For Class XII

ISHWAR RIJAL

Little Angels’ College

ISHWAR RIJAL 1
 @ Topics for Long questions from
aliphatic compounds.
 Lab preparations:- Chloroform(Trichlomethane)
Diethyl ether(Ethoxyethane) & Formic acid
(Methanoic acid).
 Victor Meyer method for the distinction between
10, 20 and 30 alcohols
 Fermentation
 Use of Grignard Reagent for the synthesis of
Alcohols
 Hofmann method for the separation of 10,20 and 30
amines.
ISHWAR RIJAL 2
 Contd……

 Name Reactions:- Wurtz reaction, Williamson

Ether synthesis, Aldol Condensation, Cannizzaro’s
reaction, Wolf-Kishner reduction, Clemmensen
reduction, Rosenmund reduction,
Hofmann’s bromamide reaction.
 Tests:- DNP-test, Tollen’s test, Fehling’s test,
Iodoform test.
 Some simple sequential reactions.
 Some frequently asked reactions.
 Some simple reason giving questions.
ISHWAR RIJAL 3
 Haloalkanes
 General formula :- R-X ( R= alkyl group, X= Cl,
Br , I )
 Preparations:-
 Adding HX(HCl, HBr,HI) to alkenes.
RCH=CH2 + HX  RCH(X)CH3
During the addition add H-atom to the C-atom
carrying more no. of H-Atoms (Markonikov’s
rule).
Cl
CH3-CH=CH2 + HCl  CH3-CH-CH3
2-chloropropane
Propene
ISHWAR RIJAL 4
 Contd….
During the addition of HBr in presence of
organic peroxide ( eg R-O-O-R) add H-atom to the
C-atom carrying lesser no. of H-atoms
(Anti-Markonikov’s rule).
CH3-CH2CH=CH2 + HBr R-O-O-R CH3-CH2-CH2-CH2-Br
1-butene 1-bromobutane

Alcohols to Chloroalkanes:- By treating with HCl+

anhy. ZnCl2(Lucas reagent), PCl3,PCl5, SOCl2+Pyridine.

R-CH2-OH + SOCl2  R-CH2-Cl + SO2 + HCl

3CH3-CH2-OH + PCl3  CH3-CH2-Cl + H3PO3
(Ethanol) ( Chloroethane)

ISHWAR RIJAL 5
 Contd…..

 Properties:-
 Insoluble in water as they cannot form H-bond with
water.
 Substitution reactions:-
R-CH2-X + KOH (aq.)  R-CH2-OH + KX
( Alcohol)

 Williamson Ether synthesis:-

R-CH2-X + NaO-R’  R-CH2-O-R’ + NaX
(Sodium alkoxide) (Ether)

CH3-CH2-Br + NaO-CH2CH3  CH3-CH2-O-CH2-CH3

Sod.ethoxide Ethoxyethane

ISHWAR RIJAL 6
 Contd……

 R-CH2-X + KCN (alc.)  R-CH2-CN + KX

(Alkane nitrile)

 Alkane nitriles(Alkyl cyanides) can be converted

to other compounds.
O
i) R-CH2-CN + H2O conc.HCl R-CH2-C-NH2
Amide
O
dil. HCl
ii) R-CH2-CN + H2O R-CH2-C-OH + NH4Cl
Acid
Ni
iii) R-CH2-CN + 2H2 R-CH2-CH2-NH2
Amine
ISHWAR RIJAL 7
 Contd…….

 R-CH2-X + AgCN (alc.) R-CH2-N C + AgX

Alkyl isocyanide or
Alkyl carbylamine
Ni
R-CH2-N C +2H2 R-CH2-NH-CH3
N-methyl amine
 For the reduction LiAlH4 or Na/Ethanol also
can be used.
 A mixture of haloalkane and excess alc. NH3 heated in
a sealed tube at 1000C gives 10 amines.
R-CH2-X + NH3(alc.)  R-CH2-NH2 + HX
(10amine)
ISHWAR RIJAL 8
 Contd……..
O
 R-X + AgNO2  R-N + AgX
O
Nitroalkane

 R-X + KNO2  R-O-N=O + KX

Alkyl nitrite

 For example
AgNO2
CH3-CH2-NO2 + AgCl
CH3-CH2-CI Nitroethane
Chloroethane KNO2
CH3-CH2-O-N=O + KCl
Ethyl nitrite

ISHWAR RIJAL 9
 Contd…..

 Dehydrohalogination:- Formation of Alkene

R-CH2-CH2-X + KOH(alc.) R-CH=CH2 + KX + H2O

CH3-CH2-Cl + KOH(alc.)  CH2=CH2 + KCl + H2O

CH3-CH2-CH(Cl)-CH3 + KOH(alc.) 
2-chlorobutane CH3-CH=CH-CH3 + KCl + H2O
2-butene

1-butene(CH3-CH2-CH=CH2) is a minor
product according to Saytzeff’s rule.
ISHWAR RIJAL 10
 Contd…..

@ Wurtz Reaction:-
Ether
R-X + 2Na + X-R R-R + 2NaX

Ether
CH3-Cl + 2Na + Cl-CH3 CH3-CH3 + 2NaCl
Chloromethane Ethane

Ether
CH3-CH-Cl + 2Na + Cl-CH-CH3 CH3-CH-CH-CH3 + 2NaCl
CH3 CH3 CH3 CH3
2-chloropropane 2,3-dimethylbutane

ISHWAR RIJAL 11
 Contd.....

 Formation of Grignard Reagent:-

dry ether
R-X + Mg Heat RMgX
Grignard reagent

Reduction:- Can be reduced to alkanes by [H] obtained

from Zn-Cu couple/ethanol,Zn/HCl, Sn/HCl, Zn/NaOH,
LiAlH4, H2/Ni.

Zn + 2HCl  ZnCl2 + 2[H]

R-X +2[H]  R-H + HX
CH3-CH2-CH2-Cl + 2[H]  CH3-CH2-CH3 + HCl
1-chloropropane Propane

ISHWAR RIJAL 12
 Lab Preparations

@Chloroform or Trichloromethane (CHCl3):-

 Principle:- By heating bleaching paste with
ethanol or propanone( acetone).

CaOCl2 + H2O Ca(OH)2 + Cl2

 From Ethanol(CH3-CH2-OH)
# Oxidation:-
CH3-CH2-OH + Cl2  CH3-CHO + 2HCl
Ethanal

ISHWAR RIJAL 13
 Contd…..

# Chlorination:-
CH3-CHO + 3Cl2  CCl3-CHO (Chloral) + 3HCl
# Hydrolysis:-
O H CCl3-CHO
Ca + 2CHCl3 + (HCOO)2Ca
O H CCl3-CHO
 From Propanone (CH3-CO-CH3)
# Chlorination:- CH3-CO-CH3 + 3Cl2CCl3-CO-CH3 + 3HCl
Trichloroacetone

# Hydrolysis:-
O H CCl3- CO-CH3
Ca + 2CHCl3 + (CH3COO)2Ca
O H CCl3- CO-CH3
ISHWAR RIJAL 14
 Contd…..

Fig:- Lab preparation of Chloroform

# Purification: Washed with dil. NaOH and then with
water in a separating funnel. Dried over anhydrous CaCl2
and redistilled between 60-650C.
ISHWAR RIJAL 15
 @ Diethyl ether or Ethoxyethane
 Principle:-By heating excess ethanol(CH3CH2OH)
with conc. H2SO4 at 1400C.
100oC
CH3CH2OH + H2SO4 CH3CH2HSO4 + H2O
Ethanol Ethyl hydrogen sulphate

1400C CH3CH2OCH2CH3+H2SO4
CH3CH2HSO4+HOCH2CH3
Ethoxyethane

 Purification:- Washed with aq.KOH to remove

acid, stirred with 50% CaCl2 solution to remove
alcohol, washed with water and dried over fused
CaCl2 and finally redistilled to obtain almost pure
ethoxyethane.
ISHWAR RIJAL 16
 Contd…..

Water

Fig- Lab preparation of Ethoxyethane

ISHWAR RIJAL 17
 @Formic acid or Methanoic acid(HCOOH)
 Principle:- By heating anhydrous glycerol with
oxalic acid crystals at 1100C.
O O
CH2-OH H-O-C-COOH CH2-O-C-COOH
Heat + H2O
CH2OH +
CH2OH
CH2OH CH2OH
Glycerol mono oxalate

O
O
CH2-O-C-COOH
CH2-O-C-H
1100C + CO2
CHOH CHOH
CH2OH CH2OH
Glycerol mono oxalate Glycerol mono formate
ISHWAR RIJAL 18
 Contd…..

O
CH2-O-C-H
CH2OH
CHOH + H-OH + HCOOH
CHOH
Formic acid
CH2OH CH2OH
Glycerol mono formate

Water

Figure: Lab preparation of aq.formic acid

ISHWAR RIJAL 19
 Contd…..

 Formic acid so obtained is aqueous as it is

mixed with water(BP of formic acid= 100.50C).
 To obtain anhydrous formic acid aq.formic acid
is treated with lead carbonate and solution is
crystallized to obtain the crystals of lead formate.
 Crystals of lead formate are dried and heated at
1000C in a current of H2S by which formic acid is
formed and is collected in a receiver.
2HCOOH + PbCO3  (HCOO)2Pb + H2O + CO2↑
(HCOO)2Pb + H2S  HCOOH + PbS↓
ISHWAR RIJAL 20
 Contd…..

vvv

Figure:- Preparation of anhydrous formic acid

ISHWAR RIJAL 21
 Alcohols
Functional Group:- -OH
 IUPAC Name: Alkanol eg. CH3CH2OH – Ethanol

OH
CH3-CH2-CH2 OH
1-propanol CH3-CH-CH3
2-propanol
Divided into three types:-
Primary alcohols  R-CH2-OH
eg. CH3CH2OH – Ethanol
 Secondary alcohols R-CH-OH = R2CH-OH
OH
R
eg. CH3-CH-CH3
ISHWAR RIJAL
2-propanol
22
 Contd…..

 Tertiary alcohols:- R
R-C-OH = R3C-OH

eg R
CH3
CH3-C-OH
CH3
2-methyl-2-propanol

Primary, secondary and tertiary alcohols are

distinguished by Victor Meyer’s method.

ISHWAR RIJAL 23
 Victor Meyer’s Method
 It involves following steps:-
 Given alcohol is treated with red P and iodine to
get iodoalkane.
Then treated with AgNO2 to get nitroalkane.
Then treated with HNO2( NaNO2 + cold dil HCl)
i) 10 alcohols give nitrolic acid ii) 20 alcohols give
pseudonitrol iii) 30 alcohols donot react.
Then treated with dil NaOH or KOH solution
 i) 10 alcohols give Red Colour
ii)20 alcohols give Blue colour
iii) 30 alcohols give No colour.
ISHWAR RIJAL 24
 RCH2-OH R-CH-OH RContd…..
 Rxns:- (10 alcohol) R-C-OH
R
P + I2 (20 alcohol) R
0
P + I2 (3 alcohol)
RCH2-I
(Iodoalkane) R-CH-I P + I2
AgNO2 R R
AgNO2 R-C-I
RCH2-NO2
Nitroalkane R-CH-NO2
R
HNO2 R
(NaNO2+ AgNO2
HNO2
cold dil HCl)
R R
R-C-NO2
R-C- NO2 R-C-NO2
NOH N O R
(Nitrolic acid) (Pseudonitrol) HNO2
aq.KOH aq.KOH
No reaction
Red colour Blue colour aq.KOH
ISHWAR RIJAL NO colour
25
 Contd…..

 For example:- 1-propanol(a 10 alohol),

2-propanol(a 20 alcohol),and
2-methyl-2-propanol(a 30 alcohol) can be
distinguished by this method.
P + I2 AgNO2
CH3-CH2CH2-OH CH3CH2CH2-I CH3CH2CH2-NO2
1-propanol 1-iodopropane 1-nitropropane
(10 alcohol)
HNO2

aq.KOH CH3CH2C-NO2
Red colour
NOH
Nitrolic acid
ISHWAR RIJAL 26
 Contd…..
AgNO2
 CH3CH-OH P + I2 CH3CH-I CH3CH-NO2
CH3 CH3
CH3
2-propanol 2-iodopropane 2-nitropropane
(20 alcohol) HNO2
CH3
aq. KOH
Blue colour CH3-C-NO2
N=O
Pseudonitrol

CH3 CH3
CH3
 CH3-C-OH
P + I2
CH3-C-I AgNO2
CH3-C-NO2
CH3 CH3 CH3
2-iodo-2-methylpropane 2-methyl-2nitropropane
2-methyl-2-propanol
(30 alcohol) HNO2
aq.KOH
No colour No reaction
ISHWAR RIJAL 27
 Fermentation
Degradation of complex organic compounds into
simpler compounds by the action of enzymes.

Ethanol can be prepared by the Fermentation of

Carbohydrates.
 Two sources are employed for the purpose
1. Molasses:- A dark brown colored mother
liquor obtained after the crystallization of Sugar
from concentrated sugarcane juice.

ISHWAR RIJAL 28
 Contd…..
Yeast is added to the molasses which is a rich
source of enzymes like invertase,zymase etc.
Following reactions take place.
Invertase
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose Glucose Fructose
Zymase
C6H12O6 2C2H5OH + 2CO2
Ethanol

The fermented liquor so obtained is called Wash

which contains 15-18% ethyl alcohol. The wash is then
fractionally distilled by which 93-95% ethyl alcohol is
obtained. Alcohol so obtained is called Rectified spirit.

ISHWAR RIJAL 29
 Contd…..

2.Starches:-
 Food materials like
rice,maize,wheat,barley,millet,potato etc
contain Starch.
 The food materials are first boiled with water to
release the granules of starch.
 Resulting solution called Mash is then mixed
with malt(dried germinated barley, a rich source
of various enzymes like diastage,maltase,zymase
etc) and left aside for few days.
 Reactions take place forming ethyl alcohol.
 The fermented liquor called Wash is then
fractionally distilled to get ethyl alcohol.
ISHWAR RIJAL 30
 Contd…..
Diastage
2(C6H10O5)n +nH2O nC12H22O11
Starch Maltose
Maltage
C12H22O11 + H2O 2C6H12O6
Glucose
Zymase
C6H12O6 2C2H5OH + 2CO2
Ethyl alcohol
Convert Ethanol to Propanoic acid.
PCl5 alc. KCN H2O/H+
C2H5OH C2H5Cl C2H5CN C2H5COOH
Ethanol Chloroethane Propanoic acid
Propane nitrile
 Convert Chloroethane to N-methylaminoethane.
alc. AgCN
CH3-CH2-Cl CH3-CH2-N C
Chloroethane Ethyl isocyanide LiAlH4

CH3-CH2-NH-CH3
N-methylaminoethane
ISHWAR RIJAL 31
 Contd…..

Preparation of Alcohols Using

Grignard Reagent:-
 Alkyl magnesium halides are called
Grignard reagent.
 When Aldehydes and Ketones are
treated with Grignard Reagent then
addition products are formed which on
hydrolysis give different types of
alcohols.

ISHWAR RIJAL 32
It can be shown as:-
III
OMgX OH
II
O
H2O/H+
+ RMgX C C + Mg(OH)X
C
I
R R
Alcohol
Aldehyde Intermediate
or
Ketone

Formaldehyde(Methanal) reacts with Grignard reagent followed by

hydrolysis giving primary alcohols.
O OMgCl OH
+
H3O
H-C-H + RMgCl R-CH-H R-CH-H+ Mg(OH)Cl
Methanal Intermediate 10alcohol

ISHWAR RIJAL 33
 Contd…..

Aldehydes react with Grignard reagent followed by hydrolysis giving

secondary alcohols.
O OMgCl OH
+
H3O
R-C-H + R'MgCl R-CH-R' R-CH-R'+ Mg(OH)Cl
Intermediate
Aldehyde 20alcohol

Ketones react with Grignard reagent followed by hydrolysis giving

tertiary alcohols.
O OMgCl OH
H3O+
R-C-R'+ R"MgCl R-C-R' R-C-R' + Mg(OH)Cl
Ketone
R" R"
0
3 alcohol
ISHWAR RIJAL 34
 Contd…..

For example:- Methanal reacts with methyl magnessium chloride

followed by hydrolysis giving Ethanol(a primary
alcohol.
O OMgCl
+
H-C-H + CH3MgCl CH3-C-H H 2O/H
CH3CH2OH +
Methyl magnessium Ethanol
H
chloride Intermediate Mg(OH)Cl

Ethanal reacts with methyl magnessium chloride followed by hydrolysis

giving 2-propanol( a secondary alcohol).
O OMgCl
CH3-C-H + CH3MgCl CH3-CH-CH3
Ethanal H3O+
OH
CH3-CH-CH3 + Mg(OH)Cl
2-propanol
ISHWAR RIJAL 35
 Contd…..

Propanone reacts with methyl magnesium chloride followed by

hydrolysis giving 2-methyl-2-propanol( a tertiary alcohol).
O OMgCl
CH3-C-CH3 + CH3MgCl CH3-C-CH3
Propanone CH3
H3O+
OH
CH3-C-CH3 + Mg(OH)Cl
CH3
2-methyl-2-propanol

ISHWAR RIJAL 36
  Amines --- Types
 Primary (10) amine:- R-NH2
eg. CH3-NH2 --- Aminomethane
 Secondary(20) amine:- R-N-H = R2NH
R
eg. CH3-NH-CH3 -- N-methylaminomethane
 Tertiary(30) amine:- R-N-R = R3N
R
CH3
eg. CH3-N-CH3--- N,N-dimethylaminomethane
ISHWAR RIJAL 37
@ Separation of 10,20 & 30 amines by
Hofmann’s Method
 Mixture of 10,20 & 30 amines can be separated
by Hofmann’s method which involves following
steps:-

1. Mixture of 10,20 & 30 amines is first treated

with diethyl oxalate.

 Primary amines form solid dialkyl oxamide.

ISHWAR RIJAL 38
 Contd…..
 Reaction
CO-OC2H5 H-NHR CONHR
+ + 2C2H5OH
CO-OC2H5 H-NHR CONHR
Dialkyl oxamide
Diethyl oxalate 10amine (Solid)

 Secondary amines form liquid dialkyl oxamic

ester.
CO-OC2H5 H-NR2 CONR2
+ + C2H5OH
COOC2H5 COOC2H5
Dialkyl oxamic ester
(liquid)
ISHWAR RIJAL 39
 Contd…..

 Tertiary amines donot react with diethyl

oxalate.
2. Mixture containing dialkyl oxamide(solid),
dialkyl oxamic ester(liquid),tertiary
amine(liquid) and ethanol(liquid) is then
filtered and residue(dialkyl oxamide) is heated
with aq. KOH to obtain primary amine.
CONHR COOK
+ 2KOH + 2RNH2
CONHR COOK

ISHWAR RIJAL 40
 Contd…..

3. Filtrare containing dialkyl oxamic ester, tertiary

amine & ethanol is then subjected to fractional
distillation.
 Tertiary amine distills out first followed by
ethanol.
 Residue, dialkyl oxamic ester, is then treated
with aq.KOH and fractionally distilled to obtain
secondary amine.
CONR2 COOK
+ 2KOH + R2NH + C2H5OH
COOC2H5 COOK
ISHWAR RIJAL 41
 Some Name Reactions
@ Williamson’s synthesis:- When haloalkanes are
heated with sodium alkoxide then ethers are
formed.
R-ONa + X-R’  R-O-R’ + NaX
CH3CH2-ONa + Cl-CH2CH3 CH3CH2-O-CH2CH3 +NaCl
Sodium ethoxide Chloroethane Ethoxyethane

 Convert ethoxyethane to methoxy methane.

PCl5 CH3ONa CH3CH2-O-CH3
CH3CH2-O-CH2CH3 CH3CH2Cl
Ethoxyethane Chloroethane Methoxyethane
PCl5
CH3-O-CH3 CH3ONa
CH3Cl + CH3CH2Cl
Metoxymethane Chloromethane
ISHWAR RIJAL 42
 @ Aldol Condensation:-
 Two molecules of aldehyde or ketone having at
least one α-H atom condense in presence of
dilute alkali to give β-hydroxy aldehyde or
ketone.
O OH
dil. NaOH
CH3-C-H + H-CH2CHO CH3-CH-CH2CHO
Ethanal 3-hydroxybutanal
O O OH O
dil. NaOH
CH3-C-CH3 + H-CH2CCH3 CH3-C-CH2CCH3
Propanone
CH3
4-hydroxy-4-methyl-2-pentanone
ISHWAR RIJAL 43
 @ Cannizzaro’s reaction
Aldehydes without α-hydrogen undergo self
oxidation & reduction(disproportionation) on
treatment with strong alkali like NaOH by which
a molecule is oxidised to acid and another
molecule is reduced to alcohol.
conc.NaOH CH3OH + HCOONa
2HCHO
Methanal Methanol Sodiummethanoate

CHO CH2OH COONa

conc.NaOH +
2
Benzaldehyde Benzyl alcohol Sodium benzoate
ISHWAR RIJAL 44
@ Rosenmund reduction
When acyl chlorides are reduced with Hydrogen
in presence of Pd catalyst deposited on BaSO4
then aldehydes are formed.
O
Pd/BaSO4
R-C-Cl + H-H RCHO + HCl
Acyl chloride Aldehyde
O
CH3-C-Cl Pd/BaSO4
+ H-H CH3CHO + HCl
Ethanoyl chloride Ethanal
Cl H
C=O C=O
Pd/BaSO4
+ H2 + HCl
Benzoylchloride Benzaldehyde
ISHWAR RIJAL 45