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18.14: Aldehydes and Ketones

Last updated

Jul 26, 2022
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- 18.13: Ethers
- 18.15: Carboxylic Acids and Esters

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Learning Objectives

Identify the general structure for an aldehyde and a ketone.
Use common names to name aldehydes and ketones.
Use the IUPAC system to name aldehydes and ketones.

The next functional group we consider, the carbonyl group, has a carbon-to-oxygen double bond.

Carbonyl groups define two related families of organic compounds: the aldehydes and the ketones.

The carbonyl group is ubiquitous in biological compounds. It is found in carbohydrates, fats, proteins, nucleic acids, hormones, and vitamins—organic compounds critical to living systems.

In a ketone, two carbon groups are attached to the carbonyl carbon atom. The following general formulas, in which R represents an alkyl group and Ar stands for an aryl group, represent ketones.

In an aldehyde, at least one of the attached groups must be a hydrogen atom. The following compounds are aldehydes:

In condensed formulas, we use CHO to identify an aldehyde rather than COH, which might be confused with an alcohol. This follows the general rule that in condensed structural formulas H comes after the atom it is attached to (usually C, N, or O).

The carbon-to-oxygen double bond is not shown but understood to be present. Because they contain the same functional group, aldehydes and ketones share many common properties, but they still differ enough to warrant their classification into two families.

Naming Aldehydes and Ketones

Both common and International Union of Pure and Applied Chemistry (IUPAC) names are frequently used for aldehydes and ketones, with common names predominating for the lower homologs. The common names of aldehydes are taken from the names of the acids into which the aldehydes can be converted by oxidation.

The stems for the common names of the first four aldehydes are as follows:

1 carbon atom: form-
2 carbon atoms: acet-
3 carbon atoms: propion-
4 carbon atoms: butyr-

Because the carbonyl group in a ketone must be attached to two carbon groups, the simplest ketone has three carbon atoms. It is widely known as acetone, a unique name unrelated to other common names for ketones.

Generally, the common names of ketones consist of the names of the groups attached to the carbonyl group, followed by the word ketone. (Note the similarity to the naming of ethers.) Another name for acetone, then, is dimethyl ketone. The ketone with four carbon atoms is ethyl methyl ketone.

Example $\PageIndex{1}$

Classify each compound as an aldehyde or a ketone. Give the common name for each ketone.

Solution

This compound has the carbonyl group on an end carbon atom, so it is an aldehyde.
This compound has the carbonyl group on an interior carbon atom, so it is a ketone. Both alkyl groups are propyl groups. The name is therefore dipropyl ketone.
This compound has the carbonyl group between two alkyl groups, so it is a ketone. One alkyl group has three carbon atoms and is attached by the middle carbon atom; it is an isopropyl group. A group with one carbon atom is a methyl group. The name is therefore isopropyl methyl ketone.

Exercise $\PageIndex{1}$

Classify each compound as an aldehyde or a ketone. Give the common name for each ketone.

Here are some simple IUPAC rules for naming aldehydes and ketones:

The stem names of aldehydes and ketones are derived from those of the parent alkanes, defined by the longest continuous chain (LCC) of carbon atoms that contains the functional group.
For an aldehyde, drop the -e from the alkane name and add the ending -al. Methanal is the IUPAC name for formaldehyde, and ethanal is the name for acetaldehyde.
For a ketone, drop the -e from the alkane name and add the ending -one. Propanone is the IUPAC name for acetone, and butanone is the name for ethyl methyl ketone.
To indicate the position of a substituent on an aldehyde, the carbonyl carbon atom is always considered to be C1; it is unnecessary to designate this group by number.
To indicate the position of a substituent on a ketone, number the chain in the manner that gives the carbonyl carbon atom the lowest possible number. In cyclic ketones, it is understood that the carbonyl carbon atom is C1.

Example $\PageIndex{2}$

Give the IUPAC name for each compound.

Solution

There are five carbon atoms in the LCC . The methyl group (CH₃) is a substituent on the second carbon atom of the chain; the aldehyde carbon atom is always C1. The name is derived from pentane. Dropping the -e and adding the ending -al gives pentanal. The methyl group on the second carbon atom makes the name 2-methylpentanal.
There are five carbon atoms in the LCC. The carbonyl carbon atom is C3, and there are methyl groups on C2 and C4. The IUPAC name is 2,4-dimethyl-3-pentanone.
There are six carbon atoms in the ring. The compound is cyclohexanone. No number is needed to indicate the position of the carbonyl group because all six carbon atoms are equivalent.

Exercise

Give the IUPAC name for each compound.

Example $\PageIndex{3}$

Draw the structure for each compound.

7-chlorooctanal
4-methyl–3-hexanone

Solution

The octan- part of the name tells us that the LCC has eight carbon atoms. There is a chlorine (Cl) atom on the seventh carbon atom; numbering from the carbonyl group and counting the carbonyl carbon atom as C1, we place the Cl atom on the seventh carbon atom.
The hexan- part of the name tells us that the LCC has six carbon atoms. The 3 means that the carbonyl carbon atom is C3 in this chain, and the 4 tells us that there is a methyl (CH₃) group at C4:

Exercise $\PageIndex{3}$

Draw the structure for each compound.

5-bromo-3-iodoheptanal
5-bromo-4-ethyl-2-heptanone

Summary

The common names of aldehydes are taken from the names of the corresponding carboxylic acids: formaldehyde, acetaldehyde, and so on. The common names of ketones, like those of ethers, consist of the names of the groups attached to the carbonyl group, followed by the word ketone. Stem names of aldehydes and ketones are derived from those of the parent alkanes, using an -al ending for an aldehydes and an -one ending for a ketone.

Learning Objectives

Explain why the boiling points of aldehydes and ketones are higher than those of ethers and alkanes of similar molar masses but lower than those of comparable alcohols.
Compare the solubilities in water of aldehydes and ketones of four or fewer carbon atoms with the solubilities of comparable alkanes and alcohols.
Name the typical reactions take place with aldehydes and ketones.
Describe some of the uses of common aldehydes and ketones.

The carbon-to-oxygen double bond is quite polar, more polar than a carbon-to-oxygen single bond. The electronegative oxygen atom has a much greater attraction for the bonding electron pairs than does the carbon atom. The carbon atom has a partial positive charge, and the oxygen atom has a partial negative charge:

In aldehydes and ketones, this charge separation leads to dipole-dipole interactions that are great enough to significantly affect the boiling points. Table $\PageIndex{1}$ shows that the polar single bonds in ethers have little such effect, whereas hydrogen bonding between alcohol molecules is even stronger.

Table $\PageIndex{1}$ : Boiling Points of Compounds Having Similar Molar Masses but Different Types of Intermolecular Forces
Compound	Family	Molar Mass	Type of Intermolecular Forces	Boiling Point (°C)
CH₃CH₂CH₂CH₃	alkane	58	dispersion only	–1
CH₃OCH₂CH₃	ether	60	weak dipole	6
CH₃CH₂CHO	aldehyde	58	strong dipole	49
CH₃CH₂CH₂OH	alcohol	60	hydrogen bonding	97

Formaldehyde is a gas at room temperature. Acetaldehyde boils at 20°C; in an open vessel, it boils away in a warm room. Most other common aldehydes are liquids at room temperature.

Although the lower members of the homologous series have pungent odors, many higher aldehydes have pleasant odors and are used in perfumes and artificial flavorings. As for the ketones, acetone has a pleasant odor, but most of the higher homologs have rather bland odors.

The oxygen atom of the carbonyl group engages in hydrogen bonding with a water molecule.

The solubility of aldehydes is therefore about the same as that of alcohols and ethers. Formaldehyde, acetaldehyde, and acetone are soluble in water. As the carbon chain increases in length, solubility in water decreases. The borderline of solubility occurs at about four carbon atoms per oxygen atom. All aldehydes and ketones are soluble in organic solvents and, in general, are less dense than water.

Oxidation of Aldehydes and Ketones

Aldehydes and ketones are much alike in many of their reactions, owing to the presence of the carbonyl functional group in both. They differ greatly, however, in one most important type of reaction: oxidation. Aldehydes are readily oxidized to carboxylic acids, whereas ketones resist oxidation.

The aldehydes are, in fact, among the most easily oxidized of organic compounds. They are oxidized by oxygen ( $\ce{O2}$ ) in air to carboxylic acids.

$\ce{2RCHO + O_2 -> 2RCOOH} \nonumber$

The ease of oxidation helps chemists identify aldehydes. A sufficiently mild oxidizing agent can distinguish aldehydes not only from ketones but also from alcohols. Tollens’ reagent, for example, is an alkaline solution of silver ( $\ce{Ag^{+}}$ ) ion complexed with ammonia (NH₃), which keeps the $\ce{Ag^{+}}$ ion in solution.

$\ce{H_3N—Ag^{+}—NH_3} \nonumber$

When Tollens’ reagent oxidizes an aldehyde, the $\ce{Ag^{+}}$ ion is reduced to free silver ( $\ce{Ag}$ ).

$\underbrace{\ce{RCHO(aq)}}_{\text{an aldehyde}} + \ce{2Ag(NH3)2^{+}(aq) -> RCOO^{-} +} \underbrace{\ce{2Ag(s)}}_{\text{free silver}} + \ce{4NH3(aq) + 2H2O} \nonumber$

Deposited on a clean glass surface, the silver produces a mirror (Figure $\PageIndex{1}$ ). Ordinary ketones do not react with Tollens’ reagent.

Figure $\PageIndex{1}$ : Aldehyde Reactions. A reaction related to the Tollens’ reaction is often used to silver mirrors. These ornaments were silvered by such a reaction. Glucose, a simple sugar with an aldehyde functional group, is used as the reducing agent. Source: Photo courtesy of Krebs Glas Lauscha, commons.wikimedia.org/wiki/File:Silvering.jpg.

Although ketones resist oxidation by ordinary laboratory oxidizing agents, they undergo combustion, as do aldehydes.

Some Common Carbonyl Compounds

Formaldehyde has an irritating odor. Because of its reactivity, it is difficult to handle in the gaseous state. For many uses, it is therefore dissolved in water and sold as a 37% to 40% aqueous solution called formalin. Formaldehyde denatures proteins, rendering them insoluble in water and resistant to bacterial decay. For this reason, formalin is used in embalming solutions and in preserving biological specimens.

Aldehydes are the active components in many other familiar substances. Large quantities of formaldehyde are used to make phenol-formaldehyde resins for gluing the wood sheets in plywood and as adhesives in other building materials. Sometimes the formaldehyde escapes from the materials and causes health problems in some people. While some people seem unaffected, others experience coughing, wheezing, eye irritation, and other symptoms.

The odor of green leaves is due in part to a carbonyl compound, cis-3-hexenal, which with related compounds is used to impart a “green” herbal odor to shampoos and other products.

Acetaldehyde is an extremely volatile, colorless liquid. It is a starting material for the preparation of many other organic compounds. Acetaldehyde is formed as a metabolite in the fermentation of sugars and in the detoxification of alcohol in the liver. Aldehydes are the active components of many other familiar materials (Figure $\PageIndex{2}$ ).

14.6.jpg — Figure $\PageIndex{2}$ Some Interesting Aldehydes. (a) Benzaldehyde is an oil found in almonds; (b) cinnamaldehyde is oil of cinnamon; (c) vanillin gives vanilla its flavor; (d) *cis*-3-hexenal provides an herbal odor; and (e) *trans*-2-*cis*-6-nonadienal gives a cucumber odor.

Acetone is the simplest and most important ketone. Because it is miscible with water as well as with most organic solvents, its chief use is as an industrial solvent (for example, for paints and lacquers). It is also the chief ingredient in some brands of nail polish remover.

To Your Health: Acetone in Blood, Urine, and Breath

Acetone is formed in the human body as a by-product of lipid metabolism. Normally, acetone does not accumulate to an appreciable extent because it is oxidized to carbon dioxide and water. The normal concentration of acetone in the human body is less than 1 mg/100 mL of blood. In certain disease states, such as uncontrolled diabetes mellitus, the acetone concentration rises to higher levels. It is then excreted in the urine, where it is easily detected. In severe cases, its odor can be noted on the breath.

Ketones are also the active components of other familiar substances, some of which are noted in the accompanying figure.

Some ketones have interesting properties: (a) Butter flavoring comes from 2,3-butanedione; (b) β-ionone is responsible for the odor of violets; (c) muscone is musk oil, an ingredient in perfumes; and (d) camphor is used in some insect repellents.

Certain steroid hormones have the ketone functional group as a part of their structure. Two examples are progesterone, a hormone secreted by the ovaries that stimulates the growth of cells in the uterine wall and prepares it for attachment of a fertilized egg, and testosterone, the main male sex hormone. These and other sex hormones affect our development and our lives in fundamental ways.

Summary

The polar carbon-to-oxygen double bond causes aldehydes and ketones to have higher boiling points than those of ethers and alkanes of similar molar masses but lower than those of comparable alcohols that engage in intermolecular hydrogen bonding. Aldehydes are readily oxidized to carboxylic acids, whereas ketones resist oxidation.

Learning Objectives

Naming Aldehydes and Ketones

Example 18.14.1\PageIndex{1}

Solution

Exercise 18.14.1\PageIndex{1}

Example 18.14.2\PageIndex{2}

Solution

Exercise

Example 18.14.3\PageIndex{3}

Solution

Exercise 18.14.3\PageIndex{3}

Summary

Learning Objectives

Oxidation of Aldehydes and Ketones

Some Common Carbonyl Compounds

To Your Health: Acetone in Blood, Urine, and Breath

Summary

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Example $\PageIndex{1}$

Exercise $\PageIndex{1}$

Example $\PageIndex{2}$

Example $\PageIndex{3}$

Exercise $\PageIndex{3}$