Aldehyde Ketone and Carbolic Acids

Chapter 13
Aldehydes, Ketones and

Carboxylic Acids
Solutions
SECTION - A
Objective Type Questions (One option is correct)
 O  O
1. H–C H–C
 O–H  O
(I) (II)
(C – O) bond length designated by , ,  and  are in order

(1) =  <  =  (2)  <  <  =  (3)  <  =  <  (4)  =  =  = 
Sol. Answer (3)
 O  O
In, H C due to complete resonance,  = , While in H C , partial resonance is present. So,
O H
 O
 < .
O
(i) DIBAL-H (1 eq)
2. CH 3CH 2 – C – O – C 2H 5 +
A+B
(ii) H3O
A and B are respectively

(1) CH3CH2CH2OH + C2H5OH (2) CH3CH2CHO + C2H5OH
(3) CH3CH2CHO + CH3CHO (4) CH3CH2CH2OH + CH3CHO
Sol. Answer (2)
O
CH3CH2 — || — O — C2H5     CH3 — CH2CHO + C2H5OH
(i) Di isobutyl
alu min ium hydride
C (ii) H3O 
3. CH 3 CHO  LiAlH 4  CH3 CH 2 OH

Nucleophile added in this reaction is
(1) AlH4
–
(2) Li+ (3) H+ (4) H
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180 Aldehydes, Ketones and Carboxylic Acids Solutions of Assignment (Set-2)
Sol. Answer (4)

LiAlH4  Li+ + Al3+ + 4H–
O O– O —H
|| – | H 3O+ |
CH3 — C — H + H CH3 — C — H CH3 — C — H
| |
H H
PhMgBr
4. Complete the reaction : Ph  CH  CH  CHO   Product
H3O 
(1) Ph – CH – CH – CHO (2) Ph – CH – CH2 – CHO

Ph OH Ph
(3) Ph – CH – CH – CHO (4) Ph – CH – CH2 – CH2 – OH
OH Ph Ph
Sol. Answer (2)
 
Ph
— CH — CH —
Ph — CH — —O CH — CH —
— CH — O MgBr
Ph 
H3O
PhMgBr Ph
CH — CH —
— CH — O
Ph
H
Ph
CH — CH 2— CHO
Ph
H Nu
5. C=O Product . Product may be
D
(1) Meso (2) Racemic (3) Inversion (4) All of these
Sol. 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.
HBr, Peroxide (i) Mg/Et2O

6. Consider the following sequence of reaction : h
[A] [B] . The final product
(ii) CO2
+
(iii) H3O
[B] in the reaction would be :
CH3
O
C OH
(1) C OH (2)
O
O O
(3) C OH (4) CH2 C OH
Solutions of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 181
Sol. Answer (4)
HBr, Peroxide Mg
CH2 CH2— Br CH2MgBr
Et2O
O
( i) CO
CH2 C OH  2 
(i i) H 3O 
O
Conc.
7. CH 3 – C – CH 2 – CH 3 Product
HNO3
The product is
(1) CH3COOH (2) CH3CH2COOH + HCOOH
(3) CH3CH2CH2COOH (4) No reaction
Sol. Answer (1)
O
CH3 — || —CH2 — CH3 Conc . HNO 3 2CH3COOH
    
C
According to Popoff’s rule, carbonyl group goes with less complex alkyl group.
O
SeO2
8.
O
O
OH
(1) (2)
O
O OH
(3) O (4)
Sol. Answer (1)
O O
O
SeO2
In this reaction, active methylene group (—CH2—) is oxidised to C—

— O group.
OH OH
+
H
9. C C A
(Major)
CH3O OCH3
CH3 CH3
CH3
CH3O
O
O
C C
(1) (2) C C CH3
CH3O OCH3
CH3O
CH3
CH3
(3) Both (1) & (2) (4) C C
CH3O OCH3
CH3 CH3
Sol. Answer (1)

OH OH OH2 OH
H+
C —— C — C —— C —
H3CO OCH3 H3CO OCH3
– H2 O
CH3 CH3 CH3 CH3

CH3
O—H
O—H
C —— C — Rearrangement 
 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.
10. LiAlH4
A
The product predominates is
HO H HO H O
(1) (2) (3) (4)
Sol. 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.
O
C A
CH3
11. H2N H2N
A is
(1) Zn – Hg/HCl (2) NH2 – NH2/OH – (3) Both (1) & (2) (4) NaBH4
Sol. 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. Which of the following carbonyl oxygen will form strongest hydrogen bond with H2O molecule?
O O O
O
H H
(1) (2) (3) (4)
H H
Sol. Answer (2)
O
forms strongest hydrogen bond with H2O molecule because in this case carbonyl carbon readily attains
+ve charge due to aromaticity
13. Consider the following sequence of reactions.
O
(i) PhMgBr H2N—C—NH—NH2
C N + [A] [B]
(ii) H3O
Major product [B] of the given reaction would be
O
C—NH—NH2
O N
(1) C—NH—NH—C—NH2 (2) C
O
NH—C—NH2
N
(3) C (4) C—NH2
Sol. Answer (3)
(i) PhMgBr
C—
—N C
||
+
(ii) H3O O
||
O [A] H2N — C — NH — NH2
N — NHCO NH2
||
C
[B]
14. The compound which is not reduced by LiAlH4 is

(1) Cyclohexanone (2) 2-Methyl-1-butanol (3) Ethyl benzoate (4) -caprolactam
Sol. Answer (2)
Alcohols can’t be reduced by LiAlH4. Only carbonyl compound, carboxylic acid and acid derivatives are
reduced by LiAlH4
15. Which of the following would be the best synthesis of benzoic acid from bromobenzene?
+ +
H3O H3O
(1) Br + KCN [A] (2) Br + AgCN [A]
Mg (i) CO2 Mg (i) KCN

(3) Br [A] + (4) Br [A] +
THF (ii) H3O THF (ii) H3O
Sol. Answer (3)
O
||
Mg (i) CO2
Br THF
Mg — Br C — O — Mg — Br
+
O (ii) H3O
||
C — OH
Benzoic Acid
16. Consider the following sequence of reactions.
O
Pd/CaCO3 HO—(CH2)3—OH/H
C—Cl [A] [B]
H2 (1eq)
The products [A] and [B] are respectively
H H O
(1) C—
—O and —C
O
O O
(2) C—OH and C—O—CH2—CH2—CH2—OH
O H O
(3) C—OH and —C
O
O O
(4) C—H and —CH2—CH
O
Sol. Answer (1)
O O H
|| || H O — (CH2)3 — O H /H
+ | O
Pd/CaCO3
C — Cl C—H C
H2(1 eq.) O
O O
17. The compound —C—CH3 can be exclusively oxidized into —C—OH by
(1) NaCN followed by hydrolysis (2) NaOI followed by H3O+

(3) KMnO4 hot followed by hydrolysis (4) K2Cr2O7 followed H3O+
Sol. Answer (2)
O O O
|| || +
||
NaOI H3O
C — CH 3 C — O — Na + CHI3 
C — OH
The above conversion is known as iodoform reaction.
18. Which of the following conversion is known as Stefen's reduction?
1. LiAlH4
(1) —C N 2. H3O
+ —CH2—NH2
1. SnCl2, HCl
(2) —C N 2. H2O, 
—CHO
1. Na, C2H5OH
(3) —N C —NH—CH3
2. H2O
O O
Pd/BaSO4
(4) —C—Cl —C—H
H2(1 eq.)
Sol. Answer (2)
SnCl2/HCl H2O
C—
—N CH — NH CHO
This is known as Stephen’s reduction.
19. Which reagent or sequence of reagents would best accomplish the following synthesis?
OEt O
?
O O
(1) (i) LiAlH4 (ii) H+,  (2) (i) NaBH4 (ii) dil. H2SO4 (iii) conc.H2SO4
(3) (i) Na / NH3 (ii) NaBH4 / H+,  (4) (i) Mg / Et2O (ii) LiAlH4 , (iii) H+, 
Sol. Answer (2)
O O  O–
|| OEt – || OEt || O
OEt
–
H(from EtO
O NaBH4) O– O O
||
20. An organic compound [x], C5H8O reacts with hydroxylamine to form [y], [y] in the presence of conc. H2SO4
gives -lactam. [x] neither give Benedicts test nor it respond positively towards haloform test. The compound
[x] is
O
H3C O
(1) (2) (3) —
—O (4)
O
Sol. Answer (3)
O N — OH H
|
H2NOH Conc. H2SO4
N
C O
Beckmann Rearrangement
(x) C5H8O (y)
 - la ctam
21. Which of the following carboxylic acid is most reluctant to form ester with a given alcohol in the presence of
a catalytic amount of concentrated H2SO4?
CH3 O O O O
|
(1) CH3—C—C (2) —C (3) CH3—C (4) F3C—CH2—C
| OH OH OH OH
CH3
Sol. 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
22. Alanine can be obtained from acetaldehyde by the following sequence of reactions
H
|
HOOC—C—NH2
|
CH3
Alanine
(1) Reaction with NaCN and NH4Cl followed by acidic hydrolysis
(2) Reaction with HCN, acidic hydrolysis and finally reaction with NH3
(3) Reaction with HCN, followed by NH3 and finally acidic hydrolysis
(4) Reaction with NaHSO3, followed by NH3 and finally acidic hydrolysis
Sol. Answer (1)
CH3 CH3 OH NH3 CH3 NH2 H3O+ CH3 NH2

C—
— O + HCN C C C
CH3 H CN H CN H COOH
Acetaldehyde Alanine
O
PCl5, 0ºC (i) LiNH2(3eq) Na / NH3
23. C—CH3 [A]
(ii) Et – Br
A is
O
(1) C—CH2—CH2—CH3 (2) CH2—CH2—CH2—CH3
Ph H Ph Et
(3) C C (4) C C
H Et H H
Sol. 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)
24. CHO + (x)

CH3COONa
+
H3O
CH CHCOOH
The compound x is
(1) CH3COOH (2) BrCH2—COOH (3) (CH3CO)2O (4) CHO—COOH
Sol. Answer (3)
25. Among the given compounds
O OH O
C O OH O OH
C C C
OH OH
HO OH
HO
OH HO OH
OH
(I) (II) (III) (IV)
The order of decreasing acidity is

(1) III > IV > I > II (2) I > IV > II > III (3) III > I > IV > II (4) III > I > II > IV
Sol. 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.
26. Trichloroacetaldehyde, CCl3CHO reacts with chlorobenzene is presence of sulphuric acid and produces
Cl
Cl
(1) Cl C Cl (2) Cl C Cl
CH2Cl H
OH
(3) Cl C Cl (4) Cl CH Cl
Cl CCl3
Sol. Answer (4)
27. Which of the following compound will exhibits positive Fehling test as well as iodoform test?
(1) Methanal (2) Ethanol (3) Propanone (4) Ethanal
Sol. Answer (4)
CHO (i) conc. NaOH

28. + ?
(ii) H2O/H
CHO
COOH COOH COOH CH2OH

(1) (2) (3) (4)
COOH CH2OH OH CHO
Sol. Answer (2)
29. An aromatic compound 'X' with molecular formula C9H10O gives the following chemical tests
(i) Forms 2,4-DNP derivative
(ii) Reduce Tollens reagent
(iii) Undergoes Cannizzaro reaction and
(iv) On vigorous oxidation, 1,2-benzenedicarboxylic acid is obtained
The compound
CHO O CHO
C2H5 CHO C
(1) (2) (3) CH3 (4)
CH3 C2H5
C2H5
Sol. Answer (1)
30. The correct order of reactivity of PhMgBr towards given compounds
O O O
|| || ||
Ph — C— Ph CH3 — C— H CH3 — C— CH3
(i) (ii) (iii)
(1) (i) > (ii) > (iii) (2) (iii) > (ii) > (i) (3) (ii) > (iii) > (i) (4) (i) > (iii) > (ii)
Sol. Answer (3)
31. The increasing order of the rate of HCN addition to compounds A–D is
(A) HCHO (B) CH3COCH3
(C) PhCOCH3 (D) PhCOPh
(1) A < B < C < D (2) D < B < C < A (3) D < C < B < A (4) C < D < B < A
Sol. Answer (3)
O
OH(–)
32. CHO + 'X' CH CH C . Identify 'X'
293K
O
(1) CH2—CHO (2) CH2–CH2–OH (3) C CH3 (4) CH CH2
Sol. Answer (3)
O O
|| ||
33. The diketone CH3 — C— (CH2 )2 — C— CH3 on intramolecular aldol condensation gives the final product
O O O O
OH
(1) (2) (3) (4)
CH3 CH3 CH3
Sol. Answer (3)
34. Which of the following aromatic acids is most acidic?
COOH COOH COOH COOH

OH
(1) (2) (3) (4)
OH
OH
Sol. Answer (2)
35. Which one of the following orders of acid strength is correct?

(1) RCOOH > HC  CH > HOH > ROH (2) RCOOH > ROH > HOH > HC  CH
(3) RCOOH > HOH > ROH > HC  CH (4) RCOOH > HOH > HC  CH > ROH
Sol. Answer (3)
36. The correct order of acidic strength of the carboxylic acid is

(1) Formic acid < Benzoic acid < Acetic acid (2) Formic acid < Acetic acid < Benzoic acid
(3) Acetic acid < Formic acid < Benzoic acid (4) Acetic acid < Benzoic acid < Formic acid
Sol. Answer (4)
37. In esterification
(1) OH– of acid is replaced by C6H5OH (2) H+ of acid is replaced by sodium metal
(3) OH– of alcohol is replaced by chlorine (4) OH– of acid is replaced by RO– group
Sol. Answer (4)
38. Enol content is high test in

(1) Acetone (2) Acetophenone (3) Acetic acid (4) Acetyl acetone
Sol. Answer (4)
NaOH
39. 2C6H5 CHO   C6H5 CH2 OH  C6H5 COONa
The similar reaction can take place with which of the following aldehyde?
(1) CH3CHO (2) CH3CH2CHO (3) (CH3)3CCHO (4) CH3CH2CH2CHO
Sol. Answer (3)
COOH
NH3
40.  A. Identify 'A'
COOH
(1) Benzene (2) Phthalimide (3) Benzamide (4) Acetaldehyde
Sol. Answer (2)
41. In the following reaction sequence, the correct structures of E, F and G are [IIT-JEE-2008]
O O I2
Heat
[E] [F] + [G]
Ph OH NaOH
*
(  implies 13C labelled carbon)
O O O O
(1) E = Ph * CH3 F = Ph * O Na G = CHI3 (2) E = Ph CH3 F = Ph
*
O Na G = CHI3
O O O O
* *
(3) E = Ph CH3 F = Ph
*
O Na G = CHI3 (4) E = Ph CH3 F = Ph
*
O Na G = CH3I
Sol. Answer (3)
O O O O
 I2 + NaOH
C C 
–CO2  iodoform reaction
Ph  OH Ph CH3 Ph ONa + CHI 3
-keto acid E G
O
(1) NaOH/Br2
42. In the reaction : H3C C O
T , the structure of the product T is [IIT-JEE-2010]
NH2 (2) C
Cl
O
NH
H3C C O
(1) (2) C CH3
O C
O
O
H3C NH H3C C O
(3) C (4) NH C
Sol. Answer (3)

O
O C
O
NaOH + Br2 Cl
H3C C H3C NH2 C
NH2
NH
H 3C
43. The number of aldol reaction(s) that occurs in the given transformation is [IIT-JEE-2012]
OH OH
conc. aq. NaOH
CH3CHO + 4HCHO
HO OH
(1) 1 (2) 2 (3) 3 (4) 4
Sol. Answer (3)
CH2OH
CH3 — CHO + H — CHO 
OH
 HOCH2 — CH2 — CHO 
+ HCHO/OH
 |
Aldol Aldol
HOCH2 — CH — CHO
CH 2OH CH 2OH
| |

+ HCHO/OH
Aldol
 HOCH 2 — C — CHO 
+ HCHO/OH
Cannizzaro
 HOCH2 — C — CH2OH
| |
CH 2OH CH 2OH
 Number of aldol reactions = 3
44. The carboxyl functional group (–COOH) is present in [IIT-JEE-2012]

(1) Picric acid (2) Barbituric acid (3) Ascorbic acid (4) Aspirin
Sol. Answer (4)
O
OH O OH
O2N NO2 NH O–C–CH3
HN
HO O COOH
, O ,
O O H
NO2 (Barbituric acid) HO OH
(Picric acid) (Ascorbic acid) (Aspirin)
45. The compound that undergoes decarboxylation most readily under mild condition is [IIT-JEE-2012]
COOH COOH COOH CH2COOH

CH2COOH O COOH O
(1) (2) (3) (4)
Sol. Answer (2)
COOH
O
 -keto acid undergoes easy decarboxylation just by heating through the formation of six
membered transition state.
46. The major product H of the given reaction sequence is [IIT-JEE-2012]
–
CN 95% H2SO4
CH3 — CH2 — CO — CH3 G H
Heat
(1) CH3 — CH = C — COOH (2) CH3 — CH = C — CN

CH3 CH3
OH
(3) CH3 — CH2 — C — COOH (4) CH 3 — CH = C — CO — NH 2

CH3 CH3
Sol. Answer (1)
O OH CN COOH
CN 95% H2SO4
CH3 – CH2 – C – CH3 CH3 – CH2 – C – CH3  CH3 – CH2 = C – CH3
47. The number of optically active products obtained from the complete ozonolysis of the given compound is
CH3 H
CH3 – CH = CH – C – CH = CH – C – CH = CH – CH3 [IIT-JEE-2012]
H CH3
(1) 0 (2) 1 (3) 2 (4) 4
Sol. Answer (1)
Ozonolysis produces CH3CHO and CH3–CH(CHO)2
48. After completion of the reactions (I and II), the organic compound(s) in the reaction mixtures is(are)
O
Br2 (1.0 mol)
Reaction I : H3C CH3 aqueous NaOH
(1.0 mol)
O
Br2 (1.0 mol)
Reaction II : H3C CH3 CH3COOH
(1.0 mol)
O O O O O
H3C CH2Br H3C CBr3 Br3C CBr3 BrH2C CH2Br H3C ONa CHBr3
P Q R S T U
[JEE(Advanced)-2013]
(1) Reaction I : P and Reaction II : P
(2) Reaction I : U, acetone and Reaction II : Q, acetone
(3) Reaction I : T, U, acetone and Reaction II : P
(4) Reaction I : R, acetone and Reaction II : S, acetone
Sol. Answer (3)
O
C Br2 (1.0 mol)

CHBr 3 + CH3CO ONa
Reaction I : CH3 CH3 aqueous NaOH
(1.0 mol)
O O
Br2 (1.0 mol)
C C
CH 3COOH
Reaction II : CH3 CH 3 CH3 CH2Br
(1.0 mol)
49. The correct order of acidity for the following compounds is [JEE(Advanced)-2016]
CO2H CO2H CO2H CO2H

HO OH OH
OH
OH
(I) (II) (III) (IV)
(1) I > II > III > IV (2) III > I > II > IV (3) III > IV > II > I (4) I > III > IV > II
Sol. Answer (1)
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
50. The major product of the following reaction sequence is [JEE(Advanced)-2016]

O
(i) HCHO (excess)/NaOH, heat
+
(ii) HCHO/H (catalytic amount)
O O O O OH HO O O
O OH
(1) (2) (3) (4)
OH
Sol. Answer (1)
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
SECTION - B
Objective Type Questions (More than one options are correct)
1. Which of the following compounds can be synthesized by intramolecular aldol condensation in very good yield
(as a major product)?
O O O
CHO
(1) (2) (3) (4)
CH3
Sol. 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.
2. Which of the following reactions involve carbanion enolate as reactive intermediates?
(1) Kolbe-Schmidt reaction (2) Reimer-Tiemann reaction

(3) Claisen condensation (4) Aldol condensation
Sol. Answer (3, 4)

Fact
3. Which of the following compounds will give over all substitution product via. addition/elimination mechanism
with Ethylamine?
O O O
(1) C—Cl (2) C—O—C
O
(3) C (4) C N
Sol. 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
|| || ||
CH3CH2NH2 + C — Cl or C —O—C
O
||
Ethyl benzamide
4. Which of the following reagents can be used to distinguish Benzaldehyde from acetophenone?
(1) Tollen's reagent (2) Sodium hypoiodite
(3) 2, 4-Dinitrophenyl hydrazone (4) Benedicts solution
Sol. 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.
5. Which of the following dicarboxylic acid will give cyclo alkanone on heating?
O O O
OH
OH OH OH
(1) (2) O (3) O (4)
OH OH
OH OH
O O O
Sol. 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.
6. Which of the following compounds could liberate CO2 with aqueous NaHCO3?
O SO3H
OH OH
C
(1) O2N NO2 (2) MeO OMe (3) O (4)
NH3
NO2 OMe
Sol. Answer (1, 4)

Only those compound which has equal or more acidic hydrogen than carboxylic acid liberates CO2 with
aqueous NaHCO3.
OH (i) I2
7. Consider the following sequence of reactions Products. Products of the
(ii) NaHCO3
O
given reaction would be
I
I
(1) ONa (2)
O O O
I
(3) (4) I O
I O O
O
Sol. Answer (2, 4)
I
I2 NaHCO3
B A
HO O
H C
O
O
(A) (B)
I
I
O O
O O
Now O– attacks on that position where the good leaving group i.e. I atom is attached and it gives two cyclic
product.
8. Which of the following intermediates are involved in the acid catalyzed esterification of carboxylic acid?
..
O: O—H
(1) R—C (2) R—C
O—H O—H
H
OH OH
H
(3) R—C—OH (4) R—C—O
H
O O
R H R
Sol. 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
9. Which of the following compounds will give tertiary butanol as the major product when treated with excess of
MeMgBr?
O O
(1) O—C—O (2) C—CH3
O O
(3) C (4) CH3—C—NH2
Cl Cl
Sol. Answer (1, 3)
10. Which of the following statements are correct regarding given reaction?
H3C
O
C—C CH3 + OH
Et O
iPr 18
[where iPr CH3—CH— group, O18 = represents labelled oxygen]

|
CH3
(1) The given reaction primarily follows SN2 mechanism

(2) In the given reaction condition inversion occurs at the chiral carbon
(3) Labelled 18O is present in formed carboxylic acid
(4) The given reaction primarily follows addition / elimination mechanism
Sol. Answer (1, 3)
– does not attack on

In this reaction, OH 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
11. Identify the set of reagents / reaction conditions X and Y in the following set of transformations
O
X Y
CH2—Br Product CH2—C—OH
(1) X = Mg / Et2O, Y = CO2, followed by H3O+
(2) X = AgCN, Y = (i) O H / H2O (ii) H3O+
(3) X = NaCN, Y = (i) O H / H2O (ii) H3O+
(4) X = alcoholic KOH, Y = (i) HCN (ii) H3O+
Sol. 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
12. Identify the binary mixture(s) that can be separated into individual compounds, by differential extraction, as
shown in the given scheme. [IIT-JEE-2012]
Binary mixture containing

Compound 1 and Compound 2
NaHCO3(aq)
NaOH(aq)
Compund 1 Compund 1
+ +
Compund 2 Compund 2
(1) C6H5OH and C6H5COOH (2) C6H5COOH and C6H5CH2OH

(3) C6H5CH2OH and C6H5OH (4) C6H5CH2OH and C6H5CH2COOH
Sol. Answer (2, 4)
C6H5COOH + NaOH  C6H5COONa + H2O ; C6H5COOH + NaHCO3  C6H5COONa + CO2 + H2O
C6H5CH2 – OH + NaOH  No reaction ; C6H5CH2OH + NaHCO3  No reaction
C6H5CH2COOH + NaOH  C6H5CH2 – COONa + H2O ; C6H5CH2COOH + NaHCO3  C6H5CH2COONa +
CO2 + H2O
C6H5CH2OH + NaOH  No reaction ; C6H5CH2OH + NaHCO3  No reaction
13. With reference to the scheme given, which of the given statement(s) about T, U, V and W is (are) correct?
[IIT-JEE-2012]
O
H3C T
LiAlH4
excess

CrO3/H (CH3CO)2O
V U W
(1) T is soluble in hot aqueous NaOH

(2) U is optically active
(3) Molecular formula of W is C10H18O4
(4) V gives effervescence on treatment with aqueous NaHCO3

O
OCOCH3
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
Give effervescence with NaHCO3
Hence answer is (1, 3, 4).
14. The major product of the following reaction is [JEE(Advanced)-2015]
O i. KOH, H2O
ii. H+, heat
CH3
O
CH3 CH3 O CH3

O
O O CH3
(1) (2) (3) (4)
Sol. Answer (1)

CH3 CH3
CH 3 O OH
O H O O O +
O
KOH, H2O H
CH 3
O
O O

+
(Minor) (Major)
15. In the following reactions, the product S is [JEE(Advanced)-2015]
H3C
i. O3 NH3
R S
ii. Zn, H2O
H3C H3C N
N
(1) (2)
N
N
(3) (4)
H3C H3C
Sol. Answer (1)
O OH
H NH
(1) O3 NH3
H
(2) Zn, H2O
O OH
–2H 2O
16. The correct statement(s) about the following reaction sequence is(are)
(i) O CHCl /NaOH

Cumene(C9H12 ) 
2  P 

3 Q(major)  R(minor)
(ii) H3O
NaOH
Q 
S [JEE(Advanced)-2016]
PhCH2Br
(1) R is steam volatile

(2) Q gives dark violet coloration with 1% aqueous FeCl3 solution
(3) S gives yellow precipitate with 2, 4-dinitrophenylhydrazine
(4) S gives dark violet coloration with 1% aqueous FeCl3 solution
Sol. Answer (2, 3)
CH3 CH3
H3C – C – H H3C – C – O – O – H OH
O
(i) O2 H3O+
+ CH3 – C – CH3
(P)
H H
OH O O O
CH
CHCl3
+
NaOH
(P) (Q)
CH = O
(Major)
(R)
(i) NaOH (Minor)
(ii) PhCH2 – Br
O – CH2 – Ph
CH = O
(S)
 Q is steam volatile due to intramolecular hydrogen bonding but (R) is a high melting solid.
 Since, Q contains a phenotic group, it forms dark brown solution with 1% aqueous FeCl3 solution.
O – CH2 – Ph O – CH2 – Ph NO2

NO2
CH = O
H+ CH = N – NH NO2
 + H2N – NH NO2
2, 4 DNP (yellow precipitate)
 Since, (S) does not contain free phenolic group, therefore it will not form violet colour with FeCl3 solution.
17. Positive Tollen's test is observed for [JEE(Advanced)-2016]
H O OH O
CHO
Ph
(1) H H (2) (3) Ph (4) Ph Ph
H O

All aldehydes gives Tollen's test as shown below
O
R – CH = O + [Ag(NH3)2 ] R – C – O– + Ag+ NH+4
+
(Silver mirror)
-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
18. Reagent(s) which can be used to bring about the following transformation is/are [JEE(Advanced)-2016]
O O
O=C O O=C
H OH
O O
COOH COOH
(1) LiAlH4 in (C2H5)2O (2) BH3 in THF (3) NaBH4 in C2H5OH (4) Raney Ni/H2 in THF
Sol. Answer (3, 4)
LiAlH4/(C2H5)2O : Reduces to esters, carboxylic acid, epoxides and aldehydes and ketones.
BH3 in T.H.F. : Reduces to –COOH and aldehydes into alcohols but do not reduce to esters and
epoxides.
NaBH4 in C2H5OH : Reduces only aldehydes and ketones into alcohols but not to others.
Raney Ni in T.H.F. : Do not reduce to –COOH, –COOR and epoxide but it can reduce aldehyde into
alcohols.
19. Compounds P and R upon ozonolysis produce Q and S, respectively. The molecular formula of Q and S is
C8H8O. Q undergoes Cannizzaro reaction but not haloform reaction, whereas S undergoes haloform reaction
but not Cannizzaro reaction
i) O3/CH2CI2
(i) P Q
ii) Zn/H2O (C8H8O)
i) O3/CH2CI2
(ii) R S
ii) Zn/H2O (C8H8O)
The option(s) with suitable combination of P and R, respectively, is(are) [JEE(Advanced)-2017]
H3C
CH3 CH3
CH3
(1) and
CH3 CH3
(2) H3C and

CH3
CH3 H3C
CH3
(3) and
H3C CH3
(4) H3C and H 3C

CH3
Sol. Answer (2, 3)
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
Undergoes
Haloform reaction
SECTION - C
Linked Comprehension Type Questions
Comprehension-I
Certain dicarboxylic acids spontaneously eliminate water when heated, forming cyclic anhydrides. But for the reaction
to be successful. The cyclic anhydrides product must normally have a ring size of five or six members. There are two
important reasons, first, the second carboxyl group can serve as the acid catalyst (by intramolecular proton transfer),
as well as the nucleophile. And second, the high temperatures involved reduce the need for catalysis.
O O
C C
O O
(CH2)n H (CH2)n
O OH
C C
OH OH
O O
C C
–H2O
(CH2)n O (CH2)n O
C C
OH
O HO
Acid-Anhydride
1. Which of the following dicarboxylic acid would you expect to form cyclic anhydride?
O O OH
(1) C C (2) O
HO CH2 OH OH
O
O O
OH OH
(3) (4)
OH OH
O O
Sol. 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. Which of the following dicarboxylic acid will not for cyclic anhydride?
O
O
C
H C OH
(1) C OH (2)
OH
C OH C
H C
O
O
O O
H C H3C C
C OH OH
(3) (4)
OH
HO C H3C C
C H
O O
Sol. Answer (3)
Those dicarboxylic acid will not form cyclic anhydride in which both —COOH groups are present on trans
position.
3. Consider the following sequence of reaction.
COOH
COOH  
[A] Product.
COOH
The final product of the reaction would be
O
C
COOH
O
(1) (2)
C
COOH
O
O
COOH C
(3) (4) O
C
O
Sol. Answer (4)
O
||
COOH COOH C
COOH  
O
–CO2
COOH COOH C
||
O
Comprehension-II
O
Both carbonyl compounds and acid derivatives though they contain C grouping yet the reactions given
by them are entirely different.
As Aldehydes and Ketones give addition product with a nucleophile, while carboxylic acid derivatives give
nucleophilic acyl substitution through addition/elimination mechanism.
O O O
|
R—C + Nu R—C—Nu R—C—Nu + X
|
X X
Acid-derivatives Substitution Product
O
where X— —Cl, —O—C—R, —OR, –NRR etc.
—
R R O R OH
+H
C O + Nu C C
R R Nu R Nu
Aldehyde Addition
or Ketone product
1. Why aldehydes and Ketones give nucleophilic addition reaction while acid derivatives prefer nucleophilic acyl
substitution reaction?
(1) Carbonyl carbon of aldehydes and Ketones are more electron deficient than acid derivatives
(2) Carbonyl carbon of acid derivatives are more electron deficient
(3) Acid derivatives also give addition reaction
(4) In acid derivatives, acyl carbon is connected with a good leaving group
Sol. Answer (4)
In acid derivatives, acyl carbon is connected with good leaving group. So, it gives nucleophilic acyl substitution
reaction.
2. Which of the following is most reactive towards a nucleophile?
O O O O
(1) C (2) C (3) C (4) C
Ph Cl Ph NH2 R R Ph H
Sol. Answer (1)
O
||
C is most reactive because —Cl is the good leaving group.
Ph Cl
3. Carbonyl character is most supressed in

.. .. ..
O: O: O: OO
(1) C .. R (2) C .. (3) CH3—C .. (4) CH3–C C–CH3
N O—R
.. .. :
Br O
R
Sol. 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
A carbonyl compound P, which gives positive iodoform test, undergoes reaction with MeMgBr followed by
dehydration to give an olefin Q. Ozonolysis of Q leads to a dicarbonyl compound R, which undergoes
intramolecular aldol reaction to give predominantly S. [IIT-JEE-2009]

(i) MeMgBr (i) O (i) OH
P   Q  3
(ii) Zn, H O
 R 
(ii) 
S
(ii) H , H2O 2
(iii) H2SO4 ,
1. The structure of the carbonyl compound P is
O
Me
(1) (2) (3) (4)
O Me O Me O Et Me
Sol. Answer (2)
2. The structures of the products Q and R, respectively, are
O O
(1) Me , H (2) , H
COMe CHO
Me Me Me Me Me Me
Me Me
O Me O
H ] CH3
(3) , (4) , CHO
CHO
Et Me Et Me Me Et
Me
Sol. Answer (1)
3. The structure of the product S is
O O O
Me
(1) (2) (3) (4)
O
Me Me Me Me Me
So. Answer (2)
Me Me Me
(i) MeMgBr H2SO4 (i) O3
(ii) H3O+ OH (ii) Zn-H2O
O Me Me Me Me Me
P Q
–
Me
O
(i) O H/H2O O
+
(ii) H ,  C
O Me
Me Me Me Me
S R
Comprehension-IV
Two aliphatic aldehydes P and Q react in the presence of aqueous K2CO3 to give compound R, which upon
treatment with HCN provides compound S. On acidification and heating, S gives the product shown below :
[IIT-JEE-2010]
H3C
OH
H3C
O O
1. The compound R is
O O
H3C H3C
C C
H C H
C H3C
(1) H3C (2)
CH2 CH
OH H3C OH
CH3 O CH3 O
CH C CH C
(3) H3C CH H (4) H3C CH H
CH2 CH
OH H3C OH
Sol. Answer (2)
2. The compounds P and Q respectively are
CH3
CH H and H3C H
(1) H3C C C
O O
CH3
CH H and H H
(2) H3C C C
O O
H3C CH2 H H3C H

(3)
CH C and C
CH3 O O
H3C CH2 H H H
CH C and C
(4)
CH3 O O
Sol. Answer (1)
3. The compound S is
CH3 O O
CH H3C
C C
H3C CH H C H
(1) (2) H3C
CH2 CH2
CN CN
CH3 CN CN
CH H3C
CH CH
H3C CH OH C OH
(3) (4) H3C
CH2 CH2
OH OH
Sol. Answer (4)
CH3 O
H3C C
1. K 2CO3
C H
2. H H C H
H 3C C H 3C
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
H 2C H3C
HO
O H CH2
 OH
(S)
OH
H3C
C O
H3C
H2C O
Comprehension-V
In the following reaction sequence, the compound J is an intermediate.
 CH3CO  O (i) H ,Pd/C
I  2
CH COONa
 J  2
(ii) SOCl
K
3 2
(iii) anhyd. AlCl3
J (C9H8O2) gives effervescence on treatment with NaHCO3 and a positive Baeyer's test. [IIT-JEE-2012]
1. The compound K is
(1) (2) (3) (4) O

O O
O
Sol. Answer (3)
2. The compound I is
H
O H OH O CH3 H H
(1) (2) (3) (4)
Sol. Answer (1)
CHO CH = CH–COOH
(CH 3CO)2O (i) H 2, Pd/C

CH 3COONa ( ii) SOC l2
(iii) Anhyd. AlCl3
O
Comprehension-VI
P and Q are isomers of dicarboxylic acid C4H4O4. Both decolorize Br2/H2O. On heating, P forms the cyclic
anhydride.
Upon treatment with dilute alkaline KMnO4, P as well as Q could produce one or more than one from S, T
and U. [JEE(Advanced)-2013]
COOH COOH COOH

H OH H OH HO H
H OH HO H H OH
COOH COOH COOH
S T U
1. Compounds formed from P and Q are, respectively

(1) Optically active S and optically active pair (T, U)
(2) Optically inactive S and optically inactive pair (T, U)
(3) Optically active pair (T, U) and optically active S
(4) Optically inactive pair (T, U)) and optically inactive S
Sol. Answer (2)
H COOH COOH
H OH
C dil. alk. KMnO4
H OH
C
COOH
H COOH
(S)
(P)
H COOH
COOH CO OH
C dil. alk . KM nO 4 H OH HO H
+
C HO H H OH
HOOC H COOH CO OH
(Q) (T) (U)
2. In the following reaction sequences V and W are respectively
H2 /Ni
Q 
V
AlCl3(anhydrous) 1. Zn-Hg/HCl
+V W
2. H3PO4
CH2OH
(1) O and (2)
and
CH2OH
V O V W
W O
O
HOH2C
O and and
(3) (4)
V CH2OH CH2OH
W
V O
W
Sol. Answer (1)
O
H CO OH
C H 2/ Ni
O

C
HOOC H
(Q) O
(V)
O O
O + AlCl3 Z n(Hg)
H 3 PO3
anhydrous HCl
HO HO
O O O O
(V) (W)
Comprehension-VII
Treatment of compound O with KMnO4/H+ gave P, which on heating with ammonia gave Q. The compound Q on
treatment with Br2/NaOH produced R. On strong heating, Q gave S, which on further treatment with ethyl 2-
bromopropanoate in the presence of KOH followed by acidification, gave a compound T. [JEE(Advanced)-2016]
(O)
1. The compound R is
O O O
NH2
Br NHBr
(1) (2) (3) (4) NBr
Br NHBr
NH2
O O O
Sol. Answer (1)
O O
NH2
KMnO4/H +
C OH NH3 C NH2 Br2/NaOH
 C OH  C NH2 (Hoffman bromamide)
NH2
O O
(P) (Q) (R)
2. The compound T is
(1) Glycine (2) Alanine (3) Valine (4) Serine
Sol. Answer (2)
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
Comprehension-VIII
The reaction of compound P with CH3MgBr (excess) in (C2H5)2O followed by addition of H2O gives Q. The
compound Q on treatment with H2SO4 at 0ºC gives R. The reaction of R with CH3COCl in the presence of
anhydrous AlCl3 in CH2Cl2 followed by treatment with H2O produces compound S. [Et in compound P is ethyl
group] [JEE (Advanced)-2017]
(H3 C)3C
CO2Et
Q R S
1. The reactions, Q to R and R to S, are

(1) Dehydration and Friedel-Crafts acylation
(2) Friedel-Crafts alkylation, dehydration and Friedel-Crafts acylation
(3) Friedel-Crafts alkylation and Friedel-Crafts acylation
(4) Aromatic sulfonation and Friedel-Crafts acylation
2. The product S is
HO3S
O CH3 H3COC
(H3C)3C
(H3C)3C H3C CH3
(1) (2)
COCH3
H3C
CH3
(H3C)3C COCH3
(H3 C)3C CH3
(3) (4)
COCH3
Solutions of Comprehension-VIII
1. Answer (2) – +
O OMgBr
2. Answer (3) C(CH3)3 C – OEt C(CH3)3 CH3–C–CH3
CH3MgBr (excess)/(C2H5)2O
(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)
CH3
CH3
C(CH3)3 C(CH3)2 C(CH3)3
(alkylation)
(R)
O
CH3–C–Cl/AlCl3
(Acylation)
CH3
CH3
C(CH3)3
COCH3
(S)
Comprehension-IX
Answer Q.1, Q.2 and Q.3 by appropriately matching the information given in the three columns of the following
table. Columns 1, 2 and 3 contain starting materials, reaction conditions, and type of reactions, respectively.
Column 1 Column 2 Column 3
(I) Toluene (i) NaOH/Br2 (P) Condensation

(II) Acetophenone (ii) Br2/h (Q) Carboxylation
(III) Benzaldehyde (iii) (CH3CO)2O/CH3COOK (R) Substitution
(IV) Phenol (iv) NaOH/CO2 (S) Haloform
[JEE (Advanced)-2017]
1. The only CORRECT combination that gives two different carboxylic acids is
(1) (III) (iii) (P) (2) (I) (i) (S) (3) (II) (iv) (R) (4) (IV) (iii) (Q)
Sol. Answer (1)
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.
2. The only CORRECT combination in which the reaction proceeds through radical mechanism is
(1) (III) (ii) (P) (2) (IV) (i) (Q) (3) (II) (iii) (R) (4) (I) (ii) (R)
Sol. Answer (4)
h
Br2 Br + Br
CH3 CH2
+ Br + HBr
CH2 CH2 – Br
+ Br2 + Br
3. For the synthesis of benzoic acid, the only CORRECT combination is

(1) (I) (iv) (Q) (2) (III) (iv) (R) (3) (IV) (ii) (P) (4) (II) (i) (S)
Sol. Answer (4)
COO–Na+
NaOH
C CH3 Br2 + CHBr3
O
H2O/H+
COOH
It is haloform reaction
SECTION - D
Assertion-Reason Type Questions
1. STATEMENT-1 : Benzaldehyde gives negative Benedict's test.
and
STATEMENT-2 : Aldehydes do not respond positively with Benedicts reagent.
Sol. Answer (3)
Only aromatic aldehyde doesn’t give Benedict’s test while aliphatic aldehyde gives positive Benedict’s test.
2. STATEMENT-1 : When PhCHO is made to react in D2O, deuterium is incorporated in product in Cannizzaro
reaction.
and
STATEMENT-2 : In Cannizzaro reaction transfer of hydride takes place from one molecule to other.
Sol. Answer (4)
– of D O doesn’t participate in Cannizzaro’s reaction.
The OD 2
3. STATEMENT-1 : Ketones in presence of highly electropositive elements such as Na, Mg, Yield 1, 2 diol or
pinacol.
and
STATEMENT-2 : Electrons released by electropositive elements convert C = O group into radical anion.
Sol. Answer (1)
Fact
4. STATEMENT-1 : Cyclohexanone on reaction with secondary amines yields Schiff's base.

and
STATEMENT-2 : The initial adduct lose water to generate product.
Sol. Answer (4)
Only primary amine reacts with carbonyl compound to form Schiff’s base.
5. STATEMENT-1 : Methanoic acid reduces mercuric chloride to mercurous chloride on heating while ethanoic acid
does not.
and
STATEMENT-2 : Methanoic acid is stronger acid than ethanoic acid.
Sol. 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.
6. STATEMENT-1 : Acetic acid does not undergo haloform test.

and
STATEMENT-2 : Acetic acid does not contain any -hydrogen.
Sol. Answer (3)
Acetic acid doesn’t undergo haloform test but it contains -hydrogen atom.
7. STATEMENT-1 : Decarboxylation of -keto acid is very difficult.

and
STATEMENT-2 : Decarboxylation takes place via a six membered cyclic transition state.
Sol. Answer (4)
-Keto acid is easily decarboxylated because it forms most stable reactive intermediate on decarboxylation.
SECTION - E
Matrix-Match Type Questions
1. Match the following
Column-I Column-II
(A) Fries rearrangement (p) Acid-catalysed rearrangement
(B) Claisen rearrangement (q) Concerned with ester
(C) Bayer Villiger’s rearrangement (r) Involves electrophilic substitution
(D) Pinacol-pincolone rearrangement (s) Intramolecular rearrangement
Sol. Answer: A(p, q, r, s), B(r, s), C(p, q, s), D(p, s)
All reactions are fact

Column-I Column-II
CHO
(A) (p) Aldol condensation
O
(B) CH3 – C – CH3 (q) Cannizzaro reaction
(C) HCHO (r) Benzoin condensation
(D) C (s) Claisen-Schmidt reaction
Sol. Answer: A(q, r, s), B(p, s), C(q, s), D(s)

(A) Benzaldehyde can give Cannizzaro reaction, Benzoin condensation and Claisen Schmidt reaction.
(B) Acetone can give aldol condensation and Claisen Schmidt reaction.
(C) HCHO can give Cannizzaro reaction and Claisen Schmidt reaction.
O
(D) C6H5 — || — C6H5 can only give Claisen Schmidt reaction.
C

Column I Column II
O
–
OH
(A) 2 C H (p) Involves carbanion enolate
(B) 2 OH (q) Involves nucleophilic addition
O
Cl
OH
(C) (r) Molecular wt. of product more than that of reactant
O O 

OEt
(D) 
EtOH
 (s) Five membered ring formation
EtO OEt
(t) Generates resonance stabilized carbanion
Sol. Answer: A(q, r), B(p, q, r, t), C(p, s, t), D(p, t)
Fact
4. Match the following.
Column-I Column-II
(Reactions) (Reagents/Catalyst)
(A) Cannizzaro's reaction (p) Al(OCHMe2)3
(B) Clemmensen's reduction (q) Conc. NaOH
(C) Wolff Kishner's reduction (r) Zn-Hg/HCl
(D) Meerwin Ponndorf's Verleys reduction (s) N2H4/ OH
Sol. Answer:A(q), B(r), C(s), D(p)
All are facts.
5. Match the compounds/ions in Column I with their properties/reactions in Column II. [IIT-JEE-2007]
Column I Column II
(A) C6H5CHO (p) Gives precipitate with 2, 4-dinitrophenylhydrazine
(B) CH3C  CH (q) Gives precipitate with AgNO3
(C) CN– (r) Is a nucleophile
(D) I– (s) Is involved in cyanohydrin formation
Sol. Answer: A(p, s), B(q), C(q, r, s), D(q, r)
6. Match each of the compounds in Column I with its characteristic reaction(s) in Column II. [IIT-JEE-2009]
Column I Column II
(A) CH3CH2CH2CN (p) Reduction with Pd-C/H2
(B) CH3CH2OCOCH3 (q) Reduction with SnCl2/HCl
(C) CH3—CH = CH—CH2OH (r) Development of foul smell on treatment with chloroform
and alcoholic KOH
(D) CH3CH2CH2CH2NH2 (s) Reduction with diisobutylaluminium hydride (DIBAL-H)
(t) Alkaline hydrolysis
Sol. Answer: A(p, q, s, t), B(p, s, t), C(p), D(r)

(A) CH3CH2CH2CN will give negative test with alkaline CHCl3. It will give mentioned reaction with other
reagents.
(B) Esters will be reduced by catalytic hydrogenation, 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
CH3CH2CH2CH2 — NH2   CH3 CH2CH2 CH2 — N  C
CHCl3
Carbyl amine
7. Match each of the compounds given in Column I with the reaction(s), that they can undergo, given in
Column II. [IIT-JEE-2009]
Column I Column II
Br
(A) (p) Nucleophilic substitution
O
OH
(B) (q) Elimination
CHO
(C) (r) Nucleophilic addition
OH
Br
(D) (s) Esterification with acetic anhydride
NO2
(t) Dehydrogenation
Sol. Answer: A(p, q, t), B(p, s, t), C(r, s), D(p)
Nu
S N2
Br
O
(A) O E2
OH ZnCl 2/HCl Cl [Nucleophilic substitution]

E li
m
ina
t io
no
rd
eh
(RCO)2O yd
ro
ge
na
(B) O t io
n
C CHO
O R
HO Nu
C
Nu H
O
OH
C
H
(C) O
OH O O
C
R C O C R H
O
O R
Br Nu
s
Nu
(D)
(SNAr)
NO 2 Mechanism NO 2
8. Match the reactions in Column-I with appropriate types of steps/reactive intermediate involved in these reactions
as given in Column-II [IIT-JEE-2011]
Column I Column II
O O
H3C
O
aq NaOH
(A) (p) Nucleophilic substitution
O O
CH3Mgl
(B) CH2CH2CH2Cl (q) Electrophilic substitution
CH3
O 18
O
H2SO4
(C)
CH2CH2CH218OH (r) Dehydration
H2SO4
CH2CH2CH2C(CH3)2
(D) OH (s) Nucleophilic addition

H3C CH3
(t) Carbanion
Sol. Answer: A(r, s, t), B(p, s, t), C(r, s), D(q, r)
CH2 O H2C O
H
O O O O
OH Nucleophilic addition
A.
Carbanion
O OH O
Dehydration HO – H
–H2O
O Cl
Cl O O
CH 3MgBr Nucleophilic
B.
CH3 substitution CH3
Carbanion
Nu cleophilic
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
SECTION - F
Integer Answer Type Questions
O O
OD / D 2 O  excess 
1. Consider the following reaction : C C CH3  Product 
24 hours
H3C CH2 CH2
Molecular weight of the product would increase by :

[Assuming that mol. wt. of C = 12, O = 16, H = 1 and D = 2]
Sol. Answer (7)
2. What would be the maximum number of atoms involved in the formation of newly constructed ring in the given
reaction?
OH  i I

 ii NaHCO 
2
O 3
Sol. Answer (5)
3. What is the net negative charge on the major product of the given species when it is treated with excess
NaOH?
O
H
N C C H
O OH
O
H
Sol. Answer (2)
OH is not enough strong to deprotonate Alkyne and aliphatic alcohol.
4. In the scheme given below, the total number of intramolecular aldol condensation products formed from 'Y' is
[IIT-JEE-2010]
1. O 1. NaOH (aq)
3
2. Zn, H O
 Y 
2. Heat

2
Sol. Answer (1)
1. O 3
2. Zn – H 2 O O
O H
1. O H
O O
O+
O O
3
+H
OH
–H2 O
+
O O
On dehydration this
alcohol will give three +
produ cts
O O
5. The total number of carboxylic acid groups is the product P is [IIT-JEE-2013]

O O
+
1. H3O , 
O P
2. O3
3. H2O2
O O
Sol. Answer (2)
O O O O O
+
OH
H 3O OH *
O
OH (–H2 O, –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.
6. Consider all possible isomeric ketones, including stereoisomers of MW = 100. All these isomers are
independently reacted with NaBH4 (Note : stereoisomers are also reacted separately). The total number of
ketones that give a racemic product(s) is/are [JEE(Advanced)-2014]
Sol. Answer (5)
O
1 2 3 4
(I) CH3 CH2 CH2 CH2 C CH3
5 6
(II) CH3 CH2 CH2 C CH2 CH3
CH3 O
(III) CH3 CH2 CH C CH3

It has chiral centre
CH 3 O
(IV) CH3 CH C CH3
CH 3
CH 3 O
(V) CH3 CH C CH2 CH3
(VI) CH3 CH CH 2 C CH 3
CH3
Only (III) form diastereomers on addition reaction so, desired ketones as per addition reaction is 5.
7. Among the following, the number of reaction(s) that produce(s) benzaldehyde is [JEE(Advanced)-2015]
CHCl2
I. 
CO, HCl
Anhydrous AlCl3 /CuCl II. H2 O

100 C

COCl CO2Me
DIBAL H
III. H2
 IV. 
Toluene,  78 C

Pd BaSO 4 H2 O
Sol. Answer (4)
CHO
CO, HCl
(Gatterman Koch Reaction)
Anhyd AlCl 3/CuCl
OH
CHCl 2 CH CHO
H2O OH
100°C –H2O
COCl CHO
H2
(Rosenmund Reduction)
Pd–BaSO4
COOMe CHO
DIBAL–H
Toluene, –78°C H2O
SECTION - G
Multiple True-False Type Questions
Identify the correct combination of true (T) and false (F) of the given three statements.
1. STATEMENT-1 : Acetophenone gives aldol condensation.
STATEMENT-2 : Benzaldehyde is more reactive than acetaldehyde towards nucleophilic addition.
STATEMENT-3 : Benzophenone has -Hydrogens.
(1) TTT (2) FFF (3) TFF (4) TFT
Sol. Answer (3)
Benzaldehyde is less reactive than acetaldehyde towards nucleophilic addition.
2. STATEMENT-1 : Formation of cyclic acetal is entropically favourable.

STATEMENT-2 : PCC converts primary alcohol into aldehydes.
STATEMENT-3 : Aliphatic alcohols are practically insoluble in aqueous NaOH.
(1) T T T (2) FFF (3) TFT (4) FTF
Sol. Answer (1)
Aliphatic alcohols can’t react with NaOH
SECTION - H
Aakash Challengers Questions
1. Example of feasible reaction(s) is/are
OH O
O
(C6H5)3P
(1) OH SCH3 (2) NaOH
O O
Et—C—N=N—C—Et O
O
CH3SH I O
O
HO
O O
O O
O O
(3) I2 (4) CH3COOH
NaHCO3 CH2Cl2
I
O
O
In (3) the product would be
I
2. Consider the following sequence of reactions :

O
H2O2/NaOH N2H4/aq. KOH

[I] [P]
Intermediate [I] and corresponding major product [P] in the given reaction are
–
O O HO H4NO O O O OH
and and ONH4
(1) (2)
[I] [P] [I] [P]
O O OH
O and O and
(3) (4)
OH
[I] [P] [I] [P]
Sol. Answer (3)
3. Draw a stepwise mechanism for the following reaction
OH
O +H
+
O O
O OH
Sol. It is an example of acid catalyzed rearrangement.
4. Consider the following sequence of reactions
Me 2+ +
(i) HCCNa Hg /H3O
(ii) H2O
I
Major product would be
OH
HO Me O
Me O OH
O O
(1) (2) (3) Me (4)
Sol. Answer (3)

In the presence of Hg2+/H3O+ hydration of alkene and alkyne both will take place.
5. Draw a mechanism for the following reaction
CO2Me CO2CH3
(1) NaOEt
(2)
Br
H2O
O O
(3) H2O
Sol. First of all most acidic hydrogen is deprotected which SN2 reaction alkyl halide.
6. Brevicomin, the aggregation pheromone of the western pine bark beetle, contains a bicyclic bridged ring
system. Brevicomin is prepared by the acid catalyzed cyclization of 6,7-dihydroxy-2-nonanone.
(i) Suggest a structure for brevicomin.
(ii) Devise a synthesis of 6,7-dihydroxy-2-nonanone from 6-bromo-2-hexanone. You may also use three carbon
alcohols and any required organic or inorganic reagents.
O O OH
Several
steps
Br
OH
6,7-dihydroxy-2-nonanono
[X]
+
H3O
Brevicomin
Sol. Acid catalyzed acetal formation will lead to the formation of Brevicomin.
7. A compound A(C4H8O) has reducing properties upon treatment with dilute alkali under careful controlled
conditions, A is converted into a dimer B which readily loses water to form C(C8H14O). Vigorous oxidation of
C with chromic acid yields equimolar quantities of carbon dioxide and two acids D and E. One of these can
be obtained directly from A by oxidation without loss of carbondioxide. Identify the lettered compounds and
account for the ready conversion of B into C.
OH CH 2—CH 3
OH
Sol. CH3CH2CH2—CHO CH3—CH2—CH2—CH—CH—CHO
(A) (B)
– H2O
CH3—CH2—CH2—CH C—CHO
(C)
CH2—CH 3
CH3—CH2—CH2—COOH + CH 3—CH 2—C—COOH

(D)
CH3—CH2—COOH + CO 2
(E)
8. Write mechanisms for the following reactions :

H2 SO4
(i) PhCHMeCHO  
 PhCOEt
OH O
NaNO2/HCl
(ii) Me
CH2—NH2 Me
+H
Sol. (i) Ph—CH—CH O Ph—CH—CH—OH
Me Me
Ph
Ph – H
Me—CH C CH—CH—OH
O
H Me
Tautomerization
O
Me—CH2—O—Ph
OH NaNO2/HCl OH
(ii) Me Me
CH2—NH2 CH2
O O—H
–H
Me Me
9. Suggest mechanisms for the following reactions which are catalyzed by strong base :
Me
COMe O O
Me O
OH C—CH3
(i) (ii)
O
O O
Sol. Answer (2)
O
Me O Me
C
C—CH3
B
CH2
H
O O
H2O
OH CH3 O CH 3
O O
It is an example of retro claisen reaction.
10. Show how you would synthesize each compounds from starting materials containing no more than six carbon
atoms.
O
—CH2—CH2—CHO
(a) C (b)
N C NMgBr O
Mg H3O
Sol. (a) Br MgBr C C
Ether
O
Mg (i) H2C CH2
(b) CH2—Br CH 2MgBr +
Ether (ii) H 3O
PCC.
CH2— CH2—CHO CH2— CH2
|
CH2—OH
11. Propose mechanism for the given reaction :

Ph Ph
O O
NaOH/H2O
C—C C—C + CH3OH
18 18
Me O—CH3 Me ONa
Et Et
Sol. Ph O Ph O
OH
C—C C— C + CH 3— OH
18
Me O—CH3 Me ONa
18
Et Et
12. Supply the structures of A and B.

O
+
(i) Ag(NH3)2
[A] +
[B] 120ºC + CO2
(ii) H
O O O O O
+
C [Ag(NH3)2] C 
H OH + CO 2
Sol.
[A] [B] [C]
13. Predict the products of the following reactions
O O
(i) CH3MgBr
(a) C—Cl + (CH3)2Cd (b) CH 3—C—CH 3 +
(ii) H3O
O
CH3
pH = 5
(c) + H—N

CH3
O OH Me
|
Sol. (a) C—CH3 (b) CH3—C—CH3 (c) N
| Me
CH3
14. An organic compound [A] C9H12 gave (B) C8H6O4 on oxidation by alkaline KMnO4. [B] on heating does not form
anhydride. Also [B] reacts with Br2 in the presence of iron to give only one monobromoderivative (C) C8H5BrO4.
What are A, B and C?
Et COOH COOH
| | |
Br
[O] Fe/Br2
|
Sol.
| | |
Me COOH COOH
[A] [B] [C]
15. Propose a synthesis of each of the following compounds from the indicated starting material(s) and any other
necessary reagents.
O
—C—OH
(a) —CHO from
O
(b) CH2—C—CH2— from CH3
O O O
PCl 5 Pd/BaSO4
Sol. (a) C—OH C— Cl C—H
H2(1 eq)
O
Br2//hv (1) Mg/Et2O
(b) CH 3 CH2—Br CH2—C—OH
(2) CO2
(1) PCl5
(2) NH3
(3) P 2O5
O
(1) PhCH2MgBr
CH 2—C—CH2 +
CH 2—CN
(2) H3O
16. How many products are formed when compound [X] is decarboxylated?
COOH
Cl—
COOH
Sol. COOH COOH H
Cl  Cl Cl
—CO2
+
COOH H COOH
H H H
17. Suggest a mechanism for each of the following reactions :

O
(CH2)3—CH—CH2
ZnCl2
(a)
CH2OH
Br
| Ag N
N—
(b)
OH O
Sol. (a) ZnCl2

..
O: O— ZnCl2
+
–H
ZnCl 2 +
+H
|
| H |
CH 2OH CH2—OZnCl2
Ag
..
:Br :
|
N— N—
(b)
O—
.. H O—H
N— N—
–H
O O—H
18. Suggest a synthesis of given product from the indicated starting material.
B
O
A NHCH2CH3
C
NH2
1. H2N—CH2CH3
Sol. O
2. H2 / Pd
(i) NH3
—NH—CH2CH3
(ii) H 2 / Pd
CH3CH2—Br
NH2 (1 eq.)
19. Identify the compounds [A] through [D] in the following sequence of reaction.
(i) OsO4 HIO4 (I) Ag(NH 3) 2+ 

[A] [B] + [C] [D]
(ii) NaHSO3 (ii) H
OH
(i) OsO4 HIO4 CHO
Sol. (ii) NaHSO3 CHO
OH
+
(i) Ag(NH3)2
+
(ii) H 3O
 COOH
O
COOH


Aldehyde Ketone and Carbolic Acids

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Chapter 13

Aldehydes, Ketones and

(C – O) bond length designated by , ,  and  are in order

A and B are respectively

3. CH 3 CHO  LiAlH 4  CH3 CH 2 OH

Sol. Answer (4)

(1) Ph – CH – CH – CHO (2) Ph – CH – CH2 – CHO

HBr, Peroxide (i) Mg/Et2O

(1) CH3COOH (2) CH3CH2COOH + HCOOH

(3) CH3CH2CH2COOH (4) No reaction

Sol. Answer (1)

Sol. Answer (1)

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

(3) Both (1) & (2) (4) C C

Sol. Answer (1)

CH3 CH3 CH3 CH3

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

The product predominates is

(1) (2) (3) (4)

Sol. Answer (1)

Sol. Answer (2)

+ve charge due to aromaticity

13. Consider the following sequence of reactions.

Major product [B] of the given reaction would be

Sol. Answer (3)

14. The compound which is not reduced by LiAlH4 is

Mg (i) CO2 Mg (i) KCN

16. Consider the following sequence of reactions.

The products [A] and [B] are respectively

(1) NaCN followed by hydrolysis (2) NaOI followed by H3O+

The above conversion is known as iodoform reaction.

18. Which of the following conversion is known as Stefen's reduction?

Sol. Answer (2)

This is known as Stephen’s reduction.

Sol. Answer (3)

Sol. Answer (1)

(1) Reaction with NaCN and NH4Cl followed by acidic hydrolysis

CH3 CH3 OH NH3 CH3 NH2 H3O+ CH3 NH2

Sol. Answer (3)

24. CHO + (x)

25. Among the given compounds

The order of decreasing acidity is

CHO (i) conc. NaOH

COOH COOH COOH CH2OH

Sol. Answer (2)

30. The correct order of reactivity of PhMgBr towards given compounds

Sol. Answer (3)

Sol. Answer (3)

34. Which of the following aromatic acids is most acidic?

COOH COOH COOH COOH

Sol. Answer (2)

35. Which one of the following orders of acid strength is correct?

36. The correct order of acidic strength of the carboxylic acid is

38. Enol content is high test in

Sol. Answer (3)

Sol. Answer (3)

 Number of aldol reactions = 3

44. The carboxyl functional group (–COOH) is present in [IIT-JEE-2012]

COOH COOH COOH CH2COOH

Sol. Answer (2)

membered transition state.

(1) CH3 — CH = C — COOH (2) CH3 — CH = C — CN

(3) CH3 — CH2 — C — COOH (4) CH 3 — CH = C — CO — NH 2