REDUCING AGENTS AND THEIR ROLE

Group Product LAH in NaBH4 B2H6 H2 /

Ether in H2O in THF Catalyst D

–CHO –CH2OH + + + +

>C = O >CH – OH + + + +

–CO2H –CH2OH + – + –

–CO2R –CH2OH + – + +

–COCl –CH2OH + + – +

–CONH2 –CH2NH2 + – + +

(RCO)2O RCH2OH + – + +

–CN –CH2NH2 + – + +

>C = NOH –CH2NH2 + – – +

>C = C< >CH – CH< – – + +

–C º C– –CH = CH– – – + +

1° RX RH + – – +

Note :
1. B2H6 in THF not able to reduce cyclic ester.

2. NaBH4 can also reduce imine group ( C = NH ).

3. Reactivity order towards Ni / H2 , D Þ –C º N > –C – O – R

O
 Name Reagent Function
H
Wolf Kishner Reduction (i) N2H4 / (ii) KOH, O
H
H
Clemenson Reduction Zn–Hg / HCl O
H
SH H
Mozingo Reduction Dry HCl, followed
O
by Raney Ni
SH H
SnCl2 / HCl followed
Stephen's Reduction + R–C N R–CH=O
by H3O
CH3 CH3
MPV Reduction Al –O–CH HO–CH O OH
CH3 3 CH3

C=C C—C
H H
Hydroboration Reduction B2H6 / AcOH, H2O
O O
H H

Bouvoult Blank Reduction Na / EtOH R–COO–R RCH2OH +ROH

Transfer Hydrogenation N2H4 / H2O2 C=C C—C

H H
O O

H2, Pd–BaSO4 R—C—Cl R—C—H

Rosenmund Reduction
* —C C— —C C—
H H
H
Birch Reduction Na / Liq. NH3 —C C— —C C—
H
—COOR
H–Al –CH2–CH–CH3 —C N
CH3 2 —COCl —CHO
DIBAL-H O O
(–78°C) followed by H3O+ —C–O–C–

—CHO —CH2OH

R–CO2H RCH3
R–CH=O RCH3
Red phosphorus in R–C–R RCH2R
presence of HI Red P + HI
O
R–OH R–H
 Reduction

EXERCISE # I - DAY 1
SH
HS
1. O ¾¾¾
H 2 / Ni
®

The end products of the reaction are :

(A) SH and SH (B) S–CH2–CH2–SH

S SH
(C) and H2O (D) and HS
S

CH2
H ,Pd
2. ¾¾¾
2 ®
CH3

Products of the above reaction will be :

(A) Racemic mixture (B) Diastereomers (C) Meso (D) Structural isomer
D
NH 2 - NH 2
3. ¾¾¾¾
H2O2
® Product :
D
D D
H H
(A) (B) (C) (D) Both (B) and (C)
D H
H D
4. On catalytic reduction with H2/Pt how many alkenes will give n-butane ?
(A) 1 (B) 2 (C) 3 (D) 4
H3C D
H / Ni
5. C=C ¾¾¾
2
®
D CH3

Product of above reaction will be :

(A) Racemic mixture (B) Diastereomers (C) Meso (D) Constitutional isomers

H3C CH3
6. C=C ¾¾¾
H 2 / Ni
®
D D

Product of above reaction will be :

(A) Racemic mixture (B) Diastereomers (C) Meso (D) Constitutional isomers
O O
CºC
7.

Which reagent will be used for the above conversion ?

(A) Na/Liq. NH3 (B) H2, Pd–CaCO3 (C) Li, Ph–NH2 (D) H2, Pt
 COOH

8. ¾¾¾¾Li
Liq.NH3
® Major product :

COOH COOH COOH CH2OH

(A) (B) (C) (D)

OCH3

9. ¾¾¾¾ ¾
Na,Liq,NH3
® Major product :

OCH3 OCH3 OCH3

(A) (B) (C) (D) None of these

10. ¾¾¾¾¾
Conc.H 2SO 4
D
® A ¾¾¾
Pt / H 2
® B

A and B respectively are :

(A) Both (B) ,

(C) , (D) ,

11. If the following compound is treated with Pd in excess of H2 gas, how many stereoisomers of the
product will be obtained ?

(A) 1 (B) 2 (C) 3 (D) 4

H2C CH2
¾¾¾ ® Product :
H 2 ,Ni
12. C—C
1 eq.
D D

H3C CH2 H3C D

(A) C—C (B) C=C
H D CH3
D D

H3C CH3
(C) C=C (D) All of these
D D
 Reduction

13. Which alkyne gives 3-ethylhexane on catalytic hydrogenation ?

(A) (B) (C) (D) All of these

O
O O
14. ¾¾¾
NaBH 4
® Product
O
O Cl
The product is :
O
(A) HO OH (B) CH3–CH2–OH

OH
O
OH
O O
(C) HO OH (D)
O
OH
OH
AgCN H2 , Ni
15. Br A B
The final product (B) is :
H
NH2 N
(A) (B) N (C) (D) NH2
H
 EXERCISE # II
1. Column-I Column-II
(Conversion) (Required Reagent)
H3C CH3
(A) H3C–CºC–CH3 ¾® C=C (P) H2 , Pd-BaSO4
H H
H3C H
(B) H3C–CºC–CH3 ¾® C=C (Q) Li , Liq.NH3
H CH3
(C) H3C–CH=CH–CH3 ¾® H3C–CH2–CH2–CH3 (R) N2H4 / H2O2 (1 eq.)
CH3 CH3

(D) ¾® (S) B2H6 , CH3COOH

O
2. R–C–R ¾¾
?
® R–CH2–R
Identify numbers of reagent that can be used for above conversion.
1 CH2–SH
(a) Zn–Hg / HCl (b) LiAlH4 (c) N2H4 / OH (d) , H2 / Ni
CH2–SH

3. Column-I Column-II
(Conversion) (Required Reagent)
O
||
(A) –C–OH ¾¾
® –CH2OH (P) LiAlH4

O
||
(B) –C–Cl ¾¾
® –CH2OH (Q) NaBH4

O
||
(C) –C–OR' ¾¾
® –CH2OH (R) B2H6 / THF

O
||
R–C
(D) O ¾¾
® R–CH2 OH (S) H2 / Catalyst, D
R–C
||
O

4. How many alkene on catalytic reduction gives following product.

(i) (A) ¾H¾ ¾® n-butane
2 / Pt (ii) (B) ¾H¾ ¾® Iso-pentane
2 / Pt

(iii) (C) ¾H¾ ¾® Neo-pentane

2 / Pt (iv) (D) ¾H¾ ¾® Cyclopentane
2 / Pt

(v) (E) ¾¾®

H2
Pt
 Reduction
5. Give the expected major product for each reaction, including stereochemistry where applicable.
D2
(a) CH3–CH2–CH=CH2 ¾¾®
H2
Pt
P1 (b) Pt P2

H3C H Me
(c) C=C ¾D¾®
2
P (d) ¾Ni
¾/ ¾
H2
® P4
Ni 3
H CH3
Me
H2/Pt
excess P5
(e) H2/Pt
1 eq. P6
H2 / Pt H2 / Pt
6. (i) CH2=CH–CH2–CH = O excess P1 (ii) CH2=CH–CH2–CºN excess P2

7. (a) Identify the product ?

lH 4
LiA lH 4
D LiA
(i) ¬¾ ¾ ¾ Me–CHO –7IBAL-
NaBH4
(ii) ¬¾ ¾ ¾ Me2CO
NaBH4 DI
BA
8°C H L-H

lH 4 lH 4
LiA LiA
(iii) ¬¾ ¾ ¾ Me–COCl
NaBH4
DI
BA (iv) ¬¾ ¾ ¾ Me–COOEt
NaBH4 DI
BA
L-H L-H

(b) Identify the product ?

(v) ¬¾ ¾ ¾ Me–COOH ¾¾ ¾ ¾® (vi) ¬¾ ¾ ¾ Me–COOMe ¾LiAlH

¾¾ ¾4 ®
NaBH4 LiAlH4 NaBH4

(vii) ¬¾ ¾ ¾ Me–CONH2 ¾LiAlH

¾¾ ¾4 ® (viii) ¬¾ ¾ ¾ Me–CONH–Me ¾¾ ¾ ¾®
NaBH4 NaBH4 LiAlH4

(ix) ¬¾ ¾ ¾ Me–CONMe2 ¾LiAlH

NaBH4
¾¾ ¾4 ® (x) ¬¾ ¾ ¾ CH3–CH = CH2 ¾LiAlH
NaBH4
¾¾ ¾4 ®
8. Give product in following reactions.

(i) ¬¾ ¾¾
NaBH4
O ¾¾ ¾ ¾®
LiAlH4
(ii) ¬¾ ¾ ¾ H–N
NaBH4
O ¾¾ ¾ ¾®
LiAlH4

O ¾¾ ¾ ¾® ¾LiAlH
¾¾ ¾4 ®
LiAlH4
(iii) ¬¾ ¾¾
NaBH4
(iv)
N N
H

(v) ¬¾ ¾¾
NaBH4 O ¾LiAlH
¾¾ ¾4 ® (vi) ¬¾ ¾¾
NaBH4
O ¾¾ ¾ ¾®
LiAlH4

O O
O

(vii) ¬¾ ¾ ¾ Me–CO–N
NaBH4 ¾LiAlH
¾¾ ¾4 ® (viii) ¬¾ ¾¾
NaBH4
¾LiAlH
¾¾ ¾4 ®
O
9. Give product in following reactions.
O COCH3
O
Re d P + HI
(a) H ¾¾ ¾¾® (b) Red P + HI
¾¾¾¾¾ ® (c) Red P + HI
¾¾¾¾¾ ®
OH (excess) HO CH2OH (excess)
CHO
10. Give product in following reactions.

LAH
(i) ¾LAH
¾¾® (ii) (iii) CH–3 CH – CH 2
N O O
LAH
AlCl3

(iv)
O

11. Give product in following reactions.

CHO
O (i) LiAlH4
NaBH4 (ii) D2O
(i) O (ii)
COOEt (i) LiAlH4
(ii) H2O

12. (a) O=C—CH3 ¾Zn ¾) ® (A) ¾NBS

¾( Hg
¾ ¾¾® (B) ¾alc
¾® .
(C) ¾HCl
¾¾® (D)
HCl KOH R 2O 2

O O
O
||
13. (a) ¾Zn
¾( Hg
¾
¾) ® (b) Ph - C - CH 3 ¾¾ ¾ ¾®
Zn ( Hg )
(c) ¾Zn
¾( Hg
¾
¾) ®
HCl , D HCl HCl , H 2 O

N2H4
KOH, heat
O O (excess)
O
Zn(Hg)
(d) ¾(¾ ¾¾ ¾®
i ) H 2 NNH 2
(e) O HCl
(ii ) KOH ,heat (excess)
 DiBAL -H
14. (a) C – OH ¾¾¾¾¾ ®

DiBAL - H
(b) C º N ¾¾¾¾
–78°C
®

DiBAL - H
(c) CH3 – C – O – CH 2 – CH3 ¾¾¾¾
–78°C
®
O
O OH
?
15.
NO 2 NO2

above conversion can be achieved by

(A) LiAlH4 (B) H2 / Ni, D (C) NaBH4 (D) All
 EXERCISE # III (MAIN & ADVANCE)
1. Hydrogenation of benzoyl chloride in the presence of Pd and BaSO4 gives : [IIT 1992]
(A) Benzyl alcohol (B) Benzaldehyde (C) Benzoic acid (D) Phenol
2. Draw the stereochemical structure of the product in the following reactions. [IIT 1994]
R–CºC–R ¾¾¾¾¾ H2
Lindlar catalyst
®
3. Under Wolff Kishner reduction conditions, the conversions which may be brought about is?
(A) Benzaldehyde into Benzyl alcohol (B) Cyclohexanol into Cyclohexane
(C) Cyclohexanone into Cyclohexanol (D) Benzophenone into Diphenylmethane [IIT 1995]
4. Which one of the following alkenes will react fastest with H2 under catalytic hydrogenation condition
[IIT 2000]

(A) (B) (C) (D)

5. The appropriate reagent for the following transformation: [IIT-2000]

O
CH2 CH3
CH3 ¾®
HO HO

(A) Zn(Hg), HCl (B) NH2NH2, OH– (C) H2/Ni (D) NaBH4
Me Me
H

6. H
Me
H
Hydrogenation of the above compound in the presence of poisoned paladium catalyst gives-
(A) An optically active compound (B) An optically inactive compound [IIT-2001]
(C) A racemic mixture (D) A diastereomeric mixture
7. When CH2 = CH–COOH is reduced with LiAlH4, the compound obtained will be -[AIEEE-2003]
(A) CH3–CH2–CH2OH (B) CH3–CH2–CHO
(C) CH3–CH2–COOH (D) CH2=CH–CH2OH
8. 2–hexyne can be converted into trans–2–hexene by the action of : [IIT-2004]
(A) H2–Pd-BaSO4 (B) Li in liq. NH3 (C) H2–PtO2 (D) NaBH4
Paragraph for Question No. 09 to 11
In the following reaction sequence, products I, J and L are formed. K represents a reagent.
1. Mg / ether
1. NaBH 4 K Cl ¾H¾®
Hex-3-ynal ¾¾ ¾ ¾® I 2. CO2
¾¾¾¾¾ ¾ ® J ¾¾® Me
2
L
2. PBr3 3. H O+
3 || Pd/BaSO4
quinoline
O
9. The structure of the product I is [JEE-2008]
(A) Me Br (B) Me
Br
Me Br
(C) Me Br (D)
 Reduction

10. The structures of compounds J and K, respectively, are [JEE-2008]

OH
(A) Me COOH and SOCl2 (B) Me || and SO2Cl2
O
(C) Me and SOCl2 (D) Me COOH and CH3SO2Cl
COOH
11. The structure of product L is : [JEE-2008]

Me CHO
(A) (B) Me CHO

CHO
(C) (D) Me CHO
Me

12. 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-2014]
13. In the reaction, [JEE-2014]

CH3COOH ¾¾¾ ® A ¾¾¾

¾ ® B ¾¾¾¾ ® C, Final product C is.
LiAlH PCl
4 AlC. KOH
5

(A) Ethylene (B) Acetyl chloride (C) Acetaldehyde (D) Acetylene

14. The reagent needed for converting is : [JEE-2014]
Ph H
Ph–CºC–Ph C=C
H Ph
(A) H2 / Lindlar Cat. (B) Cat. hydrogenation
(C) LiAlH4 (D) Li / NH3
15. The major product obtained in the following reaction is : [JEE MAIN-2017]
O
O

DIBAL-H

COOH
OH OH

CHO CHO CHO CHO

(A) (2) (3) (4)
COOH CHO COOH CHO

16. Glucose on prolonged heating with HI gives : [Jee Main - 2018]

(1) 1–Hexene (2) Hexanoic acid (3) 6-iodohexanal (4) n-Hexane
17. The trans-alkenes are formed by the reduction of alkynes with : [Jee Main - 2018]
(1) NaBH4 (2) Na/liq.NH3 (3) Sn–HCl (4) H2–Pd/C, BaSO4
18. The main reduction product of the following compound with NaBH in methanol is :-
4
[Jee Main - Onl_line Morning 2018]
O O

NMe2

O O OH O OH OH O

NMe2 NMe2 NMe2 NMe2

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

19. The major product of following reaction is : [JEE-MAIN-On-line-(Jan)-2019]

R – C º N ¾¾¾¾¾ ¾
(1)AlH(i–Bu 2 )
(2)H 2O
® ?
(1) RCHO (2) RCOOH (3) RCH2NH2 (4) RCONH2
20. Wilkinson catalyst is : [JEE-MAIN-On-line-(Jan)-2019]
(1) [(Ph3P)3RhCl] (Et = C2H5) (2) [Et3P)3IrCl]
(3) [Et3P)3RhCl] (4) [Ph3P)3IrCl]
21. The major product 'X' formed in the following reaction is :
[JEE-MAIN-On-line-(Jan)-2019]
O O
CH2–C–OCH3
¾¾¾
NaBH 4
MeOH
®X

OH O O OH OH O
CH2CH2OH CH2–C–H CH2CH2OH CH2–C–OCH3
(1) (2) (3) (4)

22. The major product of the following recation is:

[JEE-MAIN-On-line-(Jan)-2019]
O
CH3N NaBH 4
OH OH
(1) CH3N (2) CH3N
OH OH
(3) CH3N (4) CH3N

23. The major product of the following reaction is:

[JEE-MAIN-On-line-(Jan)-2019]
O
OEt ¾¾¾¾¾
(i) Ni / H2
®
(ii) DIBAL- H
CN
H
O N NH OH
(1) (2) (3) (4)
CHO NH2
 Reduction
24. The major product obtained in the following reaction is :-
[JEE-MAIN-On-line-(Jan)-2019]
O OH
Li AlH4
(excess)
CH3
NO 2 O
O OH OH OH OH

(1) CH3 (2) CH3 (3) CH3 (4) CH3

NO 2 OH NH 2 OH NH 2 OH NO 2 OH
25. The major product of the following reaction is:
[JEE-MAIN-On-line-(Jan)-2019]
CN

(i) DIBAL-H
O +
(ii) H3O
O
CHO CHO CH=NH
CHO
(1) (2) O (3) OH (4) OH
O
OH
O CHO
26. The increasing order of the reactivity of the following with LiAlH4 is :
[JEE-MAIN-On-line-(Jan)-2019]
O O
(A) C2H 5 NH2 (B) C2H5 OCH3

O O O
(C) C2H5 Cl (D) C 2H 5 O C2H5

(1) (A) < (B) < (D) < (C) (2) (A) < (B) < (C) < (D)
(3) (B) < (A) < (D) < (C) (4) (B) < (A) < (C) < (D)
27. The major product of the following reaction is:
[JEE-MAIN-On-line-(Jan)-2019]

O
NaBH4
¾¾®
EtOH

OH
OH O OH
(1) (2) (3) (4)
OEt
28. The major product of the following reaction is: [JEE-MAIN-On-line-(April)-2019]

O
Br
¾¾¾¾®
NaBH 4
MeOH,25ºC

OH OH
OMe Br
(1) (2)

OMe O
(3) (4)

29. The major product of the following reaction is : [JEE-MAIN-On-line-(April)-2019]

CH3 CH = CHCO2 CH 3 ¾¾¾

LiAlH 4
¾®

(1) CH3 CH2 CH2 CHO (2) CH3CH = CHCH2OH

(3) CH3 CH2CH2 CO2 CH 3 (4) CH3CH2CH2CH2OH
 Reduction

ANSWER KEY
EXERCISE # I
1. Ans. (D) 2. Ans. (B) 3. Ans. (C) 4. Ans. (C) 5. Ans. (A)
6. Ans. (C) 7. Ans. (B) 8. Ans. (B) 9. Ans. (C) 10. Ans. (B)
11. Ans. (C) 12. Ans. (C) 13. Ans. (D) 14. Ans. (D) 15. Ans. (B)
EXERCISE # II
1. Ans. (A)®P, R, S; (B)®Q; (C)®R, S; (D)®Q 2. Ans. (3)
3. Ans. (A)®P, R, S; (B)®P, Q, S; (C)®P, R, S; (D)®P, R, S
4. Ans.
(i) Cis & trans 2-butene & 1-butene ; (ii) C–C –C=C C–C=C–C C–C–C–C
C C C
(iii) Zero (Neo-pentane can not be prepared by catalytic hydrogenation of alkene) ; (iv) One

(v) Including optical = 4 , Excluding optical = 3.

5. Ans.
D CH 3 CH 3
H D D H
(a) (b) (c)
D H H D
D CH 3 CH3
CH3
H *
(d) (e)
CH3
H 2G.I.

6. Ans. (i) P1 = CH3–CH2–CH2–CH2–OH (ii) P2 = CH3–CH2–CH2–CH2–NH2

8. Ans.

(i) OH , OH (ii) NH OH , NH OH

(iii) No reaction, (iv)

NH NH

(v) No reaction, CH2OH (vi) No reaction, CH2OH

OH OH

(vii) No reaction, Me–CH2–N (viii) ,

HO HO

9. Ans. (a) (b) (c)

CH3
10. Ans.

OH
N OH CH OH
2

(i) (ii) (iii) CH3–CH–CH3, CH3–CH 2–CH 2OH

OH
OH

(iv)
CH2OH

CH2OH CHO CH2OH

LAH
NaBH4 +EtOH
11. Ans. (i) OH OH
O
CH COOEt COOEt CH CH2OH
CH 3 CH3

OD OH
H

(ii)

12. Ans.

O H
C–CH3 CH2–CH3 Br–C–CH3 CH=CH2 Cl–CH–CH3
Zn(Hg) NBS [Link] HCl
(a) HCl R2O2

13. (a) (b) Ph–CH2–CH3 (c) (d)

O O

(e) ,

DiBAL -H
14. (a) C – OH ¾¾¾¾¾ ® C–H
O O

DiBAL - H C–H
(b) C º N ¾¾¾¾
–78°C
® (c) CH3 – CHO
O
15. Ans.(C)
 Reduction

EXERCISE # III (MAIN & ADVANCE)

R R
1. Ans. (B) 2. Ans. C=C 3. Ans. (D) 4. Ans. (A)
H H
5. Ans. (B) 6. Ans. (B) 7. Ans. (D) 8. Ans. (B)
9. Ans. (D) 10. Ans. (A) 11. Ans. (C)
12. Ans. (5)
M. wt 100 of ketone
So m. formula = C6H12O

(1) n-Butyl –C–CH3 n-butyl CH–CH3

O OH
(2) Isobutyl –C–CH3 Isobutyl –CH–CH3 all are
O NaBH4 ± racemic mixture
OH
(3) 3º butyl –C–CH3 3ºbutyl–CH–CH3
O OH
CH 3
(4) CH3–CH2–CH–C–CH3 CH 3
CH 3–CH2–CH–CH–CH3
O
R(2ºbutyl) OH
CH 3 2-alcohols (R,R) & (R,S)
NaBH4 diastereomeric pair
(5) CH3–CH2–CH–C–CH3
O CH 3–CH2–CH–CH–CH3
S(2ºbutyl)
CH 3 OH
2-alcohols (S,S) & (S,R)
diastereomeric pair

(6) n-propyl –C–Et

n-propyl –CH–Et
O
OH (+)
– racemic
(7) Isopropyl –C–Et NaBH4 mixture

O Isopropyl CH–Et
(+) racemic
OH –
mixture
\ (1 ; 2 ; 3 ; 6 ; 7)
13. Ans. (A)
O
(A) (B) (C)
LiAlH4 alc KOH
CH3–C–OH CH3–CH2–OH PCl5 CH3CH2–Cl CH2=CH2
 Reduction of CH3COOH will produce CH3–CH2–OH(A)
Now reaction of CH3–CH2–OH(A) with PCl5 will produce CH3–CH2–Cl(B).
Now alcoholic KOH with Et–Cl will produce CH2=CH2(C) Ethylene by E2 elemination.
Thus Ans. is (1) Ethylene.
14. Ans. (D)
15. Ans. (1)
16. Ans. (4)
Sol. CHO
H OH
HO H HI/D
H OH Reduction
n-Hexane
H OH
CH 2OH
Glucose
17. Ans. (2)
Na/liq. NH3
Sol.

Birch reduction is anti addition. So trans alkene will be produced.

18. Ans. (4)
19. Ans. (1)
20. Ans. (1)
21. Ans. (4)
22. Ans.(3)
23. Ans. (2)
24. Ans. (2)
25. Ans. (3)
26. Ans. (1)
27. Ans. (4)
28. Ans. (4)
29. Ans. (2)
 Oxidation

EXERCISE#I - DAY 2
1. The given reaction

Aluminium tertiary butoxide

Acetone

is knows as :
(A) Kolbe reaction (B) Tischenko reaction (C) MPV reaction (D) Oppeneur oxidation
2. In the given reaction :

OH OH
| |
CH 3 - CH — C - CH 3 ¾HIO
¾¾4 ® (a) + (b)
|
CH 3

(a) and (b) respectively be :

(A) CH3CHO and CH3CHO (B) CH3COCH3 and CH3CHO
(C) CH3COCH3 and CH3COCH3 (D) CH3COOH and CH3COCH3

O O
|| ||
3. CH3 - C - H and CH 3 - C - CH 3 is differentiated by

(A) Tollen's reagent (B) Lucas test (C) Iodoform test (D) NaHSO3 test
4. In the given reaction

SeO
¾¾¾2 ® [X]

[X] will be:

(A) (B) (C) (D)

5. Which will give silver mirror test with Tollens reagent :

(A) C6H5CHO (B) CH3–CHO (C) HCOOH (D) All of these
6. Which one of the following compounds will give dimethyl glyoxal with SeO 2:
(A) Acetone (B) Acetophenone
(C) Ethyl methyl ketone (D) Propanaldehyde
7. Which one of the following alcohols can be oxidised by K2CrO4?
(A) Ethanol (B) Tert butyl alcohol
(C) Isopropyl alcohol (D) Allyl alcohol
[Link] solution gives red precipitate with:
(A) Aromatic aldehyde (B) Aliphatic aldehyde (C) Ketones (D) CH2 – C – CH3
OH O
9. Which of the following compound will give positive Tollens test

(A) CH3CHO (B)

(C) CH3CH2CH 2CH 2CH - OCH 3 (D)

|
OH
10. Schiff's reagent gives pink colour with :
(A) Acetaldehyde (B) Formic acid (C) Acetic acid (D) Methyl acetate
11. Which one of the following alcohols are oxidised by MnO 2?
OH
|
(A) C6H5 – CH2 – CH2–OH (B) CH 2 = CH - CH 2 - CH - CH 3
OH
|
(C) CH 3 - CH = CH - CH - CH 3 (D) CH3–CH2 – CH2 –OH
O

12. MCPBA Major product is :

COOH O O
O O
(A) (B) (C) (D) O

13. Which of the following can be oxidised by MnO2:

OH OH
OH
(A) (B) (C) (D) OH

O
C—Me O
18
14. Me—C—OOH Major product is :

O O O O
18 18
C—OMe C—OMe O—C—Me O—C—Me
(A) (B) (C) (D)
+
H / KMnO 4
15. A B Phthalic Anhydride ; A is :
Me Me
Me
(A) (B) (C) (D)
Me Me Me
Me
 Oxidation

EXERCISE#II
1. Which will give the Tollen test.

O OH O OMe O OH
|| | HO
(A) H (B) (C) R - C - CH 2 (D)
HO

2. Which of the following is an example of oxidation reaction :

(A) CH3 – CH2 – OH ¾¾¾
PCl3
® (B) CH3 – CH = CH2 ¾¾¾
Ni / H 2
® (C) CH3 – CH = CH2 ¾¾¾
Br2
®
CCl 4

H Å / KMnO 4 H Å / KMnO 4
3. (i) CH2 = CH2 ¾¾¾¾¾
® (ii) CH3–CH= CH2 ¾¾¾¾¾
®

Å Å

(iii) ¾¾¾¾ ¾
H / KMnO 4
® (iv) ¾¾¾¾ ¾
H / KMnO 4
®

Å Å

(v) ¾¾¾¾ ¾
H / KMnO 4
® (vi) ¾¾¾¾ ¾
H / KMnO 4
®

Å Å
H / KMnO 4 , D
(vii) ¾¾¾¾ ¾
H / KMnO 4
® (viii) ¾¾¾¾¾
–CO
®
2

Å Å

(ix) ¾¾¾¾ ¾
H / KMnO 4
® (x) ¾¾¾¾ ¾
H / KMnO 4
®

(xi) ¾¾¾¾ ¾
H / KMnO 4
®

4. A to F alkenes with minimum possible carbon.

Å

A ¾¾¾¾ ¾ ® MeCOOH as the only product

H / KMnO 4
(i) D

(ii) B ¾¾¾¾ ¾ ®
H / KMnO 4
D
O as the only product

O
Å Å

(iii) D ¾¾¾¾ ¾ ® (iv) F ¾¾¾¾ ¾ ® Acetone + Ethanoic acid

H / KMnO 4 H / KMnO 4
D D

O
1% alkaline
KMnO4
A
mCPBA
5. (i) m-CPBA / H3O
+ (ii)
B
Me Me
mCPBA mCPBA
(iii) hydrolysis (iv) C=C hydrolysis
Me H H
Me H Me Ag2O or 2Ag +
1
O
(v) mCPBA (vi) H 2 2
C=C C=C D
H Me hydrolysis H Ph
 OH
| KMnO ,H Å
6. (i) CH3– CH2 – CH2 – OH ¾¾¾¾¾
KMnO4 / OH¯,D
® ? (ii) CH 3 - CH - CH 2 - CH 3 ¾¾ ¾4¾ ¾® ?
Å
or K 2Cr2O 7 , H
+
K2 Cr2O7 / H ,
or conc. HNO3 ,
+
or KMnO4 / H ,

CH2 = CH – (CH2)3 – CH2 – OH ¾¾¾¾¾¾ ®

Chromic anhydride
7. (i) in glacial acetic acid

(ii) C6H5 – CH = CH – CH2 –OH ¾¾¾¾¾¾ ®

Chromic anhydride
in glacial acetic acid

OH
|
(iii) CH 3 - CH - CH 2 - CH 2 - CH 2 - OH ¾¾¾
PCC
CH 2 Cl 2
® (A)

OH
(iv) ¾¾¾
PCC
CH 2 Cl 2
® (v) CH2 = CH – CH2–OH ¾MnO
¾¾2 ® ?

CH2OH

OH
CH–CH2–CH2–OH ¾¾¾2 ® ?
MnO
(vi) CH3O Acetone

CH3O

OH
Me - CH - CH 2 - OH ¾¾¾® ¾HIO
¾¾4 ®
HIO 4
8. (i) (ii)
D D
| OH
OH
(iii) HO - CH 2 - CH 2 - CH - CH 2 - OH¾HIO
¾¾4 ® (iv) CH 2 — CH - CH - CH 3 ¾HIO
¾¾4 ®
| D D
| | |
OH OH OH OH

(v) CH 2 — CH - CH - CH 2 ¾HIO
¾¾4 ® (vi) Me - C - CH - Me ¾HIO
¾¾4 ®
| | | | D || | D
OH OH OH OH O OH

(vii) Me - C - C - Me ¾HIO
¾¾4 ®
| | || D
O O
SeO2 SeO2 ?
9. (a) CH3–CHO (b) Me2CO (c) CH3–CH=CH2 Acrolein
D D

O
CH3 C–H
1 Step O
+
SeO2 H /
(d) 2 Step (e) CH3—C—H P1 Conc. NaOH CH2OH P
– +
COO Na
10. (a) How will you differentiate HCHO and PhCHO ?
(b) How will you differentiate HCHO and MeCHO ?
 Oxidation
EXERCISE#III (MAIN & ADVANCE)
1. In the reaction, P is [IIT 1995]

SeO
CO ¾¾¾2 ® P + Se + H2O

(A) CH 3COCHO (B) CH3COOCH3 (C) CH3COCH2OH (D) None

2. The best reagent to convert pent–3–en–2–ol into pent –3–en –2–one is - [AIEEE-2005]
(A) Acidic dichromate (B) Acidic permanganate
(C) Pyridinium chloro-chromate (D) Chromic anhydride in glacial acetic acid
3. Which of the following will change the colour of acidic dichromate solution.
[JEE-MAINS 2013]

(A) OH (B) OH (C) OH (D)

OH

MCPBA
4. Product [JEE-MAINS 2013]

H
O CH3
H
O
(A) H H (B) (C) H3C H (D)
O O
H3C O
O
CH3

5. ¾¾¾®
KMnO 4
D
Major product of reaction is? [JEE-MAINS 2013]

O
|| OH
COOH C–H
(A) (B) (C) (D)
CH2OH
6. The most suitable reagent for the conversion of R–CH2–OH ® R–CHO is :-
[JEE-MAINS 2014]
(A) CrO3 (B) PCC (Pyridinium chlorochromate)
(C) KMNO 4 (D) K2Cr2O7
7. Positive Tollen's test is observed for [JEE-Advance 2016]
H O
CHO OH
Ph O
H
(A) H (B) (C) Ph (D)
Ph Ph
H O
8. The major product formed in the following reaction is :-
[Jee Main - Onl_line Evening 2018]
OCOCH 3
PCC
(pyridinium
¬¾¾¾¾¾
chlorochromate)
CHCl3
®
HO
OH
O O
O

(A) HO OH (B) HO OH
O O
O OCOCH3

(C) O OH (D) O OH
H H
9. The major product of the following reaction is:
[JEE-MAIN-On-line-(Jan)-2019]

(1) KOH (aqueous)

Br
+
(2) CrO3/H
Br (3) H2SO4/D

O O O O

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

HO Br OH Br
10. The major product of the following reaction [JEE-MAIN-On-line-(April)-2019]

(1) CrO3
HO
(2) SOCl2/D
HO (3) D

O O O O

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

HO Cl Cl HO
 Oxidation

ANSWER-KEY
EXERCISE#I
1. Ans. (D) 2. Ans. (B) 3. Ans. (A) 4. Ans. (B)
5. Ans. (D) 6. Ans. (C) 7. Ans. (A,C,D) 8. Ans. (B,D)
9. Ans. (A,B,C) 10. Ans. (A,B) 11. Ans. (C) 12. Ans. (B)
13. Ans. (C) 14. Ans. (D) 15. Ans. (C)
EXERCISE#II
1. Ans. (A,C,D) 2. Ans. (C)
3. Ans.

(i) CO2 (ii) CH3–COOH + CO2

(iii) O + CO2 + HOOC–C–C–C–COOH

COOH
(iv) O + CH3–COOH (v)
COOH

(vi) O (vii) O
COOH
O
COOH CH2–COOH
(viii) 2CH3–COOH (ix) +
COOH CH2–COOH

O O COOH
CH2–COOH
(x) + (xi)
O CH2–COOH HOOC O

4. Ans.

(i) Me–CH=CH–CH3 (ii) (iii) (iv)

OH R/S
OH *
5. Ans. (i) (A) OH (B) (ii) O
OH
OH Me Me
OH H OH HO H
(iii) (iv) HO H H OH
Me Me
OH OH Me Me
Me
H OH Me H
(v) (vi) C––C
H OH
H O Ph
Me
6. Ans.
O
(i) CH3–CH2–CH2–COO– , CH3–CH2–CH2–COOH (ii) CH3–C–CH2–CH3
7.
Ans. (i) CH2=CH–(CH2)3–CHO (ii) Ph–CH=CH–CHO
O
O
(iii) (A) H3C–C–CH2–CH2–CHO (iv)

CHO

O
(v) H2C=CH–CHO (vi) MeO C–CH2–CH2–OH

MeO
8. Ans.

CHO
(i) Me–CHO + HCHO (ii)
CHO

(iii) HO–CH2–CH2–CHO + HCHO (iv) HCHO + HCOOH + CH3–CHO

(v) 2HCHO + 2HCOOH (vi) Me–COOH + Me–CHO
(vii) 2Me–COOH
9. Ans.
(a) CH–CHO (b) Me–C–C–H
O O O
O
CH3 C H

? Acrolein 2 step
(c) CH3 – CH = CH2 (d)
(1) step etard
SeO2
SeO2
MnO2
CH2 – CH = CH2 H – C – CH = CH2
CH2 OH MnO2
OH O

O O O
SeO2
(e) CH3—C—H CH–CH
(P1)

10. (a) Ans. F and B test

(b) Ans. Iodoform test
 Oxidation

EXERCISE#III (MAIN & ADVANCE)

1. Ans. (A) 2. Ans. (D)
3. Ans. (A)
OH
[O]
R—CH2—OH R—C—OH
H

O
R—C—H
[O]
O
R—C—OH
3º alcohols do not oxidize
they undergo dehydration
4. Ans. (C)
Me Me
H O
O–O–C O O
Cl
5. Ans. (A) 6. Ans. (B)
7. Ans. (A,B,C)
Sol. Tollens's test is given by compounds having aldehyde group. Also a-hydroxy carbonyl gives positive
tollen's test.
H
C =O Tollen's CO2
–
H H + Ag mirror
(A) reagent (+ve test)
H H H H
Acraldehyde

CH=O CO2–
Tollen's
+ Ag mirror
(B) reagent (+ve test)
Benzaldehyde

(C) Ph–CH–C–Ph Tollen's (+ve test)

Ph–C–C–Ph + Ag mirror
reagent
OH O O O
Benzoin
Tollen's
(D) PhCH=CH–C–Ph No reaction (–ve test)
reagent
O
8. Ans. (D) 9. Ans. (2) 10. Ans. (4)