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Halogen Derivatives
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Chemistry : Halogen Derivatives
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®
Pre-Medical
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

®
Mono halides Di-halides Tri-halides Tetra halides

Primary halides Secondary halides Tertiary halides

3.0 MONOHALIDES :
3.1 General Methods of Preparation of Monohalides
(1) By direct halogenation of alkanes :
U.V.light
R—H + Cl2  → R—Cl + HCl
(excess)
(2) By the addition of H—X on alkenes :
R—CH = CHR + HX → RCH2—CHXR
eg: CH2 = CH2 + HX → CH3 —CH2X
eg: CH3–CH = CH2 + HX → CH3 CH CH3
X

Isopropyl halide
(3) By Alcohols :
(a) By the action of hydrogen halides :
H−X
R—CH2—OH → RCH2—X

(b) By the action of phosphorous halides :

R—OH + PCl5 → R—Cl + POCl3 + HCl
3ROH + PX3 → 3R–X + H3PO3 (X = Cl, Br)
PBr3 and PI3 are usually generated in site (Produced in reaction mixture) by the reaction of red
phosphorous with bromine and iodine, respectively.
(c) By reaction with thionyl chloride (Darzen's procedure) :
Pyridine
R—OH + SOCl2 
(1mole)→
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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Chemistry : Halogen Derivatives
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(4) Borodine – Hunsdicker's reaction :
CCl
R—COOAg + X2 →
∆
4
R—X + CO2 + AgX

Silver salt of (Cl2 or Br2)

a fatty acid
(5) By halide exchange :
Acetone
R–Cl or R—Br + KI → R–I + KCl or KBr (Conant finkelstein reaction)
2CH3Cl + Hg2F2 
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.
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

(c) R—F and R—Cl → lighter than water

R—Br and R—I → heavier than water
Decreasing order of density is : R—I > R—Br > R—Cl > R—F
(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.(Beilstein test)
(f) Dipole moment order–

(i) CH3Cl > CH3F > CH3Br > CH3I (ii) Cl > Cl

3.3 Chemical Properties

3.3.1 Nucleophilic substitution reaction ( SN ) :
R epl ac ement Produc t
HOH(Boil)
(a) X by — OH
R—OH (alcohol) + HX

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

(c) R—X→ moist Ag 2O

R—OH (alcohol) + AgX
X by — OH

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

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(g) Reaction with KCN and AgCN :
δ+ δ– ⊕ Alc.
R – X + KCN R–C ≡ N + R–NC + KX
Ionic –∆ Cyanide Isocyanide
(major) (minor)


 : C N ion is an ambident nucleophile.

δ+ δ− ..
Alc.
R—X + Ag—CN →
∆
R— N C + R—CN + AgX
covalent isocyanide Cyanide
(Major) (Minor)

(h) Reaction with KNO2 and AgNO2 :

δ+ δ−
Alc.
R — X + KO—NO →
∆
R— O—N O + R—NO2 + KX
Ionic Alkyl nitrite Nitro alkane

®
(Major) (Minor)

δ+ δ− .. Alc.
O
R—X + Ag—O—N=O →
∆
R— N + R—O—N=O + AgX
O Alkyl nitrite
covalent Nitroalkane
(major) (minor)

(i) Reaction with NaOR' (Sodium alkoxide) :

R—X + NaOR' → R—OR' + NaX
(williamson synthesis reaction)
(j) Reaction with NH3:
∆
R–X + NH3 → R − X → R–NH–R 
R–NH2  R −X →
R–N–R

R
R–X

R
⊕
R–N–R X

R
(Quaternary salt)

(k) Reaction with CH ≡ CNa :

∆
R – X + CH ≡ CNa → R – C ≡ CH + NaX

CH3
+ ∆
If CH3 – C – X + CH ≡ CNa → CH3–C=CH2 + NaX + CH ≡ CH
CH3 CH3
(3°halide) (Elimination is more)

3.3.2 Dehydrohalogenation : Alkyl halides undergo β - elimination on treatment with KOH (alc.) or NaNH2.
β α
∆
R − C H2 − C H2 − X + KOH (alc.) → R − CH = CH2 + HX
∆
CH3—CH2—CH2—CH2—Br + KOH(alc.) → CH3—CH2—CH=CH2 + HBr

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H Alc.KOH
Br → CH3 − CH = CH − CH3 + CH3 − CH2 − CH = CH2 + HBr
∆
But − 2 − ene (80%) But − 1 − ene (20%)
CH3–CH–CH–CH3

Dry ether
3.3.3 Wurtz Reaction : 2RX + 2Na 
→ R – R + 2NaX
When a mixture of different alkyl halides, (R1 - X) and (R2 - X) is used a mixture of alkane is formed -
Dry ether
R1—X + 2Na + X—R2 
→ R1—R2 + R1—R1 + R2—R2 + NaX
3.3.4 Formation of Organometallic compounds :
Dry ether
(i) R—X + Mg 
→ RMgX (Grignard reagent)
Dry ether
(ii) 2C2H5Br + 2Zn 
→ (C2H5)2 Zn (Frankland reagent) + ZnBr2
(iii) 4C2H5Cl + 4Na / Pb → (C2H5)4 Pb + 4NaCl + 3Pb
Sodium lead Alloy Tetra ethyl lead (used as antiknocking agent)

®
3.3.5 Friedel - Crafts reaction :
CH3
AlCl3(anhyd.
+ CH3Cl →
)
+ HCl

Benzene Toluene

4.0 DIHALIDES
General formula CnH2nX2 .Two H - atoms of alkanes, replaced by two halogen atoms to form dihalides.
Dihalides are classified as :
(a) Gem dihalide : The term Gem is derived from geminal means - same position.
Two similar halogen atoms are attached to same C - atom
Ex. CH3CHX2 Ethylidene dihalide (1, 1 - Dihalo ethane)
CH3
CX2 Isopropylidene dihalide (2, 2 - Dihalo propane)
CH3

(b) Vic dihalides : Vic term from - Vicinal means adjacent C - atoms
Two halogen atoms are attached on adjacent carbon atom.
H

CH2–CH2 H–C–CH–CH2
Ex. Vic and Gem dihalides are position isomers.
X X H X X
Ethylene dihalide Propylene dihalide
(1,2-Dihaloethane) (1,2-Dihaloethane)

Ethylene dihalide Propylene dihalide

(1,2-Dihaloethane) (1,2-Dihalopropane)
(c) α, ω 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)

Tetramethylene dihalide
X X

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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 + PCl 5 → CH3–C–H + POCl3

Cl
Acetaldehyde Ethylidene chloride

O Cl
|| |
CH3 − C − CH3 + PCl 5 → CH 3 − C − CH3 + POCl 3
|
Cl

®
Acetone 2, 2 - Dichloropropane
(ii) By addition of halogen acids on alkynes :
HBr
CH ≡ CH + HBr → CH2=CHBr → CH3 CHBr2
Vinyl bromide 1, 1 - Dibromoethane
Br

CH3–C≡CH + HBr → CH3–C=CH2 → CH3–C – CH3

HBr

Propyne Br Br
2, 2 - Dibromopropane

(b) Vic-dihalides :
(i) By the addition of halogens to alkenes :
CH2 CH2–Br
+ Br2
CH2 CH2–Br
1,2-Dibromoethane

CH3–CH=CH2+Br2 → CH3–CH–CH2
Br Br
1,2-Dibromo propane

(ii) By the action of PCl5 on glycols :

CH2OH CH2Cl
+ 2PCl5 +2POCl3 + 2HCl
CH2OH CH2Cl

4.2 Physical Properties

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

4.3 Chemical Properties

(i) Action of KOH(alc.) : (Dehydrohalogenation)
CH2X CH3 KOH(alc.) CH
or
CHX2 –2HX
CH2X CH

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Chemistry : Halogen Derivatives
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(ii) Action of KOH(aq.) : (Hydrolysis) It is a distinction test for gem - and vic - dihalides.

CH2–Cl CH2–OH
+ 2KOH(aq.) + 2KCl
(a) CH2–Cl CH2–OH
Glycol
Vic-dihalide 1,2-Ethanediol

KOH(aq.) CH3–CH–CH2
(b) CH3CHXCH2X
Vic-dihalide OH OH
Propane-1, 2-diol

CH3 KOH(aq) CH3

KOH (aq.)
and CH3CX2CH3 
→ CH3COCH3 (Ketone)
CHX2 CHO
Gem-dihalides

®
(iii) Reaction with KCN :

CH2Cl CH2–CN H2O/H+ CH2–COOH ∆ CH2–CO

+ 2KCN O
–2KCl –H2O
CH2Cl CH2–CN CH2–COOH CH2–CO
Vic-dihalide Succinic acid Succinic anhydride

Cl CN COOH
2KCN H2O/H+ ∆
CH3–CH CH3–CH CH3–CH CH3–CH2COOH
Cl –2KCl CN COOH –CO2
Propanoic acid
Gem-dihalide
(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.
(iii) Two – COOH group on vic. C – atom loose H2O to form cyclic anhydride on heating.
(iv) Dehalogenation :

CH2Br CH2
Vic. CH2OH
+ Zn + ZnBr2
Heat CH2
CH2Br
Same Carbon Product

CH2Br CH2
CH3OH + ZnBr2
α − ω. CH2 + Zn H2C
CH2Br ∆ CH2
α, ω-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  (2) R–X + AgF →
(3) R–X + NaF → (4) R–F + AgCl →

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5.0 TRI HALIDES (Haloform CHX3)

5.1 General Method of Preparation

hν
(i) From CH4 : CH4 + 3Cl2  → CHCl3 + 3HCl

(ii) By Haloform reaction (lab method) :

CH3CH2–OH Bleaching power [CaOCl2] (HCOO)2Ca

or CHCl3 +
H2O/∆
CH3COCH3 (CH3COO)2Ca

Mechanism :

CaOCl2 + H2O → 2Cl + Ca (OH)2

CH3CH2–OH + 2Cl → CH3CHO + 2HCl (Oxidation)

®
CH3CHO + 6Cl → CCl3CHO + 3HCl (Halogenation)

CCl3CHO + Ca (OH)2 → CHCl3 + (HCOO)2Ca (Hydrolysis)

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

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

Ex. Alcohols : CH3–CH–Z

OH

CH3–CH–CH3 CH3–CH–CH2–CH3 CH3–CH–CH2....CH3 etc.

, ,
OH OH OH

Aldehydes : Only acetaldehyde CH3–C–H

Ketones : CH3–C–Z

Ex . CH3–C–CH3 CH3–C–CH2–CH3 CH3–C–CH2....CH3 etc. (All methyl ketones)

, ,
O O O

CH3–C–COOH CH3–C–CHO Also show haloform reaction.

,
O O

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

•• •• •• ••
Ex. CH3–C–Cl CH3–C–OH CH3–C–NH2 CH3–C–O–CH3 do not show haloform reaction.
, , ,
O O O O

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(iii) Preparation of pure CHCl3 :

NaOH
CCl3CHO. 2H2O → 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 →
2 4
CCl3CH
(conc.)
Cl
Dichloro diphenyl trichloro ethane
(DDT)

(iv) Industrial preparation :

CH3CH2–OH aq. NaCl/electrolysis HCOONa

®
or CHCl3 + or
CH3COCH3 CH3COONa

5.2 Physical Properties

CHCl3 is colourless and sweet smelling liquid. It's B.P. is 61°C and it is insoluble in H2O and have density
more than H2O. Chloroform is used as Anaesthetic.
5.3 Chemical Properties

Air and light

(i) Oxidation : CHCl3 + [O] 
→ COCl2 + HCl

Phosgene gas or
Carbonyl Chloride
(Poisonous gas)
CHCl3 is stored in dark coloured bottles which are filled upto the brim to prevent oxidation of CHCl3 into
COCl2 and 1% ethanol is also added to chloroform

Cl OC2H5
O=C + 2HO – C2H5 O=C
Cl –2HCl OC2H5
[Poisonous] Diethyl carbonate
[Non-Poisonous]

GOLDEN KEY POINTS

Test of CHCl3
Reagent Pure CHCl3 Impure CHCl3 (COCl2 +HCl)

 Blue litmus No Change turns into red

 AgNO3 No reaction White ppt of AgCl

Cl OH
(ii) Hydrolysis : Cl
Aq.KOH
→ CH
—H O KOH
OH→ H C OH→ H C OK
2
CH
Cl OH
O O
Unstable

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(iii) Carbyl amine reaction or isocyanide test : (Hoffman's carbylamine reaction)

3 CHCl + KOH
Primary–Amines (Aliphatic or Aromatic) 
→ Isocyanides

Isocyanides have unpleasant or offensive smell (Isocyanide test).

3 CHCl + KOH
R—NH2 
→ R—NC

Mechanism :
KOH → :CCl
CHCl3  2

(electrophile)
H Cl
..  –2HCl ⊕
R–NH2 + :CCl2→ R – N – C R N C

®
Alkyl isocyanide
H Cl

CHCl3 + KOH
CH3CH2–NH2 → CH3CH2–NC

Ph–NH2
CHCl3 + KOH
→ Ph NC Reaction is given by only
primary amine
NH2 CHCl3 + KOH
NC
→

(iv) Reimer Tiemann's reaction :

OH OH
CHO
CHCl3 + KOH

Salicylaldehyde
(o-Hydroxy benzaldehyde)

Mechanism : :CCl2 is neutral attacking electrophile (formed by α,α− elimination reaction)

CHCl3 KOH →
 :CCl2

OH O O O
H
HO
 CCl2 Cl
→ ←→ → C
–H2O Cl



OH O O
CHO OH
 Cl
H
⊕
CH OH CH
←
–H O OH ←− Cl
2

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

OH OH
COOH
(i) (CCl4 + KOH), ∆
→
(ii) H⊕ (Salicyclic acid)

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(v) Reaction with CH3COCH3 :

CH3 – C – CH3 + H – CCl3 OH
CH3 – C – CH3
O HO CCl3
Chloritone (Hypnotic)

(vi) Reaction with HNO3 :

CCl3 – H + HO – NO2 CCl3 – NO2 + H2O

Chloropicrin or nitrochloroform
(Tear gas)

(vii) Reaction with CH3CH=CH2 :

CHCl3/Peroxide
CH3 – CH = CH2 • CH3 – CH – CH2

®
CCl3
H CCl3
A free radical addition

Ag
(viii) Reaction with Ag : CHCl3  → CH ≡ CH

3 AlCl Ph3 CH
(ix) FCR : 3Ph – H + CHCl3  →
Triphenyl methane

GOLDEN KEY POINTS

Iodoform Test

CH3CH2OH 
I2 + NaOH or NaOI or OI
or  → CHl3
or I2 + Na2CO3 + H2O
CH3COCH3 yellow crystals
of iodoform

 CHI3 give yellow ppt. of AgI with AgNO3 but CHCl3 does not give AgCl ppt.

Reason : CHI3 is thermally less stable than CHCl3.

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

(i) CH3CH2OH and CH3OH

(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)

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Nomenclature of freons :
Freon – cba
c = nc—1
b= nH+1
a = nF
c = n c −1 = 1 − 1 = 0  c = n c −1 = 2 − 1 = 1 
CF2Cl2 → b = n H +1 = 0 + 1 = 1 Freon–12 C2F4Cl2 → b = n H +1 = 0 + 1 = 1 Freon–114
=
a n= F 2  =
a n= F 4 

 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 
→ R—Mg—X
ether
(Grignard reagent)
(Alkyl magnesium halide)
The ease of formation of Grignard reagent is in the order RI > RBr > RCl
Ether is used to stablised the Grignard reagent.
6.2 Chemical Reactions
(i) O (ii) H O +

→ 2 3
R—OH 1° Alcohol
H C=O/HO +
RCH2—OH
→
2
1° Alcohol
O
+
CH –CH /H O
→ 2 2 3
R—CH2—CH2—OH 1° Alcohol
+
RCHO/H3O
R—Mg—X → R2CHOH 2° Alcohol
+
HCOOEt/H3O
→ R2CHOH 2° Alcohol
RCOR/H2O
→ R3C—OH 3° Alcohol
RCOOEt/H2O (2 : 1)
→ R3C—OH 3° Alcohol
HCOOEt (1 : 1)
→ RCHO aldehyde
RCN/H O
→ 2
RCOR Ketone
RCOOEt (1 : 1)
→ RCOR Ketone
CO2/H2O
→ RCOOH Acids
HOH or ROH or
NH3 or Ph — OH
or R—NH2 or RNH — R
or CH CH or Ph — NH2
→ R—H Alkane
R—X
→ R—R Alkane
RN
 →
3
No reaction
ClCH –CH=CH
→2 2
R—CH2—CH= CH2 Alkene
Cl—NH
 → 2
R—NH2 1° Amine
Cl—CN
 → R—CN Cyanides
ClCOOEt
 → RCOOEt Ester
(1 : 1)

13
®
 TG: @Chalnaayaaar
Chemistry : Halogen Derivatives
Pre-Medical
7.0 Haloarene

If halogen atom is directly attached to the benzene ring, then compound is called as Haloarene.

CH3 CH3
Cl Cl Cl
Ex.

Cl
(Chlorobenzene) (2-Chlorotoluene) (2,4-Dichlorotoluene)

7.1 General Methods of Preparation

Cl

AlCl3

®
(1) + Cl2 + HCl

OH Cl

∆ + POCl3 + HCl
(2) + PCl5

3C6H5OH + POCl3 → (C6H5)3 PO4 + 3HCl

7.2 Chemical Properties

Cl OH

(i) 623K, 300 atm

+ NaOH + NaCl
(1) (ii) H⊕

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

Reactivity Order : (Towards nucleophilic substitution)

Cl Cl Cl Cl
NO2 NO2 NO2
> > >

NO2 NO2 NO2

(2) Fittig reaction :

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

(3) Wurtz fittig reaction :

dry ether
Cl + 2Na + ClCH2CH2CH3 ∆ CH2CH2CH3 + 2NaCl

14

Chemistry : Halogen Derivatives
TG: @Chalnaayaaar
®
Pre-Medical
(4) Electrophilic Substitution Reaction :
Cl Cl Cl
Cl
(i) Anhy. FeCl3
+ Cl2 +

Cl
(Major)
Note : Cl is o– and p– directing group.
Cl Cl Cl
NO2
(ii) conc. H2SO4
+ HNO3 +
∆

NO2
(Major)
Cl Cl Cl

®
SO3H
(iii) ∆
+ conc. H2SO4 +

SO3H
(Major)
Cl Cl Cl
CH3
anhy. AlCl3
(iv) + CH3Cl +

CH3
(Major)

BEGINNER'S BOX-2
–
1. Which can give haloform with X2/OH ?
(1) CH3OH (2) CH3–CH2–CH=O
(3) CH3CHO (4) CH3CH2CH2OH
2. Which of the following compounds cannot be identified by carbylamine test ?
(1) C6H5–NH–C6H5 (2) CH3CH2NH2
(3) CHCl3 (4) C6H5–NH2
3. Which metal is used for preparation of Grignard reagent from haloalkanes :-
(1) Na (2) Mg
(3) Ca (4) Ag

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

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

15