Dr.

Laurance
Bourghli
Reactions of Alkyl Halides
 Dr. Laurance
Bourghli
Classification of C―X Compounds

alkyl halides vinyl halides

R―X aryl halides X
X C C

In all cases, X = Cl, Br, I

 Dr. Laurance
Bourghli
Alkyl Halides

Alkyl halides react as electrophiles in polar reactions.

δ+ δ‒
C X

Alkyl halides react two main reactions:

 Nucleophilic substitution reactions
 Elimination reactions
 Dr. Laurance
Bourghli
Nucleophilic Substitution Reactions

CH3O
Br OCH3 Br
+

nucleophile
alkyl halide leaving group

Depending on these variables, nucleophilic substitution reactions take place by either one of
two mechanisms: SN1 or SN2
 Dr. Laurance
Bourghli
SN2 Reaction

SN2 stands for: substitution, nucleophilic, bimolecular

rate = k [alkyl halide].[nucleophile]

C N
Cl C + Cl
N

I SH
HS
+ I
 Dr. Laurance
Bourghli
SN2 Reaction Mechanism
 Alkyl halides must be methyl, 1o, or 2o. (Order of reactivity: methyl > 1o > 2o).
 Nucleophiles are usually anions (strong nucleophiles).

C N
Cl C + Cl
N

I SH
HS
+ I
 Dr. Laurance
Bourghli
SN1 Reaction
SN1 stands for: substitution, nucleophilic, unimolecular
rate = k [alkyl halide]

H2O
+ HBr
Br OH

Cl OCH2CH3
CH3CH2OH
+ HCl
 Dr. Laurance
SN1 Reaction Mechanism

Bourghli
 Alkyl halides must be 3o or 2o (Order of reactivity: 3o > 2o).
 Nucleophiles are usually neutral compounds (weak nucleophiles).

+ Br
Br step 1 +
carbocation
Step 1 is slow and endothermic intermediate

Step 2 is fast and exothermic

step 2 H2O

Step 3 is fast and exothermic

Br
H
+ HBr
step 3
+O OH
Overall reaction is exothermic
H
 Dr. Laurance
Bourghli
Solvents Used in SN1 and SN2 Reactions

 Solvents that enhance reactivity in SN1 reactions are protic solvents:

CH3OH, CH3CH2OH, H2O, CH3CO2H

 Solvents that enhance reactivity in SN2 reactions are aprotic solvents:

CH3COCH3 (acetone)
CH3CN (acetonitrile)
DMSO (dimethylsulfoxide)
DMF (dimethylformamide)
 Dr. Laurance
Bourghli
Elimination Reactions
HO
+ H2O + Br

Br

 The elimination reaction of 2o and 3o alkyl halides is carried out using a strong base under
heating conditions to produce alkene(s).

 Heating is required in elimination reactions because such reactions are endothermic.

 The reaction mechanism is termed E2 (Elimination, bimolecular);

rate = k [alkyl halide].[base]
 Dr. Laurance
Bourghli
E2 Reaction Mechanism
H H
HO
+ H2O + Br

Br

Bonds broken: C―H and C―Br

Bonds formed: C=C Π bond and O―H
 Dr. Laurance
Bourghli
Elimination Reactions

Cl
CH3CH2O
+ CH3CH2OH + Cl

CH3O
+ + CH3OH + Br

Br