CARBOXYLIC ACIDS ALDEHYDES AND KETONES

ALDEHYDE, KETONES AND

CARBOXYLIC ACID
STRUCTURE USES GENERAL FORMULA CLASSIFICATION

R - C - OH
. Rubber, Textiles.
O . Food Industry. Aldehyde: Ketones
Aliphatic Aromatic
. Manufacture of O O
Soap and Detergent.
CLASSIFICATION R-C-H R - C - R'
where R is alkyl and H is where R and R' can be
Hydrogen. same or different.
Aliphatic Aromatic
CH3COOH PREPARATIONS CHEMICAL PROPERTIES
COOH CHEMICAL PROPERTIES

PHYSICAL PROPERTIES
PREPARATIONS . Esterification . Oxidation of alcohol Aldehyde > Ketones


RCOOH + R ' OH 
 RCOOR '+ H 2 O K 2 Cr2 O 7 + H 2 SO 4
1° Alcohol 
→ Aldehyde 1
Re activity ∝
. Ring Substitution in Aromatic Acids: K Cr O + H SO
2° Alcohol 
2 2 7 2 4
→ Ketone stearic factor and
Odour: Lower Aldehyde have an
. Oxidation of 1° alcohols COOH group is deactivating and K 2 Cr2 O 7 + H 2 SO 4 impleasant odour. electronic factror
(i)alk. KMnO
R − CH 2 OH 
→ RCHO + H 2 O
RCH 2 OH 
+
4 → R − COOH meta directing. COOH K Cr O + H SO
(ii) H 3 O R − CH(OH)R ' 
2 2 7 2 4
→ R − CO − R '+ H 2 O
2° alcohol
Br2 Physical State: HCHO is a gas. All Nucleophilic Addition-reaction
. Hydrolysis of Nitriles and Amides
+ COOH ∆ . Ozonolysis of alkenes other aldehyde and ketone upto C11
H or
R − C ≡ N + 2H 2 O  → RCOOH + NH 3
FeBr3,
Br OH
− H 2 O, Zn are volatile liquids. C=O + CN C
OH CH 3 − CH = CH − CH 3 + O 3 
→ 2CH 3 CHO CN
COOH
. Hydrolysis of Esters . From Gem-Dihalides:
H+ Solubility: Larger Carbonyl compounds SO2Na
RCOOR '+ H 2 O → RCOOH + R ' OH R' C=O + NaHSO3 C
Conc. HNO3 aq. KOH
R' are soluble in water due to the OH
NO2 R-C-Cl  →
. From Grignard Reagent Conc. H2SO4 ∆ Or Ba(OH) 2
R-C=O formation of H-bond.
. Reduction of Carboxylic Acid Cl C=O + H2N-Z C=N-z+H2O
Dry ether
CO 2 + RMgBr  → RCOOH + Mg(OH)Br (Aldehyde when Boiling Point and Melting Point: Boiling
+ H , H2O
O R' = H Ketone when Point or Melting point ∝ Molecular
(i) LiAlH /ether R' = alkyl group) weight
R-C-OH 
4
+
→ R − CH 2 OH
(ii) H 3 O
. Hydroboration Oxidation of Alkynes 1 Clemmensen Reduction:
∝
Branching
. Decarboxylation of Carboxylic Acid B2H6
 → R-C=C-H Zn − Hg
O
R-C≡C-H THF C=O →
HCl
CH2 + H2O
Terminal alkyne H BH2 Eue to electron donating alkyl group
PHYSICAL PROPERTIES NaOH or
R-C-OH 
CaO
→ R − H + Na 2 CO 3 -
group ketones have higher boiling point
H2O2 OH-
than aldehye.
. Reaction involving cleavage of
R-CH2=C-H R-C=C-H
-OH group Reactivity: It depends on the nature Wolff-kishner reduction
O O H OH of alkyl group. Smaller the group,
. Physical State: Polar Substances soluble in (i) NH − NH
R-C-NH2 . Rosenmund Reduction more reactive will be compound. C=O 
2 2
KOH/ethyl glycol
→ CH2 + N2
organic solvents.
O O
. Acidity: The acidic character is due to the H , Pd-BaSO
R-C-OH R-COCl R-C-Cl 
2 4
→ R-C-H
presence of resonance.
⊕ O DISTINCTION TEST FOR Aldol Condensation
: :

R-C-O-H R-C-OH
(R-CO)2O ALDEHYDE 2CH3CHO CH3CH(OH)CH2CHO
:O O . Hell-volhard Zelinsky Reaction
:

(i) X , Re d P
R-CH 2 -OH 
2 → R − CH(x)COOH TEST ALDEHYDE KETONES ∆-H2O
. Boiling Points: High boiling point due to (ii)H O 2
intermolecular hydrogen bonding. DISTINCTION TEST Schiff's Pink No colour
FOR CARBOXYLIC ACID reagent Colour CH3-CH=CH-CHO
COMPARISON OF METLING AND BOILING POINT OF ACIDIC ORDER
Fehling's Red ppt. No ppt.
AROMATIC AND ALIPHATIC ACID
. Brisk effervescence of CO2 gas with solution Cannizaro reaction
NaHCO3
. Melting Point and Boiling Point of aromatic Tollen's Silver No ppt.
acid greater than aliphatic acid. Caboxylic Acid > Phenol > Alcohol . Gives buff coloured ppt. with FeCl3
Conc. KOH
2HCHO  → CH3OH + HCOOK
reagent Mirror