Chapter 17: Alcohols and

Phenols

Based on McMurry’s Organic Chemistry, 7th edition

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17.1 Naming Alcohols and Phenols
◼ General classifications of alcohols based on
substitution on C to which OH is attached
◼ Methyl (C has 3 H’s), Primary (1°) (C has two
H’s, one R), secondary (2°) (C has one H, two
R’s), tertiary (3°) (C has no H, 3 R’s),

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IUPAC Rules for Naming Alcohols
◼ 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
◼ Number the chain from the end nearer the hydroxyl group
◼ Number substituents according to position on chain, listing
the substituents in alphabetical order

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Naming Phenols
◼ Use “phenol” (the French name for benzene)
as the parent hydrocarbon name, not
benzene
◼ Name substituents on aromatic ring by their
position from OH

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17.2 Properties of Alcohols and
Phenols
◼ The structure around O of the alcohol or phenol is similar to that in
water, sp3 hybridized
◼ Alcohols and phenols have much higher boiling points than similar
alkanes and alkyl halides
◼ A positively polarized ⎯OH hydrogen atom from one molecule is
attracted to a lone pair of electrons on a negatively polarized oxygen
atom of another molecule
◼ This produces a force that holds the two molecules together
◼ These intermolecular attractions are present in solution but not in the
gas phase, thus elevating the boiling point of the solution

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Properties of Alcohols and
Phenols: Acidity and Basicity
◼ Weakly basic and weakly acidic
◼ Alcohols are weak Brønsted bases
◼ Protonated by strong acids to yield oxonium ions,
ROH2+

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Alcohols and Phenols are Weak
Brønsted Acids
◼ Can transfer a proton to water to a very small
extent
◼ Produces H3O+ and an alkoxide ion, RO−, or
a phenoxide ion, ArO−

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Relative Acidities of Alcohols
◼ Simple alcohols are about as acidic as water
◼ Alkyl groups make an alcohol a weaker acid
◼ The more easily the alkoxide ion is solvated by water
the more its formation is energetically favored
◼ Steric effects are important

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17.3 Preparation of Alcohols: A
Review
◼ Alcohols are derived from many types of compounds
◼ The alcohol hydroxyl can be converted to many other
functional groups
◼ This makes alcohols useful in synthesis

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Review: Preparation of Alcohols by
Regiospecific Hydration of Alkenes
◼ Hydroboration/oxidation: syn, non-Markovnikov
hydration
◼ Oxymercuration/reduction: Markovnikov hydration

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1,2-Diols
◼ Review: Cis-1,2-diols from hydroxylation of an alkene
with OsO4 followed by reduction with NaHSO3
◼ Trans-1,2-diols from acid-catalyzed hydrolysis of
epoxides

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17.4 Alcohols from Reduction of
Carbonyl Compounds
◼ Reduction of a carbonyl compound in general gives
an alcohol
◼ Note that organic reduction reactions add the
equivalent of H2 to a molecule

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Reduction of Aldehydes and Ketones

◼ Aldehydes gives primary alcohols

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Reduction Reagent: Sodium
Borohydride
◼ NaBH4 is not sensitive to moisture and it does not
reduce other common functional groups
◼ Lithium aluminum hydride (LiAlH4) is more powerful,
less specific, and very reactive with water
◼ Both add the equivalent of “H-”

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Mechanism of Reduction
◼ The reagent adds the equivalent of hydride to the
carbon of C=O and polarizes the group as well

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Reduction of Carboxylic Acids and
Esters
◼ Carboxylic acids and esters are reduced to give
primary alcohols
◼ LiAlH4 is used because NaBH4 is not effective

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17.5 Alcohols from Reaction of Carbonyl
Compounds with Grignard Reagents
◼ Alkyl, aryl, and vinylic halides react with magnesium
in ether or tetrahydrofuran to generate Grignard
reagents, RMgX
◼ Grignard reagents react with carbonyl compounds to
yield alcohols

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Reactions of Grignard Reagents with
Carbonyl Compounds

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Reactions of Esters and Grignard
Reagents
◼ Yields tertiary alcohols in which two of the
substituents carbon come from the Grignard reagent
◼ Grignard reagents do not add to carboxylic acids –
they undergo an acid-base reaction, generating the
hydrocarbon of the Grignard reagent

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Grignard Reagents and Other Functional
Groups in the Same Molecule

◼ Can't be prepared if there are reactive functional

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Mechanism of the Addition of a
Grignard Reagent
◼ Grignard reagents act as nucleophilic carbon anions
(carbanions, : R−) in adding to a carbonyl group
◼ The intermediate alkoxide is then protonated to
produce the alcohol

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17.6 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 converted into halides by treatment with
SOCl2 or PBr3 via SN2 mechanism

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Conversion of Alcohols into Tosylates
◼ Reaction with p-toluenesulfonyl chloride (tosyl
chloride, p-TosCl) in pyridine yields alkyl tosylates,
ROTos
◼ Formation of the tosylate does not involve the C–O
bond so configuration at a chirality center is
maintained
◼ Alkyl tosylates react like alkyl halides

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Stereochemical Uses of Tosylates
◼ The SN2 reaction of an alcohol via a tosylate,
produces inversion at the chirality center
◼ The SN2 reaction of an alcohol via an alkyl halide
proceeds with two inversions, giving product with
same arrangement as starting alcohol

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Dehydration of Alcohols to Yield
Alkenes
◼ The general reaction: forming an alkene from an
alcohol through loss of O-H and H (hence
dehydration) of the neighboring C–H to give  bond
◼ Specific reagents are needed

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Acid- Catalyzed Dehydration
◼ Tertiary alcohols are readily dehydrated with acid
◼ Secondary alcohols require severe conditions (75%
H2SO4, 100°C) - sensitive molecules don't survive
◼ Primary alcohols require very harsh conditions –
impractical
◼ Reactivity is the result of the nature of the
carbocation intermediate

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Dehydration with POCl3
◼ Phosphorus oxychloride in the amine solvent pyridine
can lead to dehydration of secondary and tertiary
alcohols at low temperatures
◼ An E2 via an intermediate ester of POCl2 (see Figure
17.7)

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Conversion of Alcohols into
Esters

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17.7 Oxidation of Alcohols
◼ Can be accomplished by inorganic reagents, such as
KMnO4, CrO3, and Na2Cr2O7 or by more selective,
expensive reagents

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Oxidation of Primary Alcohols
◼ To aldehyde: pyridinium chlorochromate (PCC,
C5H6NCrO3Cl) in dichloromethane
◼ Other reagents produce carboxylic acids

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Oxidation of Secondary Alcohols
◼ Effective with inexpensive reagents such as
Na2Cr2O7 in acetic acid
◼ PCC is used for sensitive alcohols at lower
temperatures

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Mechanism of Chromic Acid
Oxidation
◼ Alcohol forms a chromate ester followed by
elimination with electron transfer to give ketone
◼ The mechanism was determined by observing the
effects of isotopes on rates

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17.8 Protection of Alcohols
◼ Hydroxyl groups can easily transfer their proton to a
basic reagent
◼ This can prevent desired reactions
◼ Converting the hydroxyl to a (removable) functional
group without an acidic proton protects the alcohol

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Methods to Protect Alcohols
◼ Reaction with chlorotrimethylsilane in the presence of
base yields an unreactive trimethylsilyl (TMS) ether
◼ The ether can be cleaved with acid or with fluoride
ion to regenerate the alcohol

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Protection-Deprotection
◼ An example of TMS-alcohol protection in a synthesis

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17.9 Phenols and Their Uses
◼ Industrial process from readily available cumene
◼ Forms cumene hydroperoxide with oxygen at high
temperature
◼ Converted into phenol and acetone by acid

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17.10 Reactions of Phenols
◼ The hydroxyl group is a strongly activating, making
phenols substrates for electrophilic halogenation,
nitration, sulfonation, and Friedel–Crafts reactions
◼ Reaction of a phenol with strong oxidizing agents
yields a quinone
◼ Fremy's salt [(KSO3)2NO] works under mild
conditions through a radical mechanism

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