Aldehydes and Ketones

Before you can learn about aldehydes and ketones, you must first know something about the nomenclature of carboxylic acids since many of the names of aldehydes and ketones are derived from the names of the corresponding carboxylic acids.

Carboxylic acids: R-COOH, R-CO2H,

O R C OH

Common names: HCO2H formic acid L. formica ant

CH3CO2H
CH3CH2CO2H CH3CH2CH2CO2H CH3CH2CH2CH2CO2H

acetic acid

L. acetum vinegar

propionic acid G. first salt butyric acid valeric acid L. butyrum butter L. valerans

Carboxylic acids, common names: CH3(CH2)4CO2H CH3(CH2)5CO2H CH3(CH2)6CO2H CH3(CH2)7CO2H CH3(CH2)8CO2H CH3(CH2)9CO2H caproic acid --caprylic acid --capric acid --L. caper goat

CH3(CH2)10CO2H

lauric acid

oil of lauryl

5 4 3 2 1 CCCCC=O
Br CH3CH2CH2CHCOOH

used in common names

CH3 CH3CHCH2COOH

bromovaleric acid

-methylbutyric acid
isovaleric acid

COOH

Special names!
benzoic acid

COOH CH3

COOH

COOH

CH3 CH3 o-toluic acid m-toluic acid p-toluic acid

ALDEHYDES AND KETONES carbonyl functional group:

O C
Ketones

Aldehydes

O C

O C

O C

R'

R can be Ar

Nomenclature: Aldehydes, common names: Derived from the common names of carboxylic acids; drop ic acid suffix and add aldehyde.

CH3CH2CH2CH=O butyraldehyde

CH3 CH3CHCH=O
isobutyraldehyde (-methylpropionaldehyde)

CHO

CHO CH3

benzaldehyde

o-tolualdehyde

O C

CH2CH=O

formaldehyde

phenylacetaldehyde

Aldehydes, IUPAC nomenclature: Parent chain = longest continuous carbon chain containing the carbonyl group; alkane, drop e, add al. (note: no locant, -CH=O is carbon #1.) CH3CH2CH2CH=O butanal CH3 CH3CHCH=O 2-methylpropanal

H2C=O
methanal

CH3CH=O
ethanal

Ketones, common names:

O C

Special name:

H3C

CH3

acetone

alkyl alkyl ketone or dialkyl ketone

O CH3CH2CCH3 ethyl methyl ketone O CH3CH2CCH2CH3 diethyl ketone O CH3CCH2CH2CH3 methyl n-propyl ketone

(o)phenones:

O R C

Derived from common name of carboxylic acid, drop ic acid, add (o)phenone.
O C O C

H3C

benzophenone

acetophenone

Ketones: IUPAC nomenclature:

Parent = longest continuous carbon chain containing the carbonyl group. Alkane, drop e, add one. Prefix a locant for the position of the carbonyl using the principle of lower number.
O CH3CH2CCH3 2-butanone O CH3CH2CCH2CH3 3-pentanone O CH3CCH2CH2CH3 2-pentanone

Physical properties:

C O C O
polar, no hydrogen bonding

2 sp

o 120

C O

mp/bp are relatively moderate for covalent substances

water insoluble
(except: four-carbons or less)

Spectroscopy:

IR:

C=O stretch, strong ~1700 cm-1

RCHO R2CO 1725 1710 ArCHO ArCOR 1700 1690

CH stretch for aldehydes

2720

nmr:

-CHO 9-10 ppm

acetophenone

C=O stretch

valeraldehyde

CHO CH stretch 2720 cm-1

C=O stretch

valeraldehyde

CH3CH2CH2CH2CH=O a b c d e

-CHO

Oxidation/Reduction:

oxidation numbers:

oxidation

-4 CH4
alkane

-2 CH3OH
alcohol

0 H2C=O
aldehyde

+2 HCO2H
carboxylic acid

+4 CO2

reduction

Aldehydes, syntheses: 1. Oxidation of 1o alcohols

2. Oxidation of methylaromatics
3. Reduction of acid chlorides

Ketones, syntheses:
1. Oxidation of 2o alcohols 2. Friedel-Crafts acylation 3. Coupling of R2CuLi with acid chloride

Aldehydes synthesis 1) oxidation of primary alcohols:

RCH2-OH

K2Cr2O7, special conditions RCH=O

RCH2-OH

C5H5NHCrO3Cl

RCH=O

(pyridinium chlorochromate)

[With other oxidizing agents, primary alcohols RCOOH]

CH3CH2CH2CH2CH2OH 1-pentanol

K2Cr2O7, special conditions!

CH3CH2CH2CH2CH=O pentanal valeraldehyde

CH2OH benzyl alcohol

C5H5NHCrO3Cl pyridinium chlorochromate

CH=O benzaldehyde

CH3CH2CH2CH2CH2OH + K2Cr2O7 1-pentanol

CH3CH2CH2CH2CO2H pentanoic acid

Aldehyde synthesis: 2) oxidation of methylaromatics:

O H3C C O C O H3C CH O + CrO3, (CH3CO)2O Br Br

CH3

geminal diacetate
CHO H2O, H+ Br p-bromobenzaldehyde

Aromatic aldehydes only!

CH3

CrO3 (CH3CO)2O

H2O

CHO

2-methylnaphthalene

2-naphthaldehyde

CrO3 CH3O CH3 (CH3CO)2O

H2O

CH3O

CH=O

p-methylanisole

p-anisaldehyde

Aldehyde synthesis: 3) reduction of acid chloride

O C

LiAlH(O-t-Bu)3 Cl lithium aluminum hydride tri-tert-butoxide R

O C

O Cl isovaleryl chloride

LiAlH(O-t-Bu)3

O H isovaleraldehyde

O C Cl benzoyl chloride

LiAlH(O-t-Bu)3

O C H benzaldehyde

CH3 O CH3CHCH2C Cl isovaleryl chloride

LiAlH(O-t-Bu)3

CH3 O CH3CHCH2C H isovaleraldehyde

Ketone synthesis: 1) oxidation of secondary alcohols

H OH O

NaOCl

cyclohexanol

cyclohexanone

OH CH3CHCH3

K2Cr2O7
H3C

O C

CH3

isopropyl alcohol

acetone

Ketone synthesis:

2) Friedel-Crafts acylation

AlCl3

RCOCl, AlCl3 + ArH

O R C Ar

+ HCl

O CH3CH2CH2C Cl

AlCl3

O CH3CH2CH2C butyrophenone

Aromatic ketones (phenones) only!

O C Cl O2N

AlCl3 O2N

O C

m-nitrobenzophenone
O C Cl

+
NO2

AlCl3

NR

Friedel Crafts acylation does not work on deactivated rings.

Mechanism for Friedel-Crafts acylation EAS O C

+ Cl

AlCl3

RC=O + AlCl4 O CR H

RDS + RC=O

O CR H

+ AlCl4

O C R

+ HCl + AlCl3

Ketone synthesis:

3) coupling of RCOCl and R2CuLi

O

RCOCl + R'2CuLi R
O Cl
Isobutyryl chloride +

C R'
O

(CH3CH2)2CuLi
lithium diethylcuprate 2-Methyl-3-pentanone

CuLi 2

O Cl

CHCH2CH2CH3

O CCH2CH2CH3 butyrophenone

O CH3CH2CH2C Cl

CH3 CH3CH CuLi 2

O CH3CH2CH2CCHCH3 CH3 2-methyl-3-hexanone

Aldehydes, syntheses: 1. Oxidation of 1o alcohols

2. Oxidation of methylaromatics
3. Reduction of acid chlorides

aromatic only

Ketones, syntheses: 1. Oxidation of 2o alcohols 2. Friedel-Crafts acylation aromatic only

3. Coupling of R2CuLi with acid chloride

1o alcohol

K2Cr2O7, special cond. or C5H5NHCrO3Cl

Ar-CH3

CrO3 (AcO)2O

H2O

aldehyde

acid chloride

LiAlH(O-t-Bu)3

2o

alcohol

NaOCl, etc.

acid chloride + ArH

AlCl3

ketone

acid chloride + R2CuLi

1. outline three different syntheses for benzaldehyde

2. outline three different syntheses for benzophenone

3. outline a different synthesis for each of the following compounds: cyclohexanone, 4-bromobenzaldehyde, 2-pentanone, valeraldehyde, acetophenone, isobutyraldehyde,

Synthesize benzaldehyde three different ways.

CH2OH K2Cr2O7 special conditions CH3 CrO3 (CH3CO)2O O C Cl LiAlH(O-t-Bu)3 benzaldehyde CH(OOCCH3)2 H2O CH=O

Synthesize benzophenone three different ways.

OH CH

NaOCl

O + C Cl O + C Cl

AlCl3

O C

CuLi 2

cyclohexanone, 4-bromobenzaldehyde, 2-pentanone, valeraldehyde, acetophenone, isobutyraldehyde, using a different method for each one.
O Br oxidation of 2o alcohol O CH3CH2CH2CCH3 R2CuLi + R'COCl CHO

oxidation of Ar-CH3

CH3CH2CH2CH2CHO oxidation of 1o alcohol

O CH3C Friedel-Crafts acylation

CH3 CH3CHCHO reduction of acid chloride

H OH

K2Cr2O7

(CH3CH2CH2)CuLi

CH3

O C Cl

O CH3CH2CH2CCH3

CH3

O C Cl

AlCl3 +

O CH3C

Br

CH3

CrO3 (CH3CO)2O

H2O

Br

CHO

CH3CH2CH2CH2CH2-OH

K2Cr2O7 special conditions

CH3CH2CH2CH2CHO

CH3 O CH3CHC Cl

LiAlH(O-t-bu)3

CH3 CH3CHCHO

The methods could be reversed for the last two syntheses.