Reactions of Alkenes

1. Electrophilic Addition
A. Electrophilic addition via carbocation
A.1 Hydrohalogenation: Addition of HX
HX
C C C C
H X Markovnikov's
Orientation
where HX=HCl, HBr or HI

A.2 Catalytic hydration: Addition of H2O/H+

+
H2O/H
C C C C
H OH Markovnikov's
Orientation
A.3 Addition of ROH/H+
+
ROH/H
C C C C
H OR Markovnikov's
Orientation

B. Electrophilic addition via bridged ion intermediate

B.1 Halogenation: Addition of X2

X
X2
C C C C
CH2Cl2
X
where X2= Cl2, Br2
B.2 Halohydrin Formation: Addition of X2/H2O
X
X2
C C C C
H2O
OH
 B.3 Oxymercuration/Demercuration
H
(1) Hg(OAc)2, H2O
C C C C
(2)NaBH4
OH
2. Free radical addition
HX
C C C C
ROOR
H X Anti Markovnikov's
Orientation
3. Reduction
H2
C C C C
catalyst
H H Syn Addition

catalysts can be Pd/C, PtO2, Raney Ni

4. Oxidation
A. Hydroxylation
Syn dihydroxylation

(1) OsO4
C C C C
(2)NaHSO 3, H2O
OH OH
or
KMnO4
C C
H2O, NaOH
OH OH
N-methylmorpholine N-oxide (NMO)
 Anti dihydroxylation

OH
(1) RCO3H
C C C C
(2) H2O/ (H3O+ or OH-)
HO
B. Oxidative cleavage

B.1 Ozonolysis
R R"
R R" (1) O 3
C O O C
C C R'''
R''' (2) Zn/ H3O+ R'
R'

R R'' R R''
(1) O3
C C C O + O C
(2) CH3SCH3
R' R''' R' R'''

B.2 Reaction with KMnO4 in acidic solution

R R"
R R" KMnO4
C O O C
C C + HO R'''
H R''' H3O

H R
R KMnO 4
C O + CO 2
C C + HO
H H H3O
5. Hydroboration/Oxidation
H
(1) BH3/THF
C C -
C C
(2) H2O2, OH
OH Anti Markovnikov's
Orientation

6. Polymerization

Polymerization
C C C C
initiator
n
A. Radical Polymerization

Radical
C C C C
initiator
n
B. Cationic Polymerization

+
H
C C C C
catalyst
n
Polymer
Large molecule resulting from repetitive bonding together off
small molecules called monomers.

Some alkene polymers and their uses

Monomer Formula Trade/Common Uses
Name
Ethylene H2C CH2 Polyethylene Packaging
bottles
Propene H2C CHCH3 Polypropylene Automotive
moldings
Vinyl chloride H2C CHCl PVC Pipes,
insulation
Styrene H2C CHC6H5 Polystyrene Foam

Tetrafluoroethylene F2C CF2 Teflon Coatings,

gaskets
Acrylonitrile H2C CHCN Orlon Fibers

Methylmethacrylate CH3 Plexiglass Molded

articles,
H2C C COCH3 paints
O
vinylacetate H2C CHO CCH3 Polyvinylacetate Paints,
adhesives
O