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:
O
R-COOH, R-CO2H, R C
OH

Common names:
HCO2H formic acid L. formica ant
CH3CO2H acetic acid L. acetum vinegar
CH3CH2CO2H propionic acid G. “first salt”
CH3CH2CH2CO2H butyric acid L. butyrum butter
CH3CH2CH2CH2CO2H valeric acid L. valerans
Carboxylic acids, common names:
…
CH3(CH2)4CO2H caproic acid L. caper goat
CH3(CH2)5CO2H ---
CH3(CH2)6CO2H caprylic acid
CH3(CH2)7CO2H ---
CH3(CH2)8CO2H capric acid
CH3(CH2)9CO2H ---
CH3(CH2)10CO2H lauric acid oil of lauryl
 5 4 3 2 1
C—C—C—C—C=O
δ γ β α used in common names

Br CH3
CH3CH2CH2CHCOOH CH3CHCH2COOH

 bromovaleric acid  -methylbutyric acid

isovaleric acid
 COOH
Special names!
benzoic acid

COOH COOH COOH

CH3

CH3
CH3

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

ALDEHYDES AND KETONES

O
“carbonyl” functional group: C

Aldehydes Ketones

O O O
C C C
H H R H R R'

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

CH3
CH3CH2CH2CH=O CH3CHCH=O

butyraldehyde isobutyraldehyde
(α-methylpropionaldehyde)
 CHO CHO
CH3

benzaldehyde o-tolualdehyde

O
C CH2CH=O
H H

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.)
CH3
CH3CH2CH2CH=O CH3CHCH=O

butanal 2-methylpropanal

H2C=O CH3CH=O

methanal ethanal
Ketones, common names:
O
C
Special name: H3C CH3 acetone

“alkyl alkyl ketone” or “dialkyl ketone”

O O O
CH3CH2CCH3 CH3CH2CCH2CH3 CH3CCH2CH2CH3

ethyl methyl ketone diethyl ketone methyl n-propyl ketone

 O
(o)phenones:
R C

Derived from common name of carboxylic acid, drop –ic

acid, add –(o)phenone.

O O
C 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 O O
CH3CH2CCH3 CH3CH2CCH2CH3 CH3CCH2CH2CH3

2-butanone 3-pentanone 2-pentanone

Physical properties:
2 o
C O sp 120

C O C O

polar, no hydrogen bonding

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 1725 ArCHO 1700
R2CO 1710 ArCOR 1690
C—H stretch for aldehydes 2720

nmr: -CHO 9-10 ppm

acetophenone

C=O
stretch
valeraldehyde

CHO
C—H
stretch
2720 cm-1

C=O stretch
valeraldehyde

CH3CH2CH2CH2CH=O
a b c d e

-CHO
Oxidation/Reduction:

oxidation numbers:

oxidation
-4 -2 0 +2 +4
CH4 CH3OH H2C=O HCO2H CO2
alkane alcohol aldehyde carboxylic acid

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]

 K2Cr2O7, special conditions!
CH3CH2CH2CH2CH2OH CH3CH2CH2CH2CH=O
1-pentanol pentanal
valeraldehyde

C5H5NHCrO3Cl
CH2OH CH=O
pyridinium chlorochromate
benzyl alcohol benzaldehyde

CH3CH2CH2CH2CH2OH + K2Cr2O7 CH3CH2CH2CH2CO2H

1-pentanol pentanoic acid
Aldehyde synthesis: 2) oxidation of methylaromatics:

O H3C
CH3 C O C O
H3C CH O
+ CrO3, (CH3CO)2O

Br
Br
geminal diacetate
CHO

H2O, H+

Br
p-bromobenzaldehyde
Aromatic aldehydes only!
 CH3 CrO3 H2O CHO

(CH3CO)2O

2-methylnaphthalene 2-naphthaldehyde

CrO3 H2O
CH3O CH3 CH3O CH=O
(CH3CO)2O

p-methylanisole p-anisaldehyde
 Aldehyde synthesis: 3) reduction of acid chloride

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

O O
LiAlH(O-t-Bu)3
Cl H
isovaleryl chloride isovaleraldehyde
 O LiAlH(O-t-Bu)3 O
C C
Cl H
benzoyl chloride benzaldehyde

CH3 O CH3 O
LiAlH(O-t-Bu)3
CH3CHCH2C CH3CHCH2C
Cl H
isovaleryl chloride isovaleraldehyde
Ketone synthesis: 1) oxidation of secondary alcohols

H OH O
NaOCl

cyclohexanol cyclohexanone

OH K2Cr2O7 O
CH3CHCH3 C
H3C CH3

isopropyl alcohol acetone

 Ketone synthesis: 2) Friedel-Crafts acylation

AlCl3 O
RCOCl, AlCl3 + ArH R C Ar + HCl

O AlCl3 O
CH3CH2CH2C + CH3CH2CH2C
Cl
butyrophenone

Aromatic ketones (phenones) only!

 O O
AlCl3
C Cl + C

O2N O2N

m-nitrobenzophenone

O
AlCl3
C Cl + NR

NO2

Friedel Crafts acylation does not work on deactivated rings.

Mechanism for Friedel-Crafts acylation EAS

O
C + AlCl3 RC=O + AlCl4
R Cl

O
RDS CR
+ RC=O
H

O O
CR C R + HCl + AlCl3
+ AlCl4
H
Ketone synthesis: 3) coupling of RCOCl and R2CuLi

O
RCOCl + R'2CuLi C
R R'

O O

+ (CH3CH2)2CuLi
Cl
lithium diethylcuprate
Isobutyryl chloride 2-Methyl-3-pentanone
 O
O
CuLi + CHCH2CH2CH3 CCH2CH2CH3
2 Cl
butyrophenone

CH3 O
O
CH3CH2CH2C + CH3CH CuLi CH3CH2CH2CCHCH3
Cl 2 CH3

2-methyl-3-hexanone
Aldehydes, syntheses:
1. Oxidation of 1o alcohols
2. Oxidation of methylaromatics aromatic only
3. Reduction of acid chlorides

Ketones, syntheses:
1. Oxidation of 2o alcohols
2. Friedel-Crafts acylation aromatic only
3. Coupling of R2CuLi with acid chloride
 K2Cr2O7, special cond.
1o alcohol
or C5H5NHCrO3Cl

CrO3 H2O
Ar-CH3 aldehyde
(AcO)2O

LiAlH(O-t-Bu)3
acid chloride
 NaOCl, etc.
2o alcohol

AlCl3
acid chloride + ArH 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 CH(OOCCH3)2 CH=O

CrO3 H2O
(CH3CO)2O

O benzaldehyde
C Cl
LiAlH(O-t-Bu)3
Synthesize benzophenone three different ways.

OH NaOCl
CH

O AlCl3 O
C + C
Cl

O
C + CuLi
Cl 2
cyclohexanone, 4-bromobenzaldehyde, 2-pentanone,
valeraldehyde, acetophenone, isobutyraldehyde, using a
different method for each one.
O
Br CHO

oxidation of 2o alcohol oxidation of Ar-CH3

O
CH3CH2CH2CCH3 CH3CH2CH2CH2CHO
R2CuLi + R'COCl oxidation of 1o alcohol

O CH3
CH3C CH3CHCHO

Friedel-Crafts acylation reduction of acid chloride

 H O
OH K2Cr2O7

O O
(CH3CH2CH2)CuLi + CH3 C CH3CH2CH2CCH3
Cl

O AlCl3 O
CH3 C + CH3C
Cl
 CrO3 H2O
Br CH3 Br CHO
(CH3CO)2O

K2Cr2O7
CH3CH2CH2CH2CH2-OH CH3CH2CH2CH2CHO
special conditions

CH3 O LiAlH(O-t-bu)3 CH3

CH3CHC CH3CHCHO
Cl

The methods could be reversed for the last two syntheses.