CH103 Alcohols and

Phenols

Based on McMurry’s Organic Chemistry, 7th edition

Alcohols and Phenols
 Alcohols contain an OH group connected to 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
 OH groups bonded to vinylic, sp2-hybridized carbons are called enols

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Why this Chapter?
 To begin to study oxygen-containing
functional groups

 These groups lie at the heart of biological

chemistry

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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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Acidity Measurements
 The acidity constant, Ka, measures the extent to
which a Brønsted acid transfers a proton to water
[A] [H3O+]
Ka = ————— and pKa = log Ka
[HA]
 Relative acidities are more conveniently presented on
a logarithmic scale, pKa, which is directly proportional
to the free energy of the equilibrium
 Differences in pKa correspond to differences in free
energy
 Table 17.1 presents a range of acids and their pKa
values

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pKa Values for Typical OH Compounds

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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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Inductive Effects
 Electron-withdrawing groups make an alcohol a
stronger acid by stabilizing the conjugate base
(alkoxide)

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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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Phenol Acidity
 Phenols (pKa ~10) are much more acidic than
alcohols (pKa ~ 16) due to resonance stabilization of
the phenoxide ion
 Phenols react with NaOH solutions (but alcohols do
not), forming salts that are soluble in dilute aqueous
solution
 A phenolic component can be separated from an
organic solution by extraction into basic aqueous
solution and is isolated after acid is added to the
solution

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Nitro-Phenols
 Phenols with nitro groups at the ortho and para
positions are much stronger acids

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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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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
 Ketones gives secondary 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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Grignard Reagents and Other Functional
Groups in the Same Molecule

 Can't be prepared if there are reactive functional

groups in the same molecule, including proton donors

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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 SOCl 2 or PBr3
via SN2 mechanism

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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

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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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Summary of Reactions