Aldehydes and Ketones 1293

Preparation 166 d 167 a 168 b 169 c 170 a

171 a 172 c 173 b 174 a 175 a
1 c 2 c 3 d 4 b 5 b,c 176 e 177 b
6 c 7 c 8 d 9 c 10 c
11 c 12 a 13 a 14 d 15 d Critical Thinking Questions
16 c 17 a 18 d 19 c 20 b
1 d 2 bc 3 b 4 c 5 a
21 c 22 a 23 c 24 c 25 c
6 a 7 b 8 b 9 b 10 b
26 d 27 c 28 b 29 a 30 b
11 a 12 b 13 a 14 a,d 15 c
31 c 32 d 33 b 34 b 35 a
16 d 17 b,d 18 d 19 c 20 a
36 d 37 d 38 c 39 b 40 c
21 b 22 b 23 d 24 d 25 a
41 d 42 a 43 a
26 d 27 c 28 b 29 c 30 a

Properties
Assertion & Reason
1 c 2 c 3 a 4 a 5 c
1 c 2 d 3 b 4 a 5 d
6 d 7 a 8 c 9 c 10 b
6 b 7 c 8 a 9 b 10 b
11 c 12 a 13 a 14 b 15 d
11 e 12 e 13 b 14 b 15 e
16 b 17 c 18 c 19 abd 20 abcd
16 c 17 b 18 d
21 b 22 a 23 a 24 b 25 d
26 b 27 d 28 c 29 b 30 b
31 c 32 c 33 d 34 d 35 c
36 b 37 a 38 b 39 d 40 c
41 d 42 a 43 d 44 d 45 a
46 c 47 c 48 a 49 b 50 b
51 b 52 c 53 d 54 b 55 c Introduction
56 d 57 c 58 a 59 c 60 c
O OH
61 b 62 b 63 a 64 b 65 a || |
1. (a) CH 3  C  H  HCN  CH 3  C  H (optically active)
66 d 67 a 68 a 69 c 70 a Acetaldehyde Hydrogen |
Cyanide
71 c 72 d 73 a 74 a 75 a CN
Acetaldehyde
76 d 77 c 78 b 79 a 80 b Cynohydrin

81 c 82 c 83 c 84 a 85 d 2. (b)  C  O
sp 2 hybridised
86 a 87 d 88 a 89 d 90 d
O
91 b 92 b 93 a 94 c 95 c ||
7. (b) CH 3 CCH 3
96 a 97 b 98 d 99 a 100 c 2 propanone
101 c 102 d 103 d 104 d 105 a 10. (b) CHOCHO
106 e 107 b 108 c 109 a 110 c  
R
111 a 112 a 113 c 114 b 115 d 11. (b) 
C O
R 
116 c 117 b 118 a 119 c 120 c
Cl O
121 d 122 d 123 d 124 c 125 c | ||
13. (d) Cl  C  C  H
126 d 127 c 128 a 129 a 130 a |
Cl
131 c 132 a 133 a 134 b 135 b 2, 2, 2, trichloroethanal

136 a 137 b 138 b 139 d 140 a 18. (c) Among Carbonyl Compounds, reactivity decrease with increase
in alkyl groups as alkyl groups (+I effect) decrease positive
141 a 142 b 143 b 144 d 145 b character on C-atom. Thus, the correct order of reactivity is
146 d 147 b 148 b 149 b 150 c HCHO  CH 3CHO  C6 H5 CHO
151 a 152 a 153 c 154 c 155 b
156 a 157 d 158 d 159 c 160 a
161 c 162 c 163 d 164 d 165 c Preparation
 1294 Aldehydes and Ketones
42. (a)
HC  CH   CH 3 CHO  

1% HgSO CH MgX
1. (c) 4 3
20 % H 2 SO 4 ( A) H 2O

CH 3 CHOHCH 3  CH 3 COCH 3

[O ]

(B) Acetone
CH 3
4. (b) (CH 3 )2 C  C(CH 3 )2 
 2CH 3  CO  CH 3
O3 |
43. (a) C 9 H 18  O 3  H 3 C  C  CHO  CH 3 CH 2 COCH 3
(c) Ketonic hydrolysis: CH 3  CO  CH 2COOC 2 H 5
| 2  butanone
5. CH 3
2, 2 dimethyl propanal
  CH 3 COCH 3  C2 H 5 OH  CO 2
NaOH
H 2O On the basis of product formation, it would be alkene
COCH 3
CH 3 CH 3
 CH 3 COCl  
AlCl | |
6. (c) 3
+HCl
CH 3  C  HC  C  CH 2 CH 3
It is Friedel-Crafts reaction. Acetophenone |
CH 3
9. (c) CH 3 COCl 
 CH 3 CHO  HCl 2H
2, 2, 4  trimethyl- 3 - hexene
Pd / BaSO 4
CH 3
CHO CH 3 CH 3
| |
10. (c) 
CrO 2 Cl 2
Etard reaction CH 3  C  HC  C  CH 2 CH 3 

O3

|
CH 3
CH 3 COCH 3  (CH 3 )3 COH
CH 3 MgI
11. (c)
Acetone tert  Butyl alcohol CH 3 O CH 3
| |
13. (a) It is hydration of alkynes.
CH 3 C — HC CCH 2 CH 3
O | | |
Hg  
|| CH 3 O O
CH 3  CH 2  C  CH  CH 3  CH 2  C  CH 3
H 2O Butanone
CH 3 O
O | ||
||  CH 3 C  CHO  CH 3 C  CH 2 CH 3
CH 3  C  O |
14. (d) Ca CH 3
CH 3  C  O   CH 3  CO  CH 3  CaCO 3
Dry heating
||
Acetone
O Properties
COCH 3

1. (c) CH 3 COCH 3  CH 3 MgCl  (CH 3 )3 C  OMgCl

16. (c)  CH 3 COCl   
only AlCl3
 HCl (X)


(CH 3 )3 C  OH  Mg(OH )Cl
hydrolysis
(Y )
CH 3 COO OOCH Distill
18. (d) Ca  Ca  2. (c) It is cannizzaro reaction –2
CH 3 COO OOCH
CHO COO  CH 2OH
2CH 3 CHO  2CaCO 3
19. (c) CH 3  C  N  C H 3 Mg Br  CH 3  C  N  MgBr  
KOH
+
| 
CH 3 Cl Cl Cl
Hydrolysis OH
Br |
CH 3  CO  CH 3  NH 3  Mg
OH 3. (a) R  CO  R '   R  C  R ' 
HCN

LiAlH4

|
O CN
|| ( A)
CH 3  CH  CH 2  CH 3  CH 3  C  CH 2 CH 3
KMnO 4
23. (c)
| Oxidation ethyl methyl ketone OH
OH |
2  Butanol
CH 3
CHO COOH R  C  CH 2 NH 2
CH 3 CH 3 |
R'
24. (c)  
CrO 2Cl 2
 
acidic K 2 Cr2 O7
or KMnO 4
5. (c) Reduction of  C  O to CH 2 can be carried out with Wolf
This is Etard’s reaction Kischner reduction.
R R CHO CH 2OH
32. (d) CH  OH  
[(CH 3 )3 CO ]3 Al
CO
R Aluminium ter butoxide R
Isopropyl alcohol Ketone
6. (d) 
2H

34. (b) HC  CH  H 2 O 

 CH 3 CHO HgSO 4 / H 2 SO 4
Benzaldehyde Benzylalcohol
on reduction it gives benzylalcohol and not phenol.
5 7 7
2 6 CH 5
6 CH
43 1 3
4
3

C=O
6 
ozonolysis
3
HC=O
34 1 1
5 2
2 6-oxoheptanal
 Aldehydes and Ketones 1295

9. (c) C6 H 5 CHOHCH 3  C6 H 5 COCH 3

[O ] O O
|| ||
1  Phenyletha nol Acetopheno ne
30. (b) CH 3  C  CH 3  3 I 2  NaOH  CHI 3  CH 3  C  ONa
C6 H 6  CH 3 COCl    C6 H 5 COCH 3  HCl
Friedel craft's dimethyl ketone
reaction

10. (b) Wolf-Kishner reduction does not convert  CO to CHOH 31. (c) CHI 3 is yellow compound when iodine reacts with NaOH
but converts it to  CH 2 . and ketone.
11. (c) Although both CH 3 CH 2COCH 3 and (CH 3 )3 CCOCH 3 32. (c) HCHO  HCHO   HCOOK  CH 3 OH
KOH

contain -hydrogen, yet (CH 3 )3 CCOCH 3 does not undergo

Aldol condensation due to steric hindrance. CHO COONa CH 3 OH
12. (a) C 6 H 5 CHO    C 6 H 5 CH (OH )CH 3
CH 3 MgBr CH 3
Benzaldehyde H  / H 2O 2 Alcohol 38. (b) 2  
Conc. NaOH
+
13. (a) Chloral CCl 3 CHO, has no -hydrogen atom and hence does
not undergo aldol condensation. This reaction is called as Cannizzaro’s reaction.
14. (b) Among the given compounds only acetone gives crystalline
coloured derivative with 2, 4 DNP.
15. (d) Ethanal among the given compounds gives positive iodoform CHO CHO COOK CH 3 OH
test. CH 3 CH 3 Conc .
39. (d) +  +
OH KOH
| Cl Cl Cl Cl
17. (c) 2CH 3 CHO 
 CH 3  CH  CH 2 CHO
dil.
NaOH
41. (d) The solution represented is fehling’s and it has no tendency to
18. (c) C2 H 5 CHO  2Cu 2  5 OH   Cu 2 O  3 H 2 O oxidise benzaldehyde.
Re d ppt
42. (a) Increasing alkyl group the reactivity decreases.
 C2 H 5 COO  1
43. (d) RCHO  O2  RCOOH
CH 3 COCH 3  2Cu 2  5 OH   No reaction 2
44. (d) All test for Aldehyde because ketone require strong oxidising
19. (abd)Deuterium behaves like H and hence trideuteroacetaldehyde agent.
also undergoes aldol condensation but benzaldehyde does not
since it has no -hydrogen. 2[ Ag(NH 3 )2 ]  RCHO  RCOOH  2 Ag  4 NH 3  H 2O
21. (b) 1o Primary alcohol  
ZnCl 2 / HCl 45. (a) Silver mirror test is the test of aldehyde.
White turbidity only heating 46. (c) CH 3 CH  CHCHO  2[ Ag(NH 3 )2 ] 
2 o Alcohol   White turbidity
ZnCl 2 / HCl
2 Ag  4 NH 3  CH 3CH  CHCOOH  H 2O
after 5 min heating
OH
3 o Alcohol  easily in seconds
ZnCl 2 / HCl |
49. (b) CH 3  C  H  NH 3  CH 3  C  H
24. (b) Benzaldehyde on treatment with 50% aqueous or ethanolic || |

alkali solution undergoes Cannizzaro’s reaction like HCHO O NH 2

(no  -hydrogen atom) i.e., one molecule is oxidised and one is OCH 3
reduced with the formation of benzoic acid and benzyl alcohol || |
respectively. 2CH 3  C  CH 3  NH 3  CH 3  C  CH 2  C  CH 3
|| |
2C 6 H 5 CHO   C 6 H 5 CH 2 OH  C 6 H 5 COONa
NaOH
O NH 2
25. (d) 2 HCHO 
 CH 3 OH  HCOONa
NaOH
50. (b) CH 3 CHO  2 H 
 CH 3 CH 2 OH
Na / C2 H5 OH
Conc .
It is a Cannizzaro’s reaction. 51. (b) CH 3 CH 2 CHO  4 H    CH 3 CH 2 CH 3  H 2 O
Zn / Hg
HCl
OH
| This reaction is called clemmenson’s reduction.
2CH 3 CHO   CH 3  CH  CH 2  CHO
NaOH
52. (c) In cannizaro’s reaction the one substance is oxidized and other
dil
is reduced.
It is aldol condensation reaction.
HCHO  HCHO   CH 3 OH  HCOOK
KOH
O O
|| || 55. (c) Nucleophilic as addition of HCN , NaHSO 3 etc.
27. (d) CH 3  CH 2  C  CH 2  CH 3 do not have CH 3  C  57. (c) Addition of HCN to carbonyl compounds is an example of
nucleophilic addition.
group 58. (a) Acetone forms sodium bisulphate adduct but acetophenone
O O does not. Aromatic ketones do not gives addition product with
|| || NaHSO 3 .
29. (b) CH 3  C  CH 3  3 Cl2  CH 3  C  CCl 3  3 HCl
59. (c) C 6 H 5 CHO  Cl 2  C 6 H 5 COCl  HCl
Benzaldehyde Benzoyl chloride
O O
|| || 
CH 3  C  CCl 3  NaOH  CHCl 3  CH 3  C  ONa 60. (c) CH 3  O  CH 3 The electron density of oxygen is highly

increased therefore resistant its nucleophilic attack.
 1296 Aldehydes and Ketones
CH 3 CH 3 R R CN
| | 83. (c) C  O  HCN  C is an example of
63. (a) 2CH 3  CO  CH 3  H 3 C  C  Mg / Hg
C  CH 3
Acetone H 2O
| | R R OH
OH OH nucleophilic addition reaction.
(Pinacol )
84. (a) C6 H 5 CHO  CH 3 COC6 H 5  
NaOH
 H 2O
64. (b) C6 H 5 CHO  (CH 3 CO )2 O  CH 3 CO 2 Na

C6 H5 CH  CHCO 2 H O
||
It is Perkin’s reaction. C6 H 5  CH  CH  C  C6 H 5
65. (a) Crossed aldol reaction gives benzyl alcohol and sodium Benzyl acetopheno ne
formate.
85. (d) HI/P/, Zn/Hg/conc. HCl and
C6 H 5 CHO  HCHO   
NaOH (aq )

Benzaldehyde Formaldehy de NH 2  NH 2 / OH  / C2 H 5 ONa

C6 H 5 CH 2OH  HCOONa O
Benzyl alcohol Sod. formate ||
66. (d) The substitution of alkoxy group of ester by an alcohol, is used to the reduction of  C  group into CH 2  group.
called trans-esterification. It occurs in presence of either an
acid or base.
CH 3
67. (a) 6 HCHO  4 NH 3  (CH 2 )6 N 4  6 H 2 O 86. (a) 3CH 3 COCH 3   
Conc . H 2 SO 4
Urotropine 3 H 2O

68. (a) In HCHO because -Hydrogen atom is absent.

O O H3C CH 3
|| ||
71. (c) C 6 H 5  C  H  H  C  C 6 H 5  
alc NaCN
87. (Mesitylene)
(d) 2C6 H 5 CHO  C6 H 5 COONa  C6 H 5 CH 2OH
50 % NaOH

It is Cannizzaro’s reaction.
OH O 88. (a) Because acetone require stronger oxidising agent and hence not
| ||
C6 H 5  CH  C  C6 H 5 oxidized with Fehling solution to give brick red ppt.
Benzoin 89. (d) CH 3 CHO   CH 3 COOH  Ag   NH 3
[ Ag( NH 3 )2 ]

O Silver mirror test

||
NH 2  NH 2 While acetone do not react.
72. (d) CH 3  C  CH 3 
KOH / Glycol 90. (d) Due to H  bonding all are soluble in water.
CH 3  CH 2  CH 3  H 2 O  N 2 CH 3
|
75. (a) 2CH 3 CHO   CH 3  CH  CH 2  CHO
NaOH
91. (b) CH 3  C  O  CH 3 MgBr  CH 3  C  OH
dil | | |
OH H H
(Aldol)
( 2 o alcohol)
76. (d) The amount of enolic form is highest (76%) in acetyl acetone

because keto group is a much better electron-withdrawing 92. (b) CH 3 CHO   CH 3 CH (OH ) CN 
HCN

2 H 2O / H
group.
CH 3 CH (OH ) COOH
O O O — H . . . .O
|| || | || 93. (a) This reaction is aldol condensation
CH 3 CCH 2 CCH 3 ⇌ CH 3 C  CH  CCH 3 2CH 3 CHO    CH 3  CH  CH 2  CHO
dil NaOH
acetyl acetone enolic form (76%) |
(keto form, 24%)
OH
3  hydroxy butanal
O .... H — O
|| | 94. (c) HCHO  2Cu 2  5 OH     HCOO   Cu 2 O  3 H 2 O
Fehling

 CH 3 C  CH  C  CH 3 solution Red ppt

CHO COONa CH OH OH
2 95. (c) H  CHO  CH 3 MgI  CH 3  CH 2  OH  Mg
I
78. (b)  
NaOH
+ O
||  
100. (c) CH 3 CH 2  C   H CH  CHO 
OH

| |
H
| CH  CH  CHO H CH 3
80. (b) C  O  H 2 CH .CHO  Cinnamalde hyde
OH
|
CH 3  CH 2  CH  CHCHO
82. (c) CH 3 CHO 
 CH 3  CH  CH 2  CHO
dil NaOH |
| CH 3
OH
Aldol
 OMgI 
 | 
 CH 3  CH  CH  CHO  H 2O
Heat
101. (c) CH 3 MgI  CH 3 CHO  CH 3  C  H 
 |

 CH 3 
 Aldehydes and Ketones 1297

 
H3O
 (CH 3 )2 CHOH Cl
120. (c) CH 3  CHO  PCl5  CH 3  CH  POCl3
2  Propanol Cl
102. (d) Cannizzaro’s reaction involve self oxidation and self reduction. Ethylidene Chloride
or
Gem dihalide
NO 2
121. (d) Benzaldehyde gives cannizaro’s reaction whereas acetaldehyde
gives aldol condensation.
103. (a) CH 3CHO  NH 2 NH NO  2

CHO COONa CH OH
2

Brady’s reagent (2, 4 – DNP)

NO
2  
Conc NaOH
+
2

CH 3CH  N  NH NO Cannizaro reaction

2
2CH 3 CHO    CH 3  CH  CH 2  CHO
dil NaOH
|
Orange crystalline solid OH
105. (a) 2CH 3COCH 3  Cl2 / NaOH  2CHCl 3 + ( Aldol)

2CH 3COONa  HCl O H OH H

|| | | |
106. (e) Fehling solution  Alkaline CuSO 4  Na  K tartarate 122. (d) C  CH 2  CHO  C — CH  CHO
| |
Tollen’s reagent  NH 4 OH  AgNO3
H H
Schiff’s reagent  P-rosaniline hydrochloride or magneta
Benedict’s solution  Alkaline CuSO 4  Citrate ions  CH  CH  CHO
Cinnamalde hyde
All these reagents are used to distinguish between aldehydes O
and ketones. Aldehydes reacts with all these reagents while ||
ketones do not react. 123. (d) CH 3  MgBr  CH 3  C  H  
H 2O

107. (b) Schiff' s reagent   Colourless

SO 2
CH 3  CH  OH  MgBr(OH )
(Pink) |
CH 3
 Pink colour
Aldehyde
CH 3 MgBr  CH 3  C  O  
H 2O

 
|

108. (c) CH 3  CH 2  CHO aldehydes having   H atom can CH 3

participate in aldol condensation. The H  atom attached to CH 3 CH 3

 carbon atom are called  -hydrogen. C  MgBr(OH )
109. (a) CH 3 CHO  CH 3 COOH
KMnO 4 OH CH 3
Oxidation
Acetaldehyde Acetic acid
C 6 H 5 CH  N
110. (c) CH 3 CHO  2[ Ag(NH 3 )2 ]OH  125. (c) 3 C 6 H 5 CHO  2 NH 3  CH  C 6 H 5  3 H 2 O
Tollen's reagent
C 6 H 5 CH  N
CH 3 COONH 4  2 Ag  3 NH 3  H 2O Hydrobenza mide
Silver mirror 127. (c) CuSO 4  NaOH  Roschellesalt(Na  K tartarate )
112. (a) It is used as a medicine to treat urinary infections.
128. (a) R  CHO    R  CH 2  OH
Reduction
113. (c) p-rosaniline hydrochloride. Aldehyde
1o alcohol
CH 3
129. (a) HCHO  HCHO 
 CH 3 OH  HCOONa
NaOH
Conc
NH 2  131. (c) CH 3  CO  CH 3   CH 2  C  O
Pyrolysis

C  NH 2 Cl  Acetone Ketene

NH 2 O
||
CH 3  C  CH 3 2 2 
  CH 3 COOH  HCOOH
K Cr O
132. (a) 7
H 2 SO 4

It is used for the identification of aldehydes. one carbon atom is less in the ketone group
H 2 N OH R
115. (d) R  CHO    RCH  N  OH |
Oxime
134. (b) R  C  O  R  Mg  X  R  C  OMgX
CH 3 CHO  NH 2OH  CH 3  CH  N  OH  H 2O | Grignard reagent |
Acetaldoxime H
H
116. (c) Cannizzaro’s reaction is shown by aldehydes in which -H Aldehyde
atom is absent. CH 3 CHO contains 3,  -H atoms thus, does R
not show this reaction. |
CH 3 CH 3 R  C  O  R  Mg  X  R  C  O  MgX
117. (b) C  O  NH 2 OH  C  N  OH  H 2O | |
CH 3 CH 3 Acetoxime R R
Ketone
119. (c) CH 3  CH 2  CHO    CH 3 CH 2  COOH
Oxidation

Propanal Propanoic acid

 1298 Aldehydes and Ketones

137. (b) CH 3 CHO   CHI 3

NaOH 151. (a) Two molecules of acetone condense in presence of dry HCl gas
I2 Yellowppt to form mesityl oxide.
138. (b) Fehling solution is a weak oxidising agent therefore unable to O
CH 3 ||
oxidise benzaldehyde. C  O  H 2  CH  C  CH 3  
HCl
CH 3  H 2O
O O OH O
| | | |
(CH 3 )2 C  CH .COCH 3
H–C H–C CH – C Mesityl oxide
152. (a) Formaldehyde and NaOH reacts to produce alcohol and sodium
139. (d) salt of an acid.
+  
Alc. KCN
2 HCHO  NaOH  CH 3 OH  HCOONa
Benzoin
This reaction is called benzoin condensation. Alcohol Sodium formate

140. (a) Aldehyde  Schiff' s reagent  Pink colour This reaction is Cannizzaro's reaction
(Colourless) 153. (c) Acetaldehyde reduces Fehling solution giving red ppt. while
Ketone do not give this test. acetone do not.
154. (c) It is an example of Cannizzaro reaction
CH 3 CHO 
  CCl 3 CHO  3 HCl
Cl
141. (a) 2
CH 2 OH
(Choral ) CHO
|  NaOH  |
143. (b) Benzaldehyde will undergo Cannizzaro's reaction on treatment CHO COONa
with 50% NaOH to produce benzyl alcohol and benzoic acid as 
it does not contain -hydrogen 155. (b) R  C  H ; Susceptibility of nucleophilic attack on aldehyde
||
CHO CH 2 OH COONa O
 
50% NaOH is decreased by electron releasing effect of R group. Decreasing
order of aldehyde towards nucleophilic attack is 1° > 2° > 3° R
+ group.
Benzaldehyde Benzyl 156. (a) Wolf kischner reduction : Hydrazine (NH 2  NH 2 ) followed
Sodium Benzoate
144. alcohol
(d) Butane 2-one will get reduced into butane when treated with Zinc by reaction with strong base like KOH reduce carbonyl group
and hydrochloric acid following Clemmensen reduction, whereas into alkyl group.
Zn/HCl do not reduce ester, acid, amide C  O  NH 2  NH 2  
Wolf- Kishner

145. (b) Phoron Carbonyl group Hydrazine reduction

O
||
C  N  NH 2   CH 2
KOH
CH 3 CH 3
C  O  H 2 CH  C  CHH 2  O  C Alkyl group
CH 3 CH 3 157. (d) Ketones and Aldehyde add to NaHSO 3 to give white
O precipitate
CH 3 || CH 3 R R OH
 
Dry HCl
C  CH  C  CH  C C  O  
NaHSO 3
C
 2 H 2O CH 3 Phoron CH 3 R R SO 3 Na
Zn  Hg / HCl
146. (d) RCHO  4 H    R  CH 3  H 2 O 158. (d) Fehling's solution is the solution of CuSO 4  NaOH +
R Zn  Hg / HCl R Roschel salt (Sodium potassium tartarate). Aldehyde give red
C  O  4 H    CH 2  H 2 O precipitate with Fehling's solution.
R R
147. (b) Acetone on iodination gives iodoform in the presence of NaOH 159. (c) It reduce CHO group into hydrocarbon.
O 160. (a) Molecular weight of the compound
||
 3 H 2O
CH 3  C  CH 3  3 I2  4 NaOH    2  Vapour density
Acetone
 2  29  58
CHI 3  CH 3 COONa  3 NaI
Iodoform Sodium acetate Sodium iodide Molecular weight of CH 3 CH 2CHO, CH 3 CHOHCH 3 ,
148. (b) We know that CH 3 COCH 3 and CH 3 CH 2COOH are 58, 60, 58 and 74
H H
| | respectively. Both CH 3 CH 2CHO and CH 3 COCH 3 have
 HCN
 H 2O
CH 3  C  O 
 CH 3  C  OH   molecular weight 58 but only aldehyde i.e., CH 3 CH 2CHO
Acetaldehyde |
CN on warming with aqueous alkali gives yellow precipitate.
Cyanohydri n
OH OH
H | |
|
161. (c) CH 3  CH 2  CH  CH 3 contain CH 3  CH  group by
CH 3  C  OH 2 butanol
|
COOH which it give +ve iodoform test.
Lacticacid 162. (c) In nucleophilic addition reaction, the carbonyl compound will
Thus Lactic acid is formed. respond in preference which is sterically more exposed and
149. (b) Tollen's reagent is used to detect aldehydes. Aldehyde reduce electronically have intact positive charge over carbonyl carbon.
Tollen's reagent to give Silver mirror while these are oxidised So reactivity order towards reaction with phMgBr is (II) > (III)
to acid. > (I).
R 163. (d) Tollen's reagent oxidizes the compound having aldehyde group
C  O  Ag 2 O  RCOOH  2 Ag
H Silver mirror like glucose and also oxidizes -hydroxy ketones having
150. (c) Only aliphatic aldehyde reduce fehling solution. Hence, COCH 2OH group as in fructose.
acetaldehyde give red ppt. with fehling solution.
 Aldehydes and Ketones 1299
164. (d) Acetaldehyde have CH 3 CO  group so it give positive OH Cl
| |
iodoform test with I2 and NaOH while formaldehyde does not CH 3  C  CH 2 CH 2 CH 3  CH 3 C  CH 2 CH 2 CH 3
H 2O

have CH 3 CO group so it will not give the positive | |

OH Cl
haloform test.
OH
165. (c) Aldehyde reduce silver mirror whereas acid do not reduce silver | 
mirror. 176. (e) CH 3 CHO  HCN  CH 3 C  C  CN  

H 3O

|
CH 3 OH
|
(A)
CH
OH
O O |
166. (d) 3 CH 3 CHO   
conc. H 2 SO 4
CH 3  C  COOH
room temp. CH CH |
H
CH 3 O CH 3
Paraldehyd e 177. (b) Aldehyde, which does not have the   H atom, gives
cannizzaro's reaction on heating with conc. alkali solution
168. (b) Formaline contains 40% HCHO, 8% CH 3 OH and 52%
(50%)
water. It is used as biological preservative. OCH 3
172. (c) C 2 H 5  C  CH 3  I2  NaOH  C 2 H 5 CO 2 Na   CHI 3 CH 3
|| |
O C6 H 5 CHO CH 3  CHCHO
  H atom absent   H - atom

C2 H 5 CO 2 Na  H
 C2 H 5 COOH  Na 
CHO
173. (b) Two molecules of ketones undergo reduction in the presence of   H - atom absent
Mg / Hg to form pinacol. CH 3
  |

  CH 3 C  CHO HCHO
CH 3 CH 3   H  atom absent
 | |  |
CH 3 CH 3
2 C  O   CH 3  C — C  CH 3 
Mg / Hg
  H - atom absent
CH 3 benzene as  | |

acetone
solvent  
 O O 
 Mg 
CH 3 CH 3
| |
Critical Thinking Questions
  CH 3 
HOH
C  C  CH 3  Mg(OH )2
| |
OH OH 1. (d) Acetone oxidise by K 2 Cr2 O7 & conc. H 2 SO 4 into
2, 3  dimethylbutane  2, 3  diol
(pinacol) carboxylic acid. It is not oxidised by dilute H 2 SO 4 .
174. (a) C6 H 5 CH  O  H 2 NNHCONH 2 2. (b) Acetaldehyde react with tollen's reagent while ketone do not
react with tollen's reagent.
 C6 H 5 CH  NNHCONH 2
semicarbazone 3. (b) CCl 3  CHO  H 2O  CCl 3 .CHO.H 2O 
(Chloral hydrate )
The product shows E and Z configuration
OH
CH H CCl 3 .CH
CH
6 5 H
6 5

OH
C
C
4. (c) The compound A with formula C3 H 6 O gives iodoform test, it
N is propanone forms a compound B having carbon atoms three
N
.. times, the number of carbon atoms in propanone, it is 2, 6-
.. NHCONH 2
H NCOHN
2 dimethyl-2, 5-heptadien-4-one.
Z-
E- CH 3
175. (a) As A reacts with hydroxylamine it means A may be |

aldehyde or ketone. but it does not react with fehling solution 5. (a) CH 3 CH 2  C  O  CH 3 CH 2 CH 2 CH  PPh3
2  Butanone
hence A must be a ketone. Secondly it forms iodoform which
is a characteristic reaction of methyl ketone. CH 3
|
O NOH  CH 3 CH 2 C  CHCH 2CH 2CH 3  Ph3 PO
|| || 3  methyl, 3  heptene
CH 3 C  CH 2 CH 2 CH 3   CH 3 C  CH 2 CH 2 CH 3
NH 2OH

6. (a) CH 3  CH 2  CH 2OH  CH 3  CH 2  CHO

[O ]
I2 / NaOH (A) (B)

H 2O CHI 3 H
|
CH 3  CH 2  C  O  H 2 NNHCONH 2 
HCl
 1300 Aldehydes and Ketones
CH 3CH 2CH  N  NHCONH 2
7. (b) Acetophenone is a ketone and does not react with Tollen’s
reagent to give silver mirror.
O  OH 
||  | 
8. (b) CH 3  C  CH 3 CH 3  C  CH 2  ⇌
Acetone (ketoform)  enol form 
  13. (a) Amongst aldehyde & the acid derivatives, acid chloride are the
most susceptible to nucleophilic attack due to strong –I effect
OD O & weak +R effect of the Cl-atom as a result of which carbonyl
| || carbon has the highest electron deficiency. The actual order is
CH 3  C  CH 2 ⇌ CH 3  C  CH 2 D MeCOCl >MeCOOCOMe >MeCOOMe >MeCHO.
OH OD 14. (ad) ICH 2COCH 2CH 3    CHI3  CH 3 CH 2COONa
I2 / NaOH
| |
D2O
CH 2  C  CH 2 D CH 2  C  CH 2 D ⇌ CH 3  CH  CH 2 CH 3 

I2
CH 3CH 2COONa  CHI3
| NaOH
O O OH O
|| ||
H 2O / H 
OH
DCH 2  C  CH 2 D ⇌ D3 C  C  CD3 15. (c) P 
 H 2C H3C
The enol form of acetone on treatment with D2 O undergoes  CH 3
CH 3
Q  
H 2O / H
 H 3 C
enolisation, deutration (addition of D2 O ) and dehydration
(removal of H 2 O ). The repeated enolisation, deutration and OH ⇌ H 3C
dehydration ultimately gives CD3 . COCD 3 (B) . CHO
Ketone (non-reducing) and aldehyde (reducing) can be
9. (b) Both Zn(Hg), HCl and NH 2 NH 2 , OH  can reduce distinguished by Fehling solution.
CH 3
COCH 3 group to CH 2  CH 3 group, but HCl will also 16. (d) C  CHCH 2 CH 2 CH 3 
KMnO 4

bring about dehydration of alcohol to form alkene. Therefore, CH 3
appropriate reagent for the conversion is NH 2 NH 2 , OH  . CH 3
C  O  HOOCCH 2 CH 3
10. (b) 2, 4-hexanedione (a 1, 3-diketone) has the most acidic CH 3
hydrogen. This is because the carbanion left after the removal COC 6 H 5
of H  is resonance stabilised in this case. 17. (bd)  C6 H 5 COCl 
AlCl3

O O
|| || 
CH 3  C  CH 2  C  CH 2 CH 3 
OH
 COOH
2, 4  Hexanedion e H 2O
COC 6 H 5 COC 6 H 5
O O 

Cu
 CO 2
||  || 260 o C
CH 3  C  C H  C  CH 2 CH 3
18. (d) Aldehyde & ketone are colourless & stable compound
O O 19. (c) It undergoes electrophilic substitution at m-position and also
||  ||
gives iodoform test.
CH 3  C  C H  C  CH 2CH 3
20. (a) CH 3  CH 2  C  CH  H 2 O 
But 1  yne
O O
| ||  OH 
 CH 3  C  CH  C  CH 2CH 3  |  keto- enol
CH 3  CH 2  C  CH 2  
O O   tautomerism
|| |  
 CH 3  C  CH  C  CH 2CH 3
O
(a) Aldols (-hydroxy aldehydes or -hydroxyketones) readily
||
11. CH 3  CH 2  C  CH 3
undergo dehydration to form , -unsaturated aldehydes or Butan  2  one
ketones. 21. (b) Due to electron withdrawing nature of NO 2 group, the

O OH O O H2 partial +ve charge on the carbon atom of the  C  O group
H

 in p-nitrobenzaldehyde increases and hence becomes more
-Hydroxyketone O susceptible to nucleophilic attack by CN  ion.
(A) 
 
H ,  H 2O
22. (b) Cannizzaro reaction is an example of hydride ion (H  )
CHO CHO transfer reaction.
12. (b)  o 23. (d) Except Na 2 CO 3 benzophenone react with rest of option.
  
OH / 100 C
Intramolecular 24. (d) The alcohol can be converted to aldehyde group by treating
Cannizzaro reaction
with oxidising agent Pyridinium chloro chromate
CHO CHO 

(C6 H 5 N HCrO3 Cl  ) it is abbreviated as PCC and is called
COO CH 2OH
Collin's reagent. This reagent is used in non aqueous solvent

  
H / H 2O like CH 2Cl 2 It is a very good reagent because it checks the


CHO OOC
COOH CH 2OH
 Aldehydes and Ketones 1301
further oxidation of aldehyde to carboxylic acid while rest
oxidising agent oxidise aldehyde into carboxylic acid. 30. (a) On complete oxidation the obtained compound shows
increament in molecular weight of only 16. It means only one
CH 3 CH 3 oxygen atom is added here. This condition is fulfilled by only
| |
25. (a) C6 H 5  C  O  H 2 NOH   C6 H 5  C  NOH aldehyde which on oxidation gives acid.
H O 2
Acetopheno ne oxime or
methyl phe nyl ketoxime RCHO   RCOOH
[O ]

Hence, original compound must be

2   C6 H 5 NHCOCH 3
H SO
4
Backmann Acetanilide CH 3 CHO  CH 3 COOH
[O ]
rearrangem ent
mol. wt. 44 mol. wt. 60
26. (d) Benzyl alcohol does not have the CH 3 CO  group or
CH 3 CH 2 O  so it will not give the positive iodoform test. Assertion & Reason
27. (c) This is perkin reaction
3. (b) It is true that lower aldehyde and ketones are soluble in water
O O but as the molecular mass increases their solubility decreases.
|| ||
C C On adding Tollen's reagent to a solution of Carbonyl
CH 3 O CH 2  H  CH 3 COO   compound if silver mirror is obtained than it is aldehyde.
O O Therefore Tollen's reagent is used for the identification of
|| || aldehydes and ketones. Here, assertion and reason both are
C C

true but the reason is not the correct explanation of assertion.
CH 3 O C H2
4. (a) Carbonyl compounds having -hydrogen atom condenses to
O produce aldol in presence of alkali.
||
Me C H CH 3  C H  HCH 2 CHO   
dil. NaOH
||
O O O
|| || Acetaldehyde
C C
CH 3 O CH 2  CH  O   
CH 3 COOH
CH 3  CH  CH 2 CHO
|
OH
Aldol
5. (d) Acetylene, on treatment with alkaline KMnO4 is oxidised to
Me O O
|| || produce oxalic acid.
C C
CH 3 O CH 2  CH  OH CH
|||  
4 [O ] COOH
|
CH alk. KMnO 4 COOH
Acetylene Oxalic acid
Therefore, both assertion and reason are false.
Me 6. (b) Acetophenone and benzophenone can be distinguish by
O O iodoform test. Both are carbonyl compounds. Assertion and
 || ||

H
 C C reason both are true but reason is not the correct explanation
 H 2O
CH 3 O CH  CH CH 3 
H O
of assertion.
2

CH 3
7. (c) CH  CHO

CH 3
Me O CH  CH  COOH  CH 3NCOO
 CH 3
28. (b)   
H 2 NCH 3 Isobutanol has -hydrogen atom.
 H 2O
Acetaldehyde, acetone and methyl ketones having CH 3 CO
N  CH 3 group undergo haloform reaction. The halogen atoms of the
 
LiAlH4
methyl group are first replaced by hydrogen atoms. This
29. (c) CH 3  C  C  CH 2  CH 3 

O3 reaction is used as a test of CH 3 CO –group. Due to absence
O
of CH 3 CO –group isobutanal does not give iodoform test.
CH 3  C C  CH 2  CH 3 8. (a) Benzaldehyde is less reactive than ethanol towards
| |
O O nucleophilic attack. The combined effect of –I and +R effect
H 2O of phenyl group is electron donating which increases the
electron density on the carbon atom of the C  O in
benzaldehyde.
CH 3  C  C  CH 2  CH 3  H 2 O 2
|| ||
O O

CH 3 COOH  CH 3 CH 2 COOH
 1302 Aldehydes and Ketones

9. (b) Both carbanions (formed in presence of base) and enol form

(formed in presence of an acid) act as nucleophiles and hence
add on the carbonyl group of aldehydes and ketones to give
aldols.
10. (b) The positive inductive effect of two alkyl groups in ketones
makes the carbon atom less positive and makes it less reactive
in comparison to aldehydes.
11. (e) Oximes are more acidic because, there is a delocalisation of 
electrons (i.e., resonance) and it stabilises it and its conjugate
acid. But no such resonance exists in hydroxyl amine base
( NH 2 O  )
12. (e) The bond energy of carbonyl group is 179 Kcal mol and in –1

C  C the bond energy is 145.8 Kcal. The carbonyl group

shows resonance and thus possesses higher bond energy.
CO C  O
13. (b) Both carbon and oxygen are nonmetals and try to complete
their octet. In R  C  O  each has complete octet whereas
in R  C   O, carbon atom has in complete octet.
14. (b) HCHO cannot be prepared by Rosenmund's reduction because
formyl chloride is unstable at room temperature.
15. (e) HCHO reacts with NH 3 to form urotropine
6 HCHO  4 NH 3  (CH 2 )6 N 4  6 H 2 O

16. (c) The anion left after the removal of -hydrogen is stabilized by
resonance effect.
17. (b) Aldehydes which do not contain -hydrogens undergo
Cannizzaro reaction.
CH 3
|
H 3 C  C   CHO
|
CH 3
2, 2 dimethyl propanal (no  hydrogen)

18. (d) Aldehydes having a methyl or methylene group in the -

position or more correctly having atleast one hydrogen atom in
the -position undergo dimerisation in presence of a base at
low temperature to form -hydroxy aldehydes called aldols.