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

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

CH3(CH2)5CO2H

---

CH3(CH2)6CO2H

caprylic acid

CH3(CH2)7CO2H

---

CH3(CH2)8CO2H

capric acid

CH3(CH2)9CO2H

---

CH3(CH2)10CO2H

lauric acid

L. caper goat

oil of lauryl

5 4 3 2 1
CCCCC=O

Br
CH3CH2CH2CHCOOH

bromovaleric acid

used in common names

CH3
CH3CHCH2COOH

-methylbutyric acid
isovaleric acid

COOH

Special names!
benzoic acid

COOH
CH3

COOH

CH3
o-toluic acid

m-toluic acid

COOH

CH3
p-toluic acid

ALDEHYDES AND KETONES

carbonyl functional group:

O
C

Aldehydes

O
C

Ketones

O
C

R can be Ar

O
C

R'

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
C

formaldehyde

o-tolualdehyde

CH2CH=O
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
H2C=O
methanal

CH3
CH3CHCH=O
2-methylpropanal
CH3CH=O
ethanal

Ketones, common names:

Special name:

H3C

O
C

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

benzophenone

H3C

O
C

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

O
CH3CH2CCH2CH3

2-butanone

3-pentanone

O
CH3CCH2CH2CH3
2-pentanone

Physical properties:

C O

sp2

120o

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

CH stretch for aldehydes

nmr:

-CHO 9-10 ppm

2720

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

-2
CH3OH

0
H2C=O

+2
HCO2H

alkane

alcohol

aldehyde

carboxylic acid

reduction

+4
CO2

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

K2Cr2O7, special conditions!

1-pentanol

CH2OH

CH3CH2CH2CH2CH=O
pentanal
valeraldehyde

C5H5NHCrO3Cl

CH=O

pyridinium chlorochromate
benzyl alcohol

CH3CH2CH2CH2CH2OH + K2Cr2O7
1-pentanol

benzaldehyde

CH3CH2CH2CH2CO2H
pentanoic acid

Aldehyde synthesis: 2) oxidation of methylaromatics:

O
H3C
C O
C O
H3C
CH O

CH3
+ CrO3, (CH3CO)2O
Br

Br

geminal diacetate
CHO
H2O, H+
Br
p-bromobenzaldehyde

Aromatic aldehydes only!

CH3

CrO3

CHO

H2O

(CH3CO)2O
2-methylnaphthalene

CH3O

CH3

p-methylanisole

2-naphthaldehyde

CrO3
(CH3CO)2O

H2O

CH3O

CH=O

p-anisaldehyde

Aldehyde synthesis: 3) reduction of acid chloride

O
C

LiAlH(O-t-Bu)3
Cl

lithium aluminum hydride tri-tert-butoxide

O
Cl
isovaleryl chloride

LiAlH(O-t-Bu)3

O
C

O
H
isovaleraldehyde

C
Cl
benzoyl chloride

CH3
O
CH3CHCH2C
Cl
isovaleryl chloride

LiAlH(O-t-Bu)3

C
H

benzaldehyde

LiAlH(O-t-Bu)3

CH3
O
CH3CHCH2C
H
isovaleraldehyde

Ketone synthesis: 1) oxidation of secondary alcohols

H

OH

NaOCl

cyclohexanone

cyclohexanol

OH
CH3CHCH3

isopropyl alcohol

K2Cr2O7
H3C

O
C

CH3

acetone

Ketone synthesis:

2) Friedel-Crafts acylation

O
R C Ar

AlCl3

RCOCl, AlCl3 + ArH

CH3CH2CH2C

O
Cl

AlCl3

+ HCl

O
CH3CH2CH2C
butyrophenone

Aromatic ketones (phenones) only!

O
C Cl

O
C

AlCl3

O2N

O2N

m-nitrobenzophenone
O
C Cl

AlCl3

NR

NO2

Friedel Crafts acylation does not work on deactivated

rings.

Mechanism for Friedel-Crafts acylation EAS

O
C

Cl

AlCl3

+ RC=O

O
CR
H

+ AlCl4

RC=O + AlCl4

RDS

O
CR
H
O
C R

+ HCl + AlCl3

Ketone synthesis:

3) coupling of RCOCl and R2CuLi

O

RCOCl + R'2CuLi

R'
O

O
Cl

(CH3CH2)2CuLi
lithium diethylcuprate

Isobutyryl chloride

2-Methyl-3-pentanone

CuLi

O
Cl

CHCH2CH2CH3

O
CCH2CH2CH3
butyrophenone

CH3CH2CH2C

O
Cl

CH3
CH3CH CuLi
2

O
CH3CH2CH2CCHCH3
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

1o alcohol

Ar-CH3

K2Cr2O7, special cond.

or C5H5NHCrO3Cl

CrO3

H 2O

(AcO)2O

acid chloride

LiAlH(O-t-Bu)3

aldehyde

2 alcohol
o

acid chloride + ArH

NaOCl, etc.

AlCl3

acid chloride + R2CuLi

ketone

REAKSI PADA SENYAWA KARBONIL

Reaksi adisi heteroatom nukleofil:

Reaksi adisi karbon nukleofil:

O
C

OH

HCN

C
CN

Reaksi Oksidasi Senyawa karbonil:

Prinsip:

Zat Pengoksidasi:
Zat pengoksidasi kuat

Zat pengoksidasi lemah

1. KMnO4

1. CrO3/piridin dalam
CH2Cl2, 25 C

2. HNO3 pekat
3. H2CrO4 ( CrO3/Na2Cr2O7 +
H2SO4 pekat)

2. Pereaksi Tollens (Ag+)

3. Pereaksi Fehling (Cu2+)
4. Pereaksi Benedict

Reaksi Adisi Nukleofil Senyawa

Reaksi senyawa karbonil dengan
Ammonia (NH3)
karbonil:
menghasilkan senyawa Imina

Mekanisme reaksi (pH optimum 3-4):

atau Amina

SOAL-SOAL

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, 2pentanone, valeraldehyde, acetophenone,
isobutyraldehyde,

Synthesize benzaldehyde three different ways.

CH2OH
K2Cr2O7
special conditions
CH(OOCCH3)2

CH3
CrO3

CH=O

H2O

(CH3CO)2O
benzaldehyde

O
C Cl
LiAlH(O-t-Bu)3

Synthesize benzophenone three different ways.

OH
CH

O
+
C
Cl
O
+
C
Cl

NaOCl

AlCl3

CuLi
2

O
C

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

O
CH3C
Friedel-Crafts acylation

CHO

oxidation of Ar-CH3

CH3CH2CH2CH2CHO
oxidation of 1o alcohol

CH3
CH3CHCHO
reduction of acid chloride

H
OH

(CH3CH2CH2)CuLi

CH3

O
C
Cl

K2Cr2O7

CH3

O
CH3CH2CH2CCH3

O
C
Cl

AlCl3

O
CH3C

Br

CH3

(CH3CO)2O

CH3CH2CH2CH2CH2-OH

CH3 O
CH3CHC
Cl

H2O

CrO3

Br

K2Cr2O7
special conditions

LiAlH(O-t-bu)3

CHO

CH3CH2CH2CH2CHO

CH3
CH3CHCHO

The methods could be reversed for the last two syntheses.