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14: Reactions of Alcohols

Last updated

May 30, 2020
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- 13.13: Solutions to Additional Exercises
- 14.1: Reactions of Alcohols with Hydrohalic Acids

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Learning Objectives

After reading this chapter and completing ALL the exercises, a student can be able to

predict the products, specify the reagents, and determine the mechanism of the reactions of alcohols with

hydrohalic acids (refer to section 14.1)
phosphorous halides (refer to section 14.2)
thionyl chloride (refer to section 14.2)
carboxylic acids, acid chlorides, and tosyl choride (refer to section 14.3)
dehydrating reagents – H₂SO₄/heat or POCl₃/pyridine (refer to section 14.4)
oxidizing agents (refer to section 14.6)
sodium and potassium (refer to section 14.11)

apply the most efficient and effective oxidizing agents (refer to section 14.6)
determine the alcohol classification using laboratory experiments (refer to section 14.7)
predict the products and specify the reagents of alcohol protecting group reactions (refer to section 14.9)
predict the products and specify the reagents for diol cleavage reactions (refer to section 14.10)
predict the products, specify the reagents for alkoxide ion reactions (refer to section 14.11)
describe selected alcohol oxidation reactions in biology (refer to section 14.12)
determine multiple-step synthetic pathways using alcohols (chapters 1-10 and 13-14)

14.1: Reactions of Alcohols with Hydrohalic Acids
Alcohols react with hydrohalic acids (HCl, HBr, and HI) to form alkyl halides via the SN1 or SN2 mechanism as determined by the structure of the alcohol. Since hydroxide is a poor leaving group, acid catalysis is required.
14.2: Reactions with Phosphorus Halides and Thionyl Chloride
Because of the limited synthetic utility of reacting alcohols with hydrohalic acids to form alkyl halides, the alternative reagents thionyl chloride and phosphorous tribromide. have been developed.
14.3: Alcohol conversion to Esters - Tosylate and Carboxylate
The poor electrophilicity of alcohols can be improved by converting the hydroxyl group into a tosylate ester with higher reactivity for subsequent chemical transformations. Alcohols can also react with acyl chlorides to form carboxylate esters as a synthetic product.
14.4: Dehydration Reactions of Alcohols
Alcohols can form alkenes via the E1 or E2 pathway depending on the structure of the alcohol and the reaction conditions. Markovnokov's Rule still applies and carbocation rearrangements must be considered for the E1 mechanism.
14.5: Oxidation States of Alcohols and Related Functional Groups
Organic chemistry requires an expanded definition of oxidation and reduction.
14.6: Oxidation Reactions of Alcohols
Alcohols can be oxidized using acidified sodium or potassium dichromate(VI) solution. This reaction has been used historically as a way of distinguishing between primary, secondary and tertiary alcohols.
14.7: Determining Alcohol Classifications in the Lab - alternate reactions
Qualitative chemical texts to determine alcohol classification have been developed using the differences in chemical reactivity between primary, secondary, and tertiary alcohols.
14.8: Protection of Alcohols
During the synthesis of complex molecules, one functional group may interfere or complete with the reagent intended for a second functional group on the same molecule. There are several methods for protecting and subsequently recovering alcohols during multiple step syntheses of complex molecules.
14.9: Cleavage of Diols
When analyzing reaction pathways, a loss of carbon atoms indicates a cleavage reaction, like the periodic acid cleavage of glycols.
14.10: Reactions of Alkoxides
Alcohols can be converted into alkoxide ions that are both strong bases and strong nucleophiles.
14.11: Biological Oxidation - An Introduction
The fundamental chemical process of oxidation and reduction is applied to biology and photosynthesis.
14.12: Additional Exercises
This section has additional exercises for the key learning objectives of the chapter.
14.13: Solutions to Additional Exercises
This section has the solutions to the additional exercises from the previous section.

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