26

ALDEHYDES, KETONES AND

CARBOXYLIC ACIDS

FACT / DEFINITION TYPE QUESTIONS 8. Which of the following is correct for carbonyl compounds?
R R + –
– +
1. Choose the correct IUPAC name for (a) C=O (b) C=O
CH3 C H CHO R R
| + –
(c) (d) + –
CH2 CH 3 R–C=O R–C=O
(a) Butan - 2- aldehyde
(b) 2- methylbutanal R R
(c) 3- methylisobutyraldehyde 9. Which of the following contain an aldehyde?
(d) 2- ethylpropanal (a) Vanilla beans (b) Meadow sweet
2. The IUPAC name of the compound having the molecular (c) Cinnamon (d) All of these
formula Cl3C –CH2CHO is 10. Which of the following have pleasant smell?
(a) 3, 3, 3- trichloropropanal (a) Methanal (b) Propanal
(b) 1, 1, 1- trichloropropanal (c) Ethanal (d) Hexanal
(c) 2, 2, 2- trichloropropanal 11. Which one of the following can be oxidised to the
(d) Chloral corresponding carbonyl compound?
3. The IUPAC name of CH3COCH(CH3)2 is (a) 2-hydroxy-propane
(a) 2-methyl-3-butanone (b) 4-methylisopropyl ketone (b) Ortho-nitrophenol
(c) 3-methyl-2-butanone (d) Isopropylmethyl ketone (c) Phenol
4. IUPAC name of following will be (d) 2-methyl-2 hydroxy-propane
CHO 12. Which one of the following on oxidation gives a ketone ?
(a) Primary alcohol (b) Secondary alcohol
CH3 (c) Tertiary alcohol (d) All of these
13. What is formed when a primary alcohol undergoes catalytic
dehydrogenation ?
(a) Aldehyde (b) Ketone
(c) Alkene (d) Acid
OH 14. Primary and secondary alcohols on action of reduced copper
(a) 4-formyl 3-methyl 1-hydroxy benzene give
(b) 4-formyl 3-methyl phenol (a) Aldehydes and ketones respectively
(c) 4-hydroxy 2-methyl benzaldehyde (b) Ketones and aldehydes respectively
(d) 4-hydroxy 2-methyl carbaldehyde (c) Only aldehydes
5. IUPAC name of ethyl isopropyl ketone is (d) Only ketones
(a) 4-methyl pent-3-one (b) 2-methyl pent-3-one 15. Which alkene on ozonolysis gives CH3 CH2CHO and
(c) 4-methyl pent-2-one (d) 2-methyl pent-2-one CH3CCH3
6. In > C = O group sigma bond is formed by ||
(a) sp2-p-overlapping (b) sp3-p-overlapping
O
CH3
(c) sp-p-overlapping (d) s-p-overlapping (a) CH3CH2CH = C (b) CH3CH2CH = CHCH2CH3
7. The -bond in carbonyl group is formed by CH3
(a) s-s-overlapping (b) p-p-overlapping (c) CH3CH2CH = CH CH3 (d) CH 3 C CHCH 3
(c) s-p-overlapping (d) p-d-overlapping |
CH3
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442 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
16. The catalyst used in Rosenmund's reduction is 24. Find out B in the given reactions
(a) HgSO4 (b) Pd/BaSO4
(c) anhydrous AlCl3 (d) anhydrous ZnCl2 AlCl3 CrO3 in (CH3CO)2O
+ CH3 – X A B
+
SnCl 2 / HCl H3O
17. C 6 H 5C N + [H] C 6 H 5CHO + NH 3 .
(a) acetophenone
The above reaction is
(b) benzaldehyde
(a) Mendius reaction (b) Sandorn's reaction
(c) cyclohexyl carbaldehyde
(c) Rosenmund's reaction (d) Stephen’s reaction (d) benzoic acid
18. Benzaldehyde can be prepared by oxidation of toluene by 25. The reaction
(a) Acidic KMnO4 (b) K2Cr2O7 / H+
CHO
(c) CrO2Cl2 (d) All of these AlCl3
19. The oxidation of toluene to benzaldehyde by chromyl + CO + HCl
chloride is called
(a) Rosenmund reaction (b) Wurtz reaction (a) Rosenmund’s reaction (b) Stephen’s reaction
(c) Etard reaction (d) Fittig reaction (c) Cannizzaro’s reaction (d) Gatterman-Koch reaction
20. An aldehyde group can be present 26. Which aldehyde cannot be obtained by Rosenmund’s
(a) in between carbon chain reaction?
(b) at any position in carbon atom (a) CH3CHO (b) HCHO
(c) only at the end of carbon chain (c) CH3CH2CHO (d) All of these
(d) at the second carbon atom of the carbon chain 27. The conversion PhCN PhCOCH 3 , can be achieved
21. Benzaldehyde is obtained from Rosenmund’s reduction of most conveniently by reaction with
(a) CH3MgBr followed by hydrolysis
O O
(b) I2 – NaOH, CH3I
(c) Dil. H2SO4 followed by reaction with CH2N2
(a) CH3 (b) X (d) LiAlH4 followed by reaction with CH3I
28. Which of the following is used to prepare ketone from acyl
chloride ?
(a) R-MgX (b) R2Cd
O (c) CO + HCl (d) CrO3
Cl 29. Which of the following forces explain the boiling point of
aldehydes and ketones?
(c) (d) OH (a) Hydrogen bonding (b) van der Waal’s forces
Cl
(c) Dipole-dipole attraction(d) None of these
30. Which is highly soluble in water?
22. Which of the following is not used in the preparation of (a) Methanal (b) Propanal
ketone? (c) Propanone (d) Butanone
(a) Oxidation of secondary alcohols 31. Propanal and propanone, both have same molecular
(b) Dehydrogenation of 2° alcohol formula(C3H6O), what do you expect about their boiling
(c) Pyrolysis of calcium acetate points?
(d) Acid hydrolysis of alkyl cyanide (a) Both have same boiling point
23. Product of the following reaction is (b) Boiling point of propanal is higher than the boiling
CN point of propanone.
(c) Boiling point of propanal is lower than the boiling point
SnCl 2 + HCl
+ 2(H) ? of propanone
+
H3O (d) Nothing can be predicted
32. Less reactivity of ketone is due to
COOH CHO (a) + I inductive effect decrease positive charge on
carbonyl carbon atom
(a) (b) (b) steric effect of two bulky alkyl groups
(c) sp2 hybridised carbon atom of carbonyl carbon atom
(d) Both (a) and (b)
O 33. Acetaldehyde reacts with
NH2
(a) Electrophiles only
C–CH3 (b) Nucleophiles only
(c) (d) (c) Free radicals only
(d) Both electrophiles and nucleophiles
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 443
34. Carbonyl compounds undergo nucleophilic addition (a) Cu (b) CuO
because of (c) Cu2O (d) Cu(OH)2
(a) electronegativity difference of carbon and oxygen 45. Aldol condensation would not occur in :
atoms (a) CH3COCH3 (b) CH3CH2CHO
(b) electromeric effect (c) HCHO (d) CH3CHO
(c) more stable anion with negative charge on oxygen 46. Cannizzaro reaction occurs with
atom and less stable carbonium ion
(a) CH 3 CH 2 OH (b) C 6 H 5 CHO
(d) None of the above
35. Which of the following statement is false ? (c) CH 3 CHO (d) CH 3 CO CH 3
(a) Cannizzaro reaction is given by aldehydes in presence 47. Which of the following compound will show positive silver
of alkali mirror test ?
(b) Aldol condensation is given by aldehydes in presence
(a) HCOOH (b) CH 3 (CHOH ) 3 CHO
of alkali
(c) Aldol condensation is given by aldehydes and ketones (c) CH 3CO(CHOH )CH 3 (d) Both (a) and (b)
in presence of acids 48. Aldehydes and ketones are distinguished by which of the
(d) None of the above following test ?
36. If formaldehyde and KOH are heated, then we get (a) Lucas test
(a) methane (b) methyl alcohol (b) Tollen’s test
(c) ethyl formate (d) acetylene (c) KMnO4 solution (Baeyer’s test)
37. The reagent which can be used to distinguish acetophenone (d) None of these
from benzophenone is 49. Aldehydes and ketones are generally reduced by :
(a) 2,4- dinitrophenylhydrazine
(a) Clemmensen reduction (b) H2S
(b) aqueous solution of NaHSO3
(c) H2/Ni (d) None of these
(c) benedict reagent
50. In which reaction, > C = O can be reduced to > CH2?
(d) I2and Na2CO3
(a) Wolf-Kishner reaction (b) Reimer-Tiemann reaction
38. Benzaldehyde reacts with ethanoic KCN to give
(c) Wurtz reaction (d) None of these
(a) C6H5CHOHCN (b) C6H5CHOHCOC6H5
51. A compound does not react with 2, 4-dinitrophenylhydrazine,
(c) C6H5CHOHCOOH (d) C6H5CHOHCHOHC6H5
the compound is :
39. Acetone reacts with iodine (I2) to form iodoform in the
(a) Acetone (b) Acetaldehdye
presence of
(c) CH3OH (d) CH3CH2COCH3
(a) CaCO3 (b) NaOH
52. Which gives lactic acid on hydrolysis after reacting with
(c) KOH (d) MgCO3
HCN ?
40. (CH3)3C–CHO does not undergo aldol condensation due
(a) HCHO (b) CH3CHO
to
(a) three electron donating methyl groups (c) C6H5CHO (d) CH3COCH3
(b) cleavage taking place between —C— CHO bond 53. The most appropriate reagent to distinguish between
(c) absence of alpha hydrogen atom in the molecule acetaldehyde and formaldehyde is :
(d) bulky (CH3)3C—group (a) Fehling’s solution
41. Acetaldehyde reacts with semicarbazide and forms (b) Tollen’s reagent
semicarbazone. Its structure is (c) Schiff’s reagent
(a) CH3CH = NNHCON = CHCH3 (d) Iodine in presence of base
(b) CH3CH = NNHCONH2 54. Aldehydes can be oxidised by :
(a) Tollen’s reagent (b) Fehling solution
(c) CH 3 CH N — N — CONH 2
| (c) Benedict solution (d) All the above
OH 55. 2-pentanone and 3-pentanone can be distinguished by :
(d) CH3CH = N—CONHNH2 (a) Cannizaro's reaction (b) Aldol condensation
42. Iodoform test is not given by (c) Iodoform reaction (d) Clemmensen's reduction
(a) 2-Pentanone (b) Ethanol 56. Cross aldol condensation occurs between
(c) Ethanal (d) 3-Pentanone (a) two same aldehydes
43. Phenylmethyl ketone can be converted into ethylbenzene (b) two same ketones
in one step by which of the following reagents? (c) two different aldehydes and ketones
(a) LiAlH4 (b) Zn-Hg/HCl (d) None of these
(c) NaBH4 (d) CH3MgI 57. Ketone upon treatment with Grignard Reagent gives
44. When acetaldehyde is heated with Fehling’s solution it gives (a) primary alcohol (b) secondary alcohol
a precipitate of (c) tertiary alcohol (d) aldehyde
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444 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
58. When acetaldehyde reacts with alcohol then produce 67. Schiff’s reagent gives pink colour with
(a) Acetal (b) Ketal (a) acetaldehyde (b) acetone
(c) Acetone (d) None (c) acetic acid (d) methyl acetate
59. The product formed in Aldol condensation is 68. Benzophenone can be converted into benzene by using
(a) a beta-hydroxy aldehyde or a beta-hydroxy ketone (a) fused alkali
(b) an alpha-hydroxy aldehyde or ketone (b) anhydrous AlCl3
(c) an alpha, beta unsaturated ester (c) sodium amalgam in water
(d) a beta-hydroxy acid (d) acidified dichromate
60. Clemmensen reduction of a ketone is carried out in the 69. In the reaction of NaHSO3 with carbonyl compounds to
presence of which of the following ? form bisulphite product, the nucleophile is
(a) Glycol with KOH (b) Zn-Hg with HCl (a) HSO3– (b) SO3Na
(c) LiAlH4 (d) H2 and Pt as catalyst (c) SO3– – (d) None of the above
61. Which of the following products is formed when 70. Wolf-Kishner reduction is
benzaldehyde is treated with CH3MgBr and the addition (a) reduction of carbonyl compound into alcohol
product so obtained is subjected to acid hydrolysis ? (b) reduction of carbonyl compound into alkene
(a) A secondary alcohol (b) A primary alcohol (c) reduction of carboxyl compound into alkane
(c) Phenol (d) tert-Butyl alcohol (d) reduction of nitro compound into aniline
62. During reduction of aldehydes with hydrazine and 71. Tollen’s reagent is
potassium hydroxide, the first step is the formation of (a) ammonical CuSO4
(a) R — CH — — N — NH 2 (b) R — C N (b) ammonical AgNO3
(c) R — C— NH (d) R — CH — — NH (c) alkaline solution containing complex of copper nitrate
2
|| (d) none of these
O R OR
63. A and B in the following reactions are
72. Compound of general formula C are called
OH
HCN B
R–C–R' A R– C H OR
KCN
R' CH2NH2 (a) diester (b ) acid anhydride
O
(c) hemiacetal (d) acetal
CN 73. Imine derivatives of aldehyde and ketone is called as
(a) A = RR'C , B = LiAlH4 (a) Schiff’s reagent (b) Fehling’s reagent
OH
(c) Schiff’s base (d) Schiff’s acid
OH 74. Which reaction is used for detecting the presence of
(b) A = RR'C , B = NH3 carbonyl group?
COOH (a) Reaction with hydrazine
CN (b) Reaction with phenyl hydrazine
(c) A = RR'C , B H 3O (c) Reaction with hydroxylamine
OH (d) All of the above
(d) A = RR'CH2CN, B = NaOH 75. The difference between aldol condensation and
64. The product obtained by the reaction of an aldehyde and Cannizzaro’s reaction is that:
hydroxylamine is (a) the former takes place in the presence of -H-atom.
(a) hydrazone (b) aldoxime (b) the former takes place in the absence of -H-atom.
(c) primary amine (d) alcohol (c) the former takes place in the presence of -H-atom.
65. Which one gives positive iodoform test ? (d) none of the above
(a) (CH 3 ) 2 CHCH 2 OH X
76. C6H5CH=CHCHO C6H5CH=CHCH2OH
(b) C 6 H 5 OH In the above sequence X can be :
H (a) H2/Ni (b) NaBH4
(c) K2Cr2O7/H + (d) Both (a) and (b)
|
(c) CH 3 CH 2 C CH 2 CH 3 77. Which of the following pairs of compounds will undergo
| aldol and Cannizzaro reaction respectively ?
OH
(i) acetone; benzaldehyde
(d) CH 3CH 2 OH (ii) acetaldehyde; butan–2–one
66. The compound that neither forms semicarbazone nor oxime (iii) propanone; formaldehyde.
is (iv) cyclopentanone, benzaldehyde
(a) HCHO (b) CH3COCH2Cl (a) (i), (ii) and (iii) (b) (ii) and (iii)
(c) CH3CHO (d) CH3CONHCH3 (c) (ii), (iii) and (iv) (d) (iii) and (iv)
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 445
78. Two compounds benzyl alcohol and benzoic acid are formed 88. In the given reaction
from this compound, when this compound is heated in the CH3 CHO
presence of conc.NaOH, this compound is. Cl2/h H2O
(a) Benzaldehyde (b) Benzylalcohol A
373K
(c) Acetophenone (d) Benzophenone
79. The reagent which does not react with both, acetone and A is
benzaldehyde.
CH2Cl CHCl2
(a) Sodium hydrogensulphite
(b) Phenyl hydrazine (a) (b)
(c) Fehling’s solution
(d) Grignard reagent CCl3 CH3
80. Which of the following compounds will give butanone on (c) (d)
oxidation with alkaline KMnO4 solution? Cl
(a) Butan-1-ol (b) Butan-2-ol
89. R HCl gas R O CH2
(c) Both of these (d) None of these
C = O +A C + H2O
81. Which of the following compounds is most reactive towards R dil HCl R O CH2
nucleophilic addition reactions?
A is
O O
|| || (a) CH3OH (b) CH3COOH
(a) CH3 – C– H (b) CH3 – C– CH3 CH 2COOH CH 2OH
O O (c) (d)
(c) C–H (d) C–CH3 CH 2COOH CH2OH
90. In the reaction
82. Which of the following does not represent the natural source
CHO
of the corresponding acids ?
(a) Formic acid : Red ant HNO3 /H 2SO4
(b) Acetic acid : Vinegar A
273 283K
(c) Butyric acid : Rancid butter
(d) Isobutyric acid : Automobile exhausts Benzaldehyde
83. Vinegar is a solution of acetic acid which is : A is
(a) 15 – 20% (b) 20 –25%
CHO
(c) 6 – 8% (d) 2 – 4%
CHO
84. Methyl cyanide can be converted into acetic acid by one of
the following reactions. NO2
(a) (b)
(a) Reduction (b) Hydrolysis
(c) Electrolysis (d) Decarboxylation NO2
85. Toluene can be oxidised to benzoic acid by
(a) KMnO4 (alk.) (b) K2Cr2O7 (alk.) CHO
(c) Both (a) and (b) (d) Neither (a) nor (b)
86. Which of the following does the best represent the structure
(c) (d) Both (a) and (b)
of the carboxylate ion ?
– – NO2
O O 91. Which of the following can not be oxidised to give carboxylic
(a) R–C (b) R – C acid?
O+ O– CH2CH2CH3
CH3
+
(a) (b)
O
(c) R–C (d) None of these
CH3
O+ CH3
HC CH3 C CH3
87. Select the acid(s) which cannot be prepared by Grignard CH3
reagent.
(c) (d)
(a) Acetic acid (b) Succinic acid
(c) Formic acid (d) All of the above
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446 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
92. Lower carboxylic acids are soluble in water due to 100. Which of the following acids has the smallest dissociation
(a) low molecular weight (b) hydrogen bonding constant ?
(c) dissociation into ions (d) easy hydrolysis (a) CH3CHFCOOH (b) FCH2CH2COOH
93. Dimerisation of carboxylic acids is due to (c) BrCH2CH2COOH (d) CH3CHBrCOOH
(a) ionic bond 101. Which one of the following esters is obtained by the
(b) covalent bond esterification of propan-2-ol with ethanoic acid ?
(c) coordinate bond (a) (CH3)2CHCOOCH3 (b) CH3COOCH2CH3
(d) intermolecular hydrogen bond (c) CH3COOCH(CH3)2 (d) (CH3)2CHCOOCH2CH3
94. Boiling points of carboxylic acids are 102. The major product of nitration of benzoic acid is
(a) lower than corresponding alcohols (a) 3- Nitrobenzoic acid (b) 4- Nitrobenzoic acid
(b) higher than corresponding alcohols (c) 2- Nitrobenzoic acid (d) 2, 4- dinitrobenzoic acid
(c) equal to that of corresponding alcohols
103. Among the following acids which has the lowest pK a
(d) None of the above
95. MgBr value?
(a) CH 3 CH 2 COOH (b) (CH3 ) 2 CH COOH
(c) HCOOH (d) CH 3COOH
( i ) CO 2
P 104. The correct order of increasing acidic strength is
( ii ) H 3O __________
(a) Phenol < Ethanol < Chloroacetic acid < Acetic acid
In the above reaction product 'P' is
(b) Ethanol < Phenol < Chloroacetic acid < Acetic acid
CHO COOH
(c) Ethanol < Phenol < Acetic acid < Chloroacetic acid
(d) Chloroacetic acid < Acetic acid < Phenol < Ethanol
(a) (b) 105. Which reagent can convert acetic acid into ethanol ?
(a) Na + alcohol (b) LiAIH4 + ether
(c) H2 + Pt (d) Sn + HCl
OH 106. Which is false in case of carboxylic acids?
O (a) They are polar molecules
||
(c) (d) C 6 H 5 C C6H5 (b) They form H-bonds
(c) They are stronger than mineral acids
(d) They have higher b.p. than corresponding alcohols
96. In the anion HCOO– the two carbon-oxygen bonds are found 107. The elimination of CO2 from a carboxylic acid is known as
to be of equal length. What is the reason for it? (a) hydration (b) dehydration
(a) Electronic orbitals of carbon atom are hybridised (c) decarboxylation (d) carboxylation
(b) The C=O bond is weaker than the C–C bond 108. The reaction of carboxylic acid gives effervescences of
(c) The anion HCOO– has two reasonating structures CO2 with NaHCO3. The CO2 comes from.
(d) The anion is obtained by removal of a proton from the (a) R – COOH (b) NaHCO3
acid molecule (c) Both (a) and (b) (d) None of these
97. Carboxylic acids are more acidic than phenol and alcohol 109. Acetic anhydride is obtained by the reaction of
because of
(a) sodium and acetic acid
(a) intermolecular hydrogen bonding
(b) ammonia and acetic acid
(b) formation of dimers
(c) ethanol and acetic acid
(c) highly acidic hydrogen
(d) P2O5 and acetic acid
(d) resonance stabilization of their conjugate base
110. Benzoic acid may be converted to ethyl benzoate by reaction
98. Which of the following has the maximum acidic strength ?
with
(a) o- nitrobenzoic acid (b) m-nitrobenzoic acid
(a) sodium ethoxide (b) ethyl chloride
(c) p-nitrobenzoic acid (d) p-nitrophenol
(c) dry HCl—C2H5OH (d) ethanol
99. Which of the following is the weakest acid ?
111. Propionic acid with Br2 /P yields a dibromo product. Its
OH
structure would be:
Br
(a) (b) CH3COOH |
(a) H– C – CH2COOH (b) CH2Br – CH2 – COBr
COOH |
Br
Br
|
(c) HCOOH (d) (c) CH3– C – COOH (d) CH2 Br – CHBr – COOH
|
Br
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 447
112. The product obtained when acetic acid is treated with 119. The strongest acid among the following is –
phosphorus trichloride is (a) Salicylic acid (b) m-hydroxybenzoic acid
(a) CH3COOPCl3 (b) ClCH2COCl (c) p-hydroxybenzoic acid (d) Benzoic acid
(c) CH3COCl (d) ClCH2COOH 120. Among the following, the most acidic is :
113. The reaction (a) CH3COOH (b) ClCH2COOH
RCH 2 CH 2 COOH
Red P
R CH 2 CH COOH
(c) Cl2CHCOOH (d) Cl2CHCH2COOH
Br2 | 121. Which of the following is the correct decreasing order of
Br
acidic strength of
is called as
(i) Methanoic acid (ii) Ethanoic acid
(a) Reimer- Tiemann reaction
(iii) Propanoic acid (iv) Butanoic acid
(b) Hell-Volhard Zelinsky reaction
(a) (i) > (ii) > (iii) > (iv) (b) (ii) > (iii) > (iv) > (i)
(c) Cannizzaro reaction
(c) (i) > (iv) > (iii) > (ii) (d) (iv) > (i) > (iii) > (ii)
(d) Sandmeyer reaction
122. Among the following the strongest acid is
114. Benzoic acid reacts with conc. HNO3 and H2SO4 to give :
(a) CH 3COOH (b) CH 2 ClCH 2COOH
(a) 3-Nitrobenzoic acid
(b) 4-Benzene sulphonic acid (c) CH 2 ClCOOH (d) CH3CH 2COOH
(c) 4-Nitrobenzoic acid 123. Arrange the following carboxylic acid in their decreasing
(d) 2-Nitrobenzoic acid acidity.
115. In the following reaction
1. COOH Oxalic acid
Br2 / P excess NH 3
RCH 2 COOH X Y
COOH
The major compounds X and Y are
2. HOOC – CH2 – COOH Malonic acid
(a) RCHBrCONH2 ; RCH(NH2)COOH
(b) RCHBrCOOH ; RCH(NH2)COOH 3. CH2– COOH Succinic acid
(c) RCH2COBr ; RCH2COONH4
(d) RCHBrCOOH ; RCH2CONH2 CH2– COOH
116. The yield of ester in esterification can be increased by (a) 3 > 2 > 1 (b) 1 > 2 > 3
CH3CH2OH + CH3COOH CH3COOCH2CH3 + H2O (c) 2 > 3 > 1 (d) 2 > 1 > 3
(a) removing water
(b) taking ethanol in excess STATEMENT TYPE QUESTIONS
(c) taking acetic acid in excess 124. Read the following statements and choose the correct option
(d) all the above factors (i) The carbonyl carbon atom is sp2 -hybridised
117. A carboxylic acid can best be converted into acid chloride (ii) The carbonyl carbon is an electrophilic (Lewis acid)
by using centre
(a) PCl5 (b) SOCl2 (iii) The carbonyl oxygen is a nucleophilic (Lewis base)
(c) HCl (d) ClCOCOCl centre
118. Arrange the following four acids in their decreasing order (iv) Carbonyl compounds are non- polar in nature.
of acidity (a) (i), (ii) and (iv) are correct
COOH COOH (b) (i), (ii) and (iii) are correct
CH3 (c) (ii), (iii) and (iv) are correct
(d) (ii) and (iv) are correct
125. Which of the following statement(s) is/are true regarding
preparation of aldehydes and ketones?
I II
(i) Both can be prepared by the oxidation of the concerned
COOH COOH alcohol with copper at about 250ºC.
CMe3 H3C CH3 (ii) Both can be prepared by the oxidation of the concerned
alcohol by Oppenauer oxidation.
(iii) Both can be prepared by the oxidation of respective
alcohol with acidic dichromate.
III IV
(a) (i) only (b) (ii) and (iii)
(a) I > II > III > IV (b) IV > III > II > I (c) (i) and (iii) (d) All the three
(c) II > IV > III > I (d) III > IV > II > I
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448 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
126. Which of the following statements are false? (i) It is carried out in presence of a strong acid which acts
(i) No aldehyde can be prepared by the oxidation of as a catalyst.
primary alcohol with acidic KMnO4. (ii) The strong acid makes the carbonyl carbon more
(ii) Aldehydes having a boiling point less than 100°C can electrophilic, and hence causes the alcohol, a strong
be prepared by the oxidation of primary alcohol with nucleophile to attack on the carbonyl carbon.
acidic dichromate. (iii) The strong acid makes the carbonyl group more
(iii) Secondary alcohols on oxidation with PCC in electrophilic which is thus attacked easily by an
dichloromethane give carboxylic acids having lesser alcohol, a weak nucleophile.
number of carbon atoms (iv) Esterification can be done even in absence of a strong
(iv) Tertiary alcohols can't be oxidised at all acid.
(a) (ii) and (iii) (b) (ii), (iii) and (iv) (a) (i) and (ii) (b) (i) and (iii)
(c) (i), (iii) and (iv) (d) (i), (ii) and (iii) (c) (i) only (d) (iv) only
127. Read the following statements and choose the correct option
(i) The boiling points of aldehydes and ketones are lower MATCHING TYPE QUESTIONS
than those of alcohols of similar molecular masses
131. Match the columns
(ii) Alcohols show intermolecular hydrogen bonding
Column-I Column-II
whereas aldehydes and ketones do not show
(Common names) (IUPAC names)
intermolecular hydrogen bonding.
(A) Cinnamaldehyde (p) Pentanal
(iii) The lower members of aldehydes and ketones are
(B) Acetophenone (q) Prop-2-enal
miscible with water in all proportions, because they
form hydrogen bond with water. (C) Valeraldehyde (r) 4-Methylpent-3-en-2-one
(iv) The solubility of aldehydes and ketones increases (D) Acrolein (s) 3-Phenylprop-2-enal
rapidly on increasing the length of alkyl chain (E) Mesityl oxide (t) 1-Phenylethanone
(a) TTFF (b) TFFT (a) A – (s), B – (t), C – (p), D – (q), E – (r)
(c) FTTT (d) TTTF (b) A – (p), B – (q), C – (s), D – (t), E – (r)
128. Aldehydes are generally more reactive than ketones in (c) A – (t), B – (s), C – (p), D – (r), E – (q)
nucleophilic addition reactions. Which of the following (d) A – (q), B – (t), C – (r), D – (s), E – (p)
statements accounts for this ? 132. Match the columns
(i) Sterically, the presence of two relatively large Column-I Column-II
substituents in ketones hinders the approach of (A) R CO CH 3 Zn Hg / HCl (p) Friedel-Craft’s
nucleophile to carbonyl carbon reaction
(ii) Aldehydes show resonance whereas ketones do not R CH 2 CH 3
(iii) Electronically, the presence of two alkyl groups reduce (B) 2C6 H5 CHO NaOH
(q) Kolbe’s reaction
the electrophilicity of the carbonyl carbon more
C6 H5 COONa C6 H5 CH 2 OH
effectively.
(iv) Electronically carbonyl carbon atom in ketones is more (C) C6 H 6 CH 3 COCl
Anhyd.
(r) Clemmensen’s
electrophilic than in aldehydes AlCl3
reaction
(a) (i) and (iii) (b) (i) and (iv) C6 H5 COCH3
(c) (ii) and (iii) (d) (ii) and (iv)
(D) C 6 H 5 OH CO 2 NaOH (s) Cannizzaro’s
OH
129. 2C6 H5CHO C6 H5CH 2OH C6 H5COO HOC6 H 4COONa reaction
H 2O
Which of the following statements are correct regarding (a) A – (p), B – (q), C – (r), D – (s)
the above reduction of benzaldehyde to benzyl alcohol? (b) A – (q), B – (p), C – (r), D – (s)
(i) One hydrogen is coming from H2O as H+ and another (c) A – (r), B – (s), C – (p), D – (q)
from C6H5CHO as H– (d) A – (s), B – (r), C – (p), D – (q)
(ii) One hydrogen is coming from H2O as H– and another 133. Match the columns
from C6H5CHO as H+ Column-I Column-II
(iii) One hydrogen from H2O and another from C6H5CHO, (A) Etard reaction (p) Alcoholic KOH
both in the form of H– (B) Hydroxylation (q) Anhydrous AlCl3
(iv) The reduction is an example of disproportionation (C) Dehydrohalogenation (r) Chromyl chloride
reaction (D) Friedel-Crafts reaction (s) Dilute alkaline KMnO4
(a) (i), (ii) and (iii) (b) (i) and (iv) (a) A – (p), B – (q), C – (r), D – (q)
(c) (ii), (iii) and (iv) (d) (iii) and (iv) (b) A – (s), B – (r), C – (p), D – (q)
130. Which of the following statement(s) is/are true regarding (c) A – (r), B – (s), C – (p), D – (q)
esterification of a carboxylic acid with an alcohol ? (d) A – (q), B – (p), C – (s), D – (r)
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 449
134. Match the columns 137. Match the columns
Column-I Column-II Column-I Column-II
(Reactions) (Reagents) COOH
(A) Benzophenone (p) LiAlH4 (A) CH2 (p) Glutaric acid
Diphenylmethane COOH
(B) Benzaldehyde (q) DIBAL–H
CH2 COOH
1-Phenylethanol
(B) (q) Adipic acid
(C) Cyclohexanone (r) Zn(Hg)/Conc HCl CH2 COOH
Cyclohexanol
(D) Phenyl benzoate (s) CH3MgBr (C) CH2 COOH (r) Succinic acid
Benzaldehyde
CH2
(a) A – (p), B – (s), C – (r), D – (q)
(b) A – (q), B – (s), C – (p), D – (r) CH2 COOH
(c) A – (s), B – (r), C – (q), D – (p)
(d) A – (r), B – (s), C – (p), D – (q) (D) CH2 COOH (s) Malonic acid
135. Match the columns
Column-I Column-II CH2

R CH2
(A) C = NH (p) Oxime
R
CH2 COOH
R
(B) C = NOH (q) Semicarbazone (a) A – (q), B – (p), C – (s), D – (r)
R (b) A – (r), B – (p), C – (s), D – (q)
R (c) A – (s), B – (r), C – (p), D – (q)
(C) C = N – NH2 (r) Imine (d) A – (r), B – (q), C – (s), D – (p)
R
ASSERTION-REASON TYPE QUESTIONS
O
R Directions : Each of these questions contain two statements,
(D) C = N – NH – C – NH 2 (s) Hydrazone Assertion and Reason. Each of these questions also has four
R
alternative choices, only one of which is the correct answer. You
(a) A – (q), B – (s), C – (p), D – (r) have to select one of the codes (a), (b), (c) and (d) given below.
(b) A – (r), B – (p), C– (s), D– (q) (a) Assertion is correct, reason is correct; reason is a correct
(c) A – (r), B – (s), C – (p), D– (q) explanation for assertion.
(d) A – (s), B – (r), C – (q), D– (p) (b) Assertion is correct, reason is correct; reason is not a
136. Match the acids given in Column-I with their correct IUPAC correct explanation for assertion
names given in Column-II. (c) Assertion is correct, reason is incorrect
Column-I Column-II (d) Assertion is incorrect, reason is correct.
(Acids) (IUPAC names) 138. Assertion : The boiling points of aldehydes and ketones
are higher than hydrocarbons and ethers of comparable
(A) Phthalic acid (p) Hexane-1, 6-dioic acid
molecular masses.
(B) Oxalic acid (q) Benzene-1, 2-dicarboxylic acid Reason : There is a weak molecular association in aldehydes
(C) Succinic acid (r) Pentane-1, 5-dioic acid and ketones arising out of the dipole-dipole interactions.
(D) Adipic acid (s) Butane-1, 4-dioic acid 139. Assertion : Formaldehyde is a planar molecule.
(E) Glutaric acid (t) Ethane-1, 2-dioic acid Reason : It contains sp2 hybridised carbon atom.
(a) A – (t), B – (q), C – (r), D – (p), E – (s) 140. Assertion : Compounds containing –CHO group are easily
(b) A – (p), B – (s), C – (t), D – (q), E – (r) oxidised to corresponding carboxylic acids.
(c) A – (q), B – (t), C – (s), D – (p), E – (r) Reason : Carboxylic acids can be reduced to alcohols by
(d) A – (r), B – (t), C – (p), D – (s), E – (q) treatment with LiAlH4.
 EBD_7207
450 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
141. Assertion : The molecular mass of acetic acid in benzene is O
120 instead of 60.
Reason : The carboxylic acids exist as cyclic dimers in which
the two molecules of the acid are held together by two (a) (b) OH
strong hydrogen bonds.
O
CRITICAL THINKING TYPE QUESTIONS
142. IUPAC name of the following compound is
(c) (d)
O
146. Which of the following reagent reacts in different ways
with CH3CHO, HCHO and C6H5CHO ?
H (a) Fehling solution (b) C6H5NHNH2
(c) Ammonia (d) HCl
147. A new carbon - carbon bond is formed in
(a) 2-(2-propenyl) butanal
(i) Aldol condensation (ii) Kolbe’s reaction
(b) 2-(1-propenyl) butanal
(iii) Reimer-Tiemann reaction
(c) 4-formyl 4-ethyl but-2-ene
(iv) Wurtz Fittig reaction
(d) 2-ethyl pent-3-en-l-al
(a) (i) and (iii) (b) (ii) and (iii)
143. Observe the following structures and pick up the correct
(c) (i), (ii) and (iiv) (d) All the four
statement.
148. Which of the following is an example of nucleophilic
+
C=O C = OH addition ?
I II O NNH 2
|| NH 2 NH 2 ,H ||
(a) Carbonyl carbon of I is more electrophilic than that (a) C 6 H 5 C CH 3 C 6 H 5 C CH 3
of II
(b) Carbonyl carbon of I is less electrophilic than that O OH
|| |
of II (b) C6 H 5 CCH 3
LiAlH 4
C6 H5CHCH 3
(c) Carbonyl carbon of both structures have equal
electrophilic character (c) Both (a) and (b)
(d) It depends upon the complete structure of the (d) None of the two
compound 149. Acetal formation is a reversible reaction
144. The boiling points of aldehydes and ketones lie in between R H
+
R OH R'OH, H +
alkanes and alcohols of comparable masses because C = O + R'OH C
(a) alkanes are polar H H OR'
(b) aldehydes and ketones are non-polar R OR'
C+ H2O
(c) alkanes are non-polar and aldehydes and ketones H OR'
Under what conditions, the reaction can be forced to proceed
contain polar C = O group and lower alcohols only in right (forward) direction ?
(a) Using excess of alcohol
have H-bonding. (b) Using high temperature
(d) alkanes are held together by weak van der Waal’s (c) Using dilute acid and excess of alcohol
forces (being non-polar), aldehydes and ketones (d) Using dry acid and excess of alcohol
150. In the crossed Cannizzaro reaction involving HCHO as one
of the components
contain polar C = O group and held together by (a) HCHO is always oxidised because of electronic effect
(b) HCHO is always oxidised because of steric effect
strong dipole-dipole attraction and lower alcohols (c) both of the above statements are true
have H-bonding, which is stronger than dipole-dipole (d) none of the above statement is true
attraction. 151. Which of the following acts as a nucleophile in the aldol
145. Product of the following reaction is condensation of ethanal?
CN MgX (i) OH– (ii) H2O
dry ether (iii) –CH2CHO
+
H3O
+ (a) Only (i) (b) (i) and (ii)
(c) (i) and (iii) (d) All the three
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 451
152. Which of the following acts as a nucleophile in the 161. Cannizaro’s reaction is not given by _____________
Cannizzaro reaction involving benzaldehyde ? CHO
–
(i) OH– (ii) C6H4CHO (a) (b) CHO
CH3
(iii) C6H5CH(OH)O– (iv) H2O
(c) HCHO (d) CH3CHO
(a) (i) and (iv) (b) (i) and (ii)
162. Benzophenone can be obtained by_____________.
(c) (i) and (iii) (d) Only (i)
(i) Benzoyl chloride + Benzene + AlCl3
153. Which of the following undergoes haloform reaction ? (ii) Benzoyl chloride + Diphenyl cadmium
(i) CH3CH2COCH2Cl (ii) C6H5COCH3 (iii) Benzoyl chloride + Phenyl magnesium chloride
(iii) C6H5COCHCl2 (iv) CH3CH2COCCl3 (iv) Benzene + Carbon monoxide + ZnCl2
(a) Only (ii) (b) (ii) and (iv) (a) (i), (ii) and (iii) (b) (ii) and (iii)
(c) (i), (ii) and (iv) (d) All the four (c) (iii) and (iv) (d) (i), (ii) and (iv)
154. When ethanal reacts with propanal in the presence of a 163. Which of the following conversions can be carried out by
base, the number of products formed is Clemmensen Reduction ?
(a) 2 (b) 3 (i) Benzaldehyde into benzyl alcohol
(c) 4 (d) 5 (ii) Cyclohexanone into cyclohexane
155. Aldehydes and ketones will not form crystalline derivatives (iii) Benzoyl chloride into benzaldehyde
with (iv) Benzophenone into diphenyl methane
(a) sodium bisulphite (a) (ii) and (iv) (b) (i) and (iv)
(b) phenylhydrazine (c) (i) and (iii) (d) (iii) and (iv)
(c) semicarbazide hydrochloride 164. Benzaldehyde is less reactive than propanal because
(d) dihydrogen sodium phosphate. (i) the carbon atom of the carbonyl group of benzaldehyde
is less electrophilic as in propanal.
156. Which of the following compound will undergo self aldol
(ii) the carbon atom of the carbonyl group of benzaldehyde
condensation in the presence of cold dilute alkali ?
is more electrophilic as in propanal.
(a) CH2 CH CHO (b) CH C CHO (iii) carbonyl group in benzaldehyde is more polar due to
(c) C 6 H 5 CHO (d) CH 3 CH 2 CHO . resonance
157. Which of the following is an example of aldol condensation? (iv) carbonyl group in benzaldehyde is less polar due to
resonance
CH 3
| (a) (i) and (iii) (b) (i) and (iv)
dil NaOH
(a) 2CH3COCH3 CH 3 C(OH)CH 2 COCH 3 (c) (i) only (d) (iv) only
165. Addition of hydrogen cyanide to aldehydes and ketones
dil NaOH
(b) 2HCHO CH3OH occurs in presence of a base.The role of base is to
dil NaOH
(i) catalyse the reaction
(c) C6H5CHO + HCHO C6H5CH2OH (ii) generate CN– ion
(d) None of the above (iii) slow down the reaction
158. Identify X, (iv) to stabilize the cyanohydrins
H3C (a) (i) and (iii) (b) (i) and (ii)
CH3MgI H 2O (c) (i) and (iv) (d) (ii) and (iv)
C=O Intermediate X
H3C dry ether 166. Addition of alcohols to aldehydes and ketones takes place
in presence of dry HCl gas because it
(a) CH3OH (b) Ethyl alcohol (i) Protonates the oxygen of the carbonyl compounds
(c) Methyl cyanide (d) tert-Butyl alcohol (ii) Increases the electrophilicity of the carbonyl carbon
159. An organic compound of formula, C3H6O forms phenyl (iii) Removes the excess moisture from the reaction
hydrazone, but gives negative Tollen’s test. The compound is (iv) Helps the reaction to move in the forward direction
(a) CH3CH2COCH3 (b) CH3CH2CHO (a) (i), (ii) and (iv) (b) (i), (ii), (iii) and (iv)
(c) CH3COCH3 (d) Both (a) and (c) (c) (ii) ,(iii), and (iv) (d) (i), (iii) and (iv)
167. When benzaldehyde and acetaldehyde undergoes reaction
R NH Hydrolysis
160. C = O HCN (A) 3
(B) (C) with the 2, 4–DNP ?
R (a) Benzaldehyde reacts slowly than acetaldehyde
Compound (C) in above reaction is (b) Acetaldehyde reacts slowly than benzaldehyde
(a) -hydroxy acid (b) -amino acid (c) Both reacts equally
(c) -amino alkanol (d) -amino -hydroxy acid (d) Both do not react with 2, 4-DNP
 EBD_7207
452 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
168. Suppose the reaction of compound containing ketone as Identify the product(s) formed in the given reaction.
functional group is carried in basic medium of NaOH. Which I II
of the following will one use to protect the unwanted (a) 2 molecules of benzoic acid 2 molecules of ethanoic acid
reaction due presence of carbonyl moiety.
(b) 2 molecules of benzoic acid 1 molecules of benzoic acid
(a) NaHSO3
and 1 molecule of ethanoic acid
(b) HCN
(c) ethylene glycol and HCl (c) 1 molecule of ethanoic acid 1 molecule of benzoic acid
(d) None of these (d) 1 molecule of benzoic acid 1 molecule of butanoic acid
169. A compound C5H10O forms orange–red precipitate upon 175. Ethanoic acid can’t be obtained by which of the following
reaction with 2,4–DNP, but does not give positive Tollen’s reaction ?
test and iodoform test. Possible compound is (i) KCN
(a) 2, 2–dimethylpropanal (b) 3–methylbutan–2–one (i) C2 H5Cl
(ii) H3O
(c) Pentan–3–one (d) None of the above
170. Nitration of the compound is carried out, this compound (i) AgCN
(ii) CH3Cl
gives red–orange ppt. with 2,4–DNP, this compound (ii) H3O
undergoes Cannizzaro reaction but not aldol, than possible
product due to nitration is KMnO 4 / OH
(iii) CH 3CH CH 2
(a) 3–nitroacetophenone heat
(b) (2–nitro)–2–phenylethanal
(i) Mg
(c) (2–nitro)–1–phenylpropan–2–one (iv) CH3Br
(ii) CO2
(d) 3–nitrobezaldehyde (iii) H3O
171. Structure of the compound whose IUPAC name is 3-ethyl-
2-hydroxy-4-methylhex-3-en-5-ynoic acid is : (a) (iii) and (iv) (b) (i) and (ii)
(c) (ii) and (iii) (d) (i) and (iv)
OH
OH 176. Primary alcohols can be readily oxidised to carboxylic acids
COOH by.
(a) COOH (b)
(i) KMnO4 in neutral medium.
(ii) KMnO4 in acidic or alkaline medium.
OH (iii) K2Cr2O7 in alkaline medium.
(iv) K2Cr2O7 in acidic medium.
(c)
COOH
(d) COOH (a) (i), (ii) and (iv) (b) (i), (ii) and (iii)
(c) (ii) and (iii) (d) (i) and (iii)
OH
177. Which of the following is correct order of acidity?
172. The end product B in the sequence of reactions,
(a) HCOOH > CH3COOH > ClCH2COOH > C2H5 COOH
CN NaOH
R X A B is (b) ClCH2COOH > HCOOH > CH3COOH > C2H5COOH
(a) an alkane (c) CH3COOH > HCOOH > ClCH2COOH > C2H5COOH
(b) a carboxylic acid (d) C2H5COOH > CH3COOH > HCOOH > ClCH2COOH
(c) sodium salt of carboxylic acid 178. An organic compound A upon reacting with NH3 gives B.
(d) a ketone On heating B gives C. C in presence of KOH reacts with Br2
173. Which is the most suitable reagent for the following to given CH3CH2NH2. A is :
conversion? (a) CH3COOH (b) CH3CH2CH2COOH
O
|| (c) CH3 CH COOH (d) CH3CH2COOH
CH3 – CH CH – CH 2 – C– CH 3 |
CH3
O
||
CH3 – CH CH – CH 2 – C– OH 179. The correct order of increasing acid strength of the
compounds
(a) Tollen’s reagent (b) Benzoyl peroxide
(A) CH3CO2H (B) MeOCH2CO2H
(c) I2 and NaOH solution (d) Sn and NaOH solution
174. In the given reaction, Me
(C) CF3CO2H (D) CO2H is
H 2O Me
(C 6 H 5 CO) 2 O I
H 2O (a) D < A < B < C (b) A < D < B < C
C 6 H 5 COOCOCH 3 II
(c) B < D < A < C (d) D < A < C < B
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 453
180. Through which of the following reactions number of carbon 184. Kolbe’s electrolytic method can be applied on
atoms can be increased in the chain?
(i) CH 2 COONa (ii) CHCOONa
(i) Grignard reaction (ii) Cannizzaro’s reaction | ||
(iii) Aldol condensation (iv) HVZ reaction CH 2 COONa CHCOONa
Choose the correct option.
(a) Only (iii) and (i) (b) Only (iii) and (ii) (iii) C6 H5COOK (iv) CH3COOK
(c) Only (iii) and (iv) (d) (i), (ii), (iii) and (iv) (a) (i), (ii) and (iv) (b) (i), (ii) and (iii)
181. In a set of the given reactions, acetic acid yielded a (c) (ii), (iii) and (iv) (d) (iii) and (iv)
product C. 185. Which of the following represents the correct order of the
C6 H6 acidity in the given compounds?
CH3COOH PCl5 A B
Anh.AlCl3 (a) FCH 2 COOH > CH 3 COOH > Br CH 2 COOH >
C2H5MgBr ClCH2COOH
C
Ether (b) BrCH2 COOH > ClCH2 COOH > FCH2 COOH >
Product C would be CH3COOH
C2 H 5 (c) FCH2 COOH > ClCH2 COOH > BrCH2 COOH >
| CH3COOH
(a) CH 3 C (OH)C 6 H 5 (b) CH 3 CH (OH) C 2 H 5
(d) CH3 COOH > BrCH2 COOH > ClCH2 COOH >
(c) CH 3 COC 6 H 5 (d) CH 3 CH (OH ) C 6 H 5 FCH2COOH
186. The correct order for the acidic character of the following
K 2Cr2O 7+H2SO4
182. Z. Here Z is carboxylic acids is

COOH COOH COOH

(a) HOOC OH

(b) (CH3)3CCOOH I II OH
(c) Both (a) and (b)
III

(d) HOOC COOH COOH

COOH
HO OH
183. RCOOH can be reduced to RCH2OH by OCH3
(i) NaBH4 (ii) LiAlH4
(iii) Na/C2H5OH (iv) H2/Catalyst IV
V
(a) (ii) and (iv) (b) (i) and (iii)
(a) IV > I > II > III > V (b) V > II > III > I > IV
(c) (i), (ii) and (iv) (d) (i), (iii) and (iv)
(c) V > II > IV > III > I (d) V > II > IV > I > III
 EBD_7207
454 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

FACT / DEFINITION TYPE QUESTIONS H CH3 H O CH3

O3
15. (a) CH3– CH2– C C CH3– CH 2– C– C
2 1 CH3
1. (b) CH3 – CH – CHO CH3 O O
O O
3 4
CH2 – CH3 CH3– C – CH 3+ CH3 – CH2 – CHO (–H2O)

2. (a) 16. (b) Catalyst used in Rosenmund reduction is Pd/BaSO4.

O CH3 Rosenmund reduction is used for reduction of acid
1 2 || 3| 4 chloride.
3. (c) CH 3 C C H CH 3 ; 3- methyl-2-butanone
O O
4. (c) 5. (b) 6. (a) 7. (b) Pd / BaSO4
R C Cl R C H
8. (b) O is more electronegative than C.
17. (d) Phenyl cyanide is reduced into benzaldehyde in the
9. (d) Vanillin -vanilla beans
presence of SnCl2 / HCl reagent. This reaction is
Salicylaldehyde - meadow sweet
Cinnamaldehyde -from cinnamon. known as Stephen’s reaction.
10. (d) The lower aldehydes have sharp pungent odours. As C 6 H 5C N 2[H]
SnCl 2
the size of the molecule increases, the odour becomes HCl
less pungent and more fragrant.
H 2O / H
11. (a) Carbonyl compounds (aldehydes and ketones) are C 6 H 5CH NH C 6 H 5CHO NH 3
obtained by the oxidation of 1° and 2° alcohols 18. (c)
respectively. Among the given options, only (a) is 2°
alcohol hence it can be oxidized to ketone. COOH CH3 CHO

acidic K 2 Cr2 O7 CrO 2 Cl2

OH O
or KMnO 4
| ||
oxidation
H3CCHCH3 H3CCCH 3
(Etard reaction)
2 hydroxypropane Acetone
Acidic KMnO4 and K2Cr 2O7 oxidise toluene to
12. (b) Secondary alcohols on oxidation give ketones. benzoic acid but CrO2Cl2 oxidises it to benzaldehyde.
Note : Primary alcohols form aldehydes. 19. (c) 20. (c) 21. (b) 22. (d) 23. (b)
24. (a) 25. (d)
R R
[O] 26. (b) Formyl chloride is unstable at room temperature.
CHOH C=O 27. (a) Alkanenitriles (other than methanenitrile) and
R R benzonitrile give ketones with Grignard reagents.
Isopropyl Ketone
alcohol 28. (b)
13. (a) 1° Alcohols on catalytic dehydrogenation give + –
29. (c) C=O C – O ; the polarity exists in
aldehydes.
Cu
carbonyl group due to resonance.
RCH2OH RCHO + H2 30. (a) Solubility decreases with increase in mol. wt.
300°C
1° alcohol Aldehyde 31. (c) Propanone has symmetrical structure.
14. (a) Alcohols are oxidized by removal of H2 in presence 32. (d)
of a heated metal catalyst (Cu) 33. (b) Acetaldehyde reacts only with nucleophiles. Since the
mobile p electrons of carbon–oxygen double bond are
Cu
CH3CH 2OH CH3CHO H 2 strongly pulled towards oxygen, carbonyl carbon is
300
1 alcohol Aldehyde electron-deficient and carbonyl oxygen is electron-rich.
The electron deficient (acidic) carbonyl carbon is most
H3 C susceptible to attack by electron rich nucleophilic
Cu
CH OH CH3CCH3 H2 reagents, that is, by base. Hence the typical reaction
300
H3 C || of aldehydes and ketones is nucleophilic addition.
2° Alcohol O 34. (c)
Ketone
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 455
35. (d) Cannizzaro reaction is given by aldehydes having no 44. (c) CH3 CHO + 2Cu2+ + OH– CH3COOH + Cu2O
-hydrogen atom in the presence of conc. alkali, aldol Fehling solution (red)
condensation is given by aldehydes and ketones 45. (c) Aldol condensation is given by carbonyl compounds
having at least one -atom in presence of alkali or in which have -hydrogen atoms.
presence of acids HCHO does not have any -hydrogen atom, so it
36. (b) Aldehydes containing no -hydrogen atom on does not give aldol condensation.
warming with 50% NaOH or KOH undergo 46. (b) Cannizzaro reaction is given by aldehydes and ketones
disproportionation i.e. self oxidation - reduction known which do not have -hydrogen atom. Benzaldehyde
as Cannizzaro’s reaction. (C6H5CHO) does not have -H atom and hence gives
2 HCHO
50% NaOH
HCOONa CH 3OH
Cannizzaro reaction.
47. (d) Compounds having – CHO group reduce Tollen’s
37. (d) I2 and Na2CO3 react with acetophenone (C6H5COCH3)
reagent to silver mirror. It is called silver mirror test.
to give yellow ppt. of CHI 3 but benzophenone
(C6H5COC6H5) does not and hence can be used to O O
|| ||
distinguish between them. H C OH CH3 (CHOH) 3 C H
38. (b) When benzaldehyde is refluxed with aqueous alcoholic
(a) (b)
potassium cyanide, two molecules of benzaldehyde
condense together to form benzoin O
H O Both (a) and (b) have – C – H group so both of them
KCN (alc)
—C +C— give positive silver mirror test.
O H 48. (b) Tollen’s reagent is ammonical AgNO3. Aldehydes form
H O silver mirror with it and ketones do not show any
— C– C — change. So Tollen’s reagent is used to distinguish
OH between aldehydes and ketones.
Benzoin 49. (a) Aldehydes and ketones are reduced to alkanes by
39. (b) CH 3 COCH 3 3I 2 4 NaOH Clemmensen reduction.
Acetone
Zn–Hg/HCl H
CHI 3 3NaI CH 3COONa 3H 2 O C=O C + H2O
Iodoform H
Thus acetone reacts with iodine to form iodoform in 50. (a) Wolf- Kishner reduction
the presence of NaOH. (i) NH2 – NH2 H
40. (c) Aldol condensation is given by the compounds which C=O C
(ii) KOH H
contain hydrogen atom. As the given compound
51. (c) Only aldehydes and ketones react with
does not contain hydrogen atom. Hence it does not
2, 4-dinitrophenylhydrazine.
undergo aldol condensation.
O OH
O || |
( H 2O ) HCN
41. (b) CH3–C=O + H2N–NH–C–NH2 52. (b) CH3 C H CH3 C H
acetaldehyde |
H CN
O OH
CH3–CH=N–NH–C–NH2 Hydrolysis
|
acetaldehyde semicarbazone CH3 C H
|
42. (d) Iodoform test is exhibited by ethyl alcohol, COOH
acetaldehyde, acetone, methyl ketone and those Lactic acid
alcohols which possess CH3 CH(OH)-group. As 53. (d) HCHO does not undergo iodoform test, while
3-pentanone does not contain CH3CO-group therefore
acetaldehyde undergoes iodoform test ( I 2 in presence
it does not give iodoform test.
of base) to form yellow precipitate of iodoform.
O
54. (d) Aldehydes can be oxidised by all the three given
C–CH3 CH2–CH3 reagents.
55. (c) Iodoform test is given by compounds which have
43. (b) Zn-Hg/HCl CH3CO group.
O
Phenyl methyl Ethyl ||
ketone benzene CH 3 CH 2 CH 2 C CH 3
This reaction is known as Clemmensen's reduction. 2-pentanone
 EBD_7207
456 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

O 59. (a) Aldehydes and ketones having at least one -hydrogen

|| atom in presence of dilute alkali give -hydroxy
CH 3 CH 2 C CH 2 CH 3 aldehyde or -hydroxy ketone
3-pentanone
O
2-pentanone has CH3CO group, so it gives iodoform ||
test, while 3-pentanone does not have CH3CO group, CH3 C HCH 2 CHO
|
so it does not give iodoform test. H
56. (c) In cross aldol condensation aromatic aldehydes or Acetaldehyde
ketones (with or without -hydrogen) react with
aldehydes, ketones or esters having -hydrogen atoms OH
in the presence of dilute alkali to form a -unsaturated |
dil.NaOH
CH3 C CH 2 CHO
carbonyl compound. |
Example, H
Aldol
OH
(i) C6 H5CHO CH3CHO CH3 CH CH.CHO
Benzaldehyde Acetaldehyde H 2O Crotonaldehyde
C6 H5CHOHCH 2 CHO 60. (b) Clemmensen reduction is
– H2O Zn–Hg/HCl
C=O CH 2
C6 H 5 CH CHCHO 61. (a) Aldehydes, other than formaldehyde, when treated
Cinnamaldehyde with RMgX give 2º alcohols.

CH3 O
O
| 62. (a) R C H + NH2 NH2 R C N NH2
(ii) C6 H 5 C O H 3C C C 6 H 5 H
Acetophenone Aldehyde Hydrazine Aldehyde hydrazone

CH3 O O OH
| || |
Aluminium HCN
C6 H 5 C CH C C6 H5 63. (a) R– C –R R-– C — CN
t-butoxide KCN |
Dyprone
R (A)
R R OMgX
57. (c) C = O + R'MgX C OH
R R R' |
Reduction by
HOH
R – C – CH 2 NH 2
LiAlH 4 (B) |
R R
R C – OH + Mg(OH)X 64. (b)
R'
3° alcohol 65. (d) Iodoform test is given by compounds having CH3CO–
group or secondary alcohols having CH3– as one of
58. (a) When acetaldehyde is treated with alcohol in the alkyl groups, i.e., CH3CHOHR or CH3CH2OH because
presence of dry HCl , then acetal is formed it is readily oxidised by halogen (present in reagent) to
H
CH 3 CH 3 OR |
dry HCl CH3CHO which has CH C O group.
C= O + ROH C 3
66. (d)
H H OH 67. (a) Aldehydes (e.g. CH3CHO) restore the pink colour of
Hemiacetal Schiff’s reagent.
68. (a) fusion
CH 3 OR C 6 H 5 COC 6 H 5 KOH
ROH
H2O + C C6 H 6 C 6 H 5COO K
69. (c) The nucleophile is SO3 HSO3– , SO3Na
– – not
H OR
Acetal 70. (c) Wolf-Kishner reduction is reduction of carboxyl
compound into alkane.
Hence, option (a) is correct. 71. (b) Ammonical AgNO3 is Tollen’s reagent.
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 457
72. (d) 73. (c) O
74. (d) These reactions lead to replacement of oxygen atom C OMgBr
MgBr
of carbonyl group to form hydrazones and oximes.
+
75. (a) Cannizzaro’s reaction is shown by aldehydes lacking (i) CO2 H3O
-H-atom. Aldol condensation reactions are shown
by aldehydes having -H-atoms.
O
76. (b) NaBH4 selectively reduces the aldehyde group to
alcohol without affecting double bond in a organic C O H
compound. So, X is NaBH4.
NaBH + Mg(OH)Br
4
C6 H5 CH = CHCHO C6 H5 CH = CHCH2OH
77. (a) All ketones in (i), (ii) and (iii) contain abstractable 'P'
Benzoic acid
alpha–proton while all aldehydes do not contain
alpha–hydrogen. 96. (c)
97. (d) In carboxylates (conjugate base of carboxylic acids),
78. (a) Benzaldehyde undergoes Cannizzaro reaction, which
resonance is more significant because the two
forms benzoic acid and benzylalcohol as the product.
resonating structures are similar, while in phenoxide,
79. (c) 80. (b) 81. (a) the resonating structures are not equivalent, alkoxide
82. (d) Automobile exhausts are artificial source of isobutyric ions do not show resonance.
acid. 98. (a) 99. (a)
83. (c) Vinegar is 6 - 8% solution of acetic acid. 100. (c) Bromine is less electronegative than F, further in
84. (b) The overall reaction involved is BrCH2CH2COOH, Br is more away from the –COOH
H 2O H 2O group than in CH3CHBrCOOH.
CH 3 CN CH 3 CONH 2
O CH3
HCl || |
CH3 COO NH 4 CH3COOH + NH 4 Cl 101. (c) CH 3 C OH HO– CHCH 3
Ethanoic acid Propan-2-ol
On reduction cyanides yield 1 amines. They do not
undergo decarboxylation or electrolysis.
O CH3
R || |
COOH CH3 C O– CHCH3
85. (a) KMnO 4 / OH – 102. (a)
K 2Cr2O7 or dil. HNO3 103. (c) pKa = –logKa; HCOOH is the strongest acid and hence
R = Any alkyl group it has the highest Ka or lowest pKa value.
Benzoic acid
104. (c)
86. (b) Both C–O bonds are identical and each O possesses 105. (b) LiAlH4 in presence of ether can be used to convert
partial negative charge. acetic acid into ethanol.
87. (c) Formic acid cannot be prepared by Grignard reagent.
ether
88. (b) CH3COOH + 3LiAlH4
acetic acid
CH3 CHCl2 CHO [CH3CH2O]4AlLi + 2LiAlO2 + 4H2
H 2O
Cl 2 / h
373 K H
[CH3CH2O]4AlLi CH3CH2OH
Toluene Benzal chloride Benzaldehyde ethanol
89. (d) 106. (c) Carboxylic acids are weak acids.
90. (c) Carbonyl group acts as a deactivating and 107. (c) Removal of CO2 from carboxylic acid is called
metadirecting group. decarboxylation.
91. (d) Primary and secondary alkyl groups oxidised to give 108. (b) It is a test for –COOH gp.;
carboxylic acid while tertiary alkyl group remain R–COOH+NaHCO3 RCOONa + H2O + CO2 .
unaffected. 109. (d)
92. (b) 93. (d) COOH COOC2H5
94. (b) Due to H-bonding.
HCl
95. (b) Grignard reagent forms addition product with bubbled 110. (c) + C2H5OH + H2O
Ethanol
dry
carbondioxide which on hydrolysis with HCl yields
benzoic acid. This process is known as esterification.
 EBD_7207
458 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
111. (c) This reaction is an example of Hell - Volhard Zelinsky 122. (c) Chlorine is electron withdrawing group. Further
reaction. In this reaction acids containing – H on inductive effect is stronger at position than
treatment with X2 /P give di-halo substituted acid. -position. i.e.,
Br2 /P
CH 3 – CH 2 COOH CH 3 CBr2 COOH
CH 2ClCOOH CH 2 ClCH 2 COOH
112. (c) 3CH 3COOH PCl3 CH 3 COCl + H3PO3 123. (b)
Acetyl Phosphorous
Chloride acid STATEMENT TYPE QUESTIONS
113. (b) 124. (b) Carbonyl compounds have substantial dipole moments
114. (a) –COOH group when attached to benzene ring and are polar in nature. The high polarity of the
deactivates the ring and substitution occurs at carbonyl group is due to resonance.
m-position. (HNO3 + H2SO4) is a source of + NO2 125. (a) Primary alcohols on oxidation give carboxylic acids as
(electrophile) which attacks at m-position. the final product, of course through aldehydes.
COOH COOH Oppenauer oxidation involves oxidation of 2º alcohols
to ketones, and not for the oxidation of 1º alcohols.
+ HNO3 H2SO4 126. (c) If the aldehyde has a boiling point less than 100°C, it
can be prepared by the oxidation of 1° alcohols with
NO2
3- nitrobenzoic acid
regular oxidising agents like acidic permanganate or
dichromate. Since the aldehyde has a lower boiling
115. (b) Br2 / P point than the alcohol, it is distilled off as soon as it is
RCH 2 COOH R CH COOH
HVZ reaction | formed ; so further oxidation to a carboxylic acid is
Br minimized.
'X' 127. (d) The solubility of aldehydes and ketones decreases
rapidly on increasing the length of alkyl chain.
NH3
R CH COOH 128. (a) Aldehydes are generally more reactive than ketones
(Excess) | in nucleophilic addition reactions due to steric and
NH 2 electronic reasons. Sterically, the presence of two
'Y' relatively large substituents in ketones hinders the
116. (d) The yield of product in a reversible reaction can be approach of nucleophile to carbonyl carbon than in
increased by (i) removing one of the products, (ii) aldehydes having only one such substituent.
taking either of the reactant in excess. Electronically, aldehydes are more reactive than
117. (d) Use of SOCl2 and ClCOCOCl forms gaseous by- ketones because two alkyl groups reduce the
products which can be easily removed, giving better electrophilicity of the carbonyl carbon more effectively
yield of RCOCl. Further, oxalyl chaloride is particularly than in former.
easy to use becasue any excess of it can be easily 129. (b) The hydrogen atom that is added to the carbonyl
evaporated due to its low b.p. (62ºC) carbon of the aldehyde in the reduction is derived
directly from the other aldehyde molecule as a hydride
O O O
|| || || ion. The second hydrogen that is added to the
R C OH Cl C C Cl negatively charged oxygen is coming from the solvent
O (consult mechanism of Cannizzaro reaction). Oxidation
|| of one molecule of the compound at the expense of
R C Cl HCl CO CO 2 other molecule of the same compound is known as
118. (b) disproportionation.
119. (a) Salicylic acid, because it stabilizes the corresponding 130. (b) First two steps of the esterification make the question
salicylate ion by intramolecular H-bonding. clear
120. (c) Cl 2CHCOOH is most acidic because it has two O OH
+

chlorine at -position. H
+
R–O–H
121. (a) An electron releasing substituent (+I) intensify the CH3 — C — OH CH3 — C — OH
negative charge on the anion resulting in the decrease Protonated acid
(carbonyl C is more
of stability and thus decreases the acidity of the acid. electrophilic than
Hence acid character decreases as the + I-effect of the that of parent acid)
alkyl group increases as OH
CH3– < CH3CH2– < CH3CH2CH2– < CH3CH2CH2CH2–
R–O–H
Hence the order becomes : (i) > (ii) > (iii) > (iv) CH — C — OH CH3 — C — OH
Protonated acid +
HO R
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 459
+ +
MATCHING TYPE QUESTIONS 148. (c) (a) C = O + H2NNH2 H
C – OH
H
C = NNH2
131. (a) 132. (c) 133. (b) 134. (d) 135. (b) NHNH2
136. (c) 137. (c) (b) In the reduction of carbonyl group with LiAlH4 or
NaBH4, a hydride ion is transferred from the metal
ASSERTION-REASON TYPE QUESTIONS to the carbonyl carbon (nucleophilic addition)
138. (a) 139. (a) 140. (b) H
141. (a) The molecular mass of acetic acid in benzene is 120 – –
C = O + H– AlH3 C – OAlH3
instead of 60 because the carboxylic acids exists as
cyclic dimers in which two molecules of the acid are 149. (d) Being reversible reaction, the backward reaction i.e.
held together by two strong hydrogen bond. acetal -hemiacetal step can be restricted by minimizing
water content, i.e. by using dry HCl. The step hemiacetal
CRITICAL THINKING TYPE QUESTIONS - aldehyde can be restricted by using excess of alcohol.
150. (c) First step in Cannizzaro reaction is the nucleophilic
142. (d) addition of OH– on the carbonyl carbon.
143. (b) In structure II, presence of positive charge on oxygen
causes the displacement of electrons toward oxygen, H –
H
making carbon more electron deficient than that in OH –
R–C=O (fast) R–C–O
unprotonated carbonyl group.
144. (c) It is the reason for the given fact. OH
145. (d) Higher the electron deficiency on cabonyl carbon, more
146. (c) With ammonia, HCHO forms hexamethylenetetramine, easier will be the attack of the nucleophile
CH3 CHO gives acetaldehydeammonia addition (OH–) on its carbon. Futher, the attack of OH– on the
product, while C6H5CHO gives hydrobenzamide. carbonyl carbon is more easy in case of HCHO because
147. (d) Aldol condensation : its carbon is least hindered having two hydrogens
(steric effect). Thus the intermediate I is formed very
OH New C–C bond
easily which donates hydride ion to another aldehyde
–
OH
2CH3CHO H3C–C–CH2CHO and thus itself oxidised.
H H
|
Kolbe reaction : Ist
H C O OH step
Easier because of electronic
ONa
ONa OH New C–C bond and steric effects
COOH H H H
CO
CO2,140ºC
,140ºC – –
R–C=O
Pressure
Pressure H–C–O 2nd Step
H–C=O +R–C –O
(slow)
OH OH H
OH I
151. (c) OH– and –CH2CHO act as nucleophile in the first two
steps.
CHCl3
Reimer-Tiemann reaction : O
3KOH
|
OH CH 3CHO
CH3 CHO C H 2 CHO CH 3 C H
|
New C–C bond CH 2CHO
OH
CHO OH
CHCl |
+ 3KCl + 2H2O H 2O
3KOH
CH3 CH
(as an acid) |
CH2CHO
Wurtz Fittig reaction :

Na
H3CCl + 2Na + Cl
152. (c)

H3C + 2NaCl H
C6 H5CHO –
C6H5 – C – O + C6H5 – C = O
New C–C bond
H OH
 EBD_7207
460 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
153. (d) If we observe the haloform reaction carefully, we see 157. (a) Aldol condensation involves an aldehyde or ketone
that –COCH3 group is first halogenated to the trihalo having an –hydrogen atom. This type of
–COCX3 through monohalogeno and dihalogeno condensation occurs in presence of dilute base (i.e.,
compound. It is the –COCX 3 part which then dil NaOH).
undergoes nucleophilic addition. The product easily Only CH3COCH3 will give aldol condensation (Both
loses –CX3 since it is a very good leaving group. HCHO and C6H5CHO lack -hydrogen).

O O 158. (d) H3 C
–
X2, OH C = O + CH 3 MgI
CH3 – C – CH3 CH3 – C – CH2Cl
H 3C
I II

H3 C
O O H OH H2 O
C O MgI
CH3 – C – CHCl2 CH3 – C – CCl3 H3 C
III IV CH3
– CH3
O O
OH
– |
CH3 – C – CCl3 CH3 – C – CCl3 H3C C OH + Mg(OH)I
|
OH CH3

Tert butyl
O alcohol
–
CH3 – C + CCl3 159. (d) Ketones do not respond to Tollen’s test. Aldehydes
respond to Tollen’s test.
OH
160. (b) R R OH
Thus all compounds (I to IV) are ultimately converted NH3
to CHCl3 (chloroform).
C = O HCN C
R R CN
154. (c) 2CH3CHO 1st Product,
2 CH 3CH 2CHO 2 nd Product R NH2 R NH2
HOH
C C
CH3CH 2CHO CH3CHO 3rd Product; R CN R COOH

CH3 C H 2 CHO CH 3CHO 4 th Product 161. (d) 162. (a) 163. (a)
164. (b) The car bon atom of the carbonyl group of
155. (d) Dihydrogen sodium phosphate (NaH2PO4) does not
benzaldehyde is less electrophilic than carbon atom of
have a lone pair of electrons on the P atom. As such it the carbonyl group present in propanal. The polarity
can not act as a nucleophile and hence does not react of the carbonyl group is reduced in benzaldehyde due
with aldehydes and ketones. to resonance as shown below and hence it is less
156. (d) Aldehydes which contain a -hydrogen on a reactive than propanal.
saturated carbon, i.e., CH 3CH 2CHO undergo aldol 165. (b) Aldehydes and ketones react with hydrogen cyanide
condensation. (HCN) to yield cyanohydrins. This reaction occurs
very slowly with pure HCN. Therefore, it is catalysed
H CH3 by a base and the generated cyanide ion (CN– ) being
| |
a stronger nucleophile readily adds to carbonyl
CH3CH 2 – C O H C CHO
propanol | compounds to yield corresponding cyanohydrins
H 166. (b) Dry hydrogen chloride protonates the oxygen of the
carbonyl compounds and therefore, increases the
H CH3 electrophilicity of the carbonyl carbon facilitating the
| |
OH nucleophilic attack by the alcohol molecule. Dry HCl
CH3CH 2 C CHCHO
| gas also absorbs the water produced in these reactions
OH thereby shifting the equilibrium in the forward
3-hydroxy-2-methylpentanal
direction.
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 461

167. (a) Because of resonance in benzaldehyde which is not

O
possible in case of acetaldehyde the positive charge
3 ® CH CH COO- NH+
CH3CH 2 - C- OH ¾¾¾
NH
on the carbonyl carbon decreases and hence there is 3 2 4
decrease in reactivity.
(A) (B)
168. (c) Acetal formed upon reaction of ethylene glycol and
D
HCl, which is unaffected by base hence unwanted ¾¾® CH 3CH 2 CONH 2
reaction does not occur due to presence of carbonyl (C)
group.
169. (c) 2, 2-dimethyl propanal gives Tollen’s test and KOH Br2
3-methylbutan-2-one gives iodoform test. CH 3CH 2 NH 2
170. (d)
179. (a) The correct order of increasing acid strength
OH CF3COOH > MeOCH2COOH > CH3COOH
3 1 > (Me)2CH.COOH
H3C 2 COOH
171. (a) Electron withdrawing groups increase the acid strength
6 4
and electron donating groups decrease the acid
5 CH 3
strength.
IUPAC name of the structure is 3-ethyl-2-hydroxy 180. (a) Grignard reagents and nitriles are useful for converting
-4-methylhex-3-en-5-ynoic acid. alkyl halide into corresponding carboxylic acids having
one carbon atom more than that present in alkyl halides.
172. (c) CN NaOH
R X R CN RCOONa
COCH3
173. (c) C6H 6
181. (a) CH COOH +PCl CH3COCl
3 5 AnhydAlCl 3
H 2O [A]
(C 6 H5CO)2 O 2C 6 H5 – COOH
174. (b) Friedle Craft
benzoic anhydride benzoic acid reaction

H2O OH OMgBr
C6 H5COOCOCH3 C6 H5 COOH CH 3COOH H
+
MgBrC2H5
bezoyl ethanoic benzoic acid ethanoic acid C2H5 – C – CH3 ether C2H5 – C – CH3
anhydride
hydrolysis
175. (b) 176. (a)
177. (b) Recall that presence of electron-withdrawing group (C)
increases, while presence of electron-releasing group
decreases the acidity of carboxylic acids. 182. (c) An alkyl group attached to benzene ring can be
oxidised only when it contains at least one -hydrogen
O O atom. Thus here –CH3 group is oxidised and Me3C–
|| || group not. However, Me 3 C– group may cause
ClCH 2COOH H C OH CH 3
C OH
(electron-withdrawing gp.)
oxidation of the benzene ring to –COOH.
(Electron-releasing character
increasing from Left to Right) 183. (a) 184. (a)
185. (c) Electron withdrawing substituent (like halogen, —NO2,
O C6H5 etc.) would disperse the negative charge and
|| hence stabilise the carboxylate ion and thus increase
C2H5 C OH acidity of the parent acid. On the other hand, electron-
releasing substituents would intensify the negative
charge, destabilise the carboxylate ion and thus
NH3 Br2
178. (d) A B C CH3CH 2 NH 2 decrease acidity of the parent acid.
(I) II KOH,(III)
Electronegativity decreases in order
Reaction (III) is a Hofmann bromamide reaction. Now F > Cl > Br
formation of CH3CH2NH2 is possible only from a and hence –I effect also decreases in the same order,
compound CH3CH2CONH2(C) which can be obtained therefore the correct option is
from the compound CH3CH2COO– NH+4 (B). [FCH2COOH > ClCH2COOH > BrCH2COOH >
Thus (A) should be CH3CH2COOH CH3COOH]
 EBD_7207
462 ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

186. (d) V is most stable because its anion is stabilized to a COOH COOH
greater extent through H – bonding with H atom of OH OH OH
HO
present on both ortho-positions ; followed by II in > >
which one OH group is present. Compound IV comes
next to II because here –OCH3 group is present in ortho V II

position which although is not capable of forming

COOH COOH COOH
H–bonding yet more acidic than p-HOC6H4COOH (III)
due to ortho effect. Compound III is less acidic than OCH3
benzoic acid because of electron-releasing group in > >
the para position. Thus IV I
OH
III