Chapter 8Reactions of Alkenes

Jo BlackburnRichland College, Dallas, TX

Dallas County Community College District2003,Prentice Hall

Organic Chemistry, 5th EditionL. G. Wade, Jr.

Chapter 8 2

Reactivity of C=C

• Electrons in pi bond are loosely held.

• Electrophiles are attracted to the pi electrons.

• Carbocation intermediate forms.

• Nucleophile adds to the carbocation.

• Net result is addition to the double bond. =>

Chapter 8 3

Electrophilic Addition

• Step 1: Pi electrons attack the electrophile.

C C + E+

C

E

C +

C

E

C + + Nuc:_

C

E

C

Nuc

=>

• Step 2: Nucleophile attacks the carbocation.

Chapter 8 4

Types of Additions

=>

Chapter 8 5

Addition of HX (1)

Protonation of double bond yields the most stable carbocation. Positive charge goes to the carbon that was not protonated.

X =>

+ Br_

+

+CH3 C

CH3

CH CH3

H

CH3 C

CH3

CH CH3

H

H Br

CH3 C

CH3

CH CH3

Chapter 8 6

Addition of HX (2)

CH3 C

CH3

CH CH3

H Br

CH3 C

CH3

CH CH3

H+

+ Br_

CH3 C

CH3

CH CH3

H+

Br_

CH3 C

CH3

CH CH3

HBr

=>

Chapter 8 7

Regiospecificity• Markovnikov’s Rule: The proton of an

acid adds to the carbon in the double bond that already has the most H’s. “Rich get richer.”

• More general Markovnikov’s 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 8

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 9

Free Radical Initiation

• Peroxide O-O bond breaks easily to form free radicals.

+R O H Br R O H + Br

O OR R +R O O Rheat

• Hydrogen is abstracted from HBr.

Electrophile

=>

Chapter 8 10

Propagation Steps

• Bromine adds to the double bond.

+C

Br

C H Br+ C

Br

C

H

Br

Electrophile =>

C

Br

CC CBr +

• Hydrogen is abstracted from HBr.

Chapter 8 11

Anti-Markovnikov ??

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

CH3 C

CH3

CH CH3 Br+

CH3 C

CH3

CH CH3

Br

CH3 C

CH3

CH CH3

Br

X

Chapter 8 12

Hydration of Alkenes

• Reverse of dehydration of alcohol• Use very dilute solutions of H2SO4 or

H3PO4 to drive equilibrium toward hydration. =>

C C + H2OH

+

C

H

C

OH

alkenealcohol

Chapter 8 13

Mechanism for Hydration

+C

H

C+

H2O C

H

C

O H

H+

+ H2OC

H

C

O H

H+

C

H

C

OH

H3O++

=>

C C OH H

H

++ + H2OC

H

C+

Chapter 8 14

Orientation for Hydration

• Markovnikov product is formed.

+CH3 C

CH3

CH CH3 OH H

H

++ H2O+

H

CH3CH

CH3

CCH3

H2OCH3 C

CH3

CH CH3

HOH H

+

H2OCH3 C

CH3

CH CH3

HOH

=>

Chapter 8 15

Indirect Hydration

• Oxymercuration-DemercurationMarkovnikov product formedAnti addition of H-OHNo rearrangements

• HydroborationAnti-Markovnikov product formedSyn addition of H-OH

=>

Chapter 8 16

Oxymercuration (1)

• Reagent is mercury(II) acetate which dissociates slightly to form +Hg(OAc).

• +Hg(OAc) is the electrophile that attacks the pi bond.

CH3 C

O

O Hg O C

O

CH3 CH3 C

O

O_

Hg O C

O

CH3

+

=>

Chapter 8 17

Oxymercuration (2)

The intermediate is a cyclic mercurinium ion, a three-membered ring with a positive charge.

C C+Hg(OAc) C C

Hg+

OAc

=>

Chapter 8 18

Oxymercuration (3)

• Water approaches the mercurinium ion from the side opposite the ring (anti addition).

• Water adds to the more substituted carbon to form the Markovnikov product.

C C

Hg+

OAc

H2O

C

O+

C

Hg

H

H

OAc

H2O

C

O

C

Hg

H

OAc

=>

Chapter 8 19

Demercuration

Sodium borohydride, a reducing agent, replaces the mercury with hydrogen.

C

O

C

Hg

H

OAc

4 4 C

O

C

H

H

+ NaBH4 + 4 OH_

+ NaB(OH)4

+ 4 Hg + 4 OAc_

=>

Chapter 8 20

Predict the Product

Predict the product when the given alkene reacts with aqueous mercuric acetate, followed by reduction with sodium borohydride.

CH3

D

(1) Hg(OAc)2, H2O

(2) NaBH4

=>

OHCH3

D

H

anti addition

Chapter 8 21

Alkoxymercuration - Demercuration

If the nucleophile is an alcohol, ROH, instead of water, HOH, the product is an ether.

C C

(1) Hg(OAc)2, CH3OH

C

O

C

Hg(OAc)

H3C

(2) NaBH4C

O

C

H3C

H

=>

Chapter 8 22

Hydroboration

• Borane, BH3, adds a hydrogen to the most substituted carbon in the double bond.

• The alkylborane is then oxidized to the alcohol which is the anti-Mark product.

C C(1) BH3

C

H

C

BH2

(2) H2O2, OH-

C

H

C

OH

=>

Chapter 8 23

Borane Reagent

• Borane exists as a dimer, B2H6, in equilibrium with its monomer.

• Borane is a toxic, flammable, explosive gas.• Safe when complexed with tetrahydrofuran.

THF THF . BH3

O B2H6 O+

B-

H

H

H

+2 2 =>

Chapter 8 24

Mechanism• The electron-deficient borane adds to

the least-substituted carbon.• The other carbon acquires a positive charge.• H adds to adjacent C on same side (syn).

=>

Chapter 8 25

Actually, Trialkyl

Borane prefers least-substituted carbon due to steric hindrance as well as charge distribution. =>

C CH3C

H3C

H

H+ BH3

B

CC H

CH3

H3C

H

H

C

CH

HH

CH3

CH3

C

C

HH

H3C

CH3

H

3

Chapter 8 26

Oxidation to Alcohol

• Oxidation of the alkyl borane with basic hydrogen peroxide produces the alcohol.

• Orientation is anti-Markovnikov.

CH3 C

CH3

H

C

H

H

B

H2O2, NaOH

H2OCH3 C

CH3

H

C

H

H

OH

=>

Chapter 8 27

Predict the Product

Predict the product when the given alkene reacts with borane in THF, followed by oxidation with basic hydrogen peroxide.

CH3

D

(1)

(2)

BH3, THF

H2O2, OH-

=>syn addition

HCH3

DOH

Chapter 8 28

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

=>

Chapter 8 29

Addition of Carbenes

• Insertion of -CH2 group into a double bond produces a cyclopropane ring.

• Three methods:DiazomethaneSimmons-Smith: methylene iodide and

Zn(Cu)Alpha elimination, haloform

=>

Chapter 8 30

Diazomethane

Extremely toxic and explosive. =>

N N CH2 N N CH2

diazomethane

N N CH2heat or uv light

N2 +

carbene

C

H

H

C

H

H

C

CC

CC

H

H

Chapter 8 31

Simmons-Smith

Best method for preparing cyclopropanes.

CH2I2 + Zn(Cu) ICH2ZnI

a carbenoid

CH2I2

Zn, CuCl =>

Chapter 8 32

Alpha Elimination• Haloform reacts with base.

• H and X taken from same carbon

CHCl3 + KOH K+ -CCl3 + H2O

CCl

Cl

Cl Cl-

+CCl

Cl

Cl

Cl

CHCl3

KOH, H2O =>

Chapter 8 33

Stereospecificity

Cis-trans isomerism maintained around carbons that were in the double bond.

C CH

CH3

H

H3C NaOH, H2O

CHBr3C C

H

CH3

H

H3C

BrBr

=>

Chapter 8 34

Addition of Halogens

• Cl2, Br2, and sometimes I2 add to a double bond to form a vicinal dibromide.

• Anti addition, so reaction is stereospecific.

CC + Br2 C C

Br

Br

=>

Chapter 8 35

Mechanism for Halogenation

• Pi electrons attack the bromine molecule.

• A bromide ion splits off.

• Intermediate is a cyclic bromonium ion.

CC + Br Br CC

Br

+ Br =>

Chapter 8 36

Mechanism (2)

Halide ion approaches from side opposite the three-membered ring.

CC

Br

Br

CC

Br

Br

=>

Chapter 8 37

Examples of Stereospecificity

=>

Chapter 8 38

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 39

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.

CC

Br

H2O

CC

Br

OH H

H2O

CC

Br

OH

+ H3O+

=>

Chapter 8 40

Regiospecificity

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

=>

Chapter 8 41

Predict the Product

Predict the product when the given alkene reacts with chlorine in water.

CH3

D

Cl2, H2O

=>

OHCH3

D

Cl

Chapter 8 42

Epoxidation

• Alkene reacts with a peroxyacid to form an epoxide (also called oxirane).

• Usual reagent is peroxybenzoic acid.

CC + R C

O

O O H CC

O

R C

O

O H+

=>

Chapter 8 43

Mechanism

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

OC

O

R

H

C

C

OOH

OC

O

RC

C

+

=>

Chapter 8 44

Epoxide Stereochemistry

Since there is no opportunity for rotation around the double-bonded carbons, cis or trans stereochemistry is maintained.

CCCH3 CH3

H H Ph C

O

O O H

CCCH3 CH3

H HO

=>

Chapter 8 45

Opening the Epoxide Ring

• Acid catalyzed.

• Water attacks the protonated epoxide.

• Trans diol is formed.

CC

OH3O

+

CC

O

H

H2O

CC

O

OH

H H H2O

CC

O

OH

H

=>

Chapter 8 46

One-Step Reaction

• To synthesize the glycol without isolating the epoxide, use aqueous peroxyacetic acid or peroxyformic acid.

• The reaction is stereospecific.

CH3COOH

O

OH

H

OH

H

=>

Chapter 8 47

Syn Hydroxylation of Alkenes

• Alkene is converted to a cis-1,2-diol,

• Two reagents:Osmium tetroxide (expensive!), followed by

hydrogen peroxide orCold, dilute aqueous potassium

permanganate, followed by hydrolysis with base

=>

Chapter 8 48

Mechanism with OsO4

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

C

COs

O O

OO

C

CO O

OO

Os

C

C

OH

OH+ OsO4

H2O2

=>

Chapter 8 49

Stereospecificity

If a chiral carbon is formed, only one stereoisomer will be produced (or a pair of enantiomers).

C

C

CH2CH3

H CH2CH3

C

C

CH2CH3

CH2CH3

OH

OH

H

HH2O2

H

(2)

(1) OsO4

cis-3-hexene meso-3,4-hexanediol

=>

Chapter 8 50

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 51

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 52

Example

CCCH3 CH3

H CH3 KMnO4

(warm, conc.)C C

CH3

CH3

OHOH

H3C

H

C

O

H3C

H

C

CH3

CH3

O

C

O

H3COH

+

=>

Chapter 8 53

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 54

Ozonolysis Example

CCCH3 CH3

H CH3 O3 C

H3C

H

O OC

CH3

CH3

O

Ozonide

+(CH3)2S

C

H3C

HO C

CH3

CH3

O CH3 S

O

CH3

DMSO

=>

Chapter 8 55

Polymerization

• An alkene (monomer) can add to another molecule like itself to form a chain (polymer).

• Three methods:Cationic, a carbocation intermediateFree radicalAnionic, a carbanion intermediate (rare)

=>

Chapter 8 56

Cationic Polymerization

Electrophile, like H+ or BF3, adds to the least substituted carbon of an alkene, forming the most stable carbocation.

C CCH3

H

H

H

OH

H

H

C

H

H

H

C

CH3

H

+ C CCH3

H

H

H

C

H

H

H

C

CH3

H

C

H

H

C

CH3

H =>

Chapter 8 57

Radical Polymerization

In the presence of a free radical initiator, like peroxide, free radical polymerization occurs.

C CPh

H

H

H

RO

C

H

RO

H

C

Ph

H

+ C CPh

H

H

H

C

H

RO

H

C

Ph

H

C

H

H

C

Ph

H =>

Chapter 8 58

Anionic PolymerizationFor an alkene to gain electrons, strong

electron-withdrawing groups such as nitro, cyano, or carbonyl must be attached to the carbons in the double bond.

C CCOCH3

CN

H

H

O

OH-

C

H

HO

H

C

COCH3

CN

O

+ C CCOCH3

CN

H

H

O

C

H

HO

H

C

C

CN

C

H

C

COCH3

CNH

OO OCH3

=>

Chapter 8 59

End of Chapter 8