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ALLEN
HALOGEN DERIVATIVES
1.0 HALOGEN DERIVATIVES
Compounds derived from hydrocarbons by replacement of one or more H-atoms by corresponding no. of
halogen atoms are known as halogen derivatives.
2.0 CLASSIFICATION
On the basis of nature of hydrocarbon from which they are obtained, halogen derivatives can be classified as :

Halogen Derivatives

Alkyl halides Alkenyl halides Alkynyl halides Aryl haides

N
Mono halides Di-halides Tri-halides Tetra halides

0
Primary halides Secondary halides Tertiary halides

-2
3.0 MONOHALIDES :
3.1
E
Genreal Methods of Preparation of Monohalides

19
(1) By direct halogenation of alkanes :

R—H + Cl2 ¾¾¾¾

U.V.light
® R—Cl + HCl
(excess)
20
LL
(2) By the addition of H—X on alkenes :
n
R—CH CHR + HX ¾¾® RCH2—CHXR
¾¾® CH3 —CH2X
io

eg: CH2 CH2 + HX

eg: CH3–CH CH2 + HX ¾¾® CH3 CH CH3

ss

X
Se

Isopropyl halide
(3) By Alcohols :
A
Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

(a) By the action of hydrogen halides :

H- X
R—CH2—OH ¾¾¾ ® RCH2—X

(b) By the action of phosphorous halides :

R—OH + PCl5 ¾¾® R—Cl + POCl3 + HCl
3R—OH + PCl3 ¾¾® 3RCl + H3PO3
PBr3 and PI3 are less stable, thus for bromides ( P + Br2) and for iodides ( P + I2) mixture is used.
(c) By reaction with thionyl chloride (Darzen's procedure) :
Pyridine
R—OH + SOCl2 ¾¾¾¾
(1 mole)
® R—Cl + SO2 + HCl

One mole One mole

Because of less stability of SOBr2 and SOI2, R—Br and RI can not be obtained by this method.
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(4) Borodine – Hunsdicker's reaction :
CCl4
R—COOAg + X2 ¾¾¾®
D
R—X + CO2 + AgX

Silver salt of (Cl2 or Br2)

a fatty acid
(5) By halide exchange :

R–Cl or R—Br + KI ¾¾¾¾®

Acetone R–I + KCl or KBr (Conant finkelstein reaction)

2CH3Cl + Hg2F2 ¾¾¾

Water
® 2CH3–F + Hg2Cl2 (Swart reaction)
Note : Finkelstein reaction can only be used to prepare R–I and swart's reaction can only be used to prepare R–
F
3.2 Physical Properties
(a) The lower members CH3F, CH3Cl, CH3Br , C2H5Cl and C2H5F are gases at room temp.
(b) Higher B.P. than parent alkanes.

N
Decreasing order of B.P. is : R–I > R—Br > R—Cl > R—F
among isomeric R—X, decreasing order of B.P. is : Primary > Secondary > tertiary

0
(c) R—F and R—Cl ¾¾® lighter than water

-2
R—Br and R—I ¾¾® heavier than water
E
Decreasing order of density is : R—I > R—Br > R—Cl > R—F

19
(d) R—X are polar co-valent compounds but insoluble in water because they can not form
H–bonds. They dissolve in organic solvents.
(e) R—X (except R—F) burns with a green flame when interacted with Cu wire.(Beliestein test)
(f) Dipole moment order–
20
LL
n
(i) CH3Cl > CH3F > CH3Br > CH3I (ii) Cl > Cl
io
ss

3.3 Chemical Properties

3.3.1 Nucleophilic substitution reaction ( SN ) :
Se
A

HOH(Boil)
Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

(a) X by — OH
R—OH (alcohol) + HX

KOH aq.
(b) R—OH (alcohol) + KX
X by — OH

(c) R—X¾ ® moist Ag 2O

R—OH (alcohol) + AgX
X by — OH

KSH alc.
(d) R—SH + KX
X by –SH
(Mercapto Gp.) Alkane thiol
(Mercaptane)
NaSR'
(e) RSR' + NaX
X by SR
Thioether
R' COOAg, D
(f) R' COOR + AgX
X by(R'COO)
(Alkyl alkanoate) ester

2 E
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(g) Reaction with KCN and AgCN :
d+ d–
Alc.
R— X + KCN ¾¾¾ D ® R—C N + R—NC + KX
Ionic ` cyanide Isocyanide
(major) (minor)

l CN ion is an ambident nucleophile.

d+ d- .. Alc.
R—X + Ag—CN ¾¾ ¾® R— N C + R—CN + AgX
D
covalent isocyanide Cyanide
(Major) (Minor)
(h) Reaction with KNO2 and AgNO2 :
d+ d- Alc.
R—X + KO—NO ¾ ¾ ¾ ® R — O—N O + R—NO2 + KX
D
Ionic Alkyl nitrite Nitro alkane
(Major) (Minor)

N
d+ d- .. Alc.
O
R—X + Ag—O—N=O ¾ ¾ ¾ ® R— N + R—O—N=O + AgX
D O
covalent Nitroalkane Alkyl nitrite

0
(major) (minor)

-2
(i) E Reaction with NaOR' (Sodium alkoxide) :
R—X + NaOR' ¾¾® R—OR' + NaX

19
(williamson synthesis reaction)
(j) Reaction with NH3:
D
R— X + NH 3 ¾¾® R —X
R — NH 2 ¾¾¾¾ R —X
® R—NH—R ¾¾¾®
20 R N R
LL
R
¾®
n
R X
io

R
Å
ss

R N R X1
R
Se

(Quaternary salt)
A
Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

(k) Reaction with CH CNa :

R—X + CH CNa ¾¾®

D R—C CH + NaX

CH3
–+ D
If CH3 C X + CH CNa ¾ ¾ ® CH3 C CH2 + NaX + CH CH
CH3 CH3
(3º halide) (Elimination is more)
3.3.2 Dehydrohalogenation : Alkyl halides undergo b - elimination on treatment with KOH (alc.) or NaNH2.
b a
D
R — C H2 — CH 2 — X + KOH (alc.) ¾¾ ® R—CH CH2 + HX

CH3—CH2—CH2—CH2—Br + KOH(alc.) ¾¾®

D CH3—CH2—CH CH2 + HBr

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Alc.KOH
¾¾¾¾¾D ® CH3—CH CH—CH3 + CH3—CH2—CH CH2 + HBr

But-2 -ene (80%) But-1-ene (20%)

Dry ether
3.3.3 Wurtz Reaction : 2RX + 2Na ¾¾¾¾¾
® R - R + 2NaX

When a mixture of different alkyl halides, (R1 - X) and (R2 - X) is used a mixture of alkane is formed -

R1—X + 2Na + X—R2 ¾¾¾¾¾

Dry ether D
® R1—R2 + R1—R1 + R2—R2 + NaX

3.3.4 Formation of Organometallic compounds :

(i) R—X + Mg dry ether

¾¾¾¾¾ ® RMgX (Grignard reagent)

(ii) 2C2H5Br + 2Zn dry ether

¾¾¾¾¾ ® (C2H5)2 Zn (Frankland reagent) + ZnBr2

N
(iii) 4C2H5Cl + 4Na / Pb ¾¾® (C2H5)4 Pb + 4NaCl + 3Pb
Sodium lead Alloy Tetra ethyl lead (used as antiknocking agent)
3.3.5 Friedel - Crafts reaction :

0
-2
CH3
E + CH3Cl
AlCl3(anhyd)
¾¾¾¾¾® + HCl

19
Benzene Toluene

4.0 DIHALIDES
20
General formula CnH2nX2 .Two H - atom of alkanes, replaced by two halogen atoms to form dihalides.
LL
Dihalides are classified as :
n
(a) Gem dihalide : The term Gem is derived from geminal means - same position.
io

Two similar halogen atoms are attached to same C - atom

Ex. CH3CHX2 Ethylidene dihalide (1, 1 - Dihalo ethane)
ss

Isopropylidene dihalide (2, 2 - Dihalo propane)

Se
A

(b) Vic dihalides : Vic term from - Vicinal means adjacent C - atoms
Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

Two halogen atoms are attached on adjacent carbon atom.

H
Ex. CH 2 CH2 H C CH CH2 Vic and Gem dihalides are position isomers.
X X H X X

Ethylene dihalide Propylene dihalide

(1,2-Dihaloethane) (1,2-Dihalopropane)
(c) a, w dihalides : Halogen atoms are attached with terminal C - atom. They are separated by 3 or more
C - atoms. They are also known as polymethylene halides.
Ex. CH2 CH2 CH2 CH2 (1,4-Dihalobutane)
X X Tetramethylene dihalide

4 E
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4.1 General Methods of Preparation
(a) Gem dihalides :
(i) By the reaction of PCl5 on carbonyl compound.
O Cl

CH3 C H + P C l5 ¾¾® C H 3 C H + P O C l3
Cl
Acetaldehyde Ethylidene chloride
O Cl

CH3 C CH3 + PCl5 ¾¾® CH3 C CH3 + POCl3

Cl
Acetone 2, 2 - Dichloropropane
(ii) By addition of halogen acids on alkynes :

CH CH + HBr ¾¾® CH2 CHBr ¾¾¾

HBr
® CH3 CHBr2

N
Vinyl bromide 1, 1 - Dibromoethane

0
Br

-2
HBr
CH3 C CH + HBr ¾ ¾ ® CH3 C CH2 ¾ ¾ ¾ ® CH3 C CH3
E Propyne Br Br

19
2, 2 - Dibromopropane

(b) Vic-dihalides :
(i) By the addition of halogens to alkenes : 20
LL
CH2 CH2Br
+ Br2 ¾ ¾ ®
CH2 CH2Br
n
1, 2 - Dibromoethane
io

CH3 CH CH2 + Br2 ¾ ¾ ® CH3 CH CH2

ss

Br Br
1, 2 - Dibromo propane
Se

(ii) By the action of PCl5 on glycols :

A
Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

C H 2O H C H 2C l
+ 2 PC l 5 ¾¾® + 2 P O C l3 + 2 H C l
C H 2O H C H 2C l

4.2 Physical Properties

(i) Lower members are colourless, oily liquids with sweet smell. Higher members are solid.
(ii) These are heavier than water.

4.3 Chemical Properties

(i) Action of KOH(alc.) : (Dehydrohalogenation)

CH2X CH3 CH
KO H (a lc.)
or ¾¾¾®
CH2X CHX2 – 2H X CH

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(ii) Action of KOH(aq.) : (Hydrolysis) It is a distinction test for gem - and vic - dihalides.
CH2 Cl CH2 OH
(a) + 2KOH(aq.) ¾¾¾® + 2KCl
CH2 Cl CH2 OH

Glycol
Vic-dihalide. 1, 2 - Ethanediol
(b) CH3CHXCH2X KOH(aq.)
¾¾¾¾¾ ® CH3 CH CH2
Vic-dihalide
OH OH
Propane - 1, 2 - diol

CH3 CH3 KO H (aq .)

¾¾¾¾®
KO H
(aq.) and CH 3CX 2CH 3 ¾¾¾¾® CH3COCH3 (Ketone)
CHX2 CHO

Gem-dihalides
(iii) Reaction with KCN :

N
CH2 Cl CH2 CN CH2 COOH CH2 CO
H O/H + D
+ 2KCN ¾ ¾ ¾ ¾ ® ¾ ¾2 ¾ ¾ ® ¾¾¾¾® O
CH2 Cl — 2KCl CH2 CH2 —H2 O CH2
CN COOH CO

0
Vic-dihalide Succinic acid Succinic anhydride

-2
E Cl CN + COOH
CH3 CH
2KCN
¾ ¾ ¾ ¾ ® CH3 CH ¾H¾
2O/H
¾ ® CH3 CH ¾ ¾D¾ ® CH3 CH2 COOH

19
— 2KCl —CO
Cl CN COOH 2

Gem-dihalide Propanoic acid

(i) – CN group on acid hydrolysis gives - COOH

(ii) Two – COOH group on one C – atom always loose CO2 to form monocarboxylic acid on heating.
20
LL
(iii) Two – COOH group on vic. C – atom loose H2O to form cyclic anhydride on heating.
n
(iv) Dehalogenation :
io

CH2Br CH2
Vic. + Zn
CH 3OH
¾¾¾® + ZnBr2
Heat
CH2Br CH2
ss

Same Carbon Product

Se

CH2Br CH 3OH CH2

a - w. CH2 + Zn ¾¾¾¾® H2C + ZnBr2
A

D
CH2Br CH2
Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

a, w - dihalide. Cyclopropane

BEGINNER'S BOX-1
1. Which of the following is not organometallic compound
(1) RMgX (2) R2Zn (3) RONa (4) R2Hg
2. Which is Finkelstein reaction ?

acetone
(1) R–X + NaI ¾¾¾¾ ® (2) R–X + AgF ¾¾®

(3) R–X + NaF ¾¾® (4) R–F + AgCl ¾¾®

6 E
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5.0 TRI HALIDES (Haloform CHX3)
5.1 General Method of Preparation

hn
(i) From CH4 : CH 4 +3Cl 2 ¾¾¾ ® CHCl 3 +3HCl

(ii) By Haloform reaction (lab method) :

CH3CH2 OH (HCOO)2Ca
or Bleaching powder [CaOCl2]
¾¾¾¾¾¾¾¾¾¾¾¾¾¾ ¾® CHCl3 + or
CH3COCH3 H 2O / D
(CH3COO)2Ca

Mechanism :

CaOCl2 + H2O ¾¾® 2Cl + Ca (OH)2

CH3CH2–OH + 2Cl ¾¾® CH3CHO + 2HCl (Oxidation)

N
CH3CHO + 6Cl ¾¾® CCl3CHO + 3HCl (Halogenation)

CCl3CHO + Ca (OH)2 ¾¾® CHCl3 + (HCOO)2Ca (Hydrolysis)

0
If CH3COCH3 is used then CHCl3 is formed into 2 steps (Chlorination and Hydrolysis)

-2
E
(+) ve haloform reaction : Reaction which gives haloform with alkali and X2 is called as (+) ve haloform

19
reaction.

Ex. Alcohols : CH3—CH—Z

OH
20
LL
CH CH— CH3 CH C H — C H 2— C H 3 CH C H —C H 2 ....... CH 3 etc.
n
3 3 3
, ,
OH OH OH
io

Aldehydes : Only acetaldehyde C H 3 C H

ss

O
Se

Ketones : CH 3 C Z
A
Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

Ex . C H 3 C CH3, CH 3 C C H 2 —C H 3 , C H 3 C C H 2 ........ C H 3 etc. (All methyl ketones)

O O O

CH 3 C COO H , CH 3 C C H O Also show haloform reaction.

O O

(–) ve haloform reaction : Reaction in which haloforms are not formed with X2 and alkali.

Ex. , , , . do not show haloform reaction.

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(iii) Preparation of pure CHCl3 :
NaOH
CCl3CHO. 2H2O ¾¾¾¾
D ® CHCl3 + HCOONa + 2H2O

Chloral hydrate (Pure Chloroform)

Chloral can also be used in preparation of D.D.T.

Cl
H SO
CCl3CH O + 2H Cl ¾ 2
¾®4

(conc.)
CCl3CH
Cl
Dichloro diphenyl trichloro ethane
(DDT)

(iv) Industrial preparation :

N
CH3CH2—OH HCOONa
aq. NaCl/electrolysis
or CHCl3 or
CH3COCH3 CH3COONa

0
5.2 Physical Properties

-2
CHCl3 is colourless and sweet smelling liquid. It's B.P. is 61°C and it is insoluble in H 2O and have density more
E
than H2O. Chloroform is used as Anaesthetic.

19
5.3 Chemical Properties
(i) Oxidation : CHCl3 + [O] ¾¾¾¾¾
Air and light
® COCl2 + HCl
Phosgene gas or
20
LL
Carbonyl Chloride
(Poisonous gas)
n
CHCl3 is stored in dark coloured bottles which are filled upto the brim to prevent oxidation of CHCl3 into
io

COCl2 and 1% ethanol is also added to chloroform

ss

–2HCl
Se

[Poisonous]
[Non-Poisonous]
A

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Test of CHCl3
Reagent Pure CHCl3 Impure CHCl3 (COCl2 +HCl)
l Blue litmus No Change turns into red
l AgNO3 No reaction White ppt of AgCl
l Conc. H2SO4 No reaction Yellow solution

Cl OH
Aq.KOH —H O KOH
(ii) Hydrolysis : CH Cl ¾¾¾¾® CH OH ¾¾¾¾® H C OH ¾¾¾® H C OK
2

Cl OH
O O
Unstable
8 E
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(iii) Carbyl amine reaction or isocyanide test : (Hoffman's carbylamine reaction)
CHCl3 + KOH
Primary–Amines (Aliphatic or Aromatic) ¾¾¾¾¾¾ ® Isocyanides
Isocyanides have unpleasant or offensive smell (Isocyanide test).
CHCl3 + KOH
R—NH2 ¾¾¾¾¾¾ ® R—NC

Mechanism :
KOH
CHCl3 ¾¾¾® :CCl2
(electrophile)

H Cl
.. Å 1 —2HCl
R NH2 + :CCl2 ¾¾® R N C ¾¾¾¾® R N C
Alkyl isocyanide
H Cl

N
CHCl + KOH
CH3 CH2 NH2 ¾ ¾ ¾ ¾ ¾ ® CHCH
3
3 2 NC

¾CHCl
¾ ¾+¾
KOH
¾ ® Ph Reaction is given by only
Ph NH2 3
NC

0
primary amine
NH2 NC

-2
¾CHCl
¾ ¾+¾
KOH
¾®3

E
19
(iv) Reimer Tieman's reaction :

OH OH
CHO
20
LL
CHCl3 + KOH
¾¾¾¾¾¾ ®
n
Salicylaldehyde (o–Hydroxy benzaldehyde)
io

Mechanism : :CCl2 is neutral attacking electrophile (formed by a,a- elimination reaction)

ss

KOH
CHCl3 ¾¾¾® :CCl2
1
OH O O O
Se

1 H
Cl
A

1
¾–HHO
¾O¾ ® ¬¾¾® CCl2
¾¾¾® C
Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

2 Cl

1
OH O1 O
CHO OH Cl
1
¬¾ HÅ
¾¾ CH ¬ ¾OH
¾¾ CH
–H O 2 OH Cl

Note : If CCl4 is used in place of chloroform, salicylic acid is formed as product.

OH OH
(i) (CCl4 + KOH), D COOH
¾¾¾¾¾¾¾ (ii) HÅ
¾
®
(S alicyclic acid)

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(v) Reaction with CH3COCH3 :

CH3 C C H 3 + H—CCl3 OH CH3 C CH3

O OH C C l3

Chloritone (Hypnotic)
(vi) Reaction with HNO3 :

C C l3 H + HO N O 2 ¾¾® CCl3—NO2 + H2O

Chloropicrin or nitrochloroform
(Tear gas)
(vii) Reaction with CH3CH=CH2 :

CH3—CH==CH2 ¾¾¾¾¾¾®
CCl3
.
CHCl3/Peroxide CH3—CH—CH2
| |
H CCl3

N
A free radical addition reaction
Ag
(viii) Reaction with Ag : CHCl3 ¾¾¾ ® CH CH

0
-2
AlCl
(ix) FCR :E 3Ph – H + CHCl 3 ¾¾¾
3
¾
® Ph3CH
Triphenyl methane

19
GOLDEN KEY POINTS
Iodoform Test
20
LL
CH3CH2OH 1
n
I + NaOH or NaOI or OI
or ¾ 2¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ® CHl3
or I + Na CO + H O
CH3COCH3 yellow crystals
io

2 2 3 2

of iodoform
ss

l CHI3 give yellow ppt. of AgI with AgNO 3 but CHCl3 does not give AgCl ppt.
Reason :CHI3 is thermally less stable than CHCl3.
Se

Iodoform test can be used to distinguish the following pairs of compounds.

A

(i) CH3CH2OH and CH3OH

Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

(ii) CH3CHO and CH3CH2CHO

(iii) 2–Pentanol and 3–Pentanol
(iv) Acetophenone and benzophenone
(v) 2–Propanol and 1–Propanol

Freons
The chlorofluoro derivatives of methane and ethane are called freons.
CF2Cl2 – (dichloro difluoro methane)
C2F2Cl4 – (Tetrachloro difluoroethane)
Most useful is CF2Cl2 (Freon– 12)

10 E
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Nomenclature of freons :
Freon – cba
c = nc—1
b= nH+1
a = nF

c = n C -1 = 1 - 1 = 0 ù c=n C–1 =2 – 1=1ù

ú
CF2Cl2 ¾¾® b = nH +1 = 0 + 1 = 1ú Freon–12 C2F4Cl2 ¾¾® b=n H +1 =0+1=1 úú Freon–114
a=n F =2 úû a=n F =4 úû
l Excess use of Freons is harmful for Ozone layer (depletion of Ozone layer).

6.0 Grignard Reagent

6.1 General Method of Preparation
Grignard reagents are prepared in the laboratory by the action of alkyl halides on magnesium metal in the
presence of dry ether.
dry
R – X + Mg ¾¾¾
ether
® R—Mg—X

N
(Grignard reagent)
(Alkyl magensium halide)
The ease of formation of Grignard reagent is in the order RI > RBr > RCl

0
Ether is used to dissolve the Grignard reagent by coordination.
6.2 Chemical Reactions

-2
+
(i) O2 (ii) H3O
E ¾¾¾¾¾¾¾¾¾® R—OH 1° Alcohol

19
+
H2C=O/H 3O
¾¾¾¾¾¾¾¾¾® RCH—OH
2 1° Alcohol
O
CH2–CH2/H3O+
¾¾¾¾¾¾¾¾¾® 20
R—CH2—CH2—OH 1° Alcohol
LL
+
RCHO/H3O
R—Mg—X ¾¾¾¾¾¾¾¾¾® R2CHOH 2° Alcohol
+
HCOOEt/H 3O
¾¾¾¾¾¾¾¾¾® R2 CHOH
n
2° Alcohol
RCOR/H2O
io

¾¾¾¾¾¾¾¾¾® R3C—OH 3° Alcohol

RCOOEt/H 2O (2 : 1)
¾¾¾¾¾¾¾¾¾® R3C—OH 3° Alcohol
ss

¾ ¾ ¾HCOOEt
¾ ¾ ¾(1¾
: 1)
¾¾® RCHO aldehyde
RCN/H2O
¾¾¾¾¾¾¾¾¾® RCOR Ketone
Se
A

¾ ¾ ¾RCOOEt
¾ ¾ ¾(1¾: 1)¾ ¾ ® RCOR Ketone
Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

CO2/H 2O
¾¾¾¾¾¾¾¾¾® RCOOH Acids
HOH or ROH or
NH3 or Ph — OH
or R—NH2 or RNH — R
or CH CH or Ph — NH2
¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾ ® R—H Alkane
R—X
¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾ ® R—R Alkane
R3N
¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾ ® No reaction
ClCH —CH CH
¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾ ®
2 2
R—CH—CH
2 CH2 Alkene
Cl—NH2
¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾ ® R—NH2 1° Amine
Cl—CN
¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾ ® R—CN Cyanides
ClCOOEt
¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾ ® RCOOEt Ester
E 11
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7.0 Haloarene
If halogen atom is directly attached to the benzene ring, then compound is called as Haloarene.

CH 3
CH3 Cl
Cl Cl
Ex.
Cl

(Chlorobenzene) (2–Chlorotoluene) (2,4–Dichlorotoluene)

7.1 General Methods of Preparation

Cl

N
(1) + C l2 ¾¾¾®
3 A lCl
+ HCl

0
-2
(2) D
E 3

19
3C6H5OH + POCl3 ¾¾® (C6H5)3 PO4 + 3HCl

7.2 Chemical Properties

20
LL
(i) 623K, 300 atm
(1)
n
(ii) H
io

Presence of electron withdrawing group on ring makes the nucleophilic substitution easier.
ss

Reactivity Order : (Towards nucleophilic substatitution)

Se
A

Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

(2) Fittig reaction :

dry ether
Cl + 2Na + Cl + 2NaCl
D
(Diphenyl)

(3) Wurtz fittig reaction :

dry ether
Cl + 2Na + ClCH 2CH 2CH 3 CH2CH2CH3 + 2NaCl
D

12 E
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Pre-Medical : Chemistry
ALLEN
(4) Electrophilic Substitution Reaction :

anhy. FeCl3
(i)

(Major)
Note : Cl is o– and p– directing group.

conc. H2SO4
(ii)

(Major)

N
(iii) + conc. H2SO4

0
(Major)

-2
E
19
anhy. AlCl3
(iv)

20
(Major)
LL
BEGINNER'S BOX-2
n
io

1. Which can give haloform with X2/OH– ?

(1) CH3OH (2) CH3–CH2–CH=O
ss

(3) CH3CHO (4) CH3CH2CH2OH

2. Which of the following compounds cannot be identified by carbylamine test ?
Se
A

(1) C6H5–NH–C6H5 (2) CH3CH2NH2

Z:\NODE02\B0AI-B0\TARGET\CHEM\ENG\MODULE-6\01-HALOGEN\01-THEORY.P65

(3) CHCl3 (4) C6H5–NH2

3. For preparation of Grignard reagent from haloalkanes which metal is used :-
(1) Na (2) Mg
(3) Ca (4) Ag

ANSWER KEY
Que. 1 2
BEGINNER'S BOX-1
Ans. 3 1

Que. 1 2 3
BEGINNER'S BOX-2
Ans. 3 1 2
E 13