Organic Chemistry

1
APPENDIX
IMPORTANT NAME
REACTIONS AND PROCESSES
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(In Alphabetical Order)
H^cylation
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The replacement of an active hydrogen of alcohols, phenols or amines with an acyl (RCO or ArCOi
F
A » called acylation. Acylation is usually carried out by
P^'^sence of a base. Although, in principle, any acid chloride/anhydride
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can be used for acylation but acetyl chloride, acetic anhydride and benzoyl chloride are very common. Lsed
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upon these reagents, acylation is mainly of two types :
(/) Acetylation fo
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(CBSE 2008. 2010 S)
It is usually carried out in presence of a base such as pyridine, dimethylaniline, etc. For example,
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Pyridine
CH3COCI + CH3CH2OH > CH3COOCH2CH3 + HCl
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Acetyl chloride Ethyl alcohol Ethyl acelaic

Pyridine
(CH3C0>20 + CH3CH2OH — y CH3COOCH2CH3 + CH3COOH
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Acetic anhydride Ethyl alcohol Ethyl acetate Acetic acid

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h. r with acetyl chloride is usually carried out in presence of a base such as pyridine
but that with aceuc ^ydnde may be catalysed both by acids (a few drops
(sodium acetate, pyndine, etc.). For example.
of cone. H^SOri and bases
2 4> i “‘"cs*
d
Re
in
CH jCOONa or Pyrid i ne
(CH3C0)20 + C6H5OH > CH3COOC6H5 + CH3COOH
F
orConc.HTSO^ (fewdrops)
Acetic anhydride Phenol
Phenyl acetate Acetic acid
Since amines themselves are bases, the acylation of amines is usually carried out in absence of a base.
CH3COCI + CH3CH2NH2 ^ CH3CONHCH2CH3 + HCl
Acetyl chloride Ethylamine N-Eihylacetamide
(CH3C0)20 + CH3CH2NH2 -> CH3CONHCH2CH3 + CH3COOH
Acetic anhydride Ethylamine N-Ethylacctamide
Since aromatic amines
are less basic and hence less nucleophilic, their acetylation is usually carried out
presence of a Whereas acetylation with CH3COCI is usually carried out in presence of pyridine,
in
acetylation with (CH3C0)20 is earned out in pre.sence of CH3COOH or a few drops of cone. H2SO4.
Pyridine
CH3COCI + C6H5NH2 CH3CONHC6Hg + HCl
Acetyl chloride Aniline Acetanilide
A/1
A/2 ‘P’uuUe^ 'o New Course Chemistry (XIDEIBD
CH3COOH
(CH3C0)20 + C6H5NH2 CH3CONH6H5 + CH3COOH
orConc.H2S04 (fewdrops) Acetanilide
Acetic anhydride Aniline
(ii) Benzoylation. The replacement of an active hydrogen of alcohols, phenols or amines by benzoyl
(C^H^CO) group is called benzoylation. Benzoylation is usually carried out by using benzoyl chlonde in
presence of aqueous NaOH.
Aq.NaOH
CgHjCOCl + HOCH2CH3 > C6H5COOCH2CH3 + HCl
Benzoyl chloride Ethyl alcohol Ethyl benzoate
Aq.NaOH
CgHsCOCl + CgHjOH ■>
CgHgCOOCgHs + HCl
Phenol Phenyl benzoate
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Benzoyl chloride
Aq.NaOH
CgHjCOCl + CH3CH2NH2
■>
C6H5CONHCH2CH3 + HCl
N-Ethylbenzaniide
Flo
Benzoyl chloride Ethylamine
Aq. NaOH
CgHsCONHCgHs + HCl
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CgHgCOCl + C6H5NH2
>
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Aniline Benzanilide
Benzoyl chloride
F
or N-Phenyl benzamide
Benzoylation of compounds containing an active hydrogen atom such as alcohols, phenols and amines
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with benzoyl chloride in presence of dilute aqueous NaOH solution is called Schottem Baumann reaction.
^|Aldol condensation fo
(HP Board 2011; Hr. Board 2009, 2011,2012 ; Raj. Board 2012 ; CBSE 2014)
Two molecules of aldehydes or ketones containing a-hydrogen atoms on treatment with a dilute base
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(dil. NaOH, Na2C03, Ba(OH)2, etc.) undergo condensation to form ^-hydroxyaldehydes or ^-hydroxy- ketones.
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This reaction is called aldol condensation. For example,

OH
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a NaOH 4 3I 2 1
;C=i=0 + H-PCH2CHO > CH3—c—CH2—CHO
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H
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Ethanal or Acetaldehyde 3 -Hydro xybutanal

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(two molecules) (Aldol)

CH3 OH CH3 O
5 4 3I 2I l
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CH3CH2. Dil. NaOH

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CH—CHO ► CH3—CH2—C—CH—C—H
in
X—0 + H’
H
F
propanal or Propionaldehyde 3-Hydroxy-2-methylpentanal

(two molecules) (P-Hydroxy-a-methylvaleraldehyde)
OH
|;H3_‘'c-CH2-CO-CH3
a
C=i=0 + HTCH2COCH3
CH3
Propanone or Acetone 4-Hydroxypentan-2-one
(two molecules) (Diacetone alcohol)
The products of aldol condensation when heated with dilute acids undergo dehydration leading to the
formation of a, p-unsaturated aldehydes or ketones. For example,
TolT
L|
“h]
|J H'*’,H,0 4 3 2 1
^
CH3—CH—CH—CHO CHoCH = CH—CHO + H2O
Aldol But-2-en-l-al
(Crotonaldehyde)
IMPORTANT NAME REACTIONS AND PROCESSES
A/3
Tho h“!
CH I—[—|j
m.HÔ CH 3\4 3 2 1
CH—COCH3 A
^C=CHC0CH3 + H20
CH3 CH3
Diacetone alcohol
4-Methylpenl-3-en-2-one
(Mesityl oxide)
Aldehydes such as formaldehyde, a, a-dimethylpropionaldehyde (or 2, 2-dimethylpropanaI),
benzaldehyde, etc. which do not contain a- hydrogen/s do not undergo aldol condensation.
Crossed aldol condensation. (NCERT ; CBSE 2008,2012 ; Hr. Board 2011, 2012 ; Uttarakhand Board 2012)
Aldol condensation between two different aldehydes is called crossed aldol condensation. It is a useful
synthetic reaction only if one of the aldehydes does not contain a-hydrogen atoms, i.e., formaldehyde
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benzaldehyde etc. For example,
(/) With formaldehyde
Flo
O o o
Dil.NaOH
CH3—C—H + H—C—H
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^ HO—CH2—CH2—C—H
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Acetaldehyde Formaldehyde P-Hydroxypropionaldehyde
F
O o o
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Dil.NaOH
1 2^1 ^ 4
CH3—C—CH3 + H—C—H
Acetone
Formaldehyde
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> CH3—c—CH2—CH2 —OH
4-Hydroxybutan-2-one
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{//) With benzaldehyde. Refer to Claisen Schmidt reaction on page A/6.
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Intramolecular aldol condensation. If a compound contains two aldehydes/ketones or one aldehyde

and one ketone group at 1,6 or 1,7-positions w.r.t. to each other, intramolecular aldol condensation occurs
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to
yield alicyclic a, (3-unsaturated aldehyde/ketone. For example,
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3 2 1 3 2
CH2—CH-—CHO CH2—CH
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Dil.NaOH 1
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I
C—CHO + HjO
4
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CH2—CH-—CHO
4 5 6 ^CH2—CH2
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Hexane-l, 6-dial
Cyclopent-1 -ene-1 -carbaldehyde
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in
^SBalz-Schiemann reaction (Hr. Board 2013)

F
Fluoroarenes (aryl fluorides) cannot be prepared by direction fluorination of aromatic hydrocarbons

since the reaction is very violent and cannot be easily controlled. These can, however, be easily prepared by
Balz-Schiemann reaction. In this reaction, the aromatic primary amine is first diazotised with NaNO, in
presence of HBF4 (fluoroboric acid) at 273-278 K and the aryl diazonium tetrafluoroborate thus formed is
heated to give the corresponding aryl fluoride. For example,
+
NH2 N=NBF4 F
NaN02/HBF4 A
273-278 K + N2+ BF3

Boron
Aniline Benzenediazonium trifluoride
Fluorobenzene
tetrafluoroborate
This reaction is called Balz-Schlemann reaction.

New Course Chemistry (XII)BZSisil
A/4
(West Bengal Board 2012)

IQ Benzoin condensation
On heating with an ethanolic solution of KCN, two molecules of aromatic aldehydes undergo condensation
to form benzoins. This reaction is called benzoin condensation. For example.
O 0 OH O
G Ale. KCN
+ CH—
Benzoin
H Benzaldehyde (2 molecules)
Bi Cannizzaro reaction (Pb. Board 2011 ; Chhatisgarh Board 2011 ; HP Board 2009, 2011 ;
Hr. Board 2009, 2011,2012 ; MP Board 2012 ; West Bengal Board 2012 ;
Uttarakhand Board 2012 ; Raj. Board 2012 ; Assam Board 2012 ; CBSE 2010, 2011, 2014, 2017)
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Aldehydes which do not contain an a- hydrogen atom, when U'eated with concentrated alkali solution
undergo disproportionation. Le., self oxidation-reduction. As a result, one molecule of the aldehyde is reduced
to the corresponding alcohol at the cost of the other which is oxidised to the corresponding carboxylic acid.
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This reaction is called Cannizzaro reaction. For example, formaldehyde on treatment with cone. NaOH
benzaldehyde gives benzyl alcohol and sodium
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solution gives methyl alcohol and sodium formate whereas
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benzoate.
F
O
O
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ONa
2 H—C—H -1- NaOH ^ CH3—OH + H—C
Formaldehyde (50%)
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Methyl alcohol Sod. formate
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2 CfiHsCHO + NaOH ^ C6H5CH2OH + CgHjCOONa
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Benzyl alcohol Sod. benzoate
Benzaldehyde (50%)
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CH3 CH3 CH3

B
50% NaOH
2CH,—C—CHO » CH3 C_CH,OH + CH3—(:—COONa
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Similarly,
■ I I
CH3 CH3 CH3
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2, 2-Dimethylpropanoi Sod. 2, 2-dimethylpropanoate

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2. 2-Dimeihylpropanal
If two aldehyde groups are present in the same molecule, intramolecular Cannizzaro reaction may
occur. For example.
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HO O OH O
0 O
I II
F
DM
^ H—C—C—ONa H—C—C—OH
H—C—C—H -t- NaOH HCl
Glyoxal (cone.) H H
Glycollic acid
Cross Cannizzaro reaction. It can take place between two different aldehydes to give all the four
possible products. If. however, one of the aldehydes is formaldehyde, cross Cannizzaro reaction is of great
synthetic utility since it is always the formaldehyde which is oxidised to give sodium formate while the other
aldehyde is always reduced. For example,
CH3O CHO + HCHO + NaOH > CH3O CH2OH + HCOONa

Sod. fomiatc
Formaldehyde (50%)
p-Melhoxybenzaldehyde p-Methoxybenzyl alcohol
(p-Anisaldehyde)
Similarly, cross Cannizzaro reaction between benzaldehyde and formaldehyde gives benzyl alcohol and
sodium benzoate.
IMPORTANT NAME REACTIONS AND PROCESSES A/5
^|Carbylamine reaction (Pb. Board 2009 ; HP Board 2011 ; MP Board 2011 ;

Hr. Board 2009, 2010, 2012 ; West Bengal Board 2012 ; CBSE 2010 S, 2012, 2016)
When a primary amine {aliphatic or aromatic) is warmed with chloroformand alcoholic KOH, it
fonns an isocyanide or carbylamine having offensive smell. This reaction is called carbylamine reaction. For
example.
CH3CH2NH2 + CHCI3 + 3 KOH — CH^CHjN^C + 3KC1 + 3 HÔ
Ethylamine ialv.) Eliiyl isocyanide
or Ethyl carbylamine
NH^ N^C
A
+ CHCI3 + 3 KOH + 3 KCl + 3 H->0
{ale.)
Aniline
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Phenyl isocyanide
or Phenyl carbylamine
Since secondai^ and tertiary amines (aliphatic or aromatic ) do not give this reaction, it is used as a test
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for primary amines and also for the distinction of primary amines from secondary and tertiary amines.
Q Clemmensen reduction (Hr. Board 2012 ; Assam Board 2012 ;
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HP Board 2009, 2011, 2013 ; CBSE 2009, 2010, 2011, 2012, 2017)
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The reduction of aldehydes and ketones to the corresponding hydrocarbons with amalgamated zinc and
concentrated hydrochloric acid is called Clemmensen reduction. For example.
CH3COCH3 + 4 |H]
Zn/Hg+Conc.HCI
for
^ CH3CH2CH3 + H2O
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A
Acetone
Propane
s
ook
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COCH3 CH2CH3
Zn/Hg + Conc. IICl
+ 4[H] + H2O
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Acetophenone Ethylbenzene
This reduction works better with ketones than with aldehyde s.
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dg Coupling reaction (Pb. Board 2008 ; CBSE 2009 ; Manipur Board 2011
Hr. Board 2010, 2011, 2012 ; HP Board 2008, 2010, 2011, 2013)
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The reaction ot diazonium salts with phenols and aromatic amines to form azo compounds of the general
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formula, Ar—N = N
nd
Ar is called coupling reaction. In this reaction, the nitrogen atoms of the diazo group
are retained in the product. The coupling with phenols takes place in mildly alkaline medium while with
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amines It occurs under/rt/u//v acidic conditions. For example.
273-278 K, OH"
N=NCr + OH N=N OH + HCI
(/>H 9-10)
Benzenediazoniuni Phenol
/;-Hydroxyazobenzene
chloride
(Oninge dye)
N=NCr +
273-278 K, H*
NH2 N=N—NH + HCI
Benzenediazoniuni Aniline Diazoaminobenzene

chloride
30a 310 K, warm

N=N NH2
{Rearrange.^)
/>-Aminoazobenzcnc
(Yellow dye)
A/6 ^>uidce^'A New Course Chemistry (XH)KS29D
.CH3
'/ %_N=NCr +
273-278 K. 0H“
Na^-OjS N: y
CH3
Diazonium salt of N, N-Dimethy!aniline
sulphanilic acid
,CH3
Na* ■ O3S N=N' N: + HC1
CH3
Methyl orange
Coupling generally occurs at the p-position .w.r.t the hydroxyl or the amino group, if free, otherwise it
takes place at the oposition.
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Q Decarboxylation reaction (HP Board 2011; Hr. Board 2011; Uttarakhand Board 2012 ;
CBSE 2011, 2012, 2017)
The process of removal of a molecule ofC02from a carboxylic acid is called decarboxylation. It is

usually carried out by heating a carboxylic acid or its sodium salt with soda-lime (NaOH + CaO) (in the ratio
3 : 1) at 630 K. For example.
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CaO,630K
CH3CH2COONa + NaOH > CH3—CH3 + Na2C03
F
Ethane
Sod. propanoate
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COOH
CaO, 630 K
+ 2 NaOH + Na2C03 + H2O
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Benzoic acid Benzene
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COOH
CaO, 630 K
+ 4 NaOH *■
+ 2 Na2C03 + 2 H2O
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COOH
Phthalic acid
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If, however, a carboxylic acid carries an electron-withdrawing group such as, CO, COOH, NO2, etc., at
ji-position .wri. the carboxylic group, decarboxylation can be readily achieved just by heating. For example.
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O O
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in
I I , 443-453K
CH., ~C—CH- —, COO H ^ CH3—C—CH3+CO2
F
^ p a ' ' Acetone
Acetoacetic acid
(A ^-ketoacid)
443-453K
HOOC—CH2—[cOo] Ha
^ CH3—COOH + CO2
Acetic acid
Malonic acid
443-453K
O2N—CH2—[cô]
P a
H ^ CH3—NO2 + CO2
Nitromethane
Nitroacetic acid
10. Diazotisation reaction (Hr. Board 2011; HP Board 2011 ; CBSE 2018)
When a cold solution of a primary aromatic amine in a dilute mineral acid (HCl or H2SO4) is treated
with a cold solution of nitrous acid (generated in situ by the action of dil. HCl or dil. H2SO4 on NaN02) at
273-278 K, arenediazonium salt is formed. This reaction is called diazotisation reaction For example.
NaN02 + HCl HONO + NaCl

Nitrous acid
NH2 N^NCl
273-278 K
+ HONO + HCl + 2H2O
Aniline Benzenediazonium chloride
(1 ® Aromatic amine)
NH2 NSNHSO4
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273-278 K
+ HONO + H2SO4 (1 + 2H2O
Flo
Aniline Benzenediazonium
hydrogen sulphate
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11. Esterification reaction or Fischer esterification
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(CBSE 2007 ; Pb. Board 2008, 2009 ;
West Bengal 2013)
F
Alcohols react with carboxylic acids in presence of dry HCl gas or a few drops of cone. H2SO4 as
catalyst to form esters. For example,
or
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0 O
R—C—[o^ j^H]—O—R' ^
Conc.H2S04 f
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± R_C—OR' + HÔ
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Carboxylic acid Alcohol Ester
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o O
B
Conc.H2S04
e.g. CH3—C—OH + HO—CH2CH3 ^ ± CH3—C—OCH2CH3 + H2O
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Acetic acid Ethyl alcohol Ethyl acetate

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This reaction which is slow and reversible is called esterification reaction. When dry HCl gas is used
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as a catalyst, the reaction is commonly known as Fischer-speier esteriifcation.

12. Etard reaction (UP Board 2012 ; CBSE 2017, CBSE (Foreign) 2017)
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The oxidation of toluene with chromyl chloride (Cr02Cl2) in CCI4 or CS2 to give benzaldehyde is
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called Etard reaction. In this reaction, the chromyl chloride first forms a brown complex with toluene which
in
is separated and then decomposed with dilute mineral acids to give benzaldehyde. For example
F
ÔCr(OH)Cl2
CH3 CH CHO
OCr(OH)Cl2
HiO^
i n 2Cr02Cl2 ^ ►
Toluene
CCI4
k^ Hydrolysis
Brown complex Benzaldehyde
Similarly, Etard reaction on p-nitrotoluene and p-chlorotoluene gives p-nitrobenzaldehyde and p-

chlorobenzaldehyde respectively.
13. Finkelstein reaction (Raj. Board 2012 ; Hr. Board 2012, 2013)
lodoalkanes can be easily prepared from the corresponding chloro- or bromoalkanes by heating with
sodium iodide in acetone or methanol.
A/8 New Course Chemistry (Xll)COmi
Aceione or mclhunol
CH3CH2—Br + Nal A
> CH3CH2—I + NaBr
Bromoelhane lodoelhane
This reaction is called Finkelstein reaction. The driving force for this reaction is the fact that NaBr {or
NaCl in case of chloroalkanes) is less soluble than Nal in acetone or methanol and thus gets deposited during
the reaction. As a result, equilibrium shifts in the forward direction. This reaction is very useful tor preparing
such alky! iodides which cannot be prepared by direct addition of HI to alkenes. For example,
n-butyl iodide cannot be prepared by direct addition of HI to I-butene. However, this can be prepared from
l-butene using Finkelstein reaction as shown below :
HBr.pemxide Nal/acetonc, A
CH3CH2CH = CH2 >‘1 CH3CH2CH2CH2Br (-NaBr)
^ CH3CH2CH2CH2I
(Anti-Mark.Oihln.)
I-Butene /i-Butyl bromide /f-Butyl iodide
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3 Fittig reaction (Raj. Board 2012 ; MP Board 2012 ; Hr. Board 2012, 2013)
This reaction is a useful variation of Wurtz reaction. It involves the reaction between two molecules of
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an aryl halide with sodium metal in presence of dry ether to form a diaryl. For example.
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Dry clher
Cl + 2Na + Cl + 2 NaCI
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Chlorobenzene (Two molecules) Diphenyl or Biphenyl
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(Manipur Board 2010 ; Hr. Board 2010, 2012 ; CBSE 2019)
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15. Friedel-Crafts reaction
This reaction is used for introducing an alkyl or an acyl group into an aromatic compound in presence of
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a Lewis acid catalyst. The most commonly used Lewis acid catalyst is anhydrous AICI3 while other catalysts
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which have been used are BF3, FeC^, SnClj, etc.
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(MP Board 2011; AP Board 2012)

(a) Friedel-Crafts alkylation.
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Benzene and other aromatic compounds react with alkyl halides in presence of anhydrous aluminium
chloride to form alkylbenzenes. For example.
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ou
CH3
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Anhyd. AICI3
+ CH3CI + HCl
nd
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Methyl chloride
Benzene Toluene
Fi
CH2CH3
Anhyd. AICI3
I HBr
CH3CH2Br
kk
-I- >
Ethyl bromide
Benzene Ethylbenzene
CH3 CH3 CH3

CH3
Anhyd. AICI3
(1 + CH3CI
kk
+
kk Methyl chloride
Toluene »-Xylene
(minor) CH3
/vXylene
(major)
The Friedel-Crafts alkylation of benzene with olefins and alcohols is usually carried out in presence of
protonic acids such as HF, H2SO4 or H3PO4. For example
●CH3
+ CH3CH = CH2 H3PO4 ^ CH
Propenc
Benzene CH3
isopropylbenzene or Cumene
ib) Friedel-Crafts acylation.

Benzene and other aromatic compounds react with acid chlorides or anhydrides in presence of anhyd.
AIC13 to form ketones. For example,
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Anhyd. AiCl3
-» CH3COCI COCH3 + CH3COOH
Acetyl chloride
Benzene
Acetophenone
Anhyd. AICI3
e
+
(CH3C0)20 COCH3 + CH3COOH
Fl
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Acetic anhydride
Benzene
F
Acetophenone
ur Anhyd.
or
COCI + HC1
AICI3 sf
Benzene Benzoyl chloride Benzophenone
k
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16. Garbriel phthalimide synthesis
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(Pb. Board 2010 ; Raj. Board 2011 ; CBSE 2008, 2018)

In this reaction, phthalimide is converted into its potassium salt by treating it with alcoholic pota.ssium
B
hydroxide. Then potassium phthalimide is heated with an alkyl halide to yield an N-alkylphthalimide which
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is hydrolysed to phthalic acid and a primary amine by heating with HCI or KOH solution.
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CO
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CO
KOH (ah.)
NH NK CH3CH2I ^ NCH2CH3
H2O Kl
CO
d
CO CO
Re
Phthalimide
in
Pol. phthalimide N-Ethylphlhalimide

F
COOH
H2O.
(Hydrolysis) + CH3CH2NH2
COOH Ethylamine
Phthalic acid
Similarly, arakyamines such as benzylamine can be prepared by using benzyl chloride instead of
CH3CH2I.
This synthesis is very useful for the preparation of pure aralkyl and aliphatic primary amines. However
aromatic primary amines (such as aniline) cannot be prepared by this method since aryl halides do not undergo
nucleophilic substitution reactions under ordinary conditions.
1
A/10 ^ New Course Chemistry (XII)EEiail
17. Gattermaim reaction (CBSE 2009 ; HP Board 2011: Hr. Board 2013)
This is a modification of Sandmeyer reaction in which benzenediazonium chloride is treated with copper
powder and a halogen acid (instead of cuprous halide dissolved in the corresponding halogen acid) to form
aryl halides. For example,
Cu/HCl
N=NCr ■Cl + N2
Benzenediazonium chloride Chlorobenzene
Cu/HBr
N=NCr Br + N2
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Benzenediazonium chloride Bromobenzene
The yields are around 40%

18. Gattermann-Koch reaction (Bihar Board 2012 ; R^. Board 2012 ; Pb. Board 2012)
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When a mixture of CO and HCl gas is passed through benzene at 323 K in presence of a catalyst
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rFl
consisting of anhydrous AICI3 and a small amount of CuCl, benzaldehyde is formed.
F
CO + HCl HCOCl
Formyl chloride {unstable)
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ou
CgHg + HCOCl
AiClj+CuCl
fo
» C^HsCHO + HCl
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Benzaldehyde
This eraction is called Gattermann formylation or Gattermann-Koc h aldehyde synthesis or simply
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Gattermann-Koch reaction and is used for commercial preparation of benzaldehyde.

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If CO in the above reaction is replaced by HCN, the reaction is called Gattermann formylation or
Gattermann aldehyde synthesis. (MP Board 2012)
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Anhyd.AIClj H20,boil
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CgHg + HCN + HCl ^ CgHjCH = NH.HCl ^ C^HjCHO + NH4CI

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Benzaldmine hydrochloride Benzaldehyde

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19. Grignard synthesis

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in
Alkyl and aryl halides react with magnesium turnings in presence of dry ether to form organomagnesium
F
compounds commonly known as Grignard reagents.

Dry ether
R—X or Ar—^X + Mg ■> R—MgX or Ar—MgX
Alkyl halide Aryl halide Grignard reagent
Dry Dry
CH3—I + Mg ^ CH3—Mgl ; CgHj—Cl THF
CgHj—MgCl
ether
Methyl iodide Methylmag. Chlorobenzene Phenylmag,
iodide chloride
For the same alkyl group, the order of reactivity is : R—I > R—Br > R—Cl and for the same halogen,
the reactivity of alkyl halides is higher than that of aryl halides.
Grignard reagents are extremely useful synthetic reagents since almost all classes of organic compounds
can be prepared from them. Some important examples are :
HjO
RH + Mg(OH)X
Alkane
R'OH
■>
RH + Mg(OR')X
R'NHj
» RH + Mg(NHR')X
CO2 H+/H2O
^ [RCOOMgX] —> RCOOH + Mg(OH)X
(Dry ice)
Carboxylic acid
^ RCH2OH + Mg(OH)X
HCHO
> [RCH20MgX]
1® Alcohol
w
0
CH2—CH
h [RCH2CH20MgX] ^ RCH2CH2OH + Mg(OH)X
Flo
1® Alcohol
R—MgX -
Grignard reagent
H+ZHjO
ee
RCHO
^ [R2CHOMgX] > R2CHOH + Mg(OH)X
Fr
2® Alcohol
R2CO H+/H2O
for
^ [R3COMgX] » R3COH + Mg(OH)X
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3® Alcohol
RMgX H‘*’/H20
s
RCOOR'
4 [R2CO RjCOMgX]
k
4
4 R3COH + Mg(OH)X
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-Mg(OR')X
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3® Alcohol
H+/HÔ
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HCN
4 [RCH = NMgX] ^ RCHO + NH3 + Mg(OH)X
Aldehyde
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H+/H2O
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RCN
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4 [R2C = NMgX] 4 R2CO + NH3 + Mg(OH)X

Ketone
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20. Haloform reaction (Iodoform reaction) (Pb. Board 2010 ; Hr Board 2011)
All compounds containing the grouping CH3CHOH— linked to either H or carbon (i.e. methylcarbinols
Re
nd
such as ethanol, 2-propanol, 2-buianoI, etc.) or CH3CO— {i.e. methyl ketones such as propanone, butanone,
Fi
2-pentanone, acetophenone, etc.) when treated with a halogen and excess of alkali (i.e. sodium hypohalite,
NaOX) form haloforms. If the halogen used is iodine, yellow precipitate of iodoform is formed and the
reaction is called iodoform reaction. For example,
CH3CH2OH + 412 + 6 NaOH -4 CHI3 -4 HCOONa -4 5 Nal -4 5 H2O
Ethanol Iodoform
CH3CHOHCH3 + 412 + 6 NaOH -4 CHI3 -4 CHjCOONa + 5 Nal -4 5 H2O

2-Propanol Iodoform
CH3COCH3 -1- 3 I2 + 4 NaOH -4 CHIg + CH3COONa + 3 Nal + 3 H2O

Propanone Iodoform
CH3COCH2CH3 -1- 3 I2 + 4 NaOH -4 CHI3 + CH3CH2COONa + 3 Nal + 3 HjO

2-Butanone Iodoform
CgHgCOCHg -H 3 I2 + 4 NaOH 4 CHI3 -4 CgHsCOONa + 3 Nal -4 3 H2O

Acetophenone Iodoform
I
A/12 ^ New Course Chemistry (XlDraSTM
It may be noted here that CH^CO—OH, CH^CO—Cl, (CH3C0>20, CH^CO—NH2, CH3CO—OR all
contain a CH3CO group which is not attached to either H or C and hence all these compounds do not respond
to haloform reaction.
lodofonn reaction is widely used for the distinction of melhylcarhinols and methyl ketones from other
alcohols and ketones.
Hell-Volhard Zelinsky reaction

(Pb. Board 2010 ; Hr. Board 2011, 2012 ; AP Board 2012 ; HP Board 2011, 2013 ; CBSE 2010, 2012, 2017)
The reaction of an aliphatic carboxylic acid containing a-hydrogens with CI2 or in presence of a
small amount of red phosphorus to give a-haloacids is called Hell-Volhard Zelin.sky (H..VZ.) reaction. With
exce.ss of halogen, all the a-hydrogen atoms of an aliphatic carboxylic acid are replaced by halogen atoms.
ow
For example.
a
C12.P a CU.P a CI2.P
^ CICH2COOH CLCHCOOH ^ CI3CCOOH
CH3COOH -HCl -HCl 2 *-HCl
Acetic acid Monochloro- Dichloro- Trichloro
e
acetic acid acetic acid acetic acid
re
rFl
P a
Br2.P a Br2.P
CH3CH2COOH CH3CHB1COOH CH3CBr2COOH
F
-HBr -HBr
Propionic acid a-Bromopropionic acid a, a-Dibromopropionic acid
i Brj, P
r
ou
No further substitution
fo
Hofmann Ammonolysis of Alkyl halides
ks (Hr. Board 2013)
When an alkyl or benzyl halide is heated with an alcoholic .solution of ammonia (or an amine) in a sealed
oo
tube at 373 K, a mixture of T, 2* and 3° amines with some quaternary ammonium .salt is obtained. For example.
Y
B
(/) H3N:
.r -h -K-Oi 37.1 K + NH3
R—NH2 + NHJ X"
► RNH3X"
re
Ammonia Alkyl halide 1“ Amine salt 1® Amine

ou
Y
ad
373 K
NH3
(ii) R—NII2 ♦ R2NH2 X“ RjNH 4 NHJ X"
2® Amine
d
I" Amine Alkyl halide 2" Amine sail

in
Re
373 K
NH3
R3N + NHJ X"
F
iiii) R2NH > R3NH'*'X“

3® Amine salt 3® Amine
2" Amine Alkyl halide
+
373 K
{/V) R3N R4NX*
.3" Amine Alkyl halide Quaternary ammonium
salt (4°)
The actual composition of the mixture depends upon the ratio of the alkyl halide and ammonia used.
If excess of alcoholic ammonia (approx. 10 times) is used, I® amine is the main product and if excess oi
alkyl halide is u.sed. quaternary ammonium salt is the main product.
Hofmann ammonolysis of alkyl halides is an example of a nucleophilic substitution reaction in which
NH^ or an amine displaces the halogen atom. Since aryl halides are much le.ss reactive than alkyl halides
towards nucleophilic substitution reactions, therefore, aniline and other arylamines cannot be prepared by
this method.
23. Hofmann bromamide reaction or Hofmann degradation of amides

(HP Board 2009 ; Pb. Board 2010 ; Hr. Board 2010, 2012 ; UP Board 2012 ; CBSE 2008, 2009, 2012, 2018)
The conversion of a primary amide to a primary amine containing one carbon atom less than the original
amide on heating with a mixture of Bf2 in presence of NaOH or KOH (i.e. NaOBr or KOBr ) is called
Hojmann bromamide reaction or Hofmann degradation of amides. For example,
CH3CONH2 + Br2 + 4 NaOH CH3NH2 + 2 NaBr -t- Na2C03 + 2 H2O

Acetamide Methylamine
CH3CH2CONH2 + Bt2 + 4 KOH- CH3CH2NH2 + 2 KBr + K2CO3 + 2 H2O

Propionamide Eihylamine
A
C6H5CONH2 + Br2 + 4 KOH ^ C6H5NH2 + 2 KBr + K2CO3 + 2 H2O
w
Benzamide Aniline
This reaction is extremely useful for converting a higher homologue to the next lower homologue, i.e.,
for stepping down or descending a homologous series.
Flo
QU Hydroboration-Oxidation (Hr. Board 2013)
Alkenes react with diborane (B2H^) in presence of THF to form trialkylboranes which upon subsequent
ee
oxidation with alkaline H2O2 give alcohols.
Fr
B2H6 ^2BH3
THF CH3CH=CH2
»
for
CH,—CH—CH.
ur
CU^CH = CU2 + H—BH2 HydroborationI J I I z
Hydroboration
->
Propene Borane
H
BH2
ks
CH3CH==CH2
Yo
oo
(CH3CH2CH2)2B—H Hy<.obor„.io„^ : (GH3CH,CH,)3B

Tri-n-propylborane
eB
OH'/HjO
(CH3CH2CH2)3B + 3 H2O2 Oxidation
» 3CH3CH2CH2OH + H3BO3
r
Tri-«-propylborane Propan-l*ol Boric acid

ou
ad
Thb two-step process is called hydroboration-oxidation and gives alcohols which appear to have
Y
been fanned by anti-Markownikov’s addition of water to alkenes.

Hunsdiecker reaction (Pb. Board 2010)
nd
Re
The decomposition of the silver salt of a carboxylic acid with Br2 in refluxing CCI4 to form an alkyl or-
aryl bromide with one carbon less than the original acid is called Hunsdiecker reaction For example.
Fi
CCl4,350K
RCOOAg + Bt2 Reflux
^ R—Br + CO2 + AgBr
CCI4.35OK
CH3CH2COOAg + Br2 Reflux
^ CH3CH2- ●Br + CO2 + AgBr
Silver propionate Ethyl bromide
CCl4,350K
CgHjCOOAg + Br2 Reflux
C6Hs- ●Br + CO2 + AgBr
Silver benzoate Bromobenzene '
Like Hofmann bromamide reaction, Hunsdiecker reaction is also used for stepping down the homologous ■
.senes.
Kolbe electrolytic reaction (HP Board 2011)

This reaction is used to prepare some alkanes, alkenes and alkynes by electrolysis of aqueous solution
of sodium or potassium salt of suitable acids. For example,
A/14 New Course Chemistry (XII)BZsl9S
{a) Ethane is produced when an aqueous solution of potassium acetate is electrolysed.

2 CH3COOK 2 CH3COO- + 2 K-" {Ionization)
Pot. acetate
2H2O ^ ± 2 OH- + 2 H-" (Ionization)

At anode : 2 CH3COO" - 2 e~ — ^ CH3—CH3 + 2CO2
Ethane
At cathode : Both K"*" and are present but H'*’ ions are preferentially discharged due to their lower
discharge potential.
2 H+ + 2 e- ^ H2
^ 2H-
(b) Ethylene is produced when potassium salt of succinic acid is electrolysed.

CH2COOK CH2COO-
+ 2K+ (Ionization)
CH2COOK
w
CH2COO-
Pot. succinate
F lo
2H2O ^ - 2 OH' + 2 H+ (Ionization)
CH2COO' CH.COO CH,

Atanode : -2e- > iI " I ' + 2CO2
ee
CH2COO- CH2COO CH2
Fr
(Unstable) Ethylene
At cathode : H2 is produced as above
2H+ + 2e- -
^ H2 for
ur
(c) Acetylene is produced when potassium maleate or fumarate is electrolysed.
s
CHCOO“
ook
CHCOOK
Yo
■> + 2K"- (Ionization)
CHCOOK CHCOO”
eB
Pot. maleate
2H2O ^ - 2 OH- + 2 H-" (Ionization)

r
ad
ou
CHCOO' CHCOO CH
At anode : ~le- + 2CO2
CHCOO- CHCOO CH
Y
(Unstable) Acetylene
Re
nd
At cathode : H2 is produced as above.

27. Kolbe reaction or Kolbe—Schmitt reaction
Fi
(HP Board 2011 ; Manipur Board 2011 ; Bihar Board 2012

West Bengal Board 2012, Jharkhand Board 2012 ; Hr. Board 2010, 2011, 2012, 2013 ; CBSE 2010, 2019)
Sodium phenoxide reacts with carbon dioxide under pressure (4*7) atmospheres at 400 K to form sodium
salicylate which upon acidification with mineral acids gives salicyclic acid. This reaction is called Kolbe reaction.
ONa OH OH
COONa COOH
4-7 atm H*
+ CO2 400 K H2O
Sod.phenoxide Sod. salicylate Salicylic acid
(Major product)
A small amount of p-hydroxybenzoic acid is also formed. But the two isomers are readily separated by
steam distillation. The o-isomer being more volatile steam distils leaving behind the p-isomer.
^2^ Perkin reaction (Bihar Board 2012 ; Tamil Nadu Board 2012 ; UP Board 2012 ; HP Board 2012)
When an aromatic aldehyde is heated with some aliphatic acid anhydride in presence of sodium salt of
the same acid, the product thus obtained on acid hydrolysis gives an a, ^-unsaturated acid. This reaction is
called Perkin reaction. For example, when benz^dehyde is heated with acetic anhydride in presence of
sodium acetate, the product thus formed on hydrolysis gives cinnamic acid.
CgHgCH =[0 + Hj] CHCO ^ 0 CH3COONa,453K

¥
C,H,CH
D 5 = CHCO
o
-H20 CH3CO
Benzaldehyde CH^CO
Acetic anhydride
HjO.Boii
4 CgHgCH = CHCOOH + CH3COOH
(Hydrolysis) Cinnamic acid
29. Reimer-Tiemann reaction (HP Board 2011 ; Pb. Board 2012 ; West Bengal Board 2012
w
Jharkhand Board 2012 ; AP Board 2012 ; Hr. Board 2010, 2012, 2013 ; CBSE 2010 S, 2013, 2014, 2019)
Treatment of phenol with chloroform in presence of aqueous sodium or potassium hydroxide at 340 K
followed by hydrolysis of the resulting product gives 2-hydroxybenzaldehyde (salicyladehyde). This reaction
F lo
is called Reimer-Tiemann reaction*.
OH ONa ONa
ee
CHCI2 ●CH(0H)2
Fr
NaOH, 340 K 2NaOH
>●
+ CHCI3 -2NaCl -H2O
-NaCl, -H2O
Phenol for
ur
OH
s
ONa
ook
Yo
CHO .CHO
Oil. HCl
eB
-NaCl
2-Hydroxybenzaldehyde
our
(Salicylaldehye)
ad
A small amount of p-hydroxybenzaldehyde is also formed.

If instead of chloroform, carbon tetrachloride is used, salicylic acid is formed.
Y
OH ONa ONa
Re
nd
^L/CCl3 /^/C(0H)3
Fi
NaOH 3 NaOH
+ CCI4 340 K. -3 NaCl -H2O
Phenol
ONa ONa OH
COOH .COONa COOH

NaOH Oil, HCl
>
-H2O -2 NaCl
2-Hydroxybenzoic acid
(Salicylic acid)
A small amount of p-hydroxybenzoic acid is also obtained.
♦This reaction is an example of an electrophilic substitution reaction in which the reactive electrophile is
dichlorocarbene (: CCI2).
A/16 ‘P'ustcUe^'A New Course Chemistry (XlI)CZsZ9D
30. Rosenmund reduction
(CBSE 2007 ; Pb. Board 2009, 2010 ; MP Board 2012 ;
R^j. Board 2012 ; W«st Bengal Board 2012)
Catalytic reduction of acid chlorides to the corresponding aldehydes is called Rosenmund reduction.
This reaction is carried out by passing H2 gas through boiling xylene solution of the acid chloride in presence
of Pd catalyst supported over BaS04 (partially poisoned by addition of sulphur or quinoline).
O O
Pd.BiiSO^.S
R
C—Cl + H2 Boiling xylene
R—C—H + HCl
Acid chloride Aldehyde
o o
Pd.BaS04.S
CH3—C—Cl + H2 Boiling xylene
> ● CH^—C—H + HCl
Acetyl chloride Acetaldehyde
w
o o
Pd.BaSO^.S
F lo
C^Hj—C—Cl + H2 Boiling xylene
C^Hg—C—H + HCl
Benzoyl chloride Benzaldehyde
ee
The function of BaS04 and S (or quinoline) is to poison the catalyst so that it does not allow the further
Fr
reduction of aldehydes thus produced to alcohols.
31. Sandmeyer reaction
for (CBSE 2008, 2009 ; HP Board 2011 ;
West Bengal Board 2012 ; Hr. Board 2012, 2013)
ur
The conversion of benzenediazonium chloride to chlorobenzene, bromobenzene and benzonitrile on
Ircalnienl with CuCl/HCI. CuBr/HBr or CuCN/KCN re.speclively is called Sandmeyer reaction.
s
ook
Yo
N^NCr
eB
Cl
CuCl/HCl
our
+ N2 + cr
ad
Benzenediazonium chloride Chlorobenzene

Y
Re
N^NCr
nd
Br
Fi
CuBr/HBr
A + N2 + cr
Benzenediazonium chloride Bromobenzene
N = NCr CN
CuCN/KCN
A + N2 + cr
Benzenediazonium chloride Benzonitrile
It may be noted that in this reaction, it is the halogen attached to copper which acutally enters the
benzene ring.
Saponification
Hydrolysis of an ester with aqueous NaOH or KOH to give the corresponding alcohol and the sodium or
potassium salt of the fatty acid is called saponification. For example.
Heat
CH3COOC2H5 + NaOH
^ CH^COONa + C2H5OH
Ethyl ethanoale Sod. elhaiioate Hlhunol
CH^—OCOR CH.,OH R.COONa

Heal +
CH—OCOR, + 3 NaOH
I * ? HOH + R2COONa
+
CH^—OCOR3 CHÔH R.jCOONa
ow
Oil or fat Glycerol Sodium .salt.s of
(/t triglyceride) Tally acids
(Soapx)
33. Schotten-Baumann reaction (Hr. Board 2010, 2011)
e
The process of benzoylalion of compounds containing active hydrogen such as phenol, aniline, alcohol, etc.
Fl
re
witli benzoyl chloride in the presence of aqueous NaOH is called Schoiten- Baumann reaction. For example,
F
OH OCOC6H5
ur
or
NaOH
+
QH5COCI ♦ sf + HCI
Ben/oyl chloride
Phenol
k
Phenyl benzoate
Yo
oo
NH2 NHCOCf,H5
B
re
NaOH
-1
C6H5COCI 1 1 -» HCI
Benzoyl chloride
u
ad
Aniline Benzanilide
Yo
NaOH
CH3CH2OH + C^HjCOCI ^ CH3CH2OCOC6H5 + HCI

d
Ethyl alcohol
Re
Benzoyl chloride Ethyl benzoate

in
34. Stephen reaction or Stephen reduction (Chhatisgarh Board 2011 ; CBSE 2017)
F
The partial reduction of alkyl or aryl cyanides to the corresponding aldehydes with a suspension of
anhydrous stannous chloride in dry ether saturated with hydrogen chloride at room temperature followed
by hydrolysis is called Stephen reaction or Stephen reduction. During this reaction, imine hydrochloride
first gets precipitated which on hydrolysis with boiling water gives the corresponding aldehyde. For
example.
SnCU + 2 HCI SnCl4+2tH]
Dry ether
CH3CsN + 2[H| + HC1 290-295K
^ CH3CH = NH.HCI
Acetonitrile Aceliildimine hydnK'hloride
i Boiling HiO
CH3CH = O + NH4CI
Acetaldehyde
A/18 New Course Chemistry (XH)CSI9D
Dry ether
CgHsC s N + 2 [H] + HCl 290-295 K
●>
CgHjCH = NH.HCl
Benzonitrile Benzaldimine hydrochloride
>l Boiling H2O
CgHjCH = O + NH4CI
Benzaldehyde
35. Swarts reaction (Hr. Board 2012, 2013)
Aryl fluorides are conveniently prepared by heating suitable chloro- or bromoalkanes with inorganic
fluorides, such as ASF3, Sbp3, C0F2, AgF, Hg2F2» etc. For example,
CHgBr + AgF CH3F + AgBr

Bromomeihane Fluoromethane
w
2CH3CH2CI + Hg2F2 ^ 2CH3CH2F + Hg2Cl2
Chloroethane Fluoroethane
F lo
This reaction is called Swarts reaction.
When the organic halide contains two or three halogens at the same carbon, C0F3 or the more easily
ee
available Sbp3 is used. For example.
Fr
3CH3—CCI2—CH3 +2SbF3 ^ 3 CH3—CF2—CH3 + 2 SbCl3
2,2-Dichloropropane
for
ur
36. Transesterification (HP Board 2008)
When an ester is treated with excess of another alcohol (other than the one from which the ester has
s
been derived) in presence of a base such as the corresponding sodium or potassium alkoxide or an acid
ook
Yo
{H2SO4 or HCl) as catalyst, a new ester and a new alcohol are formed. This alcoholysis (cleavage by an
alcohol) or displacement of one alcohol from an ester by another alcohol is called transesterification. For
eB
example.
o H+orR"-ONa, o
r
Reflux
ad
ou
R—C—OR' + R i R—C—OR" + R'—OH

//
OH r
Ester Alcohol New ester New alcohol
Y
Transesterification is a reversible reaction. Therefore, to shift the equilibrium in the forward direction,
Re
generally an excess of the alcohol whose ester we wish to make is used.

nd
Transesterification is a useful reaction particularly for the preparation of higher alcohols from the naturally
Fi
occurring esters.
CjHjONa
CH3C(D0C4H9 + C2H5OH ^ i CH3COOC2H5 + C4H9OH
n-Butyl acetate Ethyl alcohol Ethyl acetate n-Butyl alcohol
{Lower alcohol) {Higher alcohol)
37. Williamson synthesis
(J & K Board 2011 ; AP Board 2012 ; Hr. Board 2010, 2011, 2013 ; CBSE 2010, 2010 S, 2013, 2019)
The reaction of alkyl halides with sodium alkoxide or sodium phenoxide to form ethers is called
Williamson synthesis. For example.
R_X + R'—ONa ^ R—O—R' + NaX
Alkyl halide Sod. alkoxide Ether
CH3I + CHjCHjONa CH3—O—CH2CH3 + Nal

Methyl iodide Sod. ethoxide Ethyl methyl ether
CH3CH2I + CH3CH20Na ^ CH3CH2-O-CH2CH3 + Nal

Ethyl iodide Sod. ethoxide Diethyl ether
ONa OCH3
+ CH3I ♦ + Nal
Methyl iodide
Sod. phenoxide Anisole
This is one of the best methods for the preparation of both simple and mixed ethers.
38. Wolff-Klshner reduction
(Pb. Board 2010 ; Hr. Board 2012; HP Board 2011. 2013 ; CBSE 2014, 2016 ; CBSE Foreign 2017)
The reduction of aldehydes and ketones to the corresponding hydrocarbons by heating them with hydrazine
w
and KOH or potassium ferf-butoxide in a high boiling solvent such as ethylene glycol is called Woljf-Kishner
reduction.
Flo
NHjNH, KOH.glycol
R_CH = 0 ^ [R—CH = NNH2] ^ R—CH3 + N2
-HjO 453-473K
ee
Aldehyde Hydrazone
Fr
NH2NH2/KOH. glycol
CH3COCH3 453-473K
> CH3CH2CH3
for
Acetone Propane
ur
NH2NH2/KOH. glycol
COCH3 CH2CH3
ks
453-473 K
Yo
oo
Acetophenone Ethylbenzene
Wolff-Kishner reduction is particularly useful when the aldehydes and ketones to be reduced are sensitive
eB
to acids.
39. Wurtz reaction (CBSE 2007 ; MP Board 2011 : Manipur 2011, 2012 ; AP Board 2012 :
r
Bihar Board 2012 ; West Bengal Board 2012 ; Hr. Board 2012, 2013)
ou
ad
It involves the interaction of two molecules of an alkyl halide (preferably bromide or iodide) with
Y
metallic sodium in presence of dry ether to form symmetrical alkanes containing double the number of carbon
atoms present in the alkyl halide. For example,
nd
Re
r n Dry ether
R— X + 2Na + X — R ^ R_R + 2 NaX
Fi
L J
Alkyl halide Alkane
Dry ether
e.g.. CH-,—“"Br + 2 Na + Br"^— CH-, 4 CH3—CH3 + 2NaBr
●’l I
Methyl bromide Ethane
CH3CH2—""l + 2 Na + T— CH2CH3
Dry ether
^ CH3CH2—CH2CH3 + 2 Nal
Ethyl iodide ———— n-Butane
Thus, Wurtz reaction is a convenient method for the preparationof symmetricalalkanes (R—R), i.e.,
alkanes containing even number of carbon atoms.
However, if two different alkyl halides are used, a mixture of three alkanes is acutally obtained. For
example,
A/20 New Course Chemistry (XII)BZsZ9D
Dry ether
CH3- 1
+ 2 Na +
___J
CH^CH,
^ ■’
^ CH3—CH2CH3 + 2 Nal
Propane
Methyl iodide Ethyl iodide
Dry ether
CH3—[1 + 2 Na + l]— CH3 4 CH3—CH3 + 2 Nal
Ethane
Methyl iodide .
Dry ether
GH3CH2- I + 2 Na + CH2CH3 4 CH3CH2 — CH2CH3 + 2 Nal
n*Butane
Ethyl iodide
w
The boiling points of these alkanes are very close and hence cannot be separated by fractional distillation.
That is why Wurtz reaction is only usefulfor the preparation ofsymmetrical alkanes and notfor the preparation
of unsymmetrical alkanes, i.e., alkanes containing odd number of carbon atoms.
o
QQ Wurtz-Fittig reaction (CBSE 2007 ; HP Board 2011, 2013)
e
This reaction is a variation of Wurtz reaction and is used for preparing homologues of benzene by
re
rFl
warming a mixture of an aryl halide and an alkyl halide with metallic sodium in presence of dry ether. For
F
exaniple,
(0 / V_r;Br+ 2Na+ Bri—CH3

Drygther ^ ^ ^ CH3 +2NaBr
r
ou
fo
Methyl bromide
Bromobenzene ks Toluene
Biphenyl and ethane are obtained as by-products

oo
(») CH2CH3 Pry ether ^ ^ CH2CH3 + 2 NaBr

Y
B
Ethyl bromide
Bromobenzene Ethylbenzene
re
Biphenyl and n-butane are obtained as by products.

Wurtz-Fittig reaction is preferred to Friedel-Crafts reaction because long n-alkyl side chains can be
ou
Y
easily introduced into the benzene ring without the danger of any rearrangement. For example,
ad
r n Dry ether
—2 ^ C6H5CH2CH2CH2CH3 -b 2 NaBr
d
, Br + 2 Na + Br , CH2CH2CH2CH3
in
Bromobenzene ;i-Butyl bromide «-Butylbenzene

Re
F
APPENDIX
DISTINCTION BETWEEN
PAIRS OF COMPOUNDS
ow
Chlorobenzene (C5H5C!) and chlorocyclohexane (C^HjîCl)
Chlorocyclohexane is a haloalkane while chlorobenzene is a haloarene. Since haloalkanes are more
reactive than haloarenes, therefore, when chlorocyclohexane is healed with aq. KOH, it undergoes hydrolysis
e
re
to produce cyclohexanol and KCl.
rFl
F
Cl OH
r
+ KOH {aq) + K"" cr
fo
ou
*■ ks
Chlorocyclohexane Cyclohexanol
K+Cl- + Ag+NOj ^ AgCU + K-^NOJ

oo
{White ppt.)
Y
B
The above reaction mixture on acidification with dil. HNO3 followed by treatment with AgN03 solution
produces a white ppt. of AgCl due to the formation of KCl during the hydrolysis reaction.
e
In contrast, chlorobenzene does not undergo hydrolysis under these conditions to produce phenol and
ur
KCl.
ad
Yo
CgHj—Cl + KOH {aq) ^ > No reaction

d
Chlorobenzene
Re
in
Therefore, treatment of the reaction mixture with dil. HNO3 followed by addition of AgN03 does not
produce a white ppt. of AgCl.
F
Qj Chlorobenzene (CgHgCl) and benzyl chloride (CgH5CH2Cl)

Benzyl chloride is an aralkyl halide while chlorobenzene is an aryl halide. Since aralkyl halides are
even more reactive than alkyl halides towards nucleophilic substitution reactions, therefore, benzyl chloride
on boiling with aq. KOH produces benzyl alcohol and KCl.
Boil
C6H5CH2CI + KOH {aq) » C6H5CH2OH + K-^cr
Benzyl chloride Benzyl alcohol
The reaction mixture on acidification with dil. HNO3 followed by treatment with AgN03 solution produces
white ppt. of AgCl due to the formation of KCl.
K+Cr + Ag-^NOJ AgCl i + K+NOJ
{White ppt.)
A/21
A/22 New Course Chemistry fXIHrogrwn
In contrast, chlorobenzene does not undergo hydrolysis under these mild conditions to give phenol and
KCl.
BoU
CgHsCl + KOH {aq) > No reaction
Chlorobenzene
Therefore, acidification of the reaction mixture with

dil. HNO3 followed by addition of AgN03 solution
does not produce a white ppt. of AgCl.
Bromobenzene (CgHgBr) and benzyl bromide (C6HgCH2Br)
Benzyl bromide is an aralkyl halide while bromobenzene is an aryl halide. Since aralkyl halides are
more reactive than even alkyl halides towards nucleophilic substitution reactions, therefore, benzyl bromide
on boiling with an aqueous solution of KOH will undergo hydrolysis to produce benzyl alcohol and KBr.
Boil
C6H5CH2Br + KOH (aq) > CgHjCHoOH + K-"Br'
Benzyl bromide Benzyl alcohol
w
The reaction mixture on acidification with dil. HNO3 followed by addition of AgN03 solution produces
light yellow ppt. of AgBr due to the formation of KBr.
F lo
K+Br- + Ag+NO- AgBri + K+NOJ
(Light yellow ppt.)
ee
In contrast, bromobenzene being much less reactive than benzyl bromide does not undergo hydrolysis
Fr
under these mild conditions to give phenol and KBr.
Boil
CgHjBr + KOH (aq) > No reaction
for
ur
Bromobenzene
Therefore, acidification of the reaction mixture with dil. HNO3 followed by addition of AgN03 solution
s
ook
does not produce a light yellow ppt. of AgBr.

Yo
IQI p-Chlorotoluene (p-CICgH4CH3) and benzyl chloride (CgH5CH2CI)

eB
These may be distinguished by the following tests :—

(i) AgN03 Benzyl chloride on boiling with aq. KOH solution undergoes hydrolysis to give benzyl
alcohol and KCl.
our
ad
C6H5CH2CI + KOH (aq) ^ CgH5CH20H + K+Cr

Benzyl chloride
Y
Benzyl alcohol
The reaction mixture on acidification with dil. HNO3 followed by treatment with AgN03 solution produces
Re
nd
white ppt. of AgCl (due to the formation of KCl during hydrolysis).

K+Cr + AgN03 > AgCl i + K^NO“
Fi
(White ppt.)
In contrast, p-chlorotoluene does not undergo hydrolysis under these conditions to produce p-cresol
and KCl. Therefore, it does not give white ppt. of AgCl.
(ii) Oxidation test p-Chlorotoluene on oxidation with alkaline KMn04 solution followed by acidification
gives p-chlorobenzoic acid which gives green edged flame during Beilstein test due to the presence of Cl in
It.
(OAlk. KMn04
Cl CH3 > Cl COOH
(//) Dil. HCl
;j-ChlorotoIuene /j-Chlorobenzoic acid
(m.p. 512-514 K)
In contast, benzyl chloride on oxidation with alkaline KMn04 followed by acidification gives benzoic
acid which does not give Beilstein test due to the absence of Cl.
DISTINCTION BETWEEN PAIRS OF COMPOUNDS A/23
CH2CI COOH
(0 Aik. KMn04
(ii) Dil. HCl
Benzyl chloride Benzoic acid

(m.p, 394 K)
Chloroform (CHCI3) and carbon tetrachloride (CCI4)

These two compounds can be distinguished by the Carbylamine test as given below :
Carbylamine test. Chloroform on warming with an alcoholic solution of aniline and KOH gives
carbylamine having offensive smell while carbon tetrachloride does not give this test,
ow
warm
CHCI3 + C6H5NH2 + 3 KOH CgH5N = C + 3KC1 + 3H2O

Chloroform Aniline ialc.) Phenyl isocyanide
{Offensive smelling compound)
CCI4 + C6H5NH2 + KOH — No reaction
e
WM Methanol (CH3OH) and ethanol (CH3CH2OH) (West Bengal Board 2013)
re
rFl
These can be distinguished by the iodoform test as given below :
F
Iodoform test. Ethanol contains the grouping —CHOHCH3 (attached to H) and hence when warmed
with sodium hypoiodite (NaOI), i.e., in NaOH, it gives yellow ppt. of iodoform.
r
CH3CH2OH + NaOI ^ CH3CHO + Nal + H2O
ou
Ethanol Acetaldehyde
fo
ks
CH3CHO +3 NaOI CHI3 i + HCOONa + 2 NaOH
Acetaldehyde Iodoform Sod. formate
oo
On the other hand, methanol (CH3OH) does not contain the grouping —CHOHCH3 and hence it does
Y
not give the iodoform test.

eB
NaOI
CH3OH > No yellow ppt. of CHI3
r
Methanol
You
ad
Propanone (CH3COCH3) and ethanol (CH3CH2OH)

These cannot be distinguished by iodoform test since both these compounds give the iodoform test;
CH3CH2OH gives iodoform test because it contains the grouping CH3CHOH— attached to H while
d
CH3COCH3 contains the grouping CH3CO— linked to carbon. However, these can be easily distinguished
Re
in
by 2, 4-D.N.P. (2, 4- dinitrophenylhydrazine) test or Brady’s reagent test. Propanone being a ketone gives
this test while ethanol being an alcohol does not give this test.
F
Brady’s reagent test. When propanone is treated with 2,4-dinitrophenylhydrazine in weakly acidic
conditions, it gives crystalline orange ppt. of propanone 2, 4-dinitrophenyIhydrazone.
NO2 NO2
CH3 CH3.
C=0 + H2NNH NO2 C=NNH NO2 + H2O
pH 3-5
CH3' CH3
2, 4-Dinitrophenyl-
Propanone Propanone 2, 4-dinitrophenylhydrazone
hydrazinc {orange ppt.)
It contrast, ethanol does not give this test.

2,4-Dinitrophenylhydrazine
CH3CH2OH 4 No orange ppt.
Ethanol
A/24 New Course Chemistry fXin orsTWi
Q Ethanol (CHjCHjOH) and 1-propanol (CH3CH2CH2OH)

Iodoform test. Ethanol contains the grouping CH3CHOH — (attached to H) and hence when warmed
with sodium hypoiodite (NaOI), i.e., I2 in NaOH, it gives yellow ppt. of iodoform (CHI3).
CH3CH2OH + NaOI ■¥ CH3CHO + Nal + H2O
Ethanol Ethanal
CH3CHO + 3 NaOI > CHI3 i + HCOONa + 2NaOH

Ethanal Iodoform Sod. formate
On the other hand, 1 -propanol {CH3CH2CH2OH) does not contain the grouping CH3CHOH — (attached
to either H or C) and hence it does not give iodoform test on treatment with NaOI.
NaOI
CH3CH2CH2OH
w
> No yellow ppt. of CHI3
1 -Propanol
Q Ethyl alcohol (CH3CH2OH) and isopropyl alcohol or 2-propanol
F lo
(CH3CHOHCH3)
(Hr. Board 2013)
ee
Both ethyl alcohol and 2-propanol contain the grouping CH3CHOH (attached to either H or C) and
hence when warmed with sodium hypoiodite (NaOI), i.e., 12/NaOH, both will give iodoform test, Le., yellow
Fr
ppt. of iodoform. Therefore, these alcohols cannot be distinguished by the iodoform test.
Further since ethyl alcohol is a primary alcohol while 2- propanol is a secondary alcohol, therefore,
for
ur
these alcohols can be easily distinguished by either Lucas test or iVctor-Meyer's test.
(0 Lucas test. 2-Propanol being a 2® alcohol on treatment with Lucas reagent (anhyd. ZnCl2 -f- cone.
s
HCl) produces turbidity in aboutyive minutes due to the formation of 2-chloropropane.
ook
Yo
Anhyd. ZnCl2 + cone. HCl

CH3—CH—CH3
eB
(Lucas reagent) CH3—CH—CH3

OH Cl
r
2-Propanol 2-Chloropropane
ou
ad
(Turbidity appears in about 5 minutes)

On the other hand, ethyl alcohol being a 1° alcohol does not produce turbidity at room temperature on
Y
treatment with Lucas reagent.

Re
nd
Anhyd.ZnCl2+conc.HCl
CH3CH2OH ^ No turbidity at room temperature
Fi
(Lucas reagent)
Ethanol
(I'O Victor-Meyer’s test. Ethyl alcohol being a 1° alcohol gives blood red colouration in Victor-Meyer’s
test while 2-propanol being a 2° alcohol gives blue colouration. Thus,
P+I2 AgN02 MONO
CH3CH2OH ^ CH3CH2I » CH3CH2NO2 » CH,—C —NO.
Ethyl alcohol Ethyl iodide
-Agl
Nitroethane
' I '
NOH
Nitrolic acid
NaOH
^ CH, —C—NO,
-H2O 3 I
NO" Na+
(Blood red colouration)

P + 1 AgNOj MONO
CH3—CH—CH3 ^ CH3—CH—CH3 -Agl

> CH,—CH—CH»
^ 1 ^
OH I NO2
2-Propanol 2-Iodopropane 2-Nitropropane
CH3^^/.N02 NaOH
Blue colouration
CH3/ N = 0
10. 1-Propanol or n-propyl alcohol (CH3CH2CH2OH) and

2-propanol or isopropyl alcohol (CH3CHOHCH3)
These can be distinguished by the iodoform test, Lucas test or iYctor-Meyer's test as given below :
(0 Iodoform test. 2-Propanol (CH3CHOHCH3) contains the grouping CHOHCH3 (linked to C) and
hence when warmed with sodium hypoiodite (NaOI), i.e., I2 in NaOH, it gives yellow ppt. of iodoform. In
w
contrast, 1-propanol does not contain the grouping —CHOHCH3 (attached to either H or C) and hence does
not respond to iodoform test.
F lo
CH3—CHOHCH3 -h NaOI ^ CH3—COCH3 + Nal -P H2O
2-Propanol Acetone
ee
CH3—COCH3 -H 3NaOI CHI3 i + CH3COONa + 2NaOH
Fr
Acetone Iodoform Sod. acetate
(Yellow ppt.)
NaOH
for
ur
CH3CH3CH2OH No yellow ppt. of CHI3
1-Propanol
s
(ii) Lucas test. 2-Propanol being a 2° alcohol on treatment with Lucas reagent gives turbidity in about
ook
Yo
5 minutes but 1-propanol being a 7" alcohol does not give turbidity at room temperature on treatment with
Lucas reagent.
eB
Anhyd. ZnCl2+conc. HCl

CH3—CH—CH3 ^ CH3—CH—CH3
r
(Lucas reagent)
ad
ou
OH Cl
2-Chloropropane
Y
2-Propanol
(2" Alcohol) (Turbidity appears in about 5 minutes)
Re
nd
Anhyd. ZnCIj+conc. HCl

Fi
CH3CH2CH2—OH ^ No turbidity at room temperature

(Lucas reagent)
1-Propanol
(7® Alcohol)
(Hi) Victor-Meyer’s test. 1-Propanol being a 1° alcohol gives blood red colouration in Victor-Meyer’s
test while 2-propanol being a 2° alcohol gives blue colouration. For reactions, consult Distinction 9.
11. Propanol (CH3CH2CH2OH) and propanone (CH3COCH3)
(CBSE 2008, 2012 ; Hr. Board 2012)
As discussed above these can be distinguished by the iodoform test.

Iodoform test. Propanone (CH3COCH3) contains the grouping —COCH3 linked to carbon and hence
when warmed with sodium hypoiodite (NaOI), i.e., 12/NaOH, it gives yellow ppt. of iodoform. In contrast,
propanol does not contain the grouping CH3CHOH- (attached to either H or C) and hence does not resond to
iodoform test.
For reactions, refer to distinction 10 between 1-propanol and 2-propanol.

A/26 New Course Chemistry (XII)BOBS
12.
n«Propyl iodide (CH3CH2CH2I) and isopropyl iodide (CH3CHICH3)
These two compounds may be distinguished as follows :
Iodoform test. Isopropyl iodide on alkaline hydrolysis gives isopropyl alcohol (2-propanol) which
upon subsequent treatment with NaOI (12/NaOH) gives yellow ppt. of iodoform.
CH CH
CH3
^^CH—I + NaOH(a^) CH3
CHOH + Nal
Isopropyl iodide Isopropyl alcohol
CH
A
CHOH + 4NaOI CHI3 i + CH3COONa + Nal + 2 NaOH + H2O
w
CH3^ Iodoform
Isopropyl alcohol (Yellow ppt.)
Flo
In contrast, n-propyl iodide on alkaline hydrolysis gives n-propyl alcohol (l-propanol) which on
subsequent treatment with NaOI (12/NaOH) does not give yellow ppt. of CHI3 (iodoform test).
ee
Fr
CH3CH2CH2I + NaOH (aq) ^ CH2CH2CH2OH + Nal
n-Propyl iodide n-Propyl alcohol
for
I NaOI
ur
No yellow ppt. of CHI3
s
13.
1-ButanoI or n-Butyl alcohol (CH3CH2CH2CH2OH) and $ec->Butyl alcohol or 2-butanol
k
Yo
(CH3CHOHCH2CH3)
oo
eB
These two compounds can be easily distinguished by the iodoform test, Lucas test or Vector-Meyer's
test as given below :
(i) Iodoform test. 2-Butanol (CH3CHOH—CH2CH3) contains the grouping CH3CHOH— (attached to
r
ou
ad
C) and hence when warmed with NaOI (12/NaOH), it gives yellow ppt. of iodoform (iodoform test) but 1-
butanol (CH3CH2CH2CH2OH) does not contain the grouping CH3CHOH— (attached to either H or C) and
Y
hence does not answer the iodoform test.

Re
nd
CH3CHOH—CH2CH3 + NaOI CH3C0—CH2CH3 + m + H2O

Fi
2-Butanol 2-Butanone
CH3CO—CH2CH3 + 3 NaOI - ^ CHI3 -L -I- CH3CH2COONa -i- 2 NaOH

2-Butanone Iodoform Sod. propionate
(Yellow ppt.)
NaOI
CH3CH2CH2CH2OH No yellow ppt. of CHI3
l-Butanol
Lucas test. 2-Butanol being a 2° alcohol on treatment with Lucas reagent gives turbidity in about
5 minutes but 1- butanol being a 1° alcohol does not give turbidity at room temperature.
For reactions of 2-butanol refer to Distinction 14 given below.
(ii) Victor-Meyer’s test. 1-Butanol being a 1® alcohol gives blood red colouration in Victor Meyer’s
test while 2- butanol being a 2® alcohol gives blue colouration. For reactions, consult Distinction 9.
14. Secondary butyl alcohol (CH3CHOHCH2CH3) and tertiary butyl alcohol E(CH3)3COH]
or Butan-2-ol and 2-methylpropan>2-ol
These can be easily distinguished by the following tests :
(i) Iodoform test. 5ec.-Butyl alcohol or butan-2-ol (CH3CHOHCH2CH3) contains the grouping
CH3CHOH- (attached to C) and hence when warmed with NaOI (12/NaOH), it gives yellow ppt. of iodoform.
In contrast, tertiary butyl alcohol or 2-methylpropan-2-ol, (CH3>3COH does not contain the grouping
CH3CHOH- and hence does not respond to the iodoform test.
CH3CHOH—CH2CH3 + NaOI ^ CH3CO—CH2CH3 + Nal + H2O
iec-Buiyl alcohol 2-Butanone
or Butan-2-ol
CH3CO—CH2CH3 + 3 NaOI CHI3 i + CH3CH2COONa + 2 NaOH

2-Butanone Iodoform Sod. propionate
w
{Yellow ppt.)
CH,
F lo
I ' NaOI
CH,—C—OH > No yellow ppt. of CHI3
' I
ee
CH3
Fr
rerf-Butyl alcohol
or 2-Methylpropan-2-ol
for
(ii) Lucas test. Tertiary butyl alcohol or 2-methylpropan-2-ol on treatment with Lucas reagent (anhyd.
ur
ZnCl2 + cone. HCl) immediately produces turbidity but secondary butyl alcohol or butan-2-ol produces
turbidity in about five minutes.
s
ook
Yo
OH Cl
eB
CH3—CH—CH2CH3 {Lucas reagent)

●>
CH3—CH—CH2CH3
^cc-Butyl alcohol -Butyl chloride
or Butan-2-oI {Turbidity appears in about ifve minutes)
our
ad
CH»
CH3 I ^
Anhyd. ZnCl2 + cone. HCl
Y
CH3—C—OH
■y CH,—C—Cl
{Lucas reagent) ' I
Re
nd
CH3 CH3
Fi
/crr-Butyl alcohol ferf-Butyl chloride

or 2-Methylpropan-2-ol {Turbidity appears immediately)
(iii) Victor-Meyer’s test. 5ec-Butyl alcohol being a 2® alcohol gives blue colouration in Victor-Meyer’s
test while /er/-butyl alcohol being a 3® alcohol does not respond to Victor-Meyer’s test. For reactions, consult
Distinction 9.
15. 1-Propanol (CHjCHjCHjOH) and 2-methyl-2-propanol or tert-butyl alcohol, (CH3)3COH

(CBSE 2017)
1-Propanol (CH3CH2CH2OH) is a primary alcohol while 2-methyl-2-propanol, (CH3)3COH is a tertiary

alcohol, therefore, these can be easily distinguished by the Lucas test and Victor-Meyer’s test as given
below.
(0 Lucas test. 2-Methyl-2-propanoI (ferf-butyl alcohol) being a 3® alcohol on treatment with Lucas
reagent (anhyd. ZnCL + cone. HCl) immediately produces turbidity due to the formation of 2-chloro-2-
methylpropane (terr-butyl chloride).
A/28 “Pniidee^ A New Course Chemistry fXTnrosrwm
CH3 CH,
Anhyd.ZnCl2+conc.HCl I ^
CH3—C—OH CH^—C—Cl
(Lucas reagent) ' 1
CH3 CH3
2-Methyl-2-propanol 2-Chloro-2-methylpropane
(Turbidity appears immediately)
On the other hand, 1-propanol being a 1° alcohol does not produce turbidity at room temperature on
treatment with Lucas reagent.
CH3CH2CH2OH ■y No turbidity at room temperature
(Lucas reagent)
1-Propanol
(ii) Victor-Meyer’s test. 1-PropanoI being a 1“ alcohol gives blood red colouration in Victor-Meyer’s
low
test while 2-methyI-2-propanoI or rert-butyl alcohol being a 3“ alcohol does not respond to Victor-Meyer’s
test. For equations, refer to Distinction 9.
16.
Ethanol (CH3CH2OH) and benzyl alcohol (CgH5CH20H)
ee
F
Iodoform test. Ethanol (CH3CH2OH) contains the grouping —CHOHCH3 (linked to H) and hence
Fr
when warmed with NaOI (12/NaOH), it gives yellow ppt. of iodoform (iodoform test) but benzyl alcohol
which does not contain the grouping —CHOHCH3 does not respond to iodoform test.
for
ur
CH3CH2OH + NaOI CH3CHO + H2O + Nal
Ethanol Acetaldehyde
ks
CH3CHO + 3 NaOI ^ CHI3 i + HCOONa + 2 NaOH
Yo
oo
(Yellow ppt.)
eB
NaOI
C6H5CH2OH > No yellow ppt. of CHI3
Benzyl alcohol
r
ou
ad
Y
17.
Isopropyl alcohol f CH3—CH—CH3 ^ and benzyl alcohol CHjOH
nd
Re
OH
Fi
These can be distinguished by the iodoform test:

Iodoform test. Isopropyl alcohol contains the grouping —CHOHCH3 (attached to C) and hence when
warmed with NaOI (12/NaOH), it gives yellow ppt. of iodoform (iodoform test) but benzyl alcohol which
does not contain the grouping —CHOHCH3 (attached to either H or C), does not respond to iodoform test.
CH3—CH—CH3 + NaOI ^ CH3—CH—CH3 + H20 + Nal
OH O
Isopropyl alcohol Acetone
CH3—C—CH3+ 3NaOI ^ CHI3 + CH3COONa + 2 NaOH

Iodoform Sod. acetate
O
(Yellow ppt.)
NaOI
C6H5CH2OH > No yellow ppt. of CHI3
Benzyl alcohol
18.
Ethanol (CH3CH2OH) and phenol (C^HsOH)
(CBSE(D) 2017, CBSE 2017)
These two compounds may be distinguished by the following tests :

(0 Litmus test. Phenol being acidic turns blue litmus red while ethanol being neutral does not give this
test.
(n) FeCl3 test. Phenol gives a violet colouration with FeCl3 solution while ethanol does not.
FeCl3
CH3CH2OH > No violet colouration
Ethanol
(Hi) Br2-water test. Phenol readily undergoes electrophilic substitution reactions. Therefore, it
decolourises bromine water giving white ppt. of 2. 4, 6-tribromophenol but ethanol does not give this test.
w
OH OH
F lo
Br. Br
+ 3 Br2 (aq) + 3 HBr
ee
Phenol
Fr
Br
2.4, 6-Tribromophenol
(fVhileppt.)
for
ur
Bf2-water
CH3CH2OH » No white ppt.
s
ook
Ethanol
Yo
(iV) Iodoform test. Ethanol when warmed with NaOI (I-^/NaOH) gives yellow ppt. of iodoform while
eB
phenol does not give this test.

CH3CH2OH + 4 NaOI ^ CHI3 i + HCOONa + Nal + 2NaOH + H2O
our
Ethanol Iodoform
ad
(Yellow ppl.)
NaOI
Y
C6H5OH No yellow ppt. of CHI3

Re
Phenol
nd
19. Methanol (CH3OH) and phenol (C^jHgOH)

Fi
These two compounds may be distinguished by the following tests ;

(/) Litmus test. Phenol being acidic turns blue litmus red while methanol being neutral does not give
this test.
(ii) FeCl3 test. Phenol gives a violet colouration with FeCl3 solution while methanol does not.
(Hi) Br2“Water test. Phenol readily decolourises bromine water giving a white ppt. of 2, 4, 6-
tribromophenol but methanol does not. (For reactions, refer to distinction 18).
20. Ethanal (CH3CHO) and propanal (CH3CH2CHO) (CBSE 2008, 2009, 2013, 2018 S)
These can be distinguished by the iodoform test.

Ethanal contains the grouping CH3CO— linked to H and hence reacts with 12/NaOH (or NaOI) to give
yellow ppt. of iodoform but propanal does not contain the grouping CH3CO - (linked to H or C) and hence
does not react with 12/NaOH to give yellow ppt. of iodoform (Iodoform test)
a;30 ‘P’uxdce^'^ New Course Chemistry fXIIlFPTWn
Heat
CH3CHO + 3I2 + 4 NaOH ●»
CHI3 X + HCOONa + 3 Nal + 3 H2O
E(hanal Iodoform Sod. formate
(Yellow ppt.)
or
CH3CHO + 3 NaOI 4 CHI3 + HCOONa + 2 NaOH
U/NaOH
CH3CH2CHO - No yellow ppt. if CHI3
Propanal
21. Ethanal or Acetaldehyde (CH3CHO) and propanone or acetone (CH3COCH3)

(PI). Board 2012 ; CBSE Sample Paper 2019-2020)
Acetaldehyde is an aldehyde while acetone is a ketone. These can be distinguished by the following two
w
tests.
(/) ToHens’ reagent test. Acetaldehyde reduces Tottens' reagent to give shining silver mirror but acetone
F lo
does not.
CH3CHO + 2 [Ag(NH3)2]-^ + 3 OH- ^ CH3COO- + 2 Ag i + 2 H2O -H 4 NH3
ee
Acetaldehyde Tollens’ reagent Acetate ion Silver mirror
Fr
Tollens'reagent
CH3CCX:H3 No action.
Acetone for
ur
(if) Fehling’s solution test. Like Tottens ’ reagent, acetaldehyde also reduces Fehling's solution to a red
ppt. of CU2O but acetone does not.
s
ook
Yo
CH3CHO + 2Cu^-^+50H~ ^ CH3COO- + CU2O i + 3 H2O

eB
Acetaldehyde (From Fehling' s sola.) Acetate ion Cuprous oxide

(Red ppt.)
our
Fehling's solution
ad
CH3COCH3 > No action.

Acetone
22. Acetaldehyde (CH3CHO) and benzaldehyde (C^HsCHO) (CBSE 2008)

Y
Re
These can be distinguished by the following tests :

nd
(0 Iodoform test Acetaldehyde reacts with NaOI (12/NaOH) to form yellow ppt. of iodoform but
Fi
benzaldehyde does not give this test.

CH3CHO + 3 NaOI ■> CHIji + HCOONa + 2NaOH
(Yellow ppt.)
Ij/NaOH
CgHjCHO ■> No yellow ppt. of CHI3.
Benzaldehyde
(ii) Fehling’s solution test. Although acetaldehyde and benzaldehyde are both aldehydes yet aliphatic
aldehydes reduce Fehling’s solution but aromatic aldehydes do not. Thus, acetaldehyde gives a red ppt. of
CU2O with Fehling's solution but benzaldehyde does not.
CH3CHO + ICu^-^+SOH- ^ CH3COO- + CU2O i + 3 H2O
Acetaldehyde (From Fehling ’ssoln.) Acetate ion Cuprous oxide
(Red ppt.)
Fehling's solution
CgHgCHO ■> No red ppt. of CU2O
Benzaldehyde
23.
Propanal (CH3CH2CHO) and propanone {CH3COCH3)
(Raj. Board 2011 ; Hr. Board 2011 ; Manipur Board 2012 ; CBSE 2007, 2008, 2009, 2014, 2016)
(/) Iodoform test. Propanone being a methyl ketone on treatment with 12/NaOH (or NaOI) undergoes
iodoform reaction to give yellow ppt. of iodoform but propanal does not.
CH3COCH3 + 3 NaOI - ^ CHI3 I + CH3COONa + 2 NaOH
ow
Propanone Sod. hypoiodite Iodoform Sod. acetate
{Yellow ppt.)
NaOI
CH3CH2CHO ^ No yellow ppt. of iodoform.
e
Propanal
re
rFl
(a) Tollens’ reagent test. Propanal being an aldehyde reduces Tollens’ reagent to shining silver mirror
but propanone being a ketone does not.
F
CH3CH2CHO + 2 [Ag(NH3>2]+ + 3 OH- ^ CH3CH2COO- + 2 Ag i +4 NH3 + 2 H2O
r
Propanal Tollens’ reagent Propanoate ion Silver mirror
ou
Tollens'reagent
fo
ks
ch3C(x:H3 ^ No silver mirror
Propanone
oo
(Hi) Fehling’s solution test. Like Tollens’ reagent, propanal also reduces Fehling’s solution to red ppt.
Y
of CU2O but propanone being a ketone does not.

eB
CH3CH2CHO + 2 Cu^+ + 5 OH- ^ CH3CH2COO- + Cu20i + 3H2O

ur
Propanal (From Fehling' s sotn.) Propanoate ion Cuprous oxide

{Red ppt.)
ad
Yo
24. Butanal and Butan-2-one (CBSE 2017)

d
These can be distinguished by the following two tests :

Re
in
(0 Iodoform test. Butan-2-one being a methyl ketone on treatment with 1-,/NaOH (or NaOI) undergoes
iodoform reaction to give yellow ppt. of iodoform but butanal does not.
F
CH3CH2COCH3 +3 NaOI ■>

CHl3 + CH3CH2COONa + 2 NaOH
Butan-2-one Iodoform Sod. propanoate
(yellow ppt.)
NaOI
CH3CH2CH2CHO y No yellow ppt. of iodoform
Butanal
(it) Tollen’s reagent test. Butanal being an aldehyde reduces Tollens’ reagent to shining silver mirror
but butan-2-one being a ketone does not.
CH3CH2CH2CHO + 2[Ag(NH3)2r +3 0H- ^ CH3CH2CH2COO- + 2 Agl + 4 NH3 + 2 H2O

Butanal Tollens’ reagent Butanoate ion
Tollens’reagent
CH3CH2COCH3 ■> No silver mirror
Butan-2-one
A/32 7>fuuieefr'4, New Course Chemistry pQl)BS2aD
(Hi) Fehling’s Solution. Like Tollen’s reagent, butanal also radues Fehling’s solution to red ppt. of
CuÔ but butan-2-one being a ketone does not.
CH,CH,CH,CHO + 2Cu^-^+5H- + CH^CH^CH^COO~ + CuÔ + 3 H2O

Butanal
(From Fehling's soln.)
Buianoate ion Cuprous oxide
(Red ppt.)
Propanal (CHjCHjCHO) and diethyl ether (CHjCHjOCHjCHj)

25.
Propanal being an aldehyde gives shining silver mirror with Tollens’ reagent, produces red ppt. of
CU2O with Fehling's solution and also gives a 2, 4-DNP test while diethyl ether does not give any of these
tests.
CH3CH2CHO + 2 [Ag(NH3)2l^ + 3 OH- -4 CH3CH2COO- + 2 Ag i + 4 NH3 + 2 H2O

Propanoale ion Silver mirror
w
Propanal Tollens’ reagent
CH3CH2CHO + 2 Cu 2-^ + 5 OH“ ^ CH3CH2COO- + CU2O + 3 HoO
F lo
Propanal (Fehling' ssoln.) Propanoate ion Cuprous oxide
(Red ppt.)
ee
NO2 NO2
Fr
CH3CH2CH=: O + H : NNH NO2—► CH3CH2CH=NNH NO2 + H2O
Propanal
for
ur
2,4-Dinitrophenylhydrazine Propanal 2,4-dinitrophenylhydrazone
Tollens’ reagent or
s
CH3CH2OCH2CH3 » No silver mirror or red ppt. of CU2O
k
Yo
Fehling’s solution or
or 2, 4-DNP derivative
oo
Diethyl ether 2,4-DNP

eB
26. Benzaldehyde (CgH5CHO) and acetone (CH3COCH3)

r
(0 Iodoform test. Acetone being a methyl ketone on treatment with 12/NaOH (NaOI) undergoes iodoform
ou
ad
reaction to give yellow ppt. of iodoform but benzaldehyde does not. (For reaction of acetone, refer to distinction
23).
Y
(;■/) Tollens’ reagent test Benzaldehyde being an aldehyde reduces Tollens' reagent to produce a shining
nd
silver mirror but acetone being a ketone does not.

Re
CfiHgCHO + 2 IAg(NH3)2]-" + 3 OH" 4 CgHsCOO- + 2H2O -h 2Ag i + 4 NH3

Fi
Benzaldehyde Tollens’ reagent Benzoate ion Silver mirror
Tollens’reagent
CH3COCH3 4 No action
Acetone
27. Phenylacetaldehyde (C5H5CH2CHO) and acetophenone (C^H5COCH3)

(/) Iodoform test. Acetophenone being a methyl ketone gives iodoform test whereas phenylacetaldehyde
does not.
C6H5COCH3 + 3NaOI 4
C6H5COONa 4- CHl3i + 2NaOH
Acetophenone Iodoform
(Yellow ppt.)
NaOI
C6H5CH2CHO > No yellow ppt. of CHI3
Phenylacetaldehyde
(ii) Tollens test and Fehling’s test. Phenyiacetaldehyde being an aldehyde gives a shining silver mirror
with Tollens reagent and reduces Fehling's solution to red ppt. of CU2O but acetophenone being a ketone
does not give these tests.
C6H5CH2CHO + 2 [Ag(NH3)2]+ + 3 OH" > C6H5CH2COO- + 2 Ag i + 4 NH3 + 2 H2O

Phenylacetaldehyde Tollens’ reagent Phenylacetate ion Silver mirror
C6H5CH2CHO + 2Cu2+ + 50H- 4 C6H5CH2COO- + CU2O + 3H2O

(Fehling' s solution) Phenylacetate ion Cuprous oxide
{Red ppl.)
Tollens’reagent
C6H5COCH3 > No silver mirror or red ppt. of CU2O
orFehling’ssolution
Acetophenone
low
28.
Diethyl ketone (CH3CH2COCH2CH3) and acetone (CH3COCH3)
(0 Sodium bisulphite test When treated with a saturated solution of sodium bisulphite, acetone being
a methyl ketone gives a white ppt. of acetone sodium bisulphite addition compound whereas diethyl ketone
e
does not give this test.
re
rF
F
CH
3\ CH3\ /S03Na
C=O + NaHS03
CH3-^ OH
r
Sod. bisulphite
Acetone
fo
u
Acetone sod. bisulphite
ks
addition compound
Yo
{V/hUe ppt.)
oo
CH3CH2^
B
C=0 + NaHS03 - ■> No white ppt.

CH3CH2^ Sod. bisulphite
re
Diethyl ketone
00 Iodoform test Acetone being a methyl ketone gives
u
yellow ppt. of iodoform when treated with

ad
Yo
NaOI (12/NaOH) but diethyl ketone does not give this test.
CH3COCH3 + 3 NaOI ^ CHjCOONa + 2 NaOH + CHI3 i
Acetone
d
Sod. acetate Iodoform

Re
in
{Yellow ppt.)
NaOI
F
(CH3CH2)2C = O ^ No yellow ppt. of CHI3.

Diethyl ketone
29.
Pentanone-2 (CH3COCH2CH2CH3) and pentanone-3 (CH3CH2COCH2CH3)
(NCERT : Assam Board 2013 ; CBSE 2013, 2018 S ; CBSE Sample Paper 2019-2020)
(0 Sodium bisulphite test. 2-Pentanone being a methyl ketone when treated with a saturated solution of
sodium bisulphite gives a white ppt. of 2-pentanone sodium bisulphite addition compound whereas
3-pentanone does not.
CH.
CH3 OH
C = O + NaHSOj > 'C
CH3CH2CH2^ CH3CH2CH2 ^ SOjNa
2-Pentanone
2-Pentanone sod. bisulphite
addition compound
A/34 New Course Chemistry (XIl)E!2aai]
NaHSOj
CH3CH2COCH2CH3 > No white ppt.
3-Pentanone
(/O Iodoform test. 2-Pentanone being a methyl ketone when treated with NaOI (12/NaOH) gives yellow
ppt. of iodoform but 3-pentanone does not.
CH3CH2CH2COCH3 + 3 NaOI ^ CH3CH2CH2COONa + CHI3 i + 2 NaOH
2-Pentanone Sod. butyrate Iodoform
(Yellow ppt.)
NaOI
CH3CH2COCH2CH3 > No yellow ppt. of CHI3

3-Pentanone
w
30. Benzaldehyde (CgHsCHO) and acetophenone (CgHgCOCHj) (NCERT ; CBSE 2012, 2016)
These two compounds can be distinguished by the following tests :

(/) AgN03 test, Benzaldehyde being an aldehyde reduces Tollens’ reagent to give silver mirror test
Flo
but acetophenone does not give this test (For reactions of benzaldehyde, refer to distinction 33 discussed
above).
e
re
(«) Iodoform test Acetophenone being a methyl ketone on treatment with 12/NaOH (NaOI) undergoes
rF
iodoform test to give yeUow ppt. of iodoform but benzaldehyde does not
C6H5COCH3 + 3 NaOI ^ C^HjCOONa + CHI3 i + 2 NaOH
ur
Acetophenone
foIodoform
(Yellow ppt.)
ks
NaOI
CgHjCHO > No yellow ppt. of CHI3

Yo
oo
Benzaldehyde
31. Acetophenone (CgHgCOCHj) and benzophenone (CgHgCOCgHg)
B
(NCERT ; Hr. Board 2012, 2013 ; CBSE 2008, 2009, 2019)

re
These can be distinguished by the iodoform test.

Iodoform test. Acetophenone being a methyl ketone when treated with NaOI (12/NaOH) gives yellow
u
ad
Yo
ppt. of iodoform but benzophenone does not.

C6HgCOCH3 + 3 NaOI - ^ CgHgCOONa + CHIjvl + 2 NaOH
Sod. benzoate Iodoform
Acetophenone
nd
Re
(Yellow ppt.)
NaOI
Fi
C^HgCOCgHg No yellow ppt. of CHI3

Benzophenone
32. Methanoic acid or formic acid (HCOOH) and ethanoic acid or acetic acid (CH3COOH)
(Bihar Board 2011, CBSE 2016)
Formic acid can be easily oxidized to CO2 and H2O but acetic acid cannot. Therefore, formic acid
behaves as a reducing agent whereas acetic acid does not. These may be distinguished by the following
tests :
(i) Toliens’ reagent test. Formic acid reduces Tollens’ reagent to metallic silver but acetic acid does
not.
HCOOH + 2 [Ag(NH3)2]-" + 2 OH” ■> 2Agi + CO2 + 2 H2O + 4 NH3

Formic acid Tollens’ reagent Silver mirror
Tollens' reagent
CH3COOH > No silver mirror
Acetic acid
(/i) Fehling’s solution test Formic acid reduces Fehling's solution to red ppl. of CU2O but acetic acid
does not.
HCOOH + 2Cu2++40H" CU2O i + CO2 + 3 H2O

Formic acid (Fehling 's solution) Cuprous oxide
{Red ppt.)
Fehling's solution
CH3COOH > No red ppt. of CU2O.
Acetic acid
(Hi) HgCl2 test Formic acid reduces HgCl2 to give white ppt. of Hg2Cl2 while acetic acid does not give
this test.
HCOOH + 2 HgCl2 Hg2Cl2 i + 2 HCl + CO2

Formic acid Mercuric Mercurous chloride
w
chloride (White ppt.)
HgClj
F lo
CH3COOH ●> No white ppt. of Hg2Cl2.
Acetic acid
(iv) KMn04 test Formic acid decolourises the pink colour of acidified KMn04 solution while acetic
ee
acid does not give this test.
Fr
5 HCOOH + 2 KMn04 + 3 H2SO4 ^ K2SO4 + 2 MnS04 + 5 CO2 + 8 H2O
Formic acid
for
ur
KMn04/H2S04
CH3COOH ^ Does not discharge pink colour of KMn04 solution
s
ook
Acetic acid
Yo
33.
Benzoic acid (C^HgCOOH) and phenol (CgHgOH)
eB
(NCERT ; Manipur Board 2012 5 Hr. Board 2012, 2013 ; CBSE 2008, 2009, 2013 ; CBSE 2017)
our
These may be distinguished as follows :

ad
(0 NaHCOj test Benzoic acid being a stronger acid than carbonic acid (H2CO3) decomposes NaHC03
to evolve CO2 but phenol being a weaker acid than carbonic acid does not.
Y
Re
nd
C^HjCOOH + NaHC03 ^ C6H5COONa + CO2 T + H2O

Benzoic acid Sod. benzoate
Fi
NaHC03
CgHjOH > No evolution of CO2.
Phenol
(ii) FeCl3 test Phenol gives a violet colouration with neutral FeCl3 solution while benzoic acid gives
buff coloured ppt. of ferric benzoate.
CgHjOH + FeCl3 ●> Molet colouration

Phenol
3 CgHjCOOH + FeClj ^ (CgHjCOOjFe + 3HC1

Benzoic acid Ferric benzoate
(Buff coloured ppl.)

A/36 New Course Chemistry (Xll)BSiai]
34. Phenol (CgHsOH) and acetic acid (CH3COOH)

These may be distinguished as follows :
(0 NaHC03 test. Acetic acid being a stronger acid than carbonic acid (H2CO3) decomposes NaHC03
to evolve CO2 but phenol being a weaker acid than carbonic acid does not.
CH3COOH + NaHC03 ^ CHjCOONa + CO2T + H2O
Acetic acid Sod. acetate
NaHCOj
CeHjOH ^ No evolution of CO2 gas
(«) FeCl3 test. Phenol gives a violet colouration with neutral FeCl3 solution but acetic acid gives buff
w
coloured ppt. of ferric acetate.
■> Violet colouration
CgHgOH + FeCl3
Phenol
^ {CU^COO)^Fe + 3HC1.
o
3 CH3COOH + FeCl3
Ferric acetate
e
Acetic acid
re
{Buff coloured ppt.)
rFl
Benzaldehyde (CgHgCHO) and benzoic acid (C^HgCOOH) (CBSE 2007, 2014)
F
35.
These compounds can be distinguished by the following tests :

(0 NaHC03 test. Benzoic acid being an acid reacts with NaHC03 solution to produce brisk effervescence
r
ou
due to evolution of CO2 while benzaldehyde does not give this test.
C^HgCOOH + NaHC03 » CgHgCOONa
k sfo
Sod. benzoate
+ 002^ + H2O
Benzoic acid
oo
NaHCOj soln.
> No effervescence due to evolution of CO2 gas
Y
C^HjCHO
eB
Benzaldehyde
(»') Tollen’s reagent test. Benzaldehyde being an aldehyde reduces Tollen’s reagent to produce a shining
r
silver mirror while benzoic acid produces only white ppt. of silver benzoate
You
ad
Heat
C6H5CHO + 2[Ag{NH3)2f + 30H- ) CgHgCOO- + 2H2O + 2Ag i + 4NH3

Benzoate ion Silver mirror
Benzaldehyde Tollen’s reagent
d
[Ag(NH3)2r
Re
in
CgHjCOOH CgHjCOOAg
Silver benzoate
F
Benzoic acid
{White ppt.)
36. Methyl acetate or methyl ethanoate (CH3COOCH3) and ethyl acetate or ethyl ethanoate
(CH3COOCH2CH3)
(CBSE 2007)
These two esters can be distinguished if the iodoform test is carried out on their hydrolysis products.
Thus, when ethyl acetate is boiled with excess of NaOH, it gives ethyl alcohol and sodium acetate. If this
alkaline solution is now heated with I2, it will give yellow ppt. due to the formation of iodoform.
Boil
CH3C0CX:H2CH3 + NaOH > CH3COONa + CH3CH2OH

Ethyl acetate Sod, acetate Ethyl alcohol
Heat
CH3CH2OH + 4I2 + 6 NaOH > CHI3 + 5NaI + HCOONa + 5 H2O

Ethyl alcohol Iodoform
{Yellow ppt.)
On the other hand, methyl acetate on hydrolysis gives methyl alcohol which does not give iodoform test.
Boil
CH3COOCH3 + NaOH > CH3COONa + CH3OH
Methyl acetate Sod. acetate Methyl alcohol
l2/NaOH,A
CH3OH > No yellow ppt. of CHI3
Methyl alcohol
37.
Benzoic acid (CgHgCOOH) and eUiyl benzoate (C6H5COOCH2CH3)
(NCERT ; CBSE 2009, 2011)
(0 NaHC03 test. Benzoic acid being an acid produces brisk effervescence with NaHC03 solution
while ethyl benzoate does not.
ow
C^HjCOOH + NaHC03 ^ CgHgCOONa + CO2 T + H2O
Benzoic acid Sod. benzoate
NaHC03 soln.
C6H5COOC2H5 > No effervescence due to evolution of CO2 gas
e
Fl
re
Ethyl benzoate
(if) Iodoform test. Ethyl benzoate on boiling with excess of NaOH solution gives ethyl alcohol (and
F
sodium acetate) which on subsequent heating with iodine gives yellow ppt. of iodoform.
ur
or
Boil
C6H5COOCH2CH3 + NaOH » C6H5COONa + CH3CH2OH
sf
Ethyl benzoate Sod. benzoate Ethyl alcohol
k
Heat
Yo
CH3CH2OH + 4I2 + 6NaOH > HCOONa + CHI3 + 5NaI + 5H2O
oo
Ethyl alcohol Sod. formate Iodoform

B
(Yellow ppt.)
38.
Ethyl cyanide (C2H5CN) and ethyl isocyanide (C2H5NC)
re
or RCN and RNC (CBSE 2007)

u
These may be distinguished by the hydrolysis test:

ad
Yo
Hydrolysis test. Ethyl cyanide on hydrolysis with aqueous mineral acid gives propionic acid which
does not reduce Tollens’ reagent while ethyl isocyanide on similar hydrolysis gives formic acid (along with
d
ethylamine) which reduces Tollens' reagent to give a shining silver mirror.

Re
in
CH3CH2CN + 2H2O + HCl CH3CH2COOH + NH4CI

Ethyl cyanide
F
Propionic acid
(Does not reduce Tollens' reagent)
HCI
CH3CH2—N = C + 2H,0 > CH3CH2NH2 + HCOOH

Ethylamine Formic acid
Ethyl isocyanide
HCOOH + 2 [Ag(NH3)2]-" + 20H~ 2Ag i + CO2 + 4NH3 + 2 H2O
Formic acid Tollens’ reagent Silver mirror
39.
Methylamine (CH3NH2) or ethylamine (CH3CH2NH2) and aniline (CgHjNHj)
(Hr. Board 2011 ; Assam Board 2013 ; CBSE 2010, 2010 S ; CBSE (Foreign) 2017, 2019)
Methylamine or ethylamine is a primary aliphatic amine while aniline is a primary aromatic amine.
These may be distinguished by the azo dye test:
Azo dye test It involves the reaction of any aromatic primary amine with HNO2 (NaN02 + dil. HCI) at
273-278 K followed by treatment with an alkaline solution of 2-naphthol (p-naphthol) when a brilliant orange
or red coloured dye is obtained.
A/38 ^>undee^ New Course Chemistry (XII)
273-278 K
NH2 + HONO + HCl N^NCr + 2H2O
OH OH
2 2
Dil. NaOH
N=NCr + N=N + HC1
1
pH 9-10
Benzenediazonium
chloride
2-Naphthol 1 -Phenylazo-2-naphthol
{Orange dye)
Aliphatic primary amines such as methylamine, ethylamine, etc. under these conditions give a brisk
evolution of N2 gas with the formation of primary alcohols, i.e., the solution remains clear.
w
m-iizY.
CH3NH2 + HONO > CH3OH + Njt + H2O
F lo
Methylamine Methanol
273-278K
C2H^NH2 + HONO ■»
C2H5OH + N2 T + H2O
ee
Ethylamine Ethyl alcohol
Fr
40. Benzamide and p*aminobeiizoic acid
for
(0 NaOH test. When benzamide is boiled with cone. NaOH solution, characteristic smell of NH3 is
produced which turns red litmus paper blue, gives brown ppt. with Messier's reagent and dense white fumes
ur
with a rod dipped in HCl solution.
s
ook
Boil
Yo
C6H5CONH2 + NaOH > CgHsCOONa + NH3 T

Benzamide Sod. benzoate Ammonia
eB
However, p-aminobenzoic acid on similar treatment with NaOH solution does not give ammonia.
{if) Azo dye test. p-Aminobenzoic acid being an aromatic primary amine on treatment with HNO2
our
(NaN02 + dil. HCl) at 273-278 K followed by treatment with an alkaline solution of 2-naphthol (|3-naphthol)
ad
gives an orange coloured azo dye.

273-278 K
>■ HOOC N=NCr + 2H2O
Y
HOOC NH2 + HONO + HCl

Re
nd
p-Aminobenzoic acid
OH OH
Fi
Dil. NaOH
HOOC N=NCr + HOOC N=N + HC1
pH 9-10
Diazonium salt of
p-aminobenzoic acid
2-Naphthol Orange dye
Benzamide, on the other hand, reacts with HNO2 to give brisk effervescence due to evolution of N2 gas.
C6H5CONH2 + HONO CgHsCOONa + N2T + H2O
Benzamide
(Hi) NaHC03 test. p-Aminobenzoic acid being an acid decomposes NaHC03 solution to produce
effervescence due to the evolution of CO2 gas while benzamide does not give this test.
HOOC NH2 + NaHC03 NaOOC NH2 + CO2 t + H2O
p-Aminobenzoic acid
41.
Benzylamine (CgH5CH2NH2) aniline (C6H5NH2)
(CBSE 2010, CBSE Sample Paper 2018-19)
These amines may be distinguished by the following tests :
(0 Nitrous acid test. Benzylamine reacts with nitrous acid to from a diazonium salt which being unstable
even at low temperature, decomposes with evolution of N2 gas.
MONO + H2O
C6H5CH2NH2 HCl > [CgH5CH2~NsNCr] ^ C6H5CH2OH + Njt + HCl
Decomposes
Benzylamine (unstable) Benzyl alcohol
Aniline, on the other hand, reacts with HNO2 froni benzenediazonium chloride which is stable at
273-278 K and hence does not decompose to evolve N2 gas.
MONO, HCl
NH2 Ns NCr
low
273-278 K
(ii) Azo dye test. As stated above amline reacts with HNO2 at 273-278K to form stable benzenediazonium
chloride which on treatment with an alkaline solution of P-naphthol gives an orange dye. For reactions refer
to Distinction 51.
ee
Benzylamine, however, does not give this test.
F
Fr
42.
Ethylamine (CH3CH2NH2) and diethylamine (CH3CH2NHCH2CH3)
These may be distinguished by the following tests :
for
ur
(i) Carbylamine test. Ethylamine is a primary amine. Therefore, it gives carbylamine test, i.e., when
heated with an alcoholic solution of KOH and CHCI3, it gives offensive smell of ethyl isocyanide. In contrast,
diethylamine is a secondary amine and hence does not give this test.
k s
Yo
CH3CH2NH2 + CHCI3 + 3KOH CH3CH2NC + 3KC1 + SHjO
oo
Ethylamine (ale.) Ethyl isocyanide

eB
(/® Amine) (Offensive smell)

CHCl3/KOH(a/c.)
(CH3CH2)2NH
r
^ No reaction
A
ou
ad
Diethylamine
(2'’ Amine)
Y
(ii) Hinsbei^’s reagent test. Ethylamine and diethylamine can be distinguished using Hinsberg’s reagent,
i.e., benzenesulphonyl chloride (CgH5S02Cl). When treated with Hinsberg’s reagent, ethylamine gives N-
nd
Re
ethylbenzenesulphonamide which is soluble in aq. KOH solution.

Fi
C6H5SO2CI + CH3CH2NH2 > C6H5SO2—NHCH2CH3 -I- HCl

Benzenesulphonyl chloride Ethylamine N-Ethylbenzenesulphonamide
(Hinsberg’s reagent) i KOH (aq.)
[C6H5SO2—NCH2CH3] K"- + H2O

(Soluble in aq. KOH)
In contrast, diethylamine gives N, N-diethylbenzenesulphonamide which is insoluble in aqueous KOH
solution.
C6H5SO2CI + (CH3CH2)2NH ■>

C6H5SO2—N(CH2CH3)2 + HCl
Hinsberg’s reagent Diethylamine N, N-Diethylbenzenesulphonamide
(Insoluble in aq. KOH)
(Hi) Liebermann’s nitrosoamine reaction. Diethylamine being a 2° amine gives Liebermann's
nitrosoamine reaction while ethylamine being a T amine does not give this test.
Diethylamine on treatment with HNO2 (generated in situ by the action of dil. HCl on NaN02> gives
yellow coloured oily N-nitrosodiethylamine.
A/40 New Course Chemistry (XI1)C&I9]3
(CH3CH2)2N [h j- ho]—N = o ●> (CH3CH2)2N—N = O + H2O

Diethylamine N-Nitrosodiethylamine
N-Nitrosodiethylamine on warming with a crystal of phenol and cone. H2SO4 gives a green solution
which when made alkaline with aqueous NaOH turns deep blue and then red on dilution.
43. Methylamine (CH3NH2) and dimethylamine (CH3NHCH3)
(As-sam Board 2012 ; Hr. Board 2012 ; CBSE 2007,2010,2010 S, 2019)
These may be distinguished by carbyalmme test, Hinsberg’s test and liebermam nitrosoamme reaction as discussed
in distinction 42. For reactions, just substitute CH3NH2 for CH3CH2NH2 and (CH3)2NH for (CH3CH2)2NH.
44. ; Aniline (CgH5NH2> and N-methylaniline (CgH5NHCH3)
or Aniline and N-ethylaniline (CBSE 2007, 2010 ; Raj. Board 2012)
Aniline is a primary aromatic amine while N-methylaniline (or N-ethylaniline) is a secondary aromatic
w
amine. These may be distinguished by any of the following three tests,
(i) Carbylamine test. Aniline being a primary amine gives carbylamine test, Le., when heated with an
alcoholic solution of KOH and CHCI3, it gives offensive smell of phenyl isocyanide. In contrast,
F lo
N-methylaniline (or N-ethylaniline) being a secondary amine does not give this test.
^ CgHjN^C 3KC1 + 3H2O
ee
C6H5NH2 + CHCI3 + 3 KOH
Fr
Aniline (ale.) Phenyl jsocyanide
(1° Amine) {Offen.iive smell)
for
CHCl3/KOH(a(c.)
ur
^ No reaction
CgHj—NH—CH3 or
C6H5-NH-C2H5
N-Methylaniline (2° Amine) N-Elhylaniline {2° Amine)
s
(ii) Azo dye test/Liebermann’s nitrosoamine reaction. Aniline being a V aromatic amine gives Azo
ook
Yo
dye test while N-raethylaniline (or N-ethylaniline) being a 2° amine gives Liebermann’s nitrosoamine reaction.
Aniline on treatment with HNO2 (NaN02 + dil. HCl) at 273-278 K gives benzenediazonium chloride
eB
which on subsequent treatment with an alkaline solution of |3-naphthol gives a brilliant red azo dye. For
equations. Refer to Distinction 39.
On the other hand, N-methylaniline under these conditions gives yellow coloured oily N-methyl-N-nitroaniline.
r
ou
ad
273-278K
CgHj—NH or CgHj—NH + HO—N = 0

Y
CH3 C2H5
Re
nd
N-Methylaniline N-Ethylaniline C^Hj—N—N = 0 for C^Hj—N—N=0 -1-H2O

Fi
CH3 C2H5
N-Methyl-N-nitrosoaniline N-Ethyl-N-nitrosoaniline
{Yellow oil) {Yellow oil)
N-Methyl-N-nitrosoaniline or N-ethylaniline on warming with a crystal of phenol and cone. H2SO4
gives a green solution which when made alkaline with aqueous NaOH turns deep blue and then red on
dilution—Liebermann’s nitrosoamine reaction.
{Hi) Hinsberg’s reagent test When warmed with benzenesulphonyl chloride {Hinsberg’s reagent),
aniline gives N-phenylbenzenesulphonamide which dissolves in aqueous KOH solution.
C6H5SO2CI -h C6H5NH2 ^ C6H5SO2—NH—CgHg + HCl
Benzenesulphonyl chloride Aniline N-Phenylbenzenesulphonamide
{Hinsberg’s reagent) i KOH (09.)
[C6H5SO2—NCgHj] K-" H2O
{Soluble in aq. KOH)
In contrast, N-methylaniline (or N-ethylaniline) under similar conditions, gives N-methyl-N-

phenylbenzenesulphonamide (or N-ethyl-N-phenylbenzenesulphonamid e) which does not dissolve in aq. KOH
due to absence of H-aiom on nitrogen.
C6H5SO2CI +
C6H5NHCH3 (or C6H5NHC2H5) -HCl
Hinsberg’s reagent N-Methylaniline N-Ethylaniline
C.H^SO^ N—aH
6“5 or CgHgS02—N—CgHj
CH3
N-Methyl-N-phenylbenzene- N-Ethyl-N-phenylbenzene
sulphonamide sulphonamide
w
{Insoluble in aq. KOH) {Insoluble in aq. KOH)
45.
N-Methylaniline (CgHgNHCHa) and N,N-dimethylanaine (CgHgNfCHglj)
These amines can be distinguished by Liebermann nitroso reaction and Hinsberg’s reagent test,
Flo
(i) Libermann nitroso reaction. N-Methylaniline being a 2® amine reacts with HNO2 (NaN02 + HCl)
e
at 273-278 K to give yellow coloured oily N-methyl-N-nitrosoanil ine. This on warming with a crystal of
re
phenol and cone. H2SO4 gives a green solution which when made alkaline with aqueous NaOH turns deep
F
blue and then red on dilution.
ur
r
H N = 0
N—CH3 +HO—N = 0
273-278 K
fo N—CH3 +H2O
ks
Yo
Nitrous acid
N-Methylaniline (2®)
oo
N-Methyl-N-nitrosoaniline
B
On the other hand, N,N-dimethylamine being a S’’ aromatic amine on treatment with HNO2 undergoes
electrophilic substitution by nitrosonium ion at p-position of the phenyl ring to form green-coloured-
re
p-nitroso-N,N-dimethylaniline. For example.

u
ad
CH3. CH3.
Yo
N + HONO N N = 0
CH3 CH3
d
Re
N,N-Dimethylaniline (3®) /j-Nitroso-N,N-dimeihylaniline {green)

in
(«) Hinsberg’s reagent test N-Methylaniline being a 2^’ amine on treatment with Hinsberg’s reagent,
F
i.e., benzenesulphonyl chloride (CgHg-S02Cl) forms N-methyl-N-phenylbenzenesulphonamide which does

not dissolve in aqueous NaOH due to absence of a H atom on the N-atom.
CH,
I "
C6H5-NH-CH3 + C6H5SO2CI ^ — + HCl
N-Meihylaniline (2®) Benzenesulphonyl N-Methyl-N-phenyl-
chloride benzenesulphonamide
{Hinsberg's reagent) {Insoluble in aq. NaOH)
On the other hand, N,N-dimethylaniline being a 3° amine does not react with Hinsberg’s reagent and
hence can be easily distilled off from the reaction mixture.
^CH3 CgHjSOjCl
No action
CH3
N,N-Dimethylaniline (3®)
APPENDIX
ow
TYPICAL ALIPHATIC
AND AROMATIC CONVERSIONS
e
re
rFl
I. ASCENT OF SERIES
F
The conversion of an organic compound into its higher homologue is called ascent of series or stepping
up the series. In these conversions, the length of the carbon chain is increased by adding one or more carbon
atoms at a time. For this purpose, one or more of the following reactions are used :
r
ou
fo
(i) By Wurtz reaction (ii) Through cyanide (-C s N) group (iii) Through Grignard reaction
ks
Wurtz reaction is especially used for ascent of series of hydrocarbons while cyanide and Grignard
reactions are used for other classes of organic compounds.
oo
In all these reactions, the starting material is an alkyl halide. Therefore, to bring about these conversions,
Y
the given compound is first converted into its corresponding alkyl halide which is then subjected to any one
B
of the above three reactions. For example,

(i) Conversion of a lower alkane, R—H to a higher alkane, R—R through Wurtz reaction.
re
ou
Na/Dry ether
Y
R—H R—Br > R—R

ad
-HBr (Wurtz reaction)

Alkane Alkyl bromide Alkane
Unsymmetrical alkanes are, however, best prepared by Corey-House reaction, i.e..

d
in
R'-Br
Re
Li/ether Cul
R—Br R—Li R2CuLi ^ R—R'
-LiBr -Lil Dry ether
F
Alkyl bromide Alkyllithium Lithium dialkylcuprate

(ii) Conversion of a lower alcohol, ROH to a higher alcohol, RCH2OH through cyanide method.
P + I2 Ale. KCN UAIH4 MONO
ROH ^ R—I ^ R—CN ^ RCH2NH2 ^ RCH2OH
or PI3 A or Na/alcohol (NaNOj+dil. HCl)
Alcohol Alkyl Alkyl (Reduction) 1“ Amine Higher alcohol
iodide cyanide
(iii) Conversion of a lower alcohol, ROH to a higher alcohol, RCH2OH through Grignard reaction.
PBrj Mg HCHO H*/H20
ROH > R—Br ^ R—MgBr > [RCH20MgBr] ^ RCH2OH
in dry ether
Alcohol Alkyl Grignard Addition product Higher alcohol
bromide reagent
A/42
TYPICAL ALIPHATIC AND AROMATIC CONVERSIONS A/43
EXAMPLES ON ASCENT OF SERIES THROUGH

WURTZ REACTION/COREY-HOUSE REACTION
mMethane to Ethane
CI2, light Na/eiher
CH4 - -HCl CH3CI > CH3—CH3
(Wurtz reaction)
Methane Methyl chloride Ethane
j^Êthane to n-Butane
Bf2/Av Na/ether
CH3—CH3 -HBr > CH3CH2Br > CH3CH2—CH2CH3
(Wurtz reaction)
Ethane Ethyl Bromide ri-Butane
mPropene to 2,3-dimethylbutane
CH» CH, CH,
w
HBr I Na/ether I I
CH3CH = CH2 ■>
CH3—CH—Br > CH3—CH—CH—CH3
(Mark, addition) (Wurtz reaction)
Propene 2-Bromopropane 2, 3-Dimethylbutane
Flo
Ethane to propane
e
Cl2>hv Li/ether Cul
re
CH3CH3 -HCl
^ CH3CH2CI -LiCl
CH3CH2L1 ■)
(CH3CH2)2CuLi
-Lil
rF
Ethane Ethyl Chloride Ethyllithium Lithium diethylcuprate
CHjBr, dry ether
ur
CH3CH2CH3
fo
(Corey-House reaction)
Propane
ks
EXAMPLES ON ASCENT OF SERIES THROUGH CYANIDE METHOD
Yo
m Methanol into ethanol
oo
(CBSE 2007 ; Hr. Board 2010 ; Assam Board 2012)

P + I2 KCN
Na/C2H50H HONO
B
CH3OH ^ CH3I ^ CH3CN > CH3CH2NH2 ^ CH3CH2OH

or PI3 -KI
(Reduction) -N2,-H,0
re
Methanol Methyl iodide Acetonitrile Ethylamine Ethanol
H+/H2O UAIH4 or B2Hg/elher

u
ad
Alternatively, CH3CN ^ CH3COOH ^ CH3CH2OH

Yo
(Hydrolysis) (Reduction)
Acetonitrile Acetic acid Ethanol
iodide into ethyl iodide

nd
Re
KCN Na/C2H50H HONO P-fl2

Fi
CH3I - -KI ^ CH3CN ^ CH3CH2NH2 CH3CH2OH ^ CH3CH2I

(Reduction) or PI3
Methyl iodide Acetonitrile Ethylamine Ethanol Ethyl iodide
Methanamine to ethanamine (Methylamine into ethylamine) (Chhatisgarh Board 2012)

HONO P + I2 KCN
Na/C2H50H
CH3NH2 -N2,-H20 ^ CH3OH or PI -> CH3I —-KI ^ CH3CN > CH3CH2NH2
3 (Reduction)
Methanamine Methanol Methyl iodide Acetonitrile Ethanamine
OfFormic acid to acetic acid

LiAlH^/ether P + I2 KCN
H+/H2O
HCOOH > CH3OH
(Reduction) or PI CH3—I - - KI ^ CH3CN ^ CH3COOH
Formic acid (Hydrolysis)
Methyl alcohol Methyl iodide Acetic acid
A/44 ‘Pnadeefi.'4. New Course Chemistry (XIl)BZaMQ
^Êthanoic acid to propanoic acid (Acetic acid to propionic acid)

LiAlH 4/ether P + l2 KCN HVH2O
CH3COOH > CH3CH2OH ^ CH3CH2I -KI
» CH3CH2CN - ■>
(Reduction) or PI3 (Hydrolysis)

Ethanoic acid Ethanol Ethyl iodide Propionitrile
(Acetic acid) {Ethyl cyanide)
CH3CH2COOH
Propanoic acid
(Propionic acid)
EXAMPLES ON ASCENT OF SERIES THROUGH GRIGNARD REACTION
m Methanol to ethanol (Methyl alcohol to ethyl alcohol) (HP Board 2011 ; Assam Board 2012)
w
HCHO
Mg/elher
CH3OH > CH3I - CH3MgI [CH3CH20MgI]
F lo
or PI3 (Crignard reaction)
Methanol Methyl iodide Methylmag. iodide Addition product
H+/H2O
ee
^ CH3CH2OH
Fr
(Hydrolysis)
Ethanol
Qj Methanol to 1-propanol (Methyl alcohol to n-propyl alcohol)

for o
ur
/'A
PBr3 Mg/elher CH2—CH2/ether
CH3OH > CH3Br CH3MgBr
s
or P + Br2 (Crignard reaction)
ok
Methyl mag. bromide
Yo
Methanol Methyl bromide
H+/H2O
o
^ CH3CH2CH2OH
eB
[CH3CH2CH20MgBr]
(Hydrolysis)
Addition product I-Propanol
r
ou
ad
Q| Methanol to 2-propanol (Methyl alcohol to isopropyl alcohol)

OMgl
Y
P + 1
Mg/elher CH3CHO
CH3OH ^ CH3—I - + CH3MgI CH3—CH—CH3
(Crignard reaction) Addition product
nd
or PI3
Re
Methanol Methyl Iodide Methylmag. iodide

Fi
OH
H+/H2O I
(Hydrolysis)
^ CH3—CH—CH3
2-PropanoI
m Ethanol to 1-propanol (Ethyl alcohol to n-propyl alcohol)

PBr. HCHO
3 Mg/ether
CH3CH2OH CH3CH2Br ^ CH3CH2MgBr (Crignard reaction)
or P + Br2
Ethanol Ethyl bromide Ethylmag. bromide
H+ZHjO
[CH3CH2CH20MgBr] CH3CH2CH2OH
Addition product l-Propanol
Ethanol to 2-propanol (CBSE 2005 S)
+ OMgBr
C5H5NHCi03Cr(PCC)/CH2Cl2 CH3MgBr
CH3CH2OH ^ CH3CHO
{Grignard reaction) ^ CH3—CH—CH3
(Controlled oxidation)
Ethanol Acetaldehyde Addition product
OH
H'^/H20
-Mg(OH)Br
CH3—CH—CH3
2-PropanoI
Q| Ethanol to 1-butanol (Ethyl alcohol to n-butyl alcohol) 0,
PBr.
Mg/ether CH2—CH2/ether
^ CH3CH2Br
w
CH3CH2OH ^ CH3CH2MgBr ■>
or P + Br2 (Grignard reaction)

Ethanol Ethyl bromide Ethylmag. bromide
Flo
H'^/H20
[CH3CH2CH2CH20MgBr] ^ CH3CH2CH2CH2OH
e
Addition product 1-Butanol
re
F
1^ Methanal to ethanal (Formaldehyde to acetaldehyde)
O
ur O
r
H+/H2O
CH3MgBr
fo
Cu/573 K
H—C—H > [CH3CH20MgBr] ^ CH3CH2OH ^ CH3—C—H
ks
Methanal Addition product Ethyl alcohol or C5H5NHCr03Cr, Ethanal
Yo
CH2CI2
oo
n. DESCENT OF SERIES
B
The conversion of an organic compound into lower homologue is called descent of series or stepping
re
down the series. In these conversions, the length of the carbon chain is decreased by one carbon atom at a
time by any one of the following two methods :
u
ad
(i) By heating sodium salt of a fatty acid (decarboxylation ) with soda-lime (CaO + NaOH)
Yo
(ii) Hofmann degradation of amides or Hofmann bromamide reaction.

d
EXAMPLES ON DESCENT OF SERIES BY HEATING SODIUM

Re
in
SALT OF A FATTY ACID WITH SODA-LIME (CaO + NaOH)

F
Ethane to methane
CI2//JV Aq. KOH K2Cr207/H2S0

CH3CH3 -HCI
■> CH3CH2CI (Hydrolysis)
^ CH3CH2OH (Oxidation)
% CH3COOH
Ethane Ethyl chloride Ethanol Acetic acid
NaOH CaO + NaOH, A

^ CH3COONa ^ CH4
-H2O (Decarboxylation)
Sod. acetate Methane
(CBSE 2007)
Acetaldehyde to methane
K2Cr207/H2S04 NaOH CaO + NaOH, A
CH3CHO CH3COOH ^ CHjCoom ^ CH4
(Oxidation) -H2O (Decarboxylation)
Acetaldehyde Acetic acid Sod. acetate Methane
A/46 7\<^deefb.'<a. New Course Chemistry fXmP2gnwn
Qj Propane to ethane
Cl,/Av Ale. KOH, A
CH3CH2CH3 -HCl
CH3CH2CH2CI + CH3CHCICH3 -HCl
^ CH3CH = CH2
Propane I-Chloropropane 2*Chloropropane Propene
(1 ; 1 mixture)
(OB2H6 KjCÔ^/HjSO^ NaOH

> CH3CH2CH2OH ^ CH3CH2COOH ^ CH3CH2COONa
(H) H202~Na0H {Oxidation) -HjO
{Hydroborauon-oxidation) 1-Propanol Propanoic acid Sod. propanoate
CaO + NaOH, A
CH3CH3
-NajCOj
{Decarboxylation) Ethane
w
EXAMPLES ON DESCENT OF SERIES BY HOFMANN BROMAMIDE REACTION
This method is easier and most of the conversions are
achieved via this route. A few examples are:
F lo
KB Ethanol into methanol or Ethyl alcohol to methyl alcohol
ee
K2Cr207/H2S0 NH Heal
CH3CH2OH % CH3COOH ^ CH3COONH4 - -H2O ^ CH3CONH2
Fr
{Oxidation)
Ethanol Acetic acid Ammonium acetate Acetamide
Brj/KOH HONO
for
ur
{Hofmann
CH3NH2 ^ CH3OH
-N2.-H2O
bromanide Methanamine Methanol
reaction)
ks
KB £thyl iodide into methyl iodide
Yo
oo
Aq. KOH NH
K2Cr207/H2S0
CH3CH2I ^ CH3CH2OH ^ CH3COOH ^ CH3COONH4
eB
{Hydrolysis) {Oxidation)
Ethyl iodide Ethanol Acetic acid Amm. acetate
or Ethanoic acid
r
Br,/KOH
ou
A HONO P + I2
ad
> CH3CONH2 > CH3NH2 ● ^ CH3OH > CH3I

-H2O {Hofmann bromamide reaction) -Nj.-HjO or PI
^ Methyl iodide
Y
Acetamide Methylamine Methanol

or Methamine
Q| Acetic acid to formic acid

nd
Re
As discussed in
Fi
CH3COOH conversion 2 above ^ CH3OH HCOOH

Acetic acid Methanol
{Oxidation) Formic acid
Êthanamine to methanamine (Ethylamine into methylamine) (HP Bourd 2011 ;

Chhatisgarh Board 2012)
or Acetic acid to methylamine (Assam Board 2012)
HONO K2Cr207/H2S0 NH3
CH3CH2NH2 > CH3CH2OH CH3COOH ●»
-Nj. -H2O {Oxidation)
Ethanamine Ethanol Acetic acid
A Brj/KOH
CH3COONH4 - CH3CONH2 > CH3NH2
Amm. acetate
-HjO {Hofinann bromamide reaction)
Acetamide Methanamine
Acetic acid to methylamine (CBSE 2007)

or Ethanoic acid to methanamine (CBSE Sample Paper 2018-2019)
Included in conversion 4 above.
Acetaldehyde into formaldehyde

K2Cr207/H2S0 NH
CH3CHO ^ CH3COOH ^ CH3COONH4 —^ CHXONH,

(Oxidaiion) -H2O ^ ^
Acetaldehyde Acetic acid Amm. acetate Acetamide
Br2/KOH MONO Cu
» CH3NH2 > CH3OH -573 K
^ HCHO
{Hofmann bromamide reaction) -N2.-H2O
Methylamine Methyl alcohol Formaldehyde
Q Propanoic acid to ethanoic acid (Propionic acid to acetic acid) (CBSE 2019)
NH Heat B12/KOH
CH3CH2COOH ^ CH3CH2COONH4 -H2O
^ CH3CH2CONH2
{Hofmann
Propanoic acid Amm. propionate Propionamide bromamide reaction)
w
HONO K2Ct20-j/H2^04
CH3CH2NH2 ^ CH3CH2OH » CH3COOH
-N2.-H20 {Oxidation)
Ethylamine Ethanol Ethanoic acid
Flo
1^ Ethyl cyanide to ethanoic acid (CBSE 2012}
ee
H+/H2O
CH3CH2CN ^ CH3CH2COOH
Fr
{Hydrolysis)
Ethyl cyanide Propanoic acid
Now convert propanoic acid to ethanoic acid as explained in conversion 7 above.
for
ur
Alternatively, refer to conversion 20, page A/60.
Propionic acid to isopropyl alcohol
ks
(0 First convert propionic acid to ethyl alcohol as given in conversion 6 above.
Yo
oo
(«) Now convert ethyl alcohol to isopropyl alcohol as follows :

OMgl
B
OH
Cu CH3MgBr
H'^/H20 I
re
CH3CH2OH ^ CH3CHO CH3—CH—CH3

573 K dry ether
Addition product -Mg(OH)Br
^ CH3—CH—CH3
Ethyl alcohol Acetaldehyde Isopropyl alcohol
ou
ad
10. Propionamide into acetamide

Y
Brj/KOH HONO
CH3CH2CONH 2 > CH3CH2NH2 > CH3CH2OH
{Hofinann bromamide) -N2.-H20 {Oxidation)
nd
Re
Propionamide reaction Ethylamine Ethanol

Fi
NH A
CH3COOH ^ CH3COONH4 -H2O

^ CH3CONH2
Acetic acid Amm. acetate Acetamide
ALIPHATIC CONVERSIONS
TYPE I. TWO-STEP CONVERSIONS
m Acetylene into acetic acid

H2O. Oil. H2SO4 O2. Manganese acetate
CHsCH
^ CH3CHO ^ CH3COOH
HgS04> 333 K or K2Cf207 + H2SO4
Acetylene Acetaldehyde Acetic acid
Acetylene to ethanol
H2O. Dil. H2SO4 NaBH4
CH = CH
^ CH3—CHO in ether
>
CH3CH2OH
HgS04,333K
Acetylene Acetaldehyde Ethanol
A/48 ^>utdeep-'4r New Course Chemistry (XII)CZsnD
|cg Acetic acid to acetaldehyde (J & K Board 2011)
PCI5 Hj + Pd/BaS04 + S
CH3COOH CH3COCI ^ CH3CHO
-POCI3, -HCl {Rosenmund reduction)
Acetic acid Acetyl chloride Acetaldehyde
Q Acetic acid to acetone (J&K Board 2011)
CaCOj cn^coo^ Ca Dry distil

CH
3\
CH3COOH c=o
-CO2. -HjO CH3COO -CaC03
Acetic acid
Cal. acetate Acetone
m Propionic acid to 3-pentanone

CH3CH2C00^ Ca CH3CH2.
ow
CaCOj Dry distil
CH3CH2COOH N: = o
r CH3CH2^
■>
Propionic acid
-CO2, -H2O CH3CH2C00^ -CaCO
Cal. propionate 3-Pentanone
Q| Formic acid to formaldehyde
e
Fl
HCOO\ Ca
re
CaCOj Dry distil
HCOOH c = o
-CO2, -HjO HCOO -CaCOj H
F
Formic acid
Cal. formate Formaldehyde
ur
m l-Propanol to 2-bromopropane
or
Cone. H2SO4
sf HBr
CH3CH2CH2OH ^ CH3CH = CH2 > CH3—CH—CH3
k
433-443 K (Mark, addition)
Yo
I-Propanol (Dehydration) Propene Br
oo
2-Bromopropane
B
Q|2-Propanol to 1-bromopropane
re
OH
I Cone. H2SO4 HBr, peroxide
u
CH3—CH—CH3 > CH,CH = CH 2 CH3CH2CH2—Br

ad
3
433-443 K (Anti—Mark, addn.)
Yo
2-Propanol (Dehydration) Propene l-Bromopropene
Methyl bromide (bromomethane) to acetic acid (ethanoic acid)

d
Re
in
Mg/ether (/) Solid CO2

CH3—Br CH3MgBr ■ 4
CH3COOH
F
(ii) H'^/H20
Methyl bromide Methylmag. bromide Acetic acid
Ale, KCN, A H-^/H2®

Alternatively, CH3—Br -KBr
CH3C = N ^ CH3COOH
(Hydrolysis)
Methyl bromide Acetonitrile Acetic acid
10. Methanol to acetic acid

Asdiscussedin
P+ Br2
CH3OH ^ CH3—Br conversion 9above ^ CH3COOH
Methanol
or PBr3
Methyl bromide Acetic acid
mu n-Propylamine from ethyl chloride

LiAlH
Ale. KCN
CH3CH2CI A
> CH3CH2CN
J ^
U CH3CH2CH2NH2
in ether
Ethyl chloride Ethyl cyanide n-Propylamine
12. Ethylene to acetylene

Br^ NaNHj/liq. NH3.196K
CH2 = CH2 BrCH2—CH2Br CH^CH
Ethylene
CCI4 (Dehydrobrominalion)
Ethylene dibromide Acetylene
13. Propylene to propyne
Brj NaNH2/liq- NH3.I96K

CH3—CH = CH2 > CH3—CHBr—CH2Br CH3—CsCH
CCI4 (Dehydrobromimtion)
Propylene Propylene dibromide Propyne
14. Acetylene into propyne
NaNHj.liq NH3 CH3I
CH = CH
196 K
CHsC-Na-"
-Nal
CH3—C = CH
Acetylene Sod. acetylide Propyne
w
Propyne to 2-butyne
F lo
NaNHj. liq NH3 CH,I
CH3—CsCH 196 K ^ CH3—CsC“Na+ ..1
^ CH-—CsC—CH.,
j
-Nal
Propyne Sod. propynide 2-Butyne
ee
16. Acetylene (or methyl iodide to 2-butyne)
Fr
NaNHj/liq. NH3 2CH3I
CHsCH ^ Na-"-CsC-Na-"
^ CH3—CsC—CH3
Acetylene
l%K
Disodium acetylide for-2Nal

ur
2-Butyne
17. Ethane into ethylene
s
ook
Yo
CI2//1V Ale. KOH. A

CH3—CH3 ^ CH3—CH2CI > CH2 = CH2
eB
-HCl -HCl
Ethane Ethyl chloride Ethylene
(Dehydrochlorination)
18. Methyl bromide to ethylamine
r
ad
ou
Ale, KCN LiAlH4, dry ether

CH3—Br -KBr
CH3CN - CH3CH2NH2
(Reduction)
Y
Methyl bromide Methyl cyanide Ethylamine

Re
nd
19. Propane into propylene or propene. As discussed in conversion 3, page A/46.

Fi
S Ethane to diethyl ether

CI2/AV Dry Ag20
CH3—CH3 -HCl
^ CH3CH2CI ^ CH3CH2—O—CH2CH3
-2AgCl
Ethane Ethyl chloride Diethyl ether
21. Ethyl alcohol to diethyl ether
P/I2 CH3CH20Na
CH3CH2OH > CH3CH2—I -Nal
CH3CH2—O—CH2CH3
Ethyl alcohol Ethyl iodide (Williamson synthesis) Diethyl ether
A/50 New Course Chemistry CXII)ESsISD
22. Acetaldehyde to lactic acid (2-hydroxypropanoic acid) (CBSE 2013)
H H
H
HCN
CH3—C =0 > CH3—C—CN (Hydrolysis)

CH3—C—COOH
I
Acetaldehyde OH OH
Acetaldehyde Lactic acid

cyanohydrin 2-Hydroxypropanoic acid
23. Ethanol to 1,1-dichloroethane
CjHjNHCrOjCr (PCC) PCI5 Cl

CH3CH2OH
CH2CI2
^ CH3—CHO
Ethanal
-POCI3, -2 HCl > CH3—CHC;^ Cl
Ethanol
w
1, 1-DichJoroethane
24. Propene to isopropyl alcohol or propan-2-ol (CBSE 2007)
OH
Flo
Br
Aq. KOH, A i
HBr
CH3CH = CH2 ^ CH3—CH—CH3 4
CH3—CH—CH3
ee
-KBr
(Mark, addn.)
Propene Isopropyl bromide (Hydrolysis) Isopropyl alcohol
Fr
Cone. H2SO H2O, boil
Alternatively, CH3CH = CH2 CH3—CH—CH3 - ^ CH3—CH—CH3
for
-H2SO4
ur
(Mark, addn.)'1 I
Propene OH
OSO3H
Isopropyl hydrogen sulphate Propan-2-ol
s
ok
Yo
25. Propene to Acetone (CBSE (Foreign) 2017)
Bo
Convert propene to propan-2-ol by any one of the two methods discussesd in Conversion in 24 and
then convert prop-2-ol to propanone as follows :
re
CsHsNHCrOjCl (PCC)
^ CH3-C-CH3
ou
CH3-CH-CH3
ad
CH2CI2
Y
OH o
Propan-2-ol Acetone
nd
Re
^ Propionic acid to lactic acid

Fi
Br OH
Br2, Red P Aq. NaOH, A
CH3—CHj—COOH (H.V.Z. reaction)
^ CH3—CH—COOH (Hydrolysis) > CH3—CH—COOH
Propionic acid a*Bromopropionic acid Lactic acid
Ethyne to 3-hydroxybutanal
+ H2O
CH^CH ^ CH3—CHO
Oil. H2SO4. HgS04. 333 K
Ethyne Ethanal
OH
Dil. NaOH
CH3—CHO + H—CH2—CHO ^ CH3—CH—CH2—CHO
(Aldol condensation)
Ethanal (2 molecules) 3*Hydroxybutanal
28. Ethanol to 3-hydroxybutanal (NCERT, CBSE 2009)

OH
Cu/573 K Dil. NaOH
CH3CH2OH > CH3CHO
or PCC/CH2CI2 (Aldol condensation) ^ CH3—CH—CHjCHO
Ethanol Ethanal 3-Hydroxybutanal
29. Propanone to propene (NCERT ; CBSE 2010, CBSE (D) 2017, CBSE 2017, 2018 S)
O OH
NaBH4.CH30H Cone. H2S04.443K
CH3—C—CH3 ^ CH3—CH—CH3 ^ CH3—CH = CH2
(Reduction) (Dehydration)
Propanone 2-Propanol Propene
30. Propanal to butanone

OH O
w
(i)CH3MgBr K2Cr20-7/H2S0
CH3CH2CHO
(«●) H3O
CH3CH2—CH—CH3 or PCC/CH2CI2
U CH3CH2—C—CH3
F lo
Propanal Butan-2-ol
(Oxidation) Butanone
31. Propanoic acid to propenoic acid
ee
Br
Br2/red P I KOH (ale), A
Fr
CH3CH2COOH H.V.Z. reaction 4 CH3—CH—COOH » CH2 = CH—COOH
(Dehydrobromination)
Propanoic acid 2-Bromopropanoic acid Propenoic acid
for (Acrylic acid)
ur
Hept-l-ene to heptanal
oks
(i) BjHg/ether PCC/CH2CI2

Yo
CH3(CH2)4CH = CH2 ^ CH3(CH2)4CH2CH20H » CH3(CH2)5CH0
(II) H202/NaOH
o
Hept-l-ene Heptan-l-ol Heptanal

eB
33. Hept-l-ene to heptanoic acid

our
(/) B2Hg/ether
ad
(i) KMn04/KOH, A
CH3(CH2)4CH = CH2 ^ CH3(CH2)4CH2CH20H
(ii) H202/Na0H (11) Dil. H2SO4
Hept-l-ene Heptan-l-ol
Y
CH3(CH2)4CH2C00H
Re
nd
Heptanoic acid
1, 2-Dichloroethane to 1,1-dichIoroethane
Fi
Ale. KOH, A HCl

CICH2—CH2CI -HCl
> CH2 = CHC1 Mark. addn.
^ CH3—CHCI2
1, 2-Dichloroethane Vinyl chloride 1, 1-DichIoroethane
Ethanal to but-2-enal (CBSE 2010. 2013)
O O OH
Dil. NaOH I
CH3—C—H + H—CH^—C—H (Aldol condensation)
^ CH3—CH—CH^—CHO
Ethanal (2 molecules) 3-Hydroxybutanal
H+ZHjO, A
CH3—CH = CH—CHO
-H2O (Dehydration)
But-2-enal
A/52 ‘P'uxdetfr New Course Chemistry (XII) w«li*n
3 h 2<£thanediol (ethylene glycol) from ethanol (ethyl alcohol) or ethanol to 1,2-ethanediol

CH^ Cone. H2SO4 CH, Cold dil. alk. KMn04 CH.OH
1 II > ]I
433-443 K
CH2OH (Dehydration)
CH2 (Baeyer’s reagent)
CH2OH
Ethanol Ethylene I, 2-Ethanediol
37. 2-Bromopropane to l>bromopropane (Hr. Board 2012)
Br
Ale. KOH, A HBr. peroxide
CH3—CH—CH3 ^ CH3—CH = CH2 (Anti-Mark, addn.)
> CH3CH2CH2—Br
(-HBr)
2“Bromopropane Propene 1-Bromopropane
3 1-Bromopropane to 2-bromopropane (Hr. Board 2011)

HBr
w
Ale. KOH, A
CH3CH2CH2—Br ^ CH3- CH = CH2 (Mark, addn.)
^ CH3—CH—CH3
(-HBr)
I-Bromopropane Propene Br
Flo
2'Bromopropane
Sm 2-Chlorobutanoic acid to 3-chlorobutanoic acid
ee
Cl O
Fr
I Ale. KOH, A HCl
CH3CH2—CH—COOH CH3CH = CH—C—OH (1,4-Addition)

-KCl, -H2O
2-Chiorobutanoic acid (DehydrochJorination)
for
But-2*en-l-oic acid
ur
Cl OH Cl
Tautomerises
ks
CH3—CH—CH = C—OH > CH3—CH—CH2—COOH
Yo
oo
3-Chlorobutanoic acid
eB
40. Ethyl cyanide to ethylamine

Dissolve in cone. HCl or O
r
HjSO^ and then pour in H2O Br2-NaOH

ou
ad
CH3CH2CN CH3CH2—c NH2 (Hofinann bromamide

^ CH3CH2NH2
(Partial hydrolysis)
reaction
Ethyl cyanide Propionamide Ethylamine
Y
41. Calcium acetate to mesitylene or Acetone to mesitylene (Jharkhand Board 2011)

Re
nd
CH3
Fi
CH3COO. CH3
Dry distil Cone. H2SO4
3 Ca ► 3 c=o
-3CaC03 -3 H2O
CH3COO CH3 H3C CH3
Cal. acetate Acetone Mesitylene
42. Benzal chloride to cinnamaldehyde

(i) (CHjCOljO. CHjCOONa
Dil. NaOH 433-453 K
C6H5CHCI2 ^ CgHjCHO > CeH5CH = CHCHO
- 2 NaCl, -H2O (ii) H'^’/HjO
Benzal chloride Benzaldehyde (Perkin condensation) Cinnamaldehyde
43. Ethanol into n-butane (Bihar Board 2011)
P/Br2 Na, dry ether

CH3CH2OH 4 CH3CH2Br -2NaBr
^ CH3CH2—CH2CH3
Ethanol Bromoethane n-Butane
(Wuriz reaction)
Acetic acid to ethane (J & K Board 2011)
NaOH Koibc’s
CH3COOH ■> CH^COONa ^ CH3—CH3
-H,0 Eluctrolylic melhod
Acelic acid Sod. acelale Eihijne
TYPE 11. THREE—STEP CONVERSIONS
Q Nitroniethane to dimethylamine
Si)/HC! CHCl^.alt. KOH.A Na/C,H,OH
CH3NO2 (Redtufion)
> CH3NH2 ->
CH3NC ^ CH3NHCH3
(Carhylamhi£ reaction) {Reduction)
Nitromellnine Methyluminc Melhyl Dimclhylainine
i.socyanide
Methane to acetic acid
low
Ale. KCN, A
CH4 -HBr
^ CHiBr -KBr
^ CH3CN ^ CH,COOH
(Hydrolysis)
Mclhanc Meiliyl bromide Acetonitrile Acetic acid
ee
Bromomethane to ethanol (CHSR 2019)
F
Fr
Ale. KCN. A LiAIHj HNO,
CH3Br ■>
CH3CN (Reduction) ^ CH3CH2NH2 ^ CH3CH20H
Bromomethane
-KBr
Acetonitrile Ethanamine
-Nj.-HjO Ethanol
for
ur
3 Ethylene to succinic acid
s
CH, Br, CH,Br 2 KCN CH^CN CH.COOH
ok
Yo
> -> I ' 1 ■
CH, CCI^ CH.,Br -2KBr . CH,CN (Hydrolysis) CH^COOH
Bo
Ethylene Ethylene Butane-1.4-dinitriie Succinic acid

dihroniide
re
^3 Ethylene to oxalic acid

ou
CIU CH^Br
ad
Br, CH Cold dil. alk. KMnOj COOH

Ale. KOH. A
4 4
Y
CH^ CCl^ CH^Br -2HBr

(Ochydrobrqmination)
CH (H,0 + 0) COOH
(Daeyer's reagent)
Ethylene Ethylene Acetylene Oxalic acid
nd
Re
dibromide
Fi
(CBSE 2018)
Acetaldehyde to acetone (ethanal to propanone)
O
K,Cr,()7/H,.SO Ca(OH), Dry distillation
CH3CHO
{Oxidation)
^ CH3COOH -H2O
^ (CH3COO)2Ca 4 CH3—C—CH3
^CaCO^
Acetaldehyde Acelic acid Cal. acetate Acetone
OMgBr OH
CH^MgBr
Altemalively, CH3CHO CH3—CH—CH3 -Mg(OH)Br
4 CH3—CH CH3
dry ether
Acetaldehyde Addition product Isopropyl alcohol
O
Cii/57.^ K
> CH,—C—CH3
or K,Cr207/H2S04
Acetone
(Oxidation)
A/54 New Course Chemistry fXinraawm
Q Ethanol to acetone (CBSE 2007, 2008 ; Jharkhand Board 2011)
K2Cr207/H2S0 4 As discussed
CH3CH2OH CH3COOH Tm conversion CH3COCH3
^ ^
(Oxidation)
Ethanol Acetic acid 6above Acetone
Q Formic acid to oxalic add

NaOH 633 K COONa COOH
Dil.HCl
HCOOH ^ HCOONa I ■> I
-HjO -H2 COONa -2NaCI COOH
Formic acid Sod. formate
Sod. oxalate Oxalic acid
Q n»Propyl alcohol to isopropyl alcohol (I** alcohol to 2** alcohol)

I OH
w
Cone. H^SO^, A HI I AgOH I
CH3CH2CH2OH f_^CH3CH = CH2^ (Mark.
> CH-—CH—CH,
^ ^ -Agl
^ CH3—CH—CH3
(-H2O)
addition
n-Propyl alcohol Propylene Isopropyl iodide Isopropyl alcohol
Flo
({Âlcohol) (2® Alcohol)
e
10. Ethanol to propan-2*ol (CBSE 2019)
e
Fr
OH
(OCHjMgl i
PCC/CHjClj
CH3CH2OH > CH3—CHO ^ CH3—CH—CH3
(Oxidation) (/OH3O+
r
ur
Ethanol Ethanal Propan-2-ol
11. Isopropyl alcohol to tert'butyl alcohol (2*' alcohol to 3^ alcohol)
or Propan-2*ol to 2-methylpropan<2-ol
fo
ks
(CBSE 2015)
Yo
oo
CU/573K
CH CH CH3MgBr CH OMgBr
3\ orPCC/CHjClj 3\
CHOH C = 0
eB
CH3-^ or K2Cr207/H2S0^
(Oxidation)
Dry ether
CH3^ ^CH3
Addition product
Isopropyl alcohol or Propan-2-ol Acetone
ur
(T> Alcohol)
ad
CH OH
H"^/H20
Yo
■>
-Mg(OH)Br
CH3 '^CH3
f<?r/-Butyl alcohol or 2-Methylpropan-2-ol
nd
Re
(3® Alcohol)
12. Isopropyl alcohol to n-propyl alcohol (2" alcohol to 1** alcohol)
Fi
CH Cone. H.iSO^, A B2H^, Dry ether

3\
CHOH ) CH3—CH = CH2 » (CH3CH2CH2)3B
CH3'^ -H2O
Propylene
(Hydroboratian)
Isopropyl alcohol
(2° Alcohol) HjOj/NaOH
(Oxidation)
^ CH3CH2CH2—OH
«-Propyl alcohol (1" Alcohol)
13. Isobutyl alcohol to tert-butyl alcohol (1” alcohol to 3** alcohol)
CH, CH3 CH3
I Cone. H^SO^.A I Dil. H2SO4
CH3—CH—CH2OH
-H2O
2 CH3—C = CH2 (Mark, addition of wafer)
> CH3—C—CH3
Isobutyl alcohol Isobutylene OH
(1° Alcohol)
/er/-Butyl alcohol
(i® Alcohol)
14. Ethanolc acid to 4>hydroxy-4-methyl-2-pent8none (dlacetone alcohol)

CH Dil. NaOH
Ca(OH>2 Dry diKtil
CH3COOH ^ (CH3COO)2Ca C = 0
(Aldol condensation)
Ethanoic acid
-H1O
Cal. acetate -CaCOj
Acetone
OH o
41 II
CH3 -C—CHj—C—CH3
I 3
CH3
4-Hydroxy-4-methyl-2-pentanone (Diacetone alcohol)
15. Acetic acid to tert>butyl alcohol
w
o O CH^
2CH3MgBr I
C2H5OH
CH3—C—OH > CH3—C—OC^Hj ■> CH^—C—OMgBr
+Conc. H2SO4 -C2H50MgBr I
Flo
Acetic acid (few drops) Ethy lacetate CH3
e
Addition product
re
CH3
I
F
■>
CH3—C—OH
-Mg(OH)Br
ur
r
CH3
fo rerf-Butyl alcohol
ks
16. Acetone to acetamide
Yo
(<)l2/NaOH(-CHl3) SOCI2 NH3 (excess)
oo
CH3COCH3 ^ CH3COOH ^ CH3COCI - > CH3CONH2

Iodoform reaction -SO2.-HCI -NH4CI
B
Acetone Acetic acid Acetyl chloride Acetamide

(//)Dil.HCl
re
17. Propanoic acid to ethylamine (HP Board 2009)
Br2/KOH
u
SOCI NH3 (excess)

^ CH3CH2COCI -
ad
CH3CH2COOH > CH3CH2CONH2 ^ CH3CH2NH2

Yo
firî J 4.
-SOj.-HCl NH4CI (Hofinann
bromamide Ethylamine
Propanoic acid Propanoyl chloride Propionamide
reaction
d
18. Acetic acid to ethylamine (J&K Board 2011)

Re
in
SOCIj NH3 (excess) LiAlH4/elhcr

F
CH3COOH ^ CH3COCI » CH3CONH2 > CH3CH2NH2

-SO2.-HCI -NH4CI
Acetic acid Acetyl chloride Acetamide Ethylamine
19. Acetone to acetaldehyde

Ij/NaOH PCI3 H, + Pd/BaS04 + S
CH3COCH3 > CH3C02Na CH3COCI -(Rosenmund reduction)
^ CH3CHO
-CHI3 -Na3PO 3
Acetone (Iodoform reaction) Sod. acetate Acetyl chloride Acetaldehyde
20. Acetic acid to 2*butanol
SOCI2 (CHjCHjIjCd LiAIH
CH3COOH ^ CH3COCI ^ CH3COCH2CH3 CH3CHOHCH2CH 3

-SOj.-HCl in dry ether in dry ether
Acetic acid Acetyl chloride Butanone 2-Butanol
A/56 7>>t^dee4t'4. New Course Chemistry (Xll)ESSm]
QQ 1, l-Dichloroethane to 1, 2-dichloroethane
Ale. KOH H,.Pd Clo/CHCI^
CH3CHCI2 ^ HC = CH > H2C = CH2 > ClCHo—CH,C1
A Supported over BaSO_^
I, l-Dichloroethane Elhene (Undlar's catalyst) Elhene I, 2-Dichloroelhane
Acetoacetic ester from acetaldehyde

K2Cr207/H2S04 C,HjOH/Conc. H^SO^ {few drops)
CH3CHO (Oxidation)
> CH3COOH (Esterification) ^ CH3COOC2H5
Acetaldehyde Acetic acid Ethyl acetate
ow
C2H50Na/C,H50H
(Claisen emdensation)
CH3COCH2COOC2H5
Ethyl acetoacetate or Acetoacetic ester
23. Acrolein to 2,3’dlhydroxypropanal or glyceraldehyde
e
C2H5OH + Dry HCI gas Dil. alk. KMnOj
re
CH-, = CH—CHO > CH2 = CH—CH(0C2H5)2
(Protecion o/~CHO group) (Hydroxylation)
Frl
Acrolein Acrolein diethyl acetal
F
C H, —C H —CH(OC., H.), ^ CH.,—CH—CHO
ou
or
I “ I ' ' ■ -2C2H5OH I " I
OH OH (Hydrolysis) OH OH
2, 3-Dihydroxypropanal diethyl acetal

kfs 2. '.^-Dihydroxypropanal
(Glyceraldehyde)
oo
24. Propanal to 2-hydroxypropanpic acid (CBSE 2019)
Y
|Ag(NH3)2rOH- Br,/ied P
B
CH3CH2CHO Tollens’reagent
^ CH3CH2COOH {HVZ reaction)
re
Propanal Propanoic acid

Aq.KOH
oYu
CH3—CH—COOH CH3—CH—COOH
ad
{Hydrolysis)
Br OH
d
2-Bromopropanoic acid 2-Hydroxypropanoic acid

in
Re
TYPE III—MULTISTEP CONVERSIONS

F
Q|Benzene from lime

3C.2273 K H,0 Red hot copper tube
CaO > CaC2 CH = CH
-CO -Ca(OH)2 773 K
Lime Cal. carbide Acetylene
Benzene
Acetone from acetylene

H2O. Dil. H2SO K2Cr20? Ca(OH)^
CH^CH
^ CH3CHO H2SO4
^ CH3COOH ^ (CH^COO)2Ca
HgS04.333A' -H,0
Acetylene Acetaldehyde Acetic acid Cal. acetate
Dry distil
4
CH3COCH3
-CaCO^
Acetone
TYPICAL AUPHATIC AND AROMATIC CONVERSIONS A/57
[i’l
Cone. H2SO4 Br2 Na/Liquid NH3,196 K

CH3CH2OH ^ CH2 = CH2 » B1CH2—CH2Br -2HBr
>
433-443 K CCI4
Ethyl alcohol (Dehydration) Ethylene 1,2-Dibromoethane {Dehydrobromimtion)
CH3COOH
HCsCH ^ CH2 = CH—OCOCH3
HgS04
Acetylene Vinyl acetate
LiAlH 4 PBfj A1C.KCN

CH3CH2—COOH in ether
> CH,CH,CH5—OH > CH3CH2CH2—Br A
—>
Propanoic acid n-Propyl alcohol n-Propyl bromide
LiAlR
CH3CH2CH2—CN in ether
^ CH3CH2CH2CH2—NHo
^ ^ ^ :
n-Butyronitrilc n-Butylamine
F low
o H
CH^MgBr H+ZHjO PB«3
H—C—H H—C—OMgBr > CH3CH2OH —> CH3CH2Br
-Mg(OH)Br
H Ethyl alcohol Ethyl bromide
re
Formaldehyde Addition product
for F Na/ether
> CH3CH2—CH2CH3
(Wurtz reaction)
n-Butane
Methylmagnesium bromide needed for the reaction can itself be prepared from formaldehyde as follows:
Your
s
eBook
NaBH4 PBr, Mg
HCHO ^ CH3OH —> CH3Br > CH3MgBr
in ether
Qiihyte to
ad
our
Cone. H2SO4 H+/H2O CjHjNH+CiOjCr, CH2CI2

CH2 = CH2 CH3CH2OSO3H ~ Boil > CH3CH2OH
Ethylene Ethyl hydrogen sulphate Ethyl alcohol
Re
Y
OMgBr OH
Find
CH3MgBr H+/H2O . I
CH3CHO CH3—-CH—CH3 > CH3—CH—CH3
(Hydrolysis)
Acetaldehyde Addition product 2-Propanol
HCHO/Dil.NaOH H-^.A
CH3CHO ^ HOCH2—CHjCHO » CH2 = CH—CHO
(Cross aldol condensation ) (-H2O)
Ethanal 3-Hydroxypropanal 2-Propenal
(Acrolein)
HCN H+/H2O
(1,2-Addition) > CH2=CH—CH—CN (Hydrolysis)
» CH2 = CH—CH—COOH
I I
OH OH
2-Hydroxy-3-butenenitrile 2-Hydroxy-3-butenoic acid
I 1\
A/B6 New Course Chemistry fxinnm«n
Q Acetone to 3-methylbut-2-en-l-olc add (P, P-Dlmethylacrytlc add)

CH^
CH H+/HjO.A
I
3\ C»0 B(I(0H)2
■♦CHj C—CH COCH ♦ CH,—C = CH—COCH,3
ch/ {Althlvmiltnsatlon)
2 3 {DehyJrtulon)^ 3
3 MeNity) oxide
Acetone
OH
DIueetone uleohoi
CH 3 9«3
Ij/NttOH H+/H,0
2
♦ CH^—C*CH—COONa CH3—C « CHCOOH
-CHI3 (Aiidyictilton)
{hdoftimmuiim) Sod. 3-methylbut-2‘en--i-(iute 3-Methylbut-2>en>l-olc acid
Q| Dimethyl ether to diethyl ether

HI.373K Nn/ethor CU./iv DryAgjO
w
CH3—O—CH3 2 CH3I (iVar/z
♦ CH3CH3 CH,CHjCI -AgCi
♦ (CH3CH2)20
-HjO
Dimethyl ether muflon) Ethane Ethyl chloride Diethyl ether
F lo
in
Propionic add to Isopropyl alcohol
ee
LiAIH
Conc.H2SO Conc.H2S04
CH3CH2COOH U CH3CH2CH2OH U CHjCHriCHj ♦
Fr
Dry ether 433-443K {Mark.oddn.)
Propionic acid n-Propyl alcohol (“HjO) Propylene
for Bolting H2O

ur
CH,—CH—CH,
3 I 3 -H2SO4
♦ CH3—CH—CH3
I
s
OH
OSO3H
ook
Yo
Isopropyl Isopropyl
eB
hydrogen .sulphate alcohol
11. Ethanolc add to 2-hydroxyethanoic add (CBSE 2017, CBSE (Foreign) 2017)
our
ad
Brj/Red P Aq. KOH

CH3-COOH (H.V.Z. reaction)
> Br-CH2-COOH (Hydrolysis)
4 HOCH2-COOK
Elhanoic add 2-Bromoethanoic acid Pot. 2-hydroxyethanoate
Y
Re
H+ZHjO
nd
(Acidiifcation)
●>
HOCH2-CCOH
Fi
2-Hydroxyethanoic add
12. Propanoic acid to 2‘hydroxypropanolc acid (CBSE (Foreign) 2017)
Br2/red P Aq. KOH

CH3CH2COOH ^ CH3-CH-COOH ■>
CH3-CH-COOK
(Hy.Z. reaction) (Hydrolysis)
Propanoic acid
Br OH
2-Bromopropanoic add Pot. 2-hydroxypropanoatc
H'*‘/H20
(Acidification)
4
CH3-CH-COOH
OH
2-Hydroxypropanoic acid
13. Ethylene to propylene

Br
NuNH2/LIii.NH;,,I%K NnNHjin llq.NH^
CHjsCHj CCI ^ BrCHj—CHjBr (Dehydivhtftmlnailon)
* HCbCH
I96K
4
Bthylene * Bthylene Auetyiene

dIbromide
CHit
i Hj“Pd/BuS04
HCBCi^fl+ HC ■ C—CH-, > H.C-CH—CH
(=Nal) +Sorqultiollne
Sod. ncetyllde Propyne {Uitdlut'scaialynt) Propylene
\n. Iiopropyl chloride to n-propyl chloride
Cl
I AIc.KOH.A BjHft/THP
CHj—CH—CHj (-HCI)
+ CH,—CH-CHj Uiyihvhonillon)
> (CH;^CH2CH2)3B
iHopropyl chloride Propenc Trl-«-propylborune
w
HjOj-NiiOH SOCIj
CH3CH2CH2OH > CH3CH2CH2C1
F lo
{Oxidation) (-SOj.-HCl)
N'Propyl alcohol M-Propyl chloride
15. Iodoform to propyne
ee
Ag power. A NaNHj,liquid NH3 CH,1
I4 CH.—CaCH
Fr
2CHI3 > CHsCH » CHaCTNa^
-6Agl I96K -Nal●1 ^
lodut'orm Acetylene Sod. acetylide Propyne
16. Acetic acid to glycine for

ur
AIc.NH
3
s
Clj.redP (excess) CH-,C00H/H20
ook
CH3COOH ^ CICH2COOH - ^ NH2—CH2COONH4 NH2CH2COOH

Yo
-HCl
-NH4CI -CH3COONH4
Acetic acid Chloroacetic acid Glycine
eB
17. Ethanol to 2-hydroxybutanoic acid

Conc.H2S04
our
CH, CH- Oj.Ag CH (/)CH3Mgl

ad
433-443K
I ^ ■> I 2 I O ^ CH3CH2CH2OH
573 K
CH2 OH (Dehydration) CH2 1-Propanol
Y
Ethanol Ethene Epoxyethane

Re
OH
nd
+
HCN
C5H5 NHCr03Cr ,CH2Cl2
Fi
4 CH3CH2CHO 4
CH3CH2—CH—CN (Hydrolysis)
Propanal
OH
CH3CH2—CH—COOH
2-Hydroxybutanoic acid
18. Propanoyl chloride to dipropylamine
NH3 (excess) LiAlH4/ether CH3CH2COCI
CH3CH2COCI > CH3CH2CONH2 » CH3CH2CH2NH2
-NH4CI (Reduction) -HCl
Propanoyl chloride n-Propylamine
LiAlH4/ethcr
CH3CH2CH2NH—COCH2CH3 (Reduction)
> CH3CH2CH2—NH—CH2CH2CH3
Dipropylamine
I
A/60 New Course Chemistry (XlOKSSXm
OH
I
19. CHjCHOto (CH3>2C—Ph
K2Cr207-rH2.SO Dry distilkilion
CH3CHO (Oxidation)
^ CH^COOH -CO2.-H2O
> (C!I^CC)())2Ca ^ -O1CO3
AcelJildehyile Acetic acid Ciil. ucclJilc
0(1
(OhiNIgBr/tfltier
(CH3)2C = 0 >
(CH3)2 C—Ph
(»)HVH2()
Acetone Dimcihyiphcnylcarbinol
w
20. Ethyl cyanide to ethanoic acid (cf. with ctmversion 7, page A/47) (CBSE 2010)
O
Conc.HCl Br2-NaOH
CH3CH2CN (Partial hydrolysis)> CH3CH2—C—NH2 > CH,CH,NH,
o
{Hofmann hromamidr rraclioii)^ .1 2 2
Klhyl cyanide ■ Propionamidc Elhanaminc
e
re
HNO2 K2CI-207/H2S04
rFl
CH3CH2OH CH.COOH
3
-Nj.-HjO (Oxidation)
F
nihutu>l Gthanoic acid
or
ou
AROMATIC CONVERSIONS
TYPE I — TWO STEP CONVERSIONS ksf
Benzene to aniline
oo
NO2 NII2
Y
B
Cone. UNQj + Cone. H2SO4. '.<33 K Sn + HCI

re
(Nitration) (Rfdticlion)
oYu
Nili'obctizcnc Aniline
ad
Qj Aniline to phenol (Bihar Board 2011 ; CBSE 2015)

d
NH2 N^NCr ON
in
Re
NaN()2 + Dil. HCl,

273-278 K Boiling dil, 112^04
F
f n
(f)iazolizalion)
Aniline Benzenediazoniiim Phenol
chloride
0|Aniline to benzene
+
NH2 N=NCr
NaN02 + Dil. HCI.

273-278 K
H3PO2/CU* ^
(Diazolizalion)
Aniline Bciizcncdiazoninin Benzene

chloride
^jAniline to chlorobenzene
+
NH2 N=NCr
NoN02 + Dil. HCI.

273-278 K CuCl/HCl
(Diazotization) {SonJmeycr reaction)
Aniline Benzenediazonium Chlorobenzene

chloride
Aniline to bromobenzene
+
NH2 NsNCr Br
NaN02 + Dil. HCI.

(1
273-278 K CuBr/HBr
w
{Diazotizalion) (Sandmeyer reaction)
Aniline Benzenediazonium Bromobenzene
chloride
Flo
Aniline to iodobenzene (CBSK 2010
+
NH2 N^NCr
e
re
rS NnN02. Dil. HCI.
rF
273-278 K. Ki.A
{Oiazotizalioii) kk -N2.-KCI
ur
Aniline Benzenediazoniiim Iodobenzene
IQI Aniline to benzonitrile or cyanobenzene

chloride
fo (CBSK 2007)
ks
Yo
+
oo
NH2 N = NCr CN
B
NaNOa, Dil. HCI

273-278 K KCN/CuCN
re
k^ {Diozotization) k?^ A
k^
u
Aniline Benzenediazonium Benzonitrile

ad
Yo
chloride
^ Aniline to p*hydroxyazobenzene
d
Re
+
in
NH2 NsNCr
F
NaN02. Dil. HCI
●O
273-278 K Coupling with phenol
I I N=N OH
k;^ [Diozotization) pH 9-10
/>-Hydroxyazobenzene
Aniline Benzenediazonium
chloride
Aniline to fluorobenzene
NH2 N=NBFJ F
NaN02. HBF4
273-278 K
kS ■ A
k^ k^ ■ k=^^
-►
[Diazotizalion) -BF3. -N2
Aniline Benzenediazonium Fluorobenzene
ictrafluoroborate
A/62 New Coiifse Chemistry (XIl)CZCTD
iO. Aniline to nitrobenzene

+
NH2 NHNBF4
[As
NaNOj, HSr4
273*278 K NaNOj
{DIatotliatbn) + Cu powder. A
Aniline Benzono(ilai!onlum Nlirobenzene
lotrefluoroborate
II. Benzenesutphonlc add to aniline

SO^Na NH2
Ai
w
NbOH NnNHj, l\»fi
-NojSOj ^
Bon/.cnoHiiIphonic ucid Sod. bonxcncBulphonmc Aniline
o
{Benzene to m-nitroacetophenone
e
12. (NCERT)
re
COCH3 COCH3
rFl
A^
F
Cone. HNO-,
(CH3C0)20,Anhyd.AlCl3
>■
+ Cone. H2SO4 ^ (1
(^'C acylation) {NUfatlun)
or
NO2
ou
Benzene Acetophenone m*NI(ruucotophcnonc
13. {Benzene to benzoic acid or Toluene to Benzoic add
ksf (Hr. Board 2011 ; CBSE 2018)
CH3 COOH
oo
(/) KMnOVOH . A
Y
CH3CI, Anhyd, AIC13

rA [Oxicla(lon)
(1
B
A*
♦
{EC. alkylation) (//) HVH2O
re
Benzene Toluene Benzoic acid

oYu
14. I Benzene to Benzyl alcohol

ad
CHO CH2OH
d
CO, HCI (0 LiAlH4/ether

in
Re
AICI3/CUCI (H) H*/H20

{Gallermann Koch reaction)
F
Benzene Benzaldehyde Benzyl alcohol

15. Phenol to acetophenone (Bihar Board 2011)
OH COCH3
Zn dust, A CH3COCI + Anhyd. AICI3 ^

-ZnO (.FC. acylation)
Phenol Benzene Acetophenone
16. I Phenol to toluene
OH CH3
Zn dust distil
rA CH3CI. Anhyd. AICI3
rA
k^
>●
-ZnO (EC. alkylation)
Phenol Benzene Toluene
TYPICAL ALIPHATIC AND AROMATIC CONVERSIONS A/ea
17 Ibluene Co m-nltrob«nzolc add
CHj COOH COOH
K2Cf207 + H;S04 ^ Cone. HNO3 + Cone. H2SO4. A

rn ¥
{Ox\iia\im) {NUmthn)
Ibluone Bon/olc add
N02
w-Nltit)benKole add
ut Benzaldehyde to cyanobtnsene or btncotiUrlle
CHO CH«NOH CN
ow
fl NH;OH ^ (CH3CQ)20,A ^
-H2O Hijo) ^
Bemxnldehyde Benxaldoxime Cyunobenzene
in
I Salicylic add to benzene
e
re
COOH COOH
Fr l
,OH Soda-tlmc, A
F
Zn du8(, A (CaO + NaOH)
(1
-ZnO ^ -Na2C03
[Di>varhoxylatlon)
or
ou
Salicylic acid Benzoic acid Benzene
?0.
I Benzaldehyde to benzene kfs
CHO COOH
oo
Soda-lime, A
Y
K2Cf207 / H2SO4 ^ (CaO + NaOH)
(1
B
iOxiclailon) -NajCOa ^
(Decarboxylatlbn)
re
Toluene Benzoic acid Benzene
21. Benzoic add to benzyl chloride

oYu
ad
COOH CH2OH CH2C!

d
LiAlH4/dry ether SOCI2

(1
in
k?^
*■ *■
Re
(Reduclion) -SO2, -HCl

F
Benzoic acid Benzyl alcohol Benzyl chloride

22. I Benzamide to benzene
CONH2 COOH
Soda-lime, A
MONO (CaO + NaOH)
f l
k^ kk
¥
-N2. -HjO -NB2CO3
{Decarboxylation)
Benzamide Benzoic acid Benzene
23. Benzoic add to benzamide (CIISK 2007)
COOH COCI CONH2
S0CI2 2NH3 (excess)
k^ -SO2. -HCl -NH4CI kk

Benzoic acid Benzoyl chloride Benzamide
A/64 New Course Chemistry fXIQraCTim
24. Benzoic acid to benzaldehyde (NCERT ; CBSE 2008. 2010 ; CBSE (D) 2017 ; CBSE 2017)
COOH COCl CHO
H2/Pd + B.iS04
SOCI2 + S or quinoline
> >
SO2. -HCi Roiling xylene
(Roseumuml reduction)
Benzoic acid Benzoyl chloride Bcn7.aldcliydc
25. Benzaldehyde to acetophenone

CHO CHOHCH3 COCHj
(OCIl^MgBr CsHsNlC CrO^CT (PCC)

>
(ii) CH2CI2
w
Bcnz4iklchydc 1-Phcnylclhanol Acetophenone
26. Benzaldehyde to benzophenone (CBSE 2009)
F lo
Clio CHOHCftHs COCftHj
C5ll5NlCc'K)iCr(PCC)
ee
(i)CV,H,MgBr
^
Fr
(ii)H7H20 CH2CI2
Benzaldehyde Diphcnylcarhinol Benzophenene

27. Benzaldehyde to 3>phenylpropan‘l>ol
for (NCERT)
ur
CHO CHOHCHjCHO
s
ook
Yo
Dil. NaOH
I CH3CHO
H2O
eB
(CV»Av.v a Idol
condensalion)
Benzaldehyde 3-Hydroxy-
3-phenylpropanal
r
CH=CHCMO CH2CH2CH2OII
ou
ad
112/Ni ●
Y
{Ciihdylic hydnigeinilion)
Re
nd
3-Phcnylprop-2-cnal 3-Pheny Ipiopan-1 -ol

(CinmimaltMiydi’)
Fi
28. Benzoyl chloride to benzonitrile

COCl CONH2 CN
NM3 (excess) p205.Aor SOCI2.A
-NM4CI (-H2O)
Benzoyl chloride Benzamide Bcn7.oni(riIc
29. I Benzoic acid to /n-nitrobenzyl alcohol

COOH COOH CH2OH
Cone. HNO3
+ Cone. H2SO4 (/) B2Hf/elher
(Nitration) or NaBH4/CH3()H
NO2 NO2
Benzoic acid
m-Nilrobcnzoic acid m-Nitrobcnzyl alcohol
30. Benzaldehyde to a-hydroxyphenylacetic acid (NCI-KI)
OH OH
NaCN/HCI
C^H^CHO pH 9-10 -> C^H^—CH—CN ■>
C^H,—CH—cooil
(Hytlrolysis)
Benzaldehyde Benzaldehyde «-Hydroxyphenylaceiic acid
cyanohydrin (Manclelic acid)
31. Benzyl alcohol to phenylacetic acid

HBr.A KCN.A
CftH5CH20H orP+Br,
> C(,H5CH^Br ^ CftH^CH^CN ^ C^H5CH2C00H
(Hytlrolyxix)
Benzyl alcohol Benzyl bromide Benzyl cyanide Phenylaceiic acid
or Benzyl chloride to pheiiyethanoic acid (20IB S)
KCN.A
C^H^CH.Cl ^ C(,H5CH2CN :—> C.HcCH,COOH
w
{Hyilmly.sis)
Benzyl chloride Phenylelhaneniisile Phenylaceiic acid
F lo
32. Broroobenzene to benzoic add (CKSi: 2010)
My COo(.v)
C.HjBr Dryeiher
C(,H^MgBr » |C^H5COOMgBrl > C^H^COOH
(Oiyicc) (Hydroly.m')
ree
Bromobenzene Phenylmag. bromide Benzoic acid
33. Bromobenzene to 1-phenylethanol for F OH

(N( KKT)
My/drycihcr U)ai^C\lO
C6H5Br CftH^MgBr ^ C^H^—CH—ni^
r
{Grignard muiion)
You
oks
Bromobenzene Phenylmag. bromide l-Phenylcihanol

eBo
34. Nitrobenzene to acetanilide
NO2 NH., Niicocn 3

ad
our
Sn I MCI
(CH3C0)20
>
(Redticlioii) 1-CH3COOH
{Aceiyialioti)
Nitrobenzene
Re
Aniline Acetanilide
dY
35. Phenylbydroxylamine from benzene

Fin
NO-, NHOH
C:one. MN03-HConc. lhS04

.333 K Zn dusl/uq, NH^'I
k^
»
{Nitnitioii) {Rcdticlion under
Benzene
neutral conditions)
Nitrobenzene Phenylhydroxylamine
36. I Nitrobenzene to m-nitroaniline

NO2 NO-, NH2
Fuming HNO3 +Conc. M-,S04,
393 K
{NH4)2S
>
{Nitration) {Selecti ve rediu iion)
Nitrobenzene
NO2 NO-,
/H-Dinitrobenzene ai-Nilrounilinc
i
A/66 Vtiutee^'4. New Course Chemistry (XII)EBMD
37 Chlorobenzene to benzene
Cl MgCl
Mg/THF, A H'^/H2P
rn ♦
{Grignard reaction) -Mg(OH)Cl
Chlorobenzene Phenylmag. chloride Benzene
38 Ethylbenzene to benzene (CBSE 2017)
CH2CH3 COOH
(0 KMnQ4/QH~ A ^ Soda-lime (CaO + NaOH) ^

07) 630 K
w
(Oxidation) (Decarboxylation)
Benzoic acid Benzene
Ethylbenzene
F lo
(CBSE 2017)
39 Acetophenone to benzoic acid
O O O
ee
C—CH3 C—ONa
Fr
I,/NaOH, A
£ ^ H*/OH~ ^ OH
(Iodoform reaction) (Acidifleation)
Acetophenone for Benzoic acid

ur
TYPE 11—THREE-STEP CONVERSIONS
s
ook
Yo
Benzene to Deuterated benzene
Br MgBr D
eB
Brj
> Mg/ether ^ D20 (1
our
- Mg (OD) Br
ad
Anhyd. AlBr3
Bromobenzcnc Phenylmag. Deuterated
Benzene
bromide benzene
Y
Phenylhydrazine from aniline

Re
nd
NH2 N=NCr NHNH2.HCI

NHNH2
Fi
NaN02 + Dil. HCI
o
273-278 K SnCl2/HCl NaOH (ag)
♦ >
(Diarof/rarton) or N32S03 -NaCl. - H2O
Aniline Benzenediazonium Phenylhydrazine

chloride hydrochloride Phenylhydrazine
(NCERT)
lUI Benzaldehyde to benzophenone
KoCrjO^/HjSO CaC03 Dry distil.
CfiHsCHO i-4 CgHjCOOH
(Oxidation)
(C6HsC00)20
-CaCOj
^ C^Hg-CO-CgHs
Benzaldehyde Benzoic acid Cal. benzoate Benzophenone
Alternatively,
K2Cr207/H,S0 SOCI2 CgH^/Anh.AICl
C^HjCHO CgHjCOOH > C^HsCOCl (F.C.acylation)
C^Hs-CO-CsHs
(Oxidation)
Benzaldehyde Benzoic acid Benzoyl chloride Benzophenone
TYPICAL ALIPHATIC AND AROMATIC CONVERSIONS Ay67
IQ Benzoyl chloride to benzonltrlle

H2~Pd/BaS04 NHjOH (CHjCOjO.A
CfiHjCOCl ^CgHjCHO > C6H5CH = NOH > C^Hs-ChN
+Sorquinolinc -HjO -CH3COOH
Benzoyl chloride (RosenmunJ reduction) Benzaldoxime Benzonilrile
Alternatively,
2NH3 P2O5
C6H5COC! . C^HjCONHj ^ CgHj—CsN
-NH4CI -H2O
Benzoyl chloride Benzamide Benzonilrile
1^1 Benzene to methyl benzoate or Benzene to benzoic acid (Hr. Board 2011)
ow
Br MgBr
Br2/Anhyd. AlBf3 Mg/dry ether (/) Dry ice

>●
{Bromination) Grignard reaction (») H'^/H20
e
Benzene Bromobenzene Phenylmag. bromide
Fl
re
F
COOH COOCH3
ur CH3OH/H2SO4 (cone.)
r
fo
>
{Esieritfcatiori)
ks
Benzoic acid Methyl benzoate
Yo
Qj Benzene to m-nitrobenzoic acid
oo
eB
COOH COOH
Cone. HNO3
As above
+ Cone, H2SO4
ur
(Nitration)
ad
NO2
Yo
Benzene Benzoic acid

m-Nitrobenzoic acid
Benzene to p>nitrobenzoic acid

d
Re
in
CH3 CH3 COOH

F
Cone. HNO3 I
CHjCl.Anhyd.AICia ¥
1^^^ + Cone. H2SO4, A
¥
(0KMnO4/OH“A
¥
(EC. alkylation) (Nitration) (ii) H^/H20
Benzene Toluene
NO2 NO2
/7-Nitrotoluene p-Nitrobenzoic acid
(major isomer)
Qj Benzene to m-nitroaniline
NO2 NO2 NO2
kS
Cone. HNO3 Fuming HNO3 NH4HS
+ Cone. H2SO4 + H2SO4 orNaHS
♦
333 K 393 K (5’e/ec//ve
NO2 reduction)
Benzene
(Nitration)
Nitrobenzene
(Nitration) NH2
w-Dinitrobenzene m-Nitroaniline
A/68 New Course Cheniisli*y (X11)C&]9D
m Benzene to m-chioroaniline
NO2 NH'.
NO2
Cone. HNO3
+ cone. H2SO4 Cb/Fe Sn/HCl
>
333 K {Chlorination) [R^duclion')
Cl Cl
{Nitration) hfitrobenzene
Benzene
m-Ch!oronitrobenzene /«-Chloroaniline
10. Benzene to phenol (Ph. U(»iirri 2010 ; Asurni Hoard 2012, 2013)
SO3H S03Na
Cone. H'»S04
353-36'3 K NaOH
w
>
{Sulphonation) -H2O
F lo
Benzene Benzenesuiphonic acid Sod. benzencsiilphonale
ONa OH
ee
NaOH, 575 K, fuse Dil. H2SO4
Fr
i n
-Na2S03, -H2O {Acidiifcation)
Si>d. phenoxide
for Phenol
ur
Alternatively,
s
ook
Yo
NO^ NH2
eB
Cone. HNO3 NaNO-) Oil. Iin

Sn ^ HCI 273-278 K
+ cone. H2SO4 f n
our
ad
333 K {Reduction) {Diazotization)

{Nitration) Aniline
Benzene Nilrobenzene
Y
N=NCr OH
Re
nd
Boiling H2OIH*
Fi
>
Benzenediazonium chloride Phenol
11. Benzene to resorcinol
ONa OH
SO3H
Fuming H2SO4,
A NaOH, 573 K, fuse
-Na2$03, -H2O {Hydndyxis)

{Sulphonation) OH
Benzene
SO3H ONa
Rc-sorcinol
ni-Benzene- m-Disodium
disulphonic acid resorcinolate
12. Chlorobenzene to salicylaldehyde
Cl ONa ONa OH
CHO CHO
CHCl3/NaOH, H*/H70
NaOH, 623 K 340 K
■P P
300 atm (Reimer-Tiemiinn (Ad(/ificali(w)
(Dow process) reaction)
Salicyladchyde
Chlorobenzene Sod.phenoxide Salicyladehyde
sod. salt (major product)
13. Nitrobenzene (or aniline) to sulphanilic acid

+
ow
NO7 NH7 NH3 HSO4 NH3
Sn + HCI Cone. H7SO4 453^73 K

>
(Reduction)
e
Nitrobenzene Aniline Aniline hydrogen sulphate
re
SOJ
rFl
Sulphanilic acid
F
14. Benzene to anisole
r
ou
SO3H ONa OCH3
Cone. H7SO4
353-363 K
(Sulphonation)
NaOH/573 K. fuse
-Na2S03, -H7O
k
-►
sfo CH3-1
-Nal
P
oo
(WUlkimson
Benzene Benzenesulphonic acid Sod.phenoxide synthesis)
Anisole
Y
(Methyl phenyl
B
ether)
re
Aniline to p-bromoaniline (Hr. Houni 2011)
or N-Phenylethanamide to p-bromoaniline (('HSK 2019)

ou
Y
ad
NH2 NHCOCH3 NHCOCH3 NH2

(CH3C0>20
d
+ CH3COOH
^ Br2/CH3COOH ■P- H~"/H20 ^
in
Re
(Acetylation) 273-278 K (Hydmtysis)

.
F
Aniline Acetanilide
or N-Phenyiethanamide
/j-Bromoacelanilide />Bromoaniline
(major product)
16. Phenol to o-bromophenol
OH OH ONa OH
Br
Cone. H2SO4
A
^k/S03H Bro
NaOH
> —
HyO^ boil
(Desulphonation)
Phenol o-Bromophenol
SO3H S03Na
A/70 New Course Chemistry (XII)CZ3SD
17. Chlorobenzene to picric acid
Cl Cl OH OH
I Cone. HNO3 NO viQ Cone. HNO3 O2N NO.

^ +Conc. 112804. A 2 Aq. Na2C03 ' + Cone. HiSO.^
¥
{Nitration') A A
Chlorobenzene
NO. NO. NO2
Picric aeid
2.4-Dinilrochlorol)enêne 2,4-Dinilrophenol
18. Aniline to o- and p-nitroaniline (CBSE Sample Paper 2018-2019)
NH2 NHCOCH3
w
(CH3CO).o
(1 (1
H CH3COOH
F lo
(Aivlylalioii)
Aniline Acetanilide
Cone. llN03/Cone. H.SO4. 273-283 K
ee
{Nilralinn)
Fr
NHCOCH3 NHCOCH3
for
ur
NO.
s
ook
Yo
r>-Nitroucctanilidc
NO. (minor imulucl, soiiihlc in ethanol)
eB
/)-Nilroucclanilidc
(major pnuJiui. insoluble in ethanol)
(/) Concentrate the mother liquor and
our
sicparutc by crystallization
(/) Separate by filtration
ad
(/i)lC/H.O (Hydrolysis) (//●) lC/ll20{//i-Jm/f,vw)

Y
NH. NH2
Re
nd
NO2
Fi
f>-Nitroaniline
NO2 (minor pnxiiiel)
/vNitroaniline
(major product)
19 Toluene to o-chlorotoluene
CH3 CH3 CH3 CH3

Cl Cl
Cone. I12S04.A CI2/FC HCI/423 K
♦
(Sulphonation) (Chlorination) (Desiilphonation)
Toluene <i-Chlorololucnc
SO3H SO3H
Toluene- 2-Chlorotoliiene-4-
4-sulphonic acid sulphonic acid
20. Nitrobenzene to p'Sniinoazobenzene

+
NH2 N=NCr
N02
NaN()2, Dil. MCI,
Sii+nCI 273 - 278 K Coupling wilh aniline
f n -► ( n >
(Reduction) {Diazoti.s<ifion) pH 4-5
Nitrobenzene Aniline Benzenediazunium
chloride
// % N=N NH // \ N=N NH2

iRcairanf’c.'!)
Diazx)aininobcnzcnc /)-Aminoazo benzene
w
21. Benzoic acid to aniline (CBSE 2019)
COOH COCI CONH2 NH2
F lo
SOCh 2NH3 kS Br2 - KOH
>
ee
-SO-), -HCl -NH4CI (Hofmann hnmiamide
reaction)
Fr
Benzoic acid Benzoyl chloride Bcnzainidc Aniline
22. Benzoic acid from aniline or Aniline to benzoic acid (Tiimil Nadu Board 2012)
for
ur
+
N=NCr CN COOH
NH2
s
NaNO-) + Dil. HCl,
iC/HiO
ook
KCN/CuCN
Yo
273-278 K
k^ (Diazolizalion) k^ A (Hydinlysis)
eB
Aniline Benzenediazonium Bcnzonitrile Benzoic acid

chloride
r
23. Aniline to benzaldehyde (JEE Main 2022)

ad
ou
NH2 CN CHO
Y
(/') SnCh/HCl/ether
As given in 290-295 K
Re
nd
k?^ conversion 22 above (I'O Boiling H2O

(êphen reduction)
Fi
Aniline Bcnzonitrile Benzaldehyde
24.
I Aniline to benzylamlne
NH2 CN CH2NH2
kS As given in
kS LiAlH4
k^ conversion 22 above ether
Aniline Bcnzonitrile Benzylaininc

25.
I Benzyl alcohol from benzene
CHj CH2CI
kS
C!->(I mole),
CH3CI+Anhyd.AlCl3 3*83 K. hv Aq. KOH
k^^
¥ ¥
(.FC. alkylation) (Side chain (Hydmlyxis)

chloriiialion)
Benzene Toluene Benzyl chloride Benzyl alcohol
A/72 ^%4idcefo 'ii New Course Chemistry fXinPTSTMn
26. Toluene to 2-phenyiethanamine (p-phenylethylamine)
CH3 CH2CI CH2CN CH2CH2NH2
CI2 (f mole), Na/CoHjOH
383 K, kv Ale. KCN or L1AIH4
♦
{Side chain KCl (Reduction)
chlorination)
Toluene Benzyl chloride Phenyl- 2-Phenyielhanamine
acetonitrilc
(^-Phenylethylamine)
27. Bromobenzene to m-nitrobenzoic acid
Br COOH
MgBr COOH
Cone. HNO3 +
w
Mg/dry ether (/) Dry ice Cone. H2SO4, A
Grignard reaction (/[) H30^ (Nitration)
NO2
F lo
Broinobcn/ene Phenylmag. bromide Benzoic acid m-Nitrobcnzoic acid
28. Nitrobenzene to phenol <llr. lioiinl 2012)
ee
Fr
+
NO2 NH2 N=NCr OH
NaN02 + Dil. HCI,
for
Sn + HCI 273-278 K Bioling dil. H2SO4
ur
k^k k^
»
(Reduction) (Diazotisalion) (-N2, -HCI)
Nitrobenzene Aniline Benzenediazonium Phenol
ks
chloride
Yo
oo
29. Nitrobenzene to anisole (Tiiniil Niidu Hom'd 2012)

eB
NO2 NH2 N=NC1 OCH3

NaN02/HCl,
r
Sn/HCI 273-278 K CH3OH

ou
ad
>
(Reduction) (Diazotisation) A
Y
Nitrobenzene Aniline Benzenediazonium Anisole

chloride
nd
Re
30. Chlorob^zene to phenylhydrazine (Tumil Nadu IHuti'd 2012)

Fi
+
Cl NH2 Ns NCI
NaN02/HCl,
NaNH2 in liq. NH3 NH3 273-278 K
¥ >
(Substitution (Diazotisation)
via benzyne
Chlorobezene intermediate) Benzene Benzenediazonium
chloride
NHNH2
(i) SnCl2/HCI
>
(ii) Dil. NaOH
(to neulralize HCI)
Phenylhydrazine
31. Ethylbenzene to 2-phenylpropanoic acid
CH2CH3 CH3—CH—Br CH3—CH—CN CH3—CH—COOH
Btilhv, A f n
Ale. KCN. A H'*'/H20
{Side chain -KBr {Hydrolysis)
hmminatioji)
Ethylbenzene l-Bromo-l- 2-Phenylpro- 2-Phenylpro-
phenylethane panenitrilc panoic acid
32. Benzene to m-chloroethylbenzene
COCH3 COCH3 CH2CH3
w
(CH3C0)20, Zn - Hg +
Anhyd. AICI3 CI2, Anhyd. AICI3 Cone. HCl
>
(/\C. acylation) {Huclear chlorination) {Clemmensen
F lo
Cl reduction) Cl
Benzene Acetophenone Acetophenone m-Chloroethylbcnzene
ee
33. p-Aminobenzoic acid from toiuene
Fr
CH3 CH3
for COOH COOH
ur
Cone. HNO3
^ Cone. H2SO4. A K2Cr207/H2S04, A Sn/HCi
—-—► -►
s
{Nitration) (Oxidation) {Reduction)
ook
Yo
Toluene
eB
NO2 NO2 NH2

/7-Nilrotolucnc ;?-Nitrobenzoic /^-Aminobenzoic
{major isomer) acid acid
our
ad
34. Phenoi to aniiine 201M)

Y
Re
OH NO2 NH2
nd
Cone. HNO3 + Cone. H2SO4

Fi
Zn dust 333 K Sn + HCl

>
Distil (Nitration) (Reduction)
Phenol Benzene Nitrobenzene Aniline
35. Phenol to aspirin
OH ONa OH OCOCH3
(0 CO2.410K
4-7 atm pressure .COOH (CH3C0)20 .COOH
NaOH — drop of cone. H2SO4
(Kolbe s reaction) ^
(lO H*/H20 (Acetylation)
Phenol
Sod. phenoxide Salicylic acid Aspirin
I
A/74 ‘PtûUe^'A New Course Chemistry (XII)BQIBD
36. Benzoic acid to m*f1uorobenzoic add (in not more than three steps)
COOH COOH COOH
Cone. HNO3 + Cone. H2SO4 Sn/HCl

>
{Nitration) {Reduction)
Benzoic ucid
NO2 NH2
ni-Nitrohcn/oie ueiil »i-Aminobcnzoic
ucid
COOH COOH
NuN02/HBF4.
w
273-278 K Heal
*■
{Diazotization) -N2,-BF3
N2BF4 F
m-Fluorobcnzoic ucid
Flo
e
Alternatively,
re
COOH COOH COOH
F
Cone. H2SO4, A (/) KHF2,573 K, Fuse
ur
r
>●
Benzoic ucid
{Sulphonatlon)
SO3H fo
{ID H'*'/H20
F
ks
m-Sulpliobcnzoic ucid fli-Fluorobcnzoic ucid
Yo
oo
3/. Benzoic acid to m-nitrobenzyl alcohol (NCICR'D

B
COOH COOH COCI CH2OH

Cone. HNO3 1
re
+ Cone. II2SO4, A SOCI2 (0 N11BH4

>
u
ad
(Nitration) -SO2.-HCI (//) H3O

Yo
NO2 NO2 NO2

Benzoic ucid m-Nitrobcnzoic m-Nitrobcnzyl
m-Nitrobcnzoyl
ucid chloride alcohol
d
Re
TYPE III—MULTISTEP CONVERSIONS

in
H Benzene to benzophenone
F
CH3 COOH COCI
(/) Aik. KMn04,

Cll3CI/Anhyd. AICI3 [Oxidation) SOCI2
¥ ¥
{/.'C. alh’lalion) (ii) H VH2O SO2. -HCI
Benzene Toluene Benzoic acid Benzoyl chloride
C6lVAnhyd.AICl3
{.FC. acylation)
Benzophenone
Aniline to O’bromoanlline
NH2 NH2 NHCOCH3 NHCOCH3

H-,S04. Br
453-473 K Ac20/Pyridinc
Dr2/CH3COOH^
{Siilphonalion) {Atviyialion)
SO3H SO3H SO3H
NHCOCH3 NH2
Br Br
H2O/373 K NaOH. A
w
(Oexfilfihonailon) {llyilmiysis)
M-Brumuucetunilidc o-Bromuunilinc
Flo
Benzene to phenylacetic acid
e
re
CH CH2CI CH2CN CH2COOH
CH3CI +
F
o
Anhyd. AICI3 CI2, hv
♦
Ale. KCN
n^ H20
{.FC. ulkylaiion) 389 K KCI
ur
r
Hydrolysis
Benzene Toluene Benzyl
chloride
fo
Phenylncctonitrilc Phenylucctic
acid
ks
Yo
Q Benzene to p-nitrobenzaldehyde
oo
CHO
B
CH3 CH3 CH(0C0CH3)2

01301,+ Cone. HNO3
re
Anhyd. AICI3 + Cone. H2SO4. A C'(03 0H"/H20

{.FC. (ilkylulion) {Nilnuloii) (CH3C0)20^ ^ L
u
{Hydmiyxis)
ad
Yo
Benzene Toluene
NO2 NO2 NO2

^-Nint)toluene /j-Nitrobenzuldehyde
d
{major isomer)
Re
in
Benzaldehyde to 3>phenylpropan-l>ol
F
(NCKRT)
P+Br
NaBH4.CH30H Mg/ether
C^Hj—CHO {Reduction)
> C^HsCHjOH ^ C6H5CH2Br ^ C6H5CH2MgBr
Benzaldehyde Benzyl alcohol Benzyl bromide
/"\
(i)CH2-CH2
4 Cf,H5CH2CH2CH20H
(/OH3O* 3-Phetiylpropan-1 -ol
Allcrnafivelyy
CH3CHO.Dil.NaOH NaBH
C^HjCHO (Crosso Idol condensation)

4 CgHjCH = CHCHO 4 C6H5CH2CH2CH20H
Benzaldehyde 3-Phenylprop-2-enal 3-Pheny!propan-1-ol
A/76 Tâdee^ '4 New Course Chemistry (XII) w»tii
1^1 Benzene to salicylic acid

SO3H ONa
Cone. H2SO4, CO2.400 K,

353-363 K NaOH, 573 K. fuse 4-7 atm
»
(Sulphoiwlion) -Na2S03. - H2O (Kolhes reaction)
Benzene Bcnzcnesulphonic acid Sod. phenoxide
ONa OH
COONa COOH
H^/H2P ^
(Addijicatiori)
w
Disodium salicylate Salicylic acid
Alternatively
Flo
ee
ONa ONa OH
Fr
COONa COOH
CCI4. NaOH. 340 K H'^/H20
(Reimer-iTemann reaction) {Acidification)
for
ur
Sod. phenoxide Disodium Salicylic acid
.salicylate
s
ok
Yo
Benzene to aspirin
Bo
re
OH OCOCH3
As given in COOH COOH
(CH3C0)20
ou
conversion 6
ad
>
above f a few drop of cone. H2SO4
Y
{Acetylation)
Benzene Salicylic acid Aspirin
nd
Re
Benzene to cinnamic acid

Fi
CH3 CH(0C0CH3)2 CHO
CH3CI, Anhyd.AICl3 Ct03 OH /H2O

{EC. alkylation) (CH3C0)20 {Hydrolysis)
Benzene Toluene Bcnzaldehyde
CH=CHCOOH
(0 (CH3C0)20, CH3COONa. A
>
(ii)HVH20
(Perkin condensation) Cinnamic acid
TYPICAL AUPHATIC AND AROMATIC CONVERSIONS A/77
[Benzeiie to mrmethoxyaiiiliiie (or m-anMdine)

SO3H
Cone. H2SO4, Cone. HNO3
353-363 K + Cone. H2SO4, A NaOH, 573 K, fuse
(Sulphonatiori) (Nitration) —Na2S03, —H2O

Benzene
NO2
Benz^nesuiphonic m-Nitrobenzene-
acid
sulphonic acid
ONa OCH3
ow
3
CH3I Sn/HCl
(Williamson synthesis) (Reduction)

NO2 NO2 NH2
m-Nitroanisole m-Anisidine
e
re
10.
Frl
F
OH Br MgBr COOH
Zndust,A^ Mg/ether (0 'c®

Bf2/Fe ^
ou
or
— ► + ►
-ZnO ^ I ■ (Grignard L 00 H /H2O
Phenol Benzene Bromobenzene kfs
reaction) _
Phenylmag.
bromide
Benzoic acid
oo
Alternatively,
Y
OH COOH
B
re
Zn dust, A CH3CI,Anhyd.AlCl3 (i)Alk.KMn04

♦>
-ZnO (EC. alkylation) (iOH'"/H20 ^
oYu
(Oxidation)
ad
Phenol Benzene Toluene Benzoic acid

d
11.
in
Re
COOH
F
Soda lime
(CaO + NaOH),A Cone. H2SO4,353 K NaOH, 573 K, Fuse
>
-CO2 (Sulphonation) —Na2S03, —H2O
(Decarboxylation) Benzene
Benzoic acid Benzenesulphonic
acid
ONa OH
H~*^^H20
(Acidification)
Sod. phenoxide Phenol
e*
A/78 ûuUefr'^4 New Course Chemisti^-OCn)B&nD
COOH
Soda-lime Cone. HNO3
CH3CI.Anhyd.AICl3 + Cone. H2SO4,
I (CaO + NaOH),A^ {Nitration) j ^
{EC alkylation)
Benzoic acid {Decat^^lation) Benzene Toluene
COOH
K2Cf207, H2SO4
{Oxidation)
low
NO2 NO2
/;>Nitrotoluene /^●Nitrobenzoic ac|d
{nutfor isomer)
Alternatively,
ee
F
Fr
COOH Br Br
CottC.HN03
for
ur
Br2/CCl4,A
► ■ + Conc. H2S04,A^ CuCN/pyridlne ^
{Hunsdiecker reaîon) {Nitration) 475 K
s
Benzoic acid
ook
Bromobenzene
Yo
NO2
/^'Nitrobromobenzene
eB
{mqfor Lsomer) COOH

r
H^/H20
ou
ad
{Complete hydrolysis)
Y
NO2
Re
nd
/;-Nitrobenzonitrile /r-Nitrobenzoic acid

Fi
Cone. HNO3 + Cone. H2SO4,

333 K Sn + HCI
{Nitration) {Reduction)
Benzene Nitrobenzene Aniline
Now convert aniline to /^nitroaniline as shown in conversion 18, page A/79.

14.
Cone. HNO3 + Cone. H2SO4,

333 K
Br^Fe ^ Sn + HCl
¥
(Nitration) {Bmmination) (Reduction)
Benzene Nitrobenzene m-Bromonitrobenzene
(S' NsNCr
NaN02, DU. HCI,

273 - 278 K
¥ Boiling dll. H2S04^
(Diazotization)
m>Bromoaniline m-Bromobenzene* /n*Bromophenol
diazonium ehloride
w
4
F lo
NO2
ee
NaN02, Dii. HCI,
Fr
273-278 K
Br2/Fe ^ Sn + HCl
¥
(Bromination) (Reduction) (Dlazotization)
Nitrobenzene ffl'Bromonitrobenzene
for
m-Bromoaniline
ur
+
NsNCr
s
ook
Yo
cucimci ^
(Sandmeyer reaction)
eB
m-Bromobenzene- m-Bromoehloroberizene
diazonium ehloride
our
ad
16.
Y
Re
nd
Cone. HNO3 + Cone. H2SO4,343 K NH4HSorNaHS ^

Fi
>
(Nitration) (Selective reduction)
I
m-Dinitrobenzene m-Nitroaniline
NaN02/HCI.
273-278 K Boiling dil. H2S04
(Diazotisation) ■■■
m-Nitrobenzene- fn*Nitrophenol
diazonium chioride
A/80 pfMdee^'4. New Course Chemistry (XU)Q
iH 4-NltroanUine to 1* % 3-trlbrOmobetizeiie
+
N=NCr
Br NaN02 + Oil. HCI,

Brz/CHjCOOH ^ m-mvi
>
(Bmmination) (Diazotisation)
NO2 NO2 NO2

4-Nitroaniline 2,6-Dibromo- 2,6-DibromcMl-nitrobenzene-
4-nitroaniline diazonium chloride
w
Br
Br NaN02 + Dil. HCI

CuBr/HBr Sn/HCl 273-278 K
Flo
¥
(Sandmeyer ivacthn) (Reduction) (Diazotisation)
T
e
re
NH2
3,4,5-Tribromo- 3,4.5-Tribromoaniline
F
nitrobenzene
ur
r
Br
fo
ks
Br Br Br
H3P02/Cu^^
Yo
oo
(Reduction)
B
1,2,3-Tribromobcnzene
■"N=Ncr
re
3.4,5-Tribromobenzene-
diazx>nium chloride
u
ad
Yo
Benzamide frohi hitioboiizeite

d
Re
in
NH2 Ncr
F
NaN02 + Dil. HCI,

Sn + HCI 273 - 278 K KCN/CuCN
> . ¥
(Reduction) (Diazotization) A
Nitrobenzene Aniline Benzene-

diazonium chloride
CONH2
Dissolve in cone. H2SO4
o
and then pour in H2O
>
(Partial hydrolysis)
Benzonitrile Benzamide
19. Aniline to benzyl alcohol « MSI-: 2»l>)

Convert aniline to benzonitrile as in conversion 18, page A/80.
Now convert benzonitrile to benzyl alcohol as follows :
CN COOH CM,OH
H'^/UoO (/) LiAIHyElher

+ ►
{tlydixtlysis) {//'llljO (Rcdiulion)
Benzonitsilu Benzoic acid
Benzyl alcohol
20. Benzene into m-dichlorobenzeiie
w
NO. NH.
Cone. HNO3 +Conc. II.S04,
F lo
373 K Sn + IICI
-►
{Nitration) (Rediulioii)
Benzene
NO. NII3
ee
/M-l)initrobenzene Hi-I’licnylenediamine
Fr
+
NsNCr Cl
NaN02+Dil. MCI,
273-278 K for
ur
CiiCI f HCI
(Diazotizalion) +
{Stindmi.'yer ivucfio/i)
NsNCr
s
Cl
ook
Yo
/M-I'hciiylencdiaminc /«-l>ichlorol>cn/cnc
leiruzonium chloride
eB
21.
Toluene into ethyl p-nitrobenzyl ether
our
ad
CH3 CH3 CH3 CH 3
/^:^NO.
Y
Cone. HNO3 + Cone. H.SO4. A Separate by
k^
+
k^
Re
{Nitration)
nd
nitration
Toluene
f;-Nt(rololuenc
Fi
{IM/uid. minor) NO. NO.

//-Nilrotolucnc (niujor) /i-Nilrololiicnc
(Solid)
CH.Cl
CM. -o-cii.c:ii3
Cl.(l mole), 383 K./ir CHjCH.O' Na*
-HCI
(Side chain chlorination) k^ ( NaCI)
(H'illiamxon .yi'»///ff.v/.v)
N02 NO.
/>-Nitrobenzyl chloride Iithyl-/»-nilroben/yt ether
A/62
New Course Chemistry (XII)BZ£D9D
22. m-Bromo!odobenzene from benzene
NO2 NO2
Cone. HNO3 + Cone. HiSO^, Sn/HCi
373 K Bri/Fc
-►
{Nitraiion) {Bmniiiialion) {Rc(liicrioii)
Br
Benzene Nitrobenzjjnc
/w-Bromoniirobenzene
+
N=NCr
NH2
NaN02+Dil. HCl,
273 -27K K KI
low
♦
A
{DUtzolizalioii) Br
Br
m-Bromobenzene- m-Bromoiodobenzenc
/N-Bromoanilinc
diazonium chloride
(JEE Main 2021)
ee
23. Nitrobenzene to m-DIbromobenzene
F
Fr
+
NsNCr Br
N02
for
ur
As in CnBr/HBr
( n
conversion (Stiiidmiyt'r
Br
ks
22 above Br reaction)
Yo
Nilrobenzene m-Bromobenzene- «i-Dibromobenzcnc
oo
diazonium chloride
eB
24. Bromobenzene to p-methoxyphenol, (in not more than five steps)

r
OCH3
ou
ad
Br Br
Cone. HNO3
Y
^ Cone. H2SO4, A Sn/HCI

ri ( n CM3QNa/CH30H. A ^ (1
(Nucleophilic suhslilulion) (Reduction)
(Nitration)
Re
nd
Bromobenzene
NO2
Fi
NO2
/>-Bromonitrobenzene /;-Nitroanisole
(major ixomer)
OCH3 OCH3 OCH3

NaNO-), dil. HCl,
273-278 K ^ (1 Dil. H2SO4, A ^
(Diazotisaiion)
NH2 ■"N=Ncr
/^-Anisidine /?-Methoxybenzene- /)-Meihoxyphenol
diazonium chloride

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1

Acetyl chloride Ethyl alcohol Ethyl acelaic

Acetic anhydride Ethyl alcohol Ethyl acetate Acetic acid

This reaction is called aldol condensation. For example,

Ethanal or Acetaldehyde 3 -Hydro xybutanal

(two molecules) (Aldol)

CH3CH2. Dil. NaOH

propanal or Propionaldehyde 3-Hydroxy-2-methylpentanal

Intramolecular aldol condensation. If a compound contains two aldehydes/ketones or one aldehyde

^SBalz-Schiemann reaction (Hr. Board 2013)

Fluoroarenes (aryl fluorides) cannot be prepared by direction fluorination of aromatic hydrocarbons

273-278 K + N2+ BF3

This reaction is called Balz-Schlemann reaction.

(West Bengal Board 2012)

CH3 CH3 CH3

2, 2-Dimethylpropanoi Sod. 2, 2-dimethylpropanoate

CH3O CHO + HCHO + NaOH > CH3O CH2OH + HCOONa

^|Carbylamine reaction (Pb. Board 2009 ; HP Board 2011 ; MP Board 2011 ;

amines It occurs under/rt/u//v acidic conditions. For example.

Benzenediazoniuni Aniline Diazoaminobenzene

30a 310 K, warm

The process of removal of a molecule ofC02from a carboxylic acid is called decarboxylation. It is

^ p a ' ' Acetone

NaN02 + HCl HONO + NaCl

Acetic acid Ethyl alcohol Ethyl acetate

as a catalyst, the reaction is commonly known as Fischer-speier esteriifcation.

Brown complex Benzaldehyde

Similarly, Etard reaction on p-nitrotoluene and p-chlorotoluene gives p-nitrobenzaldehyde and p-

(MP Board 2011; AP Board 2012)

CH3 CH3 CH3

ib) Friedel-Crafts acylation.

(Pb. Board 2010 ; Raj. Board 2011 ; CBSE 2008, 2018)

Pol. phthalimide N-Ethylphlhalimide

The yields are around 40%

Gattermann-Koch reaction and is used for commercial preparation of benzaldehyde.

CgHg + HCN + HCl ^ CgHjCH = NH.HCl ^ C^HjCHO + NH4CI

Benzaldmine hydrochloride Benzaldehyde

19. Grignard synthesis

compounds commonly known as Grignard reagents.

4 [R2C = NMgX] 4 R2CO + NH3 + Mg(OH)X

CH3CHOHCH3 + 412 + 6 NaOH -4 CHI3 -4 CHjCOONa + 5 Nal -4 5 H2O

CH3COCH3 -1- 3 I2 + 4 NaOH -4 CHIg + CH3COONa + 3 Nal + 3 H2O

CH3COCH2CH3 -1- 3 I2 + 4 NaOH -4 CHI3 + CH3CH2COONa + 3 Nal + 3 HjO

CgHgCOCHg -H 3 I2 + 4 NaOH 4 CHI3 -4 CgHsCOONa + 3 Nal -4 3 H2O

Hell-Volhard Zelinsky reaction

Ammonia Alkyl halide 1“ Amine salt 1® Amine

I" Amine Alkyl halide 2" Amine sail

iiii) R2NH > R3NH'*'X“

23. Hofmann bromamide reaction or Hofmann degradation of amides

CH3CONH2 + Br2 + 4 NaOH CH3NH2 + 2 NaBr -t- Na2C03 + 2 H2O

CH3CH2CONH2 + Bt2 + 4 KOH- CH3CH2NH2 + 2 KBr + K2CO3 + 2 H2O

(CH3CH2CH2)2B—H Hy<.obor„.io„^ : (GH3CH,CH,)3B

Tri-«-propylborane Propan-l*ol Boric acid

been fanned by anti-Markownikov’s addition of water to alkenes.

Kolbe electrolytic reaction (HP Board 2011)

{a) Ethane is produced when an aqueous solution of potassium acetate is electrolysed.

2H2O ^ ± 2 OH- + 2 H-" (Ionization)

(b) Ethylene is produced when potassium salt of succinic acid is electrolysed.

CH2COO' CH.COO CH,