Ald&Ketone I

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-CO
2
H,

Common names:
HCO
2
H formic acid L. formica ant
CH
3
CO
2
H acetic acid L. acetum vinegar
CH
3
CH
2
CO
2
H propionic acid G. first salt
CH
3
CH
2
CH
2
CO
2
H butyric acid L. butyrum butter
CH
3
CH
2
CH
2
CH
2
CO
2
H valeric acid L. valerans
R C
OH
O
Carboxylic acids, common names:

CH
3
(CH
2
)
4
CO
2
H caproic acid L. caper goat
CH
3
(CH
2
)
5
CO
2
H ---
CH
3
(CH
2
)
6
CO
2
H caprylic acid
CH
3
(CH
2
)
7
CO
2
H ---
CH
3
(CH
2
)
8
CO
2
H capric acid
CH
3
(CH
2
)
9
CO
2
H ---
CH
3
(CH
2
)
10
CO
2
H lauric acid oil of lauryl
5 4 3 2 1
CCCCC=O
used in common names
CH
3
CH
2
CH
2
CHCOOH
Br
CH
3
CHCH
2
COOH
CH
3
bromovaleric acid -methylbutyric acid
isovaleric acid
COOH
COOH COOH
COOH
CH
3
CH
3
CH
3
benzoic acid
o-toluic acid m-toluic acid p-toluic acid
Special names!
ALDEHYDES AND KETONES

carbonyl functional group:

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

CH
3

CH
3
CH
2
CH
2
CH=O CH
3
CHCH=O

butyraldehyde isobutyraldehyde
(-methylpropionaldehyde)
CHO
benzaldehyde
CHO
CH
3
o-tolualdehyde
H
C
H
O
formaldehyde
CH
2
CH=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.)
CH
3

CH
3
CH
2
CH
2
CH=O CH
3
CHCH=O

butanal 2-methylpropanal

H
2
C=O CH
3
CH=O

methanal ethanal
Ketones, common names:

Special name: acetone

alkyl alkyl ketone or dialkyl ketone
H
3
C
C
CH
3
O
CH
3
CH
2
CCH
3
O
CH
3
CH
2
CCH
2
CH
3
O
ethyl methyl ketone diethyl ketone
CH
3
CCH
2
CH
2
CH
3
O
methyl n-propyl ketone
(o)phenones:

Derived from common name of carboxylic acid, drop ic
acid, add (o)phenone.
C R
O
C
O
H
3
C
C
O
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.
CH
3
CH
2
CCH
3
O
CH
3
CH
2
CCH
2
CH
3
O
2-butanone
3-pentanone
CH
3
CCH
2
CH
2
CH
3
O
2-pentanone
Physical properties:

polar, no hydrogen bonding
mp/bp are relatively moderate for covalent substances
water insoluble
(except: four-carbons or less)
C O
sp
2
120
o
C O C O
Spectroscopy:

IR: C=O stretch, strong ~1700 cm
-1

RCHO 1725 ArCHO 1700
R
2
CO 1710 ArCOR 1690
CH stretch for aldehydes 2720

nmr: -CHO 9-10 ppm
C=O
stretch
acetophenone
valeraldehyde
CHO
CH
stretch
2720 cm
-1

C=O stretch
valeraldehyde
CH
3
CH
2
CH
2
CH
2
CH=O
a b c d e
-CHO
Oxidation/Reduction:

oxidation numbers:

oxidation
-4 -2 0 +2 +4
CH
4
CH
3
OH H
2
C=O HCO
2
H CO
2

alkane alcohol aldehyde carboxylic acid

reduction
Aldehydes, syntheses:
1. Oxidation of 1
o
alcohols
2. Oxidation of methylaromatics
3. Reduction of acid chlorides

Ketones, syntheses:
1. Oxidation of 2
o
alcohols
2. Friedel-Crafts acylation
3. Coupling of R
2
CuLi with acid chloride
Aldehydes synthesis 1) oxidation of primary alcohols:

RCH
2
-OH + K
2
Cr
2
O
7
, special conditions RCH=O

RCH
2
-OH + C
5
H
5
NHCrO
3
Cl RCH=O
(pyridinium chlorochromate)

[With other oxidizing agents, primary alcohols RCOOH]
CH
3
CH
2
CH
2
CH
2
CH
2
OH
+ K
2
Cr
2
O
7
CH
3
CH
2
CH
2
CH
2
CO
2
H
1-pentanol
pentanoic acid
K
2
Cr
2
O
7
, special conditions!
CH
3
CH
2
CH
2
CH
2
CH=O
pentanal
valeraldehyde
CH
2
OH
C
5
H
5
NHCrO
3
Cl
pyridinium chlorochromate
CH=O
benzaldehyde
benzyl alcohol
CH
3
CH
2
CH
2
CH
2
CH
2
OH
1-pentanol
Aldehyde synthesis: 2) oxidation of methylaromatics:
+ CrO
3
, (CH
3
CO)
2
O
geminal diacetate
H
2
O, H
+
CH
3
Br
Br
CH O
O C C
H
3
C
O
O
H
3
C
Br
CHO
p-bromobenzaldehyde
Aromatic aldehydes only!
CH
3
CH
3
O CH
3
CrO
3
(CH
3
CO)
2
O
CrO
3
(CH
3
CO)
2
O
H
2
O
H
2
O
CHO
CH
3
O CH=O
2-methylnaphthalene 2-naphthaldehyde
p-methylanisole
p-anisaldehyde
Aldehyde synthesis: 3) reduction of acid chloride
LiAlH(O-t-Bu)
3
lithium aluminum hydride tri-tert-butoxide
O
Cl
isovaleryl chloride
O
H
isovaleraldehyde
R
C
O
Cl
LiAlH(O-t-Bu)
3
R
C
O
H
C
O
Cl
LiAlH(O-t-Bu)
3
C
O
H
LiAlH(O-t-Bu)
3
benzoyl chloride
benzaldehyde
CH
3
CHCH
2
C
O
Cl
CH
3
CH
3
CHCH
2
C
O
H
CH
3
isovaleryl chloride
isovaleraldehyde
Ketone synthesis: 1) oxidation of secondary alcohols
NaOCl
cyclohexanol
cyclohexanone
isopropyl alcohol
acetone
K
2
Cr
2
O
7
H OH
O
H
3
C
C
CH
3
O
CH
3
CHCH
3
OH
Ketone synthesis: 2) Friedel-Crafts acylation
RCOCl, AlCl
3
+ ArH + HCl
AlCl
3
Ar C R
O
Aromatic ketones (phenones) only!
CH
3
CH
2
CH
2
C
O
Cl
+
AlCl
3
CH
3
CH
2
CH
2
C
O
butyrophenone
+
AlCl
3
m-nitrobenzophenone
O
2
N
C Cl
O
C
O
O
2
N
+
AlCl
3
C Cl
O
NO
2
NR
Friedel Crafts acylation does not work on deactivated rings.
Mechanism for Friedel-Crafts acylation EAS
R
C
Cl
O
+ AlCl
3 RC=O + AlCl
4
+ RC=O
RDS
H
CR
O
H
CR
O
+ AlCl
4
C R
O
+ HCl + AlCl
3
Ketone synthesis: 3) coupling of RCOCl and R
2
CuLi
RCOCl + R'
2
CuLi
R
C
O
R'
Cl
O
+
(CH
3
CH
2
)
2
CuLi
O
Isobutyryl chloride
2-Methyl-3-pentanone
lithium diethylcuprate
CuLi
2
+ CHCH
2
CH
2
CH
3
O
Cl
CCH
2
CH
2
CH
3
O
butyrophenone
CH
3
CH
2
CH
2
C
O
Cl
+
CH
3
CH
CH
3
2
CuLi CH
3
CH
2
CH
2
CCHCH
3
O
CH
3
2-methyl-3-hexanone
Aldehydes, syntheses:
1. Oxidation of 1
o
alcohols
2. Oxidation of methylaromatics aromatic only
3. Reduction of acid chlorides

Ketones, syntheses:
1. Oxidation of 2
o
alcohols
2. Friedel-Crafts acylation aromatic only
3. Coupling of R
2
CuLi with acid chloride
aldehyde
1
o
alcohol
Ar-CH
3

acid chloride
CrO
3
H
2
O
(AcO)
2
O
LiAlH(O-t-Bu)
3

K
2
Cr
2
O
7
, special cond.
or C
5
H
5
NHCrO
3
Cl
ketone
2
o
alcohol
acid chloride + ArH
acid chloride + R
2
CuLi
NaOCl, etc.
AlCl
3

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,
CH
2
OH
K
2
Cr
2
O
7
special conditions
CH
3
CrO
3
(CH
3
CO)
2
O
CH(OOCCH
3
)
2
H
2
O
C
O
Cl
LiAlH(O-t-Bu)
3
CH=O
benzaldehyde
Synthesize benzaldehyde three different ways.
CH
OH
NaOCl
C
O
Cl
+
AlCl
3
C
O
Cl
+
CuLi
2
C
O
Synthesize benzophenone three different ways.
cyclohexanone, 4-bromobenzaldehyde, 2-pentanone,
valeraldehyde, acetophenone, isobutyraldehyde, using a
different method for each one.
O
Br CHO
CH
3
CH
2
CH
2
CCH
3
O
CH
3
CH
2
CH
2
CH
2
CHO
CH
3
C
O
CH
3
CHCHO
CH
3
oxidation of 2
o
alcohol
oxidation of Ar-CH
3
R
2
CuLi + R'COCl
Friedel-Crafts acylation
oxidation of 1
o
alcohol
reduction of acid chloride
O
CH
3
CH
2
CH
2
CCH
3
O
CH
3
C
O
OH
H
K
2
Cr
2
O
7
CH
3
C
Cl
O
+
AlCl
3
(CH
3
CH
2
CH
2
)CuLi +
CH
3
C
Cl
O
Br CHO
CH
3
CH
2
CH
2
CH
2
CHO
CH
3
CHCHO
CH
3
Br CH
3
CH
3
CH
2
CH
2
CH
2
CH
2
-OH
K
2
Cr
2
O
7
special conditions
CrO
3
(CH
3
CO)
2
O
H
2
O
CH
3
CHC
CH
3
O
Cl
LiAlH(O-t-bu)
3
The methods could be reversed for the last two syntheses.

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Aldehydes and Ketones

Before you can learn about aldehydes and

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