Chapter 18

Aldehyde, Ketone
and Carboxylic Acid

Preparation of Aldehyde & Ketone both

K2Cr2O7/H2SO4 aq. KOH
R–OH RCH2CHCl2
(1º,2º)

R–OH PCC H2SO4

RCCH
(1º,2º) Hg+2
Cu or Ag RCHO BH3/THF
R–OH – RCCH
(1º,2º) 300ºC RCOR H2O2/OH
HIO4 
R–CH–CH–R 2(RCOO)2Ca
OH OH
O3 MnO
R–CH=CH–R 2RCOOH
H2O/Zn 300ºC

Preparation of Aldehyde only

DIBAL-H (CH3CO)2O/CrO3
RCN Ar–CH3
H2O H3O+/
DIBAL-H CrO2Cl2
RCOOR Ar–CH3
H2O H3O+ (Etard reduction)
RCHO Cl2/hv
Ar–CH3
ArCHO H3O+
H2/Pd CO+HCl
RCOCl
(Rosenmund Reduction) BaSO4 anhyd AlCl3
(Gatterman Koch aldehyde synthesis)
(i) SnCl2/HCl HCN+HCl
RCN anhyd AlCl3
(Stephen's Reduction) (ii) H2O
(Gatterman aldehyde synthesis)

96
 97
ALDEHYDE & KETONE RCN
Reaction of Aldehyde & Ketone
OH (Partial
Metal/H2 OH C hydrolysis)
HCN CONH2
CH–OH C
or LiAlH4 (NAR) CN
H2O

OH (Complete
R'MgX

or NaBH4 C hydrolysis)
or Na+C2H5OH COOH
OH
Wolf kishner (i) N2H4 C
redictopm CH2 OH CH2NH2
(ii) OH/ NaHSO3
HCHO C
R SO3Na
[Bisulphite compound
RCOR'
ArCOR'

Clemmensen's Zn-Hg/HCl C=O (White crystalline)]

reduction CH2 H
R + +
C=O ROH/H OH ROH/H OR
R C C
Red P/HI OR OR
Preparation of Ketone only

Z=–H,–R,–OH,–NH2 CH2 (Hemi-acetal) (Acetal)

R2'Cd

R2'COCl

–NH –NHCONH2 
anhyd. AlCl3

H2N–Z HCCNa OH
C=N–Z C (Acetylinic alcohol)
–NH –NO2 CCH

Aldehyde, Ketone and Carboxylic Acid

NO2 Cl PCl5 or SOCl2 RMgX OH
C C (Alcohol)
R
RCOCl

Cl
 Reaction of only Ketone
CHCl3 CH3 OH
C (Chloretone)
CH3 CCl3
CH3 CH3 Mg-Hg CH3
C–C C=O
CH3 CH3 H2O CH3
OH OH [O]
CH3COOH+[HCOOH]
(Pinacol) CO2+H2O

Aldol Reaction (Aldehyde or ketone with aH)

dil.NaOH D
(i) 2CH3CHO CH3–CH–CH2–CHO CH3–CH=CH–CHO
–H2O
(Aldol condensation product)
OH
Aldol

CH3 CH3
dil.NaOH D
(ii) 2CH3COCH3 CH3–C–CH2COCH3 CH3–C=CH–COCH3
–H2O
(Aldol condensation product)
OH
Ketol

Cannizzaro reaction (Aldehyde with no aH)

conc. NaOH –
2HCHO D CH3OH+HCOO Na+

Tollen’s test
RCHO+2[Ag(NH3)2] +3–OH → RCOO–+2Ag+2H2O+4NH3
+

(Given by Aliphatic and aromatic aldehyde)

TEST
Fehling’s test
–
RCHO+2Cu+2+5 OH → RCOO– + Cu2O+3H2O
(Given by Aliphatic aldehyde) (Red-Brown ppt.)

O
K2Cr2O7 / H Preparation H3 O 
H2C–CH2–OH H3C–C–Cl
KMnO4 / H
O O
H3 O  O H3 O 
H2C–CN H3C–C–O–C–CH3
CH3–CH2–CH2 CrO3+H2SO4 H3C–C–OH Cl
Aq.KOH
O Cl–C–CH3
OH Cl
O O
H3 O
 H3C–CH2–C–OH NaOI or (NaOH+I2)
H3C–C–NH2 H3C–C–CH3
 CHI3
O
H3O O=C=O/H3O+
H3C–C–OEt CH3MgBr
or NaOH

Hand Book (Chemistry) 98

 99
CARBOXYLIC ACID
O
– + NaHCO3 Reactions NH3/ P2O5
H2O+CO2+RCOO Na H3C–C–NH2 H3C–CN
O
NaOH Na/NaOH O O
+
CH4 CaO H3C–C–ONa NH3 
NaHCO3 H3C–C–ONH4 H3C–C–NH2
O
Kolbes + Na/NaOH O
H3C–CH3 electrolysis H3C–C–ONa NaHCO3 Ag2O Br2
O H3C–C–OAg CCl4 H3C–Br
 CaCO3 Reflux
H3C–C–CH3 (H3C–C–O)2Ca + O
H
O O H3C–C–OH
MnO/300ºC P2O5/
H3C–C–CH3 O CH3–C–O–C–CH3
O O O
C2H5OH H3C–CH2–C–OH
Rate [Esterification] H3C–C–O–C2H5  O
H
PCl5/PCl3
CH3–OH>EtOH>PriOH>ButOH H3C–C–Cl
O O O O O or SOCl2
i t
H–C–OH>H3C–C–OH>Et–C–OH>Pr –C–OH>Bu –C–OH
LiAlH4
HN3 H3C–CH2–OH
H3C–NH2 H2O

Aldehyde, Ketone and Carboxylic Acid

(Schimdt Reaction) H2SO4
Cl O O
Cl2/hv Cl2/P RedP/HI
H3C–C–C–OH H3C–CH–C–OH H3C–CH3
hv 
Cl Cl
Hell Volhard Zelinsky Reaction
 TEST

Tollen’s Reagent Fehling solution

O O
2CuO
H–C–OH Ag↓+CO2↑+H2O H–C–OH Cu2O↓+CO2+H2O
red ppt.

R COOH
(1) KMnO4–KOH/∆
(2) H⊕
R[1º/2º Alkyl group,
C=C, C=C, CH3–OH, CHO, COCH3 etc]

COOH
COOH Conc. HNO3+Conc. H2SO4

No Friedel craft reagent

NO2
reaction COOH
Br2+FeBr3

Br

Hand Book (Chemistry) 100

 O
PCl5 or PCl3 or SOCl2
H3C–C–OH
O
PCl3
H3C–C–ONa+
Distill.
O
+ POCl3
H3C–C–ONa
Distill.
O O
NH2 HN–C–CH3 HN–C–CH3 NH2
H2 O NO2
–
OH
NO2 NO2
O
O O
H3C–C–OH
H3C–C–O–C–CH3

N O-
O +
O O +
C
H3C–C–ONa
H3C–C–O–C–CH3 H3C Cl
Acetyl Chloride
O
H2 O CH2N2
H3C–CH2–C–OH H3C–CH=C=O Aq2O
Arndt Estard Reaction

O
C2H5–OH
H3C–CH2–C–O–C2H5
O
NH3
H3C–CH2–C–NH2
O
C6H5–NH2
H3C–CH2–C–NH–C2H5
O Et
Et2NH
H3C–CH2–C–N
Et
O O
H3C–CH2–C H3C–CH2–C–OH
O
H3C–CH2–C
O

101 Aldehyde, Ketone and Carboxylic Acid

 O
+ – NaN3–
Curtius Reaction H3C–C–N=N=N

H3C–N=C=O
H3O+
H3C–NH2
O
HO–NH2
Lossen Reaction CH5–C–NH–O–H
H3O+ AcCl
H3C–NH2 H3C–N=C=O
–
O
H3 C Ph H3C Ph O +

C C
HO–NH2
H C–C–Ph
Ph2Cd C
+ pH = 4.8 3
N N Backmann Rearrangement H3C Cl
HO HO Acetyl Chloride
O O
Conc.
H C–NH–C–Ph + Ph–NH–C–CH3
H2SO4 3

LiAlH4/Et2O
H3C–CH2–OH
NaBH4/EtOH

O
H2/Pd
[or LiAl(Obu)3H/–78ºC] H3C–C–H
Quinoline-S BaSO4

Hand Book (Chemistry) 102

 O
Distill. 2+
Ca (O–C–CH3)2
SOCl2
O
PCl5
EtO–C–CH3
O O
PCl5
H3C–C–O–C–CH3
O
H2 O HN3
+ – H3C–C–OH CH3NH2
H /HO H2SO4 (Schimdt reaction)
O
– C2H5OH
O –HCl
H3C–C–O–C2H5
+
O
C C2H5ONa
+

H3C Cl H3C–C–O–C2H5
–NaCl
Acetyl Chloride O
C2H5O–C2H5
H3C–C–O–C2H5+H3C–CH2–Cl
ZnCl2
O
OH O
O–C–CH3 OH OH
C
AlCl3 CH3
+

(At 60ºC) O=C–CH3 (At 120ºC)

Fries - Rearrangement
.. O
NH3 Br2
H3C–C–NH2 H3C–NH2 Carbylamine Test
KOH
Hoffmann Bramoamide degradation

103 Aldehyde, Ketone and Carboxylic Acid

 O
O O
P2 O5 H3C–C–OH AlPO4
H3C–C–OH O=C=CH2 HO–C–CH3
973-1030K
O O
O O Pyrolysis
O H3C–C H3C–C–CH3
H3C–C–O 963-1045K
H3C–C–Cl O
H3C–C–OH HC–CH3
H3C–C
H3C–C–O
N O O
O Distill.
O
 H3C–C–Cl –H3C–C–H
H3C–C–ONa
–NaCl O

Hand Book (Chemistry) 104

 O
H2 O
2H3C–C–OH +
H
O
O
H3C–C C2H5O–H
OH + H3C–C–O–C2H5
H+
O O
H3C–C–ONaÅ+H3C–C 
C2H5ONa
O–C2H5 O
H3C–CH2
O H3C–C
O O
H3C–CH2
2H3C–C–O–C2H5 H3C–C
O
EtO O
H3C–C–C–C–O–C2H5
H2
O
O
PCl5
2H3C–C–Cl

O O=C–CH3
AlCl3
H3C–C–OH+

OH
O O
H3C–C–O + H3C–C–OH

O
2NH3
H3C–C–NH2

O
C2H5NH2
H3C–C–NH–C2H5

O
O C2H5
E2NH
H3C–C–N
H3C–C C2 H 5
O Et3N
H3C–C No reaction

O O
O2N–O–NO2 2H3C–C–O–NO2

LiAlH4/Et2O
2H3C–CH2–OH
Reduction
O
O
H–C
Ph–CH=CH–C–OH
H3C–C–ONa (Perkin reaction)

105 Aldehyde, Ketone and Carboxylic Acid

 Heating Effect

O a-Hydroxy acid O
O H HO C H O C
H+
H3C–CH C–CH3 ∆
H3C–CH3 HC–CH3
C OH H O C O
O O Lacitide

γ & a-Hydroxy acid

O O O O
a C C a C C
H+/∆ +

b OH γ-Lactone b OH H /∆ O d-Lactone

OH O O–H
γ γ d

b-Hydroxy acid
OH O O
H+
CH2–CH2–C–OH ∆ H2C=C–C–OH
H
OH O CH3 O
H+
H3C–CH–CH2–C–OH ∆ CH=CH–C–OH

b-Keto acid

O H O O
∆
H3C–C–C–C–OH –CO2 H3C–C–CH3
H
NO2
∆
HNO2

Hand Book (Chemistry) 106

 Nutshell preparation of Ester
O
H2SO4
H3C–C–OH+CH3–CH2–OH 
O
ThO2
H3C–C–OH+CH3–CH2–OH Vapour
Phase esterification

O O
F3CCO3H
H3C–C–CH2–CH3
H3C–C
O
CO
O–CH2–CH3
H3C–O–CH3 H3C–C–O–CH3
BF3/350K
Bayer villiger
oxidation O
H3C–CH2–I
H3C–C–OAg
–AgI

Nutshell preparation of Ester

O O
H3C–C–O–H+CH2N2 H3C–C–O–CH3

O
C2H5OH
H3C–C–O–CH3
O or CH3–CH –ONa+

H3C–C
O–CH2–CH3 O
Al(OEt)3
H–C–CH3
Tischenko Reaction

107 Aldehyde, Ketone and Carboxylic Acid

 Nutshell Chemical Properties of Ester
O
HI
H3C–C–OH
–C2H5I
O
NH3
H3C–C–NH2
O
(Irreversible) 
HONa
H3C–CH2–OH+CH3–C–ONa
H2 O
O
C2H5NH2
H3C–C–NH–C2H5
O O
NH2–NH2
H3C–C–NH–NH2 H3C–C
OH O O–CH2–CH3
CH3MgBr CH3MgBr
H3C–C–CH3 H3C–C–CH3
H3O+
CH
OH OH
LiAlH4
H3C–CH2+H3C–CH2
Et2O
O
PCl5
H3C–CH2–Cl+H3C–C–Cl
O O
Zn EtONa
C2H5O–C–CH2ZnBr H C–C–O–C2H5
Et2O 2 Br2
O O
Reformat sky reaction C–Ph Darzen
C–Ph reaction
EtO
CH3 CH3
– +
O O ZnBr O O
C2H5O–C–CH2–C–Ph Ph–C–CH–C–OC2H5
H H Br
H2O NH4Cl –Br

O OH O O

C2H5O–C–CH2–CH–Ph Ph–CH–CH–C–OC2H5
 OH/H2O
O H+
Ph–CH=CH–C–OC2H5
H
O H–O O+ O

Ph–CH2–C–H Ph–CH=C–H Ph–CH–CH–C–O

Hand Book (Chemistry) 108

 Nutshell Chemical Properties of Ester
O
Pyrolysis
H2C=CH2+CH3–C–OH
O
C3H7ONa+
H3C–C–O–C3H7
(Transesteri fication)
O
H2 O
+ H3C–C–OH+CH3–CH2–OH
H (Reversible)
O
NH3
O H3C–C–NH2
O
H3C–C H2N–OH
H3C–C–NH–OH
O–CH2–CH3 O
(CH3)2CuLi
H3C–C–CH3
O
DIBALH
H3C–C–H+CH3–CH2–OH
Bui2AlH
O OH
Na/xylene
H3C–C–C–CH3 Acyloin Condensation
H3O+
H
O O
+
EtONa
H3C–C–CH2–C–OC2H5
Claisen condensation
O
O O
C–CH3
CH2=CH–C–CH3 CH2–C–H
H3C–C=C
H C–OEt
N N O
Knoevengel Reaction

Nutshell preview and review of Amide, Cyanide and Isocyanide

O
 
H3C–C–ONH4
H2 O2
O O NC–CH3
NaOH
NH3
H3C–C–Cl H3C–C
NH2
O
–

NH3
O O
(CH3–C)2O H3C–C O
H2N–C–NH2
NH2 HO–C–CH3
O +
H2N–C–OH
NH3
H3C–C–O–C2H5 O

109 Aldehyde, Ketone and Carboxylic Acid

Hand Book (Chemistry) 110
 Nutshell preview and review of Amide, Cyanide and Isocyanide

O
H3C–C
NH2
O–
H3C–C
NH2


SOCl2 P 2O 5
 
H O
P2O5/or AC2O H 2 O2
H2C–C=N–OH H3C–C–NH2
 NaOH [Partial Hydrolysis]

KCN/EtOH
H3C–Br H3C–CN O
Mg/Et2O dil. HCl
Cl–CN H3C–C–OH
CH3MgBr Completely Hydrolysis
Et2O
O
CH3MgBr
+
H3C–C–CH3
Ag–CN H3 O
H3C–Br
EtOH

CHCl3 + – 
H3C–NH2 H3C–NC O
KOH SnCl2+HCl
O H3C–C–H
+
POCl3/ H3 O (Steynen's Red)
H3C–NH–C–H
–H2O

O
dil. HCl H2/Ni
H–C–OH+H3C–NH2 H3C–NH–CH3 H2/Pt
LiAlH4 H3C–CH2–NH2

O3 1/8S6
H3C–N=C=O H3C–N=C=S
HgO

Cl2 Cl LiAlH4
H3C–N=C H3C–CH2–NH2
Na/EtOH (Mendius Reductions)
Cl or (Sn/HCl)

111 Aldehyde, Ketone and Carboxylic Acid

Amino Acid:

NH2 O O
H3C–CH HO–C NH–C
C OH CH–CH3 ∆
H3C–CH CH–CH3
O H 2N
C–NH
O
O O

OH H+/∆ NH
NH2

O
NH2 O O
C=O
H3C–CH–CH2–C–OH ∆
H3C–CH=CH–C–OH OH H+/∆

NH2 NH

qqq

Hand Book (Chemistry) 112