Chapter 12

Alcohols
Review of Concepts
Fill in the blanks below. To verify that your answers are correct, look in your textbook at the end of
Chapter 12. Each of the sentences below appears verbatim in the section entitled Review of Concepts and
Vocabulary.

When naming an alcohol, the parent is the longest chain containing the __________ group.
The conjugate base of an alcohol is called an ____________ ion.
Several factors determine the relative acidity of alcohols, including ___________, ____________,
and _______________________.
The conjugate base of phenol is called a ____________, or _____________ ion.

When preparing an alcohol via a substitution reaction, primary substrates will require S N___
conditions, while tertiary substrates will require SN___ conditions.
Alcohols can be formed by treating a _________ group (C=O bond) with a ____________ agent.
Grignard reagents are carbon nucleophiles that are capable of attacking a wide range of
_________________, including the carbonyl group of ketones or aldehydes, to produce an
alcohol.
_______________ groups, such as the trimethylsilyl group, can be used to circumvent the
problem of Grignard incompatibility and can be easily removed after the desired Grignard reaction
has been performed.
Tertiary alcohols will undergo an SN___ reaction when treated with a hydrogen halide.
Primary and secondary alcohols will undergo an SN___ process when treated with either HX,
SOCl2, PBr3, or when the hydroxyl group is converted into a tosylate group followed by
nucleophilic attack.
Tertiary alcohols undergo E1 elimination when treated with __________.
Primary alcohols undergo oxidation twice to give a _____________________.
Secondary alcohols are oxidized only once to give a ___________
PCC can be used to convert a primary alcohol into an _____________. Alternatively, primary
alcohols can be converted into _________ with a ___________ oxidation or a DMP-based
oxidation.
NADH is a biological reducing agent that functions as a ____________ delivery agent (very much
like NaBH4 or LiAlH4), while NAD+ is an _____________ agent.
There are two key issues to consider when proposing a synthesis:
1. A change in the ___________________.
2. A change in the ____________________.

Review of Skills
Fill in the blanks and empty boxes below. To verify that your answers are correct, look in your textbook at
the end of Chapter 12. The answers appear in the section entitled SkillBuilder Review.

12.1 Naming an Alcohol

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 CHAPTER 12 393

12.2 Comparing the Acidity of Alcohols

12.3 Identifying Oxidation and Reduction Reactions

12.4 Drawing a Mechanism, and Predicting the Products of Hydride Reductions

12.5 Preparing an Alcohol via a Grignard Reaction

12.6 Proposing Reagents for the Conversion of an Alcohol into an Alkyl Halide

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394 CHAPTER 12

12.7 Predicting the Products of an Oxidation Reaction

12.8 Converting Functional Groups

12.9 Proposing a Synthesis

Review of Reactions
Identify the reagents necessary to achieve each of the following transformations. To verify that your
answers are correct, look in your textbook at the end of Chapter 13. The answers appear in the section
entitled Review of Reactions.

Preparation of Alkoxides

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 CHAPTER 12 395

Preparation of Alcohols via Reduction

Preparation of Alcohols via Grignard Reagents

Protection and Deprotection of Alcohols

SN1 Reactions with Alcohols

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396 CHAPTER 12

SN2 Reactions with Alcohols

E1 and E2 Reactions with Alcohols

Oxidation of Alcohols and Phenols

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 CHAPTER 12 397

Common Mistakes to Avoid

If you are proposing a synthesis that involves reduction of a ketone or aldehyde with LiAlH4, make sure
that the water workup is shown as a separate step:

This is important because LiAlH4 is incompatible with the proton source. In contrast, NaBH4 is used in the
presence of a proton source:

So, when using NaBH4 as a reducing agent, do not show the proton source (MeOH) as a separate step.

Also, when drawing a mechanism for the reduction of a ketone, aldehyde, or ester, make sure that
the first curved arrow is placed on the Al‒H bond, rather than on the negative charge:

In previous chapters, we have seen that it is generally acceptable to place the tail of a curved arrow on a
negative charge, but this is an exceptional case. The negative charge in this case is not associated with a
lone pair, so the tail of the curved arrow cannot be placed on the negative charge. It must be placed on the
bond. This is true for reductions involving NaBH4 as well:

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398 CHAPTER 12

Useful reagents
The following is a list of reagents that were new in this chapter:

Reagents Function
NaH A very strong base, used to deprotonate an alcohol to give an alkoxide ion.
Na Will react with an alcohol to liberate hydrogen gas, giving an alkoxide ion.
A reducing agent. Can be used to reduce ketones or aldehydes to alcohols. Will
NaBH4, MeOH
not reduce esters or carboxylic acids.
1) LiAlH4 A strong reducing agent. Can be used to reduce ketones, aldehydes, esters, or
2) H2O carboxylic acids to give an alcohol.
Reducing agent. Generally used to reduce alkenes to alkanes, but in some cases,
H2, Pt
it can also be used to reduce ketones to alcohols.
Mg Can be used to convert an alkyl halide (RX) into a Grignard reagent (RMgX).
A Grignard reagent. Examples include MeMgBr, EtMgBr and PhMgBr. These
reagents are very strong nucleophiles (and very strong bases as well), and they
will react with aldehydes or ketones. Aldehydes are converted into secondary
RMgX
alcohols (except for formaldehyde which is converted to a primary alcohol),
while ketones are converted to tertiary alcohols. Esters are converted to tertiary
alcohols when treated with excess Grignard.
Trimethylsilyl chloride, in the presence of a base (such as triethylamine), will
TMSCl, Et3N
protect an alcohol.
Tetrabutyl ammonium fluoride. Used for deprotection of alcohols with silyl
TBAF
protecting groups.
HBr and HCl are strong acids that also provide a source of a strong nucleophile.
HX
Can be used to convert an alcohol into an alkyl halide.
Will convert an alcohol into a tosylate. This is important because it converts a
TsCl, pyridine
bad leaving group (HO‾) into a good leaving group (TsO‾).
Can be used to convert a primary or secondary alcohol into an alkyl bromide. If
PBr3 the OH group is connected to a chiral center, we expect inversion of
configuration (typical for an SN2 process).
Can be used to convert a primary or secondary alcohol into an alkyl chloride. If
SOCl2, pyridine the OH group is connected to a chiral center, we expect inversion of
configuration (typical for an SN2 process).
HCl, ZnCl2 Can be used to convert an alcohol into an alkyl chloride.
A mixture of sodium dichromate and sulfuric acid gives chromic acid, which is a
Na2Cr2O7, H2SO4, strong oxidizing agent. Primary alcohols are oxidized to give carboxylic acids,
H2O while secondary alcohols are oxidized to give ketones. Tertiary alcohols are
generally unreactive.
A mild oxidizing agent that will oxidize a primary alcohol to give an aldehyde,
PCC, CH2Cl2
rather than a carboxylic acid. Secondary alcohols are oxidized to give ketones.
A mild oxidizing agent that will oxidize a primary alcohol to give an aldehyde,
DMP, CH2Cl2
rather than a carboxylic acid. Secondary alcohols are oxidized to give ketones.
1) DMSO, (COCl)2, The Swern oxidation will oxidize a primary alcohol to give an aldehyde, rather
2) Et3N than a carboxylic acid. Secondary alcohols are oxidized to give ketones.

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