Alcohols and Phenols

Chapter 9
Alcohols and Phenols
 Alcohols contain an OH group connected to a a saturated C
(sp3)
 They are important solvents and synthesis intermediates
 Phenols contain an OH group connected to a carbon in a
benzene ring
 Methanol, CH3OH, called methyl alcohol, is a common solvent,
a fuel additive, produced in large quantities
 Ethanol, CH3CH2OH, called ethyl alcohol, is a solvent, fuel,
beverage
 Phenol, C6H5OH (“phenyl alcohol”) has diverse uses - it gives
its name to the general class of compounds

Based on McMurry, Organic Chemistry, Chapter 2

17, 6th edition, (c) 2003
Naming Alcohols
 General classifications of alcohols based on
substitution on C to which OH is attached

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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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Many Alcohols Have Common Names
 These are accepted by IUPAC

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Practice

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Practice answers

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Properties of Alcohols Hydrogen
Bonding
 The structure around O of the alcohol is similar to
that in water, sp3 hybridized
 Alcohols and have much higher boiling points than
similar alkanes and alkyl halides (H-bonding)

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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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Alchols 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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pKa Values for Typical OH
Compounds

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Generating Alkoxides from Alcohols
 Alcohols are weak acids – requires a strong base to form an
alkoxide such as NaH, sodium amide NaNH2, and Grignard
reagents (RMgX)

 Alkoxides are bases used as reagents in organic chemistry

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Preparation of Alchols: an Overview
 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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Preparation of Alcohols by Regiospecific
Hydration of Alkenes
 Hydroboration/oxidation: syn, non-Markovnikov
hydration
 Oxymercuration/reduction: Markovnikov hydration

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Preparation of 1,2-Diols
 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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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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Practice

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Practice answer

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Reduction of Aldehydes and Ketones

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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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Reduction of Carboxylic Acids
and Esters

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Practice

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Practice

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Practice answer

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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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Examples of 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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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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Some Reactions of Alcohols
 Two general classes of reaction
 At the carbon of the C–O bond
 At the proton of the O–H bond

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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 (See Figure 17-5)

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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

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Practice

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Practice Answers

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Conversion of Alcohols into Alkyl
Halides
 3° alcohols are converted by HCl or HBr at low
temperature
 1° and alcohols are resistant to acid – use SOCl2 or
PBr3

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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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Practice

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Summary -Alcohols

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Based on McMurry, Organic Chemistry, Chapter 43
17, 6th edition, (c) 2003
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