CH2211 Mechanisms

Chapter 2
a. B-L acid-base proton transfer:
H
O
N H H NH3 + OH

H
B-L Base B-L Acid

b. Lewis acid-base adduct formation:

Br
Br

Lewis
Lewis Lewis Acid-Base
Base Acid Adduct

Chapter 10

a. HX addition to an alkene:
Carbocation
intermediate

R R R

H X H
H X X
X= Cl, Br, I

b. HX addition to an alkene with Carbocation rearrangement:

R H R H R H R' R H

R' R' H R' H X H

H X X

Hydride Shift
X= Cl, Br, I
Note: Methyl groups can migrate also if quaternary carbon is adjacent to a 20
carbocation.

1
 c. X2 addition to an alkene:

R R X X
R

X X R X
X X

X= Cl, Br, I

d. Halohydrin formation (X2/H2O):

X
OH2 H
R R R HO
H O + HX

X X R X
X X R X

X= Cl, Br, I

e. H2O/HX addition to an alkene:

R R R R
+ HX

H HO H HO H
H X H2O
H
X
X=Cl, Br, I

f. Oxymercuration/ Demercuration of alkane: (NOT REQUIRED)

OAc
OH2 H
R R R HO HO
H O NaBH4
+ Hg
Hg Hg R Hg R
Hg OAc R Hg
OAc OAc OAc
OAc OAc

g. Hydroboration of an alkene:
R

H BH2

R R
O
OH O B
H2O2 O

3X R

2
Chapter 11

a. HX addition to an alkyne:
R R
R
H X H
H X X

X= Cl, Br, I

b. X2 addition to an alkyne:
X X X X X X X X
X
Excess
R X2
R
X X R X R X R X R X X X
X
X= Cl, Br, I

c. Acid catalyzed hydration of an alkyne:

H2 O OH2
OH2 H H H
O O O
H OH2
H OH2

tautomerization
d. Hg catalyzed hydration of an alkyne: (NOT REQUIRED)

H OH2
OH2 H
HO HO HO
H2O
R
2- 2- 2-
2+ 2-
R Hg SO4 R Hg SO4 R Hg SO4 H
Hg SO4 R

O H
tautomerization

R H

e. Acetylide formation and alkylation of acetylide anions:

H
X
H H
HH
R C C H R C C R C C C X R C C C H
H H H
Na H2N

Alkylation of acetylide anion

Acetylide anion formation
X = Cl, Br, I

3
Chapter 12

a. Epoxidation of an alkene:
R'
R'
H O H

O + RCO2H
O
O R H
R R

b. Reduction of an alkyl halide:

R Li R

X + H AlH3 H + AlH3 + Li + X:

X=Cl, Br, I
(Alkyl halide must be primary or secondary)

Chapter 7

a. Sn2 (bimolecular substitution) reaction:

R R R
Nu Y Nu Y Nu + Y
H H
R' H R' R'

Nu= Nucleophile Transition

Y= Leaving group State

b. Sn1 (unimolecular substitution) reaction:

R R R
R'' Y Nu R'' Nu
R'' R' R'
R'
Carbocation
intermediate
Chapter 8
a. E2 (bimolecular elimination) reaction:

B B
H R'' H R'' R R''
R''' R''' + B H + Y
R R R' R'''
R' Y R' Y
B = Base Transition state –

4
 antiperiplanar
geometry
b. E1 (unimolecular elimination) reaction:

H R H R H R
H C C Y H C C + B H + Y
H R'
H R' H R'
B

Chapter 15

a. Radical halogenation of alkanes:

hv Initiation (X= Cl or Br)

X X 2 X

R H X R + HX
Propagation
R X X R X + X

R R R R

R X R X Chain Termination

X X X X