CLS ENG 22 23 XII Che Target 5 Level 1 Chapter 13

Step-1

Chapter 13
Aldehydes, Ketones and
Carboxylic Acids

Solutions

SECTION - A
1. Answer (2)
2. Answer (4)
3. Answer (2)
4. Answer (3)
5. Answer (1)
6. Answer (1)
7. Answer (2)
8. Answer (3)
9. Answer (4)
10. Answer (2)
11. Answer (3)
12. Answer (2)
SECTION - B
13. Answer (2)
14. Answer (3)
15. Answer (2)
16. Answer (4)
17. Answer (3)
18. Answer (2)
19. Answer (2)
20. Answer (1)
21. Answer (1)
22. Answer (4)
23. Answer (2)
24. Answer (3)
25. Answer (4)
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2 Aldehydes, Ketones and Carboxylic Acids Solutions of Assignment (Step-1)
SECTION - C
26. Answer (2)
(CH3CO) 2O
Ph – CHO Ph – CH = CH – COOH
CH3COONa
CHCl3/OH–
Ph – OH Ph – CHO

OH–
Ph – CHO + HCHO Ph – CH2OH + HCOO –Na+

CHO
CH3CHO + CH 3CH2CHO CH3 – C = CH – CH3 + CH 3 – CH – CH = CH – CHO
27. Answer (1)

HgSO4
CH  CH CH3CHO
H2SO4
Fehling solution does gives red colour with benzaldehyde.
Tollen's
CH3 – C  CH White ppt.
reagent
CH3 H
H2/Pd/BaSO4
CH3 – C  CH
H H
SECTION - D
PCl
28. CH3 COOH 
5
 CH3 COCl  POCl3  HCl
29. Formic acid gives silver mirror with Tollen’s reagent while acetic acid does not give this test.
C N Ph—C N.MgBr COPh
H3O+ Br
30. + PhMgBr + Mg
NH2
COOH
31. (i)
SO3H
(ii) CH3COOH + N2 + H2O

(iii) CH3CH == N —NH—C6H5 + H2O
acetaldehydephenylhydrazone
32. (i) Cannizzaro reaction: Aldehydes which do not contain any D-H atom undergo disproportionation on
treatment with conc. alkali in which one molecule is oxidised and another is reduced.
H H
Ex. C O+ C O + conc. KOH CH3OH + HCOOK
H H
Solutions of Assignment (Step-1) Aldehydes, Ketones and Carboxylic Acids 3
(ii) Cross Aldol condensation: When aldol condensation is carried out between two different aldehydes or
ketones both containing D-H atom, it is Cross Aldol condensation.
OH
CH3—CH—CH2CHO
dil.
CH3CHO + CH3CH2CHO OH
NaOH
CH3—CH—CH—CHO
CH3
OH 4 possible products
CH3CH2—CH—CH—CHO
CH3
OH
CH3CH2—CH—CH2CHO
33. (i) Acetic anhydride is used to stop the reaction at benzaldehyde otherwise the end product must be benzoic
acid.
(ii) Acids with even no. of carbon atoms fit into crystal lattice more readily than odd ones, hence they have
higher lattice energy and higher melting point.
KMnO /H Ca(OH)

dry
34. (i) CH3 CHO 
4
(O)
 CH3 COOH 
2
(CH3 COO)2 Ca 
distillation
 CH3 COCH3  CaCO3
O
||
CH3 Cl H2O/HgSO4 ,H2SO4
(ii) HC  CH  NaNH2  CH  C — Na   HC  C — CH3   CH3 — C— CH3
OH O
| ||
(i) CH3MgBr K 2Cr2O7
35. (i) CH3 CH2CHO   CH2 — CH— CH2CH3    CH3 — C— CH2 — CH3
(ii) H3 O conc. H
CH CH CH NH Zn/Hg
(ii) CH3 CH2COCl 
3 2 2 2
 CH3 — CH2CONH — CH2 CH2 CH3 
conc. HCl
 C3H7NHC3H7
dipropylamine
Cl
|
Red P/Cl2
(iii) CH3 CH2COOH  alc. KOH
 CH3 — CH — COOH  CH2  CH — COOH
COOH COCl
36. (i) + SOCl2 + SO2 + HCl
Red P
(ii) CH3 COOH  6HI   CH3 — CH3  3I2  2H2 O
(iii) 2CH3 COOH  Zn (CH3 COO)2 Zn  H2
OH ONa OH
CHO CHO
60°C H+
37. (i) + CHCl3 + 3KOH
Chloroform
Salicylaldehyde
It is Reimer Tiemann reaction.
OCH3 OCH3
anh. AlCl3
(ii) + CH3COCl p-methoxyacetophenone
Ethanoyl chloride
Anisole
C—CH3
O
38. (i) Due to resonance position of carbonyl group is changing
–
O O
+
R—C—O—H R—C OH
hence these compounds do not give reactions of carbonyl group.
(ii) On nucleophilic addition of HCN to benzaldehyde, it forms two optical isomers which have same physical
properties, hence cannot be separated by fractional distillation.
O OH OH
C—H + HCN *C—CN NC—C
H H
(iii) Aldehydes and ketones form addition products with NaHSO3, whereas impurities don not react and are left
behind. Addition products which were earlier crystallised can be easily reconverted to aldehyde and ketone.
OH
|
H3 O
CH3 CHO  NaHSO3  CH3 — CH— SO3Na  CH3 CHO  NaHSO3

Step-2
Chapter 13
Carboxylic Acids
Solutions
[Aldehydes and Ketones (Preparation and Reactions)]
1. Answer (4)
2. Answer (1)
OH OH OH2 OH
H+
C C C C
H3CO OCH3 H3CO OCH3
–H2O
CH3 CH3 CH3 CH3

CH3
O H O H
Rearrangement
C C
C C
H3CO OCH3 H3CO OCH3
CH3
CH3 CH3 CH3
O
+
–H
C C
H3CO OCH3
CH3
Migrating power of p-tolyl is more than m-anisyl.
3. Answer (2)
Product may be recemic, because carbonyl carbon is sp2 hybridised and has planar shape. So, Nu– attacks
on front as well as back side.
4. Answer (3)
O Cl Cl
|| PCl5 LiNH2
C — CH3 C — CH3 C—
— CLi
—
0°C (excess)
Et — Br
Ph H Na/NH3
C—
—C C—
— C — Et
—
H Et (Birch Reduction )
5. Answer (3)
O N — OH H
|
H2NOH Conc. H2SO4
N
C O
Beckmann Rearrangement
(x) C5H8O (y)
 - la ctam
6. Answer (2)
forms strongest hydrogen bond with H2O molecule because in this case carbonyl carbon readily attains
+ve charge due to aromaticity.

7. Answer (3)
8. Answer (3)
9. Answer (2)
 
Ph
Ph — CH —
— CH — CH —
—O CH — CH —
— CH — O MgBr
Ph 
H3O
PhMgBr Ph
CH — CH —
— CH — O
Ph
H
Ph
CH — CH 2— CHO
Ph
10. Answer (4)
LiAlH4 o Li+ + Al3+ + 4H–
O O– O —H
|| – | H 3O+ |
CH3 — C — H + H CH3 — C — H CH3 — C — H
| |
H H
11. Answer (2)
O
C
NH2NH2/OH–
CH 3

H2N H 2N
In this reaction, Zn — Hg/HCl is not used because in acidic medium, —NH2 group is affected.
12. Answer (1)
O
HO H
LiAlH4
H 2O
LiAlH4 does not reduce double bond. If double bond is conjugated with phenyl system then double bond is
reduced by LiAlH4.
13. Answer (4)
14. Answer (1)
O O
O
SeO2
In this reaction, active methylene group (—CH2—) is oxidised to C—

— O group.
15. Answer (1)
O
Conc . HNO 3
CH3 C CH2 CH3     2CH3COOH
According to Popoff’s rule, carbonyl group goes with less complex alkyl group.
16. Answer (2)
O O O
|| || – + H3O ||
NaOI
C — CH3 C — O Na + CHI3 
C — OH
The above conversion is known as iodoform reaction.

17. Answer (3)
18. Answer (4)
19. Answer (2)
20. Answer (3)
21. Answer (3)
22. Answer (3)
23. Answer (1)
[Carboxylic Acids (Preparation and Reactions)]

24. Answer (3)
 O  O
In, H C due to complete resonance, J = G, While in H C , partial resonance is present.
 O H
O
So, D < E.
25. Answer (2)
26. Answer (3)
27. Answer (4)
[Acid Derivatives (Preparation and reactions)]

28. Answer (3)
Due to ortho effect, (III) and (I) are most acidic. If —OH group is present at p-position w.r.t. —COOH group,
then it becomes less acidic.
29. Answer (2)
O
(i ) Di isobutyl
CH3CH2 C OC2H5     CH3 — CH2CHO + C2H5OH
alu min ium hydride
(ii) H3O 
30. Answer (2)
Alcohols can’t be reduced by LiAlH4. Only carbonyl compound, carboxylic acid and acid derivatives are
reduced by LiAlH4
31. Answer (4)
32. Answer (2)
O O O–
|| OEt || OEt || O
OEt
–
H (from EtO
O NaBH4) O– O O
||
33. Answer (1)
O O H
|| || H O — (CH2)3 — O H /H
+ | O
Pd/CaCO3
C — Cl C—H C
H2(1 eq.) O
34. Answer (3)
(i) PhMgBr
C—
—N C
||
+
(ii) H3O O
||
O [A] H2N — C — NH — NH2
N — NHCO NH2
||
C
[B]
35. Answer (1)
CH 3 O
| ||
CH3 — C — C is most reluctant to form ester with alcohol due to presence of bulky group.
| OH
|
CH 3
36. Answer (2)
SnCl2/HCl H2O
C—
—N CH — NH CHO
This is known as Stephen’s reduction.
37. Answer (3)
O
||
Mg (i) CO2
Br THF
Mg — Br C — O — Mg — Br
+
O (ii) H3O
||
C — OH
Benzoic Acid
38. Answer (4)
O
HBr, Peroxide Mg (i) CO2
CH 2 CH2 — Br Et2O
CH2 — MgBr (ii) H3 O+
CH2 C OH
39. Answer (1)
O
H2 N CN
CH 3 – C – H + NH 4Cl + NaCN + NaCl + H 2 O
CH3 H
H2O +
H2 N COOH
CH3 H
40. Answer (2)
41. Answer (01)
+
OH H
+
after
H
+
–H
+
several
 steps
HO HO HO HO
HO HO
x=1
Grignard reagent will not interact with product.
42. Answer (05)
OH OH O
3H2 Cu
Ni 450 K
(A) (B)
A and B are non-aromatic compounds.
Statements P, Q, R, U and V are incorrect.
43. Answer (13)

– +
O MgBr
O O  O
O – + CH3
CH3 CH3 HC CH3   HC
– CH3
LDA CH3 – C – H CH3 MgBr

 H3C H3C
(Kinetically +
controlled) H3O
HO CH3
–
HC CH3
O
CH3 H3C
< Product >



CH3

HC CH3

H3C 

< Product >
Number of hyperconjugable hydrogens = 13
44. Answer (01)

H – Br
H3C CH2 CH CH2 CH3–CH2–CH2–CH2–Br
R–O–O–R
(i) Mg / dry ether
(ii) CO2 / H +
H O O
Red P
H3C – CH2 – CH2 – C – C – OH CH3 – CH2 – CH2 – CH2 – C – OH
Br 2
Br
Asymmetric
C-atom
45. Answer (02)
+
MnO4 /H
O
O
OH
46. Answer (03)
C — C — C — C — C — COOH, C — C — C — C — C, C — C — C — C — C
COOH COOH
47. Answer (04)
O O
HO HO
P is
HO HO
O O
O O
C
H H
Q is
H H
O O
Each –CHO can produce an oxime.
Previous Years Questions

48. Answer (3)
CH2 – Cl
+ HCHO + HCl
Benzyl chloride
AgCN
CH2 – NC
Benzyl isocyanide
+
CH2 = O + H + CH2 = O – H
CH2 = OH
+ H
CH2 OH
+
–H
CH2 OH
HCl
CH2 – Cl CH 2 – NC
N  C–Ag
+ AgCl
49. Answer (2)
(1)AlH(i–Bu)2
(2) R — C  N   R — CHO
 2H O 2
AlH (i – Bu)2 is DIBALH which reduces nitrites to aldehydes.
50. Answer (4)
Alumina is an adsorbent (stationary phase)
Benzaldehyde is adsorbate.
Acetonitrile is mobile phase.
51. Answer (4)

O O
–
–
–
–
–
C – CH3 OH– C – CH2
–
–
CH3 – C – H
O OH
–
–
–
C – CH 2 – CH – CH 3
52. Answer (2)

NaBH4 selectively reduces the ketone, it does not affect alkene and ester.
O
O
CH2 – C – OCH 3
NaBH 4
MeOH
OH O
CH2 – C – OCH 3
53. Answer (3)

CH2 O
CH2 COOH 
+ CO 2 + H2 O
CH2 COOH
CH2
This compound does not form anhydride.
54. Answer (4)
Rate of reaction v positive charge on carbonyl carbon so E.W.G. increase rate while E.D.G. decrease the rate.
O2N C – OC2H5 > Cl COOC2H5

O
III > II >
COOC2H5 > MeO COOC2H5
I > IV
55. Answer (3)
C7H6O2 – A
O
COOH C — NH 2 NH2
aq. NH 3 Br2, KOH


A B C
? A is Benzoic Acid.
56. Answer (4)
CO2Et NaOEt/ CO2Et

–
O O
O
O
O O
 OH
Condensation
C=O CO2Et
|
OEt
57. Answer (4)
O
CH3N
NaBH4
OH
CH3NH
58. Answer (2)
COCH3 COOH
KMnO4/KOH/
CH3 H2SO4(dil) HOOC
59. Answer (4)
O
C CH
OEt (i) Ni/H2 N
CN (ii) DIBAL - H
60. Answer should be both (1) and (2)
Phenol or unsaturated hydrocarbon (alkene or alkyne) decolourised bromine water solution.
C2H5MgBr will react with carbonyl carbon or acidic hydrogen.
OH
reacts with C2H5MgBr and also decolourized bromine water solution
CN
CH2CO2CH3
will also give postive bromine water test and give substitution product with EtMgBr
61. Answer (1)

HCl
Aldehyde + Alcohol Acetal
more less steric

reactive alcohol
aldehyde
? Best combination is HCHO and MeOH
62. Answer (2)
O O O O
OH
H H
HO
+/
H 3O
O
63. Answer (2)

DIBAL-H followed by hydrolysis converts nitrile to aldehyde and ester to aldehyde and alcohol.
CN CHO
DIBAL-H
+
O H3O OH
O H
O
64. Answer (3)
The reactivity order of carboxylic acid derivatives depends on the leaving tendency of the leaving group. Higher
the leaving tendency of the leaving group, higher will be the reactivity of the compound. Therefore, reactivity
order towards LiAlH4 is Acid halide > Acid anhydride > Ester > Amide
65. Answer (2)
Grignard reagent will not react with aldehydes if it has a functional group which contains acidic hydrogen.
Options (B) and (D) have —COOH and —CH2OH respectively which contan acidic H-atom.
66. Answer (1)
OH
NH2 NaNO2 OH
CH3 O +
C H
O CrO 3/H+
OH OH
H2SO4 (conc.)/ 
HO O
O
67. Answer (3)
–
O O
CH2Br NaBH4 CH2 Br
MeOH, 25ºC
O
CH CH2
68. Answer (4)

CH 3
X is Meta cresol
OH
CH 3
CH3 NaOH (10%)
ONa
OH NaHCO 3 (10%)
Insoluble
Benzamide is amphoteric.
Oleic acid will dissolve in NaOH as well as NaHCO3 due to acidic nature.
69. Answer (3)
OH O
–
CH — CH3 C—O
I 2/NaOH
+ CHI3
OC2H5 OC2H5
OH
CH — CH 3
OC2H5
o Reacts with Grignard’s reagent due to acidic hydrogen.

o Fehling solution test is negative as there is no – CHO group.
o Neutral FeCl3 test is negative as there is no phenolic group.
70. Answer (3)
O
C=O
H H
OH
NaOH (dil)
O O
OH

71. Answer (4)

LiAlH4 reduces esters to alcohols but does not reduce C = C.
CH 3 – CH = CH – CO 2Me
LiAlH 4
CH3 – CH = CH – CH 2
OH
72. Answer (2)
OH OH
OH
H2SO4(cat.)
CHCl3 O
C–O–Et
O O
Acid catalysed intramolecular esterification
OH OH OH
OH
+
H+ –H
+O–H O
C–O–Et
O O O
73. Answer (3)

O
CH3 C CH3 CH3 CH 2 CHO

Generally, aldehydes are more reactive than ketones in nucleophilic addition reactions.
? Rate of reaction with alcohol to form acetal and ketal is
O
CH 3 CH 2 CHO > CH 3 C C H3
74. Answer (1)
–
O
–
CH 2==O + OH  H—C—H
OH
–
O O
C—H + H—C—H
OH
–
O O
Proton
C—H + C—H
Exchange
H OH
OH O
H3 O+
C—H + H—C—O –
H
CH2OH + HCOOH
75. Answer (3)
O O
C––CH3 C––OH
1. NaOCl
+
2. H
SOCl2
C––Cl
O
aniline
Ph––C––NH––Ph
76. Answer (2)
O O
C––CH3 C––O–Na +
I2 + NaOH
+ CHI 3
CH 3 CH3
KMnO4
O O
C––OH C
D
O + H2O
C––OH C
O O
C8 H6O 4 anhydride
77. Answer (2)
O O
O
OH CrO 3 OH SOCl2 Cl 
H+
HO HO HO HO
78. Answer (1)
CH 3 – CH = CH – CH 2 – CH – CH 3
OH
I2/NaOH
CH 3 – CH = CH – CH 2 – C – CH 3
O
I2/NaOH
CH 3 – CH = CH – CH 2 – C – ONa + CHI 3
O
79. Answer (4)

O
NaBH4
H OH
PBr3
Br
Mg/Ether

O CO2 MgBr
O
+
H
COOH
80. Answer (3)
m-chlorobenzoic acid dissolves in aq NaHCO3 while m-chlorophenol dissolves in aq NaOH
81. Answer (4)
Diborane selectively reduces carboxylic acid to alcohol in preference to other functional groups like amide,
carbonyl group and cyanide group.
82. Answer (2)
O
O3 CHO
Zn/H2O
CHO
(X) (A)
+
[Ag(NH3 )2 ]
2 1
O
3 COOH
4 5 6COOH
(B)
83. Answer (1)
CH3 CH3
CH3 MgBr
H 3O
+ CH3
O CH3 HO CH3
Conc. H2SO 4
(A)

O
C H
O O3 /Zn, H2O
CH3
C C CH3 CH3
CH3 CH3
H3C
84. Answer (2)
CH3 CH3 O
H2O
CH3–CH–C CH HgSO4, H2SO4
H3C–CH–C–CH 3
(1) EtMgBr (2) H2O
CH3 OH
H3C CH3
C=C CH3–CH–C–CH3
H 3C CH2–CH3 H2SO4, 
CH2–CH3
85. Answer (4)
Br
Br2 Alc.KOH
h
O3
CHO HO–
H
– O O
 dil.NaOH
O O
86. Answer (2)
Attack of nucleophile on carbonyl centres depends upon
(i) Sterric factor
(ii) Electronic factor
? Rate of reaction should follow the order
(ii) > (iv) > (i) > (iii)
87. Answer (4)
Increasing hindrence and electron relasing group (ERG) attached on carboxyl group decrease the reactivity.
Correct order of nucleophilic addition reaction is
CHO
CH3—CH2—C—CH3 < CH3—C—CH3 < < CH3CHO
O O
88. Answer (3)
– +
COO K CH2 – OH
(i) KOH
∵ C +
(ii) 
? C is Ph – CHO
CH3 O
Ba(OH)2
∵ D CH3 – C == CH – C – CH3

O
? D is CH3 – C – CH3
B is Ph – CH = C – CH3
CH3
O
A is C6H5 – CH2 – C – CH3
89. Answer (1)

hydrolysis
Ester   Acid alcohol
(B) (C)
Since C gives turbidity immediately with Lucas reagent (anhydrous ZnCl2 + conc. HCl). This means C should
be 3° alcohol.
O CH3
CH3 – COOH + CH3 – C – OH
O B
CH3
3° alcohol (C)
90. Answer (3)

COO H COOH
FeBr3 /Br2
Br
CH3 CH3
monobromo
 CaO
derivative
CH3
Toluene
91. Answer (2)
O
Ozonolysis + C
O C2H5 C2H5
(A) (B)
(B) I2 + NaOH
HCOONa   CHI3 (Yellow ppt )
Ag 2O
CH3 COO  Ag  (Silver mirror)
(C) I2 + NaOH
No Yellow ppt
LiAlH 4 ZnCl
C2H5  CH(OH)  C2H5 
2
 C2H5  CH(Cl)  C2H5
HCl
92. Answer (1)

CHO
CO, HCl (Gatterman koch

AlCl3 Reaction)
CN CHO
+
SnCl2 + H3O (Stephen's
HCl Reduction)
O
C—Cl CHO
H2, Pd-BaSO4 (Rosenmund

Quinoline, S Reduction)
93. Answer (1)
O
COO –Na+
CH3 Br 2
+ CHBr3
NaOH
94. Answer (3)
O O O
C S C
OH Cl Cl + HCl
Cl
N NH2
N NH2
H |
H
O
C
Cl
+
N NH3Cl–
|
H
CH3OH
O
C
OMe
N NH2HCl
|
H
95. Answer (1)
CH3  C  C  H  NaNH2  CH3  C  CNa  NH3 (g)

(A)
OH
(A)
OH OH
| H2 |
CH3  C  C  CH2  CH2  CH CH3 CH3  CH2  CH2  CH2  CH2  CH CH3
(B) Pd / C (C)
O
||
CrO3
 CH3  CH2  CH2  CH2  CH2  C  CH3
(D)
Note : The anion of (A) is a strong base and on its reaction with 4-bromobutan-2-ol, it is likely to pick up proton
from alcohol. But looking at the options, nucleophilic substitution is considered to get (B).
96. Answer (2)
Aldehydes and ketones having 3 D-hydrogen atoms undergo haloform reaction with NaOCl. The carbonyl
compound may or may not have a double bond.
O
NaOCl
CH3–CH=CH–C–CH3 –CHCl3
O O
+
– + H3O
CH3–CH=CH–C–ONa CH3–CH=CH–C–OH
97. Answer (3)

Mg
CH3 CH2 CH2Br CH3 CH2CH2MgBr
O=C= O
O
+
H3O
CH3 CH2 CH2COOH CH3CH2CH2 C O –MgBr
Butanoic
Acid
98. Answer (3)
O
CH 3MgBr + –
BrMg
O O
–
For 1 mole o 3 moles of CH3MgBr is used.

(2 moles required for ester and 1 mole for acidic H of ethyne)
99. Answer (4)
CH 3 CH3
BrMgN=C –
O MgBr
+
NC O
2CH 3MgBr
CH 3
CH3
+
H3O
O
CH3
C O=C OH
H3C H 3O
+
CH 3
100. Answer (1)

H2 SO 4
(a) CH3 COOCH2CH3 
H O
 CH3 COOH  CH3 CH2 OH
2
DIBAL-H
(b) CH3 COOCH3 
H2 O
CH3  CHO
SnCl2 , HCl
(c) CH3 C  N 
H O
 CH3  CHO
2
O
CH3MgBr
(d) CH3C  N CH3 – C – CH 3
H3O
So, the correct match is

(a)-(ii), (b)-(iii), (c)-(iv), (d)-(i)
Cyanides can be converted to aldehydes by DIBAL-H/H2O as well.
101. Answer (1)
O OH OH
NaOH (X) CN LiAlH 4 NH2
H HCN, H2O H3O
+
H
Y
Addition of HCN to aldehydes and ketones occurs slowly because HCN is weak electrolyte and does not
produce enough CN– ion. A catalytic amount of base can fasten the reaction.
HCN  OH  H2O  CN
–
O O
OH OH
+ H H2O LiAlH4 / H 2O NH2
CN
–
H H
CN
CN H
102. Answer (4)
CH3COOH + SOCl 2 CH3COCl
(A)
C6H6 AlCl 3
KCN / H2 O
HO – C – CH 3 O = C – CH3
(B)
CN
(C)
103. Answer (1)
–
O O
H + – H
Na OH OH

HOH2C
HOH2C
–
O O
H H
OH +
HOH2C HOH2C
O OH
– +
O Na
+
HOH 2C
OH
+
H3O diol
COOH
HOH2C
104. Answer (4)

• Na in presence of H2, will not release electron which are required for reduction.
• H2 gas also not get adsorbed on Na. Hence Na/H2 cannot be used as a reducing agent
105. Answer (2)
1° aromatic amines give the most stable diazonium salt
106. Answer (3)

LiAlH4
CH3 CH2 CH2 COO CH 2 CH3 +
H 3O
CH3CH 2OH + CH3CH 2CH 2CH2OH
Oxidation
CH 3COOH + CH 3CH2CH 2COOH

C 4 - Carboxylic
acid
107. Answer (2)

+
H 3O
CH3 – CH = CH 2 CH3 CH CH 3
(A)
OH
KIO/KOH
CH3COOK + CHI 3
(B) (C)
108. Answer (1)

– +
O ONa SO 3H
+ NaHSO 3
R R R R
Proton transfer
OH SO 3Na
R R
Crystalline solid
O OH
Base
+ HCN
H 2O
R R R R
CN
Cyanide as final
product not amine
109. Answer (4)

Mesityl oxide is the common name of aldol condensation product of acetone. Its structure and IUPAC name
are
CH3
110. Answer (3)
Ethylene glycol in presence of H+ will convert ketone into cyclic ketal and the ester group remains intact.
O O Ethylene Glycol
O
O O
H+
OC2 H5
OC2 H5
111. Answer (3)
(i) O3
HC C CH2 CH3 (ii) Zn
H C C CH2 CH3
O
[Ag(NH3 )2]NO 3
O
–
Ag + O C C CH2 CH 3
(bright silver
mirror) O
112. Answer (2)
CH3 COO H
(1) KMnO 4/OH–
+
(2) H
OCH3 OCH3
113. Answer (4)
C6 H5
C N – + C = N MgBr
C6H5MgBr (1 eq)
ether
OCH3 OCH3
+
H3 O
C6 H5
C=O
OCH3
114. Answer (3)

DIBAL-H – diisobutylaluminium hydride selectively reduces nitriles and esters to aldehydes.
O
O OH
i) DIBAL-H, Toluene, –78°C H
+
ii) H 3O
O
P
115. Answer (4)
O O O–
H
H –
OH–
O O O
O–
–
+
H2O
O
OH
X
O O
OH
+
H
+ H2O
Heat
Y
116. Answer (1)

CH 3 COOH
Alk. KMnO4
H+
OCH 3 OCH 3
117. Answer (1)

Reaction occur through formation of carbocation.
O OH Cl
C 2H 5MgBr Lucas
H 2O Reagent
118. Answer (2)

CN COOH
H2 O H2 O
+
H H+
119. Answer (1)

H2SO4
Cu(NO3)2 NO2
(X)
FeSO4 2+
[Fe(H2O)5NO]
conc. H2SO4
dil. HCl
Cu(NO3)2 CuS
H2S
(X) (Y)
HNO3
CuS Cu(NO3)2 + S + NO + H2O
(Y)
NH4OH 2+
Cu(NO3)2 [Cu(NH3)4]
Deep blue coloured
solution
120. Answer (1)
This problem is based on intramolecular aldol condensation reaction.
–
–
H CH O
O O 2
CHO C O
O
OH
O O O
OH
O O
+
alcohol H

O O
P(major product)
121. Answer (1)
Order of hydrolysis
O O
O
R – C – Cl > R O R
–I > + M
+M>–I
O O
> > R – C – NH2
R OR
+M>–I
+M>–I
–NH2 has greater denoting power than –OR group making –C = O less electron deficient.
122. Answer (2)
Maleic anhydride can be prepared by heating cis-but-2-enedioic acid
O O
H C H C
C OH Heat C
O + H2O 
C OH C
H C H C
O O
123. Answer (2)
Et O H (excess) OEt
Br CHO Br CH
dry HCl
OEt
(acetal)
–
tBuO
OEt
H 2C = C
OEt
124. Answer (4)
CN CH3C = NMgBr
CH3MgBr
(1 eq)
+
H3O
O
C
CH3
(P)
P can give Iodoform test.

125. Answer (2)
(i) DIBAL-H
R  CN 
 R  CHO
(ii) H2O
126. Answer (3)

O OMg Br
C2H5MgBr, dry ether
H2O, HCl
OH
Cl
127. Answer (3)
O O OH O O
O
H I2/NaOH O Na
– +
NaOH Iodoform reaction
Filtrate + HCl
O O
OH
128. Answer (4)
NH2–NH2
C2H5O –Na+
O
129. Answer (4)
O OH
O +
O (i) H 2SO 4
(ii) NaOH
O
HO OH
Derivative of phenolphthalein
130. Answer (3)

Mo O
2 3  CH  CH  CHO
O2  CH3  CH2  CH3  3 2

Mn(OAc)2 – manganese acetate oxidizes alkanes to carboxylic acids in presence of O2 and heat.
131. Answer (1)

CrO H SO
CH3 CH2 OH 
3 2 4
Jones reagent
 CH3 COOH
In the rest of the options acetaldehyde will be formed.
132. Answer (3)

+
H3O
CH3 CH2 CN  CH3 – CH2 – COOH
O
SOCl 2
CH3– CH2 – C – Cl
Pd/BaSO 4, H2
O
CH3 – CH2 – C – H
Correct option should be (3).
133. Answer (4)
COOH OH
O2 N NO2
and are acidic enough to liberate CO2 with NaHCO3 solution.
NO2
134. Answer (1)

O
C2H 5
CH3 COCl Zn – Hg
AlCl3 HCl
Br2 /AlBr3
C2H 5 C2H 5
NO 2
HNO 3/H2 SO4
Br Br
135. Answer (3)
H /CO
CH3 CH2 CH  CH2 
2
Rh catalyst
 CH3 CH2 CH2  CH2  CHO
136. Answer (1)

O
2,4 DNP test is used to identify – C – group. It gives addition reaction with carbonyl compounds. So, it can
be used to identify aldehyde in the given option. It gives yellow/orange PPt with carbonyl containing compounds.
137. Answer (1)
CH2 OH
CHO –
HCHO, OH –
(cannizzaro + HCOO
CH3O reaction)
OCH3
NaH
–
CH2OC2H 5 CH2 – O
C2 H5 Br
HI
OCH3 OCH3
CH2I
+ C2H5 OH + CH3OH
OH
138. Answer (4)
O OH
CH2 – CH 2 – CH CH2 – CH 2 – CH
NaOH
CH2 – CH – CHO CH2 – CH

CHO
H – OH 
CHO
139. Answer (4)
O
Cl Cl
Hydrolysis
373 K
(C 4H8 Cl2) (C4H 8O)
A B
B is a ketone, cannot give Tollen’s test.
A o 2, 2-Dichlorobutane
B o Butan-2-one
So, correct option should be (4).
140. Answer (66.67)
O
CH3 – C – CH2 – CH 3
(A) 1. CH3MgBr
+
2. H3O
OH
CH3 – C – CH2 – CH 3
CH3
Cu/573 K
CH3 – C = CH – CH3
CH3
A is C4H8O
48
% of C =  100 = 66.67
72
141. Answer (04)
CH – C  N
CH3
+
(i) C 2H5MgBr (ii) H3O
O
CH – C – C2H5
CH3
(A)
(i) CH3MgBr (ii) H2O

OH
* – C*– C H
* CH 2 5
*
CH3 CH3
(B)
Number of chiral centres in the product (B) = 4.
142. Answer (02)
RCHO  2[Ag(NH3 )2 ]  30H –  RCOO  2Ag  2H2 O  4NH3

For 1 mol of R-CHO, 2 mol of [Ag(NH3)2]+ is reduced.
2[Ag(NH3 )2 ]+  2e –  2Ag  2NH3

143. Answer (03)
O
O O
N–NH– C–NH2
+ NH 2 C NH NH 2 

Step-3
Chapter 13
Carboxylic Acids
Solutions
SECTION - A
Objective Type Questions (One option is correct)
1. Answer (1)
2. Answer (3)
OH
+
H Na : liq NH3
HO –H 2O C 2H 5OH
OH IH D =3
3. Answer (2)
CH3
R'SH
CH3 C CH3 CH3 C S R'
O S
R'
H2/Ni
CH3
CH3 C H
4. Answer (3)
In the presence of Hg2+/H3O+ hydration of alkene and alkyne both will take place.
5. Answer (3)
OH OH O O
CH2OH CHO –
OH
PCC (i) CH3MgBr PCC (i) OH , 
CH3 CH CH CH3 CH3 C C CH3 CH3 C COOH
(ii) H2O (ii) H+
CH2OH CHO B
A CH3
6. Answer (2)
E.D.G at para decrease the rate of reaction.
7. Answer (4)
OH
Ph C Ph
H + OH –
C H
O O
–
Ph C H
(A) O H
Ph C
–
O + PhCH2 OH Ph C OH + Ph C H
O O O –
H+ (B)
Ph C OH
O
8. Answer (4)
OH
A = Ph O
9. Answer (3)
Rate of haloform reaction is same for halogens (Cl2 = Br2 = I2)
10. Answer (1)
11. Answer (3)
CH2–CHO
A is
12. Answer (3)

Rate of nucleophilic substitution reaction v strength of leaving group.
13. Answer (3)
C OH
CH2 C
 (i) O3 O OH– –H2O
+ O
(ii) OH–:H2O CH
CH2 C C
O O
14. Answer (1)
O Cl
PCl5 NaNH 2(3eq)
CH3 CH 2 C H O °C
CH 3 CH2 CH CH 3 C C – Na+
Cl
CH 3 CH 2 Br
CH 2 CH 3 CH 3
Cold CH2 CH 3 H2
CH 3 CH CH KMnO4 C C CH 3 C C CH2 CH 3
Pd-BaSO 4
H H
OH OH
Cl OH O
2NaNH2 (i) Hg (OAc)2: H2O
CH3 CH2 CH CH3 C C H –
CH3 C CH2 CH3 C CH3
(ii) NaBH4 : OH
Cl
O
O OH O
–
 CH3 C H OH
CH3 CH CH C CH3 CH CH2 C CH2 C CH3
–H2O
CH3
CH3
15. Answer (1)
O
Acidic strength H O > H O CH COOH < CH COOH
2 2 2 3 3
16. Answer (2)
Sodalime
CH3 – CH2 – COOH  CH3 – CH3 + CO2
(a) KCN Cl2(1 eq.) / Dark

+
(b) H3O
CH3 – CH2 – Cl
17. Answer (3)

Ph
P  CH3CH2 CH CH 2 OH
18. Answer (3)
18 H3O 18
R C O CMe3 R C O H + HOCMe 3
O O
(A) (B)
SECTION - B
Objective Type Questions (One or more than one option(s) is/are are correct)
1. Answer (1, 2, 4)
O
H O O
MeEt C C Ph Me
–
OD O D2O Fast
CH3 C C Ph C C Ph
Slow
Et
Et Me C C Ph D
(I)
Et
2. Answer (2, 3)
pH = 5
NH 2 + O C N C
H H [P]
[P] is known as Schiff’s base or Aldimine.

3. Answer (1, 3)
4. Answer (1, 2, 3)
O O O O OO
NaOBr +
C OH
C C O– Na+ H
CH3 CH3 Haloform CH3 CH3
reaction
O O
H3C CH3
 LDA CH3 Cl
CH3
A B
5. Answer (2, 4)
In intramolecular aldol condensation, carbanion always attacks on aldehyde group. So, free aldehyde group
is not present in product. And only five or six membered ring products are formed. So, (1) and (3) are not the
major product.
6. Answer (1, 2)
Only benzoyl chloride and benzoic anhydride is used for the benzoylation of ethyl amine and it gives
substitution product via addition/elimination mechanism.
O O O
|| || ||
CH3CH2 NH2 + C — Cl or C—O—C
O
||
CH3CH2 C
Ethyl benzamide
7. Answer (3, 4)
Fact
8. Answer (1, 2)
Benzaldehyde reduces Tollen’s reagent while acetophenone is not while acetophenone reacts with sodium
hypoiodite and give iodoform reaction while benzaldehdye is not.
9. Answer (1, 2)
O O O CH2 OH
SeO2 OH
–
– + B
CH3 C H H C C H C O Na
A Cannizzaro
reaction O
 Al(OEt)3
Tischenko reaction
O O
CH3 MgBr
CH3 C O CH2 CH3 CH3 C CH3 + CH3 CH2OMgBr
C CH3MgBr
–
O MgBr
H3C C CH3
CH3
H3O+
OH
H3C C CH3
CH3
10. Answer (2, 3, 4)
–
O O
–
C + 2e 2 C
H3C CH3 H3C CH3
– – –
O O O OH OH
+ +
H2O; H H
C H3C C C CH3 CH3 C C CH3 –H2O
H3C CH3
CH3 CH3 CH3 CH3
(A)
+
OH OH CH3 O H CH3 O CH3
CH3
+ +
–H CH3 C C CH3
H3C C C CH3 C C CH3 CH3 C C CH3
+
CH3
CH3 CH3 CH3 CH3
(B)
11. Answer (1, 4)
Only those compound which has equal or more acidic hydrogen than carboxylic acid liberates CO2 with
aqueous NaHCO3.
12. Answer (1, 2)
In (1) and (2) cyclopentanone is formed. While in (3) and (4) cyclobutanone and propanone is formed which
is less stable due to ring strain and almost no yield is observed.
13. Answer (1, 3)
Mg/Et2O CO2
(1) CH2 — Br CH2 — Mg — Br H3O+ CH2 — COOH
NaCN
–
(i ) OH/H2O
(2) CH2 — Br CH2 — CN (ii) H3O+ CH2 — COOH
14. Answer (2, 3, 4)
In acid catalyzed esterification of carboxylic acid H+ attack on double bonded oxygen atom not on
O
single bonded oxygen atom. So, R C is not formed.
O H
H
15. Answer (1, 3)
–
In this reaction, OH does not attack on C—
— O due to steric hinderance and it attacks on the back side of
O18 and abstracts CH3. This is the SN2 mechanism
H3C O H 3C O
OH
Et
C C
Et
C C
18 H + CH3OH
18 O CH 3 O
iPr iPr
SECTION - C
Linked Comprehension Type Questions
Comprehension-I
1. Answer (1)
O O H
O O O H O
C C C C
CH3 CH2 CH3 CH3 C CH3
H
O O O H O
C C CH3 C C CH3
CH3 CH2 CH2 CH3 CH CH2
O O O H O
C C CH3 C C CH3
CH3 CH2 O CH3 CH O
2. Answer (2)
O O H
O O

unstable
due to dipole-dipole  100%
repulsion
Comprehension-II
1. Answer (4)
In acid derivatives, acyl carbon is connected with good leaving group. So, it gives nucleophilic acyl substitution
reaction.
2. Answer (1)
O
||
is most reactive because —Cl is the good leaving group.
C
Ph Cl
3. Answer (1)
O
Carbonyl character is most suppressed in C R because in this case the lone pair of e of N

N R
atom more strongly participate in resonance with C O group.
Comprehension-III
1. Answer (3)
O
|| O
C ||
OH – H2O
OH O
C ||
||
O O
Only it forms stable five membered ring compound other forms 4 membered or seven membered ring
compound which is least stable.
2. Answer (3)
Those dicarboxylic acid will not form cyclic anhydride in which both —COOH groups are present on trans
position.
3. Answer (4)
O
COOH ||

COOH 
C
COOH O
–CO2
COOH COOH C
||
O
SECTION - D
Matrix-Match Type Questions
1. Answer A(q), B(r), C(s), D(p)
All are facts.
2. Answer A(q, r), B(p, q, r, t), C(p, s, t), D(p, t)
Fact.
3. Answer A(q, r), B(p, s), C(s), D(p, s)
(A) Benzaldehyde can give Cannizzaro reaction and Benzoin condensation.
(B) Acetone can give aldol condensation and haloform reaction.
(C) Chloral can give haloform reaction.
(D) Acetaldehyde can give aldol condensation and haloform reaction.
4. Answer A(p, q, r, s), B(r, s), C(p, q, s), D(p, s)
All reactions are fact.
SECTION - E
Assertion-Reason Type Questions
1. Answer (1)
Fact
2. Answer (4)
Only primary amine reacts with carbonyl compound to form Schiff’s base.
3. Answer (4)
The OD of D2O doesn’t participate in Cannizzaro’s reaction.
4. Answer (3)
Only aromatic aldehyde doesn’t give Benedict’s test while aliphatic aldehyde gives positive Benedict’s test.
5. Answer (3)
Acetic acid doesn’t undergo haloform test but it contains D-hydrogen atom.
6. Answer (2)
Methanoic acid is stronger acid than ethanoic acid. Methanoic acid also acts as reducing agent while ethanoic
acid doesn’t acts as reducing agent.
7. Answer (4)
E-Keto acid is easily decarboxylated because it forms most stable reactive intermediate on decarboxylation.
SECTION - F
Integer Answer Type Questions
1. Answer (7)
2. Answer (13)
+
O H O H O
OH OH
TsOH + –H
+
(I)
–H2O +
OH
Product (P)
CH3
OH CH3
TsOH + + CH3
(II) C OH + –H+
–H2O C O H C O
OH CH3
OH CH3 H3C H3C
CH3
(Q)
3. Answer (14)
H3C CH3 H3C CH3 H3C CH3

Zn Hg
HCl + a = 15, b = 1 then a – b = 14
O O O CH3
(X) (Y)
4. Answer (20)
O OH
(I)NaOH
(II) H+ COOH (Q)
O
O O OH
C H KCN C CH
(P)
C(sp3 ) in P and Q = x = 1 + 5 = 6
x + y = 6 + 14 = 20
C(sp2 ) in P and Q = y = 13 + 1 = 14
5. Answer (2)
OH is not enough strong to deprotonate Alkyne and aliphatic alcohol.
6. Answer (5)
7. Answer (18)
O
C O–Na+
(I) NaNH2; liq NH3 H3C CH3
CH  CH CH  C Na
– +
H3C C C C H
CH3
NH4Cl/H2O
OH
CH3 C C C H
CH3
Hg2+;H3O+
OH O
CH3 C C CH3
CH3
OH– O
Ph C H
OH O OH
H3C C C CH2 CH Ph
CH3
OH O
CH3 C C CH CH Ph
CH3
8. Answer (53)
CH3 MgBr
C  C– Mg Br
+
H CC H CH4 + H
O C O
O C O–
O (G) O O
HO H+ C
H C CH2 C OH + 2 2+ H CC C OH

H /Hg C
KMnO4 H
COOH
CH2 (H)
COOH
 O
CH3 C O H (I)
Number of –COOH is H is 2, number of V bonds = 7, then x = 2 and y = 7, x2 + y2 = 4 + 49 = 53
9. Answer (13)
4 acid isomers
O
H3C H2C H2C H2C C OH (I)
O
H3C H2C CH C OH (II)
CH3
O
H3C CH CH2 C OH (III)
CH3
CH3 O
H3C C C OH (IV)
CH3
9 ester isomers
O O O
H C O CH2 CH2 CH2 CH3, H C O CH CH2 CH3, H C O CH2 CH CH3

CH3 CH3
O O O CH3
H3C C O CH2 CH2 CH3, CH3 C O CH CH3, H C O C CH3
CH3 CH3
O O O
H3C CH2 C O CH2 CH3, H3C CH2 CH2 C O CH3, H3C CH C O CH3
CH3
SECTION - G
Previous Years Questions
1. Answer (A)
O3 CHO intramolecular
CHO
Zn, H2O CHO aldol condensation
E F
2. Answer (C)
O O O O
 I2 + NaOH
–CO2 C  C 
iodoform reaction
Ph  OH Ph CH3 Ph ONa + CHI3
-keto acid E G
3. Answer (C)
O H O
–
C C
O –H

O
H H
O O
Most acidic Stabilized by strong
intramolecular hydrogen
bonding
4. Answer (B)
H
– H :O – CH2 – R
:
CH2
O O O O R
H

–H
CH2 – R
O O
An acetal
5. Answer (C)
CH2OH
|
OH + HCHO/OH
CH3 — CHO + H — CHO 
Aldol
 HOCH2 — CH2 — CHO 
Aldol
HOCH2 — CH — CHO
CH2OH CH2OH
| |
+ HCHO/OH + HCHO/OH

Aldol
HOCH2 — C — CHO 
Cannizzaro HOCH2 — C — CH2OH
| |
CH2OH CH2OH
? Number of aldol reactions = 3
6. Answer (B)
COOH
O
E-keto acid undergoes easy decarboxylation just by heating through the formation of six membered
transition state.
7. Answer (B)
O OH CN CN
CN 95% H2SO4
CH3 – CH2 – C – CH3 CH3 – CH2 – C – CH3 
CH3 – CH = C – CH3
8. Answer (D)
Carbolic acid (Phenol) is weaker acid than carbonic acid and hence does not liberate CO2 on treatment with
aq. NaHCO3 solution. Benzoic acid, benzenesulphonic acid and salicylic are more acidic than carbonic acid
and hence will liberate CO2 with aq. NaHCO3 solution.
9. Answer (D)
O O– CH3
Cl Cl
CH3
CH3
O
CH3 – MgI
10. Answer (A)
COOH O– O
H C H
HO OH
O O
(I)
(stabilizes by H-bonding)
COOH O O– H
OH O
(II) (stabilizes by H-bonding)

COOH COO–
OH OH
(III) (stabilizes by –I effect)
COOH COO–
OH OH
(IV) (destabilizes of +m effect)
? Acidity order is I > II > III > IV.
11. Answer (A)
O O
C C
H – CH = O, NaOH, 
(crossed aldol condensation)
CH2
OH
OH O O
H H
C=O C=O
H H
–
OH ,  H+
HO
12. Answer (B)
I. HC  C  COOH
sp
II. H2C  CH
2
 COOH
sp
III. MeO COOH

(EDG) 2
sp
IV. H3 C  CH2  COOH

sp3
+I effect decreases the acidic character of carboxylic acid and –I effect increases the acidic character.
Since the electronegativity order of 'C' attached to carboxylic acid is sp > sp2 > sp3, hence the order is
I > II > III > IV.
II is more acidic than III since the electron donating group is attached to benzene ring.
13. Answer (B, D)
C6H5COOH + NaOH o C6H5COONa + H2O
C6H5COOH + NaHCO3 o C6H5COONa + CO2 + H2O
C6H5CH2 – OH + NaOH o No reaction
C6H5CH2OH + NaHCO3 o No reaction
C6H5CH2COOH + NaOH o C6H5CH2 – COONa + H2O
C6H5CH2COOH + NaHCO3 o C6H5CH2COONa + CO2 + H2O
C6H5CH2OH + NaOH o No reaction
C6H5CH2OH + NaHCO3 o No reaction
14. Answer (A, C, D)
O
OCOCH 3
CH2OH CH2
O LiAlH4 OH Excess (CH3CO)2O OCOCH3
H3C H3C H3C

T Optically W
inactive (Molecular formula
(U) C10H18O4)
COOH
+
CrO3/H
COOH
H3C
V
Hence answer is (A, C, D).

15. Answer (A, B, C, D)
AlCl3
(i) Cl AlCl4 (P)
(AROMATIC)
Na
NaH
(ii) (Q) + H2
(AROMATIC)
(NH4)2CO3
(iii) R
100–115ºC
O O

(NH4)2CO3 2NH3 + CO2 + H2O
 IMPE
+ NH3
O O O O NH2 O NH2 OH
H
H H H H
N N N
 IMPE
–2H2O
HO OH O OH
(R) AROMATIC
HCl
(iv) O OH Cl (S)
(AROMATIC)
16. Answer (C)
Reaction I : C Br2 (1.0 mol)

CHBr3 + CH3COONa
CH3 CH3 aqueous NaOH
(1.0 mol)
O O
Br2 (1.0 mol)
Reaction II : C CH3COOH
C
CH3 CH3 CH3 CH2Br
(1.0 mol)
17. Answer (A)
CH3 CH3
CH3 O OH
O H O O O +
O
KOH, H2O H
CH3
O
O O

+
(Minor) (Major)
18. Answer (A, B, C)
All aldehydes gives Tollen's test as shown below
O
R – CH = O + [Ag(NH3)2 ] R – C – O– + Ag+ NH+4
+
(Silver mirror)
D-hydroxy ketones are oxidised to 1, 2 diketones and Ag+ is reduced to Ag.
OH O O O
+
[Ag(NH3)2] +
Ph – CH – C – Ph Ph – C – C – Ph + Ag+ NH4
19. Answer (B, C)
O O
(i) O3/CH2Cl2
CH3 CH3 C–H+H–C–H
(ii) Zn/H2O
Undergoes
Cannizzaro's
reaction
CH2 O O
O3/CH2Cl2
C C + H–C–H
Zn/H2O
CH3 CH3
Undergoes
Haloform reaction
O O
O3/CH2Cl2
CH3 C – H + CH3 – C – H
Zn/H2O
CH3 CH3 Undergoes

Cannizzaro's reaction
CH3
CH3 O CH3 CH3
O3/CH2Cl2
C +
Zn/H2O
CH3 O
CH3
CH3 Undergoes
Haloform reaction
20. Answer (A, B, D)
H
H
C
H O Me Me
Me C C Me Conc.H2SO4
(A) + 3H2O
O C H 
H H H
H Me
C O
H C
Me
Me
|
C H Me Me
H C
C Heated iron tube
(B) 873K
C C
Me C Me
Me
|
H
O O
|| O Na
C—Me C
| |
Br2/NaOH
(C)
(Haloform reaction)
Me
Me—C C C C—O Na
|| || Na O || ||
O O O O
+
3H3O
COOH
Soda lime

(decarboxylation)
COOH
COOH
CHO CH3
Zn/Hg,HCl
(D) (Clemmensen reduction)
OHC CHO CH3 CH3
21. Answer (B, D)
O
C C – CH2 – CHO C – CH2 – CH2 – CHO
HgSO4, H2SO4 (dil.)
OMe OMe AgNO3, NH4OH
O O
–
CH2 – CH2 – CH2 – COOH C – CH2 – CH2 – C – O
Zn-Hg
(Q)
HCl
OMe OMe
SOCl2 , Py
O
CH2 – CH2 – CH2 – C – Cl
AlCl3 O Zn-Hg
(S)
HCl
OMe OMe OMe

(R)
22. Answer (B, D)
O
O
CH3 H C CH 3 CH3 H C CH3
H3C 3 CH3 3
O (i) Zn - Hg/HCl
H 3C CH 3
AlCl 3 (ii) H 3PO 4
(P)
C=O
HOOC
(Q)
CH3 CH3
H3C H 3C CH3 H 3C H3C CH 3
(i) CH3 MgBr
H 3C + H3C
(ii) H 3O
H 3C
O (iii) H 2SO 4/D
(R) (S)
23. Answer (A, B)
CH 3 CH3
N2Cl CN
CuCN
(A)
273 K
DIBAL – H

then HO
3
O
N2H4 C H
KOH, 
CH 3 O O
Br C OH C Cl
(1) Mg/THF SOCl2
(B)
(2) CO2
+
(3) H /H2O
H2 /Pd-BaSO4
O
C H
Zn-Hg
HCl
CH 3 CH 3 CH 3
(i) BH3 H 2O2/OH
–
(C)
BH 2 OH
PBr3
Zn
dil HCl
Br
O
C H
O3 O N2H4
(D)
Zn/H2O C H KOH, 
24. Answer (C)

25. Answer (C)
26. Answer (B)
27. Answer (D)
28. Answer (A)
29. Answer (C)
Solution of Q. Nos. 27 to 29
O
(1) NaBH4
H3C CH2 C C CH2 C H CH3CH2 C C CH2 CH2Br
(2) PBr3
(I)
(1) Mg/Ether
(2) CO2
+
(3) H3O
Me Cl SOCl2
CH3 CH2 C C CH2 CH2COOH
O (J)
(K)
H2/Pd, BaSO4, quinoline

(Lindlar’s calatyst)
CHO
(cis product) (L)
30. Answer (B)

31. Answer (A)
32. Answer (D)
O OH
Ph – C – CH3 + PhCH2MgBr Ph – C – CH2 – Ph
CH3 H
Conc. H2SO4 dehydration
Ph – C = CHPh Ph CH3
or
CH3 H Ph
I
Ozonolysis
O
Ph – C = O + Ph – C – H
CH3 J
K
Cannizzaro's
KOH reaction
Aldol followed
KOH
by dehydration
PhCH2OH + PhCOOK
O
H3C L
Ph
Ph H
M
33. Answer (B)
34. Answer (A)
35. Answer (B)
Me Me Me
(i) MeMgBr H2SO4 (i) O3
(ii) H3O
+ OH (ii) Zn-H2O
O Me Me Me Me Me
P Q
– Me
(i) OH/H2O O
O
+
(ii) H ,  C
O Me
Me Me Me Me
S R
36. Answer (B)
37. Answer (A)
38. Answer (D)
Solution of Q.Nos. 36 to 38
CH3 O
H3C
1. K2CO3 C
C H
2. H H C H
H3C C H3C
H C
(Q) CH2
(P) O 3. H+
O OH
(R)
HCN
OH
H3C CN
CH O
C C H3C
H3C CH
Hydrolysis
C OH
H2C HO H3C
O H CH2
 OH
(S)
OH
H3C
C O
H3C
H2C O
39. Answer (C)

40. Answer (A)
Solution of Q. Nos. 39 and 40
CHO CH = CH–COOH
(CH3CO)2 O (i) H2 , Pd/C

CH3 COONa (ii) SOCl2
(iii) Anhyd. AlCl3
O
41. Answer (B)

H COOH COOH
dil. alk. KMnO4 H OH
C
H OH
C
COOH
H COOH
(S)
(P)
H COOH
COOH COOH
C dil. alk. KMnO4 H OH HO H
C HO H + H OH
HOOC H COOH COOH
(Q) (T) (U)
42. Answer (A)
O
H COOH
C H2/Ni
O

C
HOOC H
(Q) O
(V)
O O
Zn(Hg)
O+ AlCl3 H3PO3
anhydrous HCl
HO HO
O O O O
(V) (W)
43. Answer (A)
O O
NH2
KMnO4/H +
C OH NH3 C NH2 Br2/NaOH
 C OH  C NH2 (Hoffman bromamide)
NH2
O O
(P) (Q) (R)
44. Answer (B)
C
Br – C
C=O
O
O O O
CH2
C – NH2 C C C
 CH3
–NH3
N–H N–C
C=O
C – NH2 C C
(Q) (S)
O (Phthalimide) O O O
CH2
+
H3O
CH3
O
O C – OH
C – C – C – OH+
NH2 C – OH
(alanine)
(T) O
45. Answer (C)
46. Answer (C)
Solution of Q. Nos. 45 and 46
– +
O OMgBr
C(CH3)3 C – OEt CH3MgBr (excess)/(C2H5)2O C(CH3)3 CH3–C–CH3
(P)
H2O
H H
O O–H
C(CH3)3 C(CH3)2 H2SO4/ C(CH3)3 CH3–C–CH3
0°C
(Q)
–H2O (dehydration)
O CH3
CH3 CH3
CH3 CH3–C–Cl/AlCl3 C(CH3)3
C(CH3)3 C(CH3)2 C(CH3)3 (Acylation)
(alkylation)
(R) COCH3
(S)
47. Answer (C)
CHO O—H
COOH
Ac2O Br Moist
CO/HCl Br2/Na2 CO3
AlCl3 AcONa COOH KOH
(anhy.) D
(X) (473 K) (Y)
CuCl
48. Answer (A)
O
CO/HCl – C– H AC2O/NaOAC – CH = CH – COOH
AlCl3/CuCl
(X)
H2/Pd–C
– CH 2 – CH2 – COOH
H3PO4
O
(Z)
49. Answer (A)
CH2–CH2 O
(C11H12O2) dibasic acid OH OH O
oxidation C C (CH 2)2 O
(P must have O
P, Organic acid
multiple bond) O
dacron
dibasic acid must be terephthalic acid i.e.
COOH
to give dacron, compound must have benzene based structure
COOH
Ozonolysis
C11H12O2 ketone + oxidized products of benzene.
COOH
Possible structure of P is (C11H12O2)
COOH COOH
O
oxidation
+
COOH
(P)
COOH
ozonolysis
O
+ oxidized product
ketone
(P)
O O Me
COOH COOH C–Cl C–Me H–C–OH
H 2/Pd-C SOCl2 MeMgBr, CdCl2 NaBH 4
(P) (Q)
Me Me
– +2 –
CH–OH CH–Cl Me–CH Mg Cl Me–CH–COOMgCl Me–CH–COOH
+
HCl Mg, Et2O CO2 H 3O
(Q) (R)
50. Answer (B)
 –
COOH COOH CONH 2 NH2 N C NH CH3
H2 /Pd-C NH3 / Br2 /NaOH CHCl3/KOH H2 /Pd-C
P
51. Answer A(p, s); B(q); C(q, r, s); D(q, r)
52. Answer A(p, q, s, t), B(s, t), C(p), D(r)
(A) CH3CH2CH2CN will give mentioned reaction with other reagents.
(B) Esters will be reduced by DIBAL-H and it will be hydrolyzed by alkaline hydrolysis.
(C) Alkenes are only reduced by catalytic hydrogenation.
(D) Primary amines will give +ve carbyl amine test with NaOH and CHCl3.
 
O
NaOH
CH3 CH2CH2CH2 — NH2 
CHCl
 CH3 CH2CH2CH2 — N  C
3
Carbyl amine
53. Answer A(p, q, t); B(p, s, t); C(r, s); D(p)
NCl
SN2
Br
O
(A)
O E2
(B) OH ZnCl2/HCl Cl [Nucleophilic substitution]
(RCO)2O
O
C
O R
HO NCl
C
NCl H
O
OH
C
(C) H
O
OH O O
C
R C O C R H
O
O R
Br s
Nu
Nu
(D) (SNAr)
NO2 Mechanism NO2
A and B can undergo dehydrogenation.
54. Answer A(r, s); B(t); C(p, q); D(r)
(A) NN + O—H

Cl–
OH
N=N O
H
N=N O
? Coupling reaction and electrophilic substitution reaction.
OH OH OH OH2
+H
(B) CH3 — C — C — CH3 CH3 — C — C — CH3
CH3 CH3 CH3 CH3
O CH3 OH
CH3
CH3 — C — C — CH3 CH3 — C — C
CH3
CH3 CH3
Carbocation intermediate
O OH
O H3O
+
LiAlH4 H
(C) C Nucleophilic addition
C H C H
CH3
CH3 CH3
Racemic mixture
Nucleophilic
H Base S substitution S
(D)
S Cl Cl
B
55. Answer A(r, s, t), B(p, s), C(r, s), D(q, r)
O O
H CH2 H2C
O O O O
OH Nucleophilic addition
A.
Carbanion
O OH O
Dehydration HO – H
–H2O
O Cl
Cl O O
B. CH3MgBr Nucleophilic
CH3 substitution CH3
Carbanion
Nucleophilic
addition
H
..
.O
. O H H
18 18 18
H–O H–O O  H–O O O
–H
Nucleophilic +H Dehydration
C. addition
H

+H Electrophilic
D. OH Dehydration substitution
H
Me Me
56. Answer (A)
O
O
(1) C6H5CH2 – C – O CH3 C6H5CH2 + CO2 + CH3 – O
O
O CH3 CH3
(3) C6H5CH2 – C – O C CH3 CO2 + C6H5CH2 + CH3 – C – O
CH2 – C6H5 CH2 – C6H5
O
C O CH3 O CH3
(4) C6H5 O C – CH3 C6H5 – C – O + O – C – CH3

CH3 CH3
O O
C O C
(2) C6H5 O CH3 C6H5 O + CH3 – O
57. Answer (D)

h
Br2 Br + Br
CH3 CH2
+ Br + HBr
CH2 CH2 – Br
+ Br2 + Br
58. Answer (C)

– +
COO Na
NaOH
C CH3 Br2 + CHBr3
O
H2O/H+
COOH
It is haloform reaction.
59. Answer (C)
O
CH3 – C
O
CH3 – C
CH = O CH = CH – COOH
O
CH3 COOK
Cinnamic acid
It exists in two geometrical forms.
C –H C –H
H – C – COOH HOC – C – H
Trans O
isomer Cis isomer
It is basic example of Perkin's reaction.
60. Answer (D)
Ph Ph O O
Me Ph
I2/NaOH
(P) HO + H2SO4 Me Me C – OH
Ph HO Me Ph Me Ph
O
Ph
NaOBr
Me C – OH
Ph
P o 1, 5
Ph Ph O Ph
H [Ag(NH3)2]OH
(Q) H2N OH + HNO2 Me Me COOH
Ph Me Ph H Ph
Ph
Fehling
Me COOH
Solution
Ph
Q o 2, 3
Ph Ph O
Ph
(R) HO OH + H2SO4 Ph
Me Me Me Me
NaOBr I2/NaOH
Ph Ph
Me COOH Me COOH
Ph Ph
R o 1, 5
Ph Ph
Ph
(S) Ph OH + AgNO3 Ph CHO
Br Me Me
Fehling [Ag(NH3)2]OH
solution
Ph Ph
Ph COOH Ph COOH
Me Me
S o 2, 3
61. Answer (A)
Cl KCN CN +
H 3O / COOH LiAH 4
(III)
CO 2CH3 CO 2CH 3 CO 2H
Conc.
CH 2OH H 2SO 4 CH 2 OH –H 2 O
:
+ –H
+
O
CH 2 OH CH2 OH2
(Q) (R)
CH2OH
CO2Me CH2OH Conc.
LiAH4 H2SO4
(IV) +
CH2Me CH2OH CH2—OH2
(Q)
+ –H
+
O—H O
(R)
(III), (Q), (R) ; (IV), (Q), (R)
62. Answer (B)
CN DIBAL-H CHO dil. HCl CHO NaBH 4 CH2OH

(I)
O O
CHO CH 2OH
O O
(Q)
+
Conc. CH 2 OH2 –H
+
H2 SO 4 + O O
CH 2 OH 2 H
(R)
OH Conc.
(i) O3 CHO NaBH4 H2SO4
(II)
(ii) Zn/H2O O
COOH COOH COOH
O
(P) (S) (U)
(I), (Q), (R); (II), (P), (S), (U)
63. Answer (1)
O
O
1. O3 1. NaOH(aq)
2. Zn-H2O 2. Heat
64. Answer (4)

Carboxylic acids and aromatic alcohols dissolves in aqueous NaOH.
COOH OH OH COOH
, , ,
N
H3C CH3
will be soluble in aqueous NaOH.
65. Answer (2)
O O O O O
+
OH
H3O OH *
O
OH (–H2O, –CO2)
O O O O O
O
HOOC (i) O3
HOOC (ii) H2O2
O (P)
So, final product (P) has two carboxylic acid
Heating causes evaporation of water and due to which concentration of acid increases and in concentrated
acidic medium decarboxylation as well as dehydration will take place.
66. Answer (5)
O
1 2 3 4
(I) CH3 CH2 CH2 CH2 C CH3
5 6
O
(II) CH3 CH2 CH2 C CH2 CH3

CH3 O
(III) CH3 CH2 CH C CH3

It has chiral centre
CH3 O
(IV) CH3 CH C CH3
CH3
CH3 O
(V) CH3 CH C CH2 CH3

O
(VI) CH3 CH CH2 C CH3
CH3
Only (III) form diastereomers on addition reaction so, desired ketones as per addition reaction is 5.
67. Answer (4)
CHO
CO, HCl
(Gatterman Koch Reaction)
Anhyd AlCl3/CuCl
OH
CHCl2 CH CHO
H2O OH
100°C –H2O
COCl CHO
H2
(Rosenmund Reduction)
Pd–BaSO4
COOMe CHO
DIBAL–H
Toluene, –78°C H2O
68. Answer (24.00)
H
O O +
O
O CH3 O CH3
C C C+
H5 C6 C6H5 H5C6 C6H5
conc. H2SO 4 —CH 3OH
C6H5 C6H5
(P)
+
O
SO3H
O SO3H O C
C
C6H5
H 2SO4
SO3 H
(Q)
Degree of unsaturation of Q = 24
69. Answer (1.62)
70. Answer (3.20)
Solution of Q.Nos. 69 and 70
H 2O NaNH 2
Mg2C3 C3H 4 (P) CH3 C C CH 3
4g MeI
(Q)
Hg /H
2+ +
Red hot
iron tube
O
CH3 C CH 3 (S)
Ba(OH)2/ (R)
O
CH 3 C CH C CH3
CH3
(T)
NaOCl
O
CH 3 C CH C OH (U) + CHCl 3
CH3
4 g of C3H4 = 0.1 mol
From 0.1 mol of P,
0.01 mol of R will be produced
1.62 g of R is produced
From 0.1 mol of P,
0.032 mol of U is produced
3.2 g of U is produced


CLS ENG 22 23 XII Che Target 5 Level 1 Chapter 13

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Step-1

27. Answer (1)

Fehling solution does gives red colour with benzaldehyde.

C N Ph—C N.MgBr COPh

(ii) CH3COOH + N2 + H2O

KMnO /H Ca(OH)

(iii) 2CH3 COOH  Zn (CH3 COO)2 Zn  H2

It is Reimer Tiemann reaction.

CH3 CH3 CH3 CH3

Migrating power of p-tolyl is more than m-anisyl.

+ve charge due to aromaticity.

In this reaction, active methylene group (—CH2—) is oxidised to C—

15. Answer (1)

The above conversion is known as iodoform reaction.

[Carboxylic Acids (Preparation and Reactions)]

[Acid Derivatives (Preparation and reactions)]

29. Answer (2)

30. Answer (2)

31. Answer (4)

32. Answer (2)

33. Answer (1)

34. Answer (3)

35. Answer (1)

36. Answer (2)

This is known as Stephen’s reduction.

38. Answer (4)

39. Answer (1)

40. Answer (2)

41. Answer (01)

Grignard reagent will not interact with product.

42. Answer (05)

A and B are non-aromatic compounds.

Statements P, Q, R, U and V are incorrect.

43. Answer (13)

< Product >

< Product >

Number of hyperconjugable hydrogens = 13

44. Answer (01)

45. Answer (02)

Each –CHO can produce an oxime.

Previous Years Questions

49. Answer (2)

AlH (i – Bu)2 is DIBALH which reduces nitrites to aldehydes.

50. Answer (4)

Alumina is an adsorbent (stationary phase)

Acetonitrile is mobile phase.

51. Answer (4)

52. Answer (2)

53. Answer (3)

O2N C – OC2H5 > Cl COOC2H5

III > II >

COOC2H5 > MeO COOC2H5

aq. NH 3 Br2, KOH

CO2Et NaOEt/ CO2Et

57. Answer (4)

58. Answer (2)

59. Answer (4)

60. Answer should be both (1) and (2)

Phenol or unsaturated hydrocarbon (alkene or alkyne) decolourised bromine water solution.

C2H5MgBr will react with carbonyl carbon or acidic hydrogen.