CHEMISTRY CLASS XII WORK SHEET

Alcohol (CnH2n+2O) Isomerism in Alcohol

1. Chain isomerism

CH3–CH2–CH2–CH3 and CH3–CH–CH3

CH3

2. Position isomerism

CH3–CH2–CH2–OH and CH3–CH–CH3

OH

3. Functional isomerism
CH3–CH2–OH and CH3–O–CH3

4. Optical isomerism
*
CH3–CH2–CH–CH3
OH

General methwds of preparation

1. From alkane

1 Cu tube
(a) CH4 + O2 CH3–OH
2 100 atm
9 :1 200 oC

(b) Alkane having 3o–H atoms are oxidised to 3o– alcohol by KmnO4
H+/KMnO4
(CH3)2 C – H (CH3)2 C – OH

CrO3
(c) CrO3 also oxidised a t-hydrogan to –OH (CH3)3 C – H (CH3)3 C – OH


2. From alkene
(a) By acid hydration
 OH
H3O
CH3–CH=CH2 CH3–CH–CH2–H

(b) Oxymercuration demercuration method (OMDM)

OH
(CH3COO)2Hg + H2O
CH3–CH=CH2 CH3–CH–CH2–H
NaBH4

(c) Hydroboration – Oxidation (HBO)

H
(i) BH3/THF
CH3–CH=CH2 – CH3–CH–CH2–OH
(ii) H2O2/OH
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3. Hydrolysis of Alkyl halide
Aq. KOH
R–X R – OH
AgOH

4. From grignard reagent

R1
R1MgX + R2 – C – R3 R2 – C – R3
(ii) H+
O OH
(1–o),(2o)-, (3o)–alcohol

5. By hydrolysis of ether :-
Dil. H2SO4
R – O – R1 R – OH + R' – OH
SN, or SN2

6. By hydrolysis of ester
Dil. H2SO4
R – C – O – R' R – C – OH + R' – OH
|| ||
O O
NaOH
R – C – O – R' R – C – O–Na+ + R' – OH
|| ||
O O

7. From primary (1o-) amine (Diazotisation)

(NaNO HCl)
R – NH2 
2
 R – OH  N2  H2O

8. By reduction of carbonyl compound

Re ducing agent
R – CH  O   R – CH2 – OH
Reducing agent
R – C –R R – CH –R
|| |
O OH

Reducing agent : H2 / Pd , H2 / Ni , Na  C2H5OH , LiAlH4 , NaBH4 , B2H6 in THf, PH3SnH (TTH)

Triphenyl tinhydride

9. By Reduction of carboxylic acid and its derivatives

O
|| LiAlH4
R – C – OH  R – CH2 – OH
O
LiAlH4,NaBH4
R – C – Cl R – CH2 – OH
H2/Pd, Na+EtOH
O
LiAlH4,NaEtOH
R – C – OR' R – CH2 – OH
O O
LiAlH4
R – C – O–C–R' R – CH2 – OH + R'–CH2–OH
O
LiAlH4
R – C – NH2 R – CH2 – NH2

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10. By Meervein pondroff-varley (mPv) reduction

It is relective reduction of carbonyl compound into alcohol

(i) Al(OCH Me )
2
R – C – R 
(ii)H3 O
 R – CH – R
|| |
O OH

Ex-1 H2/Pd
O OH

MPV
reduction
OH

O O O O
Ex-2 CH3–C–(CH2)3–C–OEt MPV reduction CH3–CH–(CH2)3–C–OEt

11. By fermetation method

It is an inductrial method for the manufacturing of alcohol.

C6H12O6+ yeast Zymase 2C2H5OH + 2CO2

Glucose/fructose

Physical Properties of alcohol

1. Monohydric alcohols are colour less compound. The lower members have sweet octour and burning

taste.

2. Lower members are volable liquids, middle members are oily liquids and the higher merbers are

solids.

3. Soluble in water due to H–bonding.

4. B.P.  moleculer weight

(i) CH3OH  C2H5OH  C3H7OH

(ii) Alcohal > ether > Alkane

(iii) 1o–alcohal > 2o–alcohal > 3o–alcohal

Chemical properties of alcohal

(A) Reaction involving breaking of O–H bond

1. Reaction with metals

R – O – H  Na  R – O–Na  1 / 2 H2
Reactivity order
CH3OH  1o  alcohal  2o  alcohal  3o  alcohal
Note:- williamsons synthesis
SN
R – O– Na  R '– X 
2
R – O – R '
ether
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2. Reaction with grignard reagent, metal hydride and sodamide
Reactivity order CH3OH > 1o  alc > 2o  alc > 3o  alc
R – OH  R ' mg  R – H  mg(x)(OR)

R – OH  NaH  R – O– Na  H2 ()

–
R – OH  Na NH2  R – O– Na  NH3
3. Esterification
O O
R–C–OH+H–O–R' R–C–O–R'+H2O

Reactivity order

(i) CH3 – OH > 1o  alc. > 2o  alc. > 3o  alc.

(ii) HCOOH > CH3COOH > (CH3 )2 CH COOH

4. Reaction with sulphonyl chloride

OH–
R'SO2Cl + H–O–R R'–SO3–R+HCl
Alkyl sulphonyl Alkyl sulphonate
chloride

5. Reaction with diazomethone (CH2N2)

R – OH  CH2N2  R – O – CH2 – H  N2

(B)Reaction involving breaking of C–OH bond

1. Reaction with hydrogen halide (HX)

R – OH  HX 

 R – X  H2O

Lucas test
HCl  anhy.ZnCl
R – OH 
Lucas reagent
2
 R – Cl  H2 O

2. Rxn with PCl5 , PCl3 and SOCl2

PCl
R – OH 
5
 RCl  HCl  PoCl3

PCl3
R–OH R–Cl
PBr3
R–Br
(P+I2)
R–I
SOCl2
R–OH+SO2(  ) +HCl(  )
Dargen's Reaction

3. Dehydration of alcohol
Conc.H2SO4
C–C C=C

H OH
 o
H /170 C
C2H5OH   CH2  CH2  H2O
Al O
C2H5OH 
2 3
o  CH2  CH2  H2O
350–400 C

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 Al O
2 C2H5OH 
2 3
o  C2H5 – O – C2H5  H2O

250 C

4. Oxidation of alcohol
mild oxidi sin g
R – CH2 – OH 
agent
 R – CH  O

1o–alcohol
O
||
Strong oxidi sin g
R – CH2 – OH 
agent
 R – C – OH
1o alcohol

mild or strong
R – CH – R 
Oxidi sing agent
R – C – R
| ||
OH O
2o – alcohol

Mild oxidising agent Pcc, collins reagent.

Strong oxidising agent H / KmNO4 , H / K2Cr2O7 , chromic acid (H2CrO4 )

5. Oppenour oxidation of alcohol

6. Catalytic oxidation of alcohol

o
Cu/350 C
R – CH2 – OH   R – CH  O
Cu/350o C
R – CH(OH) – R 
R – C – R
||
O

CH3
| Cu/350oC
CH3 – C – OH CH3 – C = CH2
| |
CH3 CH3
7. Haloform Reaction
CH3CH2OH  4I2  6NaOH 

 CHI3 ()  5NaI HCOONa
8. Reaction with NH3
Al O
C2H5OH  NH3 
2 3
o  C2H5 – NH2
400–500 C
1o – amin e
Al O
2 C2H5OH  NH3 
2 3
o  C2H5 – NH – C2H5
400–500 C
2o – amin e
Al O
3 C2H5OH  NH3 
2 3
o (C2H5 )3 N
400–500 C
3o – amin e

Test of alcohol
Distinction between 1o, 2o and 3o–alcohol

1. Lucas test

2. Victor mayer's test

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 NO2
HI AgNO2 KOHHON  O
R – CH2 – OH  RCH2I   RCH2NO2  R–C Red colour
o
1 – alcohol N–OH
NO2
R 2CH2 – OH HI AgNO2 HO–N  O KOH
 R 2CH2I   R 2CHNO2  R2C Blue colour
2o – alcohol
N=O
HI AgNO2
R3C – OH   R3C – I  
R3C – NO2 
HO–N  O
No Reaction
KOH
  No colour

3. Oxidation test:- 1o– and 2o– alcohol are distinguished form 3o– alcohol by their oxidation with

KmNO4 or K2Cr2O7.
H /K Cr O
R – CH2 – OH 
2 2 7
 R – CH  O  Green colour
R – C – R  Green colour
H /K Cr O
R 2 – CH – OH 
2 2 7
 ||
O

R3C – OH 
H /K2Cr2O7
 No reaction

4. CAN test
CAN
R – OH   deep red colour
(NH4 )2 Ce(NO3 )6
Ceric Ammonium nitrate (CAN) :

Ether

Methods of preparation
1. Addition of alcohol to alkenes

H /R–OH
CH2  CH2   H – CH2 – CH2 – OR

2. Willianson's continuous ether

fication process
Conc H SO
C2H5OH 
o
2 4
 C2H5O – C2H5
140 C

3. By catalytic dehydration of alcohol

Al O
2C2H5OH 
2 3
o  C2H5 – O – C2H5

250 C

4. Willianson's ether synthesis

SN
R – O–Na  X – R ' 
2
 R – O – R ' NaX

5. Reaction alcohol with diazomethane

HBf
R – OH  CH2N2 

4
 R – O – CH2 – H

6. By grignard reagent

RngCl + Cl–CH2–O–C2H5  R–CH2–O–C2H5 + MgCl2

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