H.D.A. 2021

10} Halogen Derivatives of Alkanes & Arenes
I. General Methods of Preparation 3. Halide exchange method
RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * * RCC * *
1. From Alcohol dry

 Finkelstein
i) R – Cl + NaI acetone RI + NaCl
i. Action of hydrogen halides [NSR Reaction
3° alc > 2° > 1°] dry
HCl/anhyd. ZnCl2
RCl + H2O ii) R – Br + NaI  
 RI + NaBr
acetone
HBr/H2SO 4reflux
R–OH R–Br + H2O iii) Swarts rean : RF are prepared by heating RBr or RC
HI Reflux
R–I + H2O in presence of metallic fluorides like
or KI+ H 3PO4reflux
AgF, CoF2, SbF3, or Hg2F2.
Lucas Reagent = anh ZnCl2 + conc. HCl 4. Hunsdiecker or Borodine-Hunsdiecker
Reactivity = 3°alc > 2° > 1°
CCl
3o ROH + LR  immediatly turbid soln i. RCOOAg  Br2 or Cl 2  4
Reflux
 RBr + CO2 + AgBr
2o ROH + LR  5 min. turbid soln
1 : 1
CCl
Δ ii. CH3CH2COOAg+Br2  4
 CH3CH2Br+CO2+AgBr
1o ROH + LR  turbid soln obtn on heating Reflux
Mechanism Free radical mechanim

ii. Action of phosphorus halides
i. RCOOAg + Br2 RCOOBr + AgBr
PCl5
R– Cl + POCl3+ HCl ii. RCOOBr RCOO+ Br
PCl3 iii. RCOO R+ CO2
R–Cl + H3PO 3
R–OH PBr3 iii. R + RCOOBr RBr + RCOO and so on
R–Br + H3PO3
( P + Br2) • Reaction with I2 gives ester : (Simonini Reactn)
PI3
R–I + H3PO3 O O
( P + I2) || ||
R– C –OAg + I2 R– C –OR + AgI 
iii. Action of thionyl chloride (Darzen) method 2 : 1
5. Action of hdyrogen halides on ethers
R–OH + SOCl2 Pyridine
  R–Cl + SO2+ HCl 
R – O – R + 2HX 2R – X + H2 (X = Br or I)
iv. Rydon method
R – OH + (C6H5O)3 PO + Cl2 6. Addition of hdyrogen halides to alkene
(HI > HBr > HCl)
R–Cl + ClOP(OC6H5)2 + C6H5OH
a. Symmetrical alkenes :
2. Halogenation of alkanes Δ
CH2=CH2 + H+Br–  CH3–CH2–Br [E+Addition]
i. Chlorination (Reactive) : F2 >Cl2>Br2>I2
ethene Ethyl bromide
R-I > R-Br> R-Cl
R - H + Cl2 U.V b. Unsymmetrical alkene :
 R– Cl + HCl
 3OH>2OH>1OH
Alkane excess Alkyl chloride
(EòvÉÒ{ÉhÉ 2-Bromo, 2-Chloro, 2-Iodo ×´ÖôûŸÖÖê.)
[Free radical Sbustn] i. Markonikov addition E+Addition
Cl0 Int-carbocation
ii. Bromination (Selective): [E+ Substitution Br+] Initial attack=H+
AlBr3 [E+Substitution] Δ
R - H + Br2   R - Br + HBr CH3  CH =CH2+H+Br-  CH3– CH –CH3
Lewis acid HgO 2 : 2 : 1 propene |
Alkane Akyl Bromide HIO3 5 : 2 : 1 Br
HNO3  8:4:1 ii. Antimarkonikov addition Free Radical addn
hν
R–H + Br2  R–Br + HBr [Free radical] Initial attack = Br
(EòvÉÒ{ÉhÉ 1-Bromo “Ö Product †ÃÖŸÖÖê.)
iii. Iodination : (Peroxide effect/kharsch-Myo effect)
2R- H + 2l2 + Hgo Δ

 2R-I+H2O+ Hgl2 CH3  CH =CH2+HBr Peroxide
  CH 3  CH 2  CH 2  Br
propene 1-Bromo propane
Alkane Alkyl Iodide
Note :- Only HBr gives peroxide effect (87 kcal gives) not
HCl (104 kcal) & HI (71 kcal)
Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified Page: 1
7. Allylic halogenation 2. Nucleophilic substitution reactions:
R–X + Nu– R – Nu + X–
5000 C KOH(aq)
 CH2 –CH=CH2+HCl
i. CH3–CH=CH2+Cl2  
R– OH + KX
|
Cl alcohol
Moist Ag 2O
(Allyl Chloride) R– OH + AgX
alcohol
2000 C dry Ag 2 O
ii. CH3–CH = CH2 + SO2Cl2 hv


R– O – R + 2AgX
ether
Dil. acid or alkali
RCOOH
CH2 –CH= CH2 + SO2 + HCl (Complete
Carboxylic acid
| hydrolysis)
Cl KCN (alc.)
conc. acid or
alkali + H 2 O2
R–CN RCONH2
–KX Alkyl
(Partial hydrolysis)
Acid amide
CH2 CO 0 H 2/Pd or LiAlH 4
cyanide
iii. CH3–CH = CH2 + N Br 200

C
 or Na/C 2H 5OH
RCH2NH2
CH2 CO hv (Mendius reduction)
1° amine
NBS
AgCN R–N = C
 Na/C2H 5OH
Reduction
RNHCH3
–AgX Alkyl 2° amine
CH2 CO
CH2 –CH = CH2 + NH isocyanide
| CH2 CO R’ONa
Cl R–O–R’ + NaX
(Sodium alkoxide)
(Williamson’s synthesis)
8. Addition of HX R’COOAg
RCOOR’ + AgX
0 Ester
HgCl ,70 C
CH CH + HCl  2

KSH
RSH + KX
R–X
CH2 CH2 =CH–Cl HCl

 CH3 =CHCl2 Thio alcohol (mercaptan)
Vinyl chloride 1, 1-Dichloroethane Na2S
R–S–R + NaX
Thio ether
II. Chemical Properties of Alkyl Halides R’C  C–Na+
R–CC–R’ + NaX
1. Elimination reactions-Dehydrohalogenation (Sodium alkynide)
NH3(alc.) RX RX RX + –
Δ RNH2 –HX
R2NH –HX
R3N R4N X
i) CH3  CH2  Br   
alc.KOH CH2 = CH2 + KBr + H2O (Hoffmann’s
1° amine 2° amine 3° amine Quaternary
ethyl bromide ethene ammonium
ammonolysis) salt
Δ
ii) CH3  CH  CH3  CH3  CH =CH2+KI+H2O KNO2
| alc.KOH R–O–N = O + KX
I Alkyl nitrite
Pr opene
Isopropyliodide O
AgNO2
R–N + AgX
O
iii) CH3  CH  CH2 –CH3 Nitro alkane
|
Br Corey-House reaction
R–R’
sec . butyl bromide (i)Li (ii) CuX (iii) R’–X
Reduction
CH2 = CHCH2–CH3 LiAlH4 or NaBH4 or Ph3 SnH
R–H
 1-butene (major) 20%
3 alc. KOH
+ KBr + H2O R–MgX or RLi or RNa or R2 Zn
CH3 – CH=CH–CH3 or R2CuLi
R–R
2-butene (major) 20% (Organo metallic reagents)
Saytzeff rule (Disubstituted) R–CH–CH–MgX
R–CH–CH–R
Saytzeff Rule  In dehydrohalogenation more substituted
(Streker reaction) Na2SO3
double bond is formed & which is more stable R–SO3Na
3. Reduction Aryl Halides
Zn Cu/C H OH
2 5
I. General Methods of Preparation
i. CH3CH2Cl      CH3CH3+HCl
or Zn/HCl or LiAlH 4
1. Direct halogenation of aromatic hydrocarbon
Red P
ii. CH3CH2–I + HI  
 CH3–CH3–I2
0
150 C
iii. CH3CH2Cl + H2 Pd

 CH3–CH3+HCl
4. Reduction with metals

i. With Magnesium
1. CH3I + Mg Ether
 CH3MgI
ii. Reaction with Na (Wurtz Reaction) Anhyd.
R–X + 2Na + X–R Dry


ether
 R–R + 2NaX
iii. Reaction with Li
CH3– CH –CH3+2LiCH3– CH –CH3+LiBr

| |
Br Li
iv. Reaction with Zn
CH3CH2CH2I + Zn (CH3CH2CH2)2Zn
v. Reaction with sodium-lead alloy
Dry ether
4C2H5Cl+4Na/Pb (C2H5)4Pb+4NaCl+ 3Pb
(TEL) 2. From Diazonium Salt

vi. Corey-House reaction i. Sandmeyer’s reaction
RX Li/Et
 2 O
 RLi CuI
 R2 CuLi
R’X + R2CuLi R’–R + RCu + LiX
With acetone
i. CH3COCH3 + 3I2 CI3COCH3 + 3HI
ii. CI3COCH3 + NaOH CHI3 + CH3COONa

Sodium acetate

ii. Gettermann reaction II. Chemical Properties of Aryl Halides
1. Nucleophilic Substitution Reactions
iii. Balz-Schiemann reaction
3. Rasching Process
4. Hunsdiecker Reaction
5. Side Chain Halogenation

4. Reaction with Lithium
5. Fitting Reaction
2. Electrophilic substittuion reactions
6. Wurtz Fitting Reaction
(major)
7. Ullmann Reaction
(major)
(major) 8. Reduction
(major)
9. Reaction with Chloral
(major)
3. Formation of Grignard Reagent

Diffn betn
SN1 Reaction SN2 Reaction
1. It is unimolecular Nu–Subn. 1. It is bimolecular Nu–Subn.
2. Ex. Alkaline hydrolysis of tert. butyl bromide 2. Alkaline hydrolysis methyl bromide
(CH3)3CBr + aq. KOH (CH3)3–C–OH + KBr CH3Br + aq. KOH  CH3OH + KBr.
3. Rate of reaction depends upon only one 3. Rate of reaction depends upon both the
reactant. reactant.
R  [ R- X] R  [ R- X] [OH–]
5. It is first order reaction. 5. It is second order reaction.
6. It is two step reaction. 6. It is one step reaction.
7. First step is breaking of C– Br and 7. Breaking of C– Br and formation of C– OH
II step is formation of C– OH . takes place simultaneously.
8. Formation of carbo-cation is slow and R.D.S. 8. Formation of transition state is slow and R.D.S.
9. Product formed has 50% reatention & 50% 9. Product formed has 100% inversion
inversion configuration i.e. 100 % racemisation. [Walden Inversion]
10. It is not sterioselective & not stereospecific 10. It is sterioselective as well as stereospecific
reaction. reaction.
11. Reactivity of RX : 11. Reactivity :

3°RX > 2° RX > 1° RX 1°RX > 2° RX > 3° RX
12. It has only one T. S.
12. It has two T. S.
13. One energy of activation.
13. Two energy of activation
14. No Catalyst required
14. Catalysed by Lewis acid
15. No Carbonium ion
15. Intermediate = Carbonium ion
16. No rearranged products
16. Rearranged products are formed
Uses and Environmental Effects of some B) Trichloromethane or Chloroform : CHCl3

Alkyl and Aryl Halides Uses i) It is used to prepare Freon (R-22)
A) Dichloromethane : CH2Cl2 ii) Solvent in pharmaceutical industry and for
Uses producing pesticides and dyes.
i) Solvent iii) Uses as a source of dichlorocarbene (CCl2)
ii) Paint remover Environmental effects :

iii) Used to decaffeinate tea and coffee. i) Anaesthetic
iv) It is volatile so used as aerosol spray propellant ii) It in air and sunlight forms a poisonous
and as a fumigant pesticide for grains and compound phosgene (COCl2).
strawberries. iii) If mixed with air it is hazardous and causes
Environmental effects : headache and fatigue.
i) It is highly volatile so in air it causes nausea, iv) It affects on CNS.

numbness in fingers and toes, dizziness. C) Tetrachloromethane or carbon tetrachloride CCl4
ii) If it is in less amount causes impaired vision Uses i) Dry cleaning ii) Pesticide
and hearing .
iii) A solvent, in (production of refrigerants).
iii) Dangerous for eyes (damaging cornea).

Environmental effects : iii) If it exists for a long time in soil, plants and animals
as well, it produces unforeseen ecological effects.
i) On contact it causes eye irritation, damages
nerve cells, vomiting sensation, dizziness,
unconsciousness or death. Cl
ii) When mixed with air it c auses ozone

depletion, which affects human skin leading
Cl
to cancer.
Cl Cl
D) Iodoform : CHI3 Cl H
Uses
i) It is used as an antiseptic for dressing of
wounds and sores.(The antiseptic property is SN2 Mechanism :
due to liberation of free iodine.) 1) The alkaline hydrolysis of methyl bromide follows
ii) It is used as disinfectant. SN2 mechanism.
S = Substitution
Environmental effects : It has strong smell.
N = Nucleophilic
E) Freons
2 = Bimolecular
Uses
2) Reaction
i) They are used as propellants in aerosol products of
food, cosmetics and pharmaceutical industries. + + –
ii) Freons containing bromine in their molecules are CH3– Br + NaOH CH3 – OH + NaBr
used as fire extinguishers.
iii) They are also used in aerosol insecticides, solvent 3) Kinetics
for cleaning clothes and metallic surfaces. The rate of this rean depends upon both the
iv) As foaming agents in preparation of foamed plastics reactant, so second order bimolecular rean.
and in production of certain fluoro carbons.
R  [CH3Br] [OH–]
v) They are used as refrigerants (which causes ozone
depletion) R = K [CH3Br] [OH–] K – is constant
vi) Freons are also used for air conditioning, as are 4) Mechanism
noncorrosive. i) It is one step rean, as breaking of C – Br & formation
Environmental effects : of C – OH take place simultaneously.
It causes ozone depletion. ii) Back side attack
Freons from propane group are more toxic in nature. OH– stronger nucleophile so attack from back side
not from front side because Br– also nucleophile.
F) D.D.T : p, p’ – Dichloro di phenyl trichloro ethane
(Paul Muller) H H H

+

–
– Slow 
–
–
H C – Br + OH HO C Br
Uses R.D.S
H H
i) Insecticide against malaria.
ii) It kills housefly and mosquitoes.
Environmental effects H H H
HO C Br fast HO – C H
i) It is not readily metabolized and not destroyed R.D.S
easily. H H
100% Inervsion (Walden inversion)
ii) It is deposited and stored in fatty tissues.

iii) Transion state 7) Stereochemistry of SN2
i) Formation of T.S. is slow & RDS Stereo chemistry of SN2 , can be studied by
ii) In T.S. OH ....... C ........Br– + –
lie in same plane using optically active sec. butyl bromide not by
er
iii) Three H are 1 to plane making on angle of 120° using methyl bromide.
among hydrogens. Back Side Attack
iv) In T.S. OH & Br are partially bonded to central
carbon CH3 H
CH3
v) In T.S. OH & Br carries equal partial – ve charge.   –
+ –
Slow
H C – Br + OH HO C Br
vi) The rate at which C – OH bond formed at the R.D.S
C2H5 C2H5
same rate C – Br bond breaks so, Octet rule is
not violated.
vii) During formation of C – OH bond energy libreated
(Exothermic) & this is used to break C – Br bond. H CH3
viii) In T.S. carbon is pentavalent so it is highly C Br OH C H
energetics and unstable & gives the product. R.D.S
C2H5
ix) Generally bond breaking steps are slow & RDS.
& bond formation steps are fast & Exothermic Sec. butyl alcohol
5) Product When attack of OH– takes place from back side the
The product formed in SN2 Rean is 100% inversion tetraheral geometry of carbon is 100% inverted.
called as walden inversion Front Side Attack
6) Energy profile diagram (E P D) • When attack of OH– takes place from front side the
product formed have 100% retention but it is not
It is the graph obtained by plotting PE v/s Rean
possible for SN2.
path is called E.P.D.
Some Defination
1) EPD :- It is the graph obtained by plotting PE
v/s reaction path.
Transition state
2) Energy of activation (E)
Potential energy
Eacl It is the energy difference bet n reactants &

Transtion states
Reactants
H
3) Heat of Reaction (H)
CH3Br + OH
Products It is the energy difference bet n reactants &
CH3OH + Br products
Reaction co-ordinate
4) Transition state (T.S.)
It is imaginary highly unstable having
R = Reactant (CH3Br + aq. NaOH)
maximum P.E. Every reactant before convert
P = Product (CH3OH + NaBr) into product pass through this state.
T.S. = Transition state SN1 Mechanism :
H H

–

–
1) The alkaline hydrolysis of tert. butyl bromide
HO C Br follows SN1 mechanism
H S = Substitution N = Nucleophilic
n
H = Heat of rea 1 = Unimolecular
E = Energy of activation

2) Reaction iii) Product :
The product formed in SN 1 mechanism 100%
CH3 aq CH3
recemisation (50% Retention & 50 % Inversion)
–
+ + 
CH3 – C – CH3 + Na – OH CH3 – C – CH3 + NaBr
5) Energy profile diagram (E P D)
– OH
Br
tert. butyl bromide tert. butyl alc.
T.S.1
T.S.2
3) Kinetics :
E1 2
E
Potential energy
The rate of this rean depends upon only one reactant
so first order unimolecular. C+
R  [(CH3)3 C – Br]
Reactants H
R = k [(CH3)3 C – Br]
Products
4) Mechanism : It is two step rean
Step I : - Breaking of C – Br bond. Reaction co-ordinate
CH3 CH3 R = Reactant

+
 
+ – – Slow 
CH3 C – Br + OH CH3 C Br P = Product
R.D.S + –
CH3  
CH3 T.S.1. = Transition state 1 ( C Br )
+ –
 
CH3
T.S.2 = Transition state 2 ( C OH)
C Br + – E1 = Energy of activation of T.S.1

R.D.S C + Br
CH3 E2 = Energy of activation of T.S.2
CH3
H = Heat of rean
i) In C – Br bond Br is more electronegative so
it’s breaks heterolytically & forms carbocation. Sterao chemistry of SN1 mechanism
i) It can be sutdied by using optically active chiral
ii) Breaking of C – Br slow & R.D.S.
compound 1–bromo–1–phenyl ethane.
iii) The energy required to breaking of C – Br bond
ii) Two products are formed one product with retention
is given by polar solvent
of configuration due to front side attact & another
iv) C – Br bond is more polar due to + I effect of with inversion of configuration due to back side
methyl group attack.
Step II : Formation of product
Ph CH3
CH3 H C Br C + Br–
CH3 C OH (50% Retention) CH3 Ph H
–
OH
CH3
CH3
+ + – – –
C C OH OH (Front side) OH (back side)
T.S.2
CH3 CH3 CH3
– Ph Ph
OH OH C CH3 (50% Inversion)
H C OH HO C H
CH3
CH3 CH3
(50% Retention) (50% Inversion)
i) Carboc ation is planer SP 2 hybridised,
e– deficient species.
ii) So, OH– attack from front side as well as back side.

OPTICAL ACTIVITY 8) Laevo rotatory molecules
1) Ordinary light It rotates the plane of PPL to the left hand side
(LHS). e.g. l-lactic acid, l-glucose, etc.
It is the light of different colour & different
wavelength, vibrating in all possible planes, 9) Optically inactive molecules
perpendicular to the direction of propagation of light. The molecules which do not rotate the plane of plane
2) Monochromatic light polarized light are called optically inac tive
molecules.
It is the light of single colour & single wavelength
vibrating in all planes, perpendic ular to the e.g. 1-chloropropane, tert-butyl bromide, ethyl chloride,
direction of propogation of light. water, ethanol etc.
3) Plane polarized light (PPL)

Water
When an ordinary light is passed through Nicol’s or ethanol
prism the light vibrates in only one plane only is
Plane polarized light Plane polarized light
called as PPL.
10) Asymmetric carbon atom (Chiral)
• It is the tetrahedral carbon atom which is bonded to
four different atoms or groups.
Ordinary light Nicol’s Prism Plane polarized light • It is denoted by an asterisk (*) on it.
4) Nicol’s Prims CH3 CH3

It is made up of calcite crystals (CaCO3). It is fix with H – C * – Cl Cl – C * – H
Canada balsam. C2H5 C2H5
Geometry of Calcite = Rhombic (d) or (+) (l) or (–)
mirror
5) Optical activity
11) Enantiomers / Enantimorphs / Antipodes
It is the property of certain organic substances
which rotates the PPL towards right (clockwise) or Defn : Sterio isomers which are non superimposable mirror
towards left (anticlockwise). image of each other & rotate the plane of PPL through
same angle but in opposite direction are known as
enantiomers.
Glucose
 or 
solution
in water
i) They are optically acitve.
ii) They are optical isomers of same compound.
Plane polarized light
iii) Their have same physical and chemical properties.
6) Optically active molecules iv) They differ only in their action on plane polarised
The molecules which can rotate the plane of PPL light, i.e. one rotates plane of plane polarised light
are known as optically active molecules, towards right and other rotates equally towards left.
e.g. Glucose, lactic acid, 2–chlorobutane etc. v) They do not have a plane of symmetry. Therefore,
they have the same specific rotation but of opposite
COOH CH3 sign.
H – C * – OH H – C* – Cl
CH3 CH3
e.g. CH3 C2H5 Br
i. Br
lactic acid 2-Chlorobutane H5C2 H H C2H5
7) Dextro rotatory molecules (+ or d)
CH3 CH3
It rotates the plane of PPL to the right hand side Cl NH2 Cl NH2
ii.
(RHS). eg. (+) d-lactic acid, (+) d-glucose etc.
H H

CH3 CH3
3) Fisher projection formula
H OH HO H i) Representation of 3 dimensional structure in to 2
iii. H Cl Cl H dimenstional way.
C2H5 C2H5
ii) Groups on vertical line away from observer (i.e. which
are behind plane of paper)
CH3 CH3
iii) Groups on horizontal line towards observer. (i.e.
which are above the plane of paper)
iv.
iv) Longest carbon chain is on vertical line.
Cl Cl
v) More oxidised group present at the top.
12) Racemic mixture or racemates e.g. 2 – hydroxy proponic acid (Latctic acid)
n
Def : It is equimolar mixture of dextro and laevo isomers. It a) Tetrahedral structure b) Fischer
is optically inactive due to external compensation.
COOH COOH
• It is represented as ( ) or dl, e.g. ( ) lactic acid or dl
lactic acid. H OH
C
H
13) Chirality CH3 OH CH3
A molecule containing asymmetric carbon atom

4) Resolution
would lack symmetry and is referred to as
asymmetric molec ule. This asymmetry of the Racemic mixture can be separated or resolved into
molecule renders it optically active. its optically active forms by physical or chemical
methods called resolution.
NEET SPECIAL
5) Racemisation :
1) Optical Activity
The conversion of a dextro or laevo form into is
i) Given by J.B. Biot (1811) racemic mixture is called racemisation. It is a reverse
of resolution.
ii) Optic al ac tivity is firstly noted for inorganic
compound like quatz, rocks, solid KClO3. 6) Diastereomers
iii) Biot said that optical activity is due to crystalline The stereoisomers which are not mirror images and
nature of solid. non-super imporsable of each other are called
diastereomers. They have different physical
iv) In 1815, Biot finaly conclude that, It is a molecular
properties.
phenomenon.
7) Meso compound
v) In 1848, Pasture seprate the dextro & laevo form, from
dl mixture optically inactive mixture of sodium The compound although contains chiral centre but
ammonium teartarate. optically inactive due to POS.
vi) Pasture said that, optically activity is due to non- Ex – Tartaric acid molecule has two asymmetric
super imposable mirror image. carbon atoms hence, it has four stereomers having
the structures I, II, III and IV as
vii) Lebel & Vant Hoff optically activity is due to
Tetrahedral nature of carbon.
2) Conditions of optically activity.

i) Presence of chiral carbon
i. ii.
ii) Absence of any symmetry
iii) Non-super imposable mirror image.

Ex –
CHO CHO
H – C – OH HO – C – H Epimeric C - atom showing
enatiomeric condition rest
iii. iv. HO – C – H HO – C – H
of the structure of both the
H – C – OH H – C – OH compounds is exactly same.
HO – C – H HO – C – H
CH2OH CH2OH
(+) Glucose (+) Mannose
10) Anomers
v. vi.
The pair of diastereomers which differ in
configuration about a single terminal C – atom are
called anomers.
H OH OH H Anomeric terminal C-atoms

vii. viii. with rest of the structure
C C
are exactly same.
(CHOH)3 O (CHOH)3 O
H–C H–C
CH2OH CH2OH
ix. x.  - Glucose  - Glucose
11) Mutarotation
8) Erythro & Threo Notation :
The spontaneous change in the optical rotation of
• This notation are used in those compounds which compound on standing in a solution of an optically
contain only two chiral centers. When two identical active substance is called mutarotation.
groups are ins ame side in Fischer projection, such
 – (d) glucose Equilibrium mixture  - (d) glucose.
structure are known as erythro, but if two identical
groups are in opposite side in Fischer projection, then + 112.2° + 52.5° + 18.7°
they are known as threo isomer. JEE:  - stereoisomer has specific rotation of + 112.2 and
 - stereoisomer has + 18.7°. When either of these
CH3 CH3 CH3 CH3 pure stereoisomer are dissolved in water, a specific
H Br H Br H Cl H Cl
rotation undergoes of slow change to a value of
H Br Br H H Br Br H + 52.5°.
C2H5 C2H5 C2H5 C2H5
12) D & L - Notation
Erthro Threo Erythro Threo • D-Notation : When in Fischer projection formula
Erythro and threo form of same compounds are –OH group of last chiral center on RHS it is called
diastereomers of each other. as D-configuration.
• L-Notation : When in Fischer projection formula
9) Epimers
–OH group of last chiral center on LHS. It is called
The pair of diastereomers which differ in as L-configuration D & L - Confn are enatiomers
c onfiguration about a single interstital (non-
terminal) C-atom are called epimers. CHO CHO
H OH HO H ;
CH2OH CH2OH
D-Glyceraldehyde L-Glyceraldehyde

(c) Neither ring should have plane of symmetry.
CHO CHO
H OH HO H CH3 Cl Cl CH3
HO H H OH
H OH HO H ;
H OH HO H
Br NH2 NH2 Br
CH2OH CH2OH
Non superimposable image (optically active)
D-Glucose L-Glucose
COOH COOH CH3 OH CH3 OH

H NH2 H2N H
R R
CH3 Cl Cl
D-amino acid L-amino acid CH3
Optically inactive Optically active
plane of symmetry
13) Optical Isomerism in Allenes :
• Presence of chiral center is not essential condition
CH3 NH2 NO2 Cl
for optical activity. Essential condition is that
compound should exhibit non superimposable
image.
i.g., compound should exhibit chirality. NO2 CH3 Br CH3 Cl
No plane of symmetry Plane of symmetry
optically active optically inactive
Allenes have general formula C=C=C
15) Optical activity of lactic acid
in whcih valencies of first and third carbon are
perpendicular. (2–hydroxypropan–1–oic acid)
Allenes are optically active when two groups i) Presence of asymmetric carbon atom
attac hed to eac h terminal c arbon atom are Lactic acid contains one asymmetric carbon atom,
different. If two same gorup are attached to any to which four different groups or atoms
terminal carbon then compound contain plane of
i.e. – H , – OH , – CH 3 and – COOH are attached.
symmetry.
CH3
Cl CH3 H3C Cl
C C C C C C H – C * – OH
;
H 2N Br Br NH2 COOH
Non-superiomposable image (optically active) ii) Number of optical isomers

Lactic acid contain one asymmetric C atom, hence it
H3C OH Cl CH3 has two optical isomers, a = 21 = 2.
C C C C C C
Br CH3 CH3 iii) Non super imposable mirror image structures
HO
(Enantiomers)
Optically active Optically inactive These two optic al isomers of lac tic acid are
14) Optical Isomerism in Biphenyl nonsuperimposable object and mirror of each other,
hence they are called enantiomers.
• For biphenyl compounds to exhibit optic al
isomerism:
CH3 CH3
(a) Both phenyl ring should be perpendicualr to each
H – C* – OH HO – C * – H
other.
COOH COOH
(b) Both ring should be substituted at ortho position.
d-lactic acid mirror l-lactic acid

a) Dextro isomer Polyphalogen Compounds
One optical isomer of lactic acid, rotates plane of A. Vicinal Dihalides or Alkylene Halides
plane polarised light in clockwise right direction
 Preparation
is called dextro isomer (d, lactic acid)
1. From Alkens
b) Laevo isomer
Another optical isomer lf lactic acid, rotates plane
of plane polarised light in anticlockwise or left
i.
iv) Racemic mixture
The equimolar mixture of d-lactic acid and l-lactic
acid is called racemic mixture or dl or () mixture ii.
and it is optically inac tive due to external
compensation.
Explain optical activites of lactic acid. 2. From glycols
COOH 1.
H – C – OH
CH3
1) Chiral carbon 2.
In lactic acid, is chiral because it is attached to four

different atoms and groups, i.e., H, CH3, OH, COOH.
2) Enantiomers
As it contains one chiral carbon, it has two optical is  Properties
omers.
1. Hydrolysis with aqueous alkali
COOH COOH
CH2Cl + 2KOH (aq.)  CH2OH + 2KCl
H – C – OH HO – C – H
CH2Cl CH2OH
CH3 CH3
Ethylene glycol
d-lactic acid mirror l-lactic acid

2. Dehydrohalogenation
Above two structures are non-superimporable mirror – KCl, –H 2O KOH(alc.)
CH2Cl + KOH (alc.) CH2 CH + KCL + H2O
images. so, they are enantiomers. structure 1st rotates
the plane of PPL towards RHS is called d - lactic acid. CH2Cl CH–Cl CH
Structure 2nd rotates the plane of PPL towards LHS CH3CHBr – CH2Br + 2KOH CH3– C  CH + 2KBr + H2O
is called l-lactic acid 3. Reaction with alkali cyanide
3) Racemic mixture O/H 
  CH
CH2  Cl + 2KCN 2KCl
|
2  CN H
2 
|
50% d - lactic acid and 50% l- lactic acid is called as CH2  Cl CH2  CN
Racemic Mixture.
CH2  COOH
It is optically inactive due to external compensation. |
CH2  COOH
Succinic acid

4. Dehalogenation 3. Reaction with alkali cyanide
CH3Cl–CH2Cl + Zn CH
3OH
 CH2=CH2+ZnCl2
B. Geminal Dihalides or Alkylidene Halides
 Preparation
1. Fromaldehydes and ketones
CH3CHO + PCl5 CH3CHCl2 + POCl3
CH3COCH3 + PCl5 CH3CCl2CH3 + POCl3

Trihalogen Derivatives
2. From alkynes
Chloroform (Trichloromethane-CHCl3
HCl HCl CH  CHCl  Preparation
HC  CH
 CH2=CH–CL 3
 Ethylideine 2
chloride
1. Laboratory method
Br i. CaOCl2 + H2O Cl2 + Ca(OH)2

HCl |
CH3–CCH HBr
  CH 3
– C = CH 2

 CH 3  C  CH3 Bleaching powder
| |
Br Br
Propylidene bromide
ii. CH3CH2OH + Cl2 Oxidation
  CH3CHO + 2HCl
 Properties iii. CH3CHO + 3Cl2 Chlorinati

   on
  CCl3CHO+3HCl
1. Hydrolysis with aqueous alkali Chloral
iv. 2CCl3CHO+Ca(OH) Hydrolysis 2CHCl + (HCOO) Ca

2    3 2
Chloroform Calcium formate
2. Reduction of carbon tetrachloride
CCl4 + 2[H] Fe/H

 2O
 CHCl3 + HCl
3. Chlorination of methane
CH4Cl , hv
2 
Cl , hv
 CH3Cl 2   CH2Cl
Cl 2 , hv
2   CHCl3
HCl HCl HCl
2. Dehydrohalogenation
CH3–CHCl2 + 2KOH(alc.) CH  CH + 2KCl + H2O

Preparations Properties
X2/h  (or)  H2O/NaOH, H2 O

H3C – CH3 CH3–CH2–OH (hydrolysis)
– +
HX RO Na
H2C = CH2 C2H5–O–R’ (Williamson’s syn)
+ –
HCl (ZnCl 2 ) Na SH
H3C – CH2 – OH C2H5–SH
O Na2S
– + Cl2 / (or) Br2,  C2H5 – S – C2H5
H3C – CH2 – C – O Ag NaCN / KCN
X  Cl, Br C2H5 CN
KBr/H2SO4, (X = Br) NaN3
CH3 – CH2 – OH C2H5 N3
KI / H2SO4 (X = I) H3C – C  C Na
– +
C2H5 N3
(C2H5O)3P/X2
CH3 – CH2 – OH O
– +
R – C – O Na
CH3 – CH2 – OH
PCl5 (or) PCl3 X = Cl C2H5 N3
LiAlH4
P/Br2, (X = Br) C2H6
CH3 – CH2 – X
CH3 – CH2 – OH KNO2 (or) NaNO2
CH3 – CH2 – O – N = O
P/I2, (X = I)
CH3 – CH2 – OH AgNO2
H3C – CH2 – NO2
SOCl2 / Pyridine (or)
CH3 – CH2 – OH AgCN
SOCl2 ether (X = Cl) H3C – CH2 – NC
TsCl / Pyridine CH3MgX
CH3 – CH2 – OH CH3 – CH2 – CH3
ii) NaX
CH3 – CH2 – Cl NaI / Acetone (X = I) R’–Li
(or) Finkelstein reaction (R=CH3 etc.)
H3C – CH2 – R
CH3 – CH2 – Br
(CH3)2 CuLi
CH3 – CH2 – Cl AgF (or) SbF3 (or) Hg 2F2
H3C – CH2 – CH3
(or) Swartz reaction (X = F) Moist Ag2O
CH3 – CH2 – Br CH3 – CH2 – OH
Cl – N = O (X = Cl) Dry Ag2O
CH3 – CH2 – NH2 CH3 – CH2 – O – CH2 – CH3
(Tilden reagent)
Alc. KOH 
elimination
H2C = CH2
BH3 SnH
CH3 – CH3
Na/dry ether
H3C – CH2 – CH2 – CH3 +
H2C = CH2 + H3C – CH3
Mg/dry ether
H3C – CH2 – MgX (grignard)
2Li
LiX + CH3 – CH2 – Li
Zn/dry ether
H3C – CH2 – CH2 – CH3
NH3
CH3 – CH2 – NH2

Preparation Properties X X
Cl
+ CuX/HX (X = Cl, Br, CN) Cl2/FeCl3
C6H5N2Cl
– +
Sandmeyer reaction
Cl
+ Cu/HX (X = Cl, Br)
C6H5N2Cl
–
X X
Gattermann reaction
HNO3/H2SO4
NO2
+
+ – KI/ (X = I)
C6H5N2Cl
C6H5 – X
NO2
+ HBF4 ,  X X
C6H5N2Cl– SO3H
(Balz-Schiemann reaction) Conc. : H2SO4
X=F +
SO3H
X2/FeX3,  (X = Cl, Br)
C6H6 X X
R–X
R
– + X2/ , (X = Cl, Br)
C6H5COO Ag Anhy. AlCl3 +
R
X O X
O
R–C–Cl
C–R
Anhy. AlCl3 +
O=C–R
NaOH/300°C
300 atm
C6H5–OH
NH3/Cu2O
C6H5–NH2
200° C
CuCN/Pyridine
200° C
C6H5–CN
i) Ni-Al alloy/NaOH/
ii) Mg/dry ether /H2O
C6H6
Na/dry ether
fittig reaction
C6H5 – C6H5
R–X/Na, dry ether
Wurtz - fittig
C6H5 – R
Cu - Zn alloy
Ullmann’s reaction
C6H5 – C6H5
NaNH2/NH3(liq.)
C6H5 – NH2
O H Cl
Cl3C – C – H
Cl C – C – Cl
Conc. H 2SO4, 
Cl
Cl
DDT.

Nutshell Preparation & Properties of
DI, TRI and Tetra Halides
OH C aO Cl2 O2 Cl
H 3 C CH H' Light
O C +HCl
Bleachin g po wder
Cl
O CaO Cl2 Zn/ H Cl
CH 2 Cl2
H 3 C C CH 3 Bleaching powder EtOH
Zn/ Aq.H Cl
O NaO H CHCl
3
Cl3 C C H Zn/ H 2 O
H-C -O Na CH 4
O Aq. KO H 
CHCl3 H C OK
Fe/ HC l
CCl4 O
H NO 3
3Cl 2 /hv Cl3 C NO 2 (C hloropicrin) (tear gas)
CH 4
H3C O AgI
OH HC C H

C H 3C C CH 3
H3 C CCl3 OH O
OCH
25
C hloretone O—CH NaO H C

25
O—CH
H
 KO H 25
OH
H 3 C CH 2 N C Ethyl ortho formate
C H 3 CH 2 NH 2
C arbylamine Test Riemer Tiemann Reaction
Cl2 / hv
CH 4
3Cl 2 /AlCl 3
CS 2
S 2 Cl 2
Fe/ H 2 O
Cl2 /hv
CH 4
CHCl3 CCl4 H2O
COCl2
500°C
OH O
SbF 5 OH C
CCl2 F2 O H
(Freo n) KOH/ 
OH O
Aq. KO H 
H 3 C CH H3 C C H
O HCl -H 2 O
PCl5
Cl OH
H3 C C H Alc. KO H
P OCl3
H 3 C CH H C C H
2HCl Zn/ dust
H C C H H 3 C CH CH CH 3 O
2+ Cl
Hg
CN H 3O +
C OH
Alc. KC N
H 3 C CH H 3 C CH
CN C OH
O
Aq. KO H CH 2 CH 2
Cl2 / KCl4 OH OH
H 2 C CH 2 CH 2 Cl Alc. KO H
NaNH 2
CH3 CH 2 Cl H C CH
PCl5 Zn/ MeO H
CH 2 CH 2 CH 2 Cl H C CH O
O
OH OH C C
CH 2 CH 2 H 3O + H2C OH  H2 C
KC N/ EtO H
O
CN CN H2C OH H2 C
C C
O
O

Chiral Centre
21.  .....
Q.1) Find out total no. of 11.  .....
chiral centre?
1. CH3– CH  CH2  CH3  ..... 22.  .....

| 12.  .....
OH
2. CH3– CH – CH –CH2–CH3  .....

| | 13.  .....
Me Cl
3. CH3– CH – CH – CH –CH3 .....

| | |
Br Cl OH
14.  .....
23.  .....
4. CH3–CH=CH– CH  CH2–CH3.....
|
CH3
15.  .....
5. CH2=CH– CH –CH3  .....
|
Cl
6.  ..... 16.  .....

24.  .....
7.  .....
17.  .....
25.  .....
8.  .....
18.  .....
26.  .....
19.  .....
27.  .....
9.  .....
28.  .....
10.  ..... 20.  .....

38.  ..... 50.  .....
29.  .....
51.  .....
39.  .....
30.  .....
(shikimic acid) 52.  .....
31.  .....
40.  .....
41.  .....
53.
32.  .....
42. (a)  .....

 ..........
33.  ..... 54.  .....

43.  .....
CH 3
CH3 55.  .....
44.  .....
34.  .....
45.  .....
Pseudo Chiral Carbon : If chirality of

35.  ..... carbon depends on the
46.  ..... stereoisomeric unit attached to it, it
is known at pseudo chiral carbon.
(Counted as chiral carbon)
36.  .....
47.  ..... OH
|
CH3–CH=CH– C  CH =CH–CH3
|
H
48.  .....
OH
|
37.  ..... CH3–CH(Cl)– C  CH (Cl)–CH3
|
H
49.  .....

Q. 2) Find out Stereocentre
13.  .....
4.  .....
1.  .....
14.  .....
5.  .....
2.  ..... 15.  .....
6.  .....
16.  .....
3.  .....
Q. 4) Draw enantiomers
7.  .....
1.
4.  .....
8.  .....
Q. 3)Give R & S configuration 2.

9.  .....
1.  ..... 3.
10.  .....
4.
2.  .....
11.  .....
2
5.
12.  .....
3.  .....
6.

Q. 5) Identify Meso Compound CH3 CH3 CH3
H OH HO H H OH
2. I) H Br II) Br H III) H3C Br
CH3 CH3
1..  H
I) (2S, 3R) - 3-bromo-2-butanol
............... ...................... .................. II) (2R, 3S)-3-bromo-2-butanol

III) (2S, 3S)-3-Bromo-2-butanol
Q. 6) Identify Enantiomer?
 Meso mirror image of comp. never 1) I and II  ................................

enantiomers
2) II and III  ................................
1.
3) I and III  ................................
CH3 CH3
3. I) Cl NH2 (S) II) H2N Cl (R)
............... ...................... ..................
H H
Q. 7) Identify Enantiomers pair,
Cl
Diastereomers pair and identical pair
III) H2N CH3 (S)
H
I & II  ................................
1. .............
II and III  ................................

Q. 8) Identify Enantiomers, Diastereomers, Identical
I and III  ................................

1. I) II)
NH2
(2R, 3R) - 3-bromo-2-butanol (2R, 3S)-3-bromo-2butanol 4.
III)
(2S, 3S)-3-bromo-2-butanol P and Q  ................................
1) I & II  ................................
P and R  ................................
2) II and III  ................................
3) I and III  ................................ Q and R  ................................

CH3 CH3
5. I) HO H (R) II) C2H 5 OH (R)
8.  ...........................
C2H5 H
C2H5
III) H CH3 (S)
9.  .....................
OH
I & II  ................................
T
II and III  ................................
10.  .........................
I and III  ................................
CH3 CH3 CH3 CH3

H OH HO H H OH HO H
6. 11.  .........................
H Br Br H Br H H Br
CH3 CH3 CH3 CH3
(2S, 3R) (2R, 3S) (2S, 3S) (2R, 3R)
(a) (b) (c) (d)
a and b  ................................ 12.  ...........................
a and c  ................................
a and d  ................................
b and c  ................................ 13.  .........................
b and d  ................................
c and d  ................................
14.  .........................
7.
15.  .........................
a and b  ................................
a and c  ................................ 16.  .........................
b and c  ................................

25.  .........................
17.  .........................
26.  .........................
18.  .........................
CH3
H
27. C  .........................
OH
Br
19.  .........................
28.  .........................
20.  .........................
29.  .........................
21.  .........................
30.  .........................
22.  .........................
31.   .........................
23.
32.   .........................
 .........................
24. 33.  .........................
 .........................
34.  .........................

9. Which intermediate is will be aromatic ion when
AgNO3 reacts with the following compounds ?
v) [ ]
a)  .........................
b)  ......................... vi) [ ]
vii) [ ]
c)  .........................
viii) [ ]
d)  .........................
ix) [ ]
e)  .........................
f)  .........................
x) [ ]
g)  ......................... xi) [ ]
h)  .........................
xii) [ ]
10. Tick which carbocations undergo rearrangements?
i) [ ]
ii) [ ]
iii) [ ]
iv) [ ]

VVIMP ho dmMmdM bmJob Oa SN1, SN2, E1, E2 O‘m¶Mr Agob Va Substitution v/s Elimiantion
-Elimiantion
E1 E2 E1CB
H
H H
C––C B B B B
• + C –––C C –––C
C––C • H B C=C •
Cl
C–––C Cl Cl
C = C + BH
Cl –Cl

• C Fromed• Two step • One step
• R  (substrate) C=C
• Polar solventROH, H2O, RCOOH • R  (substrate) [ B ] • Poor leaving group
• High temp.
• Resonance stablised carbanion formed
SN1 Stable C SN2 - Back side attack

1) Solvolysis [H2O, EtOH, MeOH, RCOOH] 1) 1°/2°  RX
2) 2°/3° RX 2) Strong Nu –ve charge aq KOH, C2H5O ,

3) Moist Ag2O NaNH2, O , N3 , CN , I
4) AgNO3
3) Polar aprotic solvent
5) High temper Favours Elimination E1 • DMF, DMSO, acetone, crownethers solvents
having  (µ 0, No H–Bonding)
E1 E2
Compare with SN1 two step • Compare with SN2 Nu one step

• C formation
• Strong Base  O , Alc KOH, RO ,
• Dehydration of Alc  H / 
• Pinacol-pinacolone rearrangement
NaNH2, EtOH/Et O
• Solvolysis Ethanol / Temp high
• High temp. & Base XoIZm nS>Vm h¡ • Bulky base always gives elimnation O
1. 1°RX + – OH
aq. KOH
Cl SN2
• Undergo SN 2 / E2 reaction. iv.
H2O –
• SN2 reaction with almost any nucleophile. +
OH
SN1
• Alcoholic KOH alwasy give E2 product with any
halide. OH
– aq. KOH
i. CH3CH2CH2Br CH 3O
CH3CH2CH2–OCH3 (SN2) Ph OH
SN 2
v. Ph Cl CH3OH + ..
CH2 CH3OH CH2
ii. CH3CH2–Cl
K CN
CH3CH2–CN (SN2) SN 1 Ph
CH3O– Ph OCH3
+ –
Cl aq. KOH OH SN 2
iii. 2
Ph OCH3
SN
[SN2 – strong Nu  aq. KOH]

2. 2°RX ‘ñV aq. KOH
OH
2
SN
• E2  Strong base H2O
OH
Cl + H2O
1
SN
[alc.KOH, C2H5 O , NaNH2, (CH3)3C–O , etc.] ii.
CH3OH + OCH3 OCH3
• SN 2  Strong nucleophile SN
1
+
OCH3
[ I , Br , CN, SH , aq. KOH, CH3 COO , etc] CH3–O
–
2
SN
• SN 1  Weak nucleophile in polar solvent
3. 3°RX
[H2O, ROH, HCOOH, RCOOH, H2S, etc.] • SN2 reaction cannot take place.
• E2 reaction is favoured with the use of strong base.
• E1  reaction is favoured with weak base at high
[EtOH/Et O ]
temperature in polar protic solvents. • SN1 reaction is favoured in polar protic solvent.
[H2O, ROH, HCOOH, H2S, NH3, etc.] [H2O, ROH, RCOOH]
• E1 reaction is favoured in polar protic solvent at high
‘ñV temperature.
‘ñV
• When primary alkyl halide is stearically hindered

then SN2 and E2 reaction occur according to Reaction
condition of 2° halide.
OH
–
aq. KOH +
‘ñV SN1
OH
Cl OH
–
1. H2O +
OH
1
SN
OCH3
+ –
• When base is stearically hindered then E2 reaction CH3–OH CH3O
1
SN
is favoured.
CN
Br + (CH3)3C–– OK
KCN
Cl
‘ñV aq. KOH
2
OH DMF SN2
SN OH OCH3 OCH3
+
OH 2.
H2O H2O
Cl 1 + CH3OH
SN +
SN1
+
OCH3 OCH3
i. CH3OH Cl PhS
SN
1 +
– +
OCH3 PhS Na
–
CH3–O 3. DMF
2
SN
Br Br
1. Example of SN2 reactions Br

HO
12. Br  
1 equivalent
H3C CH3
1.
CH3 NaI/acetone
13. H 
Br 
2. (SN 2)condition
H Cl
CH3
Br CH3
14. SN 2
+ OH–  
3. H H
Cl
LiBr/acetone
15. 
S 2condition

N
4. Cl
CH 2–Cl
5. 16. Ph–S Na
Br
6. CH3 Br
17. K SH
7. Br
2. Example of SN1 Reactions
8.
1.
9.
2.
10.
3. -
O
C (i) KOH 4.
NH
11. (ii) Br CH2Cl
C
O

16.
5.
H2O
17. Cl 
S 1

N
6.
Cl
Cl
HO
18. or 
2

7.
Cl
O
+
8. 19. CH3–C–ONa
CH3COOH
Cl
9. Cl
20. CH OH
3

O Cl
10. CH2–OH
21. (x)HBr
 
OH
C 2 H5
11. |
NaI/HOH
23. CH3–– C  Br  
|
C3 H7
Br
12. CH3
CH3–CH–CH
24. CH3 
EtOH
P
CH 3
13. CH3– C – CH – CH 3
25. 
CH 3 I
CH3OH
14. P + HBr
Br
26. CH3

15. CH3OH
P + HBr

I
I I I
27. 
CH 3COOH 9. (I) 
(II) (III)
P + HBr O
Br Br CH2–Br
28. MeO
P
Me Br 10. (I) (II) (III) 

P should be
CH3
MeOH |
29. 11. I. CH3– C  Br II. CH3– CH  Br III. CH3–CH2–Br
| |
Me Br CH3 CH3
I. Arrange decreasing reactivity for SN1 reaction 
CH3 Br Br
CH – OTs CH2  CH CH2  OTs CH2–Br
1. CH 3  CH 2  OTs CH3 III
I 12. (I) 
II (II) (III)

CH 3 CH3 –OTs
CH – OTs CH  CH CH  OTs 13. I. II. III.
2. CH3 2 2
II Br Br
I III
Br
 
Br Br Br
14. I. II. III. 

4. 
I I I
II. Arrange decreasing reactivity for SN1 reaction
15. (I) (II) (III) 
AgNO3 reaction
O
16. I. Ph Br II.
5. (I) (II) (III)  Br
Br Br Br III. Br IV. 
Cl
Br Br Br O~aXñV
• A better leaving group increases rate of SN2 Reacn
6. 
(I) (II) (III) CH3–F < CH3–Cl < CH3–Br < CH3–I 3Rate of SN2
Rate of SN1
Br Br Br • A better leaving group increasing rate of SN1 reaction
CH3 CH3 CH3 CH3
7. (I) (II) (III)  1. H3C F < H3C Cl < H3C Br < H3C I
CH3 CH3 CH3 CH3
OTf OTs Br Cl
I I I
2. > > >
8. (I) (II) (III) 
O 3. Ph3C–X > Ph2CH–X > R3C–X > Ph–CH2–X > CH2=CH–
CH2 –X > R–CH2–X
••
Br
4. i. H3C O
••
CH2–X ii. H3C CH2–X | C 2 H5 O

12. CH3–CH2CH2 CHCH3 
C H OH 2 5
iii. CH2–X iv. O2N CH2–X
‘ñV CH3 Cl
 i > ii > iii > iv (SN1  C Stability) | |
13. C6H5– C  CH2 – C  CH3 
alc.KOH

3. Examples of E2 Reactions | |
CH3 H
• alc. KOH, C2H5 O , NaNH2, (CH3)3C– O etc.
1. alc.KOH
CH3–CH2–Br   • As the number of anti position increases, the rate of
E2 reaction increases.
2.
3.
4. Examples of E1 Reactions
4. CH3
| 
1. H3C–CH2– C  CH3 + H2O  
|
Cl
5.
CH 3 OH
2. CH3–CH2– CH  CH 3   
Δ
6. |
Br
3.
7.
4.
8.
5.
9.
10. 6.
11. 7.

E2
7. CH2 – CH – CH – CH3 – +
8. t-Bu OK
CH 3 Br
Br
CH3 E2
8. – +
9. t-BuO K
9. E
10. CH3 
2

Br
Cl CH3
tBuOK, tBuOH
11.   E2
Heat
10. Br – +
t-BuO K
CH3
CH3
12.
tBuOK
  E2
tBuOH 11. – +
t-BuO K
Cl Br
CH 2D
6. Co-planarity
1. In which of the following molecules, all atoms
EtOH,NaOH are coplanar?
13. 
H O,Heat2
Cl
CH3 1) 2)
CH2––C––CH3 alcohol
14. + KOH 
heat

Br
5. Elimination Reaction
Br E2
1. – + 3) 4)
t-BuO K
CH3
2. In which of the following molecules, –NO 2
2. E
Cl

2
 group is not coplanar with phenyl ring?
CH3
3. Cl E

2

Br 1) 2)
4. E2

Br
|
5. CH3  CH 2  CH2  C  CH 3 
E2

|
CH3
3) 4)
Br
E
6. CH3 – CH2 – CH – CH – CH3 
2
CH 3
3. In which of the following molecules both 4. In which of the following molecules, all atoms
phenyl rings are not coplanar? are not coplanar?
1) 2)
1) 2)
3) 4)
3) 4)
I. NCERT BOOK Extract CH3

iv) + HI
Q. Write the products of the following reactions :
v) CH3CH2Br + NaI
i) H + HBr
heat
vi) + Br2
H H UV light
ii) CH3 – CH2 – CH = CH2 + HCl Q. In the following pairs of halogen compouds, which
would undergo SN2 reaction faster ?
CH2– C= CH2 + H Br Peroxide
iii) H CH2Cl and Cl ;
I and Cl
Q. Draw the structures of major monohalo products in
each of the following reactions : Q. Which alkyl halide from the following pairs would
you expect to react more rapidly by an SN2 mecha-
OH nism ? Explain your answer.
i) + SOCl2
i) CH3CH2CH2CH2Br or CH3 CH2 C HCH3
|
Br
CH2CH 3
Br2, heat or
ii)
O2 N UV light CH3
|
ii) CH 3 CH 2 C HCH 3 or H 3 C  C  Br
| |
CH2OH Br CH3
heat
+ HCl
iii)
OH iii) CH 3 C HCH 2 CH 2 Br or CH 3 CH 2 C HCH 2 Br
| |
CH3 CH 3

Q. Predict the order of reactivity of the following
11) Propene propyne
compounds in SN1 and SN2 reactions :
12) Ethanol ethyl fluoride
i) The four isomeric bromobutanes
ii) C6H5CH2Br, C6H5CH(C6H5)Br, 13) Bromomethane propanone
C6H5CH(CH3)Br, C6H5C(CH3)C6H5)Br 14) But-1-ene but -2-ene
Q. In the following pairs of halogen compounds, which 15) 1-Chlorobutane n-octane

compound undergoes faster SN1 reaction?
16) Benzene biphenyl.
Cl Cl Cl
i) and ii) and Cl 17) CH3CH2CH2Cl + NaI acetone

heat
Q. Identify A, B, C, D, E, R and R1 in the following :

18) (CH3)3CBr + KOH ethanol

heat
Br + Mg dry
ether
 A H
 2O
 B
19) CH3CH(Br)CH2CH3 + NaOH water

dry ether D O
 C 
R – Br + Mg   
2
 CH 3 C HCH3 20) CH3CH2Br + KCN aq
.ethanol

|
D
21) C6H5ONa + C2H5Cl 

CH3 CH3
Na / ether
CH3 CH3    R1 – X Mg
 22) CH3CH2CH2OH + SOCl2 

CH 3 CH 3
D 

2
E H O 23) CH3CH2CH = CH2 + HBr peroxide
 
Q. A hydrocarbon C5H10 does not react with chlorine in 24) CH3CH = C(CH3)2 + HBr 

dark but gives a single monochloro compound
C5H9Cl in bright sunlight. Identify the hydrocarbon. 25) Propene propan-1-ol
Q. How will you convert 26) Ethanol but -1-yne
1) 1 - butanol 1 - Iodobutane 27) 1-Bromopropane 2-bromopropane
2) 1 - chlorobutane 1 - Iodobutane 28) Toluene benzyl alcohol
3) but - 1 - ene 1 - Iodobutane 29) Benzene 4-bromonitrobenzene
4) 1-Bromo-1-methylcyclohexane C
2 H 5 ONa
 30) Benzyl alcohol 2-phenylethanoic acid
31) Ethanol propanenitrile

5) 2-Chloro-2-methylbutane C
2 H 5 ONa

32) Aniline chlorobenzene
6) 2,2,3-Trimethyl-3-bromopentane C
2 H 5 ONa

33) 2-Chlorobutane 3,4-dimethylhexane
7) Ethanol but - 1 - yne
34) 2-Methyl-1-propene
8) Ethane bromoethene
2-chloro-2-methylpropane
9) Propene 1-nitropropane
35) Ethyl chloride propanoic acid
10) Toluene benzyl alcohol

36) But-1-ene n-butyliodide 58) 1–Chloro propane + aq. potassium
37) 2-Chloropropane 1-propanol hydroxide
38) Isopropyl alcohol iodofornr 59) aniline + NaNO2/HCl
39) Chlorobenzene p-nitrophenol 60) C6H5 – CH2 – CH = CH2 + HBr
40) 2-Bromopropane 1-bromopropane 61) C6H5 – CH = CH2 + HBr Peroxide

 
41) Chloroethane butane
CH3 CH3
| |
42) Benzene diphenyl 62) CH 2  C  C  CH 3  HI 
43) tert-Butyl bromide isobutyl bromide
CH3
44) Aniline phenylisocyanide |
63) CH 3  C  CH  CH 3  HBr 
alc
45) n-butyl chloride 
KOH OH
64) + SOCl2
Mg
46) bromobenzene 
B.E .
Q. Arrange the compounds of each set in order of
H  reactivity towards SN2 displacement:
47) chlorobenzene 
1) 1) 2–Bromo-2-methylbutane
aqueous KOH
48) ethyl chloride   
2) 1-Bromopentane
49) methyl chloride KCN

 3) 2-Bromopentane
Na 2) 1) 1-Bromo-3-methylbutane
50) C2H5OH  A C
2 H 5 Br
 B
2) 2-Bromo-2-methylbutane
Ag
51) CH3COOH  A C
2 H 5 Br
 B
Na
52) CH3– CH2–CH2–Cl  A Cl B
 2
3) 1) 1–Bromobutane
 A alc
53) CH3–CH = CH2 HBr
 KOH B
 2) 1-Bromo-2, 2-dimethylpropane,
54) Cl+Mg  dryether H2O
 A 
 B 4) 1-Bromo-3-methylbutane
NH 2
Cu X
55) NaNO
 2 /
HX
 A 22  B+N2
273 K
56) isobutyl chloride + sodium ethoxide
57) n-butyl chloride + sodium

II. MCQs 7. Incorrect statement is
1) Lower alkyl halides are either colourless gases or
1. Preperation colourless liquids
RCC-Lecture Task 2) For the same alkyl radical the b.pt. of alkyl halides
1. In iodination of alkane HgO is are in the order RI > RBr > RCl > RF
1) To reduce HI & stop backward reaction 3) Alkyl halides are very soluble in water
2) To oxidise HI & stop backward reaction 4) Alkyl bromides and alkyl iodides are heavier than
water
3) To remove HI & stop backward reaction
8. Isopentane on monochlorination gives .......... isomers
4) All
and out of them .......... are optically active.
2. Which of the following halides is most reactive
1) 3, 1 2) 4, 2 3) 6, 4 4) 4, 1
towards nucleophilic substitution reactions ?
9. Draw the structure of major monohalo product in
1) C2H5Br 2) C2H5F
the following reaction
3) C2H5Cl 4) C2H5I
3. When propene is reacted with HBr in the presence
of peroxide. The species first attack on propene is
1) Br + 2) H 
3) Br – 4) Br
4. The intermediate compound formed in Frankland’s 1) 2)
reaction is :
1) RZnI2 2) R2Zn
3) RZnI 4) R2ZnI
5. During photochemical bromination of the following 3) 4)
compound which hydrogen is abstracted most
readily? Cl ( g )
 (A)   (X).
2
10. C3H7Cl KOH
 ( alc .)
770 K
(X) can be :
1) Vinyl chloride 2) Allyl chloride
3) Ethyl chloride 4) Ethyl iodide
11. Chlorination of methane proceeds by :
1) l 2) m 1) Electrophilic substitution
3) n 4) o 2) Nucleophilic substitution
6. What is ‘A’ in the following reaction ? 3) Free radical mechanism
4) None of these
12. In iodination of alkanes, iodic acid is used to
1) catalyse the reaction
2) remove HI by reduction and to prevent reverse
reaction
3) oxidise HI to prevent reverse reaction
1) 2) 4) to liberate free I2 necessary for iodination
13. When hydrochloric acid gas is treated with propene
in presence of benzyl peroxide, it gives
1) 2-chloropropane 2) allyl chloride
3) 4) 3) n-propyl chloride 4) isopropyl chloride
14. C – X bond is strongest in
1) CH3Cl 2) CH3Br 3) CH3F 4) CH3I

15. CH3– CH –CH=CH2 + HBr A 23. Propane on monochlorination gives -------
enantiomeric pairs
CH3 1) 2 2) 3 3) 4 4) 0
(Predominatly A is) 24. Easily hydrolisable with aq KOH
1) CH3– CH CH – CH3 2) CH3– CH CH –CH3 1) C6H5CHCl C6H5 2) C6H5CH2Cl
CH3 Br 3) (CH3)3–C–Cl 4) (C6H5)3C–Cl
Br CH3
25. The number of mono chloro product obtained during
Br the reaction of 2, 3–dimethyl butane with Cl2 in the
presence of sunlight is (do not consider optical
3) CH3– CH –CH2–CH2–Br 4) CH3–– C–– CH2–CH3
isomers)
CH3 CH3 1) 2 2)3 3) 4 4) 5
16. Crotyl bromide is 26. A sp2-hybridised C-atom is present in both the
1) CH3–CH=CH–CH2–Br compounds in the pair
2) CH3–CH2–CH=CH–Br 1) carbanion and ethene
3) CH2=CH–CH2–CH2–Br 2) ethene and benzene
3) propyne and benzene
4) CH3–CH= C –CH3
4) ethane and propene
Br
27. The reactivity of halogens to form alkyl halides is in
17. Possible number of eanantiomers can be produces the order
during monochlorination of n-butane
1) Cl > Br > I 2) I > Br > Cl
1) 4 2) 3
3) Cl > I > Br 4) I > Cl > Br
3) 2 4) 1
28. + HBr A (major product) A is
18. Which of the following statements is true ?
1) Allyl chloride is more reactive than vinlyl chloride Br
1) Br 2)
2) Vinyl chloride is as reactive as allyl chloride
3) Vinyl chloride is more reactive than allyl chloride
4) Both 1 & 3 Br
19. Which of the following is fast de-brominated? 3) 4)
1) 2) 29. For finkelstein reaction more reactive R–Cl is


1) 1 R–Cl 2) 2 RCl
3) 4) 
3) 3 RCl 4) Ph 3C–Cl
20. Reaction of trans-2-phenyl-1-bromocyclopentane on RCC-Student Task

reaction with alcoholic KOH produces 30. Among the isomeric alkanes of molecular formula
1) 4-phenyleyclopentene C5H 12 identify the one that on photochemical
2) 2-phenylcyclopentene chlorination yields four isomeric monochlorides.
3) 1-phenylcyclopentene 1) 2-methybutane 2) 2,2-dimethylpropane
4) 3-phenylcyclopentene 3) 3-methylbutane 4) n-pentane
n
31. Markonikov Rea is
21. The compound C7H8 3
Cl / 
 X Br
2
/ Fe
Y 2
1) E+ Addn 2) E+ substn
Zn
/HCl
 Z. The compound Z is 3) Nu– Addn 4) Nu– substn
1) m-bromotoluene 2) p-bromotoluene 32. When isopropyl iodide in ethereal solution is
warmed with sodium, the product formed is
3) o-bromotoluene 4) 2,45,6-trichlorotoluene
1) n-hexane
22. Which halide will be least reactive with respect to
hydrolysis ? 2) Neohexane
1) Vinyl chloride 2) Allyl chloride 3) 2, 3-dimethyl butane
3) Ethyl chloride 4) t-butyl chloride 4) 2, 2-dimethyl butane

33. The major product obtained in the reaction, 40. The correct order of boiling points is
CH3 1) CH3I > CH3Br > CH3Cl > CH3F
Br2 2) CH3F > CH3Cl > CH3Br >CH3I

is :
hv 3) CH3I > CH3F > CH3Cl > CH3Br
CH3 4) CH3Br > CH3Cl > CH3F > CH3I
CH2Br CH3 CH3
Br Br 41. IUPAC name of tertiary isomer of C5H11Br is
1) 2) 3) 4) 1) 1-Bromo-1,1-dimethyl propane
2) 2-Bromo-2-methyl butane
Br 3) Ter-pentyl bromide
34. Methyl bromide reacts with AgF to give methyl 4) 2-Bromo-2-ethyl propane
fluoride and AgBr. This reaction is called : 42. Swarts reaction is
1) Finkelstein reaction 2) Fittig reaction 1) R –Cl + AgF R–F + Ag Cl
3) Swarts reaction 4) Wurtz reaction 2) R – Br + Nal RI + NaBr
35. CH3Br + Nu–  CH3Nu + Br dry
3) 2R – Cl + 2Na R – R + 2NaCl
The decreasing order of the rate of the above reaction ether
with nucleophiles (Nu–) A to D is 4) R – Cl + NaI RI + NaBr

– – – –
(Nu = (A) PhO , (B) AcO , (C) HO , (D) CH3O –
43. The number of -hydrogen atoms is ter. butyl
1) D > C > A > B 2) D > C > B > A bromide is/are
3) A > B > C > D 4) B > A > D > C 1) 0 2)3 3)6 4)9
36. A hydrocarbon of molecular mass 72 g mol–1 gives a 44. Hydrogenation of the following compound in the
single monochloro derivative and two dichloro presence of palladium catalyst gives
derivatives on photochlorination. Give the name of
the hydrocarbon.
1) n-pentane 2) 2,2-dimethyl propane 1) optically active compounds
3) 2,2-dimethyl pentane 4) iso-pentane 2) optically inactive compound
37. In the following sequence of reactions 3) racemic mixture
HBr HBr aq 4) diasteroisomers
CH3CH2CH2OH  A alc
 B  C  D;
Peroxide KOH
KOH 45. In the chlorination of isobutane the major product
the original compound and D are is
1) same 2) isomers 1) CH3CH2CH2CH2Cl 2) CH2CH(CH3)CH2Cl
3) metamers 4) homologues
3) CH3CH2CH(CH3)Cl 4) (CH3)3CCl
46. How many isomers are possible for compounds
38. having the molecular formula C5H11Br
1) Nine 2) eight
3) six 4) seven
47. On monobromination of 2-methyl butne, the total
1) 2)
number of optical isomers is
1) 2 2)4 3) 6 4) 8
48. Finkelstein reaction is used to prepare
3) 4) 1) R – F 2) R – Cl
3) R – Br 4) R – I
39. 2-Methylbutane on reacting with bromine in the
presence of sunlight gives mainly 49. Aryl halide undergoes electrophilic substitution
reaction slowly as compared to benzene why?
1) 1-bromo-2-methylbutane
1) more resonance stabilization
2) less resonance stabilization
3) –I effect of halogen
4) + I effect of halogen

50. When benzene diazonium chloride is treated with 59. In comparison to alkyl halids. the aryl halids are less
Cu2Cl2 in HCl. Chlorobenzene is formed. reactive towards nucleophilic substitution reactions,
The reaction is called due to
1) Perkin’s reaction 2) Ullmann reaction 1) inductive effect
3) Sandmeyer’s reaction 4) Etard reaction 2) large, C–Cl bond
51. How many trichloroethanes would be produced 3) stability of carbonium ion
when 1, 1-Dichloroethane reacts with chlorine ? 4) resonance stabilisation
1) One 2) Two 60. In which of the following molecules p-electron of
3) Three 4) Four halogen is delocalised over the entire structure ?
52. Which of the following is the correct order of 1) Picryl chloride 2) Benzyl chloride
decreasing reactivity towards nucleophilic 3) Allyl chloride 4) Benzal chloride
substitution? 61. A hydrocarbon C 6H 14 gives two monochloro
1) Vinyl chloride > Allyl chloride > Propyl chloride derivatives on monohalogenation.
2) Allyl chloride > Propyl chloride > Vinyl chloride 1) n-hexane 2) 2,2-dimethyl butane
3) Allyl chloride > Vinyl chloride > Propyl chloride 3) 2,3-dimethyl butane 4) 2-methyl pentane
4) Propyl chloride > Vinyl Chloride > Allyl chloride 62. In chloro benzene, all the six C – C bonds have the
53. Isobutene will be obtained on treatment of which of same length because of
the following compounds, by alcoholic KOH ? 1) inductive effect 2) isomerism
1) (CH3)3 C – Cl 2) (CH3)3 CH – CH2Cl 3) tautomerism 4) sp2-hybridisation
63. When ethyl iodide and n-propyl iodide are allowed
Cl
| to react with sodium metal in ether, the number of
3) CH3 – (CH2)2–CH2Cl 4) CH 3  CH  CH 2  CH 3 alkanes containing even number of C atoms that
could be produced is
54. Benzyl chloride (C6H5CH2Cl) can be prepared from
toluene by chlorination with 1) only one 2) two alkanes
1) SO2Cl2 2) SOCl2 3) three alkanes 4) four alkanes
3) Cl2|hv 4) NaOCl 64. Bromination of neo-pentane gives
1) 2-bromo 2-methyl pentane
55. H 3 C  C  CH  CH  CH 3 is
| | 2) 2-bromo 2-methyl butane
Cl CH 3 3) 1-bromo 2, 2 dimethyl butane
1) 2-chloro-4-methyl-2-pentene 4) 1-bromo 2, 2 dimethyl propane
2) 4-chloro-2-methyl-3-pentene 65. Not used for swart rean is
3) 4-methyl-2-chloro-2-pentene 1) Ag2 F 2) Hg2F2
4) 2-chloro-4, 4-dimethyl-2-butene 3) SbF3 4) CoF2
56. The total number of alkens possible by 66. An alkane with molecular mass 30 a.m.u. when
dehydrobromination of brominated gives only one monobrominated
product. The alkane is
3-bromo-3-cyclopentylhexane using alcoholic KOH
is 1) pentane 2) ethane
1) 3 2) 4 3) bu tane 4) neopentane
3) 5 4) 6 67. Only two isomeric monochloro derivative are
possible for
57. Which of the following haloalkanes is most reactive?
1) n–hexane 2) 2–methyl propane
1) 1-chloropropane 2) 1-bromopropane
3) n–heptane 4) 2–methyl butane
3) 2-chloropropane 4) 2-bromopropane
68. Vinyl chloride undergoes
58. 2-bromopentane is heated with potassium ethoxide
in ethanol. The major product obtained is 1) addition reaction 2) elimination reaction
1) pentene-1 2) 2-ethyoxypentane 3) substitution reaction 4) none of these
3) trans-pentene -2 4) cis-pentene-2

69. Ethyl chloride is reacted with sodium ethoxide to 78. Removal of hydride ion from methane gives
form 'A'. Which of the following reaction also yield 1) methyl carbocation
'A'
2) methyl radical
1) C2H5Cl + KOH(alc.)
3) methyl group
2) 2C2H5OH + cone. H2SO4, 140°C
4) methyl carbanion
3) C2H5Cl + Mg dry ether
79. 1–Pentene + HCl  Major porduct will be
4) C2H2 + dil. H2SO4, HgSO4
1) 3 – Chloropentane
70. In Swarts reaction reagent used is / are
1) AgF 2) Hg2F2
3) 1, 2 – Dichloropentane
3) SbF2 4) one of these
71. The no. of sp2– and sp3– hybridized C-atoms in benzyl
80. NOT correct is
chloride are respectively
1) 1–Butene + HBr peroxide
  1–Bromobutane
1) 1, 6 2) 2, 5
3) 6, 1 4) 5, 2 2) Propylene + HCl 
 2 – Chloropropane
72. Silver propionate when heated with iodomethane 3) 1–Butene + HCl peroxide
  2–Chlorobutane
gives
4) 1–Butene + HBr 
 1–Bromobutane
1) ethyl propionate 2) methyl propionate
81. The IUPAC name of (CH3)2CH–CH2–CH2Br is
3) ethyl acetate 4) methyl acetate
1) 1-bromopentane
73. Ethyl bromide reacts with silver nitrite to form
1) nitroethane 2) ethyl nitrite
3) 2-methyl-4-bromobutane
3) ethane 4) nitropropane
4) 2-methyl-3-bromopropane
74. Which one of the following groups is trivalent?
1) phenyl 2) benzyl 2) Chemical properties
3) benzo 4) benzal RCC-Lecture Task
75. The reactivity of halogenation of alkanes decreases 82. Which of the following is the least reactive towards
in order : nucleophile?
1) F2 > Cl2 > Br2 > I2 2) I2 > Br2 > Cl2 > F2 1) CH3CH2Cl 2) CH2 = CH–CH2Cl
3) Cl2 > F2 > I2 > Br2 4) F2 > Br2 > I2 > Cl2 3) CH3Cl 4) C6H5Cl
76. The structure of the major product formed in the 83. For the following :
following reaction
(A) I– (B) Cl– (C) Br–
Cl the increasing order of nucleophilicity would be
1) Cl– < Br– < I– 2) I– < Cl– < Br–
NaCN
  is
DMF 3) Br– < Cl– < F– 4) I– < Br– < Cl
I
84. 1-Phenyl-2-Chloropropane on treatement with
CN Cl alcohol KOH gives mainly
1) 2) NC
1) 1Phenyl propan-1-ol
CN I 2) 2-Phenyl propene
3) 1-Phenyl propan-2-ol
Cl CN
4) 1-Prenyl propene
3) 4)
CN I 85. The raw materials for the commerical manufacture
of DDT are
77. Which is synthesized from single alkyl halide?
1) Chlorobenzene and chloroform
1) 2) 2) Chlorobenzene and chloromethane
3) Chlorobenzene and chloral
4) Chlorobenzene and BHC
3) 4)

86. Which of the following is liquid at room temperature 94. Which of the following will give
ppt .ofAgCl
1) CH3I 2)CH3Br 3)C2H5Cl 4)CH3F white     in cold with alcoholic AgNO3
87. Butyronitrile may be prepared by heating 1) CH3CH = CHCl 2) CH2 = CHCH2Cl
1) propyl alcohol with KCN 3) CH3CH2CH2Cl 4) None of these
2) butyl alcohol with KCN 95. Alkyl halides + Mg  (G) H
2O
  Propane. The
Boil
3) propyl chloride with KCN alkyl halide is
4) butyl chloride with KCN 1) Ethyl bromide 2) n-Propyl iodide
88. Elimination reaction is carried out in the presence 3) Isopropyl iodide 4) Both B & C are correct
of alc. KOH and not aq. KOH because
Mg
C2 H 5OH
1) RX is soluble in alc. KOH & not in aq. KOH 96. A  B    (CH3)2CH–CH3
( C 2 H 5 )2 O
2) RX is soluble in aq. KOH & not in alc. KOH
In the above sequence the starting compound A is
3) KOH is soluble in both alcoholic & aq. medium
1) 2-Bromobutane
4) All
2) 1-Bromobutane
89. In the elimination reaction of ethyl halide carbon
3) 2-Bromo-2-methylpropane
atom the change its hybridisation is,
4) 1-Bromo-2-methylpropene
1) sp2 to sp3 2) sp3 to sp2
97. Carbon - halogen bond is most susceptible to cleave
3) sp3 to sp 4) sp to sp3
in
90. (X) + KCN  CH3CN 2
H 2 / NI
 CH3CH2NH2 what 1) Benzyl bromide 2) Bromobenzene
is (X) ?
3) Vinyl bromide 4) Benzyl chloride
1) CH3CH2Cl 2) CH3Cl
98. In the reaction,
3) CH3CH2CH2Cl 4) (CH3)2CHCl
C2H5I alc
.KOH
 X Br
2  Y KCN
 Z; X, Y and Z
91. Which of the following reaction is incorrect?
are respectively
1) C2H4, C2H5Br, C2H5CN
1) 2) C2H5OH, C2H5Br, C2H5CN
3) C2H4, CH2Br-CH2Br, CH2CN. CH2CN
4) C2H4, C2H4Br2, C2H5CN
99. Which of the following is liquid at room
temperature?
2) 1) CH3–F 2) CH3–Br
3) CH3–CH2–I 4) CH3–F
100. Identify E from the following reaction
CH3 CH3
Mg
CH3 Na / ether
CH3   D H
 R’–X  2O
E
CH3 CH3
3)
1) Propane 2) n-butane
3) isobutane 4) ter.butane
4) None of these 101. Chlorobenzene on heating with aq. NH 3 under
92. Alkyl halides react with dialkyl copper reagents to pressure in the presence of Cu2Cl2, gives
give 1) benzamide 2) aniline
1) alkenes 2) alkyl copper halides 3) o-aminochlorobenzene
3) alkanes 4) alkenyl halides 4) dichlorobenzene
93. The C–Mg bond in CH3CH2MgBr is 102. In the following reaction,
1) ionic KOH/alc.
CH3CH2CHICH3   KI+H2O+CH3CH=CHCH3
2) non-polar covalent
The hybridisation state of carbon atom changes from
3) polar covalent
1) sp2 to sp3 2) sp3 to sp
4) hydrogen
3) sp3 to sp2 4) sp to sp2
103. In CH3–X the order of C–X bond strength is
1) CH3F > CH3Cl > CH3Br > CH3I 111. What is X ?
2) CH3Cl > CH3Br > CH3I > CH3F
3) CH3Br > CH3 I > CH3 F > CH3Cl
4) CH3I > CH3 Br > CH3F > CH3 Cl
1) 2)
104. Compound A on elimination gives 2-methyl 2-
butene. The compound A is
1) neo-pentyl bromide 2) sec. pentyl bromide
3) t-pentyl bromide 4) all of these 3) 4)
105. Dehydrochlorination of (CH3)2 CHCHClCH3 gives
major product, 112. Which of the following will be hydrolysed with
1) (CH3)2 C = CHCH3 2) (CH3)2 CH – CH = CH2 warm water
3) both ‘a’ and ‘b’ 4) (CH3)2 CHCHOHCH3 1) Chlorobenzene
106. Suitable reaction to prepare iodobenzene is 2) p-Nitrochlorobenzene
1) Sandmeyer’s reaction 2) Wurtz reaction 3) 2, 4-Dinitrochlorobenzene
3) Fitting reaction 4) Grignards reaction 4) 2, 4, 6-Trinitrochlorobenzene
107. Anhydrous AlCl3 is used in Friedel -Craft reaction 113. Ethyl chloride on heating witgh AgCN, forms a
because it is compound ‘X’. The functional isomer of ‘X’ is
1) electron rich 1) C2H5NC 2) C2H5NH2
2) electron efficient 3) C2H5CN 4) None of the above
3) soluble in ether 114. CH3Br + KCN(alc)  X NaRe duction
 Y
/ C H OH
2 5
4) ionisable to Al and Cl ions What is Y in the series ?
108. Incorrect for inductive effect 1) CH3CN 2) C2H5CN
1) It involves only breaking of sigma bond 3) C2H5NH2 4) CH3NH2
2) Polarisation of single covalent bond takes place Na C2H5Br
115. C2H5OH A B ‘B’ is
3) It is due to E.N. difference
1) n-butane 2) Diethyl ether
4) It affects on physical & chemical reactivity of
molecule. 3) sod. ethoxide 4) ethoxy ethane
109. Compound ‘X’ reacts with alcoholic KOH to yield 116. In Benzyl chloride halogen bearing carbon is linked
compound ‘Y’ which on ozonolysis followed by to ............. hybridized carbon
reaction with Zn/H2O gives methanal and propanal. 1) sp3 2) sp2 3) sp 4) sp3d
Compound ‘X’ is 117. Major product formed when toluene on
1) 1-propanol monochlorination.
2) 1-butanol CH3 CH3
3) 1-chlorobutane Cl
4) 1-chloropentane 1) 2)
110. Assertion (A) It is necessary to avoid traces of Cl
moisture from Grignard reagent.
CH3
Reason (R) RMgX + H2O  RH + Mg(OH)X
CH3
1) Both A and R are correct and R is correct Cl Cl
explanation of A.
3) 4)
2) Both A and R are correct but R is not the correct
explanation of A Cl
3) A is correct ; R is incorrect 118. Iodobenzene reacts with iodomethane in Na and dry
4) R is correct ; A is incorrect ether. Which of the following is not formed in this
reaction
1) C6H6 2) (C6H5)2
3) (CH3)2 4)C6H5CH5

RCC-Student Task 128. In the reaction,
KCN [H]
119. In the following sequence of reactions A  B 
   C2H5NH2.
H 3O + LiAlH The compound ‘B’ is
4  C.
KCN
CH3–Br  B 
 A  ether
1) CH3I 2) CH3CN
the end product (C) is
3) C2H5I 4) C2H5CN
1) Ethyl alcohol 2) Acetone
129. The reaction of toluene with Cl2 in presence of FeCl3
3) Methane 4) Acetaldehyde gives predominantly
120. Which one of the following reactions is an example 1) benzoyl chloride 2) benzyl chloride
of nucelophilic substitution reaction?
3) o-and p-chlorotoluene 4) m-chlorotoluene
1) 2RX + 2NaR–R + 2NaX
130. The reaction of 4-bromobenzyl chloride with NaCN
2) RX + H2 RH + HX in ethanol leads to
3) RX + Mg RMgX 1) 4-bromobenzyl cyanide
4) RX + KOH ROH + KX 2) 4-cyanobenzyl chloride
121. Which of the following compound has the highest 3) 4-cyanobenzyl cyanide
boiling point?
4) 4-bromo-2-cyanobenzyl chloride
1) CH3CH2CH2Cl 2) CH3CH(CH3)CH2Cl
131. The Wurtz - Fittig reactions involves
3) CH3CH2CH2CH2Cl 4) (CH3)3CCl
1) two molecules of aryl halides
122. 1, 2-Dibromoethane when heated with alcoholic
2) two molecules of alkyl halides
potash gives
3) one molecule of each of aryl halide and alkyl halide
1) Ethane 2) Acetylene
4) one molecule of each of aryl halide and phenol
3) Ethylene 4) Methane
132. A solution of (+) -2-chloro-2-phenylethane in toluene
123. Which of the following are arranged in the
reacemises slowly in the presence of small amount of
decreasing order of dipole moment?
SbCl5, due to the formation of
1) CH3Cl, CH3Br, CH3F 2) CH3F, CH3Cl, CH3Br
1) carbanion 2) carbene
3) CH3Br, CH3Cl, CH3F 4) CH3Br, CH3F,CH3Cl
3) free radical 4) carbocation
124. The reaction of benzyl chloride with sodium cyanide
133. In the reaction,
followed by reduction with hydrogen in the presence  +
of nicket gives CH3C  CNa + (CH3)2CHCl 
1) -Phenyl ethylamine 2) N-Isobutyl aniline the product formed is
3) Benzyl amine 4) Aniline 1) 4-Methyl -2-pentyne only
125. Out of C6H5CHCl6H5 and C6H5CH2Cl which is more 2) Propyne
easily hydrolysed by aqueous KOH? 3) Propyne and propylene
1) C6H5CHClC6H5 4) Mixture of propene, propyne and 4-methyl-2-
2) C2H5CH2Cl pentyne
3) Both get equally hydrolysed Re duction
134. C2H5Br AgCN
 X   Y. Here Y is
4) Unpredictable Zn Hg / HCl
1) n-Propylamine 2) Ethylamine
126. Positively charged carbon in ethyl carbocation is
sp2 – hybridised & then in tertiary butyl carbonium 3) Isopropylamine 4) Ethylmethylamine
ion is 135. Which of the following compounds will undergo
1) Only sp 2 3
2) sp & sp 2 chemical reactions with ethanolic solution of KCN?
2
3) sp & sp 3
4) sp 3 1) C6H5Cl 2) C2H5Cl
127. Reactivity oder of halides for dehydro-halogenation 3) CH3COOH 4) All
is P4 / I 2 i ) KOH ( alc .)
136. Ethanol   X   
 Y
1) R – F > R – Cl > R – Br > R – I ii ) HBr
2) R – I > R – Br > R – CI > R – F In this sequence of reactions Y is

3) R – I > Cl > R – Br > R – F 1) Ethene 2) Bromoethane
4) R – F > R – I > R – Br > R – Cl 3) Ethanol 4) none

137. Dehydrohalogenation is possible in
1) (C6H5)3C – Cl 2) (CH3)3CCl 147.
3) CH3Br 4) None
138. In order of convert aniline into chlorobenzene the
reagents needed are
1) CuCl 2) NaNO2/HCl and CuCl
1) P > R > Q > S 2) S > Q > R > P
3) Cl2/ CCl4 4) Cl2/AlCl3
3) Q > R > P > S 4) Q > S > P > R
139. CH3MgI is an organometallic compound due to
Arrange the following in decreasing order of
1) Mg – I bond 2) C – I bond
reactivity toward SN1 reaction.
3) C – Mg bond 4) C – H bond
140. 1-chloropropane   B HX
alc .KOH
 C. In this

reaction C is 148.
1) 1-chloropropene 2) alkyl halide
3) 2-chloropropane 4) sec. alkyl halide
KCN HOH
141. In the reaction RX  B  C, C is a/an
HCl
1) S > R > Q > P 2) R > S > Q > P
1) alcohol 2) aldehyde
3) Q > R > S > P 4) P > Q > R > S
3) amine 4) fatty acid
142. The compound which undergoes fastest reaction
with aq. KOH solution is :
149.
1) C 6 H 5  CH  OCH 3 2) C 6 H 5  CH  CH 3
| |
Cl Cl
3) C6H6–CH2–CH2– Cl 4) C 6 H 5  CH  CH 2  CH 3 1) S > P > Q > R 2) R > Q > P > S

|
Cl 3) Q > R > P > S 4) S > Q > P > R
143. n-Propyl alcohol on treatment with ethanolic
potassium hydroxide produces :
1) Propene 2) Propyne 150.
3) Propanol 4) None
144. A mixture of 1-chloropropane and 1) P > Q > R > S 2) S > P > Q > R
2-chloropropane when treated with alcoholic KOH, 3) R > Q > P > S 4) R > P > Q > S
it gives 151. The rate of SN1 reaction is fastest with :
1) iso - propylene
2) 2-propene 1) 2)
3) 1-propene
4) A mixture of 1-propene and 2-propene
3) 4)
145. n-Butyl alcohol reacts with alc. KOH (elimination)
it gives
1) But -1-ene 2) But - 2-ene 152. Major product of the reaction
C 2 H 5ONa
3) Both a & b 4) None CH 3  CH  CH  CH 3   is ?
| |
Br CH 3
1) 2)
146.
3) 4)
1) Q > R > P > S 2) R > Q > S > P
3) P > Q > R > S 4) S > P > R > Q

153. A seconedary alcohol having six carbon atoms 161. Which of the following alkane is synthesised from
containg a quaternory carbon on heating with HI single alkyl halide?
form ........ as major product. 1) (CH3)2 CHCH2CH3 2) (CH3)2 CHCH3
1) 2-iodo-2, 3-dimethyl butane 3) (CH3)3 C – C (CH3)3 4) CH3CH(CH3)CH2CHCH3
2) 2-iodo-2, 3-dimethyl butane 162. An alkyl halide when treated with sodium metal in
3) 1-iodo-3, 3-dimethyl butane presence of ether gave 2, 2, 5, 5-tetramethyl hexane.
4) 1-iodo-2, 2-dimethyl butane The alkyl halide is
154. Benzylic halide among the following is 1) 2-chloro-2-methyl butane
1) 1-Bromo-3-phenylpropane 2) 1-chloropropane
2) 2-Bromo-1-phenylpropane 3) 1 chloro-2, 2-dimethyl propane
3) 1-Bromo-2-phenylpropane 4) 3-chloro-2, 2-dimethyl butane
HBr
4) 2-Bromo-2-phenylpropane 163. A  HBr
 1  pentene  R 2O 2
 B A and B are
155. Which one of the following is the correct order of isomers, which of the following statements is true?
decreasing SN2 reactivity 1) Both are chain isomers
1) RCH2X > R3 CX > R2CHX 2) Both are optical isomers
2) RCH2X > R2 CHX > R3CX 3) ‘A’ shows optical isomerism ‘B’, is not
3) R3CX > R2 CHX > RCH2 X 4) Both are metamers
4) R2CHX > R3 CX > RCH2X 164. The change in the state of hybridization of the
156. 2, 3-dimethylbutane can be obtained from wurtz asterisks carbon in the following reaction
reaction by using * H O *
CH3– C N 3  CH3 C ONH2 is
1) n-iodine alone
1) sp3 to sp2 2) sp3 to sp
2) ethyl chloride and methyl chloride
3) sp to sp2 4) sp2 to sp3
3) iso-propyl iodide alone
4) 2-iodobutane alone 165. Final out (Z) in the following reaction,
C2H5I KOH
/ alc . Cl 2 KCN
157. In aryl halides the C-X bond is less reactive than    X  Y  Z
alkyl halides because 1) CH3CH2CN 2) CNCH2CH2CN
1) sp2-hybridized C-atom is more electronegative 3) ClCH2CH2CN 4) CNCH = CHCl
than sp3-hybridized C-atom 166. Find out Z in the following reaction,
2) aryl halides and not alkyl halides exhibit 
CH3CH(Br)CH3 KOH
 / alc
. X H
3O Y Cu
523K
resonance  Z
3) both these 4) none of these 1) CH3CH(OH)CH3 2) (CH3)COO)2Cu

158. If isobutane is one of the products in wurtz reaction, 3) CH3COCH3 4) CH3CH = CH2
then the reactants are 167. Indicate which of the following is correct?
1) methyl chloride and n-propyl chloride 1) Increasing the concentration of nucleophile
2) methyl chloride and 2-chloropropane favours an SN1 reaction over an SN2 reaction
3) ethyl chloride and isopropyl chloride 2) Ethyl iodide is more reactive than ethyl chloride
4) none of these in an SN2 reaction
159. In the reactions 3) In an SN1 reaction, a greater yield of the product
with retained configuration is obtained
X
CH3CH2CH2Br  Y (CH3)2CHBr,,
A  4) SN2 reaction is favoured by compounds which
X and Y are respectively have maximum branching and bulky alkyl
1) aq. KOH, HBr 2) Na/ether, HBr groups
168. (CH3)3 C–MgBr on reaction with D2O produces
3) ROH, Br2 4) alc. KOH, HBr
1) (CH3)3 CD 2) (CD3)3 CD
160. It is difficult to break C–Cl bond in
3) (CH3)3 COD 4) (CH3)3 OD
CH2=CH–Cl due to
169. Benzene diazonium chloride is converted in to
1) electromeric effect 2) resonance iodobenzene by use of
3) hyperconjugation 4) inductive effect 1) KI/ 2) PI3
3) HIO3 4) CuI
170. Which of the following is used in Friedel Craft 180. In the following sequence of reactions, the compound
acetylation reaction ‘D’ is
Mg HCHO
1) (CH3CO)2O 2) CH3Cl CH 3CH 2OH P
 I2
 A  B  C
ether
3) C2H5–OH 4) C2H5COOCH3 H 2O

 D
171. Compound (A) is heated with KCN produces
butyronitrile. The compound (A) is 1) butanal 2) n-butyl alcohol
1) n-propyl alcohol 2) n-butyl chloride 3) n-propyl alcohol 4) propanal
3) n-propyl chloride 4) n-propyl amine 181. Which one is most reactive towards an electrophilic
reagent ?
172. Not electrophile
1) PCl5 2) Br 2 CH3 CH3
3) PCl3 4) HCl 1) OH 2) CH2OH
173. Incorrect for Nucleophile
1) Lewis bases
2) One of the atom must posses lone pair of electron CH3 CH3
3) Oxidant 3) NHCOCH3 4) OCH3
4) Nucleus loving
174. Wrong for homolysis 182. Identify Z in the following reaction series,
1) Favours at high temp
2) Favours in polar solvent CH3CH2CH2Br Aq
. NaOH
 (X) Al
2O3
 (Y)
heat
3) Favours in non polar solvent HOCl
 (Z)
4) Usually occurs in non polar covalent bond.
1) mixture of CH3– CH  CH 2 & CH3– CH – CH
175. Ethyl carbyl amine is obtained from | | | |
Cl Cl OH Cl
1) C2H5 – Br + AgcN
2) CH3 – Br + CHCl3 + alc KOH 2) CH3– CH – CH 2
| |
3) C2H5 – Br + CHCl3 + alc KOH OH Cl
4) both (1) and (3)
3) CH3– CH  CH 2 4) CH3– CH  CH 2
176. The intermediate during the addition of HBr to | | | |
propene in presence of peroxide is Cl OH Cl Cl
 
1) CH3 C HCH2 Br 2) CH3CH2 C H 2 183. In the following reaction
  1.Mg ,Ether
3) CH3 C HCH3 4) CH3CH2 C H 3 C6H5CH2Br   X, the product ‘X’ is
2. H O  3
177. Addition of HI on the double bond of propene yields 1) C6H5CH2OCH2C6H5 2) C6H5CH2OH
isopropyol iodide and not n-propyl iodide as the
3) C6H5CH3 4) C6H5CH2CH2C6H5
major product. This is because addition proceeds
through 184. Chlorobenzene can be prepared by reacting amiline
with
1) A more stable secondary carbonium ion
1) Hydrochloric acid
2) A more stable carbanion
2) Cuprous chloride
3) A more stable free radical
3) Chlorine in presence of anhydrous aluminium
4) A more stable nucleophile
chloride
178. Total number of electrons present in the outermost
4) Ice cold nitrous acid followed by treatment
shell of carbanion are
with cuprous chloride and HCl
1) 10 2) 6 3) 4 4) 8 HNO Cl
185. C6H6 HSO
3  X  2
179. Phenyl magnesium bromide reacts with methanol FeCl

Y
2 4 3
to give In the above sequence Y can be

1) a mixture of anisol and Mg(OH)Br 1) ortho or p-Chloronitrobenzene
2) a mixture of benzene and Mg(OMe)Br 2) 3-Nitrochlorobenzene
3) a mixture of toluene and Mg(OH)Br 3) only 4-Nitrochlorobenzene
4) a mixture of phenol and Mg(Me)Br 4) equal 4-Nitrochlorobenzene
186. On treating phenol with PCl5 the main product is 194. Bonds present in benzene diazonium chloride are
1) Chlorobenzene 2) Triphenylphosphate 1) only ionic
3) Hexachlorobenzene d) BHC 2) ionic, covalent and co–ordinate
187. Benzotrichloride reacts with milk of lime to form 3) only covalent
1) Benzal 2) Benzoic acid 4) ionic and covalent
3) Benzyl alcohol 4) Phenol 195. The alkane that will not be formed from isopropyl
bromide and ethyl bromide together or separately
CH 3 with sodium in ether is
| NaI , Acetone
188. CH3– C  CH  CH 2   (X) 1) Isopentane 2) n-hexane
| 3) 2, 3-dimethyl butane 4) n-butane
Br
196. 1-Methyl cyclohex-1-ene on reacting with HI form
........ as major product.
CH 3 CH 3
| | I
1) CH2= C  CH  CH 2 2) CH3– C  CH  CH 2 CH3
| CH3 I
I 1) 2)
CH 3 CH 3
| | CH3
3) CH3– C  CH  CH 2I 4) CH2= C  CH  CH 3 CH2 I
|
I 3) 4)
I
189. Grignard reacts with following reagent & gives
hydrocarbon (alkane) 197. Molecular formula of amyl alcohol is
1) Amines 2) Alcohols 1) C5H12O 2) C7H14O
3) H2O 4) All 3) C6H14O 4) C5H10O
190. Order of reaction between methyl bromide and 198. An organic comound A reacts with PCl5 to give B. B
aqueous KOH is reacts with sodium metal to give n-butane. A and B
are respectively
1) First 2) Second
1) C2H5OH, C2H5ONa
3) Third 4) Forth
2) C2H5Cl, C2H5OH
191. The reaction of t–butyl chloride and sodium ethoxide
gives mainly 3) C2H5Cl, C2H5ONa
1) t–butyl ethyl ether 4) C2H5OH, C2H5Cl
2) 2–methyl 1–propene 199. Which among the following is wrong?
3) 2–2–dimethyl butane 1) The p orbital of halogen atom contain lone pair
of electrons in haloarenes
4) isopropyl n–propyl ether
2) The delocalization of electrons gives double bond
192. Product of following reaction is
character to C-X bond
3) The lone pair of electrons on halogen atom forms
conjugated system with electrons of aromatic ring
dil. NaOH
  ? 4) Due to double bond character of C-X bond in aryl
halide is longer than C-X bond in alkyl halide
1) 4–hydroxy 1,3–dinitrobenzene
2) 2,4 – dinitro phenol
193. Wurtz – Fittig reaction is used to prepare
1) alkyl benzene 2) higher alkane
3) diphenyl 4) phenyl benzene

3) Optical activity SN 1& SN 2
208.
RCC-Lecture Task
Which statement is true for the above reactions
200. Meso tartaric acid is optical inactive due to
1) Retention of configuration
1) External compensation
2) Inversion of configuration
2) Internal compensation
3) Inversion and retention both
3) Two chiral atoms
4) None of the above
4) Molecular asymmetry
209. The reactivity of 2-bromo-2-methylbutane(I),
201. SN1 reaction is favoured by
1-bromopentane(II) and 2-bromopentane(III)
1) non-polar solvents
towards SN2 displacement is such that
2) more no. of alkyl group on the carbon atom
1) I > II > III 2) I > III > II
attached to the halogen atom
3) II > III > I 4) II > I > III
3) small groups on the carbon attached to the
halogen atom 210. Which is the most effective ion in an SN 2
displacement on methyl bromide ?
4) none of the above
1) C2H5O– 2) NO3–
202. The correct statement, among the following, is
3) C6H5O– 4) CH3COO–
1) SN1 reaction is accompanied always by only
inversion in configuration 211. Non superimposable not for
2) In C-X bond, the C-atom is more electronegative 1) Feet
in aryl halide than in alkyl halide 2) English car & America car
3) The electrophilic substitution in chlorobenzene 3) Glass of bottle
takes place at meta-position. 4) Shoes
4) With aqueous alcoholic AgCN, alkyl halide gives 212. Entantiomers donot have
alkyl cyanide. 1) same M.P & B.P, density
203. Which is least reactive towards nucleophilic 2) same angle of rotation in opposite direction
substitution (SN2) ?
3) same angle of rotation in same direction
1) 2) Me3C – Cl
4) same chemical properites
3) PhCl 4) MeCH (Cl) Me
204. In SN2 reactions, the order of reactivity of the halides
RCC-Student Task
CH3X, C2H5X, n–C3H7X, n-C4H9X is 213. The hydrolysis of 2–Bromo–3–methylbutane with
1) aqueous KOH yields mainly
1) 2–Methylbutan–2–ol
2)
2) 3–Methylbutan–2–ol
3)
3) 2–Methylbut–2–ene
4)
4) None
205. In case of alkaline hydrolysis of a primary
214. Optically active compound
alkylhalide, the followign is correct regarding its
kinetic expression 1) CH3CHBrC2H5 2) CH3CHCNC2H5
1) rate [CH3Br] 2) rate [CH3Br] [OH–] 3) CH3CHOHC2H5 4) All of these
2
3) rate [OH–] 4) rate K [CH3Br] 215. In SN reaction at an asymmetric carbon of a
compound always gives,
206. The compounds which gives the most stable
carbonium ions on dehydrohalogenation is, 1) An enantiomers of the substrate
1) CH3I 2) C2H5I 2) A product with opposite ptical rotation with same
angle
3) (CH3)3CI 4) (CH3)2CHI
3) A product with opposite optical rotation with
207. For R & S configuration highest priority for
different angle
1) –COOH 2) –CONH2
4) None of these
3) –NO2 4) –COOCH3

216. Which of the following undergoes nucleophilic 223. Which halide will be least reactive with respect to
substitution exclusively by SN1 mechanism? hydrolysis ?
1) Benzyl chloride 2) Ethyl chloride 1) Vinyl chloride 2) Allyl chloride
3) Chloro benzene 4) Isopropyl chloride 3) Ethyl chloride 4) t-butyl chloride
217. An alkyl halide produces a single alkene when it 1
224. Best condition for SN reaction is
reacts with sodium ethoxide and ethanol. This 1) weak nucleophile and less polar solvent
alkene undergoes hydrogenation and produces 2-
2) weak nucleophile and more polar solvent
methyl butane. What is the identify of the alkyl
bromide? 3) strong nucleophile and more polar solvent
1) 1-bromo-2, 2-dimethyl propane 4) strong nucleophile and less polar solvent
2) 1-bromo butane 225. A racemic mixture is a mixture of
3) 1-bromo-2-methyl butane 1) meso and its isomers
4) 2-bromo-2-methyl butane 2) d and its l-isomers in equal proportions
1
218. In SN reaction mechanism what % of C–Br bond is 3) d and its l-isomers in different proportions
broken when 40% formation of 4) meso and d-isomers
C – OH bond is completed 226. Product-I  aq .KOH C H Br alc .KOH
  2 5    Product-II
1) 0 % 2) 100 %
The correct statement is
3) 40 % 4) 60 %
1) Product - I is obtained by the elimination reaction
219. Consider the following bromides
2) Product-II is obtained by the substitution reaction
3) the molecular formula of product - I is C2H4, while
A) B) the molecular formula of product-II is C2H6O
4) product-I is the isomer of dimethyl ether, while
product-II is the dehydrated compound of product-I
C) 227. In R–S configuration – C N group can be represent
as
C
The correct order of SN1 reactivity is 1) – C = N – C 2) – C =N
1) B > C > A 2) B > A > C
N
3) C > B > A 4) A > B > C
220. The expermimntally determined rate equation for the 3) C =N–C 4) – C – N –C
alkaline hydrolysis of RBr is given by: N N C

Rate = K [RBr] [ O H ] 228. The correct order of increasing reactivity of
Which of the following statements is inconsistent C –X bond towards nucleophile in the following
with these observations ? compounds is
1) The reaction is first order with respect to RBr.
X
2) The reaction is second order overall. X NO2
3) The reaction process is false
4) The rate-determining step is bimolecular I) II)
221. The correct decreasing order of SN1 reactivity of the NO2
following is
I. PhCH2X II. CH2 = CHCH2X III) (CH3)3C–X IV) (CH3)2CH–X
III. Me2CHX IV. C2H5X 1) I < II < IV < III 2) II < III < I < IV
1) I > II > III > IV 2) IV > III > II > I 3) IV < III < I < II 4) III < II < I < IV
1
3) II > I > III > IV 4) IV > III > I > II 229. Faster SN for
222. Tertiary alkyl halides are practically inert to 1) 1-Bromo-2-, 2-dimethyl propane
substitution by SN2 mechanism because of 2) 2-iodo-2-methyl butane
1) insolubility 2) instability 3) 1-butyl chloride
3) inductive effect 4) steric hindrance 4) 2-iodo-3-methyl butane

230. NSR of Aryl halide is similar to NEET Previous Year MCQ’s
1) Vinyl chloride 2) Allyl chloride
Topic : 1 Preparation & Properties of Haloalkanes
3) Benzyl chloride 4) Ethyl chloride
1. Elimination reaction of 2-Bromo-pentane to form
231. 1-Bromo-1- phenyl ethane is 20RX it undergoes
pent-2-ene is [2020]
1) Only SN1 2) Only SN2
(A) -elimination reaction
3) both SN1 & SN2 4) Either SN1 or SN2
(B)Follows Zaitsev rule
232. For SN2
(C) Dehydrohalogenation reaction
1) E = –ve H = –ve 2) E = +ve H = +ve
(D) Dehydration reaction
3) E = –ve H = +ve 4) E = +ve H = –ve
1) (A), (C), (D) 2) (B), (C), (D)
233. In SN1 reaction, the hybridisation changes in rate
dtermination step select the correct change among 3) (A), (B), (D) 4) (A), (B), (C)
the following 2. Which of the following alkane cannot be made in
3
1) from sp to sp 2 2
2) from sp to sp 3 good yield by Wurtz reaction ? [2020]
3) from sp to sp 3
4) from sp2 to sp 1) 2,3-Dimethylbutane
234. In SN1 reaction which of the following is true? 2) n-Heptane
1) H is always negative 3) n-Butane
2) The order of reactivity of alkyl halide is; 4) n-Hexane
pri > sec > ter 3. In an SN1 reaction on chiral centres there is : [2015]
3) It is a second order reaction 1) 100% racemization
4) It is favoured by polar solvents 2) inversion more than retention leading to partial
235. Ethyl bromide when heated with dry silver salt of racemization
carboxylic acid gives 3) 100% retention
1) diethyl ether 2) ethanol 4) 100% inversion
3) ethyl ethanoate 4) ethane 4. Two possible stereo-structures of CH3CHOH.COOH,
which are optically active, are called [2015]
1) Diastereomers
2) Atropisomers
3) Enantiomers
4) Mesomers
5. Which of the following acids does not exhibit optical
isomerism ? [2012]
1) Maleic acid
2) -amino acids
3) Lactic acid
4) Tartaric acid
6. Consider the reactions : [2011]
C 2 H5 OH
i) (CH3)2CH–CH2Br  (CH3)2CH–CH2OC2H5
+ HBr

C 2 H 5O
ii) (CH3)2CH–CH2Br  
(CH3)2CH–CH2OC2H2 + Br–
The mechanics of reactions (i) and (ii) are respectively:
1) SN1 and SN2 2) SN1 and SN1
3) SN2 and SN2 4) SN2 and SN1

7. Which one is a nucleophilic substitution reaction 12. CH3–CHCl–CH2–CH3 has a chiral centre. Which one
among the following ? [2011] of the following represents its R-configuration?

[2007]
H
1) CH3–CH = CH2 + H2O CH 2  CH  CH 3
| C 2H 5 C 2H 5
OH | |
1) H– C  CH 3 2) Cl– C  CH 3
2) RCHO + R'MgX  R  CH  R' | |
| Cl H
OH
CH 3 CH 3 C2H 5
| | |
3) H– C  Cl 4) H3C– C  Cl
3) CH 3  CH 2  CH  CH 2 Br  | |
C2H 5 H
CH 3
| 13. For (i) I–, (ii) Cl–, (iii) Br– the increasing order of
CH 3  CH 2  CH  CH 2 NH 2 nucleophilicity would be [2007]
4) CH3CHO + HCN  CH3CH(OH) CN 1) Cl– < Br– < I– 2) I– < Cl– < Br–
3) Br– < Cl– < I– 4) I– < Br– < Cl–
8. Which of the following reactions is an example of
nucleophilic substitution reaction ? [2009] 14. Which of the following is not chiral? [2006]
1) 2RX + 2Na  R – R + 2NaX 1) 2, 3-Dibromopentane
2) RX + H2  RH + HX 2) 3-Bromopentane
3) RX + Mg  RMgX 3) 2-Hydroxypropanoic acid

4) 2-Butanol
4) RX + KOH  ROH + KX
15. The configuration of the compound [2005]
9. In an SN2 substitution reaction of the type
DMF
R –Br + Cl–   R–Cl + Br– [2008]
is
Which one of the following has the highest reactivity
rate ?
1) R 2) S
1) CH3–CH2–CH2Br 2) CH 3  CH  CH 2 Br 3) E 4) Z
|
CH 3 16. Which of the following undergoes nucleophilic
substitution exclusively by SN1 mechanism? [2005]
1) Ethyl chloride 2) Isopropyl chloride
CH 3
| 3) Chlorobenzene 4) Benzyl chloride
3) CH 3  C  CH 2 Br 4) CH3CH2Br 17. The molecular formula of diphenylmethane,
|
CH 3
CH2 , is C13H12.
10. How many stereoisomers does this molecule have?
CH3CH = CHCH2CHBrCH3 [2008] How many structural isomers are possible when one
of the hydrogens is replaced by a chlorine atom?
1) 4 2) 6
[2004]
3) 8 4) 2 1) 6 2) 4
11. If there is no rotation of plane polarised light by a
3) 8 4) 7
compound in a specific solvent, though to be chiral,
it may mean that [2007] 18. Which of the following is least reactive in a
nucleophilic substitution reaction. [2004]
1) the compound is certainly meso
1) (CH3)3C–Cl 2) CH2=CHCl
2) there is no compound in the solvent
3) CH3CH2Cl 4) CH2=CHCH2Cl
3) the compound may be a racemic mixture
4) the compound is certainly achiral
19. Which of the following pairs of compounds are 25. 2-Bromopentane is heated with potassium ethoxide
enantiomers? [2003] in ethanol. The major product obtained is [1998]
1) 2-ethyoxypentane 2) pentene-1
1) 3) trans-2-pentene 4) cis-pentene-2
26. Which of the following compounds is not chiral?
1) DCH2CH2CH2Cl 2) CH3CH2CHDCl [1998]
2) 3) CH3CHDCH2Cl 4) CH3CHClCH2D
27. Which one of the following compounds is resistant
to nucleophilic attack by hydroxyl ions? [1998]
3)
1) Methyl acetate 2) Acetonitrile
3) Diethyl ether 4) Acetamide
4) 28. The reaction :
20. Reactivity order of halides for dehdyrohalogenation

is [2002]
1) R–F > R–Cl > R–Br > R–I
2) R–I > R–Br > R–Cl > R–F is described as [1997]
3) R–I > R–Cl > R–Br > R–F 1) S E 2 2) S N 1
4) R–F > R–I > R–Br > R–Cl 3) S N 0 4) S N 2
NaCN
21. CH3CH2Cl  Ni/H 2
 X  Y 29. Which of the following will exhibit chirality? [1996]
1) 2-Methylhexane 2) 3-Methylhexane
Acetic
Y  Z
anhdyride 3) Neopentane 4) Isopentane
30. The process of separation of a racemic modification
Z in the above reaction square is [2002]
into d and l-enatiomers is called [1994]
1) CH3CH2CH2NHCOCH3
1) Resolution 2) Dehydration
2) CH3CH2CH2NH2
3) Revolution 4) Dehydrohalogenation
3) CH3CH2CH2CONHCH3
31. When chlorine is passed through propene at 400°C,
4) CH3CH2CH2CONHCOCH3 which of the following is formed? [1993]
22. When CH3CH2CHCl2 is treated with NaNH 2, the 1) PVC 2) Allyl chloride
product formed is [2002]
3) Alkyl chloride 4) 1, 2-Dichloroethane
1) CH3–CH=CH2 2) CH3–CCH
32. Which of the following is an optically active
NH2 Cl compound? [1988]
3) CH3CH2CH 4) CH3CH2CH
1) 1-Butanol 2) 1-Propanol
NH2 NH2
3) 2-Chlorobutane 4) 4-Hydroxyheptane
23. CH 3 –CH 2 – CH  CH 3 obtained chlorination of Topic : 2 Preparation & Properties of Haloarenes
|
Cl 33. The hydrolysis reaction that takes place at the slowest
n-butane, will be [2001] rate, among the following is [2019]
1) l-form 2) d-form aq. NaOH

1) CH2Cl   CH2OH
3) Meso form 4) Racemic mixture
24. Which is a chiral molecule? [1999]
Cl  –+
1) 2, 2-dimethylbutanoic acid 2) aq. NaOH
 ONa
2) 4-methylpentanoic acid CH3 CH3
3) 3-methylpentanoic acid
aq. NaOH
4) 3, 3-dimethylbutanoic acid 3) H3C–CH2–Cl   H3C–CH2–OH
aq. NaOH
4) H3C=CH–CH2Cl   H2C=CH–CH2OH

34. The compound C 7H 8 undergoes the following 38. What products are formed when the following
reactions : compounds is treated with Br2 in the presence of
3Cl 2 / Br2 /Fe
FeBr3 ? [2014]
Zn/HCl
C7H8  A   B  C
The product 'C' is [2018]
1) m-bromotoluene
2) o-bromotoluene
3) p-bromotoluene
4) 3-bromo-2,4,6-trichlorotoluene
35. For the following reactions : [2016] 1)
1. CH3CH2CH2Br+KOH  CH3CH=CH2+KBr+ H2O
H3C CH3 H 3C CH3

2. + KOH 
 +KBr
Br OH 2)
Br
3. + Br2 

Br
Which of the following statements is correct ? 3)
1) (1) and (2) are elimination reactions and (3) is
addition reaction
2) (1) is elimination, (2) is substitution and (3) is
addition reaction
4)
3) (1) is elimination, (2) and (3) are substitution
reactions
4) (1) is substitution, (2) and (3) are addition 39. Which of the following compounds undergoes
reactions nucleophilic substitution reaction most easily ?
36. Which of the following biphenyls is optically active? [2011]
1) 2) [2016] 1) 2)
3) 4)
3) 4)
37. In which of the following compounds, the C–Cl bond
ionisation shall give most stable carbonium ion ?
40. The reaction of toluene with Cl2 in presence of FeCl3

gives 'X' and reaction in presence of light gives 'Y'.
Thus, 'X' and 'Y' are : [2010]
1) 2) [2015]
1) X = Benzal chloride, Y = o-chlorotoluene
2) X = m-chlorotoluene, Y = p-chlorotoluene
3) 4)
3) X = o- and p-chlorotoluene,
Y = Trichloromethyl-benzene
4) X = Benzyl chloride, Y = m-Chlrotoluene

41. Which one is most reactive towards SN1 reaction ? 46. Chlorobenene reacts with Mg in dry ether to give a
[2010] compound (A) which further reacts with ethanol to
yield [1993]
1) C6H5CH(C6H5)Br 2) C6H5CH(CH3)Br
1) Phenol 2) Benzene
3) C6H5C(CH3)(C6H5)Br 4) C6H5CH2Br
3) Ethylbenzene 4) Phenyl ether
42. The correct order of increasing reactivity of C–X bond
47. Which chloro derivative of benzene among the
towards nucleophile in the following compounds is
[2010] following would undergo hydrolysis most readily
with aqueous sodium hydroxide to furnish the
X X corresponding hydroxy derivative? [1989]
NO2
(CH3)3C–X, (CH3)2CH–X NO2
1) O2N Cl 2) O2N Cl
NO2
NO2
(I) (II) (III) (IV)
1) I < II < IV < III 2) II < III < I < IV
3) IV < III < I < II 4) III < II < I < IV 3) Me2N Cl 4) C6H5Cl
43. Benzene reacts with CH 3Cl in the presence of
anhydrous AlCl3 to form : [2009] Topic : 3 Some Important Polyhalogen Compounds
1) chlorobenzene 2) benzylchloride 48. Which of the following is responsible for depletion
of the ozone layer in the upper strata of the
3) xylene 4) toluene
atmosphere? [2004]
44. The replacement of chlorine of chlorobenzene to give
1) Polyhalogens 2) Forrocene
phenol requires drastic conditions, but the chlorine
of 2, 4-dinitrochlorobenzene is readily replaced since, 3) Fullerenes 4) Freons
[1997] 49. Chloropicrin is obtained by the reaction of [2004]
1) nitro groups make the aromatic ring electron rich 1) steam on carbon tetrachloride
at ortho/para positions 2) nitric acid on chlorobenzene
2) nitro groups withdraw electrons from the meta 3) chlorine on picric acid
position of the aromatic ring
4) nitric acid on chloroform
3) nitro groups donate electrons at meta position
50. Industrial preparation of chloroform employs
4) nitro groups withdraw electrons from ortho/para acetone and [1993]
positions of the aromatic ring
1) Phosgene 2) Calcium hypochlorite
45. Benzene reacts with n-propyl chloride in the presence
3) Chlorine gas 4) Sodium chloride
of anhydrous AlCl3 to give [1993]
51. Phosgene is a common name for [1988]
1) 3-Propyl-1-chlorobenzene
1) phosphoryl chloride
2) n-Propylbenzene
2) Thionyl chloride
3) no reaction
3) Carbon dioxide and phosphine
4) Isopropylbenzene
4) Carbonyl chloride

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10} Halogen Derivatives of Alkanes & Arenes

I. General Methods of Preparation 3. Halide exchange method

Mechanism Free radical mechanim

2R- H + 2l2 + Hgo Δ

CH2 CH2 =CH–Cl HCl

iii. CH3CH2Cl + H2 Pd

4. Reduction with metals

ii. Reaction with Na (Wurtz Reaction) Anhyd.

R–X + 2Na + X–R Dry

iii. Reaction with Li

CH3– CH –CH3+2LiCH3– CH –CH3+LiBr

iv. Reaction with Zn

v. Reaction with sodium-lead alloy

(TEL) 2. From Diazonium Salt

i. CH3COCH3 + 3I2 CI3COCH3 + 3HI

ii. CI3COCH3 + NaOH CHI3 + CH3COONa

Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified Page: 3

5. Side Chain Halogenation

Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified Page: 4

2. Electrophilic substittuion reactions

6. Wurtz Fitting Reaction

3. Formation of Grignard Reagent

Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified Page: 5

11. Reactivity of RX : 11. Reactivity :

Uses and Environmental Effects of some B) Trichloromethane or Chloroform : CHCl3

i) Solvent iii) Uses as a source of dichlorocarbene (CCl2)

ii) Paint remover Environmental effects :

i) It is highly volatile so in air it causes nausea, iv) It affects on CNS.

Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified Page: 6

ii) When mixed with air it c auses ozone

It causes ozone depletion. ii) Back side attack

Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified Page: 7

Eacl It is the energy difference bet n reactants &

Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified Page: 8

CH3 CH3 R = Reactant

C Br + – E1 = Energy of activation of T.S.1

Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified Page: 9

3) Plane polarized light (PPL)

4) Nicol’s Prims CH3 CH3

Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified Page: 10

A molecule containing asymmetric carbon atom

2) Conditions of optically activity.

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H OH OH H Anomeric terminal C-atoms

ix. x.  - Glucose  - Glucose

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COOH COOH CH3 OH CH3 OH

Non-superiomposable image (optically active) ii) Number of optical isomers

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Explain optical activites of lactic acid. 2. From glycols

In lactic acid, is chiral because it is attached to four

d-lactic acid mirror l-lactic acid

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CH3COCH3 + PCl5 CH3CCl2CH3 + POCl3

Br i. CaOCl2 + H2O Cl2 + Ca(OH)2

 Properties iii. CH3CHO + 3Cl2 Chlorinati

iv. 2CCl3CHO+Ca(OH) Hydrolysis 2CHCl + (HCOO) Ca

Chloroform Calcium formate

2. Reduction of carbon tetrachloride

CCl4 + 2[H] Fe/H

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X2/h  (or)  H2O/NaOH, H2 O

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