H
=>

H2O

H2O

Chapter 8

26

One-Step Reaction
To synthesize the glycol without isolating the epoxide, use aqueous peroxyacetic acid or peroxyformic acid. The reaction is stereospecific.
O CH3COOH H OH H OH
=>

Chapter 8

27

Syn Hydroxylation of Alkenes


Alkene is converted to a cis-1,2-diol, Two reagents:
Osmium tetroxide (expensive!), followed by hydrogen peroxide or Cold, dilute aqueous potassium permanganate, followed by hydrolysis with base =>
Chapter 8 28

Mechanism with OsO4


Concerted syn addition of two oxygens to form a cyclic ester.
O C C O O
H2O2

O Os C C

O Os O

C OH C OH + OsO4
=>

Chapter 8

29

Oxidative Cleavage
Both the pi and sigma bonds break. C=C becomes C=O. Two methods:
Warm or concentrated or acidic KMnO4. Ozonolysis

Used to determine the position of a double bond in an unknown. =>


Chapter 8 30

Cleavage with MnO4 Permanganate is a strong oxidizing agent. Glycol initially formed is further oxidized. Disubstituted carbons become ketones. Monosubstituted carbons become carboxylic acids. Terminal =CH2 becomes CO2. =>
Chapter 8 31

Example
H CH3 CH3 CH3 KMnO4 (warm, conc.) H CH3 H3C C C CH3 OH OH
H H3C C O + CH3 C CH3 O
=>

C C

H3C C
Chapter 8

OH
32

Ozonolysis
Reaction with ozone forms an ozonide. Ozonides are not isolated, but are treated with a mild reducing agent like Zn or dimethyl sulfide. Milder oxidation than permanganate. Products formed are ketones or aldehydes. =>
Chapter 8 33

Ozonolysis Example
H CH3 CH3 CH3 O3 H C H3C O O O C CH3 CH3

C C

Ozonide
(CH3)2S H C O H3C O C CH3 + CH3 CH3 O S CH3 =>

DMSO

Chapter 8

34

Addition to C=O
Highly polar carbonyl bond >C+=OAttack on +ve charge carbon-=carbanion Attack on -ve charge carbon-=carbanium ion

Structure & Reactivity of Carbonyl Compounds: +I effect groups - decreases reactivity - I effect groups -Increases reactivity

addition of hydrogen cyanide to the carbonyl group of an aldehyde or ketone

Reduction of aldehydes and ketones with sodium tetrahydridoborate(III) or lithium tetrahydridoaluminate(III)