Chapter 14 Aldehydes, Ketones, and Chiral Molecules 14.1 Aldehydes and Ketones Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Carbonyl Group in Aldehydes and Ketones A carbonyl group In an aldehyde is attached to at least one H atom. In a ketone is attached to two carbon groups. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Naming Aldehydes An aldehyde Has an IUPAC name in which the -e in the alkane name is changed to -al. Has a common name for the first four aldehydes that use the prefixes form­ (1C), acet­ (2C), propion­ (3C), and butyr­ (4C), followed by aldehyde. O O O ║ ║ ║ H−C−H CH3−C−H CH3−CH2−C−H methanal ethanal propanal (formaldehyde) (acetaldehyde) (propionaldehyde)

Naming Aldehydes Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Aldehydes in Flavorings Several naturally occurring aldehydes are used as flavorings for foods and fragrances. Benzaldehyde (almonds) Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings Cinnamaldehyde (cinnamon)

Naming Ketones Ketones are named In the IUPAC system by replacing the -e in the alkane name with ­one. The carbonyl carbon is indicated by a number. With a common name by indicating the alkyl groups attached to the carbonyl group in alphabetical order followed by ketone. O O ║ ║ CH3−C−CH3 CH3−C−CH2−CH3 propanone 2-butanone (dimethyl ketone) (ethyl methyl ketone)

Ketones in Common Use Butter flavoring Nail polish remover, Solvent Propanone, Dimethylketone, Acetone Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Learning Check Classify each as 1) aldehyde or 2) ketone. O O || || || || A. CH3—CH2—C—CH3 B. CH3—C—H CH3 O | || C. CH3—C—CH2—C—H D. | CH3

Solution A. 2) ketone B. 1) aldehyde C. 1) aldehyde D. 2) ketone

Learning Check Classify each as an aldehyde (1), ketone (2), alcohol (3), or ether (4). O ║ A. CH3─CH2─C─CH3 B. CH3─O─CH3 CH3 O OH │ ║ │ C. CH3─C─CH2─C─H D. CH3─CH─CH3 │ CH3

Solution Classify each as an aldehyde (1), ketone (2), alcohol (3), or ether (4). O ║ A. CH3─CH2─C─CH3 B. CH3─O─CH3 (2) ketone (4) ether CH3 O OH │ ║ │ C. CH3─C─CH2─C─H D. CH3─CH─CH3 │ CH3 (1) aldehyde (3) alcohol

Learning Check Name each of the following: O ║ 1. CH3─CH2─CH2─CH2─C─H 2. Cl─CH2─CH2─C─H 3. CH3─CH2─C─CH3

Solution O ║ 1. CH3─CH2─CH2─CH2─C─H pentanal 2. Cl─CH2─CH2─C─H 3-chloropropanal 3. CH3─CH2─C─CH3 2-butanone; ethyl methyl ketone

Learning Check Name the following compounds. O || A. CH3—CH2—CH2—C—CH3 B. CH3 O | || C. CH3—C—CH2—C—H | CH3

Solution A. 2-pentanone; methyl propyl ketone B. cyclohexanone C, 3,3-dimethylbutanal

Learning Check Draw the structural formulas for each: A. 4-methylpentanal B. 2,3-dichloropropanal C. 3-methyl-2-butanone

Solution CH3 O │ ║ A. 4-methylpentanal CH3─CH─CH2─CH2─C─H Cl O │ ║ │ ║ B. 2,3-dichloropropanal Cl─CH2─CH─C─H CH3 O C. 3-methyl-2-butanone CH3─CH─C─CH3

Chapter 14 Aldehydes, Ketones, and Chiral Molecules 14.2 Physical Properties Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Polar Carbonyl Group The polar carbonyl group Provides dipole-dipole interactions. + - + - C=O C=O Does not have H on the oxygen atom. Cannot form hydrogen bonds.

Boiling Points Aldehydes and ketones have Polar carbonyl groups (C=O). + - C=O Attractions between polar groups. + - + - C=O C=O Higher boiling points than alkanes and ethers of similar mass. Lower boiling points than alcohols of similar mass.

Comparison of Boiling Points 58 Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Learning Check Select the compound in each pair that would have the Higher boiling point. A. CH3—CH2—CH3 or CH3—CH2—OH B. C. CH3—CH2—OH or CH3—O—CH3

Solution A. CH3—CH2—OH B. C. CH3—CH2—OH

Solubility in Water The electronegative O atom of the carbonyl group in aldehydes and ketones forms hydrogen bonds with water. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Learning Check Indicate if each is soluble or insoluble in water. A. CH3—CH2—CH3 B. CH3—CH2—OH O || C. CH3—CH2—CH2—C—H D. CH3—C—CH3

Solution A. CH3—CH2—CH3 insoluble B. CH3—CH2—OH soluble O || C. CH3—CH2—CH2—C—H soluble D. CH3—C—CH3 soluble

Chapter 14 Aldehydes, Ketones and Chiral Molecules 14.3 Oxidation and Reduction Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Oxidation Aldehydes are easily oxidized to carboxylic acids. O O CH3—C—H CH3—C—OH Acetaldehyde Acetic acid

Tollens’ Test Tollens’ reagent, which contains Ag+, oxidizes aldehydes, but not ketones. Ag+ is reduced to metallic Ag, which appears as a “mirror” in the test tube. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Benedict’s Test In the Benedict’s Test, Cu2+ reacts with aldehydes that have an adjacent OH group. Aldehydes are oxidized to carboxylic acids. Cu2+ is reduced to give Cu2O(s). Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Learning Check Write the structure and name of the oxidized product when each is mixed with Tollens’ reagent. 1. butanal 2. acetaldehyde 3. ethyl methyl ketone

Solution 1. butanal O || CH3—CH2—CH2—C—OH butanoic acid 2. acetaldehyde O CH3—C—OH acetic acid 3. ethyl methyl ketone None. Ketones are not oxidized by Tollen’s reagent.

Chapter 14 Aldehydes, Ketones and Chiral Molecules 14.4 Addition Reactions | + - + - | —C=O + X—Y —C—O—X | Y

Addition Reactions When a polar molecule adds to the carbonyl group of an aldehyde or ketone The negative part of the added molecule bonds to the positive carbonyl carbon. The positive part of the added molecule bonds to the negative carbonyl oxygen. | + - + - | —C=O + X—Y — C—O—X | Y

Acetal Formation Alcohols add to the carbonyl group of aldehydes and ketones. The addition of two alcohols forms acetals. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Hemiacetal Formation The addition of one alcohol to an aldehyde or ketone forms an intermediate called a hemiacetal. Usually, hemiacetals are unstable and difficult to isolate. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Cyclic Hemiacetals A stable cyclic hemiacetal forms when the C=O group and the —OH are both part of a five- or six-atom carbon compound. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Learning Check Identify each as a 1) hemiacetal or 2) acetal. O—CH3 | A. CH3—CH2—C—H OH O—CH2CH3 B. CH3—CH2—C—CH2—CH3

Solution O—CH3 | A. CH3—CH2—C—H 1) hemiacetal OH O—CH2CH3 B. CH3—CH2—C—CH2—CH3 2) acetal

Learning Check Draw the structure of the acetal formed by adding CH3OH to butanal.

Solution O—CH3 | CH3—CH2—CH2—C—H | Draw the structure of the acetal formed by adding CH3OH to butanal. O—CH3 | CH3—CH2—CH2—C—H |

Chapter 14 Aldehydes, Ketones, and Chiral Molecules 14.5 Chiral Molecules Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Chiral Compounds Chiral compounds Have the same number of atoms arranged differently in space. Have one or more chiral carbon atoms bonded to four different groups. Are mirror images like your hands. Try to superimpose your thumbs, palms, back of hands, and little fingers. Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Mirror Images The mirror images of Chiral compounds cannot be superimposed. Two compounds of bromochloroiodomethane can align the H and I atoms, which places the Cl and Br atoms on opposite sides. Copyright © 2007 by Pearson Education, Inc Publishing as Benjamin Cummings

Achiral Structures are Superimposable When the mirror image of an achiral structure is rotated, the structure can be aligned with the initial structure. Thus this mirror image is superimposable. Copyright © 2007 by Pearson Education, Inc Publishing as Benjamin Cummings

Some Everyday Chiral and Achiral Objects

Learning Check Identify each as a chiral or achiral compound.

Solution Identify each as a chiral or achiral compound. chiral achiral chiral

Fischer Projections A Fischer projection Is a 2-dimensional representation of a 3-dimensional molecule. Places the most oxidized group at the top. Uses vertical lines in place of dashes for bonds that go back. Uses horizontal lines in place of wedges for bonds that come forward.

Drawing Fischer Projections Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

D and L Notations By convention, the letter L is assigned to the structure with the —OH on the left. The letter D is assigned to the structure with the —OH on the right. Copyright © 2007 by Pearson Education, Inc Publishing as Benjamin Cummings

Learning Check Indicate whether each pair is a mirror image that cannot be superimposed.

Solution Indicate whether each pair is a mirror image that cannot be superimposed Yes No