Conversion of Alcohols into

Alkyl Halides

Reactions with HX, SOCl2, PBr3

 Conversion of Alcohol into a
Leaving Group
• Form Tosylate (p-TsCl, pyridine)

• Use strong acid (H3O+)

• Convert to Alkyl Halide (HX, SOCl2, PBr3)

 Alcohols to Alkyl Halides

OH HX (HCl or HBr)
X
+ HOH
rapid SN1
o
3 alcohol

HX X
OH + HOH
moderate SN1
o
2 alcohol
SN1: Carbocations can Rearrange

HO Br
Br
HBr
+

cis & trans

HO Br
Br
H-Br
+

cis & trans

H Br
HO

- H2O H

Br
 Lucas Test
CH3 CH3
ZnCl2
CH3COH CH3CCl forms is seconds
12M HCl
CH3 CH3 + HOZnCl2

CH3 CH3
CH3C OZnCl2 CH3C
Cl
CH3 H CH3
Qualitative test for Alcohol
Characterization
OH Cl
primary >10 minutes
(if at all)
OH Cl
ZnCl2, HCl

secondary <5 minutes

OH Cl

tertiary 1-2 seconds

1 and 2 Alcohols: best to use
o o

SOCl2, PBr3, or P/I2

All are SN2 Reactions

SOCl2
pyridine Cl
PBr3
OH Br
P, I2
(in situ prep. I
of PI3)
Thionyl chloride mechanism
O
S
Cl Cl
SOCl 2
OH Cl + SO2 + HCl
pyridine

O O
O Cl
Cl S -H
+
S
S O Cl O Cl
O
Cl H
H N