ORGANIC CHEMISTRY

ORGANIC CHEMISTRY Dr.Ramu

OXIDATIONS (NCERT)
Oxidation of hydrocarbons:
Baeyer’s reagent: Bayers reagent is cold dilute alkaline KMnO4 or cold dilute KMnO4

Alkenes can be converted in to corresponding diols, this is a syn addition

H H3C HC CH2 H2C CH2

H3C C CH2 dil KMnO4, 273 K H2CCH2
OH OH OH OH
Ethylene glycol

Decolorisation of KMnO4 solution is used as a test for unsaturation.

Oxidation with hot KMnO4:

CO2H

O
R'
No rxn Ph CH3 R' + CO2 + H2O
Ph R O
R

CH3
CO2H hot KMnO4/-OH O
or R + CO2
KMnO4 / H+ R OH +
or H2O
Ph K2Cr2O7/H+ R
R'
O
CO2H R +
Ph OH O
R'
OH
CO2H
CO2H

Consider the acidic workup wherever its required

Etard reaction:

CH3 CH(OCrOHCl2)2 CHO

CrO2Cl2 H3O+
CS2
chromium complex Benzaldehyde
 Toluene or substituted toluene is converted to benzylidene diacetate on treating with chromic oxide in
acetic anhydride. The benzylidene diacetate can be hydrolysed to corresponding benzaldehyde with
aqueous acid.
CH3 CH(OCOCH3)2 H3O+ CHO
CrO3
∆
(CH3CO)O
Benzylidene diacetate Benzaldehyde

Ozonolysis:
H3C H
Reductive
cleavage O + O
H3C H O3 H3C O CH3 H CH3

H H
H CH3 O O OH
H3C
Oxidative
cleavage O + O
HO CH3

Reagents for reductive cleavage: Me 2 S, PPh 3 , Zn+H 2 O; Reagents for oxidativecleavage: H 2 O 2 , H 2 O, Ag 2 O

R H
H H Reductive
Reductive cleavage O + O
cleavage O + O
R H H R
H H H H O3
O3
H R
H H R OH
H OH Oxidative
Oxidative cleavage O + O
cleavage O + O
HO R
HO H

R R R
Reductive R Reductive
+ cleavage O + O
cleavage O O
R R H R R R R
O3 R O3

R H R R
R R R
R Oxidative
Oxidative cleavage O + O
cleavage O + O
OH R R
R

OXIDATION OF ALCOHOLS:PCC (pyridinium chlorochromate)

O
O
O HCl
N Cr O
N Cr N Cr O H
Cl-
O O O
O
PCC

PCC is the best reagent to convert 1º alcohol to aldehyde and 2º alcohol to ketone

R
R R OH pyH+CrO3Cl- H
or R OH
R O PCC R O
Ketone Aldehyde

Jones reagent: CrO 3 + H 2 SO 4 + H 2 O + Acetone or Na 2 Cr 2 O 7 + H 2 SO 4 + H 2 O + Acetone

1 º alcohol to carboxylic acids, 2º alcohol to ketones

 R
R R OH
OH R OH
H2CrO4
R O R O
Ketone carboxylic acid

Phenol also can be oxidized with Jones reagent

Na2Cr2O7
OH O O
H2SO4

In anhydrous medium 1º alcohols stops at aldehyde stage

R
R
R OH CrO3 H
R anhydrous R OH
O
e
K t one medium R O
aldehyde

Over oxidation of aldehydes takes place via hydrate intermediate

Tertiary alcohols do not undergo oxidation reaction. Under strong reaction conditions such as strong
oxidising agents (KMnO4) and elevated temperatures, cleavage of various C-C bonds takes place and a
mixture of carboxylic acids containing lesser number of carbon atoms is formed.

Aldehydes are easily oxidised to carboxylic acids on treatment with common oxidising agents like nitric
acid, potassium permanganate, potassium dichromate, etc.

Heating with Cu:

When the vapours of aprimary or a secondary alcohol are passed over heated copper at 573 K,
dehydrogenation takes place and an aldehyde or a ketone is formed while tertiary alcohols undergo
dehydration.
 R
R
H
R OH Cu R OH
R O 573 K
e ro
d hyd g enation dehydrogenation R O
Ketone
dehydration OH

OXIDATION OF ALDEHYDES AND KETONES:

Tollens reagent or Silver mirror test: Ammonical solver nitrate is nothing but a tollens reagent

No rxn

Ag O
+ OH O OH CO2 + Ag
O
R O
R
R
OOH
R HC
O
R-CO-R R-CHO
No rxn [Ag(NH3)2]OH + Ag
warming R OH

R
R

R O OH R C-Ag+
No rxn
OH
HO
O
+ Ag

Fehling’s Reagent:
Fehilings solution is the combination of Fehilings A + Fehilings B

Fehilings A: CuSO4 solution ( aq CuSO4)

Fehilings B: Alkaline sodium potassium tartrate ( aq NaOH + tartaric acid salt)

 R − CHO + 2CuO → RCOO − + Cu 2 O ↓
(Re d)
Benzaldehyde (aromatic aldehyde) is the only aldehyde which donot respond to fehiling solution
CHO
Fehilings tollens reagent
No red ppt reagent silver mirror

Haloform reaction:

Aldehydes and ketones having at least one methyl group linked to the carbonyl carbon atom (methyl
ketones) are oxidised by sodium hypohalite to sodium salts of corresponding carboxylic acids having
one carbon atom less than that of carbonyl compound. The methyl group is converted to haloform.

This oxidation does not affect a carbon-carbon double bond, if present in the molecule.

Iodoform reaction with sodium hypoiodite is also used for detection of CH3CO group or CH3CH(OH)
group which produces CH3CO group on oxidation

So all the alcohols which can oxidize and give aldehydes or ketones with methyl group is also respond
to iodoform test
 Ketones are generally oxidised under vigorous conditions, i.e. strong oxidising agents and at elevated
temperatures. Their oxidation involves carbon-carbon bond cleavage to afford a mixture of carboxylic
acids having lesser number of carbon atoms than the parent ketone.

Other reagents which never asked in JEE MAINS

SeO2-----> allylic C-H will be oxidized to allylic alcohol, Benzylic C-H can be oxidized to benzyl
alcohol or benzaldehyde

MnO2------> allylic and benzylic alcohol will be converted in to corresponding aldehyde

CAN -------> alcohol will be oxidized in to corresponding carbonyl compounds

1. The major product of the following reaction is? (NTA april 9th first shift)
(i) alkaline KMnO4
+
(ii) H3O

Ans Benzoic acid

2. Compound A(C9H10O) shows positive isoform test. Oxidation of A with KMnO4/KOH gives acid
B(C8H6O4). Anhydride of B is used for the preparation of phenolphthalein. Compound A is (NTA
april 10th second shift)

O
O O CHO
A) B) C) D)
Ans A
3. Major organic product formed in the given reaction is? (NTA april 10th second shift)
O
NaOCl

Taken from series

Benzoic acid and chloroform
4. Major organic product formed in the given reaction is? (NTA april 12th second shift)
O3/Me2S

Taken from series

Ans Glyoxal and butanedial
5. Major organic product formed in the given reaction is? (NTA jan 9th first shift)
Br
CrO3/H+
OH
Taken from series
Br O

OH
Ans
6. Which is the most suitable reagent for the following transformation? (NTA jan 10th second shift)
? OH

OH O

A) Tollens reagent B) I2/NaOH C) CrO2Cl2/CS2 D) Alkaline KMnO4

Ans B
7. Major organic product formed in the given reaction is? (NTA jan 11th first shift)
COCH3 i) KMnO4/KOH/∆
ii) H2SO4 (dil)
H3C

Ans 1,4-benzene dicarboxylic acid

8. Major organic product formed in the given reaction is? (NTA jan 12th second shift)
H3COCO CrO3/H+

HO Taken from series

H3COCO

Ans HO O

9. In the following sequence identify B (AIEEE-2008)

O3 Zn/H2O
H3C HC CH CH3 A B

Ans Acetaldehyde
10. One mole of a symmetrical alkene on ozanolysis gives 2-moles of an aldehyde having a molecular mass
of 44u. The alkene is (AIEEE-2008)
Ans: 2-butene
11. Ozanolysis of an organic compound gives formaldehyde as one of the products. This confirms the
prescence of (AIEEE-2011)
Ans vinyl group
12. Ozanalysis of an organic compound A produces acetone and propeonaldehyde in equimolar mixture.
Identify A from the following compounds (AIEEE-2011)
A) 2-methyl-1-pentene B) 1-pentene C) 2-pentene D) 2-methyl-2-pentene
Ans D
13. The best reagent to convert pent-3-en-2-ol into pent-3en-2-one is (AIEEE-2005)
A) PCC B) CrO3/CH3CO2H C)K2Cr2O3/H+ D) KMnO4/H+
Ans A
14. Among the following the one that gives +ve iodoform test with I2 and NaOH is (AIEEE-2006)
 A) 2-methylpropan-1-ol B) 1-phenylethanol C) 3-pentanol D) 2-phenylethanol
Ans B
15. Silver mirror test is given by which one of the following compounds? (AIEEE-2011)
A) CH3CHO B) CH3COCH3 C) HCHO D) Benzophenone
Ans AC

00. Compound A (C4H9Br) gives a white precipitate with when warmed with alcoholic AgNO3. Oxidation
of A gives an acid (B), C8H6O4. B easily forms anhydride on heating. Identify the compound A.(JEE
mains 2013)
CH2Br
C2H5 CH2Br CH2Br

A) CH3
B) Br C) H3C D) CH3

Ans D
00. In the following sequence of reaction the product A is (JEE mains 2015)
SOCl2 H2/Pd
KMnO4 B C
Toluene A
BaSO4

Ans Benzoic acid

00. The most suitable reagent for the conversion of R-CH2-OH -- R-CHO (JEE mains 2014)
A) KMnO4 B) K2Cr2O7 C) CrO3 D) PCC
00. The correct sequence of reagents for the following conversion will be (JEE mains 2017)
OH
O
CH3

OHC
HO

A) CH3MgBr; H+/CH3OH; [Ag(NH3)2]+OH- B) CH3MgBr; [Ag(NH3)2]+OH- ; H+/CH3OH

C) [Ag(NH3)2]+OH- ; CH3MgBr; H+/CH3OH D) [Ag(NH3)2]+OH- H+/CH3OH CH3MgBr
Ans D
00. Which compound would give 5-keto-2-methyl hexanol upon ozanolysis? (JEE mains 2015)

A) B) C) D)
Ans D
IIT ADVANCE QUESTIONS
00. The product formed when ethanol vapour is passed over heated copper (IIT 1983)
Ans Ethanal
19. A compound that gives +ve iodoform test is (IIT 1983)
A) 1-pentanol B) 2-pentanone C) 3-pentanone D) pentanal
Ans B
20. Which of the following compounds is oxidized to prepare methyl ethyl ketone (IIT 1987)
A) 2-propanol B) 1-butanol C) 2-butanol D) t-butylalcohol
Ans C
21. The compound that will not give iodoform on treatment with alkaline and iodine is (IIT 1985)
A) Acetone B) Ethanol C) diethylketone D) isopropyl alcohol
Ans C
22. How will you convert Butane-2-one to propanoic acid (IIT-2005)
A) Tollens reagent B) Fehilings solution C) NaOH / I2/H+ D) NaOH/NaI/H+
Ans C
23. After completion of the reaction (I and II) , the organic compounds in the reaction mixture is are (IIT-
Adv-2013)
O O
Br2 (1.0 mol) Br2 (1.0 mol)
Reaction-1 Reaction-2
aq NaOH CH3COOH
1.0 mol 1.0 mol

O O O
O O
Br Br Br Br Br
Br
Br Br Br ONa
Br Br Br Br Br
P Q R S T

A) Reaction-I: P and Reaction-II: P

B) Reaction I: U, acetone and Reaction II:Q, acetone
C) Reaction-I: T,U, acetone and reaction-II: P
D) Reaction I: U, acetone and Reaction II: S, acetone
Ans C
24. Identify A, B, C and give their structures.
O
Br2
(A) + (B)
NaOH
H+
O C7H12O (C)
∆