ORGANIC CHEMISTRY

ORGANIC CHEMISTRY Dr.Ramu

REDUCTIONS (NCERT)
CATALYTIC HYDROGENATION:

OH

R
O
R NH2 O HO R
R R
NO2 H R

R H2
R
R R
Pt / Pd / Ni syn adn
O
R
C O R'
N
R
R C N R + R OH
OH
H contra versy
N
R but
given in NCERT
R NH2

Partial reduction:
R H R R
R R R R
H R
H2 H H
Na in liq NH3 Pd / BaSO4
Birch reduction quinoline O
Lindlars catalyst O
R H R Cl
R Na+ R H
Rosenmund
terminal alkynes cant reduced reduction
with Na in liq NH3 due
to acidic hydrogen

HYDRIDE TRANSFER REAGENT

NaBH 4 [Sodium borohydride]
NaBH 4 less reactive than LiAlH 4 , Here water, MeOH, EtOH also can be used as a solvent
 R OH
OH
NH2

H+ (dil) or H2O
R O
H
R
NH
O **
R O
H+ R H 2
( dil or
R il )
) or + (d
H H
2O
O

R O OH
R OH Cl OH
+ NaBH4 HO
H (dil) or H2O H+ (dil) or H2O
O

CHO
O Br
** r H2 ***
H+ (dil) or H2O
Ph o
il ) R' O
+ (d O
H
Ph OH R

OH

R * R'

DIBAL-H (diisobutylaluminium hydride)

O
R' O
R O + R' OH
R H
toluene(solvent)
work up H2O
O
O
OH
DIBAL-H O
H or
H O
Al toluene(solvent)
work up H2O OH

O
R C N
toluene(solvent) R H
work up H2O

DIBAL-H at -78ºC ester will be converting in to aldehyde but at room temperature ester will be converting in to alcohol, but
jee mains they are not bothering about temperature so just write aldehyde

LiAlH 4 [Lithium Aluminium Hydride]

LAH is a moisture sensitive reagent it will be quenched with water
Solvent should be either Dry ether or dry dioxane
The work up reagent we should add after the reaction
For mechanism see the types of reactions in nucleophilic addition reactions
Some times in work up they will give H 3 O+ heat which means work up followed by dehydration go carefully based on
options.
 R OH OH
R OH
R * R'

H+ (dil) or H2O
R O R
H OH

2O
+
OH O R'

H
O

(d
Cl

il )

) or
O

2O
R R R OH

or

rH
(dil
H
O

l) o
H+ R R

2
O

H+
R OH + R'-OH

( di
( di
l) O R'

H+
or
OH H O
O 2O R O
H+ or H2
(dil l
+ di )
) or H (
H
2O
R C N O OH
R NH2 LiAlH4 + HO
OH
+
H (dil) or H2O H (dil) or H2O

NO2

H+ O O
H H O ( dil
Ph N N Ph l or H 2 ) or OH
+ di ) HO
H ( NO2 2 HO
Ph N N Ph O R O
R
H+

r H2
o O
H+ (dil) or H2O
(dil

H
il ) R O

+
+ (d R
(d
) or

il )
NH H R
O O

or
2
NH
H

R
2O

2H
NH2
O
2 R OH

R NH R NH2

Reduction using metals in strong acid

R --C HO Along with these functional groups if there is a acid sensi

-
mm
cleem
c meen
nsse
enn R -C H 3 tive groups like –OH, double bond, epoxide are there this a no
-t a good method for that
R --C O--R
R --C H 2--R
Sn n+
+ HC l
orr
o
+ HCl
Fee +
orr
o R NO2
n--Hg +
Zn + HCl R NH2

A rr NO2
A rr NH 2

WOLFF-KISHNER REDUCTION:

R R KOH / Ethylene glycol R

H2N NH2 + N2
O N NH2
-H2O R Heat R
R
hydrazone

Alcoholic KOH also can do the elimination while writing product plz keep this point in mind

METALS IN NEUTRAL MEDIUM

 Bouveault–Blanc reduction

R NH2

R C N
O O
OH R H
R R Na or Na-Hg R OH
R R EtOH
O
R'
R O

R OH + R' OH

BORANE (BH 3 or B 2 H 6 ):

O
BH3 or B2H6
R OH R OH

STEPHENS REDUCTION:

SnCl2 H3O+
R C N R C NH R CHO
dry HCL H hydrolysis
intermediate

MEERWEIN–PONNDORF–VERLEY REDUCTION:

O Al(Oi -P r )3 OH O
+
R' R'' i -P r-OH R' R''

REDUCTION OF ALKYL HALIDE:

Zn, H+
R X R H + HCl
x = Cl or Br or I

Additional reagent Red P + HI but never asked in IIT

R CH3 + R' H R COOR' R OH

R H

2 R CH3 (R CO)2O R CHO

R CH3
Red P + HI
R CH3 RCOCl 150-200 ºC RCOR
RCH2R

R-CONH2
R CH3 R-CO2H
R CH3
1. The major product of the following reaction is (Jee mains april-8 morning shift)
O
Br NaBH4

MeOH, 25 ºC

NC
H2, Pd/C

2. CN O write the major organic product (Jee mains april-8 evening shift)

O
LiAlH4
OCH3
H2O
3. write the MOP (Jee mains april-9 morning shift)

O
CN H2 / Pd

4. write the MOP (Jee mains april-9 evening shift)

5. Which of the following is not a correct method for the preparation of benzyl amine from
cyanobenzene? (Jee mains april-10 evening shift)
A) i) HCl/H2O ii) NaBH4 B) i) LiAlH4, ii) H3O+
C) i) SnCl2 / HCl (gas), ii) NaBH4 D) H2/Ni
Ans A

1) AlH(i-Bu)2
R C N
2) H2O
6. write the MOP (Jee mains jan-9 morning shift)

O
OCH3 NaBH4

O MeOH
7. write the MOP (Jee mains jan-10 morning shift)

O
N NaBH4
8. write the MOP (Jee mains jan-10 evening shift)

O
1) Ni/H2
OEt
CN 2) DIBAL-H
9. ** write the MOP (Jee mains jan-11 morning shift)
 O
OH
H NH N
CN NH2
A) B) C) D)

O OH

LiAlH4 (excess)
CH3

NO2 O
10. write the MOP (Jee mains jan-11 evening shift)

O
NaBH4

EtOH
11. write the MOP (Jee mains jan-12 evening shift)

12. Increasing order of reactivity of following with LiAlH4 is (Jee mains jan-12 evening shift)
O O O O O

C2H5 NH2 C2H5 OCH3 C2H5 Cl C2H5 O C2H5

1 2 3 4

CN
i) DIBAL-H

O ii) H3O+

13. O Write the MOP (Jee mains jan-12 morning shift)

OH LiAlH4

14. O write the MOP (Jee mains 2003)

COCH3 CH2CH3
reagent

15. HO HO (Jee mains 2012)

A) N2H4/OH- B) Zn-Hg/ HCl C) Na, Liq NH3 D) NaBH4
LiAlH4
CH3-COOH
16. MOP? Taken from series (Jee mains 2014)

O
H2/Pd
Cl
BaSO4
17. MOP? Taken from series (Jee mains 2015)
 O
O
DIBAL-H

18. COOH MOP? (Jee mains 2017)

COOH i) LiAlH4

ii) H3O+
19. MOP? (Jee –adv-1995)

O
reagent
CH3 CH3

HO HO
20. (Jee –adv-2000)
A) Zn-Hg/HCl B) N2H4/OH- C) H2/Ni D) NaBH4

O O Reagent O O
O

H OH
CO2H O CO2H O
21. (Jee Adv. 2016)
A) LiAlH4 in diethyl ether B) BH3 in THF
C) NaBH4 in C2H5OH D) Raney NI in H2 in THF
Ans C,D
HO CN LiAlH4

22. H Subjective (Jee Adv. 1996)

A) B) C) D)
CN
H2/Ni
23. MOP? Taken from series (Jee 1991)

NaBH4
H3C HC CH CHO
24. MOP? Taken from series (Jee 1991)

O
CHC6H5 i)LiAlH4
ii) H+ heat
25. MOP? Taken from series (Jee 1998)

paragraph ( observe the nature of reducing agent) (Jee Adv. 2019)

Column-I Column-II
I i) DIBAL-H P CHO
ii) dil HCl
CN
CO2H
O iii) NaBH4
iv) con H2SO4
O
 II i) O3 Q OH
ii) Zn, H2O
OH
iii) NaBH4
CO2H iv) con H2SO4

III i) KCN R
Cl ii) H3O+ ∆
O
CO2CH3 iii) LiAlH4
iv) con H2SO4

IV CO2CH3 i) LiAlH4 S OH

CO2CH3 ii) con H2SO4

CO2H

T CO2H

CO2H

U
O

26. Which of the following options has a correct combination considering List-1 and List-2
A) II-P-S-U B) I-S-Q-R C) II-P-S-T D) I-Q-II-U
Ans-A
27. Which of the following options has a correct combination considering List-1 and List-2
A) III-S-R B) IV-Q-U C) IV-Q-R D) III-T-U
Ans-C
H2
Cl
Pd/BaSO4
28. O quioline MOP? Taken from series (Jee 2008)

H2 (lindlar catalyst)

29. MOP? (Jee 2000)

H
poisoned palladium catalyst
H
30. H MOP? (Jee 2001)

reagent
31. (Jee 2004)

32. Match each of the compounds in column-1 with characteristic reaction with column-2 (Jee 2009)
Column-1 Column-2
A CH3CH2CH2CN p Reduction with Pd-C/H2
 B ***CH2CH3OCOCH3 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 DIBAL-H
t Alkaline hydrolysis
Ans: A-pqst, B-pst (st), C-p, D-r

33. ****The hydrocarbon which can react with sodium in liq NH3
A) Et B) CH3-CH=CH-CH3 C) Et Et D) Pr Pr

Ans A (controversy)
O NaBH4
D3O+
34. MOP? (NSEC 2000)

H2 (1 eq)
catalyst
35. MOP? (NSEC 2000)

HCl H2O
H3C CN + 2H [X] [Y]
ether ∆
36. X and Y respectively (NSEC 2001)

37. Reduction of an isonitrile gives (NSEC 2002)

reagent
H3C Cl CH4
38. (answer it based on NCERT) (NSEC 2002)

39. The compound that does not react with Lithium aluminium hydride is (NSEC 2003)
A) 3-pentene-2-one B) methyl benzoate C) 2-pentanol D) propane nitrile

40. *** Reduction of methyl benzoate (C6H5COOCH3) to benzyl alcohol (C6H5CH2OH) can be
accomplished using (NSEC 2005)
A) H2/Pd B) LiAlH4 C) NaBH4 D) Zn-Hg/HCl

H reagent OH

O2N O2N
41. Best reagent among the given (NSEC 2008)
A) LiAlH4 B) NaBH4 C) Molecular H2 D) SnCl2
 O
i) NaBH4
H
OH
ii) aq Acid
42. O (NSEC 2009)
O O O
O OH
O OH
A) B) OH C) D)

O
DIBAL-H (excess)
EtO CN toluene -78 ºC
then H3O+
43. MOP? (KVPY 2019)

44. Bouveault-Blanc reduction involves (Jee mains 2016)

A) Reduction of ester with Na/EtOH B) Reduction of an ester with H2/Pd
C) Reduction of carbonyl compound with Na/Hg and HCl
D) Reduction of an anhydride with LiAlH4
45. The reagent(s) require for the following conversion are
EtO2C CO2H OH

CN HO2C CHO

A) i) LiAlH4 ii) H3O+

B) i) B2H6 ii) DIBAL-H iii) H3O+
C) i) B2H6 ii) SnCl2/ dil HCl iii) H3O+
D) i) NaBH4 ii) Raney Ni/H2 iii) H3O+

ANSWERS

1- O H OH A
N OH
5 CH2NH2

OH
H2N

6- CHO OH OH D OH
R H
N
10 CO2Me

CH3

NH2 OH
11 OH 3>4>2>1 CHO OH A
-
OH
15

16 OH O O OH B
OH
- H
20

COOH
21- CD HO CH2NH2 NH2 C6H5
OH
25 H

26 A C H H
- O H
30 H

31 Na in liq NH3 ** A OD
-
35
36 X Y 2º amine Zn/H+ C B(cont)
- H3C C NH H3C C O
H H
40

41 B A CHO A 3
- CHO
45