1

Generally the reaction is exothermic because one p and one s bond are converted to two s bonds.

Electrophilic Addition: Mechanism

The p electrons of the double bond are loosely held and are a source of electron density, i.e. they are nucleophilic

10

In addition reactions the alkene changes from a nucleophile in the first step to an electrophile in the second
Slow, RDS

Step I

HX = HCl, HBr, HI, H2SO4, H3O

Step II

X- = Cl-, Br-, I-, HSO4-, H2O

11

Electrophilic Addition of HX
The reaction has a highly endergonic first step (rate determining) and a highly exergonic second step

12

13

The Step I is slow & it largely or entirely controls the overall rate of addition, thus it is RDS. It involves attack by an acidic , e- seeking reagent (electrophile) thus called Electrophilic Addition. The electrophile can be Bronsted acid or any e- deficient molecule a Lewis acid.

General mechanism for HCl addition

H3C H3C CH H C CH2 CH3 + H Cl H3C H3C H C H C Cl
14

CH3 + Cl CH3

+ Cl

General mechanism for H2SO4 addition

H3C H3C CH H C CH2 + H OSO3H CH3 + OSO3H H3C H3C H C H C CH3 + OSO3H CH3

OSO3H

General mechanism for H2O addition

H3C H3C CH H C CH2 CH3 + H OH2 + OH 2 H3C H3C H C H C OH2 H3C H C OH2 CH3 + OH2 H3C H C OH CH3 + H OH2
15

CH3 + CH3

OH2

Evidence for the proposed mechanism:

1. Rate depends on the concentration of both reactants

2. Reaction requires acidic reagent

3. Where ever structure permits, reaction is accompanied by rearrangement

The proposed mechanism is consistent with: 1. The orientation of addition 2. The relative reactivities of alkenes
16

Electrophilic Addition: Rearrangement

CH3 H3C C CH3
3,3-dimethyl-1-butene

CH3 CH CH2 + H I H3C C CH3 Methyl shift H C

o

CH3

H3C

CH3 C H C CH3

2 cation

CH3 I
3-iodo-2,2-dimethylbutane

CH3 H3C
o

H C CH3

CH3

H3C

CH3 C I H C CH3 CH3

3 cation

2-iodo-2,3-dimethylbutene

The formation of rearranged product proves that the electrophilic addition occurs via carbocation intermediate.
17

18

Orientation & Reactivity

19

20

21

22

Addition of HCl to Propylene

H3 C HCl H C CH3 Cl H3C H C CH3

2o cation

H3C

CH

CH2

Cl isopropyl chloride H2 C

propylene

H3 C

H2 C

CH2

Cl

H3 C

CH2 Cl
23

1o cation

Addition of HCl to 2-methyl-2-butene

H3C CH3 HCl CH C CH3 2-methyl-2-butene H2 C CH3 C CH3 Cl H3C H2 C CH3 C CH3

3o cation

Cl tert-pentyl chloride CH3 CH3 CH3 Cl H3C H C Cl C H CH3

H3C

H3C

H C

C H

2o cation

Orientation in addition is determined by the relative rates of the two competing reactions : formation of one carbocation or the other.
24

Orientation & Reactivity

25

Rate of formation of carbocations

3o > 2o > 1o > CH3+

Stability of carbocations 3o > 2o > 1o > CH3+

C Z H C

+ H:Z

C H

+ :Z

Reactants

Transition state

Products

Can we relate the rate of formation of carbocation in the Addition reaction with its stability ???
26

Eact

PE

H3 C

H2 C

Eact CH2 H3C H C CH3

1o cation +:Z H3 C CH CH2 +H:Z

2o cation +:Z

Progress of reaction

Progress of reaction

More stable the carbocation, the faster it is formed.27

Orientation & Reactivity

Electron releasing groups tend to disperse the partial positive charge developed on carbon & stabilize the T.S. This stabilization of T.S. lowers the Eact and permits a faster reaction.

The rate of addition of a proton to double bond depends upon the stability of the carbotaion being formed.

This factor determines not only the orientation of addition to a single alkene, but also relative reactivities of differ alkenes.
28

Reactivity of alkenes towards acids

H3C C H3C H3C CH CH2 CH2

>

H3C

CH

H C

CH3 H2C

>

H3C CH2

H2 C

CH C H

CH2 Cl

>

>

>

H2C

A 3o carbocation is formed faster than a 2o cation thus isobutyelene is more reactive than 2-butene The e- release by alkyl groups disperse the positive Charge & stabilizes a carbocation. The e- withdrawal by halogens intensifies positive charge & destabilizes a carbocation. Thus vinyl chloride is less reactive than ethylene.

29

H3C C H3C CH2 + H: Z

H3 C C H3 C CH3 3o cation H3C H2 C 2o cation H2 C H C H C CH3 + : Z + :Z

isobutylene CH H C CH3 + H: Z

H3C

2-butene H2 CH C 1-butene

H3C

CH2 + H: Z

H3C

CH3 + : Z

2o cation H C

H3C CH CH2 prophylene H2C CH2

+ H: Z

H3C

CH3

+ :Z

2o cation H3 C
o

+ H: Z

CH2

+ :Z
30

ethylene

1 cation

Addition of Halogens to Alkenes

Addition produces vicinal dihalides

Note: Alkanes do not react with bromine in the dark. 31 Above reaction used as test for alkenes.

Mechanism of Halogen Addition

32

Stereochemistry of Halogens addition

The net result is anti addition because of the SN2 attack on the bromonium ion intermediate
When cyclopentene reacts the product is a racemic mixture of trans-1,2-dibromocyclopentane enantiomers

33

Evidences / facts to support this mechanism :

1. Effect of the structure of alkene on reactivity

2. Effect of added nucleophile on the products obtained

3. Halogen add with complete stereoselctivity and its Anti addition 4. Direct observation of halonium ions under superacid conditions

5. Role played by halonium ion is neighbouring group effect

34

1. Alkenes show the same order of reactivity toward halogens as toward the acids.
Support: e- relaing groups activate alkenes whereas, ewithdrawing groups deactivate them. 2. Halonium ion intermediate is formed during reaction, which can react with other added nucleophiles (negative ion or basic molecule) to give other products. Experimental support:

if ethylene is bubbled into aq. solution of bromine & NaCl, then products obtained are Dibromo compound & Bromoalcohol.
35

Br

Br H2C CH2 1,2-dibromoethane Br

Cl

Br H2C CH2 2-bromo-1-chloroethane Cl

Br H2C CH2 Br2 H2C CH2 I ethylene

Br H2C CH2 2-bromo-1-iodoethane I

NO3

Br H2C CH2 ONO2 2-bromoethyl nitrate

H2O

Br H2C CH2 OH2 - H+

Br H2C CH2

36 OH 2-bromoethanol

Stereospecific Reactions
A reaction is stereospecific if a particular stereoisomeric form of the starting material reacts in such a way that it gives a specific stereoisomeric form of the product Example: cis- and trans-2-butene give stereoisomeric products when halogenated

37

Halohydrin Formation
Addition of Hypohalous acids
H3C CH CH2 Br2 H2O H3C Br H C CH2

propylene

OH 1-bromo-2-propanol (propylene chlorohydrin) Cl H2 C OH 2-chloroethanol (ethylene chlorohydrin) CH2

H2C

CH2

Cl2 H2O

ethylene

Halohydrins are not formed by direct addition of preformed Hypohalous acid (HOX), but by the successive addition of 38 Halogen and water according to the mechanism.

39

Step I
CH2 CH2

X X2 H2C CH2 + :X

Halonium ion Step II

X H2C CH2 H2O X H2C CH2 OH2 - H+ Br H2C CH2

OH Halohydrin

For unsymmetrical alkenes orientation follows Markonikov,s Rule: the positive halogen going to the same carbon that the hydrogen of a protic acid would go. For Propylene, Bromine attached to the terminal carbon.
40

Addition of Alkenes : Dimeraization

CH3 H2C CH3 H3 C C CH2 H2SO4 80 C CH3 H3 C C C H CH3 C CH3
o

CH3 H2 C C CH3 CH3 CH3 H2 Ni H3C C H H2 C CH3 C CH3 2,4,4-trimethylpentane (isooctane) CH3

2,4,4-trimethyl-1-pentene

isobutylene

CH3 2,4,4-trimethyl-2-pentene

The alkene produced contain exactly twice the number of carbon & hydogen atoms as the isobutylene, this reaction called Dimerization. Other alkenes undergoes analogous reaction by treatment 41 with sulfuric or phosphoric acid.

CH3 H3C C CH2 + H:B

Step I

CH3 H3C C CH3 + :B

3o cation Addition of proton to isobutyelene gives carbocation

CH3 H3C C CH2 + CH3 C CH3 CH3

isobutylene

Step II
H3C

CH3 C H2 C

CH3 C CH3 CH3

Addition of isobutylene to carbocation to yield another 3o carbocation. Which may undergo similar addition to one more isobutylene to give larger molecule or may loose a proton to give dimer alkene products.
42

CH3

CH3 H2 C C CH3 CH3

Step III
CH3 H3 C C H2 C

H2 C

CH3 C CH3 CH3 + :B

2,4,4-trimethyl-1-pentene

CH3 H3C C C H

CH3 C CH3

CH3 2,4,4-trimethyl-2-pentene

Indeed in the given case it looses a proton to give dimer alkene products. Since the proton can be lost from either side of the positively charged carbon, two alkenes should be formed. 43

Addition of Alkanes : Alkylation

CH3 H3C C CH2 + CH3 HC CH3 H2SO4 or HF 0-10 oC H3C CH3 C H H2 C CH3 C CH3

isobutylene

CH3 isobutane

CH3 2,2,4-trimethylpentane

isooctane
CH3 H3C C CH2 +

Step I
H:B H3C

CH3 C CH3 + :B

isobutylene

3o cation

CH3 H3C C CH2 +

CH3 C CH3 CH3

Step II
H3C

CH3 C H2 C

CH3 C CH44 3 CH3

Step III
CH3 H3C C H2 C CH3 C CH3 CH3 + H CH3 C CH3 H3C

CH3 C H H2 C

CH3 C CH3 CH3

CH3 isobutane

CH3 + C CH3 CH3

The carbocation abstracts a hydride ion ( :H- ) from alkane. This step yields an alkane and a new carbocation to continue the chain. This reaction is an example of intermolecular hydride shift and shows that carbocation is extremely strong acid (Lewis acid).
45

Summary of carbocation reactions:

A carbocation may 1. Combine with negative ion of basic molecules 2. Rearrange to a more stable carbocation 3. Eliminate a proton to form alkene 4. Add to an alkane to form larger carbocation 5. Abstract a hydride ion from an alkane In all the above reactions, the octet of positively charged carbocation is completed by a pair of electrons supplied by donor atoms.

46

Oxymercuration-Demercuration:
We can make Alcohols from Alkenes : Markovnikov Addition

The procedure gives high yields of alcohols and avoids rearrangements

47

Oxymercuration-Demercuration The reaction shows Markovnikov selectivity

48

Oxymercuration-Demercuration
CH3 Hg(OAc)2 / THF-H2O H3CH2C C CH2 2-methyl-1-butene NaBH4, OH CH3

H3CH2C

CH3

OH tert-pentyl alcohol

Hg(OAc)2 / THF-H2O H3C(H2C)2 C H CH2 NaBH4, OH

H3C(H2C)2 1-hexanol H3C HO

H C OH

CH3

1-hexene H3C

Hg(OAc)2 / THF-H2O NaBH4, OH

1-methylcyclopentene

49 1-methylcyclopentanol

Mechanism involves formation of a bridged mercurinium ion

50

51

Hydroboration-Oxidation Anti-Markovnikov, Syn Hydration

Alkenes undergoes hydroborantion on treatment with diborane to yield alkylboranes (R3B), which on oxidation give alcohols.
H2C CH2 H2C CH2 (CH3CH2)2BH

(BH3)2 diborane H2C CH2

CH3CH2BH2

(CH3CH2)3B triethylboron

3 H2O2 / OH

3 CH3CH2OH ethyl alcohol

B(OH)3 boric acid

52

Hydroboration-Oxidation Anti-Markovnikov : Syn Hydration

The reaction leads to syn and anti-Markovnikov addition of water to alkenes

Hydroboration: Synthesis of Alkylboranes

The elements of hydrogen and boron are added across the double bond

53

H3C

C H

CH2

(BH3)2

H2O2 / OH

H3C

H2 C

H2 C

OH

propylene H3CH2C C H CH2 (BH3)2 H2O2 / OH

n-proyl alcohol

H3CH2C

H2 C

H2 C

OH

1-butene CH3 H3C HC C CH3 (BH3)2

n-butyl alcohol CH3 H3C H C C H CH3

H2O2 / OH

2-methyl-2-butene CH3 H3 C C CH3 3,3-dimethyl-1-butene C H CH2 (BH3)2

OH 3-methyl-2-butenol

H2O2 / OH H3C

CH3 C CH3 3,3-dimethyl-1-butenol

54

H2 C

H2 C

OH

In practice, a borane complex with the solvent (THF) tetrahydrofuran is often used

Step I : Boron hydride adds successively to three molecules of alkene

Mechanism of Hydroboration

Step I

55

Boron becomes attached to the least substituted carbon of the double bond. The bulky boron group can approach the least sterically hindered carbon more easily This orientation also allows a + charge in the transition state to reside at the most substituted carbon

This orientation leads to anti-Markovnikov product Reaction is highly regioselective. The boron and hydride add with syn stereochemistry

56

Step I

57

Step I

58

Step II : Oxidation and Hydrolysis of Alkylboranes Oxidation and hydrolysis to the alcohol takes place with retention of stereochemistry at the carbon bonded to boron

Step II
59

Step II

60

Hydroboration of methylcyclopentene gives the anti-Markovnikov product with syn addition of the elements of water

61

Summary of Alkene Hydration Methods

1. Acid-catalyzed hydrolysis: Markovnikov addition, Rearrangement possible
2. Oxymercuration, demercuration: Markovnikov addition, Anti-addition Usually NO rearrangement, Product is more substituted alcohol 3. Hydroboration-Oxidation: Anti-Markovnikov and Syn addition NO rearrangement, Product is least substituted alcohol
62