Introduction to General and Organic Chemistry III

Chapter 8
Reactions of Alkenes

Department of Chemistry

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 2

Electrophilic Addition

Chapter 8

Carbocation Formation

Chapter 8

Types of Additions

Chapter 8

Addition of HBr (1)

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

Chapter 8

Addition of HBr (2)

Chapter 8

Regiospecificity
Markovnikovs Rule: The proton of an acid adds to the carbon of 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 8

Examples:

Chapter 8

In some cases, product(s) resulting From rearrangement of the initially Formed carbocation is observed!
HCl

2o R+

Cl
Chapter 8 10

Rearrangement occurs by a methyl shift.

~CH3

2o R+

3o R+

Cl
Product of rearrangement
Chapter 8 11

Free-Radical Addition of HBr

In the presence of peroxides (ROOR), HBr adds to an alkene to form the antiMarkovnikov product. Only HBr has the right bond energy. HCl bond is too strong. HI bond tends to break heterolytically to form ions. =>
Chapter 8 12

Mechanism
Initiation:

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

Hydrogen is abstracted from HBr.

Chapter 8

13

Propagation Steps:
Bromine adds to the double bond.

Hydrogen is abstracted from HBr.

Chapter 8

Why Anti-Markovnikov ?

CH3 CH3 C CH CH3 + Br

Tertiary radical is more stable, so that intermediate is formed faster.

Chapter 8 15

Hydration of Alkenes
H C C alkene + H2O
+

H OH C C alcohol

Reverse of dehydration of alcohols. Use very dilute solutions of H2SO4 or H3PO4 to drive equilibrium toward hydration. =>
Chapter 8 16

Mechanism of Hydration

17

Orientation for Hydration

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

Chapter 8

18

Example:

Chapter 8

19

Indirect Hydration
Oxymercuration-Demercuration
Markovnikov product formed Anti addition of H-OH No rearrangements

Hydroboration-Oxidation

Anti-Markovnikov product formed Syn addition of H-OH

Chapter 8 20

Oxymercuration (1)
Reagent is mercury(II) acetate Hg(OAc)2 which dissociates slightly to form +Hg(OAc). +Hg(OAc) is the electrophile that attacks the pi bond. The intermediate is a cyclic mercurinium ion, a three-membered ring system with a positive charge. 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.
Chapter 8 21

Oxymercuration (2)

Chapter 8

22

Demercuration
Sodium borohydride, NaBH4 , a reducing agent, replaces the mercury with hydrogen.
OAc Hg 4 C C O H _ + NaBH4 + 4 OH H 4 C C O H + NaB(OH) 4 _ + 4 Hg + 4 OAc

=>
Chapter 8 23

Example:

Chapter 8

24

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

CH3 D

(1) Hg(OAc) 2, H 2O (2) NaBH 4

Chapter 8

25

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

C C

(1) Hg(OAc) 2, CH 3OH O

Hg(OAc) C C H3C

(2) NaBH4 O

H C C H3C

=>
Chapter 8 26

Example:
CH 3 1) Hg(OAc)2, EtOH 2) NaBH4 H CH 3 OEt CH 3 OEt

CH 3 OEt

Not Formed !!
Chapter 8 27

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-Mkv product.
(1) BH3 C C H BH2 (2) H2O2, OH
-

C C

C C H OH

=>
Chapter 8 28

Borane Reagent
Borane exists as a dimer, B2H6, in equilibrium with its monomer. Borane is a toxic, flammable, explosive gas. Safe when complexed (Lewis acid-base) with tetrahydrofuran, THF.
H 2 O
THF
Chapter 8

B2H6

O B H H
THF . BH3

=>

29

Mechanism
The electron-deficient borane (remember Boron does not have a filled octed) adds to the least-substituted carbon. The other carbon acquires a positive charge. H adds to adjacent C on the same side (syn).

Chapter 8

=>30

Note: The Borane molecule actually reacts with three equivalents of the alkene forming a trialkyl borane.
H H3C C C H H3C 3 H3C C C H H + BH3 H H C H3C C H H B H C H CH3

H C CH3 CH3

CH3

Note: Borane prefers the least-substituted carbon due to steric hindrance as well as charge distribution. Chapter 8 31

Oxidation to Alcohol
Oxidation of the alkyl borane with basic hydrogen peroxide produces the alcohol. Orientation is anti-Markovnikov.
CH3 H CH3 C C H B H CH3 H CH3 C C H OH H

H2O2, NaOH H2O

Chapter 8

32

Example:
Predict the product when the given alkene reacts with borane in THF, followed by oxidation with basic hydrogen peroxide.
CH3 D (1) BH3, THF (2) H2O2, OH
-

Chapter 8

33

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

Chapter 8

34

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

=>

Chapter 8

35

Mechanism

Chapter 8

36

Example:

Chapter 8

37

Stereospecific Reactions
A reaction is stereospecific when a Specific stereoisomer reacts to give Only one stereoisomer of the product.

Chapter 8

38

Examples:

=>
Chapter 8 39

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 a chemical test for the presence of a double bond. =>
Chapter 8 40

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 41

+ H3O

=>

General Mechanism:

Chapter 8

42

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

Chapter 8

43

Example:
Predict the product when the given alkene reacts with chlorine in water.
CH3 Cl2, H 2O D

OH CH3 D Cl
=>

Chapter 8

44

Example:

Br 2 H2O OH Br Br OH
Chapter 8

Br OH

Not Formed !!

45

Epoxidation
Alkenes react with a peroxyacid to form an epoxide (also called oxirane). Usual reagent is peroxybenzoic acid.
O O H O

General Peroxyacid: RCO3H

O C C O + R C O H

O C C + R C O O H

Epoxide
Chapter 8 46

Mechanism
Reaction takes place in a single step (concerted). Bond cleavage and bond formation occurring simultaneously.
C

O O

C O C +

O
H

C O

H O

Chapter 8

47

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

Epoxidation is Stereospecific!!
O H CH3 C C H CH3
Chapter 8

Ph C O O H

H CH3

O C C

H CH3
48

Examples:
H H RCO 3H CHCl 3 H O H CH3 O H + CH3 O H

CH3 RCO H 3 H CHCl 3

Enantiomers
Chapter 8 49

Opening the Epoxide Ring

Acid catalyzed. Water attacks the protonated epoxide. Trans diol (Glycol) is formed.

Chapter 8

50

One-Step Synthesis of Diols

To synthesize the glycol without isolating the epoxide, use aqueous peroxyacetic acid or peroxyformic acid. The reaction is stereospecific.
O CH3COOH

OH H H
Chapter 8

H2O

=>
51

OH

Syn Hydroxylation of Alkenes

Alkene is converted to a cis-1,2-diol. Two reagents commonly used:
Osmium tetroxide (OsO4 expensive!), followed by hydrogen peroxide or Cold, dilute aqueous Potassium permanganate ( KMnO4), followed by hydrolysis with base =>
Chapter 8 52

Example:
H H H KMnO4 NaOH 0oC H OH OH

OH

NOT FORMED !!
OH

Chapter 8

53

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

=>
54

Chapter 8

Stereospecificity
If a chiral carbon is formed, only one stereoisomer will be produced (or a pair of enantiomers).
H C C H CH2CH3 cis-3-hexene
Chapter 8

CH2CH3

(1) OsO4 (2) H2O2

CH2CH3 H H C C OH OH

CH2CH3 m eso-3,4-hexanediol
55

The 2-Butenes
H CH3 KMnO4 NaOH 0oC CH3 H OH H OH CH3

CH3

CH3

KMnO4 NaOH 0oC

H3C

CH3 H OH HO H CH3
Chapter 8

CH3 HO H + H OH CH3
56

Rationale:
CH3 H H3C H H3C KMnO4 NaOH 0oC H OH CH3OH H

Rotation
CH3 H OH HO H CH3
Chapter 8

H OH HO H CH3
57

CH3

Oxidative Cleavage
Both the pi and sigma bonds break. C=C becomes two C=O. Ketones, carboxylic acid or even CO2 may be obtained. Two methods:
Warm or concentrated or acidic KMnO4. Ozonolysis

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

Chapter 8 58

Cleavage with KMnO4

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 59

Permanganate Cleavage

Chapter 8

60

Example
H CH3 C C CH3 CH3 KMnO4 (warm, conc.) H CH3 H3C C C CH3 OH OH

H H3C C O +

CH3 C CH3 O

H3C C
Chapter 8

OH
61

Examples:
1) KMnO4, Conc 2) H3O+ HO 2C

CO2H

CH3

1)KMnO4, NaOH heat 2) H3O

+

O CO2H

Chapter 8

62

Ozonolysis
Reaction with ozone forms an ozonide. Ozonides are not isolated, but are treated with a mild reducing agent like Zn or dimethyl sulfide, (Me2S). Milder oxidation than permanganate. Products formed are ketones or aldehydes. =>
Chapter 8 63

Mechanism

Chapter 8

64

Example
O C H3C O O C

H CH3

C C

CH3 CH3

O3

CH3 CH3

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

DMSO
65

Chapter 8

Example

CH3

1) O3, CH2Cl2 2) Zn, H2O

O CHO

1) O3, CH2Cl2 2) Zn, H2O

O + HCHO

Chapter 8

66

Question
An alkene adds hydrogen in the presence of a catalyst to give 3,4-dimethylhexane. Ozonolysis of the alkene followed by treatment with zinc and acetic acid gives a single organic product. The alkene is:

A.

C.

B.

D.

Chapter 8

67

End of Chapter 8

Chapter 8

68