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,

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
Special names!
ALDEHYDES AND KETONES

“carbonyl” functional group:

Aldehydes Ketones
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)
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:

Special name: acetone

“alkyl alkyl ketone” or “dialkyl ketone”

(o)phenones:

Derived from common name of carboxylic acid, drop –ic

acid, add –(o)phenone.
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.
Physical properties:

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
CH4 -2 CH OH0 +2
H2C=O HCO2+4
H CO2
3
alkane alcohol aldehyde carboxylic acid

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

Ketones, syntheses:
7. Oxidation of 2o alcohols
8. Friedel-Crafts acylation
9. 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]

Aldehyde synthesis: 2) oxidation of methylaromatics:

Aromatic aldehydes only!

Aldehyde synthesis: 3) reduction of acid chloride
Ketone synthesis: 1) oxidation of secondary alcohols
Ketone synthesis: 2) Friedel-Crafts acylation

Aromatic ketones (phenones) only!

Friedel Crafts acylation does not work on deactivated
rings.
Ketone synthesis: 3) coupling of RCOCl and R2CuLi
Aldehydes, syntheses:
2. Oxidation of 1o alcohols
3. Oxidation of methylaromatics aromatic only
4. Reduction of acid chlorides

Ketones, syntheses:
7. Oxidation of 2o alcohols
8. Friedel-Crafts acylation aromatic only
9. 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

3. outline three different syntheses for benzophenone

5. outline a different synthesis for each of the

following compounds:
cyclohexanone, 4-bromobenzaldehyde, 2-
pentanone, valeraldehyde, acetophenone,
isobutyraldehyde,
Synthesize benzaldehyde three different ways.
Synthesize benzophenone three different ways.
cyclohexanone, 4-bromobenzaldehyde, 2-pentanone,
valeraldehyde, acetophenone, isobutyraldehyde, using a
different method for each one.
The methods could be reversed for the last two syntheses.