Organic Chemistry — Part 2

17 • Why This Chapter?

Up to this point, we’ve focused on developing some general ideas of organic reactivity, looking at the chemistry of hydrocarbons and alkyl halides, and examining some of the tools used in structural studies. With that background, it’s now time to begin a study of the oxygen-containing functional groups that lie at the heart of organic and biological chemistry. We’ll look at alcohols in this chapter and move on to carbonyl compounds in Chapters 19 through 23.

Alcohols and phenols can be thought of as organic derivatives of water in which one of water’s hydrogens is replaced by an organic group: H–O–H versus R–O–H and Ar–O–H. In practice, the name alcohol is restricted to compounds that have their –OH group bonded to a saturated, sp3-hybridized carbon atom, while compounds with their –OH group bonded to a vinylic, sp2-hybridized carbon are called enols. We’ll look at enols in Chapter 22.

Alcohols occur widely in nature and have many industrial and pharmaceutical applications. Methanol, for instance, is one of the most important of all industrial chemicals. Historically, methanol was prepared by heating wood in the absence of air and thus came to be called wood alcohol. Today, approximately 173 million tons (50 billion gallons) of methanol is manufactured worldwide each year, most of it by catalytic reduction of carbon monoxide with hydrogen gas. Methanol is toxic to humans, causing blindness in small doses (15 mL) and death in larger amounts (100–250 mL). Industrially, it is used both as a solvent and as a starting material for production of formaldehyde (CH2O) and acetic acid (CH3CO2H).

Ethanol was one of the first organic chemicals to be prepared and purified. Its production by fermentation of grains and sugars has been carried out for perhaps 9000 years, and its purification by distillation goes back at least as far as the 12th century. Today, approximately 88 million tons (26 billion gallons) of ethanol are produced worldwide each year, most of it by fermentation of corn, barley, sorghum, and other plant sources. Almost all of this ethanol is used for bus and automobile fuel.

Ethanol for industrial use as a solvent or chemical intermediate is largely obtained by acid-catalyzed hydration of ethylene at high temperature.

Phenols occur widely throughout nature and also serve as intermediates in the industrial synthesis of products as diverse as adhesives and antiseptics. Phenol itself is a general disinfectant found in coal tar; methyl salicylate is a flavoring agent found in oil of wintergreen; and urushiols are the allergenic constituents of poison oak and poison ivy. Note that the word phenol is the name both of the specific compound (hydroxybenzene) and of the class of compounds.

17.1 • Naming Alcohols and Phenols

Alcohols are classified as primary (1°), secondary (2°), or tertiary (3°), depending on the number of organic groups bonded to the hydroxyl-bearing carbon.

Simple alcohols are named in the IUPAC system as derivatives of the parent alkane, using the suffix -ol.

RULE 1 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. The -e is deleted to prevent the occurrence of two adjacent vowels: propanol rather than propaneol, for example.

RULE 2 Number the alkane chain beginning at the end nearer the hydroxyl group.

RULE 3 Number the substituents according to their position on the chain, and write the name, listing the …