Aldehydes, Ketones and Carboxylic Acids 307

5
Aldehydes, Ketones and
Carboxylic Acids

[A] Aldehydes and Ketones

5.1 INTRODUCTION; NOMENCLATURE AND STRUCTURE OF CARBONYL GROUP

1. Carbonyl compounds impart fragrance to several natural substances. In this regard, select the
correctly matched :
(a) Cinnamaldehyde-cinnamon (b) Salicylaldehyde-meadow sweet
(c) Vanilin-vanilla beans (d) all of these
CHO

2. IUPAC name of is :

(a) Cyclohexanal (b) Cyclohexane carbaldehyde

(c) Cyclohexyl carbaldehyde (d) None of these
O
||
3. IUPAC name of CH 3 CH 2 C CH 2 CHO is:
(a) 1-formyl-3-pentanone (b) 3-oxopentanal
(c) Pentan-1-al-3-one (d) none of these
4. IUPAC name of OHC — CH 2 — CH — CH 2 — CHO is:
|
CHO
(a) 3-formylpentandial (b) 1,3,5-hexantrial
(c) propane-1,2,3-tricarbaldehyde (d) none of these
5. Carbonyl carbon atom behaves as :
(a) Lewis acid (b) Lewis base
(c) Sometimes acid and sometimes base (d) Neither as acid nor as base
308 Elementary Organic Chemistry for Medical

6. Formic acid is not a representative member of the carboxylic acids because :

(a) it is the first member of the series
(b) it does not contain in alkyl group
(c) it is a gas
(d) it contains an aldehydic group while the other acids not have the aldehydic acid group
7. Carboxylic acids do not give the characteristic properties of :
(a) ‚ƒ C == O
group (b) —COOH group
(c) alkyl group (d) none of these
8. Which of the following is not the functional isomer of monocarboxylic acid ?
(a) Amide (b) Ester
(c) Hydroxy aldehyde (d) Hydroxy ketone
9. What is the main reason for the fact that carboxylic acids can undergo ionization ?
(a) Absence of alpha-hydrogen
(b) Resonance stabilization of the carboxylate ion
(c) High reactivity of alpha-hydrogen
(d) Hydrogen bonding
10. Which is the IUPAC name for the following compound ?
O O

OH
(a) 2-Oxohexanoic acid (b) 5-Oxohexanoic acid
(c) Methyl butyroxo ketone (d) 4-Ketopentanoic acid
11. Which structures are correctly named ?
O
O HO
OH
(a) OH (b)
O Acrylic acid
Formic acid
O
O O
OH
(c) OH OH (d)
Malonic acid Methacrylic acid

12. What is the IUPAC name for ?

O O

(a) 2,3-Dimethylbutyl acetate (b) 2,3-Dimethyl-4-oxoethanal

(c) 2,3-Dimethylbutyl methanoate (d) 2,3-Dimethylbutyl methylate
Aldehydes, Ketones and Carboxylic Acids 309

5.2 METHODS OF PREPARATION OF ALDEHYDES AND KETONES

13. PhCH 2 OH + PCC (pyridinium chlorochromate) in methylene chloride ® product
(a) benzophenone (b) benzoic acid (c) benzaldehyde (d) benzyl chloride
14. In which of the following reactions, product will be aldehyde ?
3 (i) O CO/H /CO (CO)
2 2 8
(a) CH 3 ¾ C == C ¾ C 2 H 5 ¾¾¾¾¾® (b) CH 3 ¾ CH == CH 2 ¾¾¾¾¾¾¾®
D
(ii) H 2O/Zn
½ ½
CH 3 CH 3

2 PdCl / HOH HOH/HgSO / H SO

4 2 4
(c) CH 3 ¾ CH == CH 2 ¾¾¾¾¾® (d) CH 3 ¾ C ºº CH ¾¾¾¾¾¾¾¾®
air /CuCl 2

(X)
15. C 6 H 5 ¾ CH 2 ¾ Cl ¾¾¾® C 6 H 5 ¾ CHO , ( X ) is :
(a) Cu(NO 3 ) 2 (b) Pb(NO 3 ) 2 (c) (CH 2 ) 6 N 4 (d) All of these
O
(i) Conc. NaOH
½
½
16. CH 3 ¾ CH ¾ NO 2 ¾¾¾¾¾® CH 3 ¾ C ¾ CH 3 , The given reaction is known as :
(ii) H 2SO 4
½
CH 3
(a) Stephans reduction (b) Rosenmund reduction
(c) Nef carbonyl synthesis (d) Claisen condensation
OH O

Aluminium tertiarybutoxide
17. ; The given reaction is known as :
Acetone

(a) Kolbe reaction (b) Tischenko reaction

(c) MPV reaction (d) Oppeneur oxidation

5.3 PHYSICAL AND CHEMICAL PROPERTIES

18. Predict which of the following compounds will have a lower boiling point than 1-butanal ?
(a) 1-butanol (b) 2-butanol (c) 1-butene (d) butanoic acid
19. Arrange the given four compounds in decreasing order of acidic strength :
O O O
½½ ½½ ½½
CH 3 ¾ C ¾ CH 2 ¾ C ¾ CH 3 ; CH 3 ¾ C ¾ CH 3 ; CH ºº CH ; CH 3 ¾ CHO
(I) (II) (III) (IV)
(a) I > IV > III > II (b) I > IV > II > III (c) III > I > IV > II (d) II > IV > I > III
20. Which of the following structures will give a positive test with Tollens’ reagent?
O
OH O
(a) (b) (c) O (d)
O
310 Elementary Organic Chemistry for Medical

21. Which of the following sets of reaction conditions will give the product indicated?
O OCH3
OCH3
¾¾¾¾®
HO HO
s
(a) (CH 3 O) 2 Ag , heat (b) CH 3 OH , HO, separate water
(c) (1) CH 3 ONa , (2) MeI (d) CH 3 OH , H + , separate water
22. What are the starting materials needed for the following reaction?
O

HCl O
¾¾¾¾®

OH

(a) O (b) O
+ OH + O

OH

OH
O
(c) + (d) + O
HO
OH
O
CH NH
3 2
23. ¾¾¾¾® Product of the reaction is :
pH 4.5

CH3 H CH3 CH3

N HO NH2 N H—N OH

(a) (b) (c) (d)

24. Which compound is formed when the enolate of 2-methylcyclohexanone, formed from lithium
diisopropylamide (LDA), reacts with methyl iodide?
O O OH

a b c d
(a) a (b) b (c) c (d) d
Aldehydes, Ketones and Carboxylic Acids 311

25. Which of the following compounds is a hydrazone ?

CH3
NHNH2 N
CH3
(a) (b)

NH—NH N—NH2
(c) (d)

26. The compound :

O
||
HOCH 2 CH 2 CH 2 CH 2 CH
can form a hemiacetal by reacting with itself in solution. What is the structure of this
hemiacetal?
HO H HO H HO OH
O OH
(a) O (b) (c) (d) CH 3 (CH 2 ) 3 CH
OH
27. How many hydrogens are replaced by deuterium ?
O

2 D O/DOs
¾ ¾¾¾®
(a) 1 (b) 2 (c) 3 (d) 4
(i) xPCl 5
28. ¾ ¾¾¾¾¾® CH 3 — C ºº C — CH 3 , Sum of x + y is :
O (ii) y - moles NaNH 2

(a) 2 (b) 3 (c) 4 (d) 5

29. PhMgBr act as a nucleophile with:
(a) CH 3 SH (b) CH 3 — C ºº CH
O O
|| ||
(c) CH 3 —C — OH (d) H — C — H
O
LiAlH
30. ¾ ¾¾4® ; Which type of reaction it is ?
Hr
(a) Electrophilic addition (b) Nucleophilic addition
(c) Nucleophilic substitution (d) Electrophilic substitution
31. Which of the following is least reactive toward Grignard reagent ?
O
||
(a) H — C — H (b) CH 3 — CH == O
O
||
(c) C 2 H 5 — CH == O (d) CH 3 — C — CH 3
312 Elementary Organic Chemistry for Medical

32. Compare reactivity toward Grignard reagent ?

O O
|| O ||
CH 3 — C — H C—H CH 3 — C — CH 3
(i) (iii)
(ii)

(a) i > ii > iii (b) i > iii > ii (c) ii >i > iii (d) iii > ii > i
33. What is/are the major product(s) of the following reaction ?
O
||
CH 3 MgBr + HOCH 2 CH ¾¾® ?
(One mole)
O OMgBr
|| |
(a) HO — CH 2 CCH 3 + HMgBr (b) HO — CH 2 CH
|
CH 3
O O
|| ||
(c) CH 4 + BrMgOCH 2 CH (d) BrMgCH 2 CH + CH 3 OH
34. Which of the following reagents does not form an alcohol from an aldehyde as shown below ?
O
||
?
R — C — H ¾®¾ R — CH 2 — OH
(a) H 2 Pt (b) 1. NaBH 4 /2. H 3 O +
(c) 1. LiAlH 4 /2. H 3 O + (d) 1. Ag 2 O, NH 3 /2. H 3 O + (e) H 2 /Raney Ni
35. Compare rate of reaction with RMgBr :
O O O
|| || ||
(i) H — C — H (ii) CH 3 —C — H (iii) CH 3 — C — CH 3
(a) i>ii>iii (b) ii>i>iii (c) iii>i>ii (d) i>iii>ii
O
||
36. CH 3 — C — Et + PhMgBr ¾®
¾ A ¾ ¾r® B , Final product ( B ) of the reaction is:
(2)H
OH OH
| |
(a) CH 3 — C — Ph (b) Ph — C — Ph
| |
Et CH 3

(c) (d)
OH
Aldehydes, Ketones and Carboxylic Acids 313
O
||
(i) KCN
37. H ¾ ¾¾
¾®‘ P’
(ii) H 3Or

Find out the incorrect statement about the above given reaction:
(a) It is a nucleophilic addition reaction
(b) Product obtained is present in racemic mixture
(c) If the hydrolysis of obtained product give a-hydroxy acid
(d) It is a electrophilic addition reaction
38. The K eq. values in HCN addition to following aldehydes are in the order:
O O O

H H H

MeO Me2N
(i) (ii) (iii)
(a) i > ii > iii (b) ii > iii > i (c) iii > i > ii (d) ii > i > iii
39. Arrange the following compounds in decreasing order of K eq for hydrate formation:
O
(1) C 6 H 5 COCH 3 (2) Cl C—CH3

O O
(3) NO2 C—CH3 (4) CH3 C—CH3

(a) 3>2>1>4 (b) 2>1>3>4

(c) 3>1>2>4 (d) 4>2>1>3
OH OH O
| K1
O | K2
40. (1) CH 3 — C — CN +HCN (2) CH 3 — C — CN +HCN
| | H
CH 3 H
Relation between K 1 and K 2 is:
(a) K 1 = K 2 (b) K 1 > K 2 (c) K 2 > K 1 (d) K 1 = K 2 = 1

D 2O/DOs
41. ¾ ¾¾¾ ¾® ; How many hydrogen replaced by ( D) ?
(Prolonged)

O
(a) 2 (b) 3 (c) 4 (d) 5
314 Elementary Organic Chemistry for Medical

42. Which of the following reagents is best used for the conversion shown below ?
O OH
C—H H
?
¾¾¾® D
CH3
(a) 1. NaBH 4 2. D 3 O + (b) 1. NaBD 4 2. H 3 O +
(c) 1. LiAlH 4 2. D 3 O + (d) 1. H 2 Pt 2. D 2 O
43. Benzaldehyde is more reactive than.......... toward nucleophilic attack.
O O O CHO
|| || ||
(a) H — C — H (b) CH 3 — C — H (c) Ph — C — Ph (d)
NO2

OH H+
44. Product is :
CHO

(a) Cyclic acetal (b) Cyclic hemiacetal

(c) Open chain acetal (d) Open chain hemiacetal
NaCN /HCl 2 H O/Hr / D
45. C 6 H 5 CHO ¾¾¾¾® ( X ) ¾¾¾¾¾® Product of the reaction is :
(a)
optically inactive acid
(b)
optically inactive a -hydroxy acid
(c)
racemic mixture of two optically active a -hydroxy acids
(d)
racemic mixture of two optically active secondary alcohols
O
½½ CH 3OH (excess) H 2O/ Hr
46. CH 3 ¾ CH 2 ¾ C ¾ CH 3 ¾¾¾¾¾¾® r
( X ) ¾¾¾® (Y ) ; Product (Y ) is :
H

OH OCH 3
½ ½
(a) CH 3 ¾ C ¾ C 2 H 5 (b) CH 3 ¾ C ¾ C 2 H 5
½ ½
OCH 3 OCH 3

O OH
½½ ½
(c) CH 3 ¾ C ¾ C 2 H 5 (d) CH 3 ¾ CH ¾ C 2 H 5
47. One of the most common alcohol for the protection of carbonyl group is :
(a) glycol (b) glycerol
(c) 1,3-propanediol (d) ethanol
Aldehydes, Ketones and Carboxylic Acids 315

48. In the reaction sequence :

r
2NH OH/H 2 5 PO
C 6 H 5 ¾ C ¾ CH 3 ¾¾¾¾¾¾® ( X ) ¾¾® (Y ) ; Product (Y ) is :
½½
O
O O
½½ ½½
(a) C 6 H 5 ¾ C ¾ NHCH 3 (b) CH 3 ¾ C ¾ NH ¾ C 6 H 5
O
½½
(c) C 6 H 5 ¾ CH 2 ¾ C ¾ NH 2 (d) Mixture of (a) and (b)
49. In the reaction sequence :
r
2NH OH/H
C 6 H 5 ¾ C ¾ H ¾¾¾¾¾¾® ( X ) ; ( X ) is :
½½
O
(a) Mixture of syn and anti oxime (b) Only syn oxime
(c) Only anti oxime (d) Reaction will not take place (NR)
50. Schiff’s base is prepared from :
(a) Carbonyl compound and primary amine (b) Carbonyl compound and secondary amine
(c) Carbonyl compound and tertiary amine (d) All of these
51. Fehling solution gives red precipitate with :
(a) Aromatic aldehyde (b) Saturated aliphatic aldehyde
(c) Unsaturated aliphatic aldehyde (d) Both (b) and (c)
KMnO /Hr / D
4
52. Carbonyl compound; C 8 H 16 O ; ( X ) ¾¾¾¾¾¾® 2 moles of butanoic acid ( X ) is :
(a) 2-Octanone (b) 3-Octanone
(c) 4-Octanone (d) 2-Methyl-3-heptanone
53. In the reaction sequence, ( X ) is ketone :
CH 3
KMnO 4 /Hr ½
( X ) ¾¾¾¾¾® HOOC ¾ (CH 2 ) 3 ¾ CH ¾ COOH ; ( X ) is :
O O
O O
CH3
CH3 H C CH3
(a) (b) (c) (d) 3

54. Which one of the following compounds will give dimethyl glyoxal with SeO 2 ?
(a) Acetone (b) Acetophenone
(c) Ethyl methyl ketone (d) propanaldehyde
316 Elementary Organic Chemistry for Medical

O
CH3 SeO
2
55. ¾¾¾® ( X ) ; Product ( X ) is :

O O
O O
O CH3 CH3
CHO CH3
(a) (b) (c) (d)
O
O O
s
½½ D 2O/OD
56. CH 3 ¾ C ¾ CH 3 ¾¾¾¾®
(Excess)
( X ) ; Product ( X ) is :

O O O O
½½ ½½ ½½ ½½
(a) CD ¾ C ¾ CH 3 (b) CD 3 ¾ C ¾ CHD 2 (c) CD 3 ¾ C ¾ CD 3 (d) CH 3 ¾ C ¾ CH 2 D
57. Which one of the following carbonyl compounds will give racemisation reaction in the
presence of acid or base ?
O OH OCH 3 O CH 3
½½ ½½ ½ ½½ ½ ½½ ½
(a) CH 3 C ¾ CH 2 CH 3 (b) CH 3 C C ¾ C 2 H 5 (c) CH 3 C C ¾ C 2 H 5 (d) CH 3 C ¾ C ¾ CH 3
½ ½ ½
CH 3 CH 3 CH 3

O
2NH OH 2 4 H SO
58. ¾ ¾¾ ¾®( A) ¾ ¾¾ ®( B ). Product B is:

N—OH NH O O
O NH NH
(a) (b) (c) (d)

59. Which of the following compounds will give a positive iodoform test ?
(a) propanal (b) 2-pentanone (c) 3-pentanone (d) benzophenone
OH

PCC dil. KOH

60. ¾¾® (A) + HCHO ¾¾¾¾® (B) ; Give structure of ( B ) is:
O O OH O O
OH
(a) (b) CH3 (c) (d)
61. Cannizzaro reaction is given by :
(a) CCl 3 ¾ CHO (b) CBr 3 ¾ CHO (c) CH 3 ¾ CH ¾ CHO(d) CH 3 ¾ CHO
½
CH 3
Aldehydes, Ketones and Carboxylic Acids 317

62. Cannizzaro reaction is an example of :

(a) Redox reaction (b) Disproportionation (c) Both (a) and (b) (d) Only oxidation
63. In the given reaction, ( X ) and (Y ) will respectively be :
(i) Conc. NaOH
C 6 H 5 CHO+HCHO ¾¾¾¾¾®
r ( X ) + (Y )
(ii) HOH/H

(a) C 6 H 5 COOH and CH 3 OH (b) C 6 H 5 CH 2 OH and HCOOH

(c) Only C 6 H 5 COOH (d) Only CH 3 OH
64. In the given reaction, ( X ) will be :
(X)
NO2 CHO NO2 CH2OH
s
(a) Zn/HCl (b) Sn/HCl (c) LiAlH 4 (d) HCHO/OH
65. Acetaldehyde can be converted into ( A) by which reaction ?
CH 2 OH
½
HOCH 2 ¾ C ¾ CH 2 OH
½
CH 2 OH

( A)
(a) Aldol condensation (b) Cannizzaro reaction
(c) Tollens’ reaction (d) Benzoin condensation
66. Benzoin condensation is given by :
(a) C 6 H 5 CHO (b) CH 3 ¾ CHO (c) C 6 H 5 CH 2 CHO (d) All of these
67. Formaldehyde reacts with Ca(OH) 2 to give C 6 H 12 O 6 which is :
(a) Glucose (b) Fructose (c) Formose (d) Galactose
68. Formaldehyde forms polymer with :
(a) Phenol (b) Urea (c) (a) and (b) both (d) Acetaldehyde
69. Formaldehyde reacts with ammonia to give :
H H
N N
(a) H 2 C==NH (b)
N

HOH2C CH2OH H
N N
(c) N (d) Hexamethylenetetramine

CH2OH
70. In the formation of hexamethylene tetramine intermediate compounds are :
H H
N N
(a) H 2 C==NH (b)
N
H
318 Elementary Organic Chemistry for Medical

CH2OH

(c) N (d) All of these

N N CH2OH
HOH2C

71. Acetaldehyde reacts with ammonia to form :

CH2
H H CH3 N N CH3
N N
(a) N (b) CH2 CH2
H N

CH3 CH3

CH
NH NH
(c) (d) Mixture of (a) and (c)
CH3 CH CH CH3
N

H
O
½½ Conc. H 2SO 4
72. CH 3 ¾ C ¾ CH 3 ¾¾¾¾¾®
Distillation
( X ) ; Product ( X ) is :

(a) Mesityl oxide (b) Phorone

(c) 1, 3, 5-Trimethylbenzene (d) 2-Butyne
73. What is the product of the following reaction?
O
10% NaOH, H2O
¾¾¾¾¾¾® ?
5°C

HO HO
(a) (b) O

O
OH

(c) HO (d)
O
O
Aldehydes, Ketones and Carboxylic Acids 319

O Ph
OH
210% NaOH, H O
74. A ¾¾¾¾¾¾® ; A is :
O
O
(a) 2 (b) 2 OH (c) 2 (d) 2
O
75. Which of the following compounds is the product of an aldol condensation reaction?
O
O OH O O
HO OH
(a) (b) (c) (d)
OH
O
O + NaOH, H2O
76. 100°C
¾¾¾¾¾¾® ? ; Major product of the reaction is :

HO O
O O O

(a) (b) (c) (d)

77. What is the major product of the following reaction?

NaOH
¾¾¾¾® ?
O Heat
O

(a) O (b) (c) (d)

O O
O
78. Which of the following is not the product of an intramolecular aldol condensation?
O O O O

(a) (b) (c) (d)

O
NaOH, H O
2
79. ¾¾¾¾¾® ; Product(s) formed in the reaction is/are :
O
O O

O O
a b c d
(a) a and b (b) a , b , and c (c) c and d (d) c only
320 Elementary Organic Chemistry for Medical

80. dil. KOH

¾¾¾® (A) ; Product ( A) is:
D
O OH
O O OH

(a) (b) (c) (d)

OH

O CH == O

CH3 NaOH
81. + ¾¾¾® (A) 99% yield. Product ( A) is:
H O; D
2

NO2
O O NO2
|| ||
(a) Ph — C — CH == CH — Ph (b) Ph — C — CH == CH

O
||
(c) Ph — C — CH == CH NO2 (d) Ph — CH 2 — CH == CH — Ph

O
CH

OH–
82. 2 ¾¾® ? Major organic product of the aldol addition is :

O O
OH
O CH CH
OH OH
CH
(a) (b) (c)

OH O OH
O
CH CH
CH
(d) (e)

O O
|| ||
OHs
¾® ? Major organic product of the addition is :
83. CH 3 CH 2 CH + H — C — H ¾ ¾
(excess)
Aldehydes, Ketones and Carboxylic Acids 321

O OH O O
|| | || ||
(a) CH 3 CH 2 CHCH (b) CH 3 C — CH (c) HOCH 2 CH 2 CH 2 CH
| |
OH CH 3
O O
||
OH
(d) CH 3 CHCH (e)
|
CH 2 OH
84. Which of the following aldehydes does not undergo an aldol addition when mixed with base ?
O
O O O
|| CH2CH || ||
(a) H — C — H (b) (c) CH 3 CH (d) CH 3 CH 2 CH

CHO ¾¾¾¾®
conc. KOH Hr
85. (A) ¾® (B) ; Structure of ( B ) is:
CHO D D
cyclic product

O O

COOH O COOK
(a) O (b) (c) (d)
CH2OH CH2OH

For Q. No. 86 to 90
Compound ( A) gives positive test with Fehling solution and with I 2 / NaOH. Compound ( A)
also gives following sequence of reactions :
r
(i) PhLi H/ D 2 6 (i) B H /THF PCC
( A) ¾¾¾¾®( B ) ¾¾¾¾® (C ) ¾¾¾¾¾®r
( E ) ¾¾¾®( D)
r
(ii) H (ii) H 2O 2 /OH

86. Compound ( A) will be :

OH
½
(a) CH 3 ¾ CHO (b) CH 3 ¾ CH ¾ CH 3
O
½½
(c) C 6 H 5 ¾ C ¾ CH 3 (d) HCHO
 322 Elementary Organic Chemistry for Medical

87. Compound ( B ) will be :

OH OH
½ ½
(a) CH 3 CH ¾ C 6 H 5 (b) C 6 H 5 ¾ C ¾ CH 3
½
CH 3

OH
½
(c) C 6 H 5 ¾ C ¾ CH 3 (d) C 6 H 5 ¾ CH 2 OH
½
C 6H 5

88. Compound (C ) will be :

(a) C 6 H 5 ¾ C == CH 2 (b) C 6 H 5 CH==CH 2
½
CH 3
(c) C 6 H 5 ¾ C ºº CH (d) C 6 H 5 CH 2 CH==CH 2
89. Compound ( D) will be :
OH O
½ ½½
(a) C 6 H 5 CHOHCH 3 (b) C 6 H 5 ¾ C ¾ CH 3 (c) C 6 H 5 CH 2 CH 2 OH (d) C 6 H 5 ¾ C ¾ CH 3
½
CH 3

90. Compound ( E ) will be :

O
½½
(a) C 6 H 5 ¾ CH 2 ¾ CH 2 ¾ CHO (b) C 6 H 5 ¾ C ¾ CH 2 ¾ CH 3
O
½½
(c) C 6 H 5 ¾ CH 2 ¾ C ¾ CH 3 (d) C 6 H 5 ¾ CH 2 ¾ CHO

5.5 MISCELLANEOUS
91. Which of the following pair is differentiated by iodoform test ?
O O O O

(a) (b) H H H
O O O O
||
(c) Ph H — C— H (d) I
CH2—I CH
I
Aldehydes, Ketones and Carboxylic Acids 323

92. Two isomeric ketones, 3-pentanone and 2-pentanone can be distinguished by :

(a) I 2 / NaOH only (b) NaSO 3 H only
(c) NaCN/HCl (d) Both of (a) and (b)
93. Schiff’s reagent is used for the differentiation between :
(a) HCHO and CH 3 CHO
(b) CH 3 COCH 3 and CH 3 CHO
O O
½½ ½½
(c) C 6 H 5 ¾ CH 2 ¾ C ¾ CH 3 and C 6 H 5 ¾ C ¾ CH 2 ¾ CH 3
(d) HCHO and C 6 H 5 CHO
94. Benzoin is a :
(a) Alcohol (b) Ketone
(c) a -Hydroxy ketone (d) a -Hydroxy aldehyde
95. Metaformaldehyde is :
(a) Dimer of HCHO
(b) Trimer of formaldehyde
(c) Tetramer of formaldehyde
(d) Polymer in which number of HCHO unit is more than 100
 324 Elementary Organic Chemistry for Medical

[B] Carboxylic Acids

5.6 INTRODUCTION , NOMENCLATURE AND STRUCTURE OF CARBOXYLIC GROUP

96. The name butyric acid has been derived from latin word :
(a) butter (b) butyreum (c) bitter (d) none of these
97. Number of e-atoms in adipic acid is :
(a) 4 (b) 5 (c) 6 (d) 7
98. Which acid was extracted from red ant ?
(a) Acetic acid (b) Valeric acid (c) Formic acid (d) Caproic acid
99. Select the correct statement :
(a) C-atom in —COOH group is more electrophilic than in carbonyl group.
(b) C-atom in —COOH group is less electrophilic than in carbonyl group.
(c) C-atom in —COOH group has equal electrophilic nature as in carbonyl group.
(d) None of these
100. In —COOH group, C-atom is less electrophilic than in carbonyl group. It is due to :
(a) resonance (b) steric hindrance
(c) electromeric effect (d) none of these

5.7 METHODS OF PREPARATION

101. Which is the best method for carrying out the following reaction ?
COOH

¾¾¾¾®
NO2
(a) HCOOH;HNO 3 H 2 SO 4
(b) CH 3 Cl AlCl 3 ;HNO 3 H 2 SO 4 ;KMnO 4 H + , heat
(c) CH 3 Cl AlCl 3 ;KMnO 4 H + , heat; HNO 3 H 2 SO 4
(d) HNO 3 H 2 SO 4 ;CH 3 Cl AlCl 3 ;KMnO 4 H + , heat
O
||
102. CH 3 — C — OH; the given carboxylic acid is prepared by:
14
14
(a) C H 3 MgBr + O == C == O ¾ ¾
¾r® (b) CH 3 MgBr + O == C == O ¾ ¾
¾r®
2H 14 2H
14 14
(c) CH 3 MgBr + CH 3 OH ¾® (d) C H 3 MgBr + CH 3 OH ¾®
Aldehydes, Ketones and Carboxylic Acids 325

103. Product of Perkin reaction is :

(a) a , b -unsaturated acid (b) b -cyclohexyl a , b -unsaturated acid
(c) b -Aryl-a, b -unsaturated acid (d) All of these
104. The product ( X ) of the reaction will be :
NO2 CHO + (C6H5—CH2COO)2O

C6H5—CH2COONa/D

(X)

(a) C 6 H 5 ¾ CH == CH ¾ COOH (b) NO2 CH CH COOH

(c) C6H5—CH C COOH (d) NO2 CH C COOH

C6H5

NO2
105. Cinnamic acid is b -phenyl-a, b -unsaturated acid. This acid can be prepared from Perkin
reaction from :
(a) C 6 H 5 CHO (b) CH 3 COOH
(c) C 6 H 5 CHO and CH 3 COOH (d) C 6 H 5 CHO and Ac 2 O
s
106. Which of the following compounds will not give benzoic acid with KMnO 4 / OH / D ?
CH 3
| CH3
(a) C 6 H 5 — C — CH 2 OH (b) C 6 H 5 — CH
| CH3
CH 3
(c) C 6 H 5 — CH 2 OH (d) C 6 H 5 — CH — COOH
|
CH 3
107. Carbon monoxide reacts with sodium hydroxide at 200°C under pressure to give:
(a) Sodium formate (b) Sodium oxalate (c) Formic acid (d) Oxalic acid
108. RCONH 2 + HNO 2 ¾® X + N 2 + H 2 O product X is :
(a) ROH (b) RCHO (c) RCOOH (d) either of these
109. Which of the following reaction produces benzoic acid ?
Br
Mg 1. CO 1. KMnO 4 , HO -
(a) ¾¾® ¾ ¾¾2+® (b) ¾ ¾¾¾¾¾ ®
Et 2O 1. H 3O Heat
2. H 3O+
Br
NaCN 1. HO - , H O
2 1. O , CH CO H
3 3 2
(c) ¾ ¾¾® ¾ ¾¾¾¾ ® (d) ¾ ¾¾¾¾¾ ®
+ 2. H 2O 2
2. H 3O
 326 Elementary Organic Chemistry for Medical

110. Which of these combinations will not produce benzoic acid ?

(a) C 6 H 5 CH 2 OH + KMnO 4 / OH - / H 2 O , heat; then H 3 O +
(b) C 6 H 5 CH 3 + KMnO 4 / OH - / H 2 O , heat; then H 3 O +
(c) C 6 H 6 + CO 2 , high pressure
(d) C 6 H 5 COCH 3 + I 2 / OH - / H 2 O; then H 3 O +
111. What is the reactant of the following reaction sequence ?
1. LAH, Et 2O PBr3 1. Mg, Et 2O CO2H
? ¾ ¾¾¾¾ ® ¾¾¾® ¾ ¾¾¾ ¾®
2. H 2O 2. CO 2
3. H 3O +

Br CO2H
(a) (b) Br

(c) CO2H (d)

CO2H

112. The compound formed as a result of oxidation of ethylbenzene by KMnO 4 is :

(a) benzyl alcohol (b) benzophenone
(c) acetophenone (d) benzoic acid

5.8 PHYSICAL AND CHEMICAL PROPERTIES

113. Which of the following is the strongest acid?
Cl
COOH COOH
(a) (b)

Cl
Cl Cl COOH
COOH
(c) (d)
Cl Cl
Cl Cl

114. Which of the following compounds is most reactive towards NaHCO 3 ?

OH OH O
CO2H S—O—H
(a) (b) (c) (d)
O
NO2
O 1. Excess MeMgBr
115. O ¾¾¾¾¾¾¾® ? ; Product of the reaction is :
2. H O, neutralize
HO 2

O OH O OH
(a) (b)
H3CO CH3 HO CH3
Aldehydes, Ketones and Carboxylic Acids 327

CH3 CH3
H3C H3C OH
(c) O (d)
HO HO CH3

116. Which of the following compounds loses carbon dioxide upon heating to 100°C?
OH OH OH OH

O O O O
(a) (b) (c) (d)
O

O OH
117. Which of the following compounds loses carbon dioxide upon heating to 100°C?
O O O O O O

(a) (b) (c) OH (d) OH

O
OH
O O
HO OH
Heat
118. ¾¾¾¾® ? ; Product of the reaction is :
O O
O
O HO O
O
(a) HO (b) O
OH
HO
O
O
O O
(c) (d) HO

O O
Heat
119. ¾¾¾¾® ? ; Product of the reaction is :
OH
(a) 3-methyl-2-butanone (b) 3,3-dimethylmalonic acid
(c) propane (d) 3,3-dimethyl-2,4-pentadione
Heat
120. CH—COOH ¾¾¾¾® ? ; Product of the reaction is :
|
COOH
(a) toluene (b) benzoic acid
(c) phenylacetic acid (d) cyclohexylacetic acid
 328 Elementary Organic Chemistry for Medical
Br D
2
121. Consider the given reaction, RCOOAg ¾ ¾ ¾® R — Br which one of the following acids will
give maximum yield of R — Br in the above reaction ?
(a) CH 3 — CH — COOH (b) CH 3 — CH 2 — CH 2 — COOH
|
CH 3
CH 3
|
(c) CH 3 — C — COOH (d) All will give same yield
|
CH 3
122. Which one of the following acids will not form acid chloride with SOCl 2 ?
CH 3
|
(a) C 6 H 5 COOH (b) C 6 H 5 CH 2 COOH (c) CH 3 C — COOH (d) HCOOH
|
CH 3
123. Consider the following reaction:
O O
|| ||
Hr
CH 3 — C — OH + CH 3 — OH ¾¾® CH 3 — C — O — CH 3 + HOH
the above reaction is:
(a) Nucleophilic substitution reaction
(b) Nucleophilic addition followed by elimination reaction
(c) Nucleophilic addition only
(d) 1,2-Elimination only
C2H5 C2H5
3 2N H/conc.H SO
4
124. The given reaction, CH3—C—COOH ¾¾¾¾¾¾® CH3—C—NH2 is called:

C3H7 C3H7

(a) Schmidt reaction (b) Curtius reaction

(c) Hofmann rearrangement (d) Lossen rearrangement
125. Which one of the following compounds will give HVZ reaction ?
(a) Benzoic acid (b) Formic acid
(c) 2,2-Dimethyl propanoic acid (d) 2-Methylpropanoic acid
126. Which of the following compounds gives a-halogenation reaction?
(a) C 6 H 5 — CH 2 COOH (b) C 6 H 5 — CH 2 — COOCH 3
(c) HCOOCH 2 — CH 3 (d) Both (a) and (b)
127. Which of the following statements is correct for CH 3 — CH — COOH ?
|
Br
(a) It will give nucleophilic substitution due to bromo group
(b) It will give nucleophilic addition followed by elimination due to —COOH group
Aldehydes, Ketones and Carboxylic Acids 329

(c) Gives elimination reaction due to bromo group.

(d) All of these
OH
COOH
PCl5
128. In the given reaction: ¾¾®(X) . Product ( X ) is:

Cl OH Cl
COOH
COCl O COCl
(a) (b) (c) O (d)
C
O
129. Sodium bicarbonate reacts with salicylic acid to form:
OH ONa ONa
COONa
COOH COONa
(a) C 6 H 5 ONa (b) (c) (d)

130. Arrange the following carboxylic acids in decreasing order of ease of esterification with
CH 3 OH H r :
(I) CH 3 — CH — COOH (II) CH 3 — CH — CH 2 — COOH
| |
CH 3 CH 3

CH 3
|
(III) CH 3 — C — COOH (IV)(CH 3 — CH 2 ) 3 — C — COOH
|
CH 3
(a) II > I > III > IV (b) I > II > III > IV
(c) III > IV > II > I (d) IV > III > II > I
2 (i)Br /P
131. CH 3 — COOH ¾ ¾¾¾® ( X ). Product ( X ) is:
(ii)NaCN
(iii)H 2O Hr
COOH
(a) CH 2 (b) HOOC — CH 2 — CH 2 — COOH
COOH
CH2—CO CO
(c) O (d) CH 3 — CH O
CH2—CO CO
 330 Elementary Organic Chemistry for Medical

COOH

HBr
132. ¾ ¾® ( X ), product ( X ) is:

COBr COOH COOH COOH

Br
Br
(a) (b) (c) (d)

133. Reducing property of formic acid is due to the presence of:

O O
|| ||
(a) — OH (b) — C — H (c) — C — OH (d) All of these

5.9 USES OF CARBOXYLIC ACID

134. Formic acid is not used in which of the following industry ?
(a) rubber (b) food (c) dyeing (d) electroplating
135. Ethanoic acid is used as :
(a) solvent (b) vinegar (c) both (a) and (b) (d) none of these
136. Which acid is used in manufacturing of nylon 6,6 ?
(a) hexane-1,6 dioic acid (b) valeric acid
(c) pentane-1,6-dioic acid (d) none of these
137. Esters of which carboxylic acid are primarily used in perfume industry ?
(a) ethanoic acid (b) benzoic acid (c) caproic acid (d) lauric acid
138. Food preservatives contains :
(a) sodium acetate (b) sodium formate (c) sodium benzoate (d) none of these

5.10 DERIVATIVES OF CARBOXYLIC ACIDS

[A] General Introduction and Methods of Preparation

139. Which of the following compounds is not an acid anhydride?
O O
O O
(a) O (b) (c) O (d)
O
O O
O O

140. Which of the following is not an acid derivative?

O O O
O
(a) (b) Cl (c) (d) O
O
O
Aldehydes, Ketones and Carboxylic Acids 331

141. An acetic acid reacts with isotopically labelled methanol to produce :

(a) methyl acetate having the labelled oxygen
(b) water having all the labelled oxygen
(c) both methyl acetate and water contain isotopic
(d) no esterification
142. What is the expected product, A, of the following reaction sequence ?
Cl ¾ ¾¾¾¾¾¾
1. NaCN
® A + NH +
2. 70% H 2SO 4 , reflux 4

(a) HCO 2 CH 2 C 6 H 5 (b) C 6 H 5 CH 2 OSO 3 H

(c) C 6 H 5 CH 2 COOH (d) C 6 H 5 CHClCOOH
143. An acid chloride is prepared from the related carboxylic acid by reaction with which of these ?
(a) HCl (b) SOCl 2
(c) Cl 2 (d) HOCl

[B] Physical and Chemical Properties

144. Which of the following compounds is most reactive toward nucleophilic acyl substitution ?
O O O O O
|| || || || ||
(a) R — C — NH 2 (b) R — C — OCH 3 (c) R — C — Cl (d) RC — O — OR
145. Which of the following compounds is the least reactive toward nucleophilic acyl substitution ?
O O O O O
|| || || || ||
(a) R — C — N H 2 (b) R — C — OCH 3 (c) R — C — Cl (d) RC — O — CR
O O
|| || D
RO—C
A C find out the reactivity order with LiAlH 4 :
146.
CHO
|
B COCl

(a) A > B > C > D (b) B > C > D > A (c) D > C > B > A (d) B>D>C>A

O OH
O O
147. || ||
H

O O

In the above given compound how many functional group reduced by LAH (Lithium
aluminium hydride) and SBH (Sodium borohydride) respectively ?
(a) 4, 4 (b) 4, 3 (c) 3, 4 (d) 4, 2
 332 Elementary Organic Chemistry for Medical

O 1. DIBAL-H, hexane, –78°C

148. ¾¾¾¾¾¾¾¾¾® ? Major product of the reaction is :
2. H O 2
O

(a) O (b) O
O O
O
O
(c) O O (d) O
O
149. Rank the acid derivatives with respect to their reactivity with water.
Hint: Most reactive >least reactive
(a) acid halide > ester > acid anhydride > amide
(b) acid anhydride > amide > acid halide > ester
(c) amide > ester > acid anhydride > acid halide
(d) acid halide > acid anhydride > ester > amide
150. What is the acid anhydride that is hydrolyzed?
O O
+
3 2 H O ,H O OH + HO
? ¾¾¾¾¾¾®

O O
O O
(a) (b) O
O
O O O O

(c) O (d) N
H
O
+
O 3 2H O ,H O
151. O ¾¾¾¾¾¾® ? , Product of the reaction is :
O
O O
OH
HO OH
(a) HO (b) O O
O

O O OO O
(c) HO OH (d) HO
Aldehydes, Ketones and Carboxylic Acids 333

O
|| ND 3 Br
¾®( A) ¾¾2®( B ) ; Product (B) is:
152. CH 3 — C — OH ¾ ¾
D KOH
O O
(a) CH 3 — ND 2 (b) CH 3 — NH 2 (c) (d)
OH
O
C—OH
2NaNH
153. HO CH2—C SO3H ¾ ¾¾¾2® Product of the reaction is:

C
CH
CO2H COs
2

(a) HO CH2— C s SOs

SO3 (b) HO CH2—C 3

C C
Cs CH
COs 2

(c) sO CH2—C SO3H (d) None of these

CH
O
O
LiAlH4 O
154. ¾¾¾® ¾¾¾¾¾® ; Major product of the reaction is :
O—CH3 + H +
H

O O
(a) O (b) O

O
(c) (d) O
O
O
 334 Elementary Organic Chemistry for Medical

O
O 18
H +
155. + H2O ¾¾® ? Product of the reaction is :

18O O
18 || 18 ||
(a) HOCH 2 CH 2 CH 2 CH 2 COH (b) HOCH 2 CH 2 CH 2 CH 2 COH
O O
18 ||18 ||18
(c) HOCH 2 CH 2 CH 2 CH 2 COH (d) HOCH 2 CH 2 CH 2 CH 2 COH

156. O—Et
O O
Number of functional group reduced by NaBH 4 and LiAlH 4 respectively is :
(a) 2, 2 (b) 2, 3 (c) 3, 3 (d) 1, 3
O

157.
O
NO2
Number of functional group reduced by LiAlH 4 and NaBH 4 respectively is :
(a) 3, 0 (b) 3, 1 (c) 3, 2 (d) 2, 2
O
||
158. Et — O — C — O — Et+PhMgBr ¾® ¾ ( A) ; Product (A) is:
(excess) 2Hr

OH O
| ||
(a) Ph — CH — Ph (b) Ph — C — Ph

OH
|
(c) Ph — C — Ph (d) Ph — CH 2 — OH
|
Ph
O O
|| ||
KOBr LAH
159. CH 3 — C — NH 2 ¾ ¾¾®( A) ; CH 3 — C — NH 2 ¾ ¾
¾® ( B )
Relation between ( A) and ( B ) is:
(a) Chain isomer (b) Homologues (c) Functional isomer (d) Identical
Aldehydes, Ketones and Carboxylic Acids 335

O
POCl3
160. Ph—C—NH2 ¾¾® (A) ; Product (A) is:
P O /D 2 5

OH
(a) Ph — NH 2 (b) Ph — CH 2 — NH 2 (c) Ph—CH—NH2 (d) Ph — C ºº N
161. What is the major product of the following reaction ?
O
CNH2
1. LiAlH
4
¾¾¾¾®
r ?
2. H3O
OH
r r r
NH3 CH2NH3 C—NH3
(a) (b) (c) H

O
Li
C—N CH2OH
AlH2
(d) (e)

O
||
P2O 5 (i) CH 3 MgBr (i) I2 +Ca(OH)2
162. C — NH 2 ¾ ¾¾® A ¾ ¾¾¾¾ ® B ¾ ¾¾¾¾ ¾® C; Product (C ) is:
(ii) H 3Or (ii) D

O O
|| ||
(a) C — CH 3 (b) C — OH

(c) C (d) C — CH 2 CH 3
||
O O
163. Which of the following reactant on reaction with conc. NaOH followed by acidification gives
the following lactone as the only product ?
O

O
|| CO2H
C—OCH3 CO2H CHO
(a) (b) (c) (d)
CHO CHO CO2H
CO2H
 336 Elementary Organic Chemistry for Medical

164. Which of the following will not undergo Hofmann bromamide reaction?
O
O
||
(a) Ph — C — NH — Br (b) NH2

O
O
(c) NH—CH3 (d) CH3—C—NH2

165. Number of moles of Br 2 consumed in Hofmann bromamide reaction?

(a) 1 (b) 2 (c) 3 (d) 4
O
|| Br2
166. CH 3 — C — NH 2 ¾ ¾¾ ¾®( A) ; Product (A) is:
KOD/ D 2O

(a) CH 3 NH 2 (b) CH 3 ND 2 (c) CH 3 OH (d) CH 3 OD

O
C—OH 18
H r
167. + CH3OH ¾¾® ?, Product obtained from the reaction is :

O O
18
C—O—CH3 18 C—O—CH3 18
(a) + H2O (b) + H 2O

18
O O
18
C—O—CH3 18 C—O—CH3
(c) + H2O (d) + H 2O

168. What is the major organic product of the following reaction ?

COOH
Hr
2 + HOCH2CH2OH ¾¾® ?

CH2CH2
(a)
HOOC COOH

CH2CH2O COOH
(b)
HOOC
Aldehydes, Ketones and Carboxylic Acids 337

O O O O
CCH2CH2C COCH2CH2OC
(c) (d)
O
½½ (X) (i) LiAlH 4
169. CH 3 ¾ CH 2 ¾ C ¾ CH 2 COOC 2 H 5 ¾¾® ( A) ¾¾¾¾¾®
(ii) H 2O/Hr

O
½½
CH 3 ¾ CH 2 ¾ C ¾ CH 2 ¾ CH 2 OH+C 2 H 5 OH
( X ) will be :
CH 2 ¾ OH CH 2 ¾ OH
r s
(a) HCHO (b) ½ H (c) ½ OH (d) HCN
CH 2 OH CH 2 ¾ OH
170. Which one of the following is least reactive for nucleophilic substitution reaction?
(a) Acid (b) Acid chloride (c) Acid amide (d) Ester
O
||
CH 3 MgBr
171. In the given reaction, C 6 H 5 — C — Cl ¾ ¾¾¾ ®( X ), product X is:
1 mole
OH OH O
| | ||
(a) C 6 H 5 C CH 3 (b) C 6 H 5 C C 6 H 5 (c) C 6 H 5 C CH 3 (d) C 6 H 5 CHCH 3
| |
CH 3 CH 3
172. Benzoyl chloride is less reactive than acetyl chloride for nucleophilic substitution reaction
because:
O
||
(a) — C — group of benzoyl chloride is in conjugation to benzene ring
(b) CH 3 group of acetyl chloride makes C — Cl bond stronger due to +I effect
(c) C 6 H 5 group of benzoyl chloride makes C — Cl bond weaker due to +R effect
(d) CH 3 — groups makes C — Cl bond weaker due to + I effect and C 6 H 5 group makes C — Cl
bond stronger due to – I effect
173. Which of the following reactions is an example of alcoholysis ?
(a) C 6 H 5 COOH + CH 3 OH ¾®
¾ C 6 H 5 COOCH 3
O
||
(b) C 6 H 5 COCl + CH 3 OH ¾®
¾ C 6 H 5 — C — O — CH 3
(c) C 6 H 5 COOC 2 H 5 + CH 3 OH ¾®
¾ C 6 H 5 COOCH 3
(d) C 6 H 5 COOC 2 H 5 + HOH ¾®
¾ C 6 H 5 COOH + C 2 H 5 OH
 338 Elementary Organic Chemistry for Medical

174. Claisen condensation takes place between:

(a) two molecules of esters having no a-hydrogen atom
(b) two molecules of esters having a-hydrogen atom
(c) two molecules of ketones
(d) one molecule of ester having a-hydrogen and one molecule of ketone having no
a-hydrogen.
O O
2 5 C H ONa
175. C—CH3+CH3—C—OC2H5 ¾¾¾®
C H OH (X). Product ( X ) will be:
2 5

OH O O
C—CH2—C—CH3 HC == CH—C—CH3
(a) (b)
H
O O O
||
(c) CH3 == C—CH2—C (d) CH 3 — C — CH 2 — COOH

176. Number of cross products in the given reaction will be:

C H ONa
2 5
CH 3 COOC 2 H 5 + C 6 H 5 — CH 2 — COOC 2 H 5 ¾ ¾¾¾ ®
C 2H 5OH

(a) One (b) Three (c) Two (d) Four

177. Arrange the following compounds in decreasing order of reactivity for hydrolysis reaction:

(I) C 6 H 5 COCl (II) NO2 COCl

(III) CH3 COCl (IV) OHC C—Cl

(a) II > IV > I > III (b) II > IV > III > I (c) I > II > III > IV (d) IV > III > II > I
178. In the given reaction,
O
r
HOH H
O ¾® ( X ), product (X) is:
¾ ¾¾

CH3
OH
|
(a) HOOCCH 2 CH 2 CH CH 3 (b) CH 3 CH 2 CH 2 CH 2 COOH
(c) HOCH 2 CH 2 CH 2 COOH (d) CH 3 CH 2 CH CH 2 COOH
|
OH
Aldehydes, Ketones and Carboxylic Acids 339

O LiAlH4
179. (A) ; (A) and (B) respectively are:

O
®¾

NaBH4

(B) O

(a) CH 2 OH — CH 2 — CH 2 — CH — CH 2 OH and O
|
OH
OH
O

(b) O and CH OH — CH — CH — CH — CH OH
2 2 2 2
|
OH
OH

(c) Both are O

OH
OH
|
(d) Both are CH 2 OH — CH 2 — CH 2 — CH 2 — CH — CH 2 OH
180. Which optically active compound on reduction with LiAlH 4 will give optically inactive
compound?
(a) CH 3 — CH — COOH (b) CH 3 — CH 2 — CH — COOH
| |
OCH 3 OH
(c) CH 3 — CH 2 — CH — COOH (d) CH 3 — CH — CH 2 — COOH
| |
CH 2 OH OH
181. In the given reaction sequence (X) is :
O
r ||
H 2O O H H 2O Hr
( X ) ¾ ¾¾¾ ® R — C — NH 2 ¾ ¾¾ ¾® RCOOH.
(a) RCN (b) RNC (c) RCHO (d) R 2 CO
 340 Elementary Organic Chemistry for Medical

A nswers

1. (d) 2. (b) 3. (b) 4. (c) 5. (a) 6. (d) 7. (a) 8. (a) 9. (b) 10. (b)

11. (c) 12. (c) 13. (c) 14. (b) 15. (d) 16. (c) 17. (d) 18. (c) 19. (b) 20. (c)

21. (b) 22. (a) 23. (c) 24. (b) 25. (d) 26. (b) 27. (c) 28. (b) 29. (d) 30. (b)

31. (d) 32. (b) 33. (c) 34. (d) 35. (a) 36. (a) 37. (d) 38. (d) 39. (a) 40. (b)

41. (a) 42. (b) 43. (c) 44. (b) 45. (c) 46. (c) 47. (a) 48. (d) 49. (a) 50. (a)

51. (d) 52. (c) 53. (b) 54. (c) 55. (b) 56. (c) 57. (b) 58. (d) 59. (b) 60. (a)

61. (c) 62. (c) 63. (b) 64. (d) 65. (c) 66. (a) 67. (c) 68. (c) 69. (d) 70. (d)

71. (c) 72. (c) 73. (a) 74. (d) 75. (c) 76. (c) 77. (d) 78. (c) 79. (d) 80. (b)

81. (a) 82. (b) 83. (d) 84. (a) 85. (a) 86. (a) 87. (a) 88. (b) 89. (c) 90. (d)

91. (b) 92. (d) 93. (b) 94. (c) 95. (b) 96. (b) 97. (c) 98. (c) 99. (a) 100. (a)

101. (d) 102. (b) 103. (c) 104. (d) 105. (d) 106. (a) 107. (a) 108. (c) 109. (a) 110. (c)

111. (d) 112. (d) 113. (d) 114. (d) 115. (b) 116. (a) 117. (c) 118. (d) 119. (c) 120. (d)

121. (b) 122. (d) 123. (d) 124. (a) 125. (d) 126. (d) 127. (d) 128. (d) 129. (b) 130. (a)

131. (a) 132. (b) 133. (b) 134. (b) 135. (c) 136. (a) 137. (b) 138. (c) 139. (b) 140. (c)

141. (a) 142. (b) 143. (c) 144. (c) 145. (a) 146. (b) 147. (d) 148. (b) 149. (d) 150. (b)

151. (c) 152. (b) 153. (b) 154. (c) 155. (d) 156. (b) 157. (c) 158. (c) 159. (b) 160. (d)

161. (b) 162. (c) 163. (c) 164. (c) 165. (a) 166. (b) 167. (d) 168. (d) 169. (b) 170. (c)

171. (c) 172. (d) 173. (c) 174. (b) 175. (c) 176. (c) 177. (a) 178. (a) 179. (a) 180. (c)

181. (a)
Aldehydes, Ketones and Carboxylic Acids 341

Level-2 Assertion and Reason

Instructions : In each of the following questions, a Statement of Assertion (A) is given followed by
a corresponding Reason (R) just below it. Read the Statement carefully and mark the correct
answer—
(A) If both Assertion and Reason are true and Reason is the correct explanation of Assertion.
(B) If both Assertion and Reason are true but Reason is not the correct explanation of
Assertion.
(C) If Assertion is true but Reason is false.
(D) If both Assertion and Reason are false.

1. Assertion (A) : Enol form of cyclohexane-1, 3, 5 trione is more stable than its keto form.
Reason (R) : Enol form contains a-hydrogen atoms.
2. Assertion (A) : p-dimethylamino-benzaldehyde does not undergo benzoin condensation.
Reason (R) : The aldehydic ( ¾ CHO) group is meta directing.
3. Assertion (A) : In Tischenko reaction two moles of acetaldehydes combine to form ethyl
acetate.
Reason (R) : One mole is oxidised while other is reduced in presence of aluminium
ethoxide.
4. Assertion (A) : Benzaldehyde with HCN gives two isomeric compounds.
Reason (R) : Both nitrile and isonitrile compounds are possible when HCN reacts with
carbonyl group.
5. Assertion (A) : Carbonyl compounds react with phenyl hydrazine to form phenyl
hydrazones.
Reason (R) : Hydrazones of aldehydes and ketones are prepared in highly acidic
medium.
6. Assertion (A) : In formaldehyde, all the four atoms are in the same plane.
Reason (R) : The carbon atom in formaldehyde is sp 2 -hybridised.
7. Assertion (A) : a-Hydrogen atoms in aldehydes and ketones are acidic.
Reason (R) : Anions formed after loss of a-hydrogens are stabilised due to inductive
effect.
8. Assertion (A) : Benzaldehyde is more reactive than ethanol towards nucleophilic attack.
Reason (R) : All the carbon atoms of benzaldehyde are sp 2 -hybridised.
9. Assertion (A) : ¾CHO group can be easily oxidised to ¾COOH group even with mild
oxidants.
Reason (R) : ¾COOH group can be easily reduced to ¾CHO group by using LiAlH 4 .
10. Assertion (A) : Lower members of aldehydes and ketones are miscible with water.
Reason (R) : Solubility of carbonyl compounds increases with increase in molecular
weight.
 342 Elementary Organic Chemistry for Medical

11. Assertion (A) : Oximes are less acidic than hydroxyl amine.
Reason (R) : Oximes of aldehydes and ketones show geometrical isomerism.
12. Assertion (A) : Halogen acids do not add on to carbonyl bond.
Reason (R) : Addition depends upon the polarisation of HX and carbonyl bond.
13. Assertion (A) : Pentan-2-one can be distinguished from pentan-3-one by iodoform test.
Reason (R) : Former is a methyl ketone while the latter is not.
14. Assertion (A) : 2-methylpropanal undergoes Cannizzaro’s reaction.
Reason (R) : It has an a-hydrogen atom.
15. Assertion (A) : Acetaldehyde undergoes aldol condensation with dil. NaOH.
Reason (R) : Aldehydes which do not contain a-hydrogen undergo aldol condensation.
16. Assertion (A) : Presence of acids and bases activates carbonyl compounds for reaction.
Reason (R) : Carbonyl compounds possess positive and negative centres and provide
seat for electrophilic and nucleophilic attack.
17. Assertion (A) : R ¾ C ºº O + is more stable than R ¾ C + == O.
Reason (R) : Resonance in carbonyl compound provides C + and O - .
18. Assertion (A) : Benzaldehyde gives a positive test with Benedict’s and Fehling solution.
Reason (R) : Benzaldehyde forms black precipitate or silver mirror with Tollen’s
reagent.
19. Assertion (A) : Lower aldehydes and ketones are soluble in water but the solubility
decreases as the molecular masses increase.
Reason (R) : Distinction between aldehydes and ketones can be made by Tollen’s
reagent.
20. Assertion (A) : The boiling point of ethanol is much higher than that of diethyl ether.
Reason (R) : In ethanol, the molecules are associated by the formation of
intermolecular hydrogen bonding whereas in diethyl ether it is not
possible.
21. Assertion (A) : Boiling points of carboxylic acids increase regularly with increasing
molecular weight.
Reason (R) : Carboxylic acids are known to form dimers due to hydrogen bonding.
22. Assertion (A) : Formic acid do not undergo halogenation reaction in presence of
phosphorus.
Reason (R) : Carboxylic acids are reduced by HI in presence of phosphorus to alkane.
23. Assertion (A) : The overall reactivity of acid derivatives follows the order:
Acetyl Chloride>Acid Anhydride>Acid Ester>Acid Amide.
Reason (R) : Reactivity order is as per the basicity order of leaving group
-
Cl - > RCOO - > RO - > NH 2 .
24. Assertion (A) : Dry distillation of calcium salt of benzoic acid gives acetophenone.
Reason (R) : Dry distillation of calcium salt of carboxylic acids is good method to
prepare ketones.
25. Assertion (A) : Unlike the > C == O group of aldehydes and ketones, the > C == O group of
O
||
R ¾ C ¾ OH does not undergo nucleophilic addition reactions.
Aldehydes, Ketones and Carboxylic Acids 343

Reason (R) : Carboxylic acids exist as dimers,

O-----H–––O
R––C C––R
O–––H-----O
due to intermolecular hydrogen bonding.
26. Assertion (A) : Acetic acid does not undergo haloform reaction.
Reason (R) : Acetic acid has no alpha hydrogens.
27. Assertion (A) : 6, 6'- dinitrodiphenic acid shows enantiomerism.
Reason (R) : Enantiomers rotate the plane of polarised light in the oppssite direction
but to the same extent.
28. Assertion (A) : Lactic acid is optically active.
Reason (R) : A symmetry in the inner structure of the organic compound causes optical
activity.
29. Assertion (A) : During acid catalysed esterification oxygen atom of alcohol is present in
ester molecule.
Reason (R) : Esterification is a reversible reaction.
30. Assertion (A) : Alcohols react with acid anhydride and acid chloride to form esters.
Reason (R) : Dissociation constant of alcohols are higher than the dissociation constant
of water.
31. Assertion (A) : ¾COOR group activates substitution in benzene.
Reason (R) : Meta directing groups are electron acceptors.
32. Assertion (A) : Fluoroacetic acid is a stronger acid than chloroacetic acid.
Reason (R) : Carboxylic acids are weak acids and turn blue litmus red.
°
33. Assertion (A) : Formate has both the C ¾ O bonds have same value 1.27 A .
Reason (R) : Same bond length is due to the phenomenon of resonance.
34. Assertion (A) : Boiling points of acids are lower than the corresponding alcohols.
Reason (R) : Boiling points of liquids depend upon interparticle forces.
35. Assertion (A) : Carboxylic acids are stabilised by resonance.
Reason (R) : Chloroacetic acid is weaker than acetic acid.
36. Assertion (A) : Benzoic acid does not give Friedel Craft’s reaction.
Reason (R) : Benzoic acid is obtained by catalytic oxidation of toluene with air in
presence of Co–Mn as catalyst.
37. Assertion (A) : Carboxylic acids do not give characteristic reactions of carbonyl group.
Reason (R) : Carboxylic acids exist as cyclic dimers in solid, liquid and even in vapour
state.
38. Assertion (A) : Pure acetic acid is converted into ice like solid called glacial acetic acid.
Reason (R) : Acetic acid is stronger than HCOOH.
39. Assertion (A) : CH 3 COOH but not HCOOH can be halogenated in presence of red P and
Cl 2 .
Reason (R) : Both formic acid and CH 3 COOH are highly soluble in water.
40. Assertion (A) : Highly branched carboxylic acids are more acidic than unbranched acids.
Reason (R) : Hydrogen bonding in carboxylic acid is stronger than alcohols.
 344 Elementary Organic Chemistry for Medical

41. Assertion (A) : First four aliphatic monocarboxylic acids are colourless.
Reason (R) : Carboxylic acids with more than five carbon atoms are insoluble in water.
42. Assertion (A) : Acetic acid in vapour state shows a molecular mass of 120.
Reason (R) : It undergoes intermolecular hydrogen bonding.
43. Assertion (A) : Esters which contain a-hydrogen undergo Claisen condensation.
Reason (R) : LiAlH 4 reduction of esters gives acids.
44. Assertion (A) : RCOCl,( RCO) 2 O and RCOOR ' all react with Grignard reagents to form 3 o
alcohols.
Reason (R) : RCOCl reacts with R 2 Cd to form ketones but ( RCO) 2 O and RCOOR ' do
not react at all.
45. Assertion (A) : Cannizzaro reaction is gives by aldehydes having no a-hydrogen atom.
Reason (R) : Cannizzaro reaction is a redox reaction.
46. Assertion (A) : Perkin reaction is given by aliphatic aldehydes.
Reason (R) : Product of the reaction is a,b unsaturated acid.
47. Assertion (A) : Benzaldehyde does not reduce Fehling’s solution.
Reason (R) : It gives Cannizzaro’s reaction in presence of NaOH present in the Fehling’s
solution.
48. Assertion (A) : Benzaldehyde gives a positive test with Tollens’ reagent but not with
Benedict’s and Fehling solution.
Reason (R) : Alkali present in these reagents convert benzaldehyde into benzoic acid
and benzyl alcohol, hence no reaction with these reagents.
49. Assertion (A) : 2,4,6-trimethyl acetophenone does not form an oxime.
Reason (R) : Methyl groups are electron-releasing hence they decreases the stability of
s-complex.

50. Assertion (A) : CH 3 O C ¾ CH 3 is more reactive than

||
O

O 2N C ¾ CH 3 for nucleophilic addition reaction.

||
O
Reason (R) : ¾OCH 3 group is +R group whereas ¾NO 2 is ¾ R group.
-
51. Assertion (A) : Benzoin condensation take place in the presence of CN ion.
-
Reason (R) : CN ion is not a specific catalyst.
52. Assertion (A) : Acetyl chloride is rapidly decomposed by water but benzoyl chloride very
slowly.
Reason (R) : The electrophilic character of the carbon atom of the carbonyl group is
much less than CH 3 COCl.
53. Assertion (A) : o-hydroxy benzoic is more acidic than benzoic acid but p-hydroxy benzoic
is less acidic than benzoic acid.
Reason (R) : Salicylate ion is resonance stabilized.
Aldehydes, Ketones and Carboxylic Acids 345

54. Assertion (A) : Benzoic acid does not undergo Friedel-Crafts reaction.
Reason (R) : Benzoic acid forms salt with AlCl 3
55. Assertion (A) : p-hydroxy benzoic acid is a weaker acid than benzoic acid although ¾OH
exerts -I effect.
Reason (R) : Resonance effect being stronger overweighs the inductive effect.
56. Assertion (A) : Both C 6 H 5 CH 2 ¾ C ¾ CH 2 Cl and C 6 H 5 ¾ C H ¾ C ¾ CH 3 form
|| || ||
O Cl- O
C 6 H 5 CH 2 CH 2 COOH when treated with OH followed by acidification.
Reason (R) : Removal of an a-H by OH - is followed by S N 2 displacement of Cl - to give
a cyclopropanone ring.
57. Assertion (A) : Isobutanal does not give idoform test.
Reason (R) : It does not have a-hydrogen.
58. Assertion (A) : The pKa of acetic acid is lower than that of phenol.
Reason (R) : Phenoxide ion is more resonance stabilized.
59. Assertion (A) : p - O 2 N - C 6 H 5 COCH 3 is prepared by Friedel Crafts acylation of
nitrobenzene.
Reason (R) : Nitrobenzene easily undergoes electrophilic substitution reaction.
60. Assertion (A) : Alkyl isocyanides in acidified water gives alkyl formamides.
Reason (R) : In isocyanides, carbon first acts as a nucleophile and then as an
electrophile.
61. Assertion (A) : Carboxylic acid is reduced into primary alcohol by diborane.
Reason (R) : Diborane is more reactive than NaBH 4 .
62. Assertion (A) : Ketone gives DNP test easily than aldehyde.
Reason (R) : Ketone is more reactive than aldehyde.
63. Assertion (A) : Mixture of benzaldehyde and acetaldehyde in hot alkaline medium gives
cinnamaldehyde.
Reason (R) : Benzaldehyde is strong electrophile than acetaldehyde.
64. Assertion (A) : Acetophenone shows aldol condensation.
Reason (R) : Acetophenone contains carbonyl group.
65. Assertion (A) : p-methoxy benzoic acid is less acidic than m-methoxy benzoic acid.
Reason (R) : Methoxy group acts electron releasing group at para position.
66. Assertion (A) : Carboxylic acid is less acidic than phenol.
Reason (R) : The-I effect of benzene ring stabilizes phenoxide ion.
67. Assertion (A) : Ethyl acetoacetate forms butane-1, 4-diol with NaBH 4 .
Reason (R) : NaBH 4 can reduces ketone and esters group.
68. Assertion (A) : Aldehyde are more reactive than ketone.
1
Reason (R) : Nucleophilic addition reaction in carbonyl compound µ
Steric hindrene
and µ positive charge at carbon of carbonyl group.
 346 Elementary Organic Chemistry for Medical

A nswers

1. (B) 2. (D) 3. (A) 4. (C) 5. (C) 6. (A) 7. (C) 8. (D) 9. (C) 10. (C)
11. (D) 12. (A) 13. (A) 14. (D) 15. (C) 16. (B) 17. (B) 18. (D) 19. (B) 20. (A)
21. (B) 22. (B) 23. (C) 24. (D) 25. (B) 26. (C) 27. (B) 28. (B) 29. (B) 30. (C)
31. (D) 32. (B) 33. (A) 34. (D) 35. (C) 36. (B) 37. (B) 38. (C) 39. (B) 40. (C)
41. (C) 42. (A) 43. (C) 44. (B) 45. (B) 46. (D) 47. (A) 48. (A) 49. (C) 50. (D)
51. (C) 52. (A) 53. (B) 54. (D) 55. (A) 56. (A) 57. (C) 58. (C) 59. (D) 60. (A)
61. (A) 62. (D) 63. (C) 64. (B) 65. (A) 66. (D) 67. (D) 68. (A)
Aldehydes, Ketones and Carboxylic Acids 347

S olutions

1. (B) Enol form of cyclohexane -1, 3, 5,-trione i.e., phloroglucinol is stabilised by resonance
i.e., aromatic character.

[Link]
N CHO
2. (D)

O OH
N C C

C6H5 H H
C6H5
4. (C)
and
N N
OH

5. (C) In highly acidic medium, the protonation of hydrazine decreases its nucleophilic
character, so formation of hydrazone becomes difficult.
H
C=O
6. (A) H
sp2 Hybridised carbon
7. (C) The conjugate base is resonance stabilised.
O O
|| ||
- -
R ¾ CH 2 ¾ C ¾ R ¾® R CH ¾ C ¾ R
b
O-
|
R ¾ CH ¾ C ¾ R ¢

8. (D) Benzaldehyde is less reactive towards nucleophilic substitution as it carries less positive
character on ––CHO group carbon. This is because it gets delocalised over benzene ring.
Ammonical
9. (C) RCHO ¾ ¾¾¾ AgNO
¾® RCOOH
3

This is due to low potential.

10. (C) Carbonyl compounds are soluble in water due to H-bonding. An increase in molecular
weight of carbonyl compounds shows an increase in hydrophobic character of alkyl
chain which ultimately predominates over H-bonding and thus decreases solubility.
348 Elementary Organic Chemistry for Medical

11. (D) Oximes are more acidic as there is a delocalisation of p-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. (A) Degree of polarity in HX as well as in carbonyl bond predicts the easy addition of HX on
carbonyl bond. However, as soon as the addition products are formed, the products
loses HX to show the backward reaction.
O
||
13. (A) CH 3 ¾ C ¾ containing pentan-2-one gives iodoform test positive.
CH 3
\
14. (D) CH ¾ CHO
/
CH 3
(2-methyl propanal)
It has a-hydrogen, so it cannot undergo Cannizzaro’s reaction, as only those aldehydes
give this reaction which do not contain a-hydrogen.
15. (C) Aldehydes which contain a-hydrogen can yield carbanion to undergo aldol
condensation.
O O O O
|| || || ||
R ¾ C - CH 2 ¾ C ¾ R ® R ¾ C ¾ CH 2 ¾ C ¾ R
| |
R R
16. (B) Presence of acid increases the partial positive charge on carbonyl carbon and thereby
activates the group.
g
+
\ \C - +
/ C == O + H / ¾O - - -H
Presence of base activates a-methylene component of the carbonyl compounds by
converting them in carbanions.
-
R ¾ CH 2 ¾ CHO + :B- ® RCHCHO + BH
17. (B) Both carbon and oxygen are non-metals and try to complete their octet. In R ¾ C ºº O +
each has complete their octet whereas in R ¾ C + == O, carbon atom has incomplete
octet.
18. (D) Benedict’s solution (Cu 2+ +citric acid+base) and Fehling solution (Cu 2+ + tartaric
acid+base) are weak oxidising agents in comparison to Tollen’s reagent [Ag(NH 3 ) 2 + ] .
Thus, they oxidise aliphatic aldehydes but are not capable of oxidising aromatic
aldehydes.
19. (B) With increasing molecular weight hydrophobic hydrocarbon chain length increases.
This decreases the solubility.
21. (B) The association due to H-bonding increases with +I effect of alkyl chain.
22. (B) The formic acid does not contain a-hydrogen, which can be replaced.
23. (C) The correct basicity order of leaving group is Cl - < RCOO - < RO - < NH 2 - .
Aldehydes, Ketones and Carboxylic Acids 349

24. (D) Dry distillation of calcium salt of benzoic acid forms benzophenone.
25. (B) The ¾OH group of carboxylic acid does not allow the carboxyl carbon to be sufficiently
positive to get a nucleophilic attack.
26. (C) Acid undergoes reaction at carboxyl group.
27. (B) 6,6'-dinitrodiphenic acid has steric hindrance between the bulky o-substituents on
benzene rings and forces the benzene rings to be perpendicular to each other. As a
result two o-substituents in one benzene ring lie in the plane of the paper while the two
o-substituents in the other benzene ring lie in a plane perpendicular to the plane of the
paper. So, its mirror image is non-superimposable and hence shows enantiomerism.
28. (B) Lactic acid is a chiral molecule because it has a chiral carbon atom of asymmetric
carbon atom and is therefore optically active.
O O
|| ||
29. (B) R ¾ C ¾ OH + H ¾ O ¾ R ' ¾®¾ R C ¾ OR '+H 2O
Oxygen of alcohol is retained.
30. (C) Dissociation constant of alcohols are much less than the dissociation constant of water.
This clearly indicates that alcohols are weaker than even water.
31. (D) COOR group is m-directing, which is deactivating because it decreases the electron
density and deactivates the benzene ring.
32. (B) The – I effect of F is greater than that of Cl and therefore fluoroacetate ion is more
stabilised to show more tendency to lose proton by its acid.
33. (A) Formate ion shows resonance and gives rise to identical bond lengths.
H ¾ C ¾ O - « H ¾ C == O
|| |
O O-
34. (D) The higher boiling points of carboxylic acids are due to greater hydrogen bonding.
The two molecules of carboxylic acid are held together by two hydrogen bonds and thus
exist as dimer.
35. (C) Chlorine has – I effect. This increases the ionisation of chloroacetic acid and stabilises
the chloroacetate ion by dispersal of negative charge. In acetic acid, methyl groups due
to + I effect destabilises the acetate ion by intensification of negative charge. Hence,
chloroacetic acid dissociates to a greater extent than acetic acid.
36. (B) The carboxyl group (¾COOH) is a deactivating group as this group is an electron
withdrawing group and therefore deactivates the benzene ring towards electrophilic
attack. Therefore, benzoic acid does not give Friedel Craft’s reaction.
37. (B) As carboxylic acids are resonance stabilised, they do not contain true carbonyl group as
is present in carbonyl compounds.

.. +
R––C––..
O––H R––C=..
O––H
38. (C) Formic acid is stronger acid than acetic acid.
H ¾ C ¾ OH w H ¾ C ¾ O - + H +
|| ||
O O
350 Elementary Organic Chemistry for Medical

CH 3 ¾ C ¾ OHy CH 3 ¾ C ¾ O - + H +
|| ||
O O
Presence of CH 3 group in acetate ion shows + I effect and thereby increasing negative
charge on O - of acetate ion than formate ion or acetate ion is destabilised. Thus
formate ion is more stable than acetate ion or HCOOH loses proton more easily than
CH 3 COOH.
39. (B) The Hell Volhard Zelinsky (HVZ) reaction shows halogen substitution at a-carbon
atom. HCOOH has no such a -carbon atom and thus does not undergo HVZ reaction.
40. (C) More branched carboxylic acids are less acidic than unbranched acids. The +I effect of
alkyl groups in branched one increases the magnitude of negative group. Thus, COO -
group is shielded from solvent molecules and cannot be stabilised by solvation as
effectively as in unbranched carboxylic acids.
41. (C) RCOOH dissolves in water due to hydrogen bonding between H-atom of ¾COOH
group and O–atom of water. As alkyl portion R-is non-polar and lyophobic, this effect
predominates as-R gets larger (over five carbon atoms).
42. (A) Acetic acid typically undergoes dimeric intermolecular hydrogen bonding. It exists as a
dimer even in the vapour state. Therefore, its molecular mass comes out to be double
than the actual molecular mass of acetic acid (molecular mass=60).
43. (C) It is known that esters with a-hydrogens form carbanion when treated with base, it
brings about nucleophilic acyl substitution at the carbonyl group of the other molecule
of the ester to yield b-keto ester.
44. (B) RCOCl, ( RCOO) 2 O and RCOOR . All add two molecules of Grignard reagent to give
tert-alcohols.
64. (B) Due to presence of a -H acetophenone show aldol condensation.
CH3
H
C=O+ CH-C
H
O