17.

Alcohols and Phenols

Based on McMurry’s Organic Chemistry, 9th edition

Learning Objectives
(17.1)
 Naming alcohols and phenols
(17.2)
 Properties of alcohols and phenols
(17.3)
 Preparation of alcohols: A review
(17.4)
 Alcohols from carbonyl compounds:
Reduction
Learning Objectives
(17.5)
 Alcohols from carbonyl compounds: Grignard
reaction
(17.6)
 Reactions of alcohols
(17.7)
 Oxidation of alcohols
(17.8)
 Protection of alcohols
Learning Objectives
(17.9)
 Phenols and their uses
(17.10)
 Reactions of phenols
(17.11)
 Spectroscopy of alcohols and phenols
Alcohols and Phenols
 Organic derivatives of water
 One of water’s hydrogens is replaced by an
organic group
 Alcohols contain an –OH group connected to
a saturated, sp3-hybridized C atom
Alcohols and Phenols
 Important solvents and synthesis
intermediates
 Phenols contain an OH group connected to a
carbon in a benzene ring
 Ethanol, CH3CH2OH, called ethyl alcohol, is a
solvent, fuel, and beverage
 Phenol has diverse uses and gives its name
to the general class of compounds
Naming Alcohols and Phenols
 General classifications of alcohols are based
on number of organic groups bonded to the
hydroxyl-bearing carbon

 IUPAC system names simple alcohols as

derivatives of the parent alkane with a suffix -
ol
Naming Alcohols
 Rule 1
 Select the longest carbon chain containing the
hydroxyl group, and derive the parent name by
replacing the -e ending of the corresponding
alkane with -ol
 Rule 2
 Number the chain from the end nearer the
hydroxyl group
Naming Alcohols
 Rule 3
 Number substituents according to position on
chain, listing the substituents in alphabetical
order
Naming Phenols
 -phenol is used as the parent name
 Not -benzene
 Name substituents on aromatic ring by their
position from –OH
Properties of Alcohols and Phenols
 Structure around O of alcohols or phenols are
similar to that in water, sp3-hybridized
 Attraction of positively polarized –OH
hydrogen atom from one molecule to the lone
pair of electrons on a negatively polarized
oxygen atom of another molecule:
 Produces weak force that holds the molecules
together
 Raises the boiling temperature
Properties of Alcohols and Phenols
 Weakly basic and weakly acidic
 Weak bases, protonated by strong acids yield
oxonium ions, ROH2+
Properties of Alcohols and Phenols
 Weak acids, dissociate slightly in dilute
aqueous solution generating H3O+ and an
alkoxide ion, RO- or phenoxide ion, ArO-
Properties of Alcohols and Phenols
 Strength of an acid in water can be
expressed by an acidity constant, Ka

 Smaller Ka and larger pKa, less acidic

 Larger Ka and smaller pKa, more acidic
 Effect of alkyl substitution on alcohol acidity is
primarily due to solvation of alkoxide ion
formed on acid dissociation
Properties of Alcohols and Phenols
 The more easily the alkoxide ion is solvated
by water, the more its formation is
energetically favored

 Inductive effects are important in determining

alcohol acidities
Properties of Alcohols and Phenols
 Electron-withdrawing groups make an alcohol
a stronger acid by stabilizing the conjugate
base

 Alcohols react with alkali metals and with

strong bases
Properties of Alcohols and Phenols
 Alkoxides are bases used as reagents in
organic chemistry
Properties of Alcohols and Phenols
 Phenols are more acidic than alcohols due to
resonance stabilization of the phenoxide ion
 Phenols with an electron-withdrawing
substituent are more acidic and phenols with
an electron-donating substituent are less
acidic
Preparation of Alcohols: A Review
 Alcohols are derived from many types of
compounds
 The alcohol hydroxyl can be converted to
many other functional groups
Preparation of Alcohols: A Review
 In the hydroboration of alkenes, indirect
methods used are:
 Hydroboration-oxidation, yielding the syn, non-
Markovnikov hydration product
 Oxymercuration-demercuration yielding
Markovnikov hydration product
Preparation of Alcohols: A Review
 Cis-1,2-diols are prepared from direct
hydroxylation of an alkene with OsO4 followed
by reduction with NaHSO3
 Trans-1,2-diols can be prepared from acid-
catalyzed hydrolysis of epoxides
Alcohols from Carbonyl
Compounds: Reduction
 Reduction of a carbonyl compound gives an
alcohol
 Addition of H to a C═O bond

 Reduction of aldehydes gives primary

alcohols
 Reduction of ketones gives secondary
alcohols
Reduction Reagent: Sodium
Borohydride (NaBH4)
 NaBH4 is not sensitive to moisture and can be
used with either water or alcohol
Mechanism of Reduction
 Addition of a nucleophilic hydride ion to the
positively polarized, electrophilic carbon atom
of the carbonyl group
 Alkoxide ion is protonated to yield the alcohol
product
Reduction of Carboxylic Acids and
Esters
 Carboxylic acids and esters are reduced to
give primary alcohols
 LiAlH4 is used because NaBH4 is not effective
Alcohols from Carbonyl Compounds:
Grignard Reagents
 Organohalides react with magnesium to
produce Grignard reagents, RMgX
 Grignard reagents react with carbonyl
compounds to yield alcohols
Alcohols from Carbonyl Compounds:
Grignard Reagents
Alcohols from Carbonyl Compounds:
Grignard Reagents
 Esters react with Grignard reagents to yield
tertiary alcohols

 Grignard reagents do not give addition

products with carboxylic acids
 Acidic carboxyl hydrogen reacts with the basic
Grignard reagent to yield a hydrocarbon and
the magnesium salt of the acid
Limitations of Grignard Reagents
 If other reactive functional groups are present
in the same molecule, Grignard reagent
cannot be prepared from an organohalide
Mechanism of the Addition of a
Grignard Reagent
 Grignard reagents act as nucleophilic carbon
anions
 Intermediate alkoxide is protonated to
produce the alcohol
Reactions of Alcohols
 Conversion of alcohols into alkyl halides
 3˚ alcohols react with HCl or HBr by SN1
through carbocation intermediate
 1˚ and 2˚ alcohols are converted into halides
by treatment with SOCl2 or PBr3 via SN2
mechanism
Reactions of 1˚ and 2˚ Alcohols
Conversion of Alcohols into
Tosylates
 Reaction of alcohols with p-toluenesulfonyl
chloride in pyridine yields alkyl tosylates,
ROTos
 C–O bond remains intact and configuration at
a chirality center is maintained
 Resulting alkyl tosylates react like alkyl
halides
Stereochemical Uses of Tosylates
 The SN2 reaction of an alcohol via an alkyl
halide proceeds with two inversions, giving a
product with same arrangement as the
starting alcohol
 The SN2 reaction of an alcohol via a tosylate,
produces inversion at the chirality center
Dehydration of Alcohols to Yield
Alkenes
 Tertiary alcohols are dehydrated using acid-
catalyzed reactions
 Follows Zaitsev’s rule and yields a more stable
alkene as the major product
 Reactivity is the result of the nature of the
carbocation intermediate
Dehydration with POCl3
 Direct E2 elimination of water does not occur
because hydroxide ion is a poor leaving
group
Conversion of Alcohols into Esters
 Reaction can be carried out in a single step
with the use of a strong acid as catalyst
 Reactivity of carboxylic acid is increased by
converting it into a carboxylic acid chloride,
which then reacts with the alcohol
Oxidation of Alcohols
 Accomplished by reagents, such as KMnO4,
CrO3, and Na2Cr2O7
Oxidation of Alcohols
 Primary alcohols are oxidized to either
aldehydes or carboxylic acids
 To prepare aldehyde from a primary alcohol,
I(V)-containing Dess–Martin periodinane in
dichloromethane is used
Oxidation of Alcohols
 Secondary alcohols oxidize easily to give
ketones
 Effective with inexpensive reagents such as
Na2Cr2O7 in acetic acid
Oxidation of Alcohols
 Cr(VI) reagent reacts with the alcohol to give
a chromate intermediate followed by
expulsion of a reduced Cr(IV) species
 Protection of Alcohols
 Done to overcome incompatibility that might arise
by protecting the interfering functional group

 Involves:
 Introduction of a protecting group to block
interfering function
 Execution of the desired reaction
 Removal of the protecting group
Protection of Alcohols
 Reaction with chlorotrimethylsilane in the
presence of base yields an unreactive
trialkylsilyl ether
Phenols and Their Uses
 Phenols are synthesized using
isopropylbenzene, commonly called cumene
 Process yields two valuable chemicals at the
same time
Reactions of Phenols
 Electrophilic aromatic substitution reactions
 Hydroxyl group is a strongly activating
substituent in electrophilic aromatic
substitution reactions
 Makes phenols substrates for:
 Electrophilic halogenation
 Nitration
 Sulfonation
 Friedel-Crafts reactions
Reactions of Phenols
 Oxidation of phenols
 Oxidation of a phenol yields a 2,5-
cyclohexadiene-1,4-dione, or quinone
 Fremy's salt [(KSO3)2NO] is used in more
complex cases

 Quinones can be easily reduced to

hydroquinones by reagents such as NaBH4
and SnCl2
Reactions of Phenols
 Ubiquinones mediate electron-transfer
processes involved in energy production
 Also called coenzymes Q
 Are components of the cells in all aerobic
organisms