17 17-1 © 2006 thomson learning, inc. all rights reserved general, organic, and biochemistry, 8e...

1717

17-1© 2006 Thomson Learning, Inc.All rights reserved

General, Organic, General, Organic, and Biochemistry, 8eand Biochemistry, 8e

Bettelheim, Brown,Bettelheim, Brown,

Campbell, and FarrellCampbell, and Farrell

1717


Chapter 17Chapter 17

Aldehydes and Aldehydes and KetonesKetones

1717


StructureStructure• The functional group of an aldehydealdehyde is a carbonyl group bonded to a hydrogen atom.• In methanal, the simplest aldehyde (formaldehyde), the carbonyl group is bonded to two hydrogens.

• In other aldehydes, it is bonded to one hydrogen and one carbon group.

• The functional group of a ketoneketone is a carbonyl group bonded to two carbon groups.

CH3CHO

HCHO

CH3CCH3

O

Propanone(Acetone)

Ethanal(Acetaldehyde)

Methanal(Formaldehyde)

1717


NomenclatureNomenclature• IUPAC names for aldehydes:

• To name an aldehyde, change the suffix -ee of the parent alkane to -alal.

• Because the carbonyl group of an aldehyde can only be at the end of a parent chain and numbering must start with it as carbon-1, there is no need to use a number to locate the aldehyde group.

• For unsaturated aldehydesunsaturated aldehydes, indicate the presence of a carbon-carbon double bond by changing the ending of the parent alkane from -aneane to -enalenal; Numbering the carbon chain begins with the aldehyde carbonyl carbon; Show the location of the carbon-carbon double bond by the number of its first carbon.

1717


NomenclatureNomenclature

• The IUPAC system retains common names for some aldehydes, including these three.

3-Methylbutanal 2-Propenal(Acrolein)

Hexanal

12

34H

O

H

O1

23

45

6

123

H

O

CHO

H

OCHO

OCH3

OHtrans-3-Phenyl-2-propenal

(Cinnamaldehyde; inoil of cinnamon)

Benzaldehyde(in almonds)

Vanillin(from vanilla

beans)

1717


NomenclatureNomenclature• IUPAC names for ketones:

• The parent alkane is the longest chain that contains the carbonyl group.

• Indicate the presence of the carbonyl group by changing the -aneane of the parent alkane -oneone.

• Number the parent chain from the direction that gives the carbonyl carbon the smaller number.

• The IUPAC retains the common name acetone for 2-propanone.

O

Acetone 2-Methylcyclohexanone5-Methyl-3-hexanone

OO

12

34

56

12

1717


NomenclatureNomenclature• To name an aldehyde or ketone that also contains an -OH (hydroxyl) or -NH2 (amino) group:• Number the parent chain to give the carbonyl carbon the lower number.

• Indicate an -OH substituent by hydroxy-hydroxy-, and an -NH2 substituent by amino-amino-.

• Hydroxy and amino substituents are numbered and alphabetized along with other substituents.

O

H

OOH

NH2

3-Hydroxy-4-methylpentanal 3-Amino-4-ethyl-2-hexanone

1345 12346

1717


NomenclatureNomenclature• Common names:

• The common name for an aldehyde is derived from the common name of the corresponding carboxylic acid; drop the word "acidacid" and change the suffix -icic or -oicoic to -aldehydealdehyde

• Name each alkyl or aryl group bonded to the carbonyl carbon as a separate word, followed by the word "ketoneketone”; the alkyl or aryl groups are generally listed in order of increasing molecular weightO

CH3CH

O

CH3COH

Acetaldehyde Acetic acid Ethyl isopropyl ketoneMethyl ethyl ketone

OO

1717


Physical PropertiesPhysical Properties• A C=O bond is polar, with oxygen bearing a partial negative charge and carbon bearing a partial positive charge• Therefore, aldehydes and ketones are polar molecules

1717


Physical PropertiesPhysical Properties• In liquid aldehydes and ketones, there are weak intermolecular attractions are between the partial positive charge on the carbonyl carbon of one molecule and the partial negative charge on the carbonyl oxygen of another molecule.

• No hydrogen bonding is possible between aldehyde or ketone molecules.

• Aldehydes and ketones have lower boiling points than alcohols and carboxylic acids, compounds in which there is hydrogen bonding between molecules.

CH

HO +-

CHHO

C

HH

O+

-C

H

HO-+

+-

1717


Physical PropertiesPhysical Properties

• Formaldehyde, acetaldehyde, and acetone are infinitely soluble in water.

• Aldehydes and ketones become less soluble in water as the hydrocarbon portion of the molecule increases in size.

pentanebutanal2-butanone1-butanolpropanoic acid

Name Structural FormulaMolecular

Weight (amu)

72727274

74

367680

117

141

bp(°C)

CH3CH2 CH2CH2CH3CH3CH2 CH2CHO

CH3CH2 CH2CH2OHCH3CH2 COOH

CH3CH2 COCH3

diethyl ether 74 34CH3CH2 OCH2CH3

1717


OxidationOxidation• Aldehydes are oxidized to carboxylic acids by a variety of oxidizing agents, including potassium dichromate.

• Liquid aldehydes are so sensitive to oxidation by O2 of the air that they must be protected from contact with air during storage.

H

OK2Cr2O7

Hexanal Hexanoic acidH2SO4

OH

O

CH

O

Benzoic acidBenzaldehyde

+ O2

COH

O

2 2

1717


OxidationOxidation• Ketones resist oxidation by most oxidizing agents, including potassium dichromate and molecular oxygen.• Tollens’ reagent is specific for the oxidation of aldehydes; if done properly, silver deposits on the walls of the container as a silver mirror.R-C-H

O2Ag(NH3)2

+ 3OH-

R-C-O-O

2Ag 4NH3 2H2O

+ +

+ + +

Tollens'reagent

Carboxylicanion

Silvermirror

Aldehyde

1717


ReductionReduction• The carbonyl group of an aldehyde or ketone is reduced to an -CHOH or -CH2OH group by hydrogen in the presence of a transition-metal catalyst:• Reduction of an aldehyde gives a primary alcohol.

• Reduction a ketone gives a secondary alcohol. H2

transition metal catalyst+H

O

PentanalOH

1-Pentanol

H2

transition metal catalyst

+O

Cyclopentanone

OH

Cyclopentanol

1717


ReductionReduction• The most common laboratory reagent for the reduction of an aldehyde or ketone is sodium borohydride, NaBHNaBH44. • This reagent contains hydrogen in the form of hydride ion, H:H:--.

• In a hydride ion, hydrogen has two valence electrons and bears a negative charge.

• In a reduction by sodium borohydride, hydride ion adds to the partially positive carbonyl carbon which leaves a negative charge on the carbonyl oxygen.

• Reaction of this intermediate with aqueous acid gives the alcohol.

1717


ReductionReduction

• Reduction by NaBH4 does not affect a carbon-carbon double bond or an aromatic ring.

HCO

1. NaBH4

2. H2O

CH2OH

Cinnamaldehyde Cinnamyl alcohol

O NaBH4O-

HH3O+ O-H

H

H - C O H C O - H3O+

H C O-H: +

Hydrideion

1717


ReductionReduction• In biological systems, the agent for the reduction of aldehydes and ketones is the reduced form of nicotinamide adenine dinucleotide, abbreviated NADH (Section 26.3)• This reducing agent, like NaBH4, delivers a hydride ion to the carbonyl carbon of the aldehyde or ketone.

• Reduction of pyruvate, the end product of glycolysis, by NADH gives lactate.CH3-C-COO-

ONADH CH3-C-COO-

H

O-

H3O+

CH3-C-COO-

H

O-H

Pyruvate Lactate

1717


Addition of AlcoholsAddition of Alcohols• Addition of a molecule of alcohol to the carbonyl group of an aldehyde or ketone forms a hemiacetalhemiacetal (a half-acetal).• The functional group of a hemiacetal is a carbon bonded to one -OH group and one -OR group.

• In forming a hemiacetal, H of the alcohol adds to the carbonyl oxygen and OR adds to the carbonyl carbon.

CH

OO-CH2CH3

HC OCH2CH3

H

O-H+

Benzaldehyde Ethanol A hemiacetal

1717


Addition of AlcoholsAddition of Alcohols• Hemiacetals are generally unstable and are only minor components of an equilibrium mixture except in one very important type of molecule:

• When a hydroxyl group is part of the same molecule that contains the carbonyl group and a five- or six-membered ring can form, the compound exists almost entirely in a cyclic hemiacetal form.

H

O

O-HC

O O

H

H

O O-H

H

4-Hydroxypentanal A cyclic hemiacetal

123

45

1345

redraw to show the -OH and -CHO close

to each other2

1717


Addition of AlcoholsAddition of Alcohols• A hemiacetal can react further with an alcohol to form an acetalacetal plus water.• This reaction is acid catalyzed.• The functional group of an acetal is a carbon bonded to two -OR groups.

C OCH2CH3H

O-HOCH2CH3

H H+

C OCH2CH3H

OCH2CH3

A hemiacetal(from benzaldehyde)

Ethanol

+ +

An acetal

H-OH

1717


Addition of AlcoholsAddition of Alcohols

• All steps in hemiacetal and acetal formation are reversible.

• As with any other equilibrium, we can drive this one in either direction by using Le Chatelier's principle.

• To drive it to the right, we either use a large excess of alcohol or remove water from the equilibrium mixture

• To drive it to the left, we use a large excess of water.

OCH2CH3

O-HOCH2CH3

HH+

OCH2CH3

OCH2CH3H2O

An acetalA hemiacetal(from cyclohexanone)

Ethanol

+ +

1717


Keto-Enol TautomerismKeto-Enol Tautomerism• A carbon atom adjacent to a carbonyl group is called an -carbon-carbon, and a hydrogen atom bonded to it is called an -hydrogen-hydrogen.

-carbons

-hydrogens

CH3-C-CH2-CH3

O

1717


Keto-Enol TautomerismKeto-Enol Tautomerism• An aldehyde or ketone that has a hydrogen on an -carbon is in equilibrium with a constitutional isomer called an enolenol.• The name “enol” is derived from the IUPAC designation of it as both an alkene (-enen-) and an alcohol (-olol).

• In a keto-enol equilibrium, the keto form generally predominates.

CH3-C-CH3

OCH3-C=CH2

OH

Acetone(keto form)

Acetone(enol form)

1717


Keto-Enol TautomerismKeto-Enol Tautomerism• example:example: Draw structural formulas for the two enol forms for each ketone:

• solution:solution:

(a)

(b)

O

O

OH OH

OH OH

1717


End End Chapter 17Chapter 17

Aldehydes and KetonesAldehydes and Ketones

17 17-1 © 2006 thomson learning, inc. all rights reserved general, organic, and biochemistry, 8e...

Documents