Xii Org Sheet Oxidation-Reduction PDF

CONTENT
S.No Pages
1. Oxidation & Reduction of organic compounds 02 – 11
2. Exercise-1 12 – 15
3. Exercise-2 16 – 19
4. Exercise-3 20 – 24
5. Answer Key 25 – 30
ORGANIC CHEMISTRY
TARGET IIT-JEE (MAIN + ADV.) 2021
XII
OXIDATION-REDUCTION
OXIDATION & REDUCTION OF ORGANIC COMPOUND
OXIDATION OF ALKENES, ALCOHOLS & CARBONYL COMPOUNDS
(I) OXIDATION OF ALKENES

OsO4
R–CH=CR2 R–CH—CR2
H2O
OH OH
Cold dil. R–CH—CR2
alkaline
KMnO4 OH OH
* Cold dil. alkaline KMnO4 is called as Bayer’s reagent.
* Overall syn addition
* Given by alkenes & alkynes
* Benzene & Cyclopropane can not give this reaction.
If we use acidic KMnO4 or warm KMnO4 or too concentrated KMnO4 the oxidative cleavage of
Glycol occurs resulting in mixture of Carboxylic acids & Ketones.

H ,KMnO
R–CH = CR2   4  RCOOH + R2C = O

Hot acidic KMnO4, Hot acidic K2Cr2O7 & hot acidic NaIO4 gives same result with alkene. The effect
is similar to that of oxidative ozonolysis on alkenes.
Preilschaive reaction :
Epoxidation of alkenes is reaction of alkenes with peroxyacids.
O O
|| ||
CH2=CH2 + CH 3  C  O  O  H  CH2–CH2 + CH 3  C  OH
O
 With the decrease in nucleophilicity of double bond, rate of reaction decreases.
 With the decrease in e withdrawing substituents in leaving group, rate decreases.
+
R H R
R R
CH dil.H 2SO 4 CH + +
+
–H HO–CH
O O–H H2O–CH
CH2 CH2
CH2–OH CH2–OH
H 2O
RCO3H
O
RCO3H OH R R
H 3O CH + 1 O Ag
OH CH
2 2  O
HCO3H OH CH2 CH2
OH
BANSAL CLASSES Page # 2

(II) OXIDATION OF ALCOHOLS

Oxidising agents
Different oxidising agents are used to oxidise alcohols in corresponding carbonyl compounds and carboxylic
acids.
mild oxidising
e.g. (I) R  CH 2  OH   R  C  H (Aldehyde)
1alcohol
agent ||
O
OH O
| mild oxidising
||
(II) R  CH  R '      R  C  R ' (Ketone)
agent
2alcohol
strong oxidising
(III) R  CH 2  OH     R  C  OH
agent ||
1alcohol
O
CH 3 CH2
| Cu 300C
(IV) CH 3  C  OH   C Dehydration takes place.
| CH3 CH3
CH 3
(1) Cu / 300°C (or Red hot Cu tube)
It oxidises only 1° alcohol in aldehyde and 2° alcohol into ketones. It does not oxidises 3°alcohol.
Dehydration of 3°alcohol takes place and alkene is formed.
(2) H /KMnO4,  (Strong oxidising agent)


(i) It oxidises 1° alcohol into carboxylic acid (ii) It oxidises 2° alcohol into ketone
(iii) It does not affect 3° alcohol
(iv) It affects carbon-carbon multiple bond and gives carboxylic acid
(3) H/K2Cr2O7,  (Strong oxidising agent)

(i) It oxidises 1° alcohol into carboxylic acid
(ii) It oxidises 2° alcohol into ketone
(iii) It does not affect 3° alcohol
(iv) It affects carbon-carbon multiple bond and give carboxylic acid
(4) PCC (Pyridinium chloro chromate)
N CrO3 Cl or CrO3 + HCl


N
H
PCC oxidises 1° alcohol into aldehyde, further oxidation is not possible.
PCC oxidises 2° alcohol into ketone. It does not oxidises multiple bond and 3° alcohol. It oxidises allylic
primary alcohol to corresponding aldehyde further oxidation is not possible.

(5) Collin’s reagent
( (2 mol) + CrO3 + CH2Cl2)

N
(i) It oxidises 1° alcohol into aldehyde
(ii) It oxidises 2° alcohol into ketone
(iii) Multiple bond is not affected
(iv) 3° alcohol is not affected
(6) Jones reagent (H2CrO4 in Anhydrous acetone) or CrO3 + H2SO4 in acetone.

Sufficiently mild so that it oxidises alcohols without oxidising or rearranging double bonds (8 or 9)
(i) It oxidised 1° alcohol into carboxylic acid (ii) It oxidised 2° alcohol into ketone
(iii) Multiple bond is not affected (iv) 3° alcohol is not affected
(7) TsCl + DMSO + NaHCO3

TsCl
RCH2OH s DMSO
 RCH2OTs
  RCHO
NaHCO3
Ts
R2CHOH Cl s DMSO
 R2CH–OTs
  R2CO
NaHCO3
TsCl DMSO
R3COH
 R3C–OTs
s 

NaHCO3
×
(i) It oxidised 1° alcohol into aldehyde
(ii) It oxidised 2° alcohol into ketone
(iii) Multiple bond is not affected
(iv) 3° alcohol is not affected
(8) M nO2-Oxidises only allylic or benzylic–OH.i.e.

1° Allylic or benzylic OH MnO
2  Aldehyde
2° Allylic or benzylic OH MnO
2  Ketone
No effect on 3° ROH and on Carbon-carbon multiple bond.

(9) Periodic cleavage

Periodic cleavage : It is done by periodic acid (H5IO6 or HIO4. 2H2O). Characteristics property of
periodic acid is the oxidative cleavage of the bonds with adjacent oxidizable groups such as 1,2-diols,
a-hydroxy carbonyl compounds, 1,2-diketones.
OH OH
R – CHOH HO OH R – CH – O OH
I I
O

O

R – CHOH HO R – CH – O
O O
2R – CHO + IO3¯ + H2O
(10) Openaur oxidation

CH3
Al O–C–CH3 O
CH3 3
R – CH – R R–C–R
O
OH CH3 –C – CH3

R2CH–OH + Al(OCMe3)3Me3COH + Al(OCHR2)3
(R2CH–O)2 Al–O
O CR2
3Me2C H
3R2C=O + (Me2C–O)3 Al
Oxidation of alcohol with aluminium tertiary
butoxide is Openaur oxidation.
OH O
Al (OCMe3)3
acetone
(11) NBS
It oxidises 1° alcohol into aldehyde.
It oxidises 2° alcohol into ketone.
3° alcohol is not affected
In case of alkene allylic position is brominated.

(III) OXIDATION OF CARBONYL COMPOUNDS.
1. RCHO + [Ag(NH3)2]OH  
 RCOOH + NH3 + Ag Ї
Aldehyde acts as reducing agent, they can reduce mild oxidizing agents like Tollen’s Reagent. Tollen’s
test Gentle Heating for 20 to 25 mins.
COONa
2. Fehling’s Solutions
H OH
Fehling’s A Fehling’s B
aq. CuSO4 Alk. solution of Roschelye H OH
salt (sodium potassium tartrate) COOK
It acts a carrier for Cu2+ as it make reversible complex with Cu2+
This test is also used is Blood and Urine test.
H 2O
RCHO + Cu2+ 

 RCOOH  Cu 
 
RCOO – Cu 2 O ( red ppt.)
3. Benedict’s solution
Sodium Citrate + NaOH + NaHCO3 + CuSO4
H 2O
RCHO + Cu2+ 

 RCOOH  Cu 
 
RCOO – Cu 2 O ( red ppt.)
4. RCHO + HgCl2 + H2O  RCOOH + 2HCl + Hg2Cl2


RCHO + Hg2Cl2 + H2O ® RCOOH + 2HCl + 2Hg  grey ppt.
5. Schiff’s Reagent
Schiff’s Reagent is aq. solution of following base decolourised by passing SO2.
Aldehyde restore pink colour of Schiff’s reagent.
NH 2 NH2
SO2 Colourless RCHO

C solution Pink colour

(Schiff’s Reagent)
+ NH Cl
2
p-Rosaniline Hydrochloride
Magenta colour (Fuschin)
Ketons are not easy to oxidize so they do not give these 5 tests. These five tests can be used to distinguish
aldehyde and ketones. Both gives 2,4 DNP test

KETONES ARE DIFFICULT TO OXIDIZE

Ketones can be oxidized from their enolic form at high temperature with very strong oxidizing agent.
Oxidation of ketones is sometimes governed by Popoff’s rule. According to this rule carbonyl group
remains with the smaller alkyl group. More electron rich alkene will be easy to oxidized.
O
[O]
Me – C – Me MeCOOH + CO2 + H2O

Oxidation by using SeO2

SeO2 is a selective oxidizing agent with converts –CH2– group adjacent to carbonyl group into carbonyl
group. The reagent, in general, oxidises active methylene and methyl groups to ketonic and aldehydic
groups respectively.
O O O O O
|| SeO 2
| | | | | | SeO2
||
 CH 2  C    C  C  ;  C  CH 3    C  CHO

Reducing agents and their role
Group Product LAH in LiAlH(OCMe3)3 NaBH4 LiAlH4 B2H6 H2+

ether in THF in EtOH +AlCl3 in THF ** catalyst
–CHO –CH2OH + – + + + +
>C=O >CH–OH + – + + + +
–CO2H –CH2OH + – – + + +
–CO2R –CH2OH + – – + + +
–COCl –CH2OH + +* + + – +
–CONH2 –CH2NH2 + – – + + +
(RCO)2O RCH2OH + – – + + +
–CN –CH2NH2 + – – + + +
>C=NOH –CH2NH 2 + – – + – +
>C=C< >CH–CH< – – – – + +
–CC– –CH=CH– – – – + + +
1° RX RH + – – + – +
* Product is RCHO
** Catalyst : Ni / Pd / Pt / Ru

LiAlH4 as a reducing agent :
H From LAH
(1) LiAlH C–O
(i) C = O   4 
( 2) H 2O
H From Solvent
Mechanism
H
H–Al–H 
Li
+ H H
H  EtOH
C=O C — OLi C — OH
(1) LiAlH
(ii) R  C  NH 2   4  R – CH2 – NH2
|| ( 2 ) H 2O
O
Mechanism
H
H–Al–H
+
Li
H 
R–C–NH Li R–C= NH

R–C–NH2 –H2O, –AlH3
O O O¯Li
+
H–Al–H
H
H H
 
R–CH=NH R–C–O–AlH2 R–C–O – Al–H Li
+
NH Li NH H
H
H–Al–H 
+
Li
H
  H–OH
R–CH2–NH Li
(1) LAH
(iii) R  C  OR '    R–CH2–OH + R'–OH
|| ( 2) H 3O 
O

Mechanism
+
H–Al–H  H
Li
H
R–C–OR' –AlH3 R–C–OR' R–C–H + R'–OLi
O O–Li
+ O H–OH
LAH R'–OH
H2O
R–CH2–OH
(iv) R – C  N (
1) LAH
 R–CH2–NH2

( 2 ) H 2O
Mechanism
H H
H–Al–H  
+ 
R – C N + Li R–C=N Li + AlH2
H
H

R–CH2–NH2 R–CH2–N–Li
AlH2
(v) R  C  OH (
1) LAH
 R–CH2–OH
|| ( 2 ) H 2O
O
Mechanism
+
H–Al–H H
Li
H + AlH3 
R–C–OH R–C–O¯Li R–C–O–Al–H Li

–H2
O O O H
H
+
(1) LiAlH4 Li O¯AlH 2
R–CH2–OH (2) H2 O R–C–H R–C–OAlH2

O O Li

Wolf Kischner reduction :

C = O NH  NH 2 / OH ¯
 2    CH2 + N2
Mechansim
–H2O
C = O + NH2 – NH2 C = N–NH2

–H2O OH
H
HO–H 
C – N=N–H C = N–NH

–H2O OH
H
 H–OH
C–N=N CH2 + N2
Clemension reduction
Zn ( Hg )
C=O  
HCl( conc.)
CH2
Mechanism

H Zn Zn2+ + 2e 
C=O C = O–H C – OH

H

–H2O H
CH CH–OH2 CH – OH

2e

H
CH CH2

EXERCISE-1
 
H / KMnO H / KMnO
Q.1 (i) CH2 = CH2   4  (ii) CH3–CH= CH2   4 
 
H  / KMnO H  / KMnO
(iii)   4  (iv)   4 
 
 
(v) H 
/ KMnO4
 (vi) H 
/ KMnO4

 
(vii)   4  (viii)   4 
 
(ix)   4  (x)   4 
 

(xi) H 
/ KMnO4



H / KMnO
(xii) C10H10   4  HOOC  CH 2  CH 2  CH 2  COOH
 |
CH 2  COOH
Q.2 A to F alkenes with minimum possible carbon.


H / KMnO
(i) A   4  MeCOOH as the only product


H / KMnO
(ii) B   4  O


H / KMnO
(iii) C   4  MeCH2COOH as the only organic product

O

H / KMnO
(iv) D   4 

O
O
 ||
H / KMnO4
(v) E     HOOC  C  C  C  C  C  C  C  C  COOH
 ||
O

H / KMnO
(vi) F   4  acetone + ethanoic acid

1% alkaline mCPBA
Q.3 (i) (A) (ii)
KMnO4
mCPBA\hydrolysis
(B)

Me Me
(1) mCPBA (1) mCPBA
(iii) (2) hydrolysis (iv) C=C (2) hydrolysis
Me H H
Me Me 1
H H Ag2O or 2Ag + O
(1) mCPBA 2 2
(v) C=C (vi) C=C 
H Me (2) hydrolysis H Ph
KMnO / OH ¯, 
Q.4 (i) CH3– CH2 – CH2 – OH  4   ?

or KMnO 4 / H ,

K 2Cr2O 7 / H , 
?
or conc. HNO 3, 
OH
| KMnO , H 
(ii) CH 3  CH  CH 2  CH 3  4 
?
or K 2 Cr2O 7 , H
OH
HO Cu/300°C
+
P
H /KMnO4/ 
Q
(iii) PCC or Collin's reagent
OH R
HO
MnO2/
S
Q.5 (i) CH2 = CH – (CH2)3 – CH2 – OH PCC


(ii) C6H5 – CH = CH – CH2 –OH PCC


OH
|
(iii) CH 3  CH  CH 2  CH 2  CH 2  OH PCC
 (A)
OH
(iv) PCC
 (v) CH2 = CH – CH2–OH MnO
2  ?
CH2OH
OH
MnO
(vi) CH3O CH–CH2 –CH2 –OH 2  ?
Acetone
CH3O

CH 3 OH
| MnO 2 |
(vii)  ?
CH  C  CH  C  CH 2  OH Acetone (viii) C6 H 5  CH  CH 3 MnO
2  ?
CCl 4
(ix) C6 H 5  CH  CH  CH 2  CH  CH 2  OH DMSO
 TsCl  NaHCO3
   ?
|
CH 3
Q.6 (i) HO Aluminium

 tert butoxide
  ?
Acetone
OH
| Aluminium tert butoxide
(ii) CH 2  CH  CH 2  CH  CH 3      
Acetone
Q.7 Which one of the following alcohols are oxidised by MnO2?

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
Q.8
HIO HIO
(i) Me  CH  CH 2  OH 4  (ii) Me 2 C — CH — Et 4 
| 
| | 
OH OH OH
OH
(iii) HIO
4  (iv) HO  CH 2  CH 2  CH
|
 CH 2  OH HIO 4


OH OH

(v) CH 2 — CH  CH 2  CH 3 HIO
4  (vi) CH 2 — CH  CH  CH 3 HIO 4 
| |  | | | 
OH OH OH OH OH
(vii) CH 2 — CH  CH  CH 2 HIO
4  (viii) Me  C  CH  Me HIO
4 
| | | |  || | 
OH OH OH OH O OH
(ix) Me  C  C  Me HIO
4 
|| || 
O O
Q.9 Which will give the Tollen test.
O OH O OMe O OH HO
|| |
(i) H (ii) (iii) R  C  CH 2 (iv)
HO

O
[O]
Q.10 (a) H3C – CH2 – C – CH3 
O
[O]
(b) Me2CH–C–Me

O
[O]
(c) Me3C–C–Me

O [O]
(d) 
SeO2
Q.11 (a) CH3–CHO

SeO2
(b) Me2CO Me – C – C – H

O
SeO2
(c) H3C – CH2 – C –C H3  P1 mCPBA
  P2 LAH
 P3
O SeO
2
(d) 

EXERCISE-2
Q.1 How many alkene on catalytic reduction give normal butane as product.
(i) (A) H
2 / Pt
 n-butane (ii) (B) H
2 / Pt
 Iso-pentane
(iii) (C) H
2 / Pt
 Neo-pentane (iv) (D) H2 / Pt
 Cyclopentane
H2
(v) (E) 
Pt
Q.2 Give the expected major product for each reaction, including stereochemistry where applicable.
H2 D2
(a) CH3–CH2–CH=CH2 
Pt
P1 (b) Pt P2
H 3C H Me
C=C D2
(c)  P
Ni 3 (d) Ni
/ H2  P4
H CH3 Me
H2/Pt
excess P5
(e) H2/Pt
1 eq. P6
H / Pt
Q.3 (i) CH2 = CH–CH2 – CH = O 2  P1
excess
H 2 / Pt
(ii) CH2=CH–CH2–CN  P2
excess
Q.4 Identify the product?

NaBH4 LiAlH 4
(i)    Me–CHO LiAlH
 4  (ii) NaBH4
   Me2CO   
NaBH4
(iii)    Me–COCl LiAlH
 4  (iv) NaBH4

LiAlH 4
  Me–COOEt   
NaBH4 LiAlH 4 NaBH4
(v)    Me–COOH    (vi)    Me–COOMe LiAlH
 4 
NaBH4 LiAlH 4
(vii)    Me–CONH2 LiAlH
 4  (viii) NaBH4
   Me–CONH–Me   
NaBH4 NaBH4 LiAlH 4
(ix)    Me–CONMe2 LiAlH
4  (x)    Me–CH=NH   
NaBH4
(xi)    CH3–CH = CH2 LiAlH
 4 
Q.5 Give product in following reactions.

NaBH4 LiAlH 4 NaBH4 LiAlH 4
(i)   O    (ii)    H–N O   
LiAlH 4
(iii) NaBH4
  O    (iv) NaBH4
  LiAlH
 4 
N N
H
(v) NaBH4
  O LiAlH
 4  (vi) NaBH4
 
LiAlH 4
O   
O O
O

(vii) NaBH4
   Me–CO–N LiAlH
 4  (viii) NaBH4

LiAlH 4
  CH2=CH–CHO   
LiAlH 4
(ix) NaBH4
   Ph–CH=CH–CHO    (x) NaBH4
  LiAlH
 4 
O

O
(a) H Re
dP  HI

(b) Re
dP  HI

OH
CHO
COCH3
(c) Re
dP  HI

HO CH2OH
(i) LAH

N O
(ii)
LAH
(iii) CH3– CH – CH2
O
LAH
AlCl3
H3CCOO COOCH3
(iv) LiAlH
 4  (A) + (B) + (C)
(v)
O


CHO
(i) NaBH4
O
COOEt
O
LAH
(ii) C—OEt (A)NaOI
 (B)
(iii) LiAlH 4, D 2O
LiAlH4
H2O
Q.9 (a) O=C—CH3    (A) NBS

Zn ( Hg )
 (B) alc
 .
(C) HCl
 (D)
HCl KOH R 2O 2
(b) Zn
( Hg
) 

HCl, 
O
|| Zn ( Hg )
(c) Ph  C  CH 3 HCl


O
(d) Zn
( Hg
) 

HCl, H 2O
O
(e) (
i ) H 2 NNH 2
 
( ii ) KOH , heat
N2H4
KOH, heat
O O (excess)
(f) Zn(Hg)
O HCl
(excess)

Q.10 Suggest appropriate reagents for following conversion.
OH
A
O O
OH
C

EXERCISE-3
OBJECTIVE
Q.1 Which of the following will decolourise alkaline KMnO4 solution? [JEE 1980]
(A) C3H8 (B) CH4 (C) CCl4 (D) C2H4
Q.2 The reagent with which both acetaldehyde and acetone react easily is [JEE 1981]
(A) Tollen's reagent (B) Schiff's reagent (C) Grignard reagent (D) Fehling reagent
Q.3 When acetaldehyde is treated with Fehling's solution, it gives a precipitate of [JEE 1982]
(A) Cu (B) CuO (C) Cu2O (D) Cu + Cu2O + CuO
Q.4 Baeyer's reagent is [JEE 1984]

(A) alkaline permanganate solution (B) acidified permanganate solution
(C) neutral permanganate solution (D) aqueous bromine solution
Q.5 Hydrogenation of benzoyl chloride in the presence of Pd on BaSO4 gives [JEE 1992]
(A) benzyl alcohol (B) benzaldehyde (C) benzoic acid (D) phenol
Q.6 The appropriate reagent for the following transformation: [JEE 2000]
O
CH2CH3
CH3
HO HO
(A) Zn(Hg), HCl (B) NH2NH2, OH¯ (C) H2 / Ni (D) NaBH4
Q.7 Statement-1: Dimethyl sulphide is commonly used for the reduction of an ozonide of an alkene to get
the carbonyl compound. [JEE 2001]
Statement-2: It reduces the ozonide giving water soluble dimethyl sulpoxide and excess of it evaporates.
(A ) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
Q.8 1-propanol and 2-propanol can be best distinguished by [JEE 2001]

(A) Oxidation with alkaline KMnO4 followed by reaction with Fehling solution.
(B) Oxidation with acidic dichromate followed by reaction with Fehling solution
(C) Oxidation by heating with copper followed by reaction with Fehling solution
(D) Oxidation with concentrated H2SO4 followed by reaction with Fehling solution.
Q.9 Butan-2-one can be converted to propanoic acid by which of the following? [JEE 2006]
(A) NaOH, NaI / H+ (B) Fehling solution
(C) NaOH, I2 / H + (D) Tollen's reagent

COMPREHENSION :
In the following sequence, product I, J and L are formed. K represents a reagent. [JEE 2008]
( i ) Mg / Ether
Cl
( i ) NaBH 4 K
Hex-3-ynal    I    J  H3C
( ii ) CO 2
 H
2
 L


( ii ) PBr3 ( iii ) H 3O Pb / BaSO 4 quinoline
O
Q.10 The structure of the product I is
(A) H C Br (B) H3C

3
Br
H3C
Br
(C) H C Br (D)
3
Q.11 The structures of compound J and K, respectively, are

H3 C COOH and SOCl2
(A) (B) H C and SO2Cl2
3 COOH
H3 C
(C) & SOCl2 (D) H3C COOH and CH3SO2Cl
COOH
Q.12 The structure of product L is

H3 C
CHO
(A) (B) H C CHO
3
H3 C
(C) (D) H C CHO
3
CHO
Q.13 The most suitable reagent for the conversion of R–CH2 – OH  R – CHO is :[JEE Main 2014]
(A) K2Cr2O7 (B) CrO3
(C) PCC (Pyridinium Chlorochromate) (D) KMnO4
Q.14 Reagent(s) which can be used to bring about the following transformation is(are) [JEE Advance 2016]
O O O O
C O C
H OH
COOH COOH
(A) LiAlH4 in (C2H5)2O (B) BH3 in THF
(C) NaBH4 in C2H5OH (D) Raney Ni/H2 in THF

Q.15 The major product 'X' formed in the following reaction is : [JEE Main 2019]
O
O
CH2–C–OCH3
NaBH
 4  X
MeOH
OH OH
CH2CH2OH CH2CH2OH
(1) (2)
O OH O
O
CH2–C–H CH2–C–OCH3
(3) (4)
Q.16 Which is the most suitable reagent for the following transformation ? [JEE Main 2019]
OH
CH3–CH=CH–CH2–CH–CH3 CH3–CH=CH–CH2CO2H
(1) Tollen's reagent (2) CrO2Cl2/CS2 (3) I2/NaOH (4) alkaline KMnO4
Q.17 The major product obtained in the following reaction is [JEE Main 2019]
(1) (2) (3) (4)
Q.18 The major product of the following reaction is : [JEE Main 2019]
CN
O (
i ) DIBAL H
 
( ii ) H 3O 
O
CHO CHO CH=NH
CHO
(1) OH (2) O (3) (4)

O OH
CHO O OH

Q.19 The major product of the following reaction is: [JEE Main 2019]
O
NaBH
 4 
EtOH
OH O OH
OH
(1) (2) (3) (4)
OEt
Q.20 The increasing order of the reactivity of the following with LiAlH4 is : [JEE Main 2019]
O O O O O
(A) C2H5 NH2 (B) C2H5 OCH3 (C) C2H5 Cl (D) C2H5 O C2H5
(1) (A) < (B) < (D) < (C) (2) (A) < (B) < (C) < (D)
(3) (B) < (A) < (D) < (C) (4) (B) < (A) < (C) < (D)
Q.21 The most suitable reagent for the given conversion is: [JEE Main 2020]
(1) LiAlH4 (2) NaBH4 (3) H2/Pd (4) B2H6
Q.22 For the following Assertion and Reason, the correct option is [JEE Main 2020]
Assertion : For hydrogenation reactions, the catalytic activity increases from Group 5 to Group 11
metals with maximum activity shown by Group 7-9 elements.
Reason : The reactants are most strongly adsorbed on group 7-9 elements.
(1) Both assertion and reason are true but the reason is not the correct explanation for the assertion.
(2) Both assertion and reason are false.
(3) Both assertion and reason are true and the reason is the correct explanation for the assertion.
(4) The assertion is true, but the reason is false.
SUBJECTIVE
Q.1 One mole of a hydrocarbon A reacts with 1 mol of bromine giving a dibromo compound, C5H10Br2.
Compound A on treatment with cold dilute alkaline potassium permanganate solution forms a compound,
C5H12O2. On ozonolysis, A gives equimolar quantities of propanone and ethanal. Deduce the structural
formula of A. [JEE 1981]
Q.2 A white precipitate was formed slowly when silver nitrate was added to compound A with the molecular
formula C6H13Cl. Compound A on treatment with hot alcoholic potassium hydroxide gave a mixture of
two isomeric alkenes B and C, having the formula C6H12. The mixture of b and C, on ozonolysis,
furnished four compounds. [JEE 1986]

(a) CH3CHO (b) C2H5CHO (c) CH3COCH3 (d) CH 3  CH  CHO

|
CH 3
What are the structures of A, B and C?
Q.3 Write the balanced chemical equations for the following: [JEE 1991]
"Ethylene glycol is obtained by the reaction of ethylene with potassium permanganate".
Q.4 When gas A is passed through dry KOH at low temperature, a deep-red coloured compound B and a
gas C are obtained. Gas A, on reaction with but-2-ene, followed by treatment with Zn/H2O yields
acetaldehyde. Identify A, B and C. [JEE 1994]
Q.5 An organic compound E(C5H8) on hydrogenation gives compound F(C5H12). Compound E on ozonolysis
gives formaldehyde and 2-ketopropanal. Deduce the structure of compound E. [JEE 1995]
Q.6 Hydrocarbon A adds 1 mol of hydrogen in the presence of a platnium catalyst to form n-hexane. When
A is oxidised vigorously with KMnO4, a single carboxylic acid, containing three carbon atoms, is isolated.
Give the structure of A and explain. [JEE 1997]
Q.7 Monomer A of a polymer on ozonolysis yields 2 mol of HCHO and 1 mol of CH3COCHO.
(a) Deduce the structure of A. [JEE 2005]
(b) Write the structure of all cis forms of polymer of compound A.
Q.8. Consider the following reactions [JEE MAIN 2020]

(i) CH 3 MgBr
Cu
A 
 B   2-methyll 2-butene
(ii) H 3O +
573K
The mass percentage of carbon in A is .

ANSWER KEY
EXERCISE - 1
Q.1 (i) CO 2 (ii) CH3–COOH + CO2
(iii) O + CO2 + HOOC – CH2 – CH2 – CH2–COOH
(iv) O + CH3–COOH
COOH
(v) (vi) O
COOH COOH
O
(vii) (viii) 2CH3–COOH
O
COOH CH 2  COOH O CH 2  COOH

(ix) | + | (x) + |
COOH CH 2  COOH O CH 2  COOH
O COOH
(xi)
HOOC O
(xii) CH  C  CH 2  CH  CH 2  C  CH
|
CH 2
|
C  CH
Q.2 (i) Me–CH=CH–CH3 (ii)
(iii) Me–CH2–CH=CH2 (iv)
(v) (vi)
OH
Q.3 (i) (A) OH (ii) O
(B)
OH
OH
OH Me Me
OH H OH HO H
(iii) (iv) HO H H OH
Me Me Me Me
OH OH
Me
H OH Me H
(v) H OH (vi) C—C
Me H O Ph
Q.4 (i) CH3–CH2–COO , CH3–CH2–COOH

O
||
(ii) CH 3  C  CH 2  CH 3
O O OH O OH

(iii) (P) (Q) O O
O O
O O
CHO OH COOH
OH OH
O HO
(R) (S)
O
O
CHO HO
Q.5 (i) CH2 = CH – (CH2)3 – CHO (ii) Ph – CH = CH – CHO

O
||
(iii) (A) H 3C  C  CH 2  CH 2  CHO
(iv) (v) H2C = CH–CHO

CHO
O
CH 3
MeO C–CH2–CH2–OH |
(vi) (vii) CH  C  CH  C  CHO
MeO
O
||
(viii) Ph  C  CH 3 (ix) Ph  CH  CH  CH 2  CH  CHO
|
CH 3
O O
||
Q.6 (i) (ii) CH 2  CH  CH 2  C  CH 3 Q.7 C
Q.8 (i) Me–CHO + HCHO (ii) O + Et – CHO
CHO
(iii) CHO (iv) HO–CH2–CH2–CHO + HCHO
(v) HCHO + CH3– CH2–CHO (vi) HCHO + HCOOH + CH3–CHO
(vii) 2HCHO + 2HCOOH (viii) Me–COOH + Me–CHO
(ix) 2 Me–COOH

Q.9 (i); (iii) ; (iv)

O
Q.10 (a) 2CH3 – COOH Me CH–C–Me (b) Me2CO + MeCOOH
O
COOH
Me CH–C–Me (c) Me3C–COOH + CO2 + H2O (d) COOH
SeO SeO
Q.11
CH –CHO (a) CH – CHO (b) Me – C – C – H
O O O
O O O O O
SeO || || || ||
mCPBA
(c) C – C – C –C  2 CC–CC–CC–CC
  C  C  O  C  CLAH
 CH3–CH2–OH
O SeO O
(d)
O
EXERCISE - 2
Q.1 (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 hyrogenation of alkene); (iv) One
(v) Including optical = 4 , Excluding optical = 3
Q.2 (a) (b)

D
CH3 CH3
CH3
H D D H
H
(c) D H H D (d) CH3
CH3 CH3 H
(e) *
2 G.I.
Q.3 (i) P1 CH3–CH2–CH2–CH2–OH (ii) P2 CH3–CH2–CH2–CH2–NH2
Q.4 (i) MeCH2–OH, Me–CH2OH (ii) Me2CH–OH, Me2CH–OH
(iii) MeCH2–OH, Me–CH2OH (iv) No reaction , Me–CH2–OH + EtOH
(v) No reduction, MeCH2–OH (vi) No reaction, MeCH2–OH + MeOH
(vii) No reduction, MeCH2NH2 (viii) No reaction, Me–CH2–NH–Me

Me
(ix) No reduction, MeCH2–N (x) M e–CH 2–NH2 , Me–CH2–NH2
Me
(xi) No reaction, No reaction
Q.5 (i) OH , OH (ii) NH OH , NH OH
(iii) No reaction, (iv) ,

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

OH OH
(vii) No reaction, Me–CH2–N (viii) CH2=CH–CH2–OH, CH2=CH–CH2–OH
(ix) Ph–CH=CH–CH2–OH, Ph–CH2–CH2–CH2–OH
(x) ,
HO HO
Q.6 (a) (b) (c)

CH3
OH CH OH
2
Q.7 (i) (ii) (iii) CH3– CH – CH3 , CH3–CH2–CH2OH
N
OH
HO CH2OH OH
(iv) + MeOH (B) + Et–OH (C) (v)

CH 2OH
(A)
CH2OH CHO CH2OH
NaBH4 OH
OH O
Q.8 (i) COOEt COOEt CH CH2OH + EtOH
CH
CH3 CH3
OD OH
H
(ii) CH2OH + EtOHNaOI
 +Iodoform test (iii)

Q.9
O
H
C—CH3 CH2—CH3 CH=CH2 Cl—CH–CH3
Br—C—CH3
(a) Zn
( Hg
) 
 NBS
 alc
.KOH

 HCl

HCl R 2O 2
(b) (c) Ph–CH2–CH3 (d) (e)
O O
(f) ,
Q.10 (A) Ni will reduce alkene, aldehyde and all it is not specific ;(B) NH2 – NH2 / H2O2 ;(C) LiAlH4
EXERCISE - 3
OBJECTIVE
Q.1 D Q.2 C Q.3 C Q.4 A Q.5 B Q.6 B Q.7 A
Q.8 C Q.9 C Q.10 D Q.11 A Q.12 C Q.13 C Q.14 CD
Q.15 D Q.16 C Q.17 B Q.18 A Q.19 D Q.20 A Q.21 D
Q.22 D
SUBJECTIVE
CH3 Br2 CH3

C = CH – CH3 C – CH – CH3
Q.1 CH3 (i) CH3
(ii O3 Br Br
)H
cold & 2O
/Z
dil. KMnO4 n
CH3
CH3 C = O + OHC – CH3
C = CH – CH3 CH3
CH3 Propanone Ethanol
OH OH
CH3 – CH – CH – CH2 – CH3

CH3 Cl (A)
Alc. KOH
Q.2 CH3 – C = CH – CH2 – CH3 + CH3 – CH – CH = CH – CH3

CH (B) (C)
3 CH 3
O3
O3
CH3
C = O + OHC – C2H5 CH3 – CH – CHO + OHC – CH3
CH3
CH3

CH2 +
CH2 – OH
cold dil. KMnO4/H
Q.3
CH2 CH2 – OH
O 3
Q.4 KOH  
Gas ( A ) KO3(B) + O2(C)
Pottasium ozonide (Deep Red Coloured)

O3 ( A )
CH3 – CH = CH – CH3   
( ii ) Zn / H 2 O 2CH3 – CHO
(A)  O3 ; (B)  KO3 ; (C)  O3
CH2 O
Q.5 CH3 – C – CH = CH2 CH3 – C – CHO + CH2O
(E) 2-Keto propanol Formaldehyde
H2
CH3
CH3 – CH – CH2 – CH3
Q.6 CH3 – CH2 – CH = CH – CH2– CH2 CH3 – CH2 – CH2 – CH2 – CH2– CH2
(A)
KMnO4 / 
2CH3 – CH2 – COOH
CH3 O
CH2 Ozonolysis O O
Q.7 (a) +
CH2 H H CH3 H
CH3 H CH3 H
CH2 CH2
C C C
C
(b) CH2 CH2
CH3
Q.8 66.66 to 66.67

Xii Org Sheet Oxidation-Reduction PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Xii Org Sheet Oxidation-Reduction PDF

Uploaded by

Copyright:

Available Formats

CONTENT

1. Oxidation & Reduction of organic compounds 02 – 11

OXIDATION OF ALKENES, ALCOHOLS & CARBONYL COMPOUNDS

(I) OXIDATION OF ALKENES

BANSAL CLASSES Page # 2

(II) OXIDATION OF ALCOHOLS

(2) H /KMnO4,  (Strong oxidising agent)

(3) H/K2Cr2O7,  (Strong oxidising agent)

(4) PCC (Pyridinium chloro chromate)

N CrO3 Cl or CrO3 + HCl

BANSAL CLASSES Page # 3

(5) Collin’s reagent

( (2 mol) + CrO3 + CH2Cl2)

(6) Jones reagent (H2CrO4 in Anhydrous acetone) or CrO3 + H2SO4 in acetone.

(7) TsCl + DMSO + NaHCO3

(8) M nO2-Oxidises only allylic or benzylic–OH.i.e.

BANSAL CLASSES Page # 4

(9) Periodic cleavage

2R – CHO + IO3¯ + H2O

(10) Openaur oxidation

BANSAL CLASSES Page # 5

(III) OXIDATION OF CARBONYL COMPOUNDS.

4. RCHO + HgCl2 + H2O  RCOOH + 2HCl + Hg2Cl2

SO2 Colourless RCHO

BANSAL CLASSES Page # 6

KETONES ARE DIFFICULT TO OXIDIZE

Oxidation by using SeO2

BANSAL CLASSES Page # 7

Reducing agents and their role

Group Product LAH in LiAlH(OCMe3)3 NaBH4 LiAlH4 B2H6 H2+

BANSAL CLASSES Page # 8

LiAlH4 as a reducing agent :

BANSAL CLASSES Page # 9

BANSAL CLASSES Page # 10

Wolf Kischner reduction :

BANSAL CLASSES Page # 11

Q.2 A to F alkenes with minimum possible carbon.

BANSAL CLASSES Page # 12

Q.5 (i) CH2 = CH – (CH2)3 – CH2 – OH PCC

(ii) C6H5 – CH = CH – CH2 –OH PCC

BANSAL CLASSES Page # 13

Q.6 (i) HO Aluminium

Q.7 Which one of the following alcohols are oxidised by MnO2?

BANSAL CLASSES Page # 14

BANSAL CLASSES Page # 15

Q.4 Identify the product?

Q.5 Give product in following reactions.

BANSAL CLASSES Page # 16

Q.6 Give product in following reactions.

Q.7 Give product in following reactions.

BANSAL CLASSES Page # 17

Q.8 Give product in following reactions.

Q.9 (a) O=C—CH3    (A) NBS

BANSAL CLASSES Page # 18

Q.10 Suggest appropriate reagents for following conversion.

BANSAL CLASSES Page # 19

Q.4 Baeyer's reagent is [JEE 1984]

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

Q.8 1-propanol and 2-propanol can be best distinguished by [JEE 2001]

BANSAL CLASSES Page # 20

(A) H C Br (B) H3C

Q.11 The structures of compound J and K, respectively, are

Q.12 The structure of product L is