ORGANIC CHEMISTRY

HALOGEN DERIVATIVES
 EXERCISE–I (A)
(Choose the correct option. Only one is correct)
Q.1 Which one of the following compounds will be most reactive for SN1 reactions:

(A) (B) (C) (D)

Q.2 The major product in the given reaction: + NH3 

(A) (B) (C) (D) All of these

Q.3 In the given reaction:

CH  C CNa
3 
Et 2O / 

the products are:

(A) and

(B) +

(C)

(D)

Q.4 Consider the following groups:

(I) —OAc (II) —OMe (III) —O—SO2—Me (IV) —O—SO2—CF3
The order of leaving power is:
(A) I > II > III > IV (B) IV > III > I > II (C) III > II > I > IV (D) II > III > IV > I

Q.5 Which one of the following compounds will give enantiomeric pair on treatment with HOH?

C 2H 5 CH 3 H C2 H5
| | | |
(A) C 6 H 5  C  I (B) CH 3  C  Br (C) C 6 H 5  C  Br (D) C 2 H 5  C  Br
| | | |
C2 H5 C2 H5 D CH 3
Q.6 Arrange the following compounds in order of decreasing rate of hydrolysis for SN1 reaction:

(I) CH2–Br (II) H3C CH2–Br

(III) CH3–CH2 CH2–Br (IV) CH CH2–Br

(A) II > III > IV > I (B) IV > III > II > I (C) III > IV > II > I (D) I > II > III > I

Q.7 Which of the following nucleophile will show minimum reactivity towards SN2 reaction:
  
(A) Me 3C O (B) MeO (C) (D) Me 2 CHO

Q.8 In the given reaction

NaOH
 [X]
HOH
25C

(A) (B)

(C) Mixture of (A) and (B) (D)

Q.9 Rate of SN2 reactions depends on:

(A) The nucleophile (B) The carbon skeleton
(C) The leaving group (D) All of these

Q.10 Consider the given reaction:

CH3–CH=CH–CH2–OH HBr
 [P]
SN 1'

In the given reaction the product [P] is :

Br
|
(A) CH3–CH=CH–CH2–Br (B) CH 3  CH  CH  CH 2

Br
|
(C) CH2=CH–CH=CH2 (D) CH 3  CH  CH 2  CH 2  OH
Q.11 For the given reaction
R1 R1
| |
R  C  X HOH
 R  C  OH
| |
R2 R2
Which substrate will give maximum racemisation?
CH 3 CH 3
| |
(A) C 6H 5  C  Br (B) CH 2  CH  C  Br
| |
C2H5 C2 H5

(C) (D)

Q.12 Consider th following four reactions:

(I) (+) C 6 H 5  CH  Cl 95% acetone
   C 6 H 5  CH  OH
| 5% water |
CH 3 CH 3

(II) (+) C 6 H 5  CH  Cl 90% acetone

   C 6 H 5  CH  OH
| 10% water |
CH 3 CH 3

(III) (+) C 6 H 5  CH  Cl 80 % acetone

   C 6 H 5  CH  OH
| 20 % water |
CH 3 CH 3

(IV) (+) C 6 H 5  CH  Cl 100% water

   C 6 H 5  CH  OH
| |
CH 3 CH 3
Arrange these reactions in decreasing order of greater proportion of inverted product and select correct
answer from the codes given below:
(A) I > II > III > IV (B) II > I > III > IV (C) III > II > I > IV (D) IV > III > II > I

Q.13 Which of the following ester will give always SN2 mechanism in acidic as well as basic conditions?
(A) CH3–O–CH3 (B) C6H5–O–CH3 (C) (D) All of these

Q.14 In the given reaction:

 * HOH
CH 3  CH 2  S  CH 2  CH 2  Br  [X]
[X] will be:
* *
(A) CH 3  CH 2  S  CH 2  CH 2  OH (B) CH 3  CH 2  S  CH 2  CH 2  OH
(C) 1 : 1 mixture of (A) and (B) (D) 2 : 1 mixture of (A) and (B)
Q.15 In the given reaction:
( i ) NaN
 3  [X]
( ii ) HOH

[X] will be:

(A) (B)

(C) Mixture of (A) and (B) (D)

Q.16 In the given reaction:

CH OH
 [X]
3

(excess)

(A) (B) (C) (D)

Q.17 In the given reaction

CH 3  CH  CH 2  CH 2  CH  CH 3
| |
OTs OTs

[X]
[X] will be:


OTs S
| |
(A) CH 3  CH  CH 2  CH 2  CH  CH 3 (B) CH 3  CH  CH 2  CH 2  CH  CH 3
| |
S S
 

(C) (D)
Q.18 In the given reaction:
NaCN
CH2–Cl   [X]
S 1 N

[X] will be:

(A) CH2CN (B) (C) NC CH3 (D) (A) and (C)

Q.19 The given compound CH3–O–CH2–Br gives which one of the following reactions:
(A) Only SN1 (B) Only SN2
(C) SN1 as well as SN2 (D) E1

Q.20 Among the bromides I–III given below, the order of reactivity is SN1 reaction is:

(I) (II) (III)

(A) III > I > II (B) III > II > I (C) II > III > I (D) II > I > III
Q.21 Which one is liquid at room temperature:
(A) CH3Cl (B) C2H5Cl (C) CH3Br (D) C2H5Br

Q.22 The correct order of melting and boiling points of the primary (1°), secondary (2°) and tertiary (3°) alkyl
halides is:
(A) P > S > T (B) T > S > P (C) S > T > P (D) T > P > S

Q.23 CCl4 + KOH (excess) end product of the reaction is:

(A) K2CO3 (B) CO2 (C) C (OH)4 (D) HCOOK

Q.24 The yield of alkyl bromide obtained as a result of heating the dry silver salt of carboxyic acid with
bromine if CCl4 is:
(A) 1° > 3° > 2° bromides (B) 1° > 2° > 3° bromides
(C) 3° > 2° > 1° bromides (D) 3° > 1° > 2° bromides

Q.25 Which of the following statements is invalid:

(A) The more stable the carbocation the faster it is formed
(B) Propyl cation changes to more stable isopropyl carbocation by 1,2 shift of a hydrogen
(C) Isopropyl chloride reacts with sodium ethoxide to form 1-ethoxypropane
(D) Propyl halides reacts with sodium ethoxide to form 1-ethoxypropane
Q.26 Nitrochloroform is prepared by the action of chloroform and:
(A) Hot aqueous solution of KNO3 (B) Hot aqueous solution of NaNO2
(C) Hot concentrated nitric acid (D) Hot dilute HCl + aq. NaNO2 solution

Q.27 Which of the following compounds is most rapidly hydrolysed by SN1 mechanism.
(A) C6H5Cl (B) Cl–CH2–CH = CH2
(C) (C6H5)3CCl (D) C6H5CH2Cl
Q.28 Which is incorrect about Hunsdicker reaction?
(A) Only Cl2 can give alkyl halide
(B) I2 will give ester when treated with RCOOAg
(C) The reaction proceeds through free radical
(D) F2 cannot give alkyl halide
Br
Q.29 Major product for the reaction 2  is:
hv

(A) (B)

(C) (D)

 
OH
Q.30  OH

II I

B A
Steps I and II are
(A) I can't be SN1 (B) II can't be SN1 (C) I SN1 & II SN2 (D) I SN2 & II SN1

Q.31 What are A & B in the following reaction?

(i ) CH CHO
Mg
 /
THF
 A  3  B
( ii ) aq. NH 4Cl

(A) & (B) &

(C) & (D) None of these

Q.32 The hydrolysis of alkyl isocyanides (R–CH2–N 

 C) gives
(A) RNHCOOH (B) R  CH  COOH (C) RNH2 + HCOOH (D) RCH2NH2 + HCOOH
|
NH 2
Q.33 What is product of the following reaction?

Mg
 ?
ET O
2

(A) (B) (C) (D) None of these

 S 2
Q.34 + OH– 
 A
N

A is:

(A) (B)

(C) Both (D) None

Q.35 Racemic mixture is obtained due to halogenation of :

(A) n-pentane (B) Isopentane (C) neopentane (D) Both A & B

Q.36 For CH3Br + OH–  CH3OH + Br–

the rate of reaction is given by the expression:
(A) rate = k [CH3Br] (B) rate = k[OH–]
(C) rate = k [CH3Br][OH ] – (D) rate = k[CH3Br]° [OH–]°

Q.37 Which will give white ppt. with AgNO3?

(A) (B) (C) (D) Both A & C

Q.38 The reaction of SOCl2 on alkanols to form alkyl chlorides gives good yields because
(A) Alkyl chlorides are immscible with SOCl2
(B) The other products of the reaction are gaseous and escape out
(C) Alcohol and SOCl2 are soluble in water
(D) The reaction does not occurs via intermediate formation of an alkyl chloro sulphite

Q.39 True about alkyl halides is / are:

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

Q.40 The product formed when glycerol reacts with PCl5 is–
(A) 1,2,3–trichloropropane (B) Glycero monochlorohydrin
(C) Glycero dichlorohydrin (D) All of these

Q.41 On heating glycerol with excess amount to HI, the product formed is–
(A) Allyl iodide (B) Isopropyl iodide (C) Propylene (D) 1,2,3–tri–iodopropane

Q.42 Non-occurence of the following reaction

Br– + CH3OH  BrCH3 + OH–, is due to
(A) Attacking nucleophile is stronger one (B) Leaving group is a strong base
(C) Alcohols are not good substrate (D) Hydroxide ions are weak bases

Q.43 When ethyl bromide is treated with moist Ag2O, main product is:
(A) Ethyl ether (B) Ethanol (C) Ethoxy ethane (D) All of the above
Q.44 When ethyl bromide is treated with dry Ag2O, main product is:
(A) Ethyl ether (B) Ethanol (C) Ethoxy ethane (D) All of the above
 C H O
2 5
Q.45   ? Major product is:
C 2 H 5OH

(A) (B)

(C) (D)

Q.46  ? Product is:

Br 2

(A) (B) (C) both (A) & (B) (D) none of these

alcoholic , KOH
Q.47    
 A
E 2

(A) (B) (C) (D) None is correct

Q.48 A gem dichloride is formed in the reaction except:

(A) CH3CHO and PCl5 (B) CH3COCH3 and PCl5
(C) CH2 = CH2 and Cl2 (D) CH2 = CHCl and HCl

Q.49 Which of the following statement is wrong:

(A) All carbonyl compounds of the general structure CH  C  R give a positive iodoform test
3
||
O
(B) All secondary alcohols give iodoform reaction
(C) Alkanols of the structure CH3CH(OH) – R (where R = H, alkyl or aryl) give iodoform reaction.
(D) The only aldehyde giving iodoform reaction is acetaldehyde.

Q.50 A KOBr
 CHBr3
Here A is nothing but:
(A) Isopropyl alcohol (B) Methanol (C) Ethanoic acid (D) n-Butyl alcohol
Q.51 The appropriate naming for the second step in the haloform reaction is:
(A) Halogenation (B) Dehydrohalogenation
(C) Reduction (D) Dehydrogenation

Q.52 Which product is obtained when bleaching powder is distilled with acetone:
(A) CCl4 (B) CHCl3 (C) CH2Cl2 (D) CH3Cl

Q.53 What will be the reduction product of following reactions:

(A) CH2Cl2, CH3Cl, CH4 (B) CH4, CH3Cl, CH2Cl2

(C) CH3Cl, CH2Cl2, CH4 (D) CH3Cl, CH4, CH2Cl

2 H O
Q.54 Me2 C=CH–CH2 –CH2–Cl 
  (X)
CaCO 3

Major product of above reaction is

OH
|
(A) Me  C  CH 2  CH 2  CH 2 (B) Me2 C=CH–CH2 –CH2 –OH
|
Me

OH
|
(C) Me 2C  CH  CH  CH 2  OH (D) CMe 2
|
OH

Q.55 Addition of bromine on propene in the presence of brine yields a mixture of:
(A) CH3CHClCH2Br and CH3CHBrCH2Cl (B) CH3CHClCH2Br and CH3CHBrCH2Br
(C) CH3CHClCH2Cl and CH3CHBrCH2Br (D) CH2CHClCH2Cl and CH3CHBrCH2Cl

Q.56 is converted into by:

(A) (i) CH3– MgI, H3O+ (ii) H2SO4,  , (iii) HBr, R2O2
(B) (i) CH3– MgI, H3O+ (ii) H2SO4,  , (iii) HBr
(C) (i) CH3– MgI, H3O+ (ii) HBr
(D) (i) HBr, R2O2 (ii) CH3– MgI, H3O+

Q.57 The reactivity of 2-bromo-2-methylbutane (I), 1-bromopentane (II) and 2bromopentane (III) towards
SN2 displacement is such that:
(A) I > II > III (B) I > III > II (C) II > III > I (D) II > I > III
Q.58 Consider the SN1 solvolysis of the following halides in aqueous formic acid:
Br
|
(I) CH  CH  CH 3 (II)

(III) C 6 H 5  CH  C 6 H 5 (IV)
|
Br
Which one of the following is correct sequence of the halides given above in the decreasing order oftheir
reactivity?
(A) III > IV > II > I (B) II > IV > I > III (C) I > II > III > IV (D) III > I > II > IV

Q.59 Arrange the following compounds in decreasing order of their reactivity for hydrolysis reaction

(I) C6H5–CH–Br (II) C 6 H 5  CH  C 2 H 5 (III) (IV)

|
Br
(A) I > II > III > IV (B) IV > II > I > III (C) III > IV > II > I (D) IV > III > II > I

Q.60 KSH


(A) (B) (C) (D)

 EXERCISE–I (B)
(Choose the correct option. One or more than one are correct)

Q.1 Consider the following statements?

(A) CH3–CH2–CH2–I will react more readily than (CH3)2 CHI for SN2 reactions.
(B) CH3–CH2–CH2–Cl will react more readily than CH3–CH2–CH2–Br for SN2 reaction.
(C) CH3–CH2–CH2–CH2–Br will react more readily than (CH3)3C–CH2–Br for SN2 reactions
(D) CH3–O–C6H5–Br will react more readily than NO2–C6H5–CH2Br for SN2 reaction

Q.2 A solution of (R)-2-iodobutane, [] = –15.9° in acetone is treated with radioactive iodied, until 1.0% of
iodobutane contain radioactive iodine, the specific rotation of recovered iodobutane is found to be
–15.58°, which statement is correct about above information.
(A) It has optical purity 96% (B) % of R in solution is 99%
(C) Racemic mixture is 2% (D) Final solution is dextrorotatory

Q.3 Which are possible products in following

moist Ag O
2
 
 

(A) (B) (C) (D)

Q.4 In which product formation takes place according to Hoffmann's rule

 
B u O K CH CH O K
(A) CH 3CH 2  CH  CH 3 t  (B) CH 3CH 2  CH  CH 3 3 2

 
| |
Br Br

 
OH
(C) 
 (D) CH 3CH 2CH  CH 3 O
H

 
|

S(CH 3 ) 2

Br , hv
Q.5 2 

CH 3 CH 3
| |
(A) CH 3  CH  CH 2 Br (B) CH 3  CBr  CH 3

Br
|
(C) CH3CH2CH2Br (D) CH 3  CH  CH 3
Q.6 Select the correct statements from following
(A) CH3CH2CH2I will react more readily than (CH3)2CHI for S
N2

(B) CH3CH2CH2Cl will react more readily than CH3CH2CH2Br for S

N2

(C) CH3CH2CH2CH2Br will react more readily than (CH3)2CH–CH2Br for S

N2

(D) CH3–O–C6H4–CH2Br will react more readily than NO2–C6H4–CH2Br for S

N2

Q.7 Which of the following will react with AcOAg

(A) R–NH2 (B) R–OTs (C) R–N3 (D) R–Br

Q.8 Consider the given reaction

CH 3
|
H  C  OTs NaCN
 CH 3CH 2CH  CN
|
C2 H 5 (S) |
CH 3
which of following statements are correct for above reaction.
(A) Product formation takes place due to the breaking of O–Ts
(B) The reaction is S 2
N

(C) The reaction is S

N1
(D) Configuration of product is (R)

Q.9 Benzoyl chloride is less reactive than acetyl chloride for nucleophilic acyl substitution reaction because
O
||
(A)  C  group of benzoyl chloride is in conjugation with benzene ring. This makes benzoyl chloride
more stable than acylchloride.
(B) CH3– group of acetyl chloride make C–Cl bond stronger due to the +I effect.
(C) C6H5– group of benzoyl chloride make C–Cl bond weaker due to +R effect.
(D) Carbonyl carbon in benzoyl chloride is less electron deficient than acetyl chloride

Q.10 Bromination can take place at

NBS
 / hv

CCl 4

(A) 1 (B) 5 (C) 3 (D) 4

Q.11 Which of following will give syn-elimination
(A) CH3CH2CH2–OCOCH3 (B) CH 3CH 2CH  CH 3
|
Cl

CH 3
| 
(C) CH 3CH 2CH 2  O  C  S  CH 3 (D) CH 3CH 2CH 2 N  O
|| |
S CH 3

Q.12 Which of following are correct for given reaction




(A) Major product of reaction is

(B) Major product is

(C) The reaction is thermal elimination reaction

(D) The reaction is E2 reaction

Q.13 Haloform reaction is given by

(A) All 2° alcohol (B) All methyl ketones
(C) All the compounds having CH 3  C  group (D) Chloral
||
O
Q.14 Identify the compounds that will undergo NGP reaction
(A) CH3CH2–S–CH2CH2Br (B) CH3–NHCH2CH2CH2Br
(C) CH 3  CH  C  O (D) CH3–O–CH2CH2CH2Br
| |
Br O

Q.15 Which alkyl halide undergo E2 elimination

(A) (B)

(C) (D)
Q.16 3-Phenyl-3-pentanol can be prepared from grignard reagent & other component which can be
(A) 3-pentanone (B) Ethylbenzoate (C) Ethyl phenyl ketone (D) Propanoyl chloride

Q.17 Rate of SN2 will be negligible in

(A) (B) (C) (D)

Q.18 SN1 & SN2 is not favourable in

(A) H2C = CH–Cl (B) Ph–CH2–Cl (C) Ph–Cl (D) H2C=CH–CH2–Cl

Q.19 SN1 & SN2 product are same in (excluding stereoisomer)

(A) (B) (C) (D) Ph  CH  CH  CH 3

| |
CH 3 Cl

Q.20 Rate of SN2 depends on

(A) Conc of Nucleophile (B) Conc of substrate
(C) Nature of leaving group (D) Nature of solvent

Q.21 G NaOI
 yellow solid
G can be
(A) CH 3  C  OCH 3 (B) CH 3  C  CH 2  C  CH 3
|| || ||
O O O

(C) CD3COH (D)

Q.22 Match the List I (reaction) with List II (reaction intermediate) and select the correct answer using the
codes given below the Lists.
List I List II
(A) CF3–CHCl2 alc /
.KOH
  CF2 = CCl2 (1) Transition state

CH 3
| 
(B) CH 3  C  OH H
 CH 3  C  CH 2 (2) Carbocation
| |
CH 3 CH 3
alc.KOH
(C) CH3–CH2–Br  CH2=CH2 (3) Carbanion


Br
|
(D) CH 3  C  CH 3 aq
. KOH
 /
  CH 3  C  CH 2 (4) Free radical
| |
CH 3 CH 3
Q.23 Match the List I with List II and select the correct answer using the codes given below the Lists.
List I List II
(A) E1CB (1) 3° Amine oxide
(B) Saytzeff alkene as major product (2) Xanthate
Cl
|
(C) E2 (3) CH 3  CH 2  CH  CH 3

C 6 H 5  CH 2  CH  CH 3
(D) Ei (4) |
Q.24 Match List I with List II and select the correct answer from the codes given below: F
List I List II

(A) CH3–O–SO2CH3 + C 2 H 5 O (1) CH3–CH2–PH2
(B) CH3–CH2–I + PH3 (2) CH3–O–C2H5
 
(C) HC  C Na + CH3–CH2–Br (3) CH3 –O–CH3

(D) CH3–Cl + CH3– O (4) CHC–CH2 –CH3
Q.25 Match List-I with List-II for given S reaction & select the correct answer from the codes given below
N2

Z–CH2Br + CH3 O  Z–CH2–OCH3 + Br
List-I List-II
(A) H– (P) 0.1
(B) CH3– (Q) 3
(C) C2H5– (R) 1

(D) (S) 100

Q.26 Match the following

List-I List-II


CH CH O
(A) 3 
2
 (P) E1



CH 3CH 2 O
(B)   
 (Q) E2
CH 3CH 2OD

Ag O
2
(C)   (R) E1cb
moist

(D) alc
. KOH
 (S) Ei
 EXERCISE–II
Q.1 Explain the following giving proper resoning :
(i) Treatment of 1,1-dimethyl oxirane with sodium methoxide in methanol gives primarily one product. Also
identify the product giving its IUPAC name
(ii) Optically active 2-iodo butane on treatment with NaI*/Acetone gives a product which do not show
optical activity.
(iii) In the solvent DM SO the order of reactivity of halide ions with methyl bromide is F— > Cl— > Br— > I—
opposite to that observed in methanol solution.
(a) (n - C3H7)3N + CH3I  (n – C3H7)3NCH3+ I—
Relative rate : in hexane, 1 ; in chloroform, 13000
(b) Br— + CH3OTs  CH3Br + TsO—
Relative rates : in methanol, 1; in HMPT, 105.
(iv) Although ethers are weakly polar, are used as solvent of choice for Grignard reagents.
(v) Treatment of either CH3– –CH2 Br or CH3– CH – with aqueous HO— gives the
|
Br
same product. Also write down mechanism involved, & IUPAC name of product.
Q.2 On reaction between an alkyl halide and KOH in a mixture of water and ethanol, compare the two
mechanisms SN1 and SN2 :
(a) relative rates of CH3X, C2H5X, iso-C3H7X & tert-C4H9X
(b) relative rates for RCl, RBr and RI
(c) effect on rate of a rise in temperature
(d) effect on rate of increasing water content of the solvent.
(e) effect on rate increasing alcohol content of the solvent.
Q.3 In the following reaction is carried out in the weakly ionizing solvent, acetone (CH3)2C=O. (Bs is brosyl,
p-bromo benzene sulfonyl)
n-C4H9OBs + X—  n-C4H9X + BsO—
The order of reactivity of halide ions depends or the salt used on their source :
if Li+X— is used, I— > Br— > Cl—
if (n-C4H9)4N+ X— is used Cl— > Br— > I—
How do you account for this contrast in behavior ?
Q.4 Which of the following is the correct method for synthesizing 4,4-dimethyl-pent-2-yne, using sodamide
in liquid NH3? Given reasons.

CH 3 CH 3
| |
(i) CH3CCH + CH 3  C  Br  (ii) CH 3  C  C  CH + CH3I 
| |
CH 3 CH 3
Q.5 Give the products and find all unknowns.
(a) H2N CH2 CH2 CH2 CH2 Br  


(b) TsCl
 A NaBr
 B
Pyridine

C
Q.6 Find out the unknown alphabets.


(a) + CH3CH2MgBr (1 eq) H
3O
 A


(b) H
3O
 B

(2 eq)
O
|| 
(c) H– C –OEt + CH3CH2MgBr H C
3O

(2 eq)

(d) H D
3O

(1 eq.)

(e) HCl
 E

C2 H5
|
Q.7 To prepare   C  C 2H 5 by RMgX which is the incorrect pair
|
OH
(a) MgBr + (C2H5)2CO H 2O
 

(b) C2H5MgBr + H

2O


(c) C2H5MgBr + –COOCH3 H

2O


(d) MgBr + C2H5COOCH3 H

2O


Q.8 alc
 .
(A) CHBr
 3
 (B)
KOH – 
t  BuO K

Cl
|
Q.9 CH 3  CH  CH  CH 2  Cl convert ?
|
CH 3
Q.10 What is/are the limitation in the formation of Grignard reagent by RX + Mg dry
ether


(a) R should not contain any acidic group
(b) R should not contain any electronegative group
(c) Alkyl halide should not be vicinal dihalide
(d) Alkyl halide can't be Tertiary.
Q.11 Write major product of the the following reactions:
EtOH
(i) ClCH2CH2CH2Br + KCN  A

SF
(ii) 4 B
PhCHO 
AgF
(iii) BrCH2CH = CHCO2Me  C
DMF
(iv) EtOH + HI  D
(v) EtOH + HCN  E

Q.12 CH3–CH2I reacts more rapidly with strong base in comparison to CD3CH2I

Q.13 2-chloro-3-methylbutane on treatment with alcohoilc potash gives 2-methylbutene-2 as major product.

Q.14 Iodoform gives precipitate with AgNO3 on heating while CHCl3 does not.

Q.15 Hydrogen atom of chloroform is definately acidic, but that of methane is not.

Q.16 A small amount of alcohol is added to chloroform bottles.

Q.17 Iodine reacts with alcohols to give alkyl iodine only in presence of phosphorous.

Q.18 KCN reacts with R – I to give alkyl cyanide, while AgCN results in isocyanide as major product.

Q.19 Dry gaseous hydro halogen acid and not their aqueous solutions are used to prepare alkyl halides from
alkenes.

Q.20 RCl is hydrolysed to ROH slowly but reaction fastens on addition of KI.

Q.21 The mechanism of decomposition of M e3 S+ OH– is SN2 whereas of Me3S+ I– is SN1.

Q.22 Alkaline hydrolysis of benzyl chloride in 50% aqueous acetone proceeds by both SN2 and SN1 mechanism,
when water is used as solvent, mechanism was now mainly SN1.

Q.23 Anhydrous AlCl3 is used as a catalyst in friedel crafts alkylation.

Q.24 Arrange following compounds according to their reactivity with alc silver nitrate.
t-Butyl chloride, sec butyl chloride and CCl4.
Q.25

(a)
(b)

What are (A) and (B) explain giving their stereochemistry.

Q.26 Complete the following by providing (A), (B), (C) and (D):
Alc.KOH HBr NH 3
(i) CH3CH2CH2OH PBr
3  (A)   (B)  (C)  (D)


H / H 2O SOCl H
(ii) CH3CH2CH2I Alc
. KOH
 (A)    (B) 2  (C)  (D)
LiAlH 4

Alc.KOH HBr
(iii) CH3CH2CH = CH2 NBS
 (A)   (B)  (C)
Light

HBr Alc.KOH
(iv) CH3CH2MgBr CH CHO / H 2O
3    (A)  (B)   (C)

Q.27 Carry out following conversions.

Cl
|
(a) CH 3  CH  CH 3 — CH3–CH2–CH2–Cl without using peroxide

(b) CH3–CH2–CH2–Cl — CH 3  CH  CH 3 in single step

|
Cl

(c) — in three steps only

(d) — in three steps only

O
||
(e) Ph  CH 2  C  Cl — Ph – CH2 – Cl

O
||
(f) Ph – CH2 – Cl — Ph  CH 2  C  Cl
 EXERCISE–III

Q.1 A primary alkyl halide (X) C4H9Br reacted with alcoholic KOH to give (Y). (Y) reacts with HBr to give
(Z) an isomer of (X). On reacting with alkali metal such as sodium/dry ether gives (S) C8H18 which was
different from the compound produced when n-butylbromide was treated with Na. What (X), (Y), (Z)
and (S).

Q.2 On electrolysis an aqueous ethanoilc solution of sodium chloride gives sweet smelling liquid (X). (X)
gives isocyanide test and condenses with acetone to from hypnotic (Y). What are (X) and (Y)?

Q.3 The alkyl halide C4H9Br (A) reacts with alcoholic KOH and gives an alkene (B), which reacts with
bromide to give dibromide (C). (C) is transformed with KOH & sodamide to gas (D) which forms a
precipitate when passed through an ammonical silver nitrate solution. Give the structure formulae of the
compounds (A), (B), (C) and (D) and explain reactions involved.

Q.4 An unsaturated hydrocarbon (A) C6H10 readily gives (B) on treatment with NaNH2 in liquid NH3.
When (B) is allowed to react with 1-chloropropane, a compound (C) is obtained. On partial hydrogenation
in the presence of Lindlar catalyst, (C) gives (D), C9H18. On ozonolysis (D) gives 2, 2-dimethylpropanal
and 1-butanal. Give structures of (A), (B), (C) and (D) with proper reasoning.

Q.5 One mole of each bromoderivative (A) and NH3 react to give one mole of an organic compound (B).
(B) reacts with CH3I to give (C). Both (B) and (C) react with HNO2 to give compounds (D) and (E),
respectively. (D) on oxidation and subsequent decarboxylation gives 2 -methoxy-2-methylpropane.
Give structures of (A) to (E) with proper reasoning.

Q.6 A chloro derivative (A) on treatment with zinc-copper couple gives a hydrcarbon with five carbon
atoms. When 'A' is dissolved in either and treated with sodium, 2,2,5,5-tetramethylhexane is obtained.
What is the original compound 'A'?

Q.7 A primary alkyl halide (A) C4H9Br reacted with alcoholic KOH to give (B). (B) reacts with HBr to give
(C) an isomers of (A). (A) on reacting with sodium gives (D) C8H18 which was different from the
compound produced when n-butylbromide was treated with Na.What are (A), (B), (C) and (D).

Q.8 One mole of a hydrocarbon (A) reacts with 1 mole of bromine giving a dibromo compound C5H10Br2.
(A) on treatment with cold dilute alkaline KMnO4 solution forms a compound C5H12O2. on ozonolysis
(A) gives edquimolar quantities of propanone and ethanal. Deduce structure of (A).

Q.9 A hydrocarbon (A) was found to contain 85.7% carbon and 14.3% H. This compound consumes 1
molar equivalent of hydrogen to give a saturated hydrocarbon. 1 g of (A) just decolourised 38.05 of 5 %
solution by weight of Br2 in CCl4. Compound (A) on oxidation with conc. KMnO4 gave a compound
(C), C4H8O and (B) acetic acid. Compound (C) can easily be prepared by the action of acidic aqueous
mercuric sulphate on 2-butyne. Deduce (A), (B) and (C).

Q.10 When a hydrocarbon (A) is treated with excess of hydrogen chloride, a dihalogen derivative (B) is
obtained. The compound (B) is treated separately with aqueous and alcoholic KOH to give compounds
(C) and (A) respectively both having three carbon atoms. Compound (C) does not reduce Tollen's
reagent and compound (A) give white precipitate with ammonical silver nitrate. Assign structures to
compounds (A) to (C).
Q.11 An organic compound (A) C7H15Cl on treatment with alcoholic caustic potash gives a hydrocarbon (B)
C7H14. (B) on treatment with ozone and subsequent hydrolysis gives acetone and butyraldehyde. What
are (A) and (B). Explain reactions.

Q.12 A dihalogen derivative (A) of a hydrocarbon having two carbon atoms react with alcoholic potash and
forms another hydrocarbon which gives a red precipitate with ammonical cuprous chloride. Compound
(A) gives an aldehyde when treated with KOH (aq). What is (A)?

Q.13 A white precipitate was formed slowly when AgNO3 was added to a compound (A) with molecular
formula C6H13Cl. Compound (A) on treatment with hot alcoholic KOH gave a mixture of two isomeric
alkenes (B) and (C) having formula C6H12. The mixture of (B) and (C) on ozonolysis furnished four
compounds (i) CH3CHO, (ii) C2H5CHO, (iii) CH3COCH3, (iv) (CH3)2CH.CHO
What are (A), (B) and (C).

Q.14 0.369 g of a bromo derivative of a hydrocarbon (A) when vaporized occupied 67.2 mL at NTP. (A) on
reaction with aqueous NaOH gives (B). (B) when passed over alumina at 250° C gives a neutral compound
(C) while at 350°C it gives a hydrocarbon (D). (D) when heated with HBr gives an isomer of (A). When
(D) is treated with dil. H2SO4 , (E) is obtained. Identify (A) to (E) and explain the reactions.

Q.15 An organic compound (X) on analysis gives 24.24 % C, 4.04% H. Further sodium extract of 1.0 g of
(X) gives 2.90 g of AgCl with acidified AgNO3 solution. The compound (X) may be represent by two
isomeric structures (Y) and (Z). (Y) on treatment with aqueous KOH solution gives a dihydroxy compound,
while (Z) on similar treatment gives ethanal. Find out (X), (Y) and (Z).

Q.16 A chloro compound (A) showed the following properties :

(i) Decolourized bromine in CCl4
(ii) Absorbed hydrogen catalytically.
(iii) Gave a precipitate with ammonical cuprous chloride
(iv) When vaporised 1.49 g of (A) gave 448 mL of vapours at STP.
Identify (A) and write down the equations of reactions.
 EXERCISE–IV (A)

Q.1 Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH gives
(A) o-cresol (B) p-cresol
(C) 2,4-dihydroxytoluene (D) Benzoic acid [IIT 1990]

Q.2 Aryl halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halides due to
(A) The formation of less stable carbonium ion (B) Resonance stabilization
(C) The inductive effect (D) sp2 hybridised carbon attached to the halogen
[IIT 1990]
Q.3 1-Chlorobutane on reaction with alcoholic potash gives:
(A) 1-butene (B) 1-butanol (C) 2-butene (D) 2-butanol [ITT 1991]

Q.4 The products of reaction of alcoholic AgNO2 with ethyl bromide are [IIT 1991]
(A) Ethane (B) Ethyl nitrite (C) Nitroethane (D) Ethyl alcohol

Q.5 When nitrobenzene is treated with Br2 in presence of FeBr3 the major product formed is:
m-bromonitrobenzene. Statements which are related obtain the m-isomer are
(A) The electron density on meta carbon is more than on ortho and para position
(B) The intermediate carbonium ion formed after initial attack of Br+ at the meta position is least
destabilized.
(C) Loss of aromaticity when Br+ attacks at the ortho and para position and not at meta position
(D) Easier loss of H+ to regain aromaticity from the meta position than from otho and para positions.
[IIT 1992]

Q.6 Arrange the following compounds in order of increasing dipole moment

Toluene m-dichlorobenzene o-dichlorobenzene p-dichlorobenzene
I II III IV
(A) I < IV < II < III (B) IV < I < II < III (C) IV < I < III < II (D) IV < II < I < III
[IIT 1996]
Q.7 In the reaction of p-chloro toluene with KNH2 in liq. NH3, the major product is:
(A) o-toluidine (B) m-toluidine (C) p-toluidine (D) p-chloraniline
[IIT 1997]
Q.8 (CH3)3CMgCl reaction with D2O produces:
(A) (CH3)3CD (B) (CH3)3OD (C) (CD3)3CD (D) (CH3)3OD [IIT 1997]

Q.9 Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with:
(A) SO2Cl2 (B) SOCl2 (C) Cl2 (D) NaOCl [IIT 1998]

Q.10 Toluene, when treated with Br2/ Fe, gives p-bromotoluene as the major product, because the CH3
group [IIT 1999]
(A) is para directing (B) is meta directing
(C) activates the ring by hyperconjugation (D) deactivates the ring

Q.11 The order of reactivity of the following alkyl halides for a SN2 reaction is: [IIT 2000]
(A) RF > RC > R–Br > R–I (B) R–F > R–Br > R–Cl > R–I
(C) R–Cl > R–Br > RF > RI (D) R–I > RBr > R–Cl > R–F
Q.12 Identify the set of reagents / reaction conditions 'X' and 'Y' in the following set of transformation:
X
CH3 – CH2 – CH2Br  Y
Product  CH 3  CH  CH 3
|
Br
(A) X = dilute aqueous NaOH, 20°C; Y = HBr / acetic acid, 20°C
(B) X = concentrated alcoholic NaOH, 80°C; Y = HBr/ acetic acid 20°C
(C) X = dilute aqueous NaOH, 20°C; Y = Br2 / CHCl3, 0°C
(D) X = concentrated alcoholic NaOH, 80°C; Y = Br2/CHCl3, 0°C [IIT 2002]

Q.13 CH3MgBr + Ethyl ester  which can be formed as product. [IIT 2003]
(excess)

(A) (B)

(C) (D)

Q.14 Match the following:

Column I Column II
(A) CH3–CHBr–CD3 on treatment with alc. KOH gives (P) E1 reaction
CH2=CH-CD3 as a major product.
(B) Ph – CHBr - CH3 reacts faster than Ph-CHBr-CD3. (Q) E2 reaction
(C) Ph-CD2-CH2Br on treatment with C2H5OD/C2H5O– (R) E1cb reaction
gives Ph-CD=CH2 as the major product.
(D) PhCH2CH2Br and PhCD2CH2Br react with same rate. (S) First order reaction

EXERCISE–IV (B)
Q.1 Fill in the blanks:
(a) Butan nitrile can be prepared by heating _____with alcohalic KCN. [IIT 1992]

(b) Amongst three isomers of nitrophenol, the one that is least soluble in water is_____ [IIT 1992]

Q.2 Identify the major product in the following reactions : [IIT 1993]
Cl
| alcoholic
(i) C 6 H 5  CH 2  CH  CH 3    ? HBr
 ?
KOH 
(ii) C6H5COOH + CH3MgI  ? + ?

Q.3 An alkyl halide X of formula C6H13Cl on treatment with potassium tertiary butoxide gives two isomeric
alkenes Y and Z (C6H12). Both alkenes on hydrogenation give 2,3–dimethylbutane. Predict the structures
of X, Y and Z. [IIT 1996]
Q.4 Predict the structure of the intermediates/products in the following reaction sequence – [IIT 1996]

NaI

 C
Acetone

Q.5
C6 H5
| Alcohalic KOH
(a) C6 H 5CH 2CHCl     A + BWrite structures of (A) and (B).
Heat

(b) (CH 3)2CHOCH3 HI

(excess
 )  A + B Write structures of A and B. [IIT 1998]
Heat

Q.6 Complete the following reaction with appropriate structures of products/reagents. [IIT 1998]

Br2 ( i ) NaNH ( 3 equi .)

 (A)   2  
  (B)
( II ) CH 3I

Q.7 What would be major product? [IIT 2000]

CH 3
|
CH 3  C  CH 2 Br C
2 H 5OH
 ?
| 
CH 3
Q.8 How would you synthesis 4 methoxyphenol from bromobenzene in NOT more than five steps? State
clearly the reagents used in each step and show the structures of the intermediate compounds in your
synthetic scheme. [IIT 2001]

Q.9 Give major products A, B, C and D in following reaction sequence. [IIT 2004]


KCN
 (A) (
i ) NaOEt / EtOH H O
   (B) 3  (C)
DMF (ii ) PhCHO / 

(D)
 ANSWER KEY
EXERCISE–I (A)
Q.1 A Q.2 A Q.3 B Q.4 B Q.5 C Q.6 A Q.7 A
Q.8 D Q.9 D Q.10 B Q.11 C Q.12 D Q.13 D Q.14 C
Q.15 C Q.16 A Q.17 C Q.18 D Q.19 C Q.20 A Q.21 D
Q.22 A Q.23 A Q.24 B Q.25 C Q.26 C Q.27 C Q.28 A
Q.29 D Q.30 C Q.31 B Q.32 D Q.33 C Q.34 B Q.35 D
Q.36 C Q.37 D Q.38 B Q.39 B Q.40 A Q.41 B Q.42 B
Q.43 B Q.44 C Q.45 C Q.46 A Q.47 A Q.48 C Q.49 B
Q.50 A Q.51 A Q.52 B Q.53 A Q.54 D Q.55 B Q.56 A
Q.57 C Q.58 A Q.59 B Q.60 D

EXERCISE–I (B)
Q.1 A,C Q.2 B,C Q.3 A,B Q.4 A,C,D
Q.5 B Q.6 A,D Q.7 B,C,D Q.8 B,D
Q.9 A,D Q.10 A,B,C,D Q.11 A,C,D Q.12 A,C
Q.13 B,D Q.14 A,B,C,D Q.15 A,B Q.16 A,B,C
Q.17 A,B,C Q.18 A,C Q.19 B,C Q.20 A,B,C,D
Q.21 B,C,D Q.22 A  3, B  ,C  1,D  2
Q.23 A  4, B  3,4, C  3, D  1,2 Q.24 A  2, B  1, C  4, D  3
Q.25 (A) – S; (B) – Q; (C) – R; (D) – P Q.26 (A) – Q; (B) – R ; (C) – P; (D) – Q

EXERCISE–II
CH 3 O  CH 3
| |
Q.1 (i) CH 3  CH  CH 2 attack take place on less sterically carbon
|
OH
Q.4 (ii)

Q.5 (a)

(b) (A) , (B) , (C)

OH
|
Q.6 (a) (b) (c) Et  CH  Et (d)

(e)

Q.7 (d) Q.8 A B

Q.9 A CH 3  CH  CH  CH 2 B C  C  C  C  Cl
| |
CH 3 C
Conversion (1) NaNH2 (2) H2/Pd BaSO4
Q.10 (a) & (c)
Q.11 The mechanism of
(i) ClCH2CH2 CH2CN (ii) PhCHF2
(iii) FCH2CH = CHCO2Me (iv) EtI
(v) no reaction
Q.12 The elimination of HI (or DI) in presence of strong base shows E2 elimination. The rate determining step
involves breaking up of C – H (or C–D) bond. the C–D bond being stronger than C–H and thus
elimination is faster in case of CH3 – CH2I.
Q.13 H 3C  CH  CH  CH 3 KOH
 ( alc
) CH 3  C  CH  CH 3  CH 3  CH  CH  CH 2
| | | |
CH 3 Cl CH 3 CH 3
major min or
Elinination occurs according to saytzeff rule. The major product is one which involves elimination of H
from less hydrogenated carbon.
Q.14 C–I bond being less stable than C–Cl bond and thus on heating heterolytic cleavage of C –I form I–
which gives yellow precipitate with AgNO3
Q.15 Due to three electronegative chlorine atoms present on carbon, the latter acquires a partial positive
charge due to –I effect of chlorine with the result it tends to attract electrons of the C–H bond towards
itself. Hence the removal of hydrogen atom as proton becomes easier.
Q.16 Alcohol acts as negative catalyst for oxidation of chloroform. Also it reacts with COCl2 to give harmless
diethyl carbonate.
Q.17 Phosphorus reacts with I2 to give PI3 which replaces OH group of alcohol to produce R – I
2P + 3I2  2 PI3
3R OH + PI3  3RI + H3PO3
Q.18 KCN is an ionic compound [K+(:C N:)–] in which both C and N carry a lone pair electron. Carbon carrying
lone pair of electrons is more reactive and thus alkyl attacks carbon to give alkyl cyanide AgCN being covalent
has Ag– CN : structure with lone pair on N thus R attacks N atom and R–N   C is formed.
Q.19 Dry gaseous hydro halogen acids are better electrophile. Also in aqueous solution H2O acting as nucleophile
may produce alcohol.
Q.20 KI reacts with RCl to form RI. This RI molecule now hydrolysed easily to give ROH because alkyl
iodide are more reactive than alkyl chloride.
RCl + KI  RI HOH  ROH (more fast)
Q.21 The more pronounced the nucleophilic activity of the attacking reagent, then the more the SN2 mechasnism
will be favoured. Since in SN1 mechanism the raegent doesnot enter into the rate determining step of
ionisation How ever it can also be expected that as the nucleophilic activtiy is so slow that the mechanism
will change from SN2 to SN1
Q.22 The dielectric constant of water is greater than that of aqueous acetone, and so ionisation of benzyl
chloride is facilitated.
Q.23 Anhydrous AlCl3 is used as a catalyst in friedel crafts alkylation
Q.24 tert-Butyl chloride, sec butyl chloride and CCl4 with alc. silver nitrate

Me3C – Cl > CHCl > CCl4

Q.25(a) A  B C D

E F G H I

(b) (A) , (B)

Q.26 (i)A, CH3CH2CH2Br ; B, CH3CH = CH2 ; C, CH3CHBrCH3; D, CH3CHNH2CH3

(ii) A, CH3CH = CH2; B, CH3CHOHCH3; C, CH3CHClCH3; D, CH3CH2CH2
(iii) A, CH3CHBrCH = CH2; B, CH2=CH–CH=CH2; C, CH3CHBrCH=CH2& CH3CH = CH–CH2Br
(iv) A, CH3CH2CHOHCH3; B, CH3CH2CHBrCH3; C, CH3CH = CH – CH3

EXERCISE–III
Br
|
Q.1 CH 3  CH  CH 2  Cl CH 3  C  CH 2 CH 3  C  CH 3
| | |
CH 3 CH 3 CH 3
( X) ( Y) 2  Bromo  2  methyl propane
( Z) (isomer of X )

(CH3)2CH – CH2–CH2–CH (CH3)2

(2,5 – dimethyl Hexane)
(S)

Q.2 (Y)

Q.3 CH3CH2CH2CH2Br CH3CH2CH = CH2 CH 3  CH 2  CH  CH 2

| |
Br Br
(A) (B) (C)

CH3– CH2– C  CH
(D)

Q.4 (CH3)3C – C  CH (CH3)3C – C C–Na+ (CH3)3C – C  CH2CH2CH3

(A) (B) (C)

(CH3)3C – CH = CHCH2CH2CH3
(D)
 OCH 3 OCH 3
| |
Q.5 CH 3  C(CH 3 )  CH 2  CH 2  Br CH 3  C(CH 3 )  CH 2  CH 2 NH 2
(A) (B)
OCH 3 OCH 3
| |
CH 3  C(CH 3 )  CH 2CH 2  NHCH 3 CH 3  C(CH 3 )  CH 2 CH 2  OH
(C) (D)
OCH 3
|
CH 3  CH  CH 2  CH 2  N  N  O
|
CH 3
(E)
Q.6 (CH3)3C – CH2Cl

CH 3 CH 3 CH 3
| | |
Q.7 CH 3  CH  CH 2 Br CH 3  C  CH H 3C  C  CH 3
|
Br
(A) (B) (C)
CH 3 CH 3
| |
CH 3  CH  CH 2CH 2  CH  CH 3
(D)

Q.8

Q.9 C = CH – CH3 CH3 –COOH C=O

(A) (B) (C)

Cl O
| ||
Q.10 CH3– C  CH CH 3  C  CH 3 CH 3  C  CH 3
|
Cl
(A) (B) (C)
 CH 3
|
Q.11 CH 3  (CH 2 )3 C  Cl CH3(CH2)2CH = C (CH3)3
|
CH 3
(A) (B)

Q.12 H3C – CHX2 ( X = Halogen)

Q.13 A (CH 3 ) 2 CH  CHCH 2CH 3 (CH3)2CH CH = CH CH3 C=C

|
Br
(A) (B) (C)
Q.14 (A) CH3CH2CH2Br , (B) CH3CH2CH2OH, (C) CH3CH2CH2OCH2CH2CH3, (D) CH3–CH=CH2,
(E) CH3CH(OH)CH3

Q.15 (X) C2H4Cl2, (Y) Cl – CH2CH2 – Cl, (Z) CH3CH

Q.16 HC C–CH2– Cl

EXERCISE–IV (A)

Q.1 D Q.2 B,D Q.3 A Q.4 C Q.5 A,B Q.6 B Q.7 B

Q.8 A Q.9 A,C Q.10 A,C Q.11 D Q.12 B Q.13 D
Q.14 A – Q; B – Q; C – R,S; D – P,S

EXERCISE–IV (B)
Q.1 (a) propyl chloride, (b) ortho

Br
|
Q.2 (i) C 6 H 5  CH  CH  CH 3 ; C 6 H 5  CH  CH 2  CH 3
(ii) C6H5COOMgI + CH4
CH 3 CH 3 CH 3 CH 3
| | | |
Q.3 (X): CH 3  C — CH  CH 3 ; (Y) : CH 2  C — CH  CH 3 ; (Z) : CH 3  C — CH  CH 3
| | |
Cl CH 3 CH 3

Q.4 (NGP due to MeO, so retention of configuration)

Q.5 (a) Cis and trans forms of stibene C6H5CH=CHC6H5 ; (b)

Q.6 (A) NaNH ( liq .) CH 3I

 2   (B)

CH 3
|
Q.7 CH 3  C  CHCH 3

NaOH
  
 conc . H SO H O
Q.8  high pressure Me 2SO 4  24  NaOH
 3
 

Alternative rout

H O
conc . H SO
 24  NaOH
 
 NaOH
  3
 
Me 2SO 4  high pressure

Q.9 (A) ; (B) ; (C) ; (D)