Preparationof Aldehydes

OFrom acyl chloride (Rosenmund reduction)

HO
a
H
Pd-Baso
Benzoyl chloride Benzaldehyde
OFrom nitries and esters (Stephen reaction)

RCN+SnClh+ HCI RCH NH RCHO

From hydrocarbons using Chromyl chloride (CrO,Cl,) (Etard reaction)

SHIOGIOHCbl CHO
+Crocl,S

Toluene Chromium complex Benzaldehyde

OFrom hydrocarbons using chromic oxide (CrO,)

HOcOCH)a
ro, +(CHcoyo 23K,

Toluene Benzaldehyde

By side chain clorination of toluene followed by hydrolysis

H HO
CHC
Chu
373
Benzal chloride
1oluene Benzaldehyde
OFrom Benzene or its derivatives by Gatterman-Koch reaction
HO
cO. Hd
Anhyd.AICl,/ CuCl
Benzene Benzaldehyde
Chemical Reactions of Aldehydes and Ketones
Nucleophilic addition reactions

ROH OR
HCIgas
R-CHO R-CH +H,O
OR
Hemiacetal Acetal

Reduction

c-0 HCI CH+H,0 (Clemmensen reduction)

NH NHcNNH,etnylene glycol
C0
(Wolff-Kishner reduction)
Oxidation

R-CHO R-COOH

R-CH-C-CH,-R R-COOH +R-CHCOOH

(By cleavage of CG bond)

R-CHCOOH +R'-COOH
(By cleavage of Ga-G, bond)

Aldol condensation
dil. NaOH
2CH,-CHO= CHs-CH-CH-CHOHOCH-CHCH-CHO
Ethanal OH But-2-enal

3-Hydroxybutanal (Aldol condensation

(Aldol) product)
 8 Cross aldol condensation

--CH, 293 K

1,3-Dipenylprop-2-en-1-one
(Benzalacetophenone)
(Major product)

Cannizzaro reaction

0+ 0 +Conc. KOH H-C-OH +H-C

H OK

Formaldehyde Methanol Potassium formate

Electrophilic substitution reaction

HNO,/H,50,
CHO 273-283K -CHO

Benzaldehyde m-Nitrobenzaldehyde

Uses of Aldehydesand Ketones

Used as a solvent, starting material and reagent
Formaldehyde - Formalin (40%) solution used to preserve biological specimens
and to prepare bakelite, urea-formaldehyde glues and other polymeric products
Acetaldehyde- Used primarily as a starting material in the manufacture of acetic
acid, ethylacetate, vinylacetate, polymersand drugs
Benzaldehyde- Used in perfumery and in dye industries.
Acetone and ethyl methyl ketone are common industrial solvents
ALDEHYDES, KETONES, AND CARBOXYLIC ACIDS - PARTIO

Carbonyl Compounds
Nomenclature ofCarbonylGroup
Carbonyl group is a functional group composed
of a carbon atom double bonded to an oxygen atom
des"

Structure Common Name IUPAC Name

Aldehydes
HCHO Methanal
Formaldehyde
CH,CHO Acetaldehyde Ethanal
(CH,CHCH0 Isobutyraldehyde 2-Methylpropanal
H CHO
Y-Methylcyclohexanecarbaldehyde 3-Methyleyclohexanecarbaldehyde
CH,CH(OCH,)CHO a Methoxypropionaldehyde 2-Methoxypropanal
CH,CH,CHCH,CHO Valeraldehyde Pentanal
CH=CHCHO Acrolein
Prop-2-ena
HO

Phthaldehyde Benzene- 1,2-dicarbaldehyde

CHO

CHO

m-Bromobenzaldehyde 3-Bromobenzenecarbaldehyde
r

3-Bromobenzaldehyde
Br

Ketones
CH,cOCH,CH,CH, Methyl n-propyl ketone Pentan-2-one
CH)CHCOCH(CH)Disopropyl ketone 2,4-Dimethylpentan-3-one

a-Methylcycdohexanone 2-Methylcyclohexanone
CH
(CHC-CHCoCHCH, | Mesytil oxide 4-Methylpent-3-en-2-one

Structure of Carbonyl Group

bond 20
spcO-bond o
sp C 12C
120
ALDEHYDES, KETONES, AND CARBOxYLIC ACIDS-PART II
Physical Properties Chemical Properties
Methanal (HCHO) is a gas at room NaHSO, s0Na
temperature

Ethanal (CH,CHO) is a volatile liquid

HCN
The boiling points of aldehydes and
ketones are higher than ) RMgk Alcohols
i) H,o
hydrocarbons and ethers of similar
HN-2 N-Z
molecular mass. (Ammonia
Derivates)
Aldehydes and ketones have lower
ompounds Alpha-H containing carbony
boiling point than those of alcohols compounds give Aldol reaction

of similar molecular mass OH Aldehydes without alpha-H

undergo Cannizzaro's reaction
The lower members of aldehydes AlOR Ester (Given by two equivalents
Tishchenko
and ketones are miscible with water reaction o f an aldehyde)

due to the formation of hydrogen

bond with water Conc.I
HCIAIkane(Clemmensen reduction)

OH/A
Alkane(Wolf Kishner reduction)
C 0 H H O=C
LIAIH, Or Alcohol
NaBH

OxidationCarboxylic Acids
Carboxylic acids
Glassification Structure of Carboxyl Group
.Monocarboxylic acids
contain one-coOH group
R-

Dicarboxylic acids
contain two-COOH groups
O-H O

SourcesS
Formula Common Name Source
HCOOH Formic acid Red ant(Latin: formica)

CH,COOH Acetic acid VinegarlLatin: acetum)

CgHCOOH Butyric acid Rancid butterlLatin: butyrum)

 Preparation of Carboxylicacids
OFrom primary alcohols and aldehydes

RCH,OH- alkaline KMindRCOOH

H,o
CH,(CH),CH,OH Jones reagent
CH,(CH,).coOH
cOOK CoOH
From alkylbenzenes
KMnOKOH
Heat

Benzoica
cacid
CHCH cOOH
KMnOO

Benzoicacia
From nitriles and amides
RCNHor
OH R - , Hor OH RCOoH
Ethanamide HO A

CH,CONH,H,O CHcoo.+NH,
Ethanamide A Ethanoic acid
coO

NH,

Benzamide Benzolc acid

OFrom Grignard reagents R-Mg-X OC-o R- RCOOH

OMgX

9From Acyl halides and anhydrides

HO RCOOH C
RCOC)
OH/ HORCoo RCOOH

.Benzoic anhydride 2CH,CoOH

Benzoic acid

CH,cooCOCH, CHCoOH CH,coOH

Benzoic ethanoic Benzoic acid Ethanoic acid

anbydride

OFrom Esters
CH,OH

Ethyl benzzonate Benzoic acid

CH,CH,CH,Cooc,H NaOH + CH,OH

Ethyl butanoate

CH,CHCHoon
Butanoic add
ALDEHYDES, KETONES, AND CARBOXYLIC ACIDS PART m g
Physical Propertiess Uses of Carboxylicacid
Aliphatic carboxylic acids up to nine carbon Methanoic acid: Rubber, textile, dyeing
atoms are colourless liquids at room leather and electroplating industries
temperature with unpleasant odours. Ethanoic acid: Used as solvent and as
Lower aliphatic carboxylic acids are
vinegar in food industry
miscible in water.
exanedioic acid: Used in the manufacture
Carboxylic acids have higher boiling points
than aldehydes, ketones and carboxylic of nylon-6, 6
acids of similar molecular masses. Esters of benzoic acid: Used in perfumery
Aliphatic carboxylic acids may show Sodium benzoate: Used as a food
0scillation or alternation effect in which the
preservative
melting point of an acid with even number
Higher fatty acids: Used for the
of carbon atoms is more than that of the
next odd homologue. manufacture of soaps and detergents
The pure or water free form of acetic acid is
also called glacial acetic acid.

R
o-H0

Chemical Properties
Reactions Involving CleavageofO-H Bond
2R-COOH + 2Na 2R-COONa
Sodium carboxylate

R-COOH +NaOH R-coONa' + H,O

R-COOH NaHCO, R-COONa + H , 0 + Co

Reactions Involving Cleavage of C-OH Bond

OFormation of anhydride

Hc- Hc H4 CH- -CH,

H,C-. or PO, Ethanoic anhydride
Esterification
RCOOH+ R'OH RCOOR +H,O

Reactions with PCl, PCI, and SOClh

RCOOH PCI, RCOCI POCl +HCI
H
3RCOOH
PCl 3RCOCI+
H,PO
H
RCOOH + SOCla RCOCd+SO + HCI
O Reaction with ammonia
CH,coOH +NH CH,COONH +CH,CONH
Ammonium acetate -HO Acetamide

coOH coONH cONH,

NH,
H,O
Ammonium benzoate Benzamide

cOOH coÓNH cONH

NH
coOH cooÑH, 2H,0 cONH
Ammonium phthalate
Strong
Reactions Involving-coOH Group -NH,
heating
O Halogenation
R-CH-COOH phosphorus
R-CH-coOH

X CI, Br N
a-Halocarboxylic acid

Ring Substitution Phthalimide

coOH coOH
Conc. HN0 Reactions Involving -CoOH Group
Conc. H,SO Reduction
NO
m-Nitrobenzoic acid D.coOH
co ) LIAIH,/ ether or B,Hs, RCH,OH
(il) H,o
coOH coOH
8r,/FeBr O Decarboxylation
Conc. H,S0
Br NaOH&Cao
R-CoONa R-HNa,co,
Heat
m-Bromobenzoic acid