Aldehyde, Ketones & Carboxylic Acids

8
M.O.P. of carbonyl Compounds OH H
o
1. From oxidation of alcohols α Cu/300 C
Q. Ph C CH2 Ph C CH2
β
R CH3 CH3
1oROH Aldehyde
R
2oROH Ketone Q. A O +CCl
o CH CH3 3 4
O + CH3 CHO
3 ROH No oxidation Zn
R Reagents O+O CH CH3

a. PCC
b. PDC M.O.P. of Aldehyde
c. Collin's reagent (CrO3 + 2Py)
1. Rosenmund reduction
d. (CrO3 + acetone)
e. Cu/300oC (dehydration) (with 3° ROH E2) O O
2. Ozonolysis H2 + Pd
R C Cl R C H
R H H BaSO4
Alkene Carbonyl compound

R 1. O + CCl /Zn 2. Stephen's reduction

3 4

2. O3 + CCl4 /Zn + H2O SnCl2 + 2HCl SnCl4 + 2[H]

3. O3 + CCl4 /Me2S H H SnCl2 + HCl
R C N R CHO
3. Kucherov Reaction H2O
dil H2SO4 + dil HgSO4 OH +
Alkyne Carbonyl compound H H2O
or R CH NH R CHO
Hg2+ / H2O HO– H+

3. Reduction by DiBAL-H
Q. H
A
CrO3

OH
acetone
AlH R CN R CHO
O 2
[O] OH
–H2O
H H 1) DIBAL– H
OH R C N
2) H2O
OH
Hg2+ 2[H]
Q. CH3 C CH CH3 C CH2
+I + –
H2O
Tauto
OH
CH3 C CH3 H H2O
R CH NH R CHO
HO H
O
OH
O O
MnO2
Q. Ph
H
Ph C CH2 CH3 1) DiBAL– H
R C OR' R CHO + R'OH
[o]
–H 2
O
H H 2) H2O
4. Etard Reaction etc 2) From nitriles

– 2+ R'
Chromium complex R'Mg X +
CH3 CH(OCrOHCl2)2 CHO R C N R C N–Mg X
H2O
CrO2Cl2 H3O+
R'

CH(OCOCH3)2 R C NH
OH H
(CH CrO OH H

3 CO
3
H 3O
+ H2O
)2 O
R C R'
Benzaldehyde diacetate
O
3) F. C acylation
5. Side Chain Oxidation
O
CH3 CHCl2
C R
2Cl2/hv
RCOCl
Anhy AlCl3
aq KOH
O
CHO +
R C

Practice
O
Q. CrO3
OH H
6. Gattermann Koch Reaction

CHO Q. CH3 CHO

1) CrO2Cl2
CO + HCl
2) H2O
Anhy AlCl3
F F
O
– MnO2
H C Cl Q. CH2 CH CH2 OH CH2 CH CHO
+
O O O3 + CCl4
Q. CH3 CH CH CH3 CH3CHO
Zn
M.O.P. of Ketones
DiBAL–H
Q. CH3 C N CH3 CHO
1) From acid chloride H2O

O
2RMgCl + CdCl2 → R2Cd + 2MgCl2
C CH3
O O + – Anhy
R2Cd Q. + CH3COCl
AlCl3
R' C Cl R' C R
O O
Q. (PhCH2)2Cd + 2CH3COCl

R' C Cl + Cd + Cl C R' O

CH3 C CH2 Ph
R R

186
Organic Chemistry
 O Mechanism:
+ – Hg /H2O2+
Q. CH3 C CH CH3 C CH3
+I * *– SO3H SO3Na
+
NaHSO3 – +
C O C O Na C OH

Properties:
C. Reaction with alcohols
1) Nucleophilic addition Reaction

A. Reaction with HCN Mechanism:

+ – H R
+ – HCN +
O OR
C O C OH
or * *
ROH
KCN/NaCN CN C O C OH C OH
H2O Cyanohydrin
xx dry HCl
H+

Mechanism: –+
+ – ROH
C O C OH
+ –
– NaCN – OR
C O C O

CN OR
H
+ 2ROH
C O C
OR
C OH HOR acetal or ketal
C O
CN HOR

O
B. Reaction with NaHSO3 HO
C O C
HO O
Aldehyde & methyl ketones
cyclic acetal or ketal

+ – NaHSO3
C O C OH
+– D. Reaction with NH2–Z
HSO3Na
SO3Na

C O + H2N Z C N Z
Aldehyde & aliphatic methyl ketone give this Rxn

Z Reagent name Product Product name

H ammonia >C=NH imine

R 1o amine >C=NR Schiff's base

NH2 Hydrazine >C=N–NH2 hydrazone

NHpH Phenyl hydrazine >C=N–NHph phenyl hydrazone

OH hydroxylamine >C=N–OH Oxime

187
Aldehyde, Ketones & Carboxylic Acids
 O
NHCONH2 Semicarbazide semicarbazone
C N NH C NH2

NO2 2, 4-dinitrophenyl NO2 2, 4-dinitrophenyl hydrazine

NO2
hydrazine (2, 4 DNP R = Orange/ Yellow ppt.
–NH
reagent) (Brady's C N NH NO2
reagent) R

Mechanism: Q.
–
H O
+ NaHSO3
H N Z CH3 C CH2 CH3
H2N Z + + –
C OH HSO3Na
C O
H+ OH
Semicarbazide NH Z
O C CH3 C CH2 CH3
* OH
H2N NH C NH2 SO3Na
More
Nu C N Z

Q.
E. Reaction with G. R CH3OH CH3 OH
o
CH3 CHO + C
Ald → 1 AlCO H
H OCH3
HCHO
CH3 – +
Ald → 2o AlCO + – CH3OH
C O Hemi acetal
RCHO
H
Ket → 3o AlCO
RCOR Q.
Practice O CH3 OCH3
Q. NH2OH 2CH3OH
O + N OH CH3 C CH3 C
H H+ CH3 OCH3
H2NOH
Ketal
Q. CH3 HOCH3
O
C O
R CH CH CHO + NH2 C NH NH2 CH3 HOCH3
+
H O

R CH CH CH N NH C NH2
2) Reduction Reaction
–
Q. O OH a) Carbonyl → Alcohol
–
CH3MgBr H H [H]
H2O C O C OH
R
Q CN H
+ –
HCN
PhCHO Ph C OH R

+ – H i. LiAlH4 (LAH) ii. NaBH4 (SBH)

Ph C O
iii. H2/Ni, pt, pd
H

188
Organic Chemistry
 b) Carbonyl → Alkane 3) K2Cr2O7
H H [H]
C O CH2
H H R
O
R
i. Zn(Hg)/ conc HCl Test for carbonyl compound:
Clemmensen reduction 1) Tollen's Test
ii. N2H4/ethylene glycol, KOH
Alipha. aldehyde Ketone
wolff kishner reduction
Aromatic Aldehyde Hemi acetal
Q.
H OH OH α-hydroxy ketone HCOOH
N2H4/ , KOH
Ph C H OH B Tollen's reagent:
H H
i. AgNO3 + NH4OH
LAH Ph CH3
ii. [Ag(NH3)2]+
–
A R–CHO + 2[Ag(NH3)2]+ + 3OH → RCOO–+
Ph CH2 OH
Ag ↓ + 2H2O + 4NH3
Q.
HO H
2) Fehling's Test
Zn(Hg) Alipha. aldehyde Ketone
HH
Conc. HCl Aromatic Aldehyde
+ + Cl
H2O Fehling's A
Q. O OH aq. CuSO4
–
H SBH RCHO +2Cu2+ + 5OH → RCOO– + Cu2O ↓ + 3H2O

O O O O red brown
3) Oxidation of Carbonyl Compound: Fehling's B
a) Oxidation of aldehyde Rochelle's salt: sodium potassium tartarate
O O COONa
[O]
R C H R C OH CHOH
R
R CHOH
1) Conc HNO3 2) KMnO4
COOK
3) K2Cr2O7
b) Oxidation of Ketones :- Popoff's rule: It states Name Rxns
that the C=O of unsymmetrical ketone always
stays at the side where smaller alkyl group is 1. Aldol condensation#
present. a) α–H
OOH O
b) Reagent # dil KOH, NaOH, Na2CO3 etc
R
OH 2CH3 C OH O O
1 2 α
1
CH3–C–H H–C–H
OH OH
1) Conc HNO3 H α–H
H
O
2) KMnO4 3
2
3 α α α
Stable enol CH3–C–CH3 –C–H
[O] α H O
α–H
2CH3COOH

189
Aldehyde, Ketones & Carboxylic Acids
 le α–H O
Ru O O
+ – + – CH3–C–H
C=O + H–Z CH2–C–H CH3–C–CH2–CHO
H H
C–O–H
OH H O HO
Z
A CH3–C–CH–C–H
dil NaOH Δ
Q 2 CH3CHO A B H
CH3 + + –
–
C=O + H–CH2CHO E1cb
H OH OH
OH
CH3–CH–CH–CHO CH3–CH–CH–CHO
OH β α crotonaldehyde
β-hydroxy CH3 Δ
CH3–CH=CH–CHO H
Aldol
C β H
H CH–CHO α, β-unsaturated B CH3–CH=CH–CHO
α
A
aldehyde dil.NaOH/Δ ≡H+
B
Mech# Q.
–
dil OH Δ
CH3CHO A B dil NaOH Δ
2 CH3COCH3 A B
O
OH
CH3 + O
H–CH2–CHO CH2–C–H – + –
Note: C=O + H–CH2–C–CH3
H+ CH3
CH3CHO B
O–
CH2=C–H Mesityl oxide
OH
enolate ion β-hydroxy CH3 C Δ
CH
H 3–C=CH–COCH
βα
3
Ketol CH3 β CH–C–CH3
α CH 3
A O α, β-unsaturated
Carbonyl comp
(ketone)

O
dil NaOH
Q. CH3–CHO+CH3–C–CH3
Δ
CH3 + + –
–
CH3 + OH C=O + H–CH2COCH3
– + – CH3
C=O + H–CH2–CHO C H H
H H CH–CHO
Δ CH3 OH
Self Aldol C H CH3–CH=CHCOCH3
CH3–CH=CH–CHO H CH–COCH3
Cross product
CH3 + + – CH3 OH
– Δ CH3 +
C=O + H–CH2COCH3 C H – + –
CH3 CH3 CH–COCH3 C=O + H–CH2CHO
CH3

CH3–C=CH–COCH3
CH3 OH
CH3 C H CH3–C=CH–CHO
CH3 CH CHO CH3
Cross product

190
Organic Chemistry
Q. R
–
dil.OH 2 HCHO HCOONa + CH3OH
PhCHO+CH3CHO Total Product
Δ
CH3 + R 1 conc NaOH or KOH
– + –
C=O + H–CH2CHO 2 50% NaOH or KOH
H
O O O
Ph + – OH – [O] KOH
C=O + a) H–C–H H–C–OH H–C–OK
CH3 + H–CH2CHO
H C H CH3–CH=CH–CHO
H CH–CHO Self HO
2[H]
Ph OH b) H–C–H CH3–OH
C H Ph CH=CH–CHO H
H CH–CHO Mech
Cross product O O
H–C–H OH H–C–H
Q. dil/NaOH OH H
O shift
Δ
H–C–H
+ –
+ O– + H O O
–+
O H–C–OH + CH3–O
O
OH Δ –
H H–C–O
+
O O CH3OH
# R.D.S → H Shift
–
Q. Ph–CHO+PhCOCH dil OH # Disproportionation Rxn
3 Δ
Major
α H α H H–CHO H–COOK + H– CH2OH
X
50%KOH
Cross product Ph–CHO Ph–COOK + Ph–CH2OH

Ph + 50%KOH
– + – (CH3)3C–CHO Me3C–COOK+Me3C–CH2OH
C=O + H–CH2COPh
H Cross cannizaro
50%KoH
Ph OH HCHO + PhCHO H COOK + PhCH2OH
Δ
C H Ph CH=CHCOPh # W
 hen one of the reactant is formaldehyde then
H CH–COPh it will be oxidised always
# Redox reaction:
2. Cannizaro Rxn# HCHO + Me3CCHO
50%NaOH
H COONa +
Me3C — CH2OH
O H O
H α–
No α-H–C–H CH3–C–H
Intramolecular cannizaro
CHO COOK
50%KOH
O CHO CH2OH
–C–H *
CHO COOK
H 50%KOH
No α-
CHO CH2OH

191
Aldehyde, Ketones & Carboxylic Acids
Q. COOH COOK COOK O O
50%KOH + OH
CHO COOK CH2OH R–C–CX3 R–C–CX3
OH
Q.
CHO COOK CH2OH
O
50%KOH R–C–OH + CX3

CH2–Cl CH2 CH2 O

OH OH R–C–O–+CHX3

OH
X2+KOH
3. Haloform Rxn Q. R–C–CH3 RCOOK+CHX3
OH H
Methyl ketones , R–CH–CH3 [O]
O
O
R–C–CH3 , CH3–CH2–OH
R–C–CH3
O
X2+KOH O
R–C–CH3 Br2+KOH
Q. Ph–C–CH Ph COOK + CHBr3
3
a) Halogenation
O O O
H X–X
R–C–C H X–X R–C–CX3 Ph–C–C Br3
H X–X Ok H

b) Hydrolysis Q.
O
KOH X2+KOH
R–C–CX3 R COOK + CHX3 CH3–CH–OH HCOOK+CHX3
Ok H Haloform H KOH
O
[O]
Mech# O H–C–CX3
3X 2 Ok H
H–C–CH3
O
Q. OH
R–C CH2 CH3–CHO + HCHO
(Excess)
H + – + –
O O C=O + H–CH2CHO
OH H
R–C–CH2–H R.D.S R–C–CH2
H OH
X–X C
H CH2–CHO
–
i) OH OH– H2C=O CH2OH
R–C–CHX2 R–C–CH2–X H2C=O
ii) X2 HOCH2–CH–CHO HOCH2–C–CHO
O – O OH–
i) OH CH2OH CH2OH
ii) X2 CH2OH HO
–
OH –
OH
HCHO+CH2–C–CHO HCOO +
R–C–CX3
OH CH2OH HO
O OH

192
Organic Chemistry
CARBOXYLIC ACIDS B. From acid derivative

O Z = Cl acid chloride
M.O.P 1. From 1° Alcohols and Aldehyde –
R–C–Z
H Z = NH2 acid amide
+
OH
R Z = OR ester
R–CH2–OH R–COOH
Z = OCOR anhydride
+ O
R → 1 KMnO4/H or Hot KMnO4
R–C–OH+Z–H
2 K2Cr2O7/H+
O
3 Conc HNO3 R–C–Cl R COOH + HCl
OH H
4 CrO3 + H2SO4 Jone’s reagent

O O O
R
R–C–NH2 R COOH + NH3
R–C–H R–C–OH OH H

O
CrO3 COOH
Q. R–C–OR R COOH + ROH
OH H2SO4 OH H

O O O
2. From alkyl benzene
R–C–O–C–R R–C–OH+ R COOH
OH H
R COOH

KMnO4/KOH Q. O
H H3O+
+
H Ph–C–Cl A Ph COOH
OH
H2+Pd
CH3 COOH BaSO4
+
A K2Cr2O7/H
KMnO4/KOH B
+ Ph–CHO
H

Cl2/hν
COOH Q. CH A CH3–Cl
4
KCN/SN2
KMnO4/KOH
D B CH3–C≡N
H+ Soda lime H3O+
C CH –COOH
3
COOH
KMnO4/KOH 4. From G.R
+
H 1 CO2
RMgX RCOOH
COOH 2 H2O+

O
3. Hydrolysis O=C=O
R R–C–O
H+
A. From cyanide
R COOH
OH H O
OH H H3O+
R–C≡N R–C–OH i) CO2
OH H CH3MgBr CH3–COOH
ii) H2O

193
Aldehyde, Ketones & Carboxylic Acids
 i) CO2 Ans. 3
PhMgBr Ph–COOH
ii) H2O
Q. Compare A.S.

+ i) CO2 COOH COOH COOH

MgBr COOH
ii) H2O CH3
+I
CH3
CHEMICAL PROPERTIES +I
a) b) c) CH3 +M
1. Acidic strength
(a) a > b > c
O O
COOH COOH COOH
R–C–OH R–C–O + H+
Stable NO2
–I
NO2
Acidic strength α –I & –M –I
a) b) c) NO2 –M
1
Ka ↑, pka↓ α (b) a > c > b
+I&+M
[H+] ↑, pH↓
Q. Compare PKa values

SA Na 1 CH3SO3H COOH
RCOO–H+ RCOONa+ H2↑ (a)
Na + 2 a) Br
OH –
Na + Ka: a > b
NH RCOONa+H2O pKa: a < b b)
–
2 WA
+ –
Na HCO3
RCOONa+NH3
WA (b) F OH
CO2+H2O COOH COOH
RCOONa+H2CO3
a) b)
WA
CH3 NO2
Order of acidic strength COOH COOH
c) d)
H3O+ > R–SO3H > HCOOH > PhCOOH > RCOOH>
Ka : d > a > b > c
nitro phenols > H2CO3 > PhOH > RNH+3 > CH3OH
> H2O > ROH > CH≡CH > CH2=CH2 > CH3–CH3 pKa : d < a < b < c

Q. How many of the following will give 2. Rxn with PCl3, PCl5, SOCl2
Na+HCO–3 test?
OH O O
R
R–C–OH R–C–Cl
CH3 SO3H , , CH3 COOH
# S
 OCl2 is the best method for preparation
OH of acid halide
O O
SOCl2
CH3CH2OH , , CH3OH R–C–OH R–C–Cl+SO2↑
Cl–SO–Cl +HCl↑
NO2

194
Organic Chemistry
3. Anhydride formation 7. Decarboxylation

O O O
H+/Δ
R–C–OH R–C–O–C–R NaOH + CaO
or R-COOH R-H
P2O5
R-COONa + NaOH R-H
O O
R–C–OH+HO–C–R
8. E.A.S

4. Esterification
+
R–COOH+R'OH H+ RCOOR' NO2
COOH COOH
O conc HNO3
R–C–OH+HOR' conc H2SO4
NO2

5. Rxn with NH3/Δ +

Br
COOH COOH
O O
NH3 Br2
– +
R–C–OH R–CO NH4
FeBr3
O Br
Δ
C–OH H
H–N # Benzoic acid does not give F.C.R
H
C–OH O
O
R–C–NH2
9. H.V.Z Rxn (Hell volhard zelinskey rxn)

COOH COONH4
NH3
X=Br, I
COOH COONH4 H α i) Red P/X2
α–
R–CH2–COOH R–CH–COOH
Δ ii) H2O

–
X
O
C Strong CONH2
NH
C Heating Q.
CONH2
O
β α
6. Reduction CH3–CH–COOH
LAH
–

R–COOH R–CH2OH i) Red P/Br2 Br

or
B2H6 CH3–CH2–COOH A
ii) H2O
H
c KO
LAH CH2=CH–CH2OH
Al

CH3–COOH CH3–CH2–OH LAH
C B
COOH CH2OH CH2=CH–COOH
PCC
B2H6
D
NO2 NO2 CH2=CH–CHO

195
Aldehyde, Ketones & Carboxylic Acids
 . O PhCH=NOH
O.P NH3/Δ M K + E

–
–
PhCOOH A Ph–C–NH2 H PhCH2OH
KO Salt
PhCOOK
0%

NH 2
SO O 5 –
Cl + O
l

OH
–
C–C H

–
NaOH/CaO 2 C
Ph– H2+Pd Ph SBH CH3COOH
C D E H O
BaSO4 H+
B PhCH2OH

–
–
CH3–C–O–CH2Ph
+–
H HCN

g)
PhCOO H3O+

Cl
(H
COOH

.H
Zn
Br2 OH

nc
L I PhCH 3 N H3O+

co
FeBr3

–
F G Ph–CH–COOH
Br + P2O5 OH
Br PhCH
NB CN
J O O +–
S
KCN
–
–

–
–

Ph–C–O–C–Ph O P Ph–CH2–CN
SN2
PhCH2Br

Shakshiyat damdar hoti hai tabi dushman

bante hai...
varna kamjoro se to log sahanubhooti
rakhte hai.

196
Organic Chemistry