54

HYDROCARBONS

EXERCISE-2 (Objective Questions)

[SINGLE CORRECT CHOICE TYPE]

Q.1 HI
 P (Major Product)
P is
I
(A) I (B) (C) (D)
I I
Q.2 Anti–Markownikoff’s addition of HBr is not observed in –
(A) Propene (B) But–2–ene (C) Butene (D) Pent–2–ene

Q.3 For the ionic reaction of hydrochloric acid with the following alkenes, predict the correct sequence of
reactivity as measured by reaction rates:
(I) ClCH=CH2 (II) (CH3)2.C=CH2 (III) OHC.CH=CH2 (IV) (NC)2C=C(CN)2
(A) IV > I > III > II (B) I > IV > II > III (C) III > II > IV > I (D) II > I > III > IV

Q.4 H Br Product (Major)

Conc . H 2SO 4 Na / ether
     
H 2O 2

(A) (B)

(C) (D)

Q.5 Which is expected to react most readily with bromine –

(A) CH3CH2CH3 (B) CH2=CH2 (C) CHCH (D) CH3–CH=CH2

Q.6 Ethylene forms ethylene chlorohydrin by the action of –

(A) Dry HCl gas (B) Dry chlorine gas
(C) Solution of chlorine gas in water (D) Dilute hydrochloric acid

O
||
Q.7 Alkene A O  CH 3  C  CH 3 + CH3COOH + CH 3  C  COOH
3 / H 2O

||
O
A can be –
C(CH 3 ) 2
||
(A) (B) CH 3  C  CH  HC  CH 3
(C) Both correct (D) None is correct
 55

HYDROCARBONS

Q.8 Ozonolysis of CH3–CH=C=CH2 will give

(A) Only CH3CHO (B) Only HCHO
(C) Only CO2 (D) Mixture of CH3CHO, HCHO & CO2

Q.9 O-xylene on ozonolysis will give

O CH 3  C  O O
CHO || ||
(A) | & CH 3  C  CHO (B) | & CH 3  C  CHO
CHO CH 3  C  O

CH 3  C  O O
CH 3  C  O CHO || CHO
(C) | & | (D) | , CH 3  C  CHO & |
CH 3  C  O CHO CH 3  C  O CHO

OH
 (i) O
Q.10 H
 A   3  Product(s). Product is/are?
 (ii) Zn / H2O

CHO
(A) + HCHO (B) || CH = O
O
O
CHO
(C) + CH3CHO (D)
OHC

CH 2
|
Q.11 CH 3  C  CH  CH 2 dil

.H 2SO 4 conc.H PO
  34  3 
(i ) O
|  ( ii ) Zn / H 2O
CH 3
Final product is / are

O O
|| ||
(A) CH 3  C  CH 3 (B) HCHO + CH 3  C  CH  CH 3
|
CH 3

(C) CH3CHO + (D) CH3CHO + HCHO

 56

HYDROCARBONS

Q.12 For the reaction

(
i ) CF3CO3H
  Final product is

( ii ) H3O

O OH OH
(A) O (B) (C) (D)
OH OH

H3C H
C alkaline KMnO
Q.13    4  A, which is true about this reaction?
C
H3C H
(A)A is meso 2, 3–butan–di–ol formed by syn addition
(B)A is meso 2, 3–butan–di–ol formed by anti addition
(C) Ais a racemic mixture of d and l, 2, 3–butan–di–ol formed by anti addition
(D)A is a racemic mixture of d and l 2,3–butan–di–ol formed by syn addition

Q.14 reagent R reagent R

  2  1 

R1 and R2 are –
(A) Cold alkaline KMnO4, OsO4/H2O2 (B) Cold alkaline KMnO4, HCO3H
(C) Cold alkaline KMnO4, CH3–O–O–CH3 (D) C6H5CO3H, HCO3H

Q.15 OsO
 4 (1 eq )
  X.
H 2 O / Acetone

Identify ‘X’.

(A) (B)

(C) (D) Reaction will not occur

 57

HYDROCARBONS

Q.16 Which alkene on heating with alkaline KMnO4 solution gives acetone and a gas, which turns lime water
milky–
(A) 2–Methyl–2–butene (B) Isobutylene
(C) 1–Butene (D) 2–Butene

Q.17 Which of the following reagents cannot be used to locate the position of triple bond in CH3–CC–CH3
(A) Br2/H2O (B) O3 (C) Cu2Cl2 (D) H/ KMnO4 , 

Q.18 Which will dehydrate at fastest rate by H3PO4:-

(A) 2-methyl butane-2-ol (B) 3-methyl butane-2-ol
(C) Butane-1-ol (D) 2-methyl butane-1-ol

Q.19 Rate of dehydration when given compounds are treated with conc. H2SO4.

(P) (Q) (R) (S)

(A) P > Q > R > S (B) Q > P > R > S (C) R > Q > P > S (D) R > Q > S > P

Q.20 How many 1,2-Shifts are involved during the course of following reaction:

conc
 . H 2SO 4



(A) 1 (B) 2 (C) 3 (D) 4


Q.21 H (X).


Product (X) is

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


Q.22 H


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

 58

HYDROCARBONS

Q.23 Br P (major)

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

Lindlar Na / NH
Q.24 B    R–CC–R  3  A
A and B are geometrical isomers (R–CH=CH–R) –
(A) A is trans, B is cis (B) A and B both are cis
(C) A and B both are trans (D) A is cis, B is trans

Q.25 CH3–CH2–CCH CH3CC–CH3

A and B are –
(A) alcoholic KOH and NaNH2 (B) NaNH2 and alcoholic KOH
(C) NaNH2 and Lindlar (D) Lindlar and NaNH2

Q.26 BrCH2–CH2–CH2Br reacts with Na in the presence of ether to produce –

(A) BrCH2–CH=CH2 (B) CH2=C=CH2 (C) (D)All of these

Q.27 During the preparation of ethane by Kolbe’s electrolytic method using inert electrodes the pH of the
electrolyte –
(A) Increases progressively as the reaction proceeds
(B) Decreases progressively as the reaction proceeds
(C) Remains constant throughout the reaction
(D) May decrease of the concentration of the electrolyte is not very high

Q.28 The correct order of rate of Wurtz recation.

Na
(I) CH2–F  CH2–CH2
Ether

Na
(II) CH2–Cl  CH2–CH2
Ether

Na
(III) CH2–Br  CH2–CH2
Ether

Na
(IV) CH2–I  CH2–CH2
Ether
(A) I > II > III > IV (B) II > I > III > IV
(C) IV > III > II > I (D) In all rate of Wurtz reaction is same
 59

HYDROCARBONS

Q.29 CH 3  CH  CO 2 K 
electrolys
 is
 (A) (Major)
|
CH 3  CH  CO 2 K 
Major product (A) of above reaction
(A) (B) (C) (D)

Q.30 Electrolysis Major product of reaction :

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

Q.31 on electrolysis gives:

(A) (B)

(C) (D)

Q.32 How many moles of O2 required for complete combustion of one mole of propane ?
(A) 7 (B) 5 (C) 16 (D) 10

Q.33 How much volume of air will be needed for complete combustion of 10 lit. of ethane ?
(A) 135 lit. (B) 35 lit. (C) 175 lit. (D) 205 lit.

Q.34 When n-butane is heated in the presence ofAlCl3/HCl it will be converted into –
(A) Ethane (B) Propane (C) Butene (D) Isobutane

Q.35 Which of the following carbocation is most stable?

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

Q.36 Which carbocation is least likely to form as an intermediate?

 
(A) (C6 H 5 )3 C (B) (C) (D)
 60

HYDROCARBONS

Q.37 Which one of the following carbocation would you expect to rearrange.

(A) (B) (C) (D)

Q.38  product is


O
D

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

C2H5

Q.39 Conc
 . H 2SO 4
 (A) H2 /
Pt
 (B)


A and B are :

(A) Both are

(B)

(C)

(D)


Q.40 H/
CO / H 2O
  P
P is
CHO COOH OH

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

CHO
COOH
Q.41 Acetylene may be prepared using Kolbe’s electrolytic method employing –
(A) Pot. acetate (B) Pot. succinate (C) Pot. fumarate (D) None of these

Q.42 Mixture of one mole each of ethene and propyne on reaction with Na will form H2 gas at S.T.P. –
(A) 22.4 L (B) 11.2 L (C) 33.6 L (D) 44.8 L
 61

HYDROCARBONS

Q.43 A mixture of CH4, C2H4 and C2H2 gaseous are passed through a Wolf bottle containing ammonical
cuprous chloride. The gas coming out is
(A) Methane (B)Acetylene
(C) Mixture of methane and ethylene (D) original mixture

BH THF
Q.44 B  3
 CH3–CCH HgSO / H SO
 4 24  A
H O OH 
2 2,

A and B are –
O O
|| ||
(A) CH 3CH 2CHO, CH 3  C  CH 3 (B) CH 3  C  CH 3 CH 3CH 2CHO

(C) CH3CH2CHO (both) (D) CH 3  C  CH 3 (both)

||
O

Q.45 In the presence of strong bases, triple bonds will migrate within carbon skeletons by the
(A) removal of protons (B) addition of protons
(C) removal and readdition of protons (D) addition and removal of protons.

NH Cl
Q.46 CHCH  4 product
Cu 2Cl 2

Product is –
(A) Cu–CC–Cu (B) CH2=CH–CCH (C) CHC–Cu (D) Cu–CC–NH4

Q.47 PMA(Poly Methyl Acrylate) polymer is formed by methyl acrylate, which is prepared as follows –
CO  CH OH
 
(A) R – C  CH CO ROH
 (B) HC  CH   
3

Ni ( CO ) 4

CO  H O
(C) HC  CH    
2
 (D) None of these
Ni ( CO ) 4

Q.48 If octane number of gasoline sample is 70, then this sample will be similar to -
(A) 70% n-heptane + 30% n-octane (B) 70% n-octane + 30% n-heptane
(C) 70% isooctane + 30% n-heptane (D) 70% n-heptane + 30% isooctane
O

Q.49 Zn/Hg NBS alc. KOH HCl

Final Product is :
HCl

Cl Cl OH
Cl OH Cl
(A) (B) (C) (D)
 62

HYDROCARBONS

Q.50 In which reaction major product is hydrocarbon?

(A) RCOOK Electrolys
 is
 2 /
(B) RCOOAg I
CH 3
Cl / hv
| C 2 H 5OH
(C) CH3–CH3 2 
 (D) CH 3  C  Cl  
|
CH 3
[MULTIPLE CORRECT CHOICE TYPE]
Q.51 Which of the following will give same product with HBr in presence or absence of peroxide.
(A) Cyclohexene (B) 1-methylcyclohexene
(C) 1,2-dimethylcyclohexene (D) 1-butene

Q.52 The ionic addition of HCl to which of the following compounds will produces a compound having Cl on
carbon next to terminal.
(A) CF3.(CH2)3.CH=CH2 (B) CH3.CH=CH2
(C) CF3.CH=CH2 (D) CH3.CH2CH=CH.CH3

Q.53 An alkene on ozonolysis yields only ethanal. There is an isomer of this which on ozonolysis yields:
(A) propanone (B) ethanal (C) methanal (D) only propanal

Ph
H H
alc.KOH
Q.54 H Cl   Product(s), Possible products are
CH3

Ph
Ph CH3
(A) (B)

(C) Ph–CH2–CH = CH2 (D) Ph –HC = C = CH2

Q.55 Which of the following can be produced by Wurtz reaction in good yield.

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

Q.56 Choose all alkane that give only one monochloro derivative upon reaction with chlorine in sun light.

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

 63

HYDROCARBONS

Q.57 Aqueous solution of potassium propanoate is electrolysed. Possible organic products are:
(A) n-Butane (B) C2H5COOC2H5 (C) CH3–CH3 (D) CH2=CH2

(i ) O
Q.58 C4H8 3  CH3 – CHO
( ii ) H 2O / Zn
Baeyer
reagent Meso compound

C4H8 is

(A) But-1-ene (B) Trans-but-2-ene (C) Cis-but-2-ene (D) Isobutylene

Q.59 CH 2 = CHCH2CH = CH2 NBS

 A, A can be
(A) CH 2  CH CH CH  CH 2 (B) CH2=CHCH=CH–CH2Br
|
Br

(C) CH2 = CH CH2 CH = CHBr (D) CH 2  CH CH 2 C  CH 2

|
Br

Q.60 Which is / are true statements/ reactions?

(A) Al4C3 + H2O  CH4 (B) CaC2 + H2O  C2H2

(C) Mg2C3 + H2O  CH3C CH (D) Me3C–H + KMnO4 H Me3C–OH

Q.61 Which reagent is the most useful for distinguishing compound I from the rest of the compounds
CH3CH2CCH CH3CCCH3 CH3CH2CH2CH3 CH3CH=CH2
I II III IV
(A) alk. KMnO4 (B) Br2/CCl4
(C) Br2/CH3COOH (D)AmmonicalAgNO3

BH3 / THF HgSO

Q.62 C    A  4  B
H 2O 2 / OH  H 2SO 4

B & C are identical whenA is –

(A) (B) (C) (D)
 64

HYDROCARBONS

[MATCH THE COLUMN]

Q.63 Column–I Column–II
C H3
|
(A) Ph  C  CH 2 Hg ( OAC) , H 2O
  2—  (P) Cis
NaBH 4 ,OH

(B) (
i ) M -CPBA
  (Q) Trans
(ii ) H  / H 2O

( i ) B H  THF
(C)   
2 6
 (R) Optically active
( ii ) H 2O 2 / OH —

Bayers
(D) Re
agent
 (S) Optically inactive

Q.64 Column I Column II

(A) CH3–CC– CH3  cis-2-butene (P) Na/NH3(l)

(B) CH 3  C  C  CH 3  trans-2-butene (Q) H2/Pd/BaSO4

(C) CH3CC–CH3 1-Butyne (R) alc. KOH, 

(D) CH3–CH3–CCH 2-Butyne (S) NaNH2 , 

Q.65 Match List-I with List-II and select the correct answer using the codes given below the lists:

List-I (Reaction) List-II (Reagents)

(A) CH3–CH=CH2CH3–CHBr–CH3 (P) HBr

(B) CH3–CH=CH2CH3–CH2–CH2Br (Q) Br2

(C) CH3–CH=CH2BrCH2–CH=CH2 (R) HBr / Peroxide

(D) CH3–CH=CH2CH3–CHBr–CH2Br (S) NBS

 65

HYDROCARBONS

Q.66 Match the column

Column I Column II

(A) RCOONa electrolys

 is
 R–R (P) Correy-House reaction

Soda lim e
(B) R–CH2–COOH   R–CH3 (Q) Kolbe electrolysis


( i ) AgNO
(C) RCOOH   3  R–Cl (R) Oakwood degradration
( ii ) Cl 2 / 

(D) R’–X + R2CuLi  R–R’ (S) Hunsdiecker reaction

Q.67 Column I Column II

( i ) BH / THF
(A) CH 3  C  CH 2  3  (P) CH3–CH2–CH=CH2
(ii ) H 2O 2 / OH
|
CH 3
(i ) Hg ( OAc) / HOH
(B) CH 3  C  CH 2     2
 (Q) CH3–CH=CH–CH3
(ii ) NaBH4
|
CH 3
Cl
|
(C) CH 3  CH 2  CH  CH 3 CH ONa / 
3   (R) CH 3  CH  CH 2OH
|
CH 3
Cl OH
| ( CH 3 )3 CONa
|
(D) CH 3  CH 2  CH  CH 3     (S) CH 3  C  CH 3

|
CH 3
 66

HYDROCARBONS

EXERCISE-3
SECTION-A
(JEE ADVANCED Previous Year's Questions)
Q.1 Alcoholic solution of KOH is a specific reagent for – [IIT ‘90]
(A) Dehydration (B) Dehydrogenation
(C) Dehydro halogenation (D) Dehalogenation

Q.2 Of the following, unsaturated hydrocarbons are – [IIT ‘90]

(A) ethyne (B) cyclohexane (C) n–propane (D) ethene

Q.3 1-chlorobutane on reaction with alcoholic potash gives – [IIT ‘91]

(A) 1–butene (B) 1–butanol (C) 2–butene (D) 2–butanol

Q.4 The hybridisation of carbon atoms in C–C single bond of HCC–CH=CH2 is – [IIT ‘91]
(A) sp3–sp3 (B) sp2–sp3 (C) sp–sp2 (D) sp2–sp2

Cl
|
Q.5 (CH 3 ) 2 C  CH 2CH 3 alc  ?
. KOH [IIT 1992]

alc. KOH
Q.6 C6 H 5CH 2CHCH 3 heat ? HBr
 ? [IIT 1993]
|
Br

Q.7 C(C6H12), an optically active hydrocarbon which on catalytic hydrogenation gives an optically inactive
compound, C6H14. [IIT 1993]

Q.8 Draw the stereochemical structure of the product in the following reactions. [IIT 1994]
H
R–CC–R 
2
Lindlar catalyst

Q.9 Write down the structures of the stereoisomers formed when cis–2–butene is reacted with bromine.
[IIT 1995]

Q.10 An organic compound E(C5H8) on hydrogenation gives compound F(C5H12). Compound E on ozonolysis
gives formaldehyde and 2–ketopropanal. Deduce the structure of compound E. [IIT 1995]

Q.11 Give the structures of the major organic products from 3–ethyl–2–pentene under each of the following
reaction conditions. [IIT 1996]
(a) HBr in the presence of peroxide
(b) Br2/H2O
(c) Hg(OAc)2/H2O; NaBH4
 67

HYDROCARBONS

Q.12 An alkyl halide, (X) of formula C6H13Cl on treatment with potassium tertiarybutoxide 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.13 3,3–Dimethylbutan–2–ol loses a molecule of water in the presence of concentrated sulphuric acid to
give tetramethylethylene as a major product. Suggest a suitable mechanism. [IIT 1996]

Q.14 One mole of the compoundA(molecular formula C8H12), incapable of showing stereoisomerism, reacts
with only one mole of H2 on hydrogenation over Pd. A undergoes ozonolysis to give a symmetrical
diketone B (C8H12O2). What are the structure of A and B? [IIT 1997]

Q.15 Compound (A) C6H12 gives a positive test with bromine in carbon tetrachloride. Reaction of (A) with
alkaline KMnO4 yields only (B) which is the potassium salt of an acid. Write structure formulae and
IUPAC name of (A) and (B). [IIT 1997]

Q.16 The central carbon–carbon bond in 1,3–butadiene is shorter than that of n–butane. Why?

Q.17 Which of the following compounds will show geometrical isomerism? [IIT ‘98]
(A) 2–butene (B) Propene (C) 1–phenylpropene (D) 2–methyl–2–butene

Q.18 The reaction of CH3– CH=CH OH with HBr gives: [JEE 1998]

(A) CH3CHBrCH2 OH (B) CH3CH2CHBr OH

(C) CH3CHBrCH2 Br (D) CH3CH2CHBr Br

Q.19 Write the intermediate steps for each of the following reaction. [IIT 1998]


H

Q.20 Write the intermediate steps for each of the following reaction [IIT 1998]
C6H5CH(OH)CCH  C6H5CHCHCHO

Q.21 Give reasons for the following in one or two sentences. [JEE 1998]
"Acid catalysed dehydration of t-butanol is faster than that of n-butanol.

Q.22 Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with:
(A) SO2Cl2 (B) SOCl2 (C) Cl2 (D) NaOCl [IIT 1998]

Q.23 Carry out the following transformation in not more than three steps. [IIT 1999]
O
||
CH3–CH2–CC–H  CH 3  CH 2  CH 2  C  CH 3
 68

HYDROCARBONS

Q.24 Discuss the hybridisation of carbon atoms in allene (C3H4) and show the –orbital overlaps.
[IIT 1999]

Q.25 Complete the following – [IIT 1999]

1 2

 
 3


Q.26 Complete the following – [IIT 1999]

4 5 6

 
 


Q.27 In the compound CH2=CH–CH2–CH2–CCH, the C2–C3 bond is of the type – [IIT ‘99]
(A) sp–sp2 (B) sp3–sp3 (C) sp–sp3 (D) sp2–sp3
Q.28 What would be the major product in each of the following reactions? [IIT 2000]
CH 3
| C2 H5OH H
(i) CH 3  C  CH 2 Br   (ii) 
2
 Lindlar's Catalyst
|
CH 3

Q.29 CH2=CH– is more basic than HCC– [IIT 2000]

Q.30 Propyne and propene can be distinguished by – [IIT ‘2000]

(A) conc. H2SO4 (B) Br2 in CCl4 (C) dil. KMnO4 (D)AgNO3 in ammonia

Q.31 Which one of the following alkenes will react fastest with H2 under catalytic hydrogenation condition –
[IIT ‘2000]

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

Q.32 In the presence of peroxide, hydrogen chloride and hydrogen iodide do not give anti–Markovnikov
addition to alkene because – [IIT ‘2001]
(A) both are highly ionic (B) one is oxidising and the other is reducing
(C) one of the step is endothermic in both the cases
(D)All the steps are exothermic in both cases

Q.33 The reaction of propene with HOCl proceeds via the addition of – [IIT ‘2001]
(A) H+ in first step (B) Cl+ in first step
(C) OH– in first step (D) Cl+ and OH– in single step
 69

HYDROCARBONS

Q.34

Hydrogenation of the above compound in the presence of poisoned paladium catalyst gives –
(A)An optically active compound (B)An optically inactive compound [IIT ‘2001]
(C)Aracemic mixture (D)Adiastereomeric mixture

Q.35 On reaction with 4N alcoholic KOH at 175 °C 1–pentyne is slowly converted into equilibrium mixture
of 1.3% 1–pentyne (A), 95.2% 2–pentyne (B) and 3.5% 1,2–pentadiene (C). Give the suitable
mechanism of formation ofA, B and C with all intermediates. [IIT 2001]

Q.36 A biologically activecompound, Bombykol (C 16H30O) is obtained from a natural source. The structure
of the compound is determined by the following reactions.
(a) On hydrogenation, Bombykol gives a compound A, C16H34O, which reacts with acetic anhydride to
give an ester.
(b) Bombykol also reacts with acetic anhydride to give another ester, which on oxidative ozonolysis
(O3/H2O2) gives a mixture of butanoic acid, oxalic acid and 10-acetoxy decanoic acid.
Determine the number of double bonds in Bombykol. Write the structures of compoundAand Bombykol.
How many geometrical isomers are possible for Bombykol? [IIT 2002]

Q.37 Identify X, Y and Z in the following synthetic scheme and write their structures. Is the compound Z
optically active? Justify your answer. [IIT 2002]
H / Pd  BaSO
( i ) NaNH
CH3CH2CC–H   2  X 2   4  Y alkaline KMnO
   4  Z
( ii ) CH 3CH 2Br

Q.38 Consider the following reactions – [IIT ‘2002]

H 3C  CH  CH  CH 3 + ‘X’ + HBr
| |
D CH 3
Identify the structure of the major product ‘X’
• •
(A) H 3C  CH  CH  C H 2 (B) H 3C  CH  C CH 3
| | | |
D CH 3 D CH 3

• •
(C) H 3C  C CH  CH 3 (D) H 3C  C H  CH  CH 3
| | |
D CH 3 CH 2

Q.39 The nodal plane in the –bond of ethene is located in – [IIT ‘2002]
(A) the molecular plane
(B) a plane parallel to the molecular plane
(C) a plane perpendicular to the molecular plane which contains the carbon–carbon –bond at right angle
(D) a plane perpendicular to the molecular plane which contains the carbon–carbon –bond
 70

HYDROCARBONS

Q.40 Identify a reagent from the following list which can easily distinguish between 1–butyne and 2-butyne-
[IIT ‘2002]
(A) bromine, CCl4 (B) H2, Lindlar catalyst
(C) dilute H2SO4, HgSO4 (D) ammonical Cu2Cl2 solution

HgSO
Q.41 C6H5–CC–CH3  
4  A [IIT ‘2003]
H 2SO 4

(A) (B) (C) C6 H 5  C  CHCH 3 (D) C 6 H 5  CH  C  CH 3

| |
OH OH


Q.42 H x Br2
 H 2O ( mixture)  5 compounds of molecular formula C4H8Br2

Number of compounds in X will be: [IIT ‘2003]
(A) 2 (B) 3 (C) 4 (D) 5

Q.43 2–hexyne can be converted into trans–2–hexene by the action of : [IIT ‘2004]
(A) H2–Pd-BaSO4 (B) Li in liq. NH3 (C) H2–PtO2 (D) NaBH4

Q.44 Cyclohexene is best prepared from cyclohexanol by which of the following:

(A) conc. H3PO4 (B) conc. HCl/ZnCl2 (C) conc. HCl (D) conc. HBr
[IIT ‘2005]
Q.45 When Phenyl Magnesium Bromide reacts with tert. butanol, which of the following is formed?
(A) Tert. butyl methyl ether (B) Benzene
(C) Tert. butyl benzene (D) Phenol [IIT ‘2005]

Q.46 1–bromo–3–chlorocyclobutane when treated with two equivalents of Na, in the presence of ether which
of the following will be formed? [IIT ‘2005]

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

Q.47 If after complete ozonolysis of one mole of monomer of natural polymer gives two moles of CH2O and
CH 3
|
one mole of O  C  CH  O . Identify the monomer and draw the all-cis structure of natural polymer..
[IIT 2005]

(i ) O
X    Y.
 3
Q.48 H ,
(ii) Zn / CH COOH 3

Identify X and Y. [IIT 2005]

 71

HYDROCARBONS

Q.49 CH3–CH=CH2 + NOCl  P [IIT 2006]

Identify the adduct.
CH 3  CH  CH 2 CH 3  CH  CH 2
(A) | | (B) | |
Cl NO NO Cl

NO
| CH 2  CH 2  CH 2
CH 3  CH 2  CH
(C) | (D) | |
NO Cl
Cl
Q.50 The number of stereoisomers obtained by bromination of trans-2-butene is [IIT 2007]
(A) 1 (B) 2 (C) 3 (D) 4

Q.51 The number of structural isomers for C6H14 is [IIT 2007]

(A) 3 (B) 4 (C) 5 (D) 6

Q.52 The reagent(s) for the following conversion, [IIT 2007]

?

 H H is / are

(A) alcoholic KOH (B) alcoholic KOH followed by NaNH2

(C) aqueous KOH followed by NaNH2 (D) Zn / CH3OH

Q.53 In the following carbocation, H/ CH3 that is most likely to migrate to the positively charged carbon is
H H
1 2 + 4 5
H3C—C—C—C—CH3
3 [JEE 2009]
HO H CH3
(A) CH3 at C-4 (B) H at C-4 (C) CH3 at C-2 (D) H at C-2

Q.54 The synthesis of 3-octyne is achieved by adding a bromoalkane into a mixture of sodium amide and an
alkyne. The bromoalkane and alkyne respectively are [IIT 2010]
(A) BrCH2CH2CH2CH2CH3 and CH3CH2CCH (B) BrCH2CH2CH3 and CH3CH2CH2CCH
(C) BrCH2CH2CH2CH2CH3 and CH3CCH (D) BrCH2CH2CH2CH3 and CH3CH2CCH

Q.55 The number of optically active products obtained from the complete ozonolysis of the given compound
is [JEE 2012]
CH3 H

CH3–CH=CH–C–CH=CH–C–CH=CH–CH3

H CH3
(A) 0 (B) 1 (C) 2 (D) 4
 72

HYDROCARBONS

Q.56 In allene (C3H4), the type(s) of hybridisation of the carbon atoms is (are) [JEE 2012]
(A) sp and sp 3 (B) sp and sp 2 (C) only sp2 2
(D) sp and sp 3

Q.57 Isomers of hexane, based on their brancing, can be divided into three distinct classes as shown in the
figure. [JEEAdvance 2014]

I and II and III

The correct order of their boiling point is

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

Q.58 In the following reaction, the major product is : [JEE Advance 2015]
CH3
1 equivalent HBr
CH2
H2C
CH3 CH 3
CH3
(A) H C (B)
2 H3C
Br Br
CH3 CH3
(C) (D)
H2C Br H3C Br

Q.59 Compound(s) that on hydrogenation produce(s) optically inactive compound(s) is(are)

[JEE Advance 2015]
H H
Br Br
(A) H C (B)
3
CH3 H2C CH 3

H Br
H2C Br H
(C) CH3 (D)
H2C CH 3
CH3

Q.60 The number of hydroxyl group(s) in Q is [JEEAdvance 2015]

+
H aqueous dilute KMnO 4(excess)
H P Q
heat 0°C
HO
H3C CH3
 73

HYDROCARBONS

Paragraph for question nos. 61 & 62

In the following reactions : [JEEAdvance 2015]


C8 H 6 Pd BaSO4
 C8 H8 i
. B2H 6
  X
H2 ii. H 2 O 2 , NaOH , H 2O
 H 2O
 HgSO 4 , H 2SO 4
C8 H 8O i
. EtMgBr , H 2O
      Y
ii. H  , Heat

Q.61 Compound X is
O OH
OH
CH3 CH3 CHO
(A) (B) (C) (D)

Q.62 The major compound Y is

(A) CH3 (B) CH3

CH2 CH3
CH3
(C) (D) CH3

Q.63 In the following monobromination reaction, the number of possible chiral products is
[JEEAdvance 2016]
CH2CH2CH3
H Br
CH3 Br
2 300
ºC 
(1.0 mole )

(1.0 mole)
(enantiomerically pure)

Q.64 The correct statement(s) for the following addition reactions is(are) [JEEAdvance 2017]
H3C H
Br / CHCl3
(i) 2  
 M and N
H CH3
H 3C CH3
(ii) Br  O and P
/ CHCl3
2  
H H
(A) O and P are identical molecules
(B) Bromination proceeds through trans-addition in both the reactions
(C) (M and O) and (N and P) are two pairs of enantiomers
(D) (M and O) and (N and P) are two pairs of diastereomers
 74

HYDROCARBONS

Q.65 Compounds P and R upon ozonolysis produce Q and S, respectively. The molecular formula of Q and
S is C8H8O. Q undergoes Cannizzaro reaction but not haloform reaction, whereas S undergoes haloform
reaction but not Cannizzaro reaction. [JEEAdvance 2017]
( i ) O 3 / CH 2Cl 2
(i) P   
(ii ) Zn / H O
Q
2 ( C8H8O )
( i ) O 3 / CH 2Cl 2
(ii) R   
(ii ) Zn / H O
S
( C8H8O )
2

The option(s) with suitable combination of P and R, respectively, is(are)

(A) H3C and

CH3

H 3C
CH3 CH3
and
(B)
CH3
H3 C

H3 C CH3
CH3 CH3
and
(C)
CH3
CH3

(D) H3C and H3 C

CH3
 75

HYDROCARBONS

SECTION-B
(JEE Main Previous Year's Questions)
Q.1 The compound
H3C  C = CH– CH2 – CH3Vigorous
  product, here product is
oxidation
[AIEEE-2002]
|
H3C

(A) CH3COOH & CH3 – C – CH3 (B) CH3 – CH2 – COOH & CH3 – C  O
|| |
O CH3

(C) CH3 – CH2 – COOH only (D) HCOOH & CH3 – C – CH3
||
O
Q.2 Reaction
H – C  C – H + HOCl  product, here product will be - [AIEEE-2002]
(A) CHCl2 – CHO (B) CHO – CHO (C) CH – Cl = CHCl (D) CHCl2 – CHCl2

Q.3 Acetylene does not react with - [AIEEE-2002]

(A) NaNH2 (B) NaOH (C) Na metal (D)AmmonicalAgNO3

Q.4 Butene-1 may be converted to butane by reaction with – [AIEEE-2003]

(A) Zn – Hg (B) Pd / H2 (C) Zn – HCl (D) Sn – HCl

Q.5 During dehydration of alcohols to alkenes by heating with conc. H2SO4 the initiation step is -
[AIEEE-2003]
(A) Elimination of water (B) Formation of an ester
(C) Protonation of alcohol molecule (D) Formation of carbocation

Q.6 On mixing a certain alkane with chlorine and irradiating it with ultraviolet light, it forms only one
monochloroalkane. This alkane could be – [AIEEE-2003]
(A) Isopentane (B) Neopentane (C) Propane (D) Pentane

Q.7 Which one of the following has the minimum boiling point ? [AIEEE-2004]
(A) n – Butane (B) 1– Butyne (C) 1– Butene (D) isobutane

Q.8 Amongst the following compounds, the optically active alkane having lowest molecular mass is-
[AIEEE-2004]
CH3
|
(A) CH3–CH2–CH2–CH3 (B) CH3  CH2  CH  CH3

(C) (D) CH3–CH2 – C  CH

 76

HYDROCARBONS

Q.9 Reaction of one molecule of HBr with one molecule of 1,3–butadiene at 40ºC given predominantly
(A)1–bromo–2–butene under thermodynamically controlled conditions [AIEEE-2005]
(B) 3–bromobutene under kinetically controlled conditions
(C) 1–bromo–2–butene under kinetically controlled conditions
(D) 3–bromobutene under thermodynamically controlled conditions

Q.10 Acid catalyzed hydration of alkenes except ethene leads to the formation of – [AIEEE-2005]
(A) secondary or tertiary alcohol (B) primary alcohol
(C) mixture of secondary and tertiary alcohols (D) mixture of primary and secondary alcohols

Q.11 Reaction of trans 2-phenyl-1 bromocyclopentane on reaction with alcoholic KOH produces
(A) 2-phenylcyclopentene (B) 1-phenylcyclopentene [AIEEE 2006]
(C) 3-phenylcyclopentene (D) 4-phenylcyclopentene

Me

Me
Q.12 N
OH
n-Bu Et
The alkene formed as a major product in the above elimination reaction is [AIEEE 2006]
Me Me
(A) CH2 = CH2 (B) (C) (D) Me

Q.13 Which of the following reactions will yield 2, 2-dibromopropane? [AIEEE 2007]
(A) CH3 – C  CH + 2HBr  (B) CH3CH = CHBr + HBr 
(C) CH  CH + 2HBr  (D) CH3 – CH = CH2 + HBr 

Q.14 In the following sequence of reactions, the alkene affords the compound ‘B’

CH3CH = CHCH3 O

3 A H2
O
 B, The compound B is [AIEEE 2008]
Zn
(A) CH3COCH3 (B) CH3CH2COCH3
(C) CH3CHO (D) CH3CH2CHO

Q.15 The treatment of CH3MgX with CH3C  C – H produces [AIEEE 2008]

H H
(A) CH3C  C – CH3 (B) CH3 C C CH3
(C) CH4 (D) CH3–CH = CH2

Q.16 The hydrocarbon which can not react with sodium in liquid ammonia to give H2 is [AIEEE 2008]
(A) CH3CH2 C CH (B) CH3CH = CHCH3
(C) CH3CH2C  CCH2CH3 (D) CH3CH2CH2C  CCH2CH2CH3
 77

HYDROCARBONS

Q.17 Out of the following, the alkene that exhibits optical isomerism is : [AIEEE 2010]
(A) 3-methyl-1-pentene (B) 2-methyl-2-pentene
(C) 3-methyl-2-pentene (D) 4-methyl-1-penten

Q.18 Which branched chain isomer of the hydrocarbon with molecular mass 72u gives only one isomer of
mono substituted alkyl halide? [AIEEE 2012]
(A) Isohexane (B) Neohexane
(C) Tertiarybutyl chloride (D) Neopentane.

Q.19 2–Hexyne gives trans-2-Hexene on treatment with : [AIEEE 2012]

(A) Pd/BaSO4 (B) LiAlH4
(C) Pt/H2 (D) Li/NH3

Q.20 A gaseous hydrocarbon gives upon combustion 0.72 g of water and 3.08 g of CO2. The empirical
formula of the hydrocarbon is: [JEE Main 2013]
(A) C3H4 (B) C6H5 (C) C7H8 (D) C2H4

Q.21 Which compound would give 5 – keto – 2 – methyl hexanal upon ozonolysis ?
CH3 CH3
CH3 CH3
(A) (B) H3C (C) CH3 (D)
CH3 CH3
[JEE Main 2015]

Q.22 The product of the reaction given below is: [JEE Main 2016]
1. NBS/hv
X
2. H2O/K2CO 3

CO2H OH O

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

Q.23 The reaction of propene with HOCl (Cl2 + H2O) proceeds through the intermediate:
[JEE Main 2016]
(A) CH3–CHCl–CH2 + +
(B) CH3 –CH –CH2 –OH
+
(C) CH3– CH –CH2 –Cl (D) CH3– CH(OH) – CH2+
 78

HYDROCARBONS

Q.24 The major product obtained in the following reaction is : [JEE Main 2017]

Br
H t
BuOK
C6H5

C6H5
(+)

(A) C6H5CH = CHC6H5 (B) (+) C6H5CH (OtBu) CH2C6H5

(C) (–) C6H5CH(OtBu) CH2C6H5 (D) (±) C6H5CH(OtBu) CH2C6H5

Q.25 3-Methyl-pent-2-ene on reaction with HBr in presence of peroxide forms an addition product. The
number of possible stereoisomers for the product is : [JEE Main 2017]
(A) Zero (B) Two (C) Four (D) Six

Q.26 The trans-alkenes are formed by the reduction of alkynes with: [JEE Main 2018]
(A) Na/liq.NH3 (B) Sn-HCl (C) H2-Pd/C, BaSO4 (D) NaBH4
 80

HYDROCARBONS

EXERCISE-5 (Rank Booster)

[SINGLE CORRECT CHOICE TYPE]

Q.1 The addition of bromine to (3S)-3-Methyl Cyclohexene in 1,2-dichloroethane (solvent) produces ____
dibromo derivatives:
(A) 2 (B) 3 (C) 4 (D) 6
Q.2 Which compound will yield 2-methyl-6-oxoheptanal upon treatment with ozone followed by Zn/H2O.

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

2 
Hg / H 3O
Q.3 H3C – C  C – OCH3     X (major)

X is
(A) H 3C  C  CH 2  O  CH 3 (B) H 3C  CH 2  C  OCH3
|| ||
O O

(C) H 3C  CH 2  C  H (D) H3C  CH 2  C  C  H

|| | | ||
O O O
Q.4 The reaction of cyclooctyne with HgSO4 in the presence of aq. H2SO4 gives

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

Q.5 Get the product P1 and P2 in the following reaction :

CH3
(i) BH3–THF
P1
(ii) H2O2/NaOH
D
CH3
dil H2SO4
P2
D
OH H H OH
CH3 CH3 CH3 CH3
(A) and (B) and
D D D D
H OH OH H

OH OH H H
CH3 CH3 H D
(C) D and H (D) H and OH
H D CH3 H
 81

HYDROCARBONS

18

(i ) CH COO OH
Q.6  3   X
(ii ) H3O

The probable structure of ‘X’ is

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

Q.7 alcoholic
  KOH  product


Major product is:

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

Q.8 conc
 .H 2SO 4
 J (Major)


OH
J is

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

H D Br NaI
Q.9 

P(Alkene) 2  
 Q (Alkene)
CCl 4 Acetone
H3 C D

O–C–CH3

O
Alkene (P) & (Q) respectively are

H D D H
(A) Both (B) Both
H2C D H2C D
H3C CH3 H 3C D H 3C D H3C CH3
& &
(C) (D)
D D D CH3 D D D
CH3
 82

HYDROCARBONS

Q.10 How many products will be formed excluding stereo when cis-1,3,5-trimethyl cyclohexene reacts with
NBS?
(A) 3 (B) 4 (C) 5 (D) 6
Q.11 How many 1,2-Shifts are involved during the course of following reaction:



(A) 1 (B) 2 (C) 3 (D) 4

A
Q.12 

A can be –
(A) Conc. H2SO4 (B) alcoholic KOH (C) Et3N (D) t-BuOK
Q.13 An organic compound of molecular formula C4H6, (A), forms precipitates with ammoniacal silver nitrate
and ammoniacal cuprous chloride. ‘A’has an isomer ‘B’, one mol of which reacts with one mol of Br2 to
form 1, 4-dibromo-2-butene. Another isomer ofA is ‘C’, one mole of C reacts with only 1 mol. of Br2
to give vicinal dibromide. A, B & C are
(A) CH3–CH2–CCH and CH2=CH–CH=CH2 ;
(B) CH3–CC–CH3 and CH3–CH=C=CH2 ; CH3–CC–CH3
CH 2  CH
(C) C=CH2 and | || ; CH2 = CH–CH=CH2
CH 2  CH

(D) CH3–CC–CH3 and ; CH2 = CH–CH = CH2

Q.14 The product of reaction between one mole of acetylene and two mole of HCHO in the presence of
Cu2Cl2 –
(A) HOCH2 – C  C – CH2OH (B) H2C = CH – C  C – CH2OH
(C) HC  C – CH2OH (D) None of these

[MULTIPLE CORRECT CHOICE TYPE]

Q.15 Ph–CH=CH2 + BrCCl3 peroxide

 
Product is:

(A) (B)

(C) (D)
 83

HYDROCARBONS

Q.16 Which of the following can be formed during this reaction?


H
3O

OH
OH

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

OH O O
OH

H / Ni Conc. H 3PO 4
Mg2C3 D2O
 2     (S)
1. BH3 .THf
Q.17     
2. H 2 O / O H 

Product (s) are :

(A) H C  CH  CD 3 (B) H 2 C CH  CD 2 (C) H2C = CH–CD3 (D) H 2 C  C CH 3
| | |
D D D
Q.18 Which of the following elimination reactions will occur to give but-1-ene as the major product?
EtOH
(A) CH3.CHCl.CH2.CH3 + KOH 
(B) CH 3 .CH.CH 2 .CH 3  NaOEt EtOH

| 

NMe3


(C) CH3.CH2.CHCl.CH3 + Me3CO¯K+  

(D) CH3.CH2.CH(OH).CH3 + conc. H2SO4 


—
Q.19 OH

The above compound undergoes elimination on heating to yield which of the following products?

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

Q.20 Which of the following reaction is/are not showing the correct major product ?

Na
(A) Br Cl Ether Cl Cl

Na
(B) CH3 – CH– Br Ether
CH3– CH2 – CH3 + CH3 –CH=CH2
CH3

Ag Cu
(C)  (D) 
 
 84

HYDROCARBONS

Q.21 Select true statement(s):

(A) I2 does not react with ethane at room temperature even though I2 is more easilycleaved homolytically
than the other halogens.
(B) HC  CH is more reactive than H2C = CH2 toward electrophilic addition reaction
(C) The rate of bromination of methane is decreased if HBr is added to the reaction mixture.
(D)Allylic chloride adds halogens faster than the corresponding vinylic chloride.

dil. H2SO4 (i) O3

Q.22 P1 (ii) Zn/H2O
P3
(Hydroboration
oxidation)

P2
The realtionship among P1, P2 & P3 are:
(A) P1 and P2 are functional isomers
(B) P2 and P3 have one common functional group.
(C) P2 can also be obtained by reductive ozonolysis of 2-hexyne.
(D) P1 can also be obtained by ozonolysis of 2,3-dimethyl butene.

[MATRIX TYPE]

Q.23 Match the column

Column I Column II
O
C CH3 CH 2-CH 3

(A)  (Q) Birch reduction

HO

(B) 

(C) Me – C  C – Me  (R) Wolf-Kishner reduction

(D)  (S) Clemmensen reduction

 85

HYDROCARBONS

Q.24 Column–I Column–II


(A) HOBr
 / H
 (P) Racemic Mix.

(B) (
i ) Per acid
  (Q) Meso

( ii ) H / H 2O

(C) Br / CCl (R) Diastereomer

2 4 

(D) Br / CCl (S) Enantiomer

2 4 

Q.25 Match the column

Column I (Reaction) Column II (Major Product)

D / D O
(A)  
2
 (P)

1. BH .THF
(B)  
3

 (Q)
2. /D 2O 2 / OH

1. Hg(OCOCH ) .D O
(C)    32 
2
 (R)
2. NaBH4 / OH

[SUBJECTIVE]

Q.26 (a) NaOH

 A. Write the structure of A.
Alc.


OH
(b)  B. Write the structure of major product A.

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HYDROCARBONS

Q.27 (a) Write a reasonable and detailed mechanism for the following transformation.

conc
 . + H2O
H 2SO 4


(b) H/
HOH


Q.28 One of the constituent of turpentine is -pinene having molecular formula C10H16. The following scheme
give reaction of -pinene. Determine the structure of –pinene & of the reaction productsAthrough E.
E(C10H18O2) A(C10H16Br2)
 H2O  Br2/CCl4
C10H16O(D)  PhCO 3 H
 –pinene Br  B (C10H17OBr)
2  H 2O

Q.29 Identify the following (A to D).

Me
Me

liq. NH3

H2O

Me
4
inactive Me
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HYDROCARBONS

Q.30 Give the structure of A, B and C.

(a) A (C4H8) which adds on HBr in the presence and in the absence of peroxide to give the same product
C4H9Br.
(b) B (C4H8) which when treated with H2SO4 / H2O give (C4H10O) which cannot be resoslved into optical
isomers.
(c) C (C6H12), an optically active hydrocarbon on catalytic hydrogenation gives an optically inactive
compound C6H14.

Q.31 AhydrocarbonA, of the formula C8H10, on ozonolysis gives compound B (C4H6O2) only.The compound
B can also be obtained from the alkylbromide (C3H5Br) upon treatment with magnesium in dry ether,
followed bycarbondioxide and acidification. IdentifyA, B and C and also give equations for the reactions.

Q.32 CompoundA(C6H12) is treated with Br2 to form compound B (C6H12Br2). On treating B with alcoholic
KOH followed by NaNH2 the compound C (C6H10) is formed. C on treatment with H2/Pt forms
2-methylpentane. The compound ‘C’ does not react with ammonical Cu2Cl2 or AgNO3. When A is
treated with cold KMnO4 solution, a diol D is formed which gives two acids E and F when heated with
KMnO4 solution. Compound E is found to be ethanoic acid. Deduce the structures fromA to F.

Q..33 What areA to K for the following reactions

PhC  CH + CH3MgX  A    B Li  C.
ArCH 2 Cl / NH 3
(i)
h
(ii)  E cold
PhCH2CH2CH3 + Br2  D alcoholic  dil. KMnO 4
  F hot
 KMnO 4
 G
KOH

(iii) 
H
 (iv) 
I

(v) CF3 – CH = CH2 HBr

 J (vi)  K
NBS


2H2
Q.34 X 
Pt

Find out total number of structures of X.