CHAPTER 4:

HYDROXYL
COMPOUNDS
Alcohol
 Introduction
• Alcohols are compounds of the general formula R-OH ,
where R is an substituted alkyl group.
• The group may be primary,secondary,or tertiary,it may be
open chain or cyclic, it may contain a double,a halogen
atom, an aromatic ring, or additional hydroxyl groups.
 Introduction
• Alcohols contain the hydroxyl (-OH) group, which
as the functional group, determines the properties
characteristic of this family the hydroxyl group is
bonded to saturated, sp3- hybridized carbon atoms.
• Variations in structure of the R group may affect
the rate at which the alcohol undergoes certain
reactions, and even, in a few cases, may affect the
kind of reaction.
 Introduction
• Alcohols can be thought of as org.
derivatives or water in which one or both of
the water hydrogens are replaced by an org.
substituent (H-O-H becomes R-OH).
• Alcohols occur widely in nature and have
many industrial and pharmaceutical
applications.
 Classification of Alcohols
• We classify a C atom as 1 º, 2 º or 3 º
according to the number of other C atoms
attached to it.An alcohol is classified
according to the kind of C that bears the –
OH group.
Classification of Alcohols
 Nomenclature of Alcohols
• Alcohols are named by 2 principal systems,common names
and the IUPAC names.
• Example of common names of alcohols(please refer to the
last slide).
• Common names sometimes called trivial names.
• In IUPAC, as discussed in the previous chapters (alkanes,
alkenes, alkynes, alkyl halides), the longest continuous C
chain that contain then –OH group is selected to be the
parent structure.The name is derived by replacing the
terminal.
 Nomenclature of Alcohols
• -ane of alkanes is replaced by –ol.
• The position of the –OH group in the parent chain,
generally using the lowest possible number.
• The other groups attached to the parent chain is indicated
by number according to the –OH group.
 Nomenclature of Alcohols
• An alcohol containing a double bond is named as an alkenol, with
numbers to indicate the positions of the double bond and the hydroxyl
(-OH ) group.

• Note that –o1 takes priority over –ene;-o1 appears last in the name,
and,where possible, is given the lower number.
Differences Between Common
Names and IUPAC Names.
Common names IUPAC names
Ethyl alcohol Ethanol
Methyl alcohol Methanol
N-propyl alcohol 1-propanol
Isopropyl alcohol 2-propanol
Sec-butyl alcohol 2-butanol
Tert-butyl alcohol 2-methyl-2-propanol
Isobutyl alcohol 2-methyl-1propanol
Benzene alcohol Phenyl methanol
Allyl alcohol 2-propen-1-o1
Alpha –phenyl ethyl alcohol Phenyl ethanol
P-nitrobenzyl alcohol 4-Nitro phenylmethanol
Tert-pentyl alcohol 2-methyl-2-butanol
 Physical Properties of Alcohols
• Alcohol, R-OH,contains lipophilic group (alkane-like
group, R-) and hydrophilic group (water-like hydroxyl
group, -OH).
• Of these two groups, it is the –OH group that gives the
alcohol its characteristic physical properties and the alkyl
group that, depending upon its size and shape, modifies the
properties.
• It is a polarized covalent compounds.
 hydrophilic
Lipophilic
R-OH
Organic solvent Water soluble
soluble

+ -
To show the polarity of
R OH } hydroxyl (-OH) group
 Physical Properties of Alcohols
• The –OH group is highly polar,must important, is capable of hydrogen
bonding.

• H bonding to alcohol molecules.

• H bonding to other neutral molecules.
• H bonding to anions.

The presence H bonding increases the b.p

 Physical Properties of Alcohols
• Alcohols show increase in b.p with increasing C
number, and decrease in b.p with branching. The
b.p of alcohols is usually higher than many other
hydrocarbon of the same corresponding carbon.
• Most of alcohols also behave as solutes that
reflects their ability to form H bond.
• The lower alcohols are miscible with water
• As the lipophilic alkyl group becomes longer,
water solubility of alcohol decreases.
 Physical Properties of Alcohols
• Due to the ease of hydrogen bonding formation of
alcohols, it also widely use as a solvent.
• Through their lipophilic alkyl group, they can also
dissolve non –ionic compounds: organic
substrates. And though their -OH groups, they can
dissolve ionic compounds:inorganic reagents
• In Elimination of the E1 kind, alcohols can serve
as the base as well as the solvent.In nucleophilic
substitution, alcohols act as the nucleophile in
SN2 reactions.
 Industrial Source of Alcohols
• Alcohols are the important starting materials in
aliphatic chemistry.
• These are 3 principal ways to get simple alcohols
that are backbone of aliphatic org. synthesis.
• These methods are:
1. by hydration of alkenes obtained from the
cracking of petroleum
2. By Oxo process from alkenes.
3. by fermentation of carbohydrates.
Preparation of Alcohols
@ Alcohols Synthesis
1) Synthesis of Alcohols From
Alkenes
 Hydration of Alkenes
General
Equation: H+ = H2SO4

• Water adds to the more reactive alkenes in the presence of

acids to yield alcohol.
• This addition follows MR.
• Example:
 Hydration of Alkenes
General Equation: OH
H2SO4 H2O
R-CH=CH2 R-CH-CH3 R-CH-CH3
H2O H+
OSO3H
 Hydroboration of Alkenes

• With the reagent diborane, alkenes undergo

hydroboration reaction to yield alkylboranes,R3B
which undergoing oxidation to give alcohols.
• The reaction procedure is simple and convenient,
the yields are exceedingly high and the products
are ones difficult to obtain from alkenes in any
other way.
Peroxide then removes the borane and
replaces it with the alcohol to form the anti-
markovnikov product.

An example of the hydroboration

mechanism:
Hydroboration of Alkenes
2) Synthesis of Alcohols From
Alkyl Halides
 Hydrolysis of Alkyl Halides
General equation:
 3) Synthesis of alcohols by
reduction of carbonyl compounds
 Intro: Synthesis of alcohols by
reduction of carbonyl compounds
• General equation of reduction of carbonyl
compounds to alcohols can be presented as
below.
 Intro: Synthesis of alcohols by reduction
of carbonyl compounds
• Aldehydes can be reduced to primary alcohols and ketones to secondary
alcohols, either by catalytic hydrogenation or by use of chemical reducing
agents like lithium aluminum anhydride, LiAlH4 and sodiumborohydride,
NaBH4.
Reduction of an aldehyde gives primary alcohol
O

NaBH4
C H CH2OH

benzaldehyde benzyl alcohol

Reduction of a ketone gives a secondary alcohol
H
O
NaBH4
OH

cyclohexanone cyclohexanol
Reduction of Aldehydes/ Ketones
Reduction of Carboxylic Acids
Reduction of Ester
 MECHANISM OF THE REACTION OF LiAlH4
WITH AN ESTER

Step 1:
The nucleophilic H from the hydride reagent adds to the electrophilic C in the polar
carbonyl group of the ester. Electrons from the C=O move to the electronegative O
creating the tetrahedral intermediate a metal alkoxide complex.

Step 2:
The tetrahedral intermediate collapses and displaces the alcohol portion of the ester
as a leaving group, in the form of the alkoxide, RO-. This produces an aldehyde as
an intermediate.

Step 3:
Now we are reducing an aldehyde. The nucleophilic H from the hydride
reagent adds to the electrophilic C in the polar carbonyl group of the aldehyde.
Electrons from the C=O move to the electronegative O creating an
intermediate metal alkoxide complex.

Step 4:
This is the work-up step, a simple acid/base reaction. Protonation of the alkoxide
oxygen creates the primary alcohol product from the intermediate complex.
 4) Preparation of Alcohols by
Using Grignard
Reagent/Grignard Synthesis
Reaction of GR With Formaldehyde
Reaction of GR With Higher Aldehydes
Reaction of GR With Ketones
Preparation of Alcohols by Using Grignard Reagent/Grignard
Synthesis
• General equation
 MECHANISM OF THE REACTION OF RMgX
WITH AN ESTER
Step 1:
The nucleophilic C in the organometallic reagent adds to theelectrophilic C
in the polar carbonyl group of the ester. Electrons from the C=O move to
the electronegative O creating thetetrahderal intermediate, a metal
alkoxide complex.

Step 2:
The tetrahedral intermediate collapses and displaces the alcohol portion of the
ester as a leaving group, in the form of the alkoxide, RO-.This produces a
ketone as an intermediate.

Step 3:
The nucleophilic C in the organometallic reagent adds to the electrophilic C in
the polar carbonyl group of the ketone. Electrons from the C=O move to the
electronegative O creating an intermediate metal alkoxide complex.

Step 4:
This is the work-up step, a simple acid/base reaction. Protonation of the
alkoxide oxygen creates the alcohol product from the intermediate complex.
 Interlude 1
Aldehydes and Ketones; An Introduction
• Aldehydes and Ketones have the general formula:

• The functional group both is the carbonyl group.

• The carbonyl group is unsaturated and it undergoes addition reaction.
• The carbonyl bond is strongly polarized.
• The typical reaction of aldehydes and ketones is nucleophilic addition.
 Interlude 2
Grignard Synthesis of Alcohols
• The GR has the formula RMgX and it is
prepared by the reaction of metallic
magnesium with the appropriate organic
halides.

• X=Cl, Br or I
 Interlude 2
Grignard Synthesis of Alcohols
• One of the most important uses of the GR lies in its
reaction with aldehydes and ketones.
• The C-Mg bond of the GR is a highly polar bond, R-MgX.
• GR acts as a nucleophilic reagent to carbonyl compounds.
 Interlude 2
Grignard Synthesis of Alcohols
• Grignard synthesis is so important due to its
ability to take two organic molecules and
convert them into a bigger one.
• The reaction is thus an example of the
typical reaction of aldehydes and ketones:
Nucleophilic addition.
 Intro: Product of the Grignard
synthesis
• The class of alcohol that is obtained from a
Grignard synthesis depends upon the type
of carbonyl compound used: formaldehyde,
HCHO, yields primary alcohol; other
aldehydes, RCHO yield secondary alcohols;
and ketones, R2CO, yield tertiary alcohols.
Intro: Product of the Grignard
synthesis
 Intro: Product of the Grignard
synthesis
• The relation ship arises directly from our
definitions of aldehydes and ketones, and our
definitions of 1º, 2º and 3º alcohols.
• The number of hydrogens attached to the carbonyl
C defines the carbonyl compound as formaldehyde
(CH2O), higher aldehydes or ketones.
• The carbonyl C is the one that finally bears the –
OH group in the product; the number of
hydrogens defines the alcohols as 1º, 2º and 3º.
Reaction of GR with formaldehyde

H2 O @ H3 O+

• Example
 Reaction of GR With Higher Aldehydes

• Example
 Reaction of GR with ketones

• Example
 5) Preparation of Alcohols by
Hydrogenation of Aldehydes And
Ketones
 Hydrogenation of Aldehydes And
Ketones
• General equation:

Aldehyde: O OH
Pt/Ni/Pd ROH 1°
R-C-H + H2 R-C-H

Ketone:
O OH
Pt/Ni/Pd ROH 2°
R-C-R + H2 R-C-R

H
Hydrogenation of Aldehydes And
Ketones
• Example:
Ni
CH3CH=CHCHO + 2H2 CH3CH2CH2CH2OH
2-butenal butanol

H OH
O
H2 / Ni

cyclopentanone cyclopentanol
 Reaction of Alcohols

1) Reaction of Alcohols:
Cleavage of the O------H Bond

2) Reaction of Alcohols:
Cleavage of the C---------OH Bond
 Intro: Reaction of Alcohols
• Alcohols reaction take into account of a
bond cleavage; C-OH or O-H cleavages.
• Alkoxides formation (from alcohols) and
esterification of alcohols are belong to the
O-H cleavage reaction. While, the reaction
of alcohols with alkyl halides, dehydration
and oxidation are belong to the C-OH
cleavage reaction.
 1) Reaction of Alcohols:
Cleavage of the O------H Bond
a) Reaction With Active Metals in the
Formation of Alkoxides
b) Esterification Reaction
Reaction of alcohols: cleavage of
the O------H bond
 a) Reaction With Active Metals in the
Formation of Alkoxides

• Alcohols acts as an acid in this particular reaction.

• The acidity of alcohols is shown by their reaction with active metals
(Na, K, Mg, Al, etc) to liberate hydrogen gas and alkoxides.
 a) Reaction With Active Metals in the
Formation of Alkoxides
• The alkoxides formed are strong base and used in the preparation of ether
(ROR).
• Example:
Na
1. CH3CH2OH CH3CH2O-Na+ + 1/2H2
Ethyl alcohol Sodium ethoxide

CH3 H3C
2. Al
CH3 C OH CH3 C O-Al+

H H

Isopropyl alcohol aluminium isopropoxide

H3C
3. CH3
K
CH3 C OH CH3 C O-K+

CH3 CH3
Tert-butyl alcohol Potassium tert-butoxide
 Esterification Reaction

• A carboxylic acid, RCOOH, is converted directly

into an ester when heated with an alcohol in the
presence of a little mineral acid, usually H2SO4 or
HCl.
• This reaction is reversible and generally reaches
equilibrium when there are appreciable quantities
of both reactants and products present.
 Esterification reaction

• For modest and mild reaction condition,

especially in pharmaceutical and cosmetic
industries, enzyme is used in replacement of
minerals acids; native lipases and
immobilized lipases (Novozyme 435,
Lipozyme, etc.)
 Esterification reaction
• Examples:
 2) Reaction of alcohols:
Cleavage of the C---------OH
bond
a) Reaction With Hydrogen Halides
b) Dehydration of Alcohols
c) Oxidation of Alcohols
 2) Reaction of alcohols:
Cleavage of the C---------OH
bond
a) Reaction With Hydrogen Halides
• General equation
 a) Reaction With Hydrogen
Halides

• This reaction requires the presence of acid

into the actual substrate.

• The protonated alcohol readily loses the

weakly basic water molecule.
 b) Dehydration of Alcohols
• General equation

• Simple mechanism:
Example of alcohol dehydration:
 Con’d: Dehydration of Alcohols
• Examples:
 c) Oxidation of Alcohols
• General equation:
 c) Oxidation of Alcohols

• KMnO4, H2Cr2O7, K2Cr2O7, H2CrO4

 c) Oxidation of Alcohols
• Examples:
 c) Oxidation of Alcohols
• Examples:
Mechanism of Chromate
oxidations
 Lucas test
• To differentiate alcohols; 1º, 2º or 3º.
ZnCl2 (becomes turbid very fast)
ROH 3° + HCl

ZnCl2
ROH 2° + HCl (becomes turbid slowly)

ZnCl2
ROH 1° + HCl (no turbidity observed)