OC - Halogen Derivatives - E

JEE (MAIN+ADVANCED)
HALOGEN DERIVATIVES
CONTENT
S.No Pages
1. Halogen Derivatives 02 – 18
2. Exercise-1 (Subjective Questions) 19 – 24
3. Exercise-2 (Objective Questions) 25 – 53
4. Exercise-3 (Section-A) 54 – 63
5. Exercise-3 (Section-B) 64 – 66
6. Exercise-4 67 – 68
7. Exercise-5 69 – 82
8. Answer Key 83 – 96
HALOGEN DERIVATIVES
ALKYL HALIDE
CHARACTERISTICS
(a) These are the organic compound in which halogen is directly linked with carbon atom.
(b) These are also called as Haloalkane.
(c) Their general formula is CnH2n+1X , (X = F, Br, Cl, I).
(d) In these compounds, hybridisation state of carbon is sp3.
(e) In these compounds, geometry of carbon is tetrahedral.
(f) Central carbon atom has a bond angle of 109º 28’.
(g) On the basis of no. of halogen atom, these are of following types –
(i) Monohalide – They possess single halogen atom.
eg. CH3 - Cl, CH3 - CH2Br
(ii) Dihalide – These are of three types
eg. gem dihalide, vicinal dihalide and , halide
(iii) Trihalide – They posses three halogen atoms.
eg. CHCl3 , CHI3
(iv) Tetrahalide – They possess four halogen atoms.
eg. CCl4
(v) Polyhalide – They possess more than four halogen atoms.
(h) Alkyl halide shows chain and position isomerism. If unsymmetrical or chiral carbon is present
then it shows optical isomerism also.
METHODS OF PREPARATION OF ALKYL HALIDES
(a) By Halogenation of Alkanes

Halogenation of alkanes takes place by free radical mechanism.
h
R–H + X–X   R–X + H–X
R–H + Cl–SO2–Cl   R–Cl + SO2 + H–Cl

Peroxide
From Alkene ( Hydrohalogenation ) :–
+ H–X 
Note : From alkyne we cannot obtain monoalkylhalide.

FromAlcohol : –
(a) Using dry H - X : –
Anhydrous ZnCl
R–OH + H–X    2  R–X + H2O
 , 300ºC
(dry)
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HALOGEN DERIVATIVES
Note :
(i) The reactivity order of HX in the above reaction is – HI > HBr > HCl
(ii) The reactivity order of alcohols in the above reaction is – 3º > 2º > 1º > MeOH
The above reaction is called as ‘Grove’s Process’.

(b) Using PCl3 : – 3ROH + PCl3  3R – Cl + H3PO3
(c) Using PCl5 : –ROH + PCl5  R – Cl + HCl + POCl3
Important Note : –
Bromine or Iodine derivatives can not be obtained from the above reaction because due to larger size of
Bromine or Iodine, PBr5 or PI5 are unstable.
(d) Darzen’s Process : – It is the best method for preparation of alkyl halide.
Pyridine
ROH + SOCl2   RCl + HCl + SO2
From Silver Salt of Carboxylic Acid :

The reaction is called as ‘Borodiene - Hunsdiecker’ reaction. It is also a good method for obtaining
alkyl halide, but from this reaction we obtain only bromo derivatives because reaction is based upon
free radical mechanism.
CCl
 
4
 R – Br + CO2  + AgBr 
Note : –
(i) In the above reaction the reactivity of alkyl group is : 1º > 2º > 3º
(ii) It is also an example of decarboxylation.
From Alkyl Halide :

Finkelstein Reaction :
Acetone
R–Br or R – Cl + KI    R – I + KCl
In this reaction only exchange takes place and the reaction is called as Halogen exchange reaction or
‘Finkelstein Reaction’.
Swarts reaction
AgF/Δ
R–Br or R – Cl    R – F
or Hg F /Δ
2 2
This reaction is called as Swarts reaction
PHYSICAL PROPERTIES
(a) Alkyl halides are colourless with sweet smell or pleasant smell oily liquid, whereas
CH3F, CH3Cl, CH3 - CH2 - F, CH3 - CH2 - Cl are gaseous in nature.
(b) Alkyl halides having 18-carbon or more than it are solid in nature.
HALOGEN DERIVATIVES
(c) Although carbon - halogen bond is polar in nature but alkyl halides are insoluble in H2O because they
cannot form bond with H2O.
(d) These are completely soluble in organic solvents.
(e) M.P & B.P.  molecular weight. For same alkyl group the order of B.P. is RI > RBr > RCl > RF
(f) Polarity order is RF > RCl > RBr > RI
(g) Reactivity order is RI > RBr > RCl > RF
(h) For same halide group reactivity order is 3º halide > 2º halide > 1º halide
Fluorides and Chlorides are lighter than water where as bromides and iodides are heavier than
H2O due to more density of bromine than oxygen. CH2I2 is heavier liquid after Hg.
CHEMICAL PROPERTIES
Oxidation reaction
(i) Only primary and secondary alkyl halides undergo oxidation. Tertiary alkyl halide does not undergo
oxidation.
(ii) Primary alkyl halides give aldehyde where as secondary alkyl halides give ketone in this reaction.
(iii) Oxidising agent is either :
(a) Dimethyl sulphoxide or
(b) Reaction with (CH2)6N4 followed by hydrolysis.
(iv) Reactivity number of hydrogens.
O
||
DMSO or
R – CH2 – X    R  C  H
(i) ( CH2 )6 N4
(ii ) H2O H
X O
| ||
DMSO or
R  CH  R    R  C  R
(i) ( CH2 )6 N4
(ii ) H2O H
O
||
( CH2 )6 N4
C6H5CH2 – X    C 6H5  C  H
H2O H
Note : (1) Oxidation of Benzyl halides by (CH2)6N4 is known as sommelet aldehyde synthesis.
(2) Oxidation of alkyl halide with DMSO is known as swern oxidation.
Reduction :
Haloalkanes on reduction produces alkanes frequently, reduction is done as follows.
R–X + 2H  R – H + HX
HALOGEN DERIVATIVES
(i) By Nascent hydrogen liberated from Na/C2H5OH or Sn / HCl or Zn / HCl or Zn-Cu couple/
C2H5OH etc.
R – X + 2H  R – H + HX
(ii) Byhydride ion [:H] liberated from LiAlH4 or NaBH4. It is completed bynucleophilic substitution
reaction.
R – X + : H  R – H + : X
(iii) By catalytic hydrogenation of haloalkane -

catalyst Pd
R – X + H2  R-H + HX
(iv) By reduction of RI with HI in presence of red P.

R – X + HI     R – H + I2
redP / 150 º C
Reaction with KOH :

(a) With aqueous KOH : –
R–X + K OH(aq.)  R – OH + K – X
(b) With alcoholic KOH : – Dehydrohalogenation takes place and alkenes are formed.
R – CH2 – CH2 – X + KOH(alc.)  R –CH =CH2
Reaction with KCN :

R – X + KCN  R – C  N + KX
Alkane nitrile
Alkane nitrile is an important compound which gives following products.
H3 O 
(i) R–CN  Complete
  R –
hydrolysis
– O – H + NH3
H2O
(ii)  
R – C N Partialhyd  R – – NH2
rolysis
(iii) R – C  N LiAlH
4 / Re duction
 R – CH2 – NH2
Reaction with AgCN :

R – X + AgCN  R– N C + AgX
hydrolysis
R– N C    R– NH2 + HCOOH
R– N C  Re
duction

2º–amine
Reaction with KNO2 :
 
R – X + K – O – N = O  R – O – N = O
alkyl nitrite
HALOGEN DERIVATIVES
Reaction with AgNO2 :
R – X + Ag – O – N= O  R –
nitro alkane
Reaction with KSH :
R– X + K – SH  R - SH
alkane thiol
Reaction with Na2S :–
2R–X + Na2S  R – S –R
dialkyl sulphide
Reaction with Na2SO3 :
R–X + Na2SO3 RSO3Na + NaX
alkyl sodium sulphonate
Reaction is know as “Strecker reaction”.
Reaction with NaOR :
R – X + NaOR  R – O – R + NaX
The above reaction is called as “Williamson ether synthesis”.
Reaction with Ag2O :
(a) Using dryAg2O :
2R–X + Ag2O  R–O – R + 2AgX
(b) Using moistAg2O :
2R–X + Ag2 O + H2O  R–OH + 2AgX
Reaction with Silver Acetate :
R – X + Ag –O–C–CH3  R – O – C – CH3
|| ||
O O
ester
The reaction is called as ‘Esterification’.
Coupling Reactions
(A) By Wutrz Reaction : An alkane having even number of carbon atoms can be obtained by Wurtz
Reaction.
R–X + 2Na + X–R   R–R + 2NaX
Dry ether

Alkane having odd number of carbon atoms can be obtained by mixed Wurtz Reaction.
Dry ether
R–X + X–R’  
Na
 R–R + R–R’ + R’–R’
Dry ether
CH3–I + CH3 –CH2–I CH3–CH3+ CH3–CH2–CH3 + CH3–CH2–CH2–CH3
Na
(B) By Wurtz-Fitting Reaction
R–I + 2Na + I–Ar   R–Ar + 2Nal
Dry ether

CH3–I + 2Na + I–C6H5   CH3–C6H5 + 2NaI

Dry ether

HALOGEN DERIVATIVES
Reaction with metals :

(a) With Na : – (Wurtz reaction)
dry ether
R – X + 2Na + X – R   R – R + 2NaX
(b) With Mg : – (Grignard reaction)

dry ether
R–X + Mg    R – Mg – X
(c) With Zn dust : – (Frankland reaction)

R – X + 2 Zn + X – R  R – Zn – R + ZnX2
dialkyl zinc
Dialkyl zinc is known as ‘Frankland - Reagent’.

(d) With Li : –
dry ether
R – Cl + 2Li  RLi + LiCl
alkyl lithium
Note : Alkyl lithium is more reactive than Grignard reagent.
(e) With Na-lead alloy : –
+ 4Na – Pb  (CH3 –CH2 )4Pb + 4NaCl
TEL (tetra ethyl lead)

Note : Tetra ethyl lead is used as antiknocking agent.
Reaction with Benzene :
AlCl3
+ R–X 180

ºC
 + H –X
The reaction is called as ‘Friedel-craft Reaction’.
Important Note :– Alkyl halide shows electrophilic substitution reaction in the above reaction, which is
exception in alkyl halide
Uses of Alkyl Halides

(i) Alkyl halides are used as weak refrigerants, but more suitable freons are now being used in place of
alkyl halides.
(ii) Synthesis of detergents is carried out from alkyl halides by Strecker’s reaction.
(iii) Synthesis of antiknock compounds.
(iv) Alkyl halides, especially alkyl bromides and alkyl iodides are used for the synthesis of other organic
compounds of almost all classes, in laboratory and in industry.
(v) Alkyl halides are generally used as starting substances for the manufacture of alcohols, ethers and
esters.
(vii) Synthesis of important organometallic compounds, like Grignard’s reagents. Frankland’s reagents, etc.,
is carried out from alkyl halides.
HALOGEN DERIVATIVES
NUECLEOPHILIC AROMATIC SUBSTUTION (SNAr) REACTION :
C–X bond in aryl halide is stable due to delocalisation of electrons by resonance. Also (C–X) bond
possesses a double bond character like vinyl chloride and is stronger than C–X bond in alkyl halide.
Cl Cl Cl Cl Cl Cl+

strong
 – –
 Nu no reaction
–

Nu – C – Nu + X
while – C – X
weak weak
Hence, SN reaction is not possible in benzene nucleus under ordinary conditions. However, under high
temperature and pressure, SN reaction is made possible.
570 K, pressure
+ OH¯ OH + Cl¯
CuCN
Cl + CN¯ CN + Cl¯
470 K, pressure
aq. NH3
+ NH3 + Cu2O NH2 + CuCl + H2 O
470 K, pressure
If the benzene ring has (1) one or more substituents that strongly withdraw electrons from the ring by
resonance, and (2) a good leaving group (such as halogens), nucleophilic aromatic substitution reac-
tions can occur without using extreme conditions. These electron-withdrawing groups must be posi-
tioned ortho or para to the leaving group. The greater the number of electron-withdrawing substituents,
the easier it will be to carryout the nucleophilic aromatic substitution reactions.
Cl
Z Cl G withdraws electron
+z: stabilies carbanian,
activates, SN reaction
G G is made favourable

G = – N (CH3)3, – NO2, – CN, – SO3H, – COOH, – CHO
HALOGEN DERIVATIVES
O2 N Cl + OH¯ 430 K O2 N OH
O2 N Cl + OH¯ 370 K O2 N OH
NO2 NO2
NO2 NO2
O2N Cl + H2O warm O2N OH
NO2 NO2
Cl
Z Cl G releases electrons destabilises
+z: carbanion, deactivates
G = – NH 2, –OH, –OR, –R
G G
Nucleophilic aromatic substitution takes place by a two-step reaction known as an SN Ar reaction by

following mechanisms :
X X Y X Y X Y X Y
+Y  
nucleophile
(slow) 
NO2  N  N  N  N
O  O O O O

O O O
  
Y
fast + X
NO2
ELIMINATION-ADDITION THROUGH BENZYNE INTERMEDIATE
An aryl halide can undergo a nucleophilic substitutoin reaction in the presence of a verystrong base such
as NH 2 . 
When chlorobenzene – that has the carbon to which chlorine is attached isotopically labelled with 14C
– is treated with amide ion in liquid ammonia, aniline is obtained as a product. Half of the product has the
amino group attached to the isotopically labelled carbon (*) as expected, but the other half has the
amino group attached to the carbon adjacent to the labelled carbon.
Cl NH2
* * * NH2
 NH3 (liquid)
+ NH2 +
(approximately in equal amounts)
HALOGEN DERIVATIVES
The mechanisms that accounts for the experimental observations involves formation of a benzene inter-
mediate which has two equivalent carbon atoms to which amino group can be attached. Benzyne has an
extra -bond between two adjacent carbon atoms of benzene and can be formed as :
Mechanism :
•• ••
NH2 NH2
•• * • 
attack at C* •
• H – NH2 • ••
+ • NH
• 2
Cl
(labelled)
14
H 
NH2
–NH3
–Cl¯  •• ••
*• • NH2 •• * NH2 
attack at C H – NH2 ••
+ •• NH2
(unlabelled)
Substitution at the carbon (*) that was attached to the leaving group is called direct substitution. Substi-
tution at the adjacent carbon is called cine substitution.
CH3 CH3 CH3

Br NH2
liquid NH3
+ NaNH2 +
NH2
o-bromotoluene
o-toluidine m-toluidine
(by direct substitution) (by cine substitution)
TYPES OF DIHALIDES
Dihalides are of two types :

(a) Gem dihalide : These are the halides in whichtwo identical halogenatoms are attached onsame carbon.
(b) Vicinal dihalide : In these halides two identical halogen atoms are attached on adjacent carbon atoms.
METHODS OF PREPARATION OF GEM DIHALIDES
(a) FromAlkyne (By hydrohalogenation) : –
HX
R – C  C –H + HX    
(b) From carbonyl compounds : –
RCHO + PCl5  + POCl3
(terminal dihalide)
Note : If ketone is taken internal dihalide is formed.
HALOGEN DERIVATIVES
METHODS OF PREPARATION OF VICINAL DIHALIDES
(a) FromAlkene (By halogenation) :–

R – CH = CH2 + Cl2  
(b) From Vicinal glycol : –

+  + 2HCl + 2POCl3
PHYSICAL PROPERTIES OF DIHALIDES
(a) Dihalides are colourless with pleasant smell liquid, Insoluble in water, soluble in organic solvent.
(b) Melting point and boiling points are directlyproportional to molecular mass but boiling point of
vicinal dihalides are more than gem dihalides.Also, reactivity of vicinal dihalide is more than
gemdihalide, but these are less reactive than monohalide.
CHEMICAL PROPERTIES OF DIHALIDES
(a) Reaction with aqueous KOH : –
+ KOH(aq.)   

KX H O
2
+ kOH(aq.) 
KX
glycol
(b) Reaction with alcoholic KOH : –
Alc.KOH NaNH2
  
 (KX H O )
  
 (NaX NH ) 3
R – C  CH
2
Alc.KOH NaNH2
      R – C  CH
 (NaX NH )
 (KX H O )
2 3
(c) Reaction with zinc dust : Gem dihalide reacts with Zn dust to form higher symmetrical alkene
while vicinal dihalide reacts with Zn dust to form respective alkene.
HALOGEN DERIVATIVES
Note – ,  dihalide form cyclic alkane.
Δ
CH 2 – CH2 – CH2 + Zn  
– ZnX2
X X
(d) Reaction with KCN :
+ 
 2KX
+ 
 2KX
(e) Other substitution reaction : –

CH2  X CH2  NH2
NH3 / 373K
|    |
CH2  X CH2  NH2
ethylene amine
2CH COONa
 
3
 + 2NaX
TRIHALIDES
Trihalo derivatives of alkanes are known as trihalides. Reaction of method of preparation of trihalides is
known as haloform reaction.
TRIHALOALKANES : HALOFORM : CHX3

Preparation of Haloform
* The following compound give haloform reaction.

* Acetaldehyde, all methyl ketones, acetone, ethylalcohol, all 2-alkanols etc.
When the following compounds are heated with alkali and halogen haloform is obtained.
or H
CH3—C— R CH3 CO — group
O alkyl group
HALOGEN DERIVATIVES
or
H
CH3—CH— R CH3 CH(OH) — group
OH alkyl group
Example of methyl ketone :

(i) Acetone (CH3–CO–CH3)
(ii) Butanone (CH3–CO–CH2–CH3)
(iii) 2-Pentanone (CH3–CO–CH2–CH2–CH3)
(iv) 3-Methylbutanone {CH3–CO–CH(CH3)2}
Haloform Reaction
C 2H5 OH  4 X 2  6NaOH  CHX3  5NaX  5H2 O  HCOONa
CH3COCH3  3 X 2  4NaOH  CHX 3  3NaX  CH3COONa  3H2 O
(i) Chloroform : CHCl3

Preparation of Chloroform
1. Laboratory Methods – Chloroform Reaction
On heating ethyl alcohol with bleaching powder, the reaction occurs in the followings steps :
(i) CaOCl2 + H2O  Ca(OH)2 + 2Cl
(ii) CH3CH2OH + 2Cl  CH3CHO + 2HCl
(iii) CH3CHO + 6Cl  CCl3 CHO + 3HCl
Chloral
(iv) 2CCl3CHO + Ca(OH)2  2CHCl3 + (HCOO)2Ca

Note : (i) Chloral is an important compound and when it reacts with chlorobenzene in presence of conc.
H2SO4, then it form an important compound DDT (Dichloro Diphenyl Trichloro ethane )
Cl Cl
|
Cl3C–CHO + 2 Cl–C–CH
|
Cl Cl
DDT [1,1,1-trichloro-2,2-bis (parachloro phenyl) ethane]

(ii) Preparation of pure Chloroform – Alkaline solution of chlorohydrate is used in the formation
of chloroform. Which on distillation gives pure chloroform as follows :
CHCl3 + HCOONa + H2O
chloral hydrate
HALOGEN DERIVATIVES
Preparation of trihalide using ‘Pyrene’ :

Fe / H2O reduction
CCl4 + 2H       CHCl3 + HCl
PHYSICAL PROPERTIES
(a) Chloroform is colourless with pleasant smell.

(b) Insoluble in water and soluble in organic solvent. Vapours of chloroform are poisonous in nature.
(c) It cause temporary unconsciousness, so used as an anaesthetic agent.
(d) Boiling point of CHCl3 is 61º C.
(e) It is best solvent for fats, oil and wax.
(f) Iodoform is yellow crystalline solid. It has melting point 119 ºC.
CHEMICAL PROPERTIES
Oxidation : In presence of light it forms poisonous gas phosgene with atmospheric oxygen or with air.
light
CHCl3 + 1/2 O2  
For protection it is kept into dark room in coloured bottle filling completely. For removal of phosgene we
can use 0.5 to 1% ethanol solution which converts poisonous phosgene into non-poisonous salt diethyl
carbonate.
COCl2 + 2C2H5OH 
Note : We use silver nitrate solution to check the impurityof phosgene in solution which will form white
ppt. of AgCl with HCl
Reaction with HNO3 :


tear gas
(chloropicrin)
Reaction with Acetone :
CCl3
|
 CH3–C–CH3
|
OH
chloretone
chloretone is used as a hypnotic agent.
HALOGEN DERIVATIVES
Reaction with Primary amine :

..
R N H2 + CHCl3 + KOH (alc.) R –N C + KCl + H2O
The reaction is called as ‘Hoffman-carbylamine Reaction’ or ‘Isocyanide-test’. These isocyanides
(product) has offensive smell. So, the reaction is used to test 1º amine. Reacting species of reaction is
dichloro carbene.
Reaction with Phenol : The reaction is called as ‘Reimer-tiemann Formylation’.
+ CHCl3+KOH(aq.)
(KCl H O)2

salicylaldehyde
or
(o-hydroxy benzaldehyde)
Reaction with 2- Butene :
+ H–CCl3  3

NaOH

 
2 –H O

3 NaCl
2–methyl butanoic acid

Reaction with aq. NaOH :
O
CHCl3 + 3NaOH(aq.)  NaOH
 
 H 2O + H–C
+
O¯ Na
Unstable
Reaction with silver powder

(Dehalogenation) :
 CH  CH + 6 AgX
CHX3 + 6 Ag high
temp
Reduction :
CHCl3 
2H
 CH2Cl2 + HCl
Zn / HCl
CHCl3 
4H
 CH3Cl + 2HCl
Zn / HCl
 6H
CHCl3 Zn

/ H2 O
CH4 + 3HCl
Uses
1. As an anaesthetic
2. As a solvent for fat, oil and non-polar substances
3. As an antiseptic
4. In the manufacture of a hypnotic drug named chloretone
5. In the manufacture of a war gas named chloropicrin
HALOGEN DERIVATIVES
6. In the manufacture of triphenylmethane dyes

7. In the manufacture of a polymer named teflon
IODOFORM CHI3
Iodoform Reaction
A yellow precipitate of CHI3 is obtained on mixing saturated solution of sodium carbonate in the com-
pound that gives haloform reaction, and heating the solution with adding iodine pinch by pinch. This
reaction is called iodoform test.
Na2CO3 is a strong base due to hydrolysis of CO32– ion.
CO32– + H2O HCO3– + OH–
2OH– + I2 I– + IO– + H2O
R R
| |
CH3–CHOH + NaOI CH3–C=O + NaI + H2O
2-Hydroxy 2º alcohol
R R
| |
CH3–C=O + 3NaOI Cl3–C=O + 3NaOH
A methyl ketone Triiodo derivative
R R
| |
Cl3–C=O + NaOH CHI3 + COONa
TETRAHALIDE ‘PYRENE’
General method of preparation :

From CS2 : –
 500 ºC
CS2 + 3Cl – Cl    CCl4 + S2Cl2
Fe dust I2
sulphur
monochloride
2S2Cl2 + CS2 CCl4 + 6S

The reaction is used for industrial production of CCl4.
From CH4 :
CH4 + Cl2  CH3Cl  Cl
 2
 CH2Cl2   CHCl3  
Cl2
 CCl4
Cl2
From CHCl3 :
CHCl3 + Cl - Cl  ultra
 CCl4 + HCl
violet light
HALOGEN DERIVATIVES
Physical Properties :
(a) It is colourless liquid with specific smell. It is insoluble in water and soluble in organic solvent.
(b) It is the only organic solvent which is non-combustible. So used as fire-extinguisher called as
‘Pyrene’.
Chemical Properties :
(a) It reacts with hot H2O or with water vapour and forms poisonous gas ‘Phosgene’.
CCl4 + H2O(g) 

 COCl2 + 2HCl.
(b) It reacts with aqueous or alcoholic KOH and forms inorganic salt potassium carbonate.
CCl4 + 4KOH (aq.)    C(OH)4    CO  
2KOH
 K2CO3 + H2O
4KCl 2H2 O 2
(unstable)
(c) It reacts with phenol and forms salicylic acid.
+ CCl4 aq
.KOH


The reaction is called as ‘Riemer-Tieman Carboxylation’.
(d) Reaction with benzene.
2 + CCl4 anhy

.AlCl3

2HCl
dichloro diphenyl methane
FREONS
These are poly chlorofluoro derivative of alkane.

Preparation of freons :
CCl4 + HF  SbCl
  5
 CCl3F + HCl
C2Cl6 + 2HF  SbCl

5
 C2F2Cl4 + 2HCl
hexachloro ethane freons–112
Nomenclature of Freons :
The common name of freons is Freon - cba or freon C - 1, H + 1, F, where
c = no. of carbon atom –1, b = no. hydrogen atom + 1, a = total no. of atoms of fluorine
eg. CFCl3 C – 1 = 0, H + 1 = 1, F = 1 Freon - 11
HALOGEN DERIVATIVES
Formula C–1 H+1 F Name
CFCl3 1–1=0 0+1=1 1 Freon-11

CF2Cl2 1–1=0 0+1=1 2 Freon-12
C2F2Cl4 2–1=1 0+1=1 2 Freon-112
C2F3Cl3 2–1=1 0+1=1 3 Freon-113
C2F4Cl2 2–1=1 0+1=1 4 Freon-114
C2F5Cl 2–1=1 0+1=1 5 Freon-115
Properties & uses of freons :

(a) Freons are colourless, odourless, unreactive & non-combustible liquids.
(b) Having very low boiling points (e.g CF2Cl2 = – 29.8ºC).They easily converted from gaseous
state to liquid state, therefore they are used as a coolant inA.C. & Refrigerator.
(c) Used as a aerosole propellant in aroplane & rockets.
(d) Also used as a solvent.
Note : CFC is the main cause of Ozone layer decay (CFC – chlorofluoro carbon)
HALOGEN DERIVATIVES
EXERCISE-1 (Subjective Questions)
Q.1 Arrange following compounds according to their reactivity with alc silver nitrate.
t-Butyl chloride, sec butyl chloride and Butyl chloride.
Q.2 Propose a mechanism for the following reactions-

CH3 OH
CH3
C—Br H
2O
 
CH3
CH3
Q.3
What are (A) & (B) and explain their stereochemistry.
Q.4 The rate law for the subsitution reaction of 2-bromobutane and OH¯ in 75% ethanol and 25% H2O at
25°C is
Rate = 4 × 10–5 [ ] [OH¯] + 1.0 × 10–5 [ ]

Br Br
What % of the reaction take place by the SN2 mechanism when [OH¯] = 1.00 M
x
If answer is x% then fill in OMR sheet
10
Q.5 Out of the followings how many compounds are more reactive than CH3 – CH2 – Br towards SN2
reaction.
Br
H3C– I Br
I Br
Ph – CH2 – I H3C I H 3C  C  CH 2  I
||
O
NaOCH
Q.6  3  I
CH 3OH
HALOGEN DERIVATIVES
Q.7 Predict the product(s) and write the mechanism of each of the following reactions
HI (1mole) excess HI
(i)  (ii) 
O O
Q.8 HBr
 KCN
 Major product.
H 2O 2
Major product is
Q.9 CHC–CH2–CH=CH2, adds up HBr to give CHC–CH2–CHBr–CH3 while CHC–CH=CH2 adds

up HBr to give CH 2  C – CH  CH 2 .
|
Br
Q.10 Find out the total no. of products (including stereo) in the given reaction :
CH3
NBS, CCl4 Products.

Peroxide, 
Q.11 What are the products of the following reactions ?
(a) PhCH = CHCH3 + HBr A (b) + HI  B
(c) + HBr Peroxide

  C (d) + HCl D
Q.12 Write all the monochlorinated products (including stereo) of isohexane.
Q.13 With the help of following data show HBr exhibits the peroxide effect.
H10/kJ mol–1 H20/kJ mol–1
   
H–X X + CH2 = CH2  X CH2 – C H2 XCH2– C H2 + H–X  XCH2CH3 + X

HCl –67 + 12.6
HBr –25.1 – 50.2
HI +46 –117.1
Q.14 How many dibromo derivative can be obtained by Cyclobutane.
HALOGEN DERIVATIVES
Q.15 Which of the following compound(s) gives haloform reaction (or Iodoform test with NaOH + I2).
O
||
(1) (2) CD3  C  CD3
CHI2
O
O O OH
|
(3) O O (4) H 3C  CH  C  OH
||
O
O
O O
(5) (6)
O O O
|| || ||
(7) CH 3  C  CCl3 (8) CH 3  C  O  C  CH 3
Cl
(9) (10) CH 3  CH 2  CH  CH 3
|
OTs
O
O O
| | ||
(11) CH 3  C  C  OH (12)
O
Q.16 Iodoform gives precipitate withAgNO3 on heating while CHCl3 does not.
Q.17 On electrolysis of aqueous ethanolic solution of sodium chloride gives sweet smelling liquid (X). (X)
gives isocyanide test and condenses with acetone to from hypnotic (Y). What are (X) and (Y)?
Q.18 Consider following compounds and give number of compounds which can show iodoform reaction.
O
O OH
Ph  C  CH 3 CH3 – CH2 – OH
||
O
O
H 3C  C  OH H 3C  C  C  OH
|| | | ||
O O O O O
HALOGEN DERIVATIVES
Q.19 CH3–CH2I reacts more rapidly with strong base in comparison to CD3CH2I
Q.20 The mechanism for dehydrohalogenation of is E1cb while for dehydrohalogentaion of
is E2 ,why?
Cl
Q.21 2-chloro-3-methylbutane on treatment with alcoholic potash gives 2-methylbut-2-ene as major product.
Q.22 Out of the followings how many nucleophiles will give major product by E2 reaction on reaction
with
Br
O
    ||    
SH , OEt , O , O C  CH 3 , I , O Me , CN , SCH 3 , C  CH

O
alc.KOH (i ) O
Q.23   A 
 B HBr

C 3  D + E
 ( ii ) H 2O / Zn
Br
Q.24 Write major product of the the following reactions:

EtOH
(i) ClCH2CH2CH2Br + KCN  A
(1eq .)
SF
(ii) PhCHO 
4 B
AgF
(iii) BrCH2CH = CHCO2Me  C
DMF
(iv) EtOH + HI  D
(v) EtOH + HCN  E
Q.25 Explain why?

(a) Hydrogen atom of chloroform is definately acidic, but that of methane is not.
(b) A small amount of alcohol is added to chloroform bottles.
(c) RCl is hydrolysed to ROH slowly but reaction fastens on addition of KI.
(d) KCN reacts with R – I to give alkyl cyanide, whileAgCN results in isocyanide as major product.
Q.26 Alkaline hydrolysis of benzyl chloride in 50% aqueous acetone proceeds byboth SN2 and SN1 mechanism,
but when water is used as solvent, mechanism is now mainly SN1. Explain
HALOGEN DERIVATIVES
Q.27 IdentifyA,B,C,D,E and F in the following series of reaction.
Br
2  A aq
. KOH
 Na
 B  C
h
alc.KOH
 E 
 F C
D NBS

Q.28 Complete the following by providing the structure of (A), (B), (C) and (D):
Alc.KOH HBr NH 3
(i) CH3CH2CH2OH PBr
3  (A)   (B)  (C)  (D)


Alc.KOH H / H 2O SOCl H
(ii) CH 3  CH 2  CH 3   (A)    (B) 2  (C)  (D)
| LiAlH4
I
Alc.KOH HBr (1eq.)
(iii)  (A)   (B)   (C) + (D)
CH3CH2CH = CH2 NBS
Light
HBr
(iv) CH3CH2MgBr CH CHO / H 2O
3    (A)  (B) Alc
. KOH
 (C)
H2SO4 AgF/DMSO
Q.29 CH2 – OH A
NBS
B C

HBr
Mg/ether B
D E (SN 2 reaction)
F
Q.30 Give the major product (with proper explanation) when following halogen compounds are heated with
sodium ethoxide.
CH2Br
(a) CH 3  CH  CHCH 3 (b) (c) CH3
| | CH3
Br CH 3
Cl
Q.31 Carry out following conversions.

(a) CH3–CH2–CH2–Cl — CH 3  CH  CH 3 in two steps only
|
Br
Br
(b) Br — in two steps only
(c) — in three steps only
HALOGEN DERIVATIVES
Q.32 Convert
(i) CH2 — CH3  CH = CH 2
(ii) CH3CH2CH=CH2 CH3CH2CH2CH2NH2
(iii) CH3CH2CH=CH2  CH2=CH—CH=CH2
Q.33 Carry out following conversions.

Cl
|
(a) CH 3  CH  CH 3 — CH3–CH2–CH2–Cl without using peroxide
O
||
(b) Ph – CH2 – Cl — Ph  CH 2  C  Cl
Q.34 Treatment of 2-bromobutane with hot alcoholic KOH gives a mixture of three isomeric butenes (A), (B)
and (C). Ozonolysis of the minor product (A), gives formaldehyde and another aldehyde in equimolar
amounts. What are the structural formulae of (A), (B) and (C)?
(i ) NBS,Benzoyl peroxide,CCl ,heat

Q.35         
4
 F
( ii ) NaSCH 3
HALOGEN DERIVATIVES
EXERCISE-2 (Objective Questions)
[SINGLE CORRECT CHOICE TYPE]

Q.1 Consider the given reaction:
H 3C  CH  CH  CH  CH 3  [P]
HBr
| SN1
OH
In the given reaction the product [P] is :
Br
|
(A) H 3C  CH  CH  CH  CH 3 (B) CH 3  CH  CH  CH 2
|
Br Br
|
(C) CH2=CH–CH=CH2 (D) CH 3  CH  CH 2  CH 2  OH
Q.2 Which of the following is most reactive toward SN1.

CH2–Cl CH2–Cl CH2–Cl CH2–Cl
(A) (B) (C) (D)
H CH3 OCH3 NO2
Q.3 Which one of the following compounds will be most reactive for SN1 reactions:
(A) (B) (C) (D)
Q.4 In the given pair in which pair the first compound is more reactive than second for SN1 reaction.
(A) Cl CH2Cl
Cl
(B)
Cl
(C)
Cl Cl
Cl Cl
(D)
HALOGEN DERIVATIVES
Q.5 Which of the following can not give SN1 reaction easily?
Br
Br Br Br
(A) (B) (C) (D)
Q.6 Among the bromides I–III given below, the order of reactivity in SN1 reaction is:
(I) (II) (III)
(A) III > I > II (B) III > II > I (C) II > III > I (D) II > I > III
Q.7 Arrange the following in the increasing order of reactivity towards SN1 reaction:
CH3–O–CH2–Cl (P) ; CH3–NH–CH2–Cl (Q);
Ph–CH2–Cl (R); Cl (S)
(A) P > Q > R > S (B) R > Q > P > S (C) Q > P > R > S (D) Q > P > S > R
Q.8 Consider the following groups:

(I) —OAc (II) —OMe (III) —O—SO2—Me (IV) —O—SO2—CF3
The order of leaving group nature is:
(A) I > II > III > IV (B) IV > III > I > II (C) III > II > I > IV (D) II > III > IV > I
Q.9 Which of the following compounds is most rapidly hydrolysed by SN1 mechanism.
(A) C6H5Cl (B) Cl–CH2–CH = CH2
(C) (C6H5)3CCl (D) C6H5CH2Cl
Q.10 Which compound undergoes hydrolysis by the SN1 mechanism at the fastest rate?
CH3 CH3 Br CH3 Br CH3
(A) (B) (C) (D)

Br Br
Q.11 Which one of the following compounds will give enantiomeric pair on treatment with HOH?
C2H5 CH 3 H C2 H5
| | | |
(A) C6 H 5  C  I (B) CH 3  C  Br (C) C 6 H 5  C  Br (D) C 2 H 5  C  Br
| | | |
C2H5 C2 H5 D CH 3
HALOGEN DERIVATIVES
Q.12 Consider the SN1 solvolysis of the following halides in aqueous formic acid:
Br
|
(I) CH  CH  CH 3 (II)
(III) C 6 H 5  CH  C 6 H 5 (IV)
|
Br
Which one of the following is correct sequence of the halides given above in the decreasing order of their
reactivity?
(A) III > IV > II > I (B) II > IV > I > III (C) I > II > III > IV (D) III > I > II > IV
Q.13 Arrange the following compounds in decreasing order of their reactivity for hydrolysis reaction
(I) C6H5–CH2–Br (II) C 6 H 5  CH  C 2 H 5 (III) (IV)

|
Br
(A) I > II > III > IV (B) IV > II > I > III (C) III > IV > II > I (D) IV > III > II > I
Q.14 Arrange the following compounds in order of decreasing rate of hydrolysis for SN1 reaction:
(I) CH2–Br (II) H3C CH2–Br
(III) CH3–CH2 CH2–Br (IV) CH CH2–Br
(A) II > III > IV > I (B) IV > III > II > I (C) III > IV > II > I (D) I > II > III > I
Q.15 For the given reaction
R1 R1
| |
R  C  X HOH
 R  C  OH
| |
R2 R2
Which substrate will give maximum racemisation?
CH 3 CH 3
| |
(A) C6 H 5  C  Br (B) CH 2  CH  C  Br
| |
C2H 5 C2H 5
Br
Br
C6H5 C NO2
C6H5 C OCH3
(C) (D)
NH3
CH3 
HALOGEN DERIVATIVES
Q.16 Which will give white ppt. withAgNO3?
(A) (B) Cl (C) CH2Cl (D) Both A & C
Q.17 Which solvent is used for SN1 reaction ?

(A) Dihydrogen oxide (B)Acetone
(C) DMSO (D)Acetonitrite
Q.18 What will be product if aqueous KCN is added to 1-chloro-3-methylbutane

(dissolved in non polar solvent)
(A) (B)
CN CN
(C) (D) There will be no reaction
Q.19 Consider following reaction
I  + CH3–Br  CH3–I + Br 
What will be effect of solvent polarity on rate of reaction.
(A) On increasing solvent polarity rate of reaction increases
(B) On decreasing solvent polarity rate of reaction decreases
(C) On increasing solvent polarity rate of reaction decreases
(D) No effect of solvent polarity on rate of reaction
Q.20 Which compound should gives white turbidityimmediately on reaction with Luca's reagent?
OH
(A) (B)
OH
OH CH 3
|
(C) CH (D) H 3C  C  CH 2  CH 2  OH
|
CH 3
Q.21 The major product in the given reaction: + NH3 
CH2NH2 CH2NH2 CH2Br
(A) (B) (C) (D)All of these

Br NH2 NH2
HALOGEN DERIVATIVES
Q.22 For CH3Br + OH–  CH3OH + Br–

the rate of reaction is given by the expression:
(A) rate = k [CH3Br] (B) rate = k[OH–]
(C) rate = k [CH3Br][OH–] (D) rate = k[CH3Br]° [OH–]°
Q.23 Non-occurence of the following reaction

Br– + CH3OH  BrCH3 + OH–, is due to
(A)Attacking nucleophile is stronger one (B) Leaving group is a strong base
(C) Alcohols are not good substrate (D) Hydroxide ions are weak bases
Q.24 Which of the following is having highest extent of SN2 mechanism.

Cl Cl CH2–Cl CH2–Cl
(A ) (B) (C) (D)
CH3 H
Q.25 Arrange these compounds in order of increasing SN2 reaction rate:
(A) III < I < II < IV (B) III < II < I < IV (C) IV < III < I < II (D) III <IV < I < II
Q.26 The reactivity of 2-bromo-2-methylbutane (I), 1-bromopentane (II) and 2bromopentane (III) towards
SN2 displacement is such that:
(A) I > II > III (B) I > III > II (C) II > III > I (D) II > I > III
Q.27 Which reaction proceeds faster with NaI in DMSO.

CH2Cl Cl CH2Cl
Cl
(A) CH3 (B) (C) (D)
S 2
Q.28 + OH– 
 A
N
Ais:
(A) (B)
(C) Both (D) None
HALOGEN DERIVATIVES
Q.29 In the given reaction

CH 3  CH  CH 2  CH 2  CH  CH 3
| |
OTs OTs
[X]
[X] will be:

OTs S
| |
(A) CH 3  CH  CH 2  CH 2  CH  CH 3 (B) CH 3  CH  CH 2  CH 2  CH  CH 3
| |
S S
 
(C) (D)
Q.30 In which of the following, replacement of Cl– is most difficult?
(A) (B) (C) (D)
Q.31 Which of the following nucleophile will show minimum reactivitytowards SN2 reaction:
  
(A) Me 3 C O (B) MeO (C) Et–O (D) Me 2CHO
Q.32 When ethyl bromide is treated with dryAg2O, main product is:
(A) Ethyl methyl ether (B) Ethanol (C) Ethoxy ethane (D)All of the above
Q.33 In the given reaction:
( 
 [X]
i ) NaN 3
( ii ) NH 4 Cl ( aq )
[X] will be:

N3
(A) (B) OH
(C) Mixture of (A) and (B) (D)
HALOGEN DERIVATIVES
Q.34 H 3C  CHBrF KOH

  Product(s)
/ DMSO
( R  Isomer ) (1.eq )
Product(s) is / are
(A) S-1-Fluoro-ethan-1-ol (B) R-1-Fluoro-ethan-1-ol
(C) R-1-Fluoro-ethan-1-ol + enantiomer (D) R-1-Bromo-ethan-1-ol
CH3
Q.35 D CH2–Br KSH
 Q, Q is
DMSO
H
CH3 CH3
(A) HS CH2D (B) D H
H CH2SH
CH3 CH3
(C) D CH2–SH (D) HSH2C D
H H
Me
SOCl2
P
Q.36 HO D
SOCl2
Q
H
N
P and Q are respectively

Me Me Me Me
(A) D Cl Cl D (B) Cl D D Cl
H H H H
Me Me Me Me
H H
(C) Cl D Cl (D) D Cl Cl
H D H D
HALOGEN DERIVATIVES
O
18
Q.37 Ph – CH2 – OH + Cl – S CH3  OH

 M
O
M is
O O
18 18  18 
(A) Ph  CH 2  OH (B) Ph–CH2O–S–O (C) Ph – CH2 – OH (D) Ph–CH 2–S–O
O O
CH3

18 PCl3 O CH
Q.38 H OH   
3  R
D
R is
CH3 CH3
18
(A) H O–CH 3 (B) H3CO D
D H
CH3 CH3
18
(C) H3CO H (D) H O–CH3
D D
Q.39 Benzyne intermediate is not observed in:

OCH3 Cl Cl +
F H3C CH3 N2
(A) (B) (C) (D)
COO
Q.40 In the reaction of p-chlorotoluene with KNH2 in liquid NH3, the major product is:
(A) o-Toluidine (B) m-Toluidine
(C) p-Toluidine (D) p-Chloroaniline
Q.41 Which chloroderivative of benzene among the following would undergo-hydrolysis most readily with
aq.NaOH to furnish the corresponding hydroxy derivative.
NO2
(A) O2N Cl (B) O2N Cl
NO2
(C) Me2N Cl (D) Cl
HALOGEN DERIVATIVES

 * HOH
CH 3  CH 2  S CH 2  CH 2  Br  [X]
[X] will be:
* *
(A) CH 3  CH 2  S  CH 2  CH 2  OH (B) CH 3  CH 2  S  CH 2  CH 2  OH
(C) 1 : 1 mixture of (A) and (B) (D) 2 : 1 mixture of (A) and (B)
Br
Q.43 CH 2=CH–CH2–CH2–CH2–CH2–SH 2  ?
CCl 4
Major product of this reaction is:

(A) Br2  CH 2  CH  CH 2  CH 2  CH 2  CH 2  SH
|
Br
(B) Br2  CH 2  CH  CH 2  CH 2  CH 2  CH 2  SH
|
CCl 3
(C) Br2  CH 2  CH  CH 2  CH 2  CH 2  CH 2  SH
|
Cl
(D)
OH
Q.44 Br / CCl 4
2  
Which compound will be major product for the above reaction?
OH Br
(A) (B)
Br O
(C) O (D) O
Br Br
Br
Q.45 2-chloropentane on halogenation with chlorine gives 2,3-dichloropentane. What will be the structure of
free radical species formed in the reaction?
(A) Planar (B) Trigonal planar (C) Square planar (D) Pyramidal
HALOGEN DERIVATIVES
Q.46 Correct order of rate of photochlorination for following compounds is:

CH 3
|
CH 3  C  CH 3
CH3–CH3 CD3–CD3 |
CH 3
(I) (II) (III)
(A) II < I < III (B) I < II < III (C) III < I < II (D) II < III < I
Q.47 What will be the major product, when 2-methyl butane undergoes bromination in presence of light?
(A) 1-bromo-2-methyl butane (B) 2-bromo-2-methyl butane
(C) 2-bromo-3-methyl butane (D) 1-bromo-3-methyl butane
Q.48 Select the incorrect statement about the product mixture in the following reaction :
Br
2  Products
CCl4
(A) it is optically active (B) it is racemic mixture
(C) it is a resolvable mixture (D) it is a mixture of erythro compounds
Q.49 The reaction of SOCl2 on alkanols to form alkyl chlorides gives good yields because
(A)Alkyl chlorides are immscible with SOCl2
(B) The other products of the reaction are gaseous and escape out
(C)Alcohol and SOCl2 are soluble in water
(D) The reaction does not occurs via intermediate formation of an alkyl chloro sulphite
Q.50 Find out the correct order of rate of reaction towards allylic substitution.
CH 3
|
(I) CH3–CH = CH2 (II) CH3–CH2–CH=CH2 (III) CH 3  CH  CH  CH 2
(A) I > II > III (B) II > I > III (C) III > II > I (D) III > I > II
Q.51 NBS
 Allylic brominated products
CCl4 , 
Find out the incorrect statement.

(A) It gives total 9 allylic brominated products (B)All allylic brominated products are optically active
(C) Substrate has 7 allylic hydrogens (D) NBS gives Br constantly to reaction mixture.
Q.52 What is the order of reactivity with HBr.
(a) (b) (c)
(A) a > b > c (B) b > a > c (C) c > b > a (D) b > c > a
HALOGEN DERIVATIVES
C = CH2
Q.53 HBr

H D CCl4
CH3
What is stereochemistry of product?

(A) Racemic mixture (B) Opticallyinactive (C) Diastereomers (D) Meso product
Q.54 Addition of CCl3Br in presence of Peroxide is example of :

(A) ElectrophillicAddition (B) Free Radical substitution
(C) Free RadicalAddition (D) Electrophillic substitution
Me
|
Q.55 Me  C  CH 2  OH HBr
 Major product.
|
Me
Me
Me Me |
(A) C=C (B) Me  C  CH 2  Br
Me H |
Me
Br
|
(C) Me  C  CH 2  Me (D) Me  CH  CH  Me
| | |
Me Me Me
CH3
Q.56 / h
Cl
2  Monochloroderivatives
Total number of monochloroderivatives formed in above reaction are

(A) 8 (B) 12 (C) 10 (D) 6
Q.57 HBr
 (1eq.)

40C
Which statement is incorrect about this reaction.
(A) Major product is formed by 1,2-addition.
(B) 1,4- addition product is KCP (Kinetically controlled product)
(C) TCP (Thermodynamically controlled product) is formed by 1,4-addition
(D) TCP forms as major product.
HALOGEN DERIVATIVES
CH3
H D
Q.58 HBr
 M, M is
D H
OH
CH3 CH3 CH3 CH3

H D D H H D H D
(A) D H (B) H D (C) H D (D) H Br
Br Br Br D
14
Q.59 SOCl
2  Product(s)
OH
Product(s) is / are
14
Cl
14
14 Cl
(A) only (B) only (C) Both (A) and (B) (D)
Cl
CH3
Q.60 C NaI
 / acetone
 P,, P is
H
F
D
CH3 CH3 CH3

C C
(A) I (B) (C) No reaction (D) C + en
H H I I
D D H
D
HALOGEN DERIVATIVES
CH3
H OH HBr
Q.61
H Br 
 Product(s)
CH3
Product(s) formed in above reaction is / are
CH3 CH3 CH3
H Br H Br Br H
(A) (B) &
H Br H Br H Br
CH3 CH3 CH3
CH3 CH3 CH3 CH3

H Br H Br Br H H Br
+ en + +
(C) Br H (D) H Br H Br Br H
CH3 CH3 CH3 CH3
KOBr
Q.62 A  CHBr3
Reactant Ais :
(A) Isopropyl alcohol (B) Methanol
(C) Ethanoic acid (D) n-Butyl alcohol
Q.63 Which product is obtained when bleaching powder is distilled with acetone:
(A) CCl4 (B) CHCl3 (C) CH2Cl2 (D) CH3Cl
Q.64 H 3C  C  R OH 
/ X2
 CHX3
||
O
Which halogen should not be used in above reaction?

(A) Cl2 (B) F2 (C) Br2 (D) I2
Ag HCl ( excess )
Q.65 CHCl3  A    B (major)

B is
Cl
(A) H 2C  CH 2 (B) H3C – CH (C) H 3C  C  Cl (D) H  C  CH 2  Cl
| | Cl || ||
Cl Cl O O
Q.66 Which of the following compound can not show haloform reaction?
(A) H 3C  CH  C  OH (B) Ph  C  CH 2  C  Ph
| || || ||
OH O O O
(C) H 3C  C  C  OH (D) H 3C  C  O  CH 3
| | || ||
O O O
HALOGEN DERIVATIVES
Q.67 The product of the reaction
CH2CH2Br   P
Alc.KOH
Pis:
(A) OH (B) O–CH2–CH2OH
O
(C) (D) CH=CH2
Q.68 In the given pairs, which pair represent correct order of rate dehydrohalogenation reaction.
(A) < (B) <
(C) < (D) CH3–CH2–Cl < CD3 – CD2 – Cl
I Br
Q.69 Consider the reaction.

CH 3
|
CH 2  CH  CH 2  CH  CH  CH 3 Alc  Product Major..
.KOH

|
Cl
The major product is
CH 3 CH 3
| |
(A) CH 2  CH  CH  CH  CH  CH 3 (B) CH 2  CH  CH  CH 2  CH  CH 3
CH 3 CH 2
| ||
(C) CH 2  CH  CH 2  CH  CH  CH 3 (D) CH 2  CH  CH 2  CH 2  C  CH 3
C H O
Q.70   ? Major product is:
2 5
C 2 H5OH
(A) (B)
(C) (D)
HALOGEN DERIVATIVES
Q.71 What will be the product of dehalogenation of (2R, 3S)-dibromobutane?

CH3 CH3 Br CH3 CH3 H CH3 CH3
(A) C=C (B) C=C (C) C=C (D) C=C
Br H CH3 H H CH3 H H
Q.72 In which of the following reaction alkene is obtained?

Br Br
Br
(A) Zn (B) OH–

 
OH Me
N
(C) H+ (D) OH¯
 
–
OH
Q.73 Major product.

NMe3
(A) (B) (C) (D)

Br
 C CNa / 
CH
3  
the products are:
(A) and
(B) +
(C)
(D)
HALOGEN DERIVATIVES
Q.75 R1 Zn
dust


R2 Zn
dust


Compound R1 & R2 respectively.
Me Me Me Me
Br H Br H Br H Br H
(A) , (B) ,
H Br Br H Br H H Br
Me Me Me Me
Me Me Br
Br Br
(C) H Br , Br H (D) ,
Br
Et Et
Br
Q.76 KI
/ 
acetone
 Product
Br
Formed product is
(A) (B) (C) (D) No reaction

I
Br
Q.77 /
EtOH
  
Which statement is correct.

(A) Major product is formed by E2 reaction.
(B) Minor product is formed by E1 reaction.
(C) Major product is formed by dehydrohalogenation by E1 mechanism
(D) Major product is formed by E1CB
HALOGEN DERIVATIVES
CH3
Cl
Q.78 alc  I
.KOH
 

Br
H
Major products of above reaction are
CH3 CH3 CH3 CH3
(A) (B)
I I Cl Cl
Cl Cl I I
CH3 CH3
(C) Cl + en (D) I + en
I Cl
Br
Ph H
Q.79 H Br NaI
  P,,
/ acetone
Ph
P is :
Ph Ph Ph Br Ph H Ph H
(A) (B) (C) C=C (D)
H Br H H Ph H H Ph

Q.80 OEt
/ EtOH
 A (Major product),

Br
A is :
(A) (B) (C) (D)

OEt OEt
Q.81 NBS
 NaI / acetone
 Q
Q on reaction with Na/ether gives
(A) (B) (C) (D)
HALOGEN DERIVATIVES
conc.H2SO4 DBr
Q.82 OH

Final major product is :
D
D Br
(A) (B)
Br
(C) (D)
D Br Br
Q.83 On heating glycerol with excess amount to HI, the product formed is–
(A)Allyl iodide (B) Isopropyl iodide (C) Propylene (D) 1,2,3–tri–iodopropane
 
OH
Q.84  OH

II I
B A
Steps I and II are
(A) I can't be SN1 (B) II can't be SN1 (C) I SN1 & II SN2 (D) I SN2 & II SN1
Q.85 The given compound CH3–O–CH2–Br gives which one of the following reactions:
(A) Only SN1 (B) Only SN2
(C) SN1 as well as SN2 (D) E1
Q.86 Which of the following compound can not decolourise bromine water-
(A) (B) (C) (D) H3C – C  C – CH3
Q.87 Rate of which reaction increases on increasing polarity of solvent?

(A) Br  + CH3 – OTs  (B) (H3C)3N + CH3 – I 
CH 3
| 
(C) CH 3  S CH 3  O H  (D) CH3Cl + NaOH 

HALOGEN DERIVATIVES

TsCl I
Q.88 (
i ) BH 3 .THF
     K,
(ii ) H 2O 2 / O H
K is :
CH3 CH2I CH3 CH3
I H H H
(A) H (B) OH (C) H (D) I
OH H I H
Q.89 Br / CCl 4

2   P,, P is
Br
(A) (B) + enantiomer

Br
Br
Br
(C) (D) No reaction
Br
Br
Q.90 Our body produces iodine containing Harmone whose deficiency leads to goiter, the hormone is:
(A) Thyroxine (B)Arenine
(C) Growth Harmone (D) Renin
Q.91 Which Halogen containing antibiotic drug is very effective for treatment of typhoid fever-
(A) Chlorine (B) Iodine (C) Flarine (D) Bromine
Q.92 Which of these compounds is used as solvent as a paint remover-

(A) Methylene chloride (B) Chloroform
(C) Iodoform (D) Carbon tetrachloride
Q.93 Which compound releases poisonous gas on exposure to air under light-
(A) Freons (B) Chloroform
(C) Carbon Tetrachloride (D) Methylene chloride
Q.94 Which compound helps in the production of Freon refrigerant 22 ?

(A) Chloroform (B) Methylene chloride
(C) Carbon tetrachloride (D) Iodoform
Q.95 Which compound widely used as anaesthetic in surgery

(A) Iodoform (B) Carbon tetrachloride
(C) Methylene chloride (D) Chloroform
Q.96 Which compound is widely used in production of drugs
(A) Methylene chloride (B) Triiodomethane
(C) Trichloro methane (D) Carbon tetrachloride
HALOGEN DERIVATIVES
Q.97 Which compound has antiseptic properties

(A) Methylene chloride (B) Freons
(C) Trichloro methane (D) Iodoform
Q.98 Which compound is used as a decreasing agent, as spot remover & as fire extinguisher ?
(A) Carbon tetrachloride (B) Methylene chloride
(C) Chloroform (D) Freons
Q.99 Breathing about 900 parts this substance per million parts of air for a short time cause dizziness headache
& fatigue, headache is-
(A) Methylene chloride (B) Chloroform
(C) Iodoform (D) Tetra chloromethane
Q.100 Exposure to this substance can make heart beat irregularly or stop.
(A) Methylene chloride (B) Tetrachloro methane
(C) Freons (D) DDT
Q.101 Which gas depletes the ozone layer ?

(A) DDT (B) Iodoform
(C) Methylene chloride (D) Carbon Tetrachloride
Q.102 Extremely stable, non toxic, non-corrosive substance is-

(A) DDT (B) Iodoform (C) Freons (D) Methylene chloride
Q.103 This substance initiate radical chain reaction in stratosphere that can upset ozone layer substance is
(A) Carbon tetrachloride (B) Freons
(C) Chloroform (D) Methylene chloride
Q.104 This organic compound is 1st chlorinated organic insecticides. Which is effective against mosquito that
spread malaria & lice that carry typhus compound is-
(A) Chloroform (B) Methylene chloride
(C) DDT (D) Carbon Tetrachloride
Cl
Cl
Q.105
Cl Cl
Cl H
Compound is
(A) Freons-2 (B) DDT (C) Urea (D) None of these
Q.106 Which reagent is not used in Swartz reaction ?

(A) AgF (B) Hg2F2 (C) CoF2 (D) NaF
HALOGEN DERIVATIVES
Q.107 Which properties is same for enantiomers-

(A) Melting point (B) Boiling point
(C) Solubility& Refractive index (D)All of these
Q.108 Which Freon is most common among the following in industrial use?
(A) C2F4Cl2 (B) C2F2Cl4 (C) CCl2F2 (D) CFCl3
Q.109 Freon-12 is manufactured generally by which reaction

(A) From CCl4 by Swartz reaction
(B) From CCl4 by Finkelstein reaction
(C) From acetone on reaction with OH¯/F2
(D) From formic acid on reaction with SnCl2 / HCl & H3O+
Q.110 Which substance is widely used after world war II for minimising the causes of malaria.
(A) Dichloro diphenyl trichloroethane (B) Methylene chloride
(C) Iodoform (D) Tetrachloro methane
Q.111 Among the following option which has highest boiling point?
(A) Bromomethane (B) Bromoform
(C) Chloromethane (D) Dibromomethane
[PARAGRAPH TYPE]
Paragraph for question nos. 112 & 113
Cl

2 Mono chloro derivatives
h
Q.112 How many dextrorotatory monochloro derivatives will form in above reaction?
(A) 4 (B) 6 (C) 3 (D) 2
Q.113 How many fractions will be obtained by fractional distillation of mixture of products?
(A) 4 (B) 6 (C) 8 (D) 5
Paragraph for question nos. 114 & 115
For the following compound.

Cl
Cl Cl
Cl
Cl Cl
(A) (B) (C)
Q.114 Which is correct order of Boiling point?
(A) A > B > C (B) A > C > B (C) C > B > A (D) A > B  C
Q.115 Which is correct order of Melting point ?

(A) C > A > B (B) C > B > A (C) B > A > C (D) B > C > A
HALOGEN DERIVATIVES
[MULTIPLE CORRECT CHOICE TYPE]
Q.116 Which compound can show faster SN1 reaction than

Cl
Cl
(A) (B) I (C) (D) H2C = CH – Br

Br
Me
Q.117 OH + SOCl2 (

C 2H 5 )3 N

or   Product
Et N
Product possible is / are
Me Me
(A) Cl (B) Cl
Et Et
 
(C) (C 2 H 5 )3 NH Cl (D) SO2
Q.118 Rate of SN2 depends on

(A) Conc of Nucleophile (B) Conc of substrate
(C) Nature of leaving group (D) Nature of solvent
Q.119 SN2 reaction will be negligible in

Br
(A) (B) (C) (D)
Q.120 In the given pair in which pair the first compound is more reactive than second to SN2 reaction.
Cl
(A) Cl CH2Cl (B)
Cl
Cl Cl
(C) (D)
Cl Cl
HALOGEN DERIVATIVES
Q.121 In which of the following case configuration about chiral C) is retained:
CH Br SOCl CH ONa
(A) Na
 3 (B) 2  3
1. TsCl
(C) PCl

3  3
CH ONa
(D) H 2  
.MeONa
Q.122 Select correct statement about the product (P) of the reaction:
Br
2 / P
CCl 4
(A) P is optically inactive due to internal compensation

(B) P is optically inactive due to the presence of plane of symmetry in the molecule
(C) The structure of P can have three optical isomers possible.
(D) P can have four possible optical isomers.
Q.123 Which of following reaction product are diastereomer of each other ?

Me
Br2
(A) CH 3  (B) D H HBr

CCl 4
Ph
(C) HBr
 (D) CH 3  CH  CH  CH  Ph HCl

CCl 4 peroxide
|
Et
Q.124 Products formed when HCl adds to 2,4- hexadiene is:
(A) 4-chloro-2-hexene (B) 2-chloro-3-hexene
(C) 2-chloro-4-hexene (D) 1-chloro-2-hexene
Q.125 HCl
  Possible products
/ ZnCl 2

OH
Cl
(A) (B) (C) (D)All of these

Cl Cl
HALOGEN DERIVATIVES
Q.126 Incorrect about alkyl halides is / are:

(A) Tertiary alkyl halides undergo SN2 substitutions
(B)Alkyl iodides on exposure to sunlight gradually darken
(C)Alkyl chlorides do not give beilstein test
(D)Anucleophilic substitution is most difficult in alkyl iodides
C7H12 (A) HBr


(A) can be
(A) (B) (C) (D)
Q.128 A gem dichloride is formed in the reaction :

(A) CH3CHO and PCl5 (B) CH3COCH3 and PCl5
(C) CH2 = CH2 and Cl2 (D) CH2 = CHCl and HCl
Q.129 Which reaction(s) is represents correct major product.

O Cl
(A) PCl
5  Cl
(B) Me – O – Et PCl
5  Et – Cl + Me – Cl
(C) H 3C  C  OEt PCl
5  H3C – Cl + Et  C  Cl
|| ||
O O
Cl
(D) OH PCl5

Q.130 In which product formation takes place according to Hoffmann's rule

 
t B u O K CH3CH 2 O K
(A) CH 3CH 2  CH  CH 3   (B) CH 3CH 2  CH  CH 3   
 
| |
Br Br
 
(C) O
H
 (D) CH 3CH 2CH  CH 3 O
H

 
|

S(CH 3 ) 2
HALOGEN DERIVATIVES
Q.131 Which of followingwill give syn-elimination

(A) CH3CH2CH2–OCOCH3 (B) CH 3CH 2CH  CH 3
|
Cl
CH 3
| 
(C) CH 3CH 2CH 2  O  C  S  CH 3 (D) CH 3CH 2CH 2 N  O
|| |
S CH 3
Q.132 Which of the following is/are  – elimination reaction?
CH3
(A) CH3 – C – Br + KOH(alc.) 
CH3
Br
:
(B) Et3N

(C) CHBr3 + Me3CO–K+  :CBr2
(D) OH + NaOH 
Br O
Q.133 Which of following are correct for given reaction


(A) Major product of reaction is (B) Major product is
(C) The reaction is thermal elimination reaction (D) The reaction is E2 reaction
CH3
H Br 
Q.134 OEt
/ EtOH
 Possible products
D H 
CH3
CH3 CH3 CH3 H CH3 CH3 CH3 H

(A) (B) (C) (D)
D H D CH3 H H H CH3
HALOGEN DERIVATIVES
Q.135 Consider the given reaction

CH 3
|
H  C  OTs NaCN
 CH 3CH 2 CH  CN
|
C 2 H 5 (S) |
CH 3
which of following statements are correct for above reaction.
(A) Product formation takes place due to the breaking of O–Ts
(B) The reaction is S 2
N
(C) The reaction is S
N1
(D) Configuration of product is (R)
Q.136 SN1 & SN2 is not favourable in

(A) H2C = CH–Cl (B) Ph–CH2–Cl (C) Ph–Cl (D) H2C=CH–CH2–Cl
Q.137 SN1 & SN2 product are same in (excluding stereoisomer)
(A) (B) (C) (D) Ph  CH  CH  CH 3

| |
CH 3 Cl
Q.138 Which are possible products in following


/ H 2O / 
Ag
 
(A) (B) (C) (D)
Q.139 Which statement(s) is / are incorrect.

(A) S-Butan-2-ol gives S-2-chlorobutane on reaction with SOCl2 / Pyridine
Cl
(B) gives white precipitate ofAgCl on reaction with alc.AgNO3.

(C) CH3–CH2–Cl on reaction with KCN / DMSO gives CH3 – CH2 – N  C¯ as major product.
(D) Acetone gives 2, 2-dichloropropane on reaction with PCl5.
HALOGEN DERIVATIVES
Q.140 Which reaction(s) do(es) not represents correct major product.
(A) HBr
OH  Br
Cl CN
(B) KCN

CH3 CH3 CH3

H OH H Br Br H
(C) HBr
 +
H Br H Br H Br
CH3 CH3 CH3

OCH 
(D)  
3
 OCH3 + Cl
Cl
Q.141 Which of the following characteristics are follows in Finkelstein reaction-

(A) Reaction of alkyl chlorides/bromides with NaI
(B) Reaction of alkyl chlorides/bromides with NaI in dry acetone
(C) Heating an alkyl chloride/bromide in presence of a metallic fluoride such as AgF, HgF2, CoF2 etc.
(D)All of these
Q.142 Which of the following,Alkyl halide are in gaseous state

(A) Methyl chloride (B) Ethyl chlorides (C) Methyl bromide (D) Ethyl bromides
Q.143 Boiling point of isomeric haloalkanes-

(A) is inverselyproportional to branching (B) is directlyproportional to branching
(C) have no relationship with branching (D) Cannot say with structure
Q.144 Which halogen derivatives are denser than water-

(A) Bromo derivatives of hydrocarbon
(B) Fluoro derivatives of hydrocarbon
(C) Iodo derivatives of hydrocarbon
(D) Polychloro derivatives of hydrocarbon
Q.145 In which compound H-bonding is strong-

(A) R – Cl – – – R – Cl (B) H  O    H  O
| |
H H
(C) R  Cl    H  O (D) None of these

|
H
Q.146 Which of the following act asAmbident Nucleophile
(A) Cyanides (B) Nitrites (C) LiAlH4(H¯) (D) RCOO¯
HALOGEN DERIVATIVES
[MATRIX TYPE]
Q.147 Match List I with List II and select the correct answer from the codes given below:
List-I List-II

(A) CH3–O–SO2CH3 + C 2 H 5 O (1) CH3–CH2–PH2
(B) CH3–CH2–I + PH3 (2) CH3–O–C2H5
 
(C) HC  C Na + CH3–CH2–Br (3) CH3–O–CH3

(D) CH3–Cl + CH3– O (4) CHC–CH2–CH3
Q.148 Match List-I with List-II for given S reaction & select the correct answer from the codes given below
N2

Z–CH2Br + CH3 O  Z–CH2–OCH3 + Br
List-I List-II (relative reactivity)
(A) H– (P) 0.1
(B) CH3– (Q) 3
(C) C2H5– (R) 1
(D) (S) 100
Q.149 Column I Column II

(A) CHCl2–CF3 alc.-KOH (P) Carbanion / Carbanionic character

Br
(B) alc
.KOH
 (Q) Two step process

Cl CH3–CH2–O
(C) (R) Carbocation

F
(D) alc-KOH (S) Transition state

Q.150 Ethers on acidic hydrolysis (H+/H2O) give alcohols / mixture of alcohols.

Ethers Mechanism followed
(A) O (P) SN1
(B) O (Q) SN2
(C) CH2–O–CH3 (R) No reaction

(D) CH3 – CH – CH 2
O
HALOGEN DERIVATIVES

(Haloalkanes) (Density)
(A) CH2Cl2 (P) 1.489
(B) CHCl3 (Q) 1.336
(C) CCl4 (R) 1.595
Q.152 ColumnI Column II

(Boiling point)
(A) 1-Chloropropene (P) 46.6°C
(B) Isopropyl chloride (Q) 78°C
(C) 1-Chlorobutene (R) 35.7°C
HALOGEN DERIVATIVES
EXERCISE-3
SECTION-A
(JEE ADVANCED Previous Year's Questions)
Q.1 Chloroform is stored in dark coloured bottles. Explain in not more than two sentences. [JEE 1980]
Q.2 The compound which reacts fastest with Lucas reagent at room temperature is [JEE 1981]
(A) butan-2-ol (B) butan-1-ol
(C) 2-methyl propan-1-ol (D) 2-methyl propan-2-ol
Q.3 The halogen which is most reactive in the halogenation of alkanes under sunlight is ______.
[JEE 1981]
Q.4 Carbon tetrachloride burns in air to give phosgene. [IIT 1983]
Q.5 Diethyl ether on heating with concentration HI gives two moles of [JEE 1983]
(A) ethanol (B) iodoform (C) ethyl iodide (D) methyl iodide
Q.6 Carbon tetrachloride is inflammable. [IIT 1985]
Q.7 Iodide is better nucleophile than bromide. [IIT 1985]
Q.8 Write down the main product of the following reaction: [JEE 1985]
Ethanol I
2 / NaOH

Q.9 HBr reacts fastest with [JEE 1986]

(A) 2-methyl propan-2-ol (B) propan-1-ol
(C) propan-2-ol (D) 2-methyl propan-1-ol
Q.10 The reaction condition leading to the best yield of C2H5Cl are [JEE 1986]
dark
(A) C2H6 (excess) + Cl2 UV
 light
 (B) C2H6 + Cl2 (excess)  
room temp.
(C) C2H6 + Cl2 (excess) UV

 light
 (D) C2H6 + Cl2 UV
 light

Q.11 HBr reacts fastest with [JEE 1986]

(A) 2-methyl propan-2-ol (B) propan-1-ol
(C) Propan-2-ol (D) 2-methyl propan-1-ol
Q.12 How may be the following transformation be carried out (in not more than six steps)? [JEE 1986]
"Ethyl alcohol to vinyl acetate".
Q.13 n-propyl bromide on treatment with ethanolic potassium hydroxide produces. [IIT 1987]
(A) Propane (B) Propene (C) Propyne (D) Propanol
Q.14 The reaction of vinyl chloride with hydrogen iodide to give 1-chloro-1-iodo ethane is an example of
anti-Markownikoff's rule. [JEE 1989]
HALOGEN DERIVATIVES
Q.15 During SN1 reactions, the leaving group leaves the molecule before the incoming group is attached to the
molecule. [IIT 1990]
Q.16 Aryl halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halides due to
(A) The formation of less stable carbonium ion (B) Resonance stabilization
(C) The inductive effect (D) sp2 hybridised carbon attached to the halogen
[IIT 1990]
Q.17 The compounds used as refrigerant are [JEE 1990]

(A) NH3 (B) CCl4 (C) CF4 (D) CF2Cl2
(E) CH2F2
Q.18 1-Chlorobutane on reaction with alcoholic potash gives:

(A) 1-butene (B) 1-butanol (C) 2-butene (D) 2-butanol [ITT 1991]
Q.19 The products of reaction of alcoholicAgNO2 with ethyl bromide are [IIT 1991]
(A) Ethane (B) Ethyl nitrite (C) Nitroethane (D) Ethyl alcohol
Q.20 Fill in the blanks:

(a) Butan nitrile can be prepared by heating _____with alcohalic KCN. [IIT 1992]
(b) Amongst three isomers of nitrophenol, the one that is least soluble in water is_____ [IIT 1992]
Q.21 Arrange the following in order of their

(i) Increasing basicity
H2O, OH¯, CH3OH, CH3O¯
(ii) Increasing reactivityin nucleophilic substitution reactions
CH3F, CH3I, CH3Bt, CH3Cl [IIT 1992]
Q.22 Write the structures of the major organic product expected from each of the following rreactions:
[IIT 1992]
CH3
(i) H3 C CH2CH3 Alc

. KOH

Cl
aq.alkali
(ii) CH3CH2CHCl2   
boil
Q.23 Photobromination of 2-methylpropane gives a mixture of 1-bromo-2-methyl propane and

2-bromo-2-methyl propane in the ratio 9 : 1. [JEE 1993]
Q.24 Identify the major product in the following reaction. [IIT 1993]
H
Alc.KOH
C6H5—CH 2 CH3   ? HBr
 ?

Br
HALOGEN DERIVATIVES
Q.25 Identify the major product in the following reactions : [IIT 1993]
Cl
| alcoholic
(i) C 6 H 5  CH 2  CH  CH 3    ? HBr
 ?
KOH 
(ii) C6H5COOH + CH3MgI  ? + ?
Q.26 Aryl halides are less reactive than alkyl halides towards nucleophilic reagents. Give reason.
[IIT 1994]
Q.27 Draw the stereochemical structure of product in the following reaction. [IIT 1994]
CH3
Br H NaOH

SN 2
C2H5
Q.28 In the following reactions, identify the compoundsA,B,C and D. [JEE 1994]
(i) PCl5 + SO2  A + B
(ii) A + CH3COOH  C + SO2 + HCl
(iii) 2C + (CH3)2Cd  2D + CdCl2
Q.29 Optically active 2-iodobutane on treatment with NaI in acetone gives a product which does not show
optical activity. Explain briefly. [ITT 1995]
Q.31 Write down the structure of the stereoisomers formed when cis-2-butene is reacted with bromine.
[JEE 1995]
Q.32 Arrange the following compounds in order of increasing dipole moment [IIT 1996]
Toluene m-dichlorobenzene o-dichlorobenzene p-dichlorobenzene
I II III IV
(A) I < IV < II < III (B) IV < I < II < III (C) IV < I < III < II (D) IV < II < I < III
Q.33 An alkyl halide X of formula C6H13Cl on treatment with potassium tertiary butoxide gives two isomeric
alkenesYand Z (C6H12). Both alkenes on hydrogenation give 2,3–dimethylbutane. Predict the structures
of X, Y and Z. [IIT 1996]
Q.34 Predict the structure of the intermediates/products in the following reaction sequence – [IIT 1996]
NaI

 C
Acetone
Q.35 A compound D (C8H8O) upon treatment with alkaline solution of iodine gives a yellow precipitate. The
filtrate on acidification gives a white solid E (C7H6O2). Write the structures of D, E and explain the
formation of E. [JEE 1996]
HALOGEN DERIVATIVES
Q.36 Which of the following is the correct method for synthesising methyl-t-butyl ether and why?
(CH3)3 CBr + NaOMe 
or CH3Br + NaO-t-Bu  [IIT 1997]
Q.37 Statement-1 : Addtition of Br2 to 1-butene gives two optical isomers. [JEE 1998]
Statement-2 : The product contains one asymmetric carbon.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
Q.38 Write the structures of the products: [IIT 1998]

C6H5CH2 CHClC6H5 Alc
. KOH

Q.39 (CH3)2CHOCH3 HI

( excess
 )  A + B Write structures of A and B. [IIT 1998]
Heat
Q.40 Complete the following reaction with appropriate structures of products/reagents. [IIT 1998]
Br2 ( i ) NaNH ( 3 equi.)

 (A)   2  
  (B)
( II ) CH 3I
Q.41 A solution of (+) 2-chloro-2-phenylethane in toluene racemises slowly in the presence of small amount
of SbCl5, due to the formation of [IIT 1999]
(A) carbanion (B) carbene (C) free radical (D) carbocation
Q.42 Explain brieflythe formation of products giving the structures of the intermediates. [JEE 1999]
(i) HCl
 + + etc.
(ii) HCl
 only. Also explain the non-formation
of cyclic product in the reaction.
Q.43 The order of reactivity of the following alkyl halides for a SN2 reaction is: [IIT 2000]
(A) RF > RC > R–Br > R–I (B) R–F > R–Br > R–Cl > R–I
(C) R–Cl > R–Br > RF > RI (D) R–I > RBr > R–Cl > R–F
Q.44 Which of the following has the highest nucleophilicity?

(A) F¯ (B) OH¯ (C) CH3¯ (D) NH2¯ [IIT 2000]
HALOGEN DERIVATIVES
Q.45 Statement-1 : 1-butene on reaction with HBr in the presence of a peroxide produces 1-bromobutane.
Statement-2 : It involves the formation of a primary radical. [JEE 2000]
Q.46 What would be major product? [IIT 2000]

CH 3
|
CH 3  C  CH 2 Br C
2 H 5OH
 ?
| 
CH 3
Q.47 An SN2 reaction at an asymmetric carbon of a compound always gives.

(A) an enantiomer of the substance (B) a product with opposite optical rotation
(C) a mixture of diastereomers (D) a single stereoisomer [IIT 2001]
Q.48 The compound that will react most readily with NaOH to form methanol is
(A) (CH3)4N+ I ¯ (B) CH3OCH3 (C) (CH3)3S+ I ¯ (D) (CH3)3Cl [IIT 2001]
Q.49 Statement-1 : Addition of bromine to trans-2-butene yields meso-2,3-dibromo butane.

Statement-2 : Bromine addition to an alkene is an electrophilic addition. [JEE 2001]
Q.50 Consider the following reaction. [JEE 2002]


H 3C  CH  CH  CH 3  Br 
 ' X ' HBr
| |
D CH 3
Identify the structure of the major product X.
 
(A) H 3C  CH  CH  CH 2 (B) H 3C  CH  C CH 3
| | | |
D CH 3 D CH 3
 
(C) H 3C  C — CH  CH 3 (D) H 3C  CH  CH  CH 3
| | |
D CH 3 CH 3
HALOGEN DERIVATIVES
Q.51 Identify the set of reagents / reaction conditions 'X' and 'Y' in the following set of transformation:
CH3 – CH2 – CH2Br 
X Product 
Y
CH 3  CH  CH 3
|
Br
(A) X = dilute aqueous NaOH, 20°C; Y = HBr / acetic acid, 20°C
(B) X = concentrated alcoholic NaOH, 80°C; Y = HBr/ acetic acid 20°C
(C) X = dilute aqueous NaOH, 20°C; Y = Br2 / CHCl3, 0°C
(D) X = concentrated alcoholic NaOH, 80°C; Y = Br2/CHCl3, 0°C [IIT 2002]
Q.52 Identify X, Yand Z in the following synthetic scheme and write their structures
( i ) NaNH 2
CH3CH2C  CH     X
( ii ) CH CH Br
[IIT 2002]
3 2
Q.53 The product of following reaction is [IIT 2003]

OH
+ C2H5 I C
2 H 5O ¯( excess )
  
anhy. C 2H 5OH
(A) C6H5OC2H5 (B) C2H5OC2H5 (C) C6H5OC6H5 (D) C6H5I

Q.54 How many chiral compounds are possible on monochlorination of 2-methyl butane? [JEE 2004]
(A) 2 (B) 4 (C) 6 (D) 8
Q.55 The following compound on hydrolysis in aqueous acetone will give: [IIT 2005]
CH3 H CH3
MeO NO 2
H Cl CH3
CH3 H CH3
(K) MeO NO 2
H OH CH3
CH3 H CH3
(L) MeO NO2
OH H CH3
CH3 H CH3
(M) MeO NO2
H CH3 OH
It mainlygives
(A) K and L (B) Only K (C) L and M (D) Only M
HALOGEN DERIVATIVES
Q.56 Match the following: [IIT 2006]

Column I Column II
(A) CH3–CHBr–CD3 on treatment with alc. KOH gives (P) E1 reaction
CH2=CH-CD3 as a major product.
(B) Ph – CHBr - CH3 reacts faster than Ph-CHBr-CD3. (Q) E2 reaction
(C) Ph-CD2-CH2Br on treatment with C2H5OD/C2H5O– (R) E1cb reaction
gives Ph-CD=CH2 as the major product.
(D) PhCH2CH2Br and PhCD2CH2Br react with same rate. (S) First order reaction
Fractional
Cl ,h
Q.57 2   (isomeric products) N
monochlorination
  M(isomeric products).
distillati on
What are N and M? [JEE 2006]

(A) 6, 6 (B) 6, 4 (C) 4, 4 (D) 3, 3
Q.58 The reagent(s) for the following conversion: [JEE 2007]
Br ?
Br  H H
is / are :
(A) alcoholic KOH (B) alcoholic KOH followed by NaNH2
(C) aqueous KOH followed by NaNH2 (D) Zn /CH3OH
Q.59 The major product of the following reaction is [IIT 2008]
H3C Br
F
PhSNa
   
dim ethyl formamide
NO2
H3C Br H3C SPh

H3C SPh H3C SPh
F F SPh SPh
(A) (B) (C) (D)
NO2 NO2 NO2 NO2
Q.60 In the reaction OCH3 HBr

 the products are [IIT 2010]
(A) Br OCH3 and H2 (B) Br and CH3Br
(C) Br and CH3OH (D) OH and CH3Br
Q.61 The total number of alkenes possible by dehydrobromination of 3-bromo-3-cyclopentylhexane using

alcoholic KOH is [IIT 2011]
HALOGEN DERIVATIVES
Q.62 KI in acetone, undergoes SN2 reaction with each of P, Q, R and S. The rates of the reaction vary as
O
Cl
H3C–Cl Cl [JEEAdvance 2013]
Cl
P Q R S
(A) P > Q > R > S (B) S > P > R > Q (C) P > R > Q > S (D) R > P > S > Q
Q.63 After completion of the reactions (I and II), the organic compound(s) in the reaction mixtures is(are):
O
Br2(1.0 mol)
Reaction I : H3C CH3 aqueous NaOH [JEEAdvance 2013]
(1.0 mol)
O
Br2(1.0 mol)
Reaction I I : H3C CH3 CH3COOH
(1.0 mol)
O O O O O
H2 C CH2Br H3 C CBr3 Br3C CBr3 BrH2C CH2Br H3C ONa CHBr3

P Q R S T U
(A) Reaction I : P and Reaction II : P

(B) Reaction I : U, acetone and Reaction II : Q, acetone
(C) Reaction I : T, U, acetone and Reaction II : P
(D) Reaction I : R , acetone and Reaction II : S, acetone
Q.64 Match the chemical conversions in List I with the appropriate reagents in List II and select the correct
answer using the code given below the lists: [JEEAdvance 2013]
List I List II
(P) Cl (1) (i) Hg(OAc)2; (ii) NaBH4
(Q) ONa OEt (2) NaOEt
OH
(R) (3) Et – Br
(S) (4) (i) BH3 ; (ii) H2O2/NaOH

OH
Codes :
P Q R S
(A) 2 3 1 4
(B) 3 2 1 4
(C) 2 3 4 1
(D) 3 2 4 1
HALOGEN DERIVATIVES
Q.65 The major product in the following reaction is [JEEAdvance 2014]

O
. CH 3MgBr , dry ether , 0C
Cl 1  
CH3 2. aq. acid
O OH
(A) H3C (B) H C CH3
CH3 2 CH3
CH3
(C) (D)
O CH2 O CH3
Q.66 The major product of the reaction is : [JEEAdvance 2015]

H3 C CO2H
NaNO2 , aqueous HCl
0°C
CH3 NH2
H3C NH2 H3C CO2H
(A) (B)
CH3 OH CH3 OH
H3C CO2H H3C NH2
(C) (D)
CH3 OH CH3 OH
Q.67 In the following monobromination reaction, the number of possible chiral products is
[JEEAdvance 2016]
CH2CH2CH3
H Br
CH3 Br
2 300
ºC 
(1.0 mole)
(1.0 mole)
(enantiomerically pure)
Q.68 For the following compounds, the correct statement(s) with respect to nucleophilic substitution reactions
is(are) [JEEAdvance 2017]
CH3
CH3
Br Br H3C – C – Br Br
CH3
(I) (II) (III) (IV)
(A) I and III follow SN1 mechanism
(B) Compound IV undergoes inversion of configuration
(C) I and II follow SN2 mechanism
(D) The order of reactivity for I, III and IV is : IV > I > III
HALOGEN DERIVATIVES
Q.69 In the following reaction sequence, the correct structure(s) of X is (are) : [JEEAdvance 2018]
Me N3
(1) PBr3,Et2O
X
(2)NaI,Me2CO
(3) NaN3,HCONMe2
enantiomerically pure
Me OH Me OH
(A) (B)
(C) Me (D) Me
OH OH
Q.70 LIST-I contains reactions and LIST-II contains major products. [JEEAdvance 2018]
LIST-I LIST-II
P. + 1.
ONa Br OH
Q. + HBr 2.
OMe Br
R. + NaOMe 3.
Br OMe
S. + MeBr 4.
ONa
O
5.
Match each reaction in LIST-I with one or more products in LIST-II and choose the correct option.
(A) P  1,5; Q  2; R  3; S  4
(B) P  1,4; Q  2; R  4; S  3
(C) P  1,4; Q  1,2; R  3,4; S  4
(D) P  4,5; Q  4; R  4; S  3,4
HALOGEN DERIVATIVES
SECTION-B
(JEE Main Previous Year's Questions)
Q.1 The reaction (CH3)3 CBr + H2O  (CH3)3 COH + HBr is a - [AIEEE-2002]
(A) Substitution reaction (B) Debromination reaction
(C) Rearrangement reaction (D) Elimination reaction
Q.2 The decreasing order of nucleophilicity among the nucleophiles [AIEEE-2005]
(a) CH 3 C  O  (b) CH3O– (c) CN– (d)

||
O
is
(A) d > c > b > a (B) a > b > c > d (C) c > b > a > d (D) b > c > a > d
Q.3 The correct order of the thermal stability of hydrogen halides (H – X) is – [AIEEE-2005]
(A) HF > HCl > HBr > HI (B) HI > HBr > HCl > HF
(C) HI > HCl < HF > HBr (D)HCl < HBr > HBr < HI
Q.4 Tertiary alkyl halides are practically inert to substitution by SN2 mechanism because of –
[AIEEE-2005]
(A) instability (B)insolubility (C) steric hindrance (D) inductive effect
Q.5 Alkyl halides react with dialkyl copper reagents to give [AIEEE-2005]
(A) alkyl copper halides (B) alkenes
(C) alkenyl halides (D) alkanes
Q.6 Elimination of bromine from 2–bromobutene results in the formation of – [AIEEE-2005]

(A) predominantly 2–butene (B) equimolar mixture of 1 and 2–butene
(C) predominantly 2–butyne (D) predominantly 1–butene
Q.7 Among the following the one that gives positive iodoform upon reaction with I2 and NaOH is –
[AIEEE 2006]
(A) C6H5CH2CH2OH (B)

(C) PhCHOHCH3 (D) CH3CH2CH(OH)CH2CH3
Q.8 CH3Br + Nu–  CH3 – Nu + Br–

The decreasing order of the rate of the above reaction with nucleophiles (Nu–) Ato D is
[Nu– = (A) PhO–, (B) AcO–, (C) HO–, (D) CH3O–] [AIEEE 2006]
(A) D > C > B > A (B) A > B > C > D (C) B > D > C > A (D) D > C > A > B
Q.9 Which of the following is the correct order of decreasing SN2 reactivity ? [AIEEE 2007]
(A) RCH2X > R3CX > R2CHX (B) RCH2X > R2CHX > R3CX
(C) R3CX > R2CHX > RCH2X (D) R2CHX > R3CX > RCH2X
(X = halogen)
HALOGEN DERIVATIVES
Q.10 The organic chloro compound, which shows complete stereochemical inversion during a SN2 reaction ,
is [AIEEE 2008]
(A) (CH3)3CCl (B) (CH3)2CHCl (C) CH3Cl (D) (C2H5)2CHCl
Q.11 Which of the following on heating with aqueous KOH produces acetaldehdye ? [AIEEE 2009]
(A) CH3COCl (B) CH3CH2Cl (C) CH2ClCH2Cl (D) CH3CHCl2
Q.12 Consider the following bromides : [AIEEE 2010]
(a) (b) (c)
The correct order of SN1 reactivity is :

(A) a > b > c (B) b > c > a (C) b > a > c (D) c > b > a
Q.13 A solution of (–) – 1–chloro –1– phenylethane on toluene racemises slowly in the presence of a small
amount of SbCl5 due to the formation of: : [JEE Main 2013]
(A) carbene (B) carbocation (C) free radical (D) carbanion
Q.14 The major organic compound formed by the reaction of 1,1,1–trichloroethane with silver powder is :
[JEE Main 2014]
(A) Ethene (B) 2 – Butyne (C) 2 – Butene (D) Acetylene
Q.15 In SN2 reactions, the correct order of reactivity for the following compounds :
CH3Cl, CH3CH2Cl, (CH3)2 CHCl and (CH3)3CCl is : [JEE Main 2014]
(A) CH3Cl > CH3CH2Cl > (CH3)2CHCl > (CH3)3 CCl
(B) CH3CH2Cl > CH3Cl > (CH3)2 CHCl > (CH3)3CCl
(C) (CH3)2CHCl > CH3CH2Cl > CH3Cl > (CH3)3CCl
(D) CH3Cl > (CH3)2 CHCl > CH3CH2Cl > (CH3)3CCl
Q.16 The synthesis of alkyl fluorides is best accomplished by : [JEE Main 2015]
(A) Finkelstein reaction (B) Swarts reaction
(C) Free radical fluorination (D) Sandmeyer's reaction
Q.17 2-chloro-2-methylpentane on reaction with sodium methoxide in methanol yields :[JEE Main 2016]
C H3
|
(a) C2 H 5CH 2 C OCH3 (b) C 2 H 5CH 2 C  CH 2 (c) C 2 H 5CH  C  CH 3
| | |
CH 3 CH 3 CH 3
(A) (a) and (b) (B)All of these (C) (a) and (c) (D) (c) only
Q.18 The major product obtained in the following reaction is : [JEE Main 2017]
Br
H t
BuOK
C6H5

C6H5
(+)
(A) C6H5CH = CHC6H5 (B) (+) C6H5CH (OtBu) CH2C6H5

(C) (–) C6H5CH(OtBu) CH2C6H5 (D) (±) C6H5CH(OtBu) CH2C6H5
HALOGEN DERIVATIVES
Q.19 The increasing order of the reactivity of the following halides for the SN1reaction is :
[JEE Main 2017]
(I) CH 3CHCH 2 CH 3 (II) CH3CH2CH2Cl (III) p–H3CO–C6H4 – CH2Cl

|
Cl
(A) (II) < (I) < (III) (B) (I) < (III) < (II) (C) (II) < (III) < (I) (D) (III) < (II) < (I)
Q.20 Which of the following, upon treatment with tert-BuONa followed byaddition of bromine water, fails to
decolourize the colour of bromine ? [JEE Main 2017]
C6H5 O
(A) (B)
Br Br
O
O
(C) (D)
Br Br
Q.21 The major product of the following reaction is : [JEE Main 2018]
Br
NaOMe
 
MeOH
OMe OMe
(A) (B) (C) (D)
HALOGEN DERIVATIVES
EXERCISE-4
(CBSE Previous Year's Questions)
Q.1 Illustrate the following with an example of reaction: [CBSE 2003, 3]

(i) Ambident nucleophile
(ii) Hinsberg test.
Q.2 Account of the following: [CBSE 2008, 2]

Cl Cl
(i) reacts faster then
(ii) The treatment of an alkyl chloride with aqueous KOH leads to the formation of an alcohol
whereas in the presence of alcoholic KOH, alkene is the major product.
Q.3 (a) Suggest a mechanism for the reaction [CBSE 2008, 3]

n Bu Br + KCN C 2 H 5OH ,H 2 O
  n Bu CN
(b) Describe carbylamine reaction.
Q.4 Which ones in the following pairs of substances undergoes SN2 substitution reaction faster and why?
(i) CH2Cl or Cl [CBSE 2009, 2]
(ii) I or Cl
Q.5 Which one in the following pairs undergoes SN1 substitution reaction faster and why?
Cl Cl
(i) or [CBSE 2009,2]
Cl Cl
(ii) or
Q.6 How would you account for the following: [CBSE 2010, 2]
Cl
undergoes faster SN1 reaction than Cl
Q.7 Explain why. [CBSE 2010, 2]

(i) The dipole moment of chlorobenzenes is lower than that of cyclohexylchloride.
(ii) Chloroform is stored in closed dark coloured bottles completely filled so that air is kept out.
Q.8 Rearrange the compounds of each of the following sets in order of reactivity towards SN2 displacement:
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane. [CBSE 2011, 3]
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 2-Bromo-3-methylbutane
(iii) 1-Bromobutane, 1-Bromo-2, 2-dimethylpropane, 1-Bromo-3-methylbutane.
HALOGEN DERIVATIVES
Q.9 (a) Write a chemical test of distinguish between: [CBSE 2011, 3]

(i) Chlorobenzene and Benzyl chloride
(ii) Chloroform and Carbon tetrachloride
(b) Why is methyl chloride hydrolysed more easily than chlorobenzene?
Q.10 Give reasons for the following: [CBSE 2013]

C–X bond length in halobenzene is smaller than C–X bond length in CH3–X.
Q.11 Write the mechanism of the following reaction : [CBSE 2014]

CH3CH2OH 
 CH3CH2Br + H2O
HBr
Q.12 Which halogen compound in each of the following pairs will react faster in SN2 reaction :
[CBSE 2014]
(i) CH3Br or CH3I (ii) (CH3)3C–Cl or CH3 – Cl
Q.13 What happens when [CBSE 2015]

(i) ethyl chloride is treated with NaI in the presence of acetone.
(ii) chlorobenzene is treated with Na metal in the presence of dry ether.
(iii) methyl chloride is treated with KNO2?
Write chemical equations in support of your answer.
Q.14 Which of the following two reactions in SN2 and why ? [CBSE 2016]
C2H5 C2H5
(i) H 
Y
 H
X CH3 Y
CH 3
C2H5 C2H5
(ii) H 
 Y
H
X Y CH3
CH3
HALOGEN DERIVATIVES
EXERCISE-5 (Rank Booster)
[SINGLE CORRECT CHOICE TYPE]

Q.1 In the given reaction [X] is:
CH OH
 [X]
3
(excess)
(A) (B) (C) (D)
Q.2 Correct order of rate of hydrolysis for following compounds is

Br
Br
[I] [II] [III] [IV]
(A) III > II > IV > I (B) I > II > III > IV (C) III > I > II > IV (D) III > II > I > IV
CH3
Q.3 H I HOH
 Products . (If 96 % racemisation takes place)
Et
Find out the correct statement about the reaction.
(A)Among the products 48% S and 48% R configuration containing molecules are present
(B)Among the products 50% S and 50% R configuration containing molecules are present
(C)Among the products 48% S and 52% R configuration containing molecules are present
(D)Among the products 52% S and 48% R configuration containing molecules are present
CH3
TsCl KSH
Q.4 H OH  (A)  Products
Et
(1 mole)
(Assuming all the substrate convert into substitution products containing 0.05 mole of S-configuration.
Calculate the percentage of SN2 mechansim.
(A) 90% (B) 80 % (C) 70 % (D) 95 %
HALOGEN DERIVATIVES
Q.5 KSH
 (P) Product P is :
(A) (B) (C) (D)
Q.6 The product P of the following reaction is

H
KCN
 Product (P) [Major]
CH2OTs Ethanol H 2O
CN
(A) (B) (C) CH2CN (D)
Q.7 In which of the following reaction ether can not be obtained as major product.
 
(A) Me3C Br + Me O K  (B) Me3C O K + MeBr 
 
(C) C 2 H 5 O Na + CH3–O–SO3–CH3  (D) RMgX + ROCH2Cl 
 [X]
NaOH
25 C
(A) (B)
(C) Mixture of (A) and (B) (D)
HALOGEN DERIVATIVES
OCH3
NaNH
Q.9  
2  A, major product A and reaction R are:
Br
OCH3 OCH3
NH2
(A) , elimination addition (B) , elimination addition
NH2
OCH3 OCH3
Br
(C) , cine substitution (D) , addition elimination
NH2
Q.10 Pick the correct statement for monochlorination of R-sec butyl Bromide.
Me
Cl2
Br H
hv
Et
(A) There are five possible product ; four are optically active & one is optically inactive
(B) There are five possible product ; three are optically inactive & two are optically active
(C) There are five possible product ; two are optically inactive & three are optically active
(D) None of these
Br2
 [X]

[X] is:
(A) (B) (C) (D)
Q.12 Which can not be the possible product of the given reaction
Br
CH 3  CH 2  C  OAg 2  product(s)
CCl4 , 
||
O
(A) CH3 – CH2 – Br (B) CH 3  CH 2  C  O  CH 2  CH 3

||
O
(C) CH3 – CH2 – CH2 – CH3 (D) CH3 – CH2 – CH3
HALOGEN DERIVATIVES
Q.13 Which reaction conditions (reagents) is suitable for the following reaction:
?


(A) Br2 / CCl4 (B) SOBr2 (C) KBr (D) PBr3
Br H
H
H3C
Q.14 alcoholic
  A
KOH
E2
Ph
Ph
CH3 Ph CH3 Ph H CH3

C C C
(A) (B) (C) (D) None is correct
C C C
H Ph Ph H Ph Ph
H
Br
Q.15 alc
.KOH
 P,, P is

CH 3
(A) (B) (C) (D)

CH 3
CH3
Q.16 The rate of elimination (using EtONa) of:
Br Br
(I) (II) (III)

Br
t-Bu t-Bu
(A) I > II > III (B) I > III > II (C) II > I > III (D) III > I > II
HALOGEN DERIVATIVES
—O–Cl
KOH (1 mole )
Q.17 h
(A) NBS
  (B)    (C)
(1eq.)


Cl
(A) (B) (C) OH (D)
Q.18 3  Product (M)

AgNO

I
OH
M is
(A) (B)
O O
(C) H (D)
O O
HALOGEN DERIVATIVES
O
18

PCl5 H 3C  CH 2 OH OH
Q.19 H3C S–OH      
O
Final products are
O
18
(A) H3C S–OH + H3C–CH2–OH
O
O
18
(B) H3C S–O + H3C–CH2–OH
O
O
18
(C) H3C S–O + H 3C  CH 2  OH
O
O
(D) H3C S–O + H3C–H2C–OH
O
[MULTIPLE CORRECT CHOICE TYPE]

Q.20 Which of the following statements is / are true?
(A) CH3–CH2–CH2–I will react more readily than (CH3)2 CHI for SN2 reactions.
(B) CH3–CH2–CH2–Cl will react more readily than CH3–CH2–CH2–Br for SN2 reaction.
(C) CH3–CH2–CH2–CH2–Br will react more readily than (CH3)3C–CH2–Br for SN2 reactions
(D) C6H5– CH2Br will react more readily than H3C Br for SN2 reaction
HALOGEN DERIVATIVES
Q.21 Which of the following reaction given is/are correct :
H
H H Br
(A) H C HBr H C
H2O2
H H
(B) HBr Br
CCl3
(C)
(D) COOHg Br

2 /
CCl 4
Br

Q.22 Which alkyl halide undergo E2 elimination
(A) (B)
CMe 3
(C) (D)
Br
D
Me
Br Me H Me Me Me H Me Me Me H
H EtONa
Q.23 EtOH
+ + + +
D H H Me H D H H H H D
(ii) Me
(i) (iii) (iv) (v)
Me
(A)
Which statement are correct about the above reaction?

(A) (i) and (ii) with small amount of (iii) are formed.
(B) (iv) and (v) with small amount of (iii) are formed.
(C) The two groups undergoing elimination must lie in anti-periplanar arrangement.
(D) Compound (A) has two conformation in which H or D is anti-periplanar to bromine.
HALOGEN DERIVATIVES
Q.24 Select which reaction is correct with major product given :

CH3
H CH3 CH3
D (i) MeI (excess)
(ii) moist Ag 2O/ C=C
(A) H NH2
D H
CH3
CH3 CH3
H D 
H D
(B) H OCOR
CH3 CH=CH2
CH3–CH2–CH–CH3 CH3COONa X 
CH3–CH2–CH=CH2
(C) CH COOH 3
Br
(D) conc.H2SO4

OH
Br CH3–CH2–OH
Q.25 Product
warm
Product is/are :
OCH2–CH3
(A) (B)
OEt
(C) (D) OEt
HALOGEN DERIVATIVES

OH
Q.26 80°C P+Q +R +S
Br
S
P.E. R
Q
P
Br
Reaction co-ordinates
Correct statement(s) about reaction & related graph is (are):
(A) P & Q are nucleophilic substitution products by SN2 reaction mechanism
(B) only R & S are elimination products by E2 reaction mechanism
(C) P is nucleophilic substitution product by SN2 reaction mechanism
(D) Q,R,S are elimination products by E2 reaction mechanism
[MATRIX TYPE]
Q.27 Each of the compounds in columnAis subjected to further chlorination. Match the following for them.
ColumnA Column B
(A) CHCl2–CH2–CH3 (P) Opticallyactive original compound
(B) CH2Cl–CHCl–CH3 (Q) Only one trichloro product
(C) CH2Cl–CH2–CH2–Cl (R) Three trichloro product.
(D) CH3–CCl2–CH3 (S) Four trichloro product

Cl Cl
(E) | | (T) Atleast one of the trichloro product is
CH 3  C — C  CH 3 opticallyactive.
| |
CH 3 CH 3 (U) Two trichloro products.
Q.28 Match the List I with List II and select the correct answer using the codes given below the Lists.
List I List II
(A) E1CB (1) 3°Amine oxide
(B) Saytzeff alkene as major product (2) Xanthate
Cl
|
(C) E2 (3) CH 3  CH 2  CH  CH 3
(D) Ei (4) C6 H 5  CH 2  CH  CH 3
|
F
HALOGEN DERIVATIVES
Q.29 Match the following.

List-I List-II
OCH3
CH2
O
CH3 O CH CH O

(A) 3 

2 (P) E1
CH3O 
CH3O
Br

CH CH O
(B) 3 

2
(Q) E2
CH 3CH 2OD
(C) MeOH
 (R) E1cb
Br Ph
(D) alc
. KOH
 (S) Ei
Q.30 Match the List I (reaction) with List II (reaction intermediate) and select the correct answer using the
codes given below the Lists.
List I List II
(A) CF3–CHCl2 alc /

.KOH

  CF2 = CCl2 (1) Transition state only
CH 3
| 
(B) CH 3  C  OH H
 CH 3  C  CH 2 (2) Carbocation
| |
CH 3 CH 3
alc.KOH
(C) CH3–CH2–Br   CH2=CH2 (3) Carbanion

Br
|
(D) CH 3  C  CH 3 aq
. KOH
 /
 CH 3  C  CH 2 (4) Free radical
| |
CH 3 CH 3
HALOGEN DERIVATIVES

CH3 CH3
CH3–OH
(A) Ph –C – CH warm (P) No Reaction
Cl CH3
CH3
CH3–OH
C CH3 warm
(B) (Q) Rearrangement
Cl
CH3
–
OH
(C) CH2 – CH – CH (R) HoffmannAlkene
Br CH3
CH2 – CH – CH2–CH3 CH3

–OH
(D) (S) Product can exist in
F
stereoisomeric form
[SUBJECTIVE]
Q.32 Heating many alkyl chlorides or bromidesin water effects their conversion into alcohol through a SN1
reaction. Order each of the following sets compounds with respect to solvolytic reactivity.
Br
Br
Br Br
(a)
(I) (II) (III)
Br
(b) Br
Br
(I) (II) (III)
Cl Cl Cl
(c)
Q.33 Discuss the mechanism of SN1 reaction of haloalkanes.
Q.34 What are the products of the following reactions?
CH 3 CH 3
| |
(a) CH 3  C  Cl  OCH 3  (b) CH 3  C  O ¯ + CH3 – X 
| |
CH 3 CH 3
HALOGEN DERIVATIVES
Q.35 Write the principal organic product in each of the following reactions:
H NNH
(i) + C6H5CH2SK  A (ii) 2 2  B
triethylene
glycol
(iii) + CH3CH2ONa  D (iv) + C6H5CH2SNa  E
Q.36 Reaction of 1,2,3-tribromo-5-nitrobenzene with sodium ethoxide in ethanol gave a single product,
C8H7Br2NO3, in quantitative yield. Suggest a reasonable structure for this compound.
Q.37 Offer an explanation for the observation that 4-chloropyridine is more reactive toward nucleophiles than
3-chloropyridine.
Q.38 2-Bromo-1,3-dimethylbenzene is inert to nucleophilic aromatic substitution on treatment with sodium

amide in liquid ammonia. It is recovered unchanged even after extended contact with the reagent. Suggest
an explanation for this lack of reactivity.
Q.39 Suggest a reasonable mechanism for each of the following reactions:

(a) C6H5Br + CH2(COOCH2CH3)2 2
NaNH2 , NH3
   C6H5CH(COOCH2CH3)2
(b) 2
NaNH 2 , NH 3
 
NaNH
 
2 
(c) ether
K CO
(d) 2 
3 
heat
Q.40 In studyof chlorination of propane four products (A,B,C,D) of molecular formula C3H6Cl2 were obtained.
On further chlorination of the above productsAgave one trichloro product, B gave two whereas C and
D gave three each. When optically active C was chlorinated one of trichloro propanes was optically
active and remaining two were optically inactive. Identify the structures of A,BC and D, and explain
formation of products.
HALOGEN DERIVATIVES
Q.41 Complete following reaction:
(a) HCl

Br
(b) 
2
CCl 4
CH3
Cl
(c) 
2
CS2
Total number of products obtained in this reaction is ?
Q.42 On chlorination, an equimolar mixture of ethane and neopentane yields neopentyl chloride and
ethyl chloride in the ratio 2.3 : 1. How does the reactivity of 1° hydrogen in neopentane compare with
that of a 1° hydrogen in ethane?
Q.43 Addition of small amount of (C2H5)4Pb to a mixture of methane and chlorine, starts the reaction at
140°C instead of the usual minimum 250°C. Why?
Q.44 Give product(s) in each of the following reactions .
(a) CH3 – CH – CH2 – CH2– CH3 Br / hv

2  (A) (major)
|
CH 3
( C H COO ) 2
(b) + NBS 6 5    (B)
hv
(c) CH3 – CH2 – CH = CH2 + Me3COCl  (C) + (D)
CH 3
|
CH3  C O  Cl / 
|
CH3
(d) C6H5 – CH2 – CH2 – CH3      (E) (major)
Q.45 Calculate the percentage of products i.e. P1, P2 & P3, if reactivity for chlorination with 1°H, 2°H & 3°H
is 1 : 3.8 : 4.5 respectively.
Cl
Cl
Cl
h + +
+ Cl2   
Monochlorination
(P1) (P2) (P3)
HALOGEN DERIVATIVES
Q.46 It required 0.7 g of a hydrocarbon (A) to react completely with Br2 (2.0 g) and form a non resolvable
product. On treatment of (A) with HBr it yielded monobromo alkane (B). The same compound (B) was
obtained when (A) was treated with HBr in presence of peroxide. Write down the structure formula of
(A) and (B) and explain the reactions involved.
Q.47 Iodine reacts with alcohols to give alkyl iodine only in presence of phosphorous.
Q.48 Each of the following alcohols has been subjected to acid catalyzed dehydration and yields a mixture of
two isomeric alkenes. Identify the two alkenes in each case, and predict which one is the major product
on the basis of the Zaitsev rule.
(a) (CH 3 ) 2 CCH (CH 3 ) 2
|
OH
(b)
OH
(c)
HALOGEN DERIVATIVES
ANSWER KEY
EXERCISE-1
Q.1 tert-Butyl chloride, sec butyl chloride and Butyl chloride with alc. silver nitrate
Me3C – Cl > CHCl > CH3– CH2– CH2– CH2– Cl
Me
Q.3 (A) , (B) Pr OEt Q.4 8 Q.5 4
H
Q.6 OCH3 Q.8 Q.10 9

N CN
Q.11 (a) Ph  CH  Et , (b) Me2C(I)–Et, (c) , (d)

|
Br
Q.12 8 products Q.14 6 Q.15 1,2,3,4,5,6,7,9,10,11,12
Q.16 C–I bond being less stable than C–Cl bond and thus on heating heterolytic cleavage of C –I form I–
which gives yellow precipitate withAgNO3
Q.18 7
Q.19 The elimination of HI (or DI) in presence of strong base shows E2 elimination. The rate determining step
involves breaking up of C – H (or C–D) bond. The C–D bond being stronger than C–H and thus
elimination is faster in case of CH3 – CH2I.
Q.21 H 3C  CH  CH  CH 3 KOH
 ( alc
)  CH 3  C  CH  CH 3  CH 3  CH  CH  CH 2
| | | |
CH 3 Cl CH 3 CH 3
major minor
Elinination occurs according to saytzeff rule. The major product is one which involves elimination of H
from less hydrogenated carbon.
Q.22 4
Q.23 (A) (B) (C) (D) CH 2

Br ||
O
HALOGEN DERIVATIVES
O
(E)
Q.24 (i) ClCH2CH2CH2CN (ii) PhCHF2

(iii) FCH2CH = CHCO2Me (iv) EtI
(v) no reaction
Q.25
(a) Due to three electronegative chlorine atoms present on carbon, the latter acquires a partial positive
charge due to –I effect of chlorine. As a result, it tends to attract electrons of the C–H bond towards
itself. Hence the removal of hydrogen atom as proton becomes easier.
(b) Alcohol acts as inhibitor for oxidation of chloroform.Also it reacts with COCl2 to give harmless diethyl
carbonate.
(c) KI reacts with RCl to form RI. This RI molecule now hydrolysed easily to give ROH because alkyl
iodide are more reactive than alkyl chloride.
RCl + KI  RI HOH  ROH (faster)
(d) KCN is an ionic compound [K+(:C N:)–] in which both C and N carrya lone pairelectron. Carbon carrying
lone pair of electrons is more reactive and thus alkyl attacks carbon to give alkyl cyanide. AgCN being
covalent hasAg– CN : structure with lone pair on N thus N atom attacks on R and R–N   C is formed.
Q.26 The dielectric constant of water is greater than that of aqueous acetone, and so ionisation of benzyl
chloride is facilitated.
 
Br OH O Na
Br2 aq. KOH Na

h
(A) (B) (C)
alc. KOH
NBS (C)
Q.27 Br
(D) (E) (F)
O
Q.28 (i)A, CH3CH2CH2Br ; B, CH3CH = CH2 ; C, CH3CHBrCH3; D, CH3CHNH2CH3

(ii) A, CH3CH = CH2; B, CH3CHOHCH3; C, CH3CHClCH3; D, CH3CH2CH2
(iii) A, CH3CHBrCH = CH2; B, CH2=CH–CH=CH2; C, CH3CHBrCH=CH2& CH3CH = CH–CH2Br
(iv) A, CH3CH2CHOHCH3; B, CH3CH2CHBrCH3; C, CH3CH = CH – CH3
HALOGEN DERIVATIVES
Q.29 A B C D
MgBr
E F
CH2OCH2CH3
Q.30 (a) (b) (c)
Cl
AlCl3 |
Q.31 (a) CH3—CH2—CH2—Cl CH3—CH—CH 3

(b) (i) 
O  (ii) HBr / H2O2
(c) (i) Mg/ether (ii) HCHO/ H2O (iii) PCl3 or SOCl2
CH2—CH 3 NBS alc KOH

Q.32 (i) CH—CH3 CH = CH2
Br
(ii) (i) B2H6/NH2 —Cl
CH3—CH2—CH = CH2 CH3—CH2—CH2—CH2—NH2
(iii) CH3—CH2—CH = CH2 NBS CH3—CH—CH = CH 2 alc KOH CH2 = CH —CH = CH 2

Br
Br
Q.34 (A) (B) (C) Q.35 CH2 OCH3

CH3S
EXERCISE-2
Q.1 A Q.2 C Q.3 A Q.4 C Q.5 C Q.6 A Q.7 C
Q.8 B Q.9 C Q.10 B Q.11 C Q.12 A Q.13 B Q.14 A
Q.15 C Q.16 D Q.17 A Q.18 D Q.19 C Q.20 C Q.21 A
Q.22 C Q.23 B Q.24 C Q.25 A Q.26 C Q.27 B Q.28 B
HALOGEN DERIVATIVES
Q.29 C Q.30 D Q.31 A Q.32 C Q.33 C Q.34 B Q.35 C
Q.36 B Q.37 A Q.38 A Q.39 B Q.40 B Q.41 A Q.42 C
Q.43 D Q.44 C Q.45 B Q.46 A Q.47 B Q.48 A Q.49 B
Q.50 C Q.51 A Q.52 B Q.53 C Q.54 C Q.55 C Q.56 B
Q.57 C Q.58 C Q.59 C Q.60 C Q.61 A Q.62 A Q.63 B
Q.64 B Q.65 B Q.66 D Q.67 D Q.68 A Q.69 A Q.70 C
Q.71 C Q.72 D Q.73 A Q.74 B Q.75 A Q.76 D Q.77 C
Q.78 C Q.79 D Q.80 D Q.81 D Q.82 C Q.83 B Q.84 C
Q.85 C Q.86 B Q.87 B Q.88 D Q.89 D Q.90 A Q.91 A
Q.92 A Q.93 B Q.94 A Q.95 D Q.96 D Q.97 D Q.98 A
Q.99 B Q.100 B Q.101 D Q.102 C Q.103 B Q.104 C Q.105 B
Q.106 D Q.107 D Q.108 C Q.109 A Q.110 A Q.111 B Q.112 A
Q.113 B Q.114 D Q.115 A Q.116 AB Q.117 BCD Q.118 ABCD Q.119 ABC
Q.120 BD Q.121 AC Q.122 ABC Q.123 ABD Q.124 AB Q.125 AB Q.126 ACD
Q.127 ABC Q.128 ABD Q.129 AB Q.130 ACD Q.131 ACD Q.132 AB Q.133 AC
Q.134 BC Q.135 BD Q.136 AC Q.137 BC Q.138 AB Q.139 ABC
Q.140 ABCD Q.141 B Q.142 ABC Q.143 A Q.144 ACD Q.145 B Q.146 B
Q.147 (A) 2 ; (B) 1 ; (C) 4 ; (D) 3 Q.148 (A) S ; (B) Q ; (C) R ; (D) P
Q.149 (A) PQS (B) S (C) S (D) PS Q.150 (A) R (B) P (C) P,Q (D) Q
Q.151 (A) Q (B) P (C) R Q.152 (A) P (B) R (C) Q

HALOGEN DERIVATIVES
EXERCISE-3
SECTION-A
Q.1 2CHCl3 + O2  2COCl2 + H2O
Phosgene (Poisonous gas)
Q.2 D Q.3 Fluorine Q.4 False Q.5 C
Q.6 False Q.7 True Q.9 A Q.10 A
Q.11 A
conc. H 2SO 4 Br2 alc.KOH

Q.12  CH 2  CH 2   H–CC–H
CH3CH2OH    CH2= CH2 
 NaNH 2
| |
Br Br
Hg
(CH 3COO ) 2
  CH 2  CH  OCOCH 3
CH 3COOH vinyl acetate
Q.13 B Q.14 False Q.15 True Q.16 BD
Q.17 AD Q.18 A Q.19 C
Q.20 (a) propyl chloride, (b) ortho
Q.21 (i) H2O < CH3OH < HO¯ < CH3O¯

(ii) CH3F < CH3Cl < CH3Br < CH3I
CH3 CH 3
|
Alc.KOH
Q.22 (i) H3 C CH2CH3   CH 3  C  CH  CH 3
Cl
OH
aq.alkali
|
(ii) CH3CH2CHCl2    [CH 3  CH 2  CH  OH] 
H 2O
 CH3CH2CHO
boil
unstable
Q.23 False
H
Alc.KOH
Q.24 C6H5—CH 2 CH3   C6H5–CH=CH–CH3 HBr
 C6 H 5  CH  CH 2  CH 3
 |
Br Br
Br
|
Q.25 (i) C 6 H 5  CH  CH  CH 3 ; C6 H 5  CH  CH 2  CH 3 (ii) C6H5COOMgI + CH4
HALOGEN DERIVATIVES
+
X X
Q.26
aryl halide
Due to the above resonance phenomena, C–X bond acquire partial double bond character and becomes
difficult to break in the rate determining step of SN2 reaction.
Q.27 SN2 reactions leads to inversion of configuration at -C.
CH3 CH3
NaOH
Br H  H OH
SN 2
C2H5 C2H5
product with inverted
configuration
Q.28 (A) SOCl2 , (B) POCl3 (C) CH3COCl (D) CH 3  C  CH 3

||
O
CH3 CH3
K=1
C – I + I¯ I–C H
Q.29 H
C2H5 C2H5
Above equilibrium is established which has equilibrium constant equal to 1.Therefore, equilibrium mixture
will have both the enantiomers in equal amount giving racemic mixture.
Q.31 + Br2 
Q.32 B
CH 3 CH 3 CH 3 CH 3
| | | |
Q.33 (X): CH 3  C — CH  CH 3 ; (Y) : CH 2  C — CH  CH 3 ; (Z) : CH 3  C  C  CH 3
| | |
Cl CH 3 CH 3
Q.34 (NGP due to MeO, so retention of configuration)
HALOGEN DERIVATIVES
Q.35 E = C6H5COOH ( benzoic acid)

O
|| I2
 C6 H 5  C  CH 3  C6H5–COONa + CHI3
NaOH
CH3
CH3
E2
Q.36 CH3 – C – Br + CH3O¯ CH2=C
CH3
CH3
CH3 CH3
SN2
CH3 – C – O¯ + CH3Br CH3 – C – OCH 3
CH3 CH3
Q.37 A Q.39
Q.40 (A) NaNH ( liq .) CH 3I

 2   (B)
Q.41 D
Q.42 (i) HCl

 
Cl
¯


(ii) H Cl
¯

CH 3
|
Q.43 D Q.44 C Q.45 C Q.46 CH 3  C  CHCH 3
Q.47 D Q.48 C Q.49 B Q.50 B
Q.51 B
HALOGEN DERIVATIVES
( i ) NaNH
Q.52 CH3CH2 – C  CH   2  CH3CH2 – C  C – CH2CH3
( ii ) CH 3CH 2 Br
X
Q.53 B Q.54 B Q.55 A
Q.56 (A) Q; (B) Q; (C) R,S; (D) P,S Q.57 B Q.58 B Q.59 A
Q.60 D Q.61 5 Q.62 B Q.63 C Q.64 A
Q.65 D Q.66 C Q.67 5 Q.68 ACD Q.69 B
Q.70 B
SECTION-B
Q.1 A Q.2 D Q.3 A Q.4 C Q.5 D
Q.6 C Q.7 C Q.8 D Q.9 B Q.10 C
Q.11 D Q.12 B Q.13 B Q.14 B Q.15 A
Q.16 B Q.17 B Q.18 A Q.19 A Q.20 D
Q.21 D
EXERCISE-4
Q.1 (i) The nucleophilic species which have more than one site of reaction are called ambident
nucleophiles.
For example, cyanide ion : C  N C=N –
CH3Br + AgCN  CH3 – NC + AgBr
CH3Br + KCN (alk)  CH3CN + KBr
(ii) This test is used to distinguish between primary, secondary and tertiaryamines by treating amine
with excess of KOH and benzene sulphonyl chloride.
(a) Primary amine forms clear solution which forms insoluble compound on acidification.
(b) Secondary amine forms an insoluble product which remains unaffected by HCl.
(c) Tertiary amine does not react.
Cl
Q.2 (i) Tertiary halide reacts faster than secondary halide because of the greater stability of
tert-carbocation.
(ii) In aqueous solution, KOH is almost completely ionized to give OH¯ ions which being a strong
nucleophile gives a substitution reaction on alkyl halides to form alcohol. But an alcoholic
solution of KOH contains alkoxide (RO¯) ions which being a much stronger base than OH¯
ions preferentially eliminates a molecule of HCl from an alkyl chloride to form alkenes.
HALOGEN DERIVATIVES
Q.3 (a) KCN is a resonance hybrid of the following two contributing structures.
K+ [¯ C  N C = N ¯]
Thus, CN¯ ion is an ambient nucleophile. Therefore, it can attack the carbon atoms of C–Br
bond in n-By Br. Since C–C bond is stronger than C–N bond, therefore attack occurs through
C to form n-butyl cyanide.
+
–
K+ CN¯ + CH3CH2CH2CH2 – Br CH3CH2CH2CH2CN + KBr
n Bu Br + KCN C 2 H 5OH ,H 2 O

  n Bu Br + KBr
(b) C2H5NH2 + Cl3CH + 3KOH  C2H5NC + 3KCl + 3H2O
Ethylamine Chloroform Ethyl isocyanide
Q.4 (i) CH2Cl : It is primary halide and therefore undergoes SN2 reaction faster..
(ii) I : As iodine is a better leaving group because of its large size, therefore
undergoes SN2 reaction faster.
Q.5 (i) Cl : Tertiary halide reacts faster than secondary halide because of the greater stability of
tert-carbocation.
Cl
(ii) : Because of greater stability of secondary carbocation than primary..
Cl
Q.6 undergoes faster SN1 reaction because of greater stability of secondary

carbocation than primary.
Q.7 (i) In chlorobenzene, the C of C–Cl bond is sp2 – hybridised while the C of C–Cl bond in cyclohexyl
chloride is sp3 – hybridised. Therefore, the sp2 – hybridised C of chlorobenzene has more s-
character and hence more electronegative than the sp3 – hybridised C of cyclohexyl chloride.
As a result, the C–Cl bond in chlorobenzene is less polar than in cyclohexyl chloride. Therefore,
chlorobenzene is less polar than cyclohexyl chloride.
(ii) Chloroform is stored in dark coloured bottles to protect it from sunlight and the bottles containing
chloroform are completely filled upto brim and are properly stoppered to keep out air.
HALOGEN DERIVATIVES
Q.8 (i) The reactivity in SN2 reactions depends upon steric hindrance, more the steric hindrance slower
the reaction.
CH3 CH 3CH 2 CH 2 CH 2 CH 2  Br CH 3  CH  CH 2 CH 2CH 3

| 1 Bromopenta ne (1) |
CH 3  C CH 2 CH 3 Br
| 2  Bromopentane (2)
Br
2 Bromo 2 methylbutane(3)
Since due to steric reasons, the order of reactivity in SN2 reactions follows the order: 1°>2° >3°,
therefore, order of reactivity of the given alkyl bromides is:
1-Bromopentane > 2-Bromopentane >2-Bromo-2-methylbutane
(ii) CH 3 CH 3 CH 3
| | |
CH 3  CH  CH 2CH 2 Br CH 3  C CH 2  CH 3 CH 3  CH  CH  CH 3
1 Bromo 3 methylbutane (1 ) | |
Br Br
2 Bromo  2  methylbutane (3 )
2 Bromo 3 methylbutane (2)
Since due to steric reason, the order of reactivity of alkyl halides in SN2 reactions follows the
order: 1° > 2° > 3°, therefore, the order of reactvity of the given alkyl bromides is
1-Bromo-3-Methylbutane > 2-Bromo-3-Methylbutane > 2-Bromo-2-Methylbutane
(iii) CH 3CH 2 CH 2CH 2 Br CH 3

1 Bromobutane β| α
(1 with no branching) CH 3  C CH 3Br
|
CH 3
1 Bromo  2,2  dimethylpr opane
(1 with two β  Methyl groups)
CH 3
|
CH 3  CH  CH 2  CH 2  Br
γ β α
1 Bromo 3 Methylbutane
(1 with one methyl group at γ  position)
Since in case of 1° alkyl halides, steric hindrance increases in the order : n-alkyl halides, alkyl
halide substitutents at the -position, therefore, the reactivity decreases in the same order–Thus,
the reactivity of the given alkyl bromides decreases in the order:
1-Bromobutane > 1-Bromo-3-methylbutane > 1-Bromo-2, 2-dimethylpropane
Q.9 (a) (i) Benzyl chloride undergoes nucleophilic substitution via resonance stabilized benzyl
carbocation and hence undergoes substitution readily.
+ CH 2 CH2 CH2 CH 2 + CH2
+ +
+
On the other hand, C–Cl bond in benzene has partial double bond character due to
resonance and hence is difficult to cleave. Therefore, benzyl chloride undergoes
nucleophilic substitution much more easilythan chlorobenzene.
HALOGEN DERIVATIVES
(ii) By partial reduction of carbon tetrachloride with iron fillings and water.
Fe / H 2O
CCl4 + 2[H]    CHCl3 + HCl
Heat
Chloroform manufactured by this method is used as a solvent as it is not of required
purity for its use as an anaesthetic agent.
+
Cl Cl

Q.10 
 due to formation of
= bond B/W carbon & halogen atom bond length  cress thats why C—X bond length in halo benzene
is smaller than C—X bond lengths in CH3—X.
Q.11 Step - 1 : Protonation of alcohol
 
: :
CH3–CH2–O–H + H CH3–CH2–O–H
H
Step - 2 : Dehydration to form carbocation and attack of nucleophile.

CH3–CH 2–O –H + Br CH3–CH2–Br + H2O
H
Q.12 (i) CH3 – I (ii) CH3 – Cl
(i) CH3–CH=CH2  CH3 – CH – CH3

oxymercuration demercuration
Q.13 Hg(OOCCH 3 )/H 2O
|
OH
Br Br
Br Br
 
COCH3
 

CH3COCl
 COCH3
(ii) 
H 2SO 4 /SO 3
AlCl3 (anhyd) 
Desulphonation

SO3H SO3H
CH 3 – CH – CH2 – CH3
(iii) | 
alc. KOH
 CH3 – CH = CH – CH3
Br
OR
(i) CH3CH2Cl 

NaI
Acetone
CH3CH2I + NaCl
HALOGEN DERIVATIVES
(ii) PhCl 

Na
ether
 Ph–Ph, Fittig Reaction
(iii) CH3Cl 

KNO 2
 CH3– O – N = O
Q.14 (i) Due to inversion of configuration.
EXERCISE-5
Q.1 A Q.2 A Q.3 C Q.4 A Q.5 D
Q.6 C Q.7 A Q.8 D Q.9 A Q.10 D
Q.11 D Q.12 D Q.13 D Q.14 A Q.15 B
Q.16 A Q.17 A Q.18 D Q.19 C
Q.20 ABCD Q.21 AB Q.22 AB Q.23 ACD Q.24 BCD
Q.25 AB Q.26 CD Q.27 (A) S,T (B) P,S,T (C) U, (D) Q, (E) T,U
Q.28 (A) 4 ; (B) 3, 4 ; (C) 3 ; (D) 1, 2 Q.29 (A) Q ; (B) R ; (C) P ; (D) Q
Q.30 (A) 3 ; (B) 2 ; (C) 1 ; (D) 2 Q.31 (A) S, (B) Q,S (C) S (D) P
Q.32 (a) III > II > I (b) III > I > II (c) II > I > III
Q.33 SN1 reactions are generally carried out in polar protic solvents (like water, alcohol, acetic acid etc.). The
reaction between tert-butyl bromide and hydroxide ion yields tert-butyl alcohol and follows the first
order kinetics.
(CH3)3 C Br + OH¯  (CH3)3C OH + Br¯
2-Bromo-2-methyl 2-Methyl propan-2-ol
propane
Q.34 (a) (b) OCH3
SCH 2–C6H5 NH–NH2 OCH2CH3 SCH 2–C6H 5

NO2 NO2 NO2 NO2
Q.35 (i) (ii) (iii) (iv)

CH3 NO2 NO2 NO2
HALOGEN DERIVATIVES
Br Br
Br OC2H5
Q.36
O2N Br O2N Br
Cl
Q.40 (A) CH3—C—CH 3
Cl
(B) CH2—CH2—CH2
Cl Cl
(C) CH3—CH—CH 2
Cl Cl
Cl
(D) CH3—CH 2—CH
Cl
CH3 Cl
H + H
Q.41 (a) Cl CH3 (diastereoisomers)
CH3 CH3
(b) + (diastereoisomers)
Me Me
H Cl Cl H
(c) + (Enantiomers)
H Cl Cl H
Et Et
Q.42 1.15 times more reaction
Br
|
Q.44 (a) A: CH 3  C  CH 2CH 2CH 3 (b) B:
|
CH 3
HALOGEN DERIVATIVES
(c) C: CH 3  CH  CH  CH 2 D: CH 3  CH  CH  CH 2 Cl
|
Cl
(d) E: Ph  CH  Et
|
Cl
Q.45 P1 = 13.26 %, P2 = 66.96 %, P3 = 19.82 %
Q.46 A=
Q.47 Phosphorus reacts with I2 to give PI3 which replaces OH group of alcohol to produce R – I
2P + 3I2  2 PI3
3R OH + PI3  3RI + H3PO3
Q.48 Stability of alkene by -hydrogen

OC - Halogen Derivatives - E

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JEE (MAIN+ADVANCED)

METHODS OF PREPARATION OF ALKYL HALIDES

(a) By Halogenation of Alkanes

R–H + Cl–SO2–Cl   R–Cl + SO2 + H–Cl

From Alkene ( Hydrohalogenation ) :–

Note : From alkyne we cannot obtain monoalkylhalide.

The above reaction is called as ‘Grove’s Process’.

From Silver Salt of Carboxylic Acid :

From Alkyl Halide :

This reaction is called as Swarts reaction

(iii) By catalytic hydrogenation of haloalkane -

(iv) By reduction of RI with HI in presence of red P.

Reaction with KOH :

Reaction with KCN :

Reaction with AgCN :

Reaction with AgNO2 :

CH3–I + 2Na + I–C6H5   CH3–C6H5 + 2NaI

Reaction with metals :

(b) With Mg : – (Grignard reaction)

(c) With Zn dust : – (Frankland reaction)

Dialkyl zinc is known as ‘Frankland - Reagent’.

TEL (tetra ethyl lead)

Uses of Alkyl Halides

NUECLEOPHILIC AROMATIC SUBSTUTION (SNAr) REACTION :

Cl Cl Cl Cl Cl Cl+

Nucleophilic aromatic substitution takes place by a two-step reaction known as an SN Ar reaction by

ELIMINATION-ADDITION THROUGH BENZYNE INTERMEDIATE

(approximately in equal amounts)

CH3 CH3 CH3

Dihalides are of two types :

METHODS OF PREPARATION OF GEM DIHALIDES

(a) FromAlkyne (By hydrohalogenation) : –

(b) From carbonyl compounds : –

RCHO + PCl5  + POCl3

METHODS OF PREPARATION OF VICINAL DIHALIDES

(a) FromAlkene (By halogenation) :–

(b) From Vicinal glycol : –

PHYSICAL PROPERTIES OF DIHALIDES

CHEMICAL PROPERTIES OF DIHALIDES

(a) Reaction with aqueous KOH : –

+ KOH(aq.)   

(b) Reaction with alcoholic KOH : –

Note – ,  dihalide form cyclic alkane.

(d) Reaction with KCN :

(e) Other substitution reaction : –

TRIHALOALKANES : HALOFORM : CHX3

* The following compound give haloform reaction.

Example of methyl ketone :

CH3COCH3  3 X 2  4NaOH  CHX 3  3NaX  CH3COONa  3H2 O

(i) Chloroform : CHCl3

(iv) 2CCl3CHO + Ca(OH)2  2CHCl3 + (HCOO)2Ca

DDT [1,1,1-trichloro-2,2-bis (parachloro phenyl) ethane]

CHCl3 + HCOONa + H2O

Preparation of trihalide using ‘Pyrene’ :

(a) Chloroform is colourless with pleasant smell.

COCl2 + 2C2H5OH 

Reaction with Primary amine :

Reaction with Phenol : The reaction is called as ‘Reimer-tiemann Formylation’.

Reaction with 2- Butene :

+ H–CCl3  3

2–methyl butanoic acid

Reaction with silver powder