Reactions of Alcohols

 Alcohols can be converted into many other

functional groups, including
 alkanes
 by reduction
 alkenes
 dehydration
 alkyl halides
 substitution
 aldehydes or ketones
 carboxylic acids by oxidation
 esters
 ethers
Reactions of Alcohols
 Oxidation:
 loss of electrons
 increase of oxidation number
 addition of O or O2
Most important
 loss of H2 definitions for
 addition of X2 (halogens) organic
compounds
 Oxidation reactions:
 increase the number of oxygens bonded to a
carbon
 increase the number of bonds between
carbon and oxygen
Reactions of Alcohols
 Reduction:
 gain of electrons
 decrease in oxidation number

 addition of H2 (or H-) Most important

 loss of O or O2 definitions for organic
 loss of X2 compounds.

 Reduction reactions:
 decrease the number of oxygens bonded to a
carbon
 decrease the number of bonds between
carbon and oxygen
 CH3CH2OH CH3CO2H

Reactions of Alcohols
Example: Classify the following reactions as an
oxidation or reduction.

OH O
CH4 CO2
CH
CH4
CO2
CO2
4
CH3CH2OH CH3CO2
CH3CH2OH CH3CO2H O H
CHC3CH2OH CO2H C
Reactions of Alcohols
 Primary and secondary alcohols are easily
oxidized by a variety of oxidizing agents.
 Substances that cause another to be
oxidized

 Some of the common oxidizing agents for

organic compounds include:
 chromium reagents
 PCC (pyridinium chlorochromate)
 KMnO4
 HNO3
 NaOCl
Reactions of Alcohols
 Oxidation of 1o Alcohols
 Depending on the oxidizing agent used,
primary alcohols can be oxidized to either
aldehydes or carboxylic acids
OH O O
[O] [O]
R C H R C H R C OH
H

 The aldehyde that forms initially is easily

oxidized to the carboxylic acid by many
reagents
Reactions of Alcohols
 Oxidation of 1o Alcohols to Aldehydes

OH O
[O]
R C H R C H
H

 The following reagents convert a primary

alcohol to the aldehyde without further
oxidation.
 Pyridinium chlorochromate (PCC)
 Swern’s oxidation
 DMP
Reactions of Alcohols
 Pyridinium chlorochromate (PCC) is used to
oxidize a 1o alcohol to the aldehyde
+ -
N H CrO3Cl

 Also oxidizes 2o alcohol to ketone

(discussed later)
O
OH [O] [O]
O
CH3CH2OH PCC
CH3CH CH3CO2H
R C H R C H
CH2Cl2
H
Reactions of Alcohols
 Swern Oxidation is used to convert 1o ROH’s to
aldehydes (or 2o ROH to ketones)
 Conditions: O
 Dimethyl sulfoxide CH3SCH3 or DMSO
O O
 Oxalyl chloride Cl C C Cl or (COCl)2
 Et3N
 CH2Cl2 (solvent)
 -60oC

OH O
DMSO, (COCl)2
R C H R C H
Et3N, CH2Cl2
H
-60oC
Reactions of Alcohols
 Dess-Martin Periodinane (DMP) can be used to
oxidize a 1o ROH to an aldehyde (or 2o ROH to
ketone)
OH O
DMP
R C H R C H
RT
H

AcO OAc
I OAc
DMP = O

O
Reactions of Alcohols
 Examples:

O
DMSO, (COCl)2
CH3(CH2)8CH2OH o CH3(CH2)8CH
Et3N, CH2Cl2, -60 C
85%

DMP
CH2OH CHO
RT

O
PCC
OH CH2Cl2 H
Reactions of Alcohols
 Oxidation of 1o Alcohols to Carboxylic Acids
OH O
[O]
R C H R C OH
H
 Common Reagents:
 Chromic acid reagent
 Na2Cr2O7/H2SO4 or K2Cr2O7/H2SO4
or
 CrO3
or
 NaOCl (aq)
Reactions of Alcohols
 Examples:

Na2Cr2O7
CH2OH CO2H
H2SO4

O
NaOCl
OH OH
H2O
Reactions of Alcohols
 Oxidation of 2o Alcohols
 2o alcohols are converted to ketones
OH O
[O]
R C H R C R'
R'

 The oxidizing agents that are used to oxidize

primary alcohols can also be used to oxidize a
secondary alcohol to a ketone:
 Chromic acid reagent
 CrO3
 PCC
 Swern oxidation
 DMP
Reactions of Alcohols
 Examples:

NaOCl
OH O
H2O

85%
OH O
K2Cr2O7
H2SO4

OH O
DMP
CHCH3 CCH3
RT
Reactions of Alcohols
Examples: Predict the major product.

PCC
OH
CH2Cl2
OH

CH3
DMSO, (COCl)2
CHCH2CH2OH
Et3N, CH2Cl2, -60oC

OH
Na2Cr2O7
OH
H2SO4
Reactions of Alcohols
 Other oxidizing agents can also be used to
oxidize alcohols:
 KMnO4 (aq), OH- Must be carefully controlled
because they can also cleave
 cold HNO3 C-C bonds.

 Tertiary alcohols cannot be oxidized easily. Na2Cr

 No hydrogen present on carbinol carbon
OH H2SO
 Oxidation would require breaking C-C bond
 severe conditions required
CH3
CH3 C OH
CH3
Reactions of Alcohols
 Dehydration of Alcohols
CC removal of water, forming an alkenes

CH3 CH3
H2SO4
CH3 C OH CH2 C + H2O
D CH3
CH3

 equilibrium process
 drive reaction to completion by removing
alkene as formed (LeChatelier’s Principle)
Reactions of Alcohols
 Typical reaction conditions
 acid catalyst
 conc. H2SO4
 conc. H3PO4
 heat

 Saytzeff’s product

 Rearrangements occur if a more stable

carbonium ion can be formed.
Reactions of Alcohols

Mechanism of Dehydration (E1)

 Step 1: Protonation of the hydroxyl group
(fast)

 Step 2: Ionization (RDS)

+
Reactions of Alcohols
 Step 3: Deprotonation to form alkene
Reactions of Alcohols
Example: Predict the major product formed in
the following reactions.

CH3
OH H2SO4
D

CH3 H3C
H2SO4
CH3CCH2OH o C=CHCH3
150 H3C
CH3
Reactions of Alcohols
 Williamson Ether Synthesis
 SN2 reaction between an alkoxide ion and an
alkyl halide to form an ether.
- +
RO Na + R'CH2X ROCH2R'

CH3CH2O- Na+ + CH3I CH3CH2OCH3

 Alkyl halide must be primary or methyl.

Reactions of Alcohols
 Williamson Ether Synthesis Mechanism
Reactions of Alcohols
Example: Give the major product for the
following reactions.

OH
(1) NaH/THF

(2) CH3I