Chemistry : Hydrocarbons

ASSIGNMENTS

SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I
1. Acid catalysed dehydration of neopentyl alcohol (CH3)3CCH2OH yields 2 methyl 2 butene as the
major product. Outline a mechanism showing all steps in its formation.
2. Identify the final products giving intermediates in each case :
(a) F3C – CH = CH2 + HCl 
(b) O2N – CH = CH2 + HCl 
3. An organic compound (D) (C5H8) on hydrogenation gives compound (E) (C5H12). Compound (D) on
ozonolysis gives formaldehyde and 2-keto-propanal. Deduce the structure of compound (D).
4. What are the products if addition of D2 to trans-2-pentene in presence of Ni- metal
H — C — CH3 D
2 
 ?
H5C2 — C — H
5. Identify final products of

4 (I) OsO , ether

(a) 

(II) Na2SO3 / H2O

(b) Now give the product(s) of the following giving mechanism :

CH3
|
2 D O / D
CH3  C  CH  CH2 

|
CH3

6. How would you synthesize CH3CH2C CH from CH3CH2I.

7. Propene reacts with HBr to give isopropyl bormide but does not give n-propyl bromide.
8. How can you diffrencitate but-1-ene and But-2-ene?
9. Indicate allylic, vinyl, 1°, 2°, 3° hydrogens in the following compound. Give the sequence of reactivity
for free radical substitution.

CH3
CH3 CH CH CH 2 CH2 CH
CH3

10. Explain why the addition of HI to 3,3-dimethylbut-1-ene gives 2-iodo-2, 3-dimethylbutane as the major
product and not the 1-iodo-3, 3-dimethyl-butane.
 LEVEL - II
1. (a) An unknown alkene with the formula C 7H12 undergoes oxidation by hot basic KMnO 4 to
yield after acidification only one product.

(i) hot alk. KMnO 4

C7 H12 (ii) H O 
 H3 C COOH. Identify the alkene.
3

(b) Starting with compounds C2H2 & C2H5Br outline a synthesis of meso 3, 4 dibromohexane.
(c) How would you distinguish between but-1-yne and but-2-yne.
2. One mole of a hydrocarbon (A) reacts with one mole of bromine giving a dibromo compound C5H10Br2.
Substance (A) on treatment with cold, dilute alkaline potassium permanganate solution forms a compound
C5H12O2. On ozonolysis, (A) gives equimolar quantities of propanone and ethanal. Deduce the structural
formula of (A).
3. Compound (A) (C5H8O2) liberated carbon dioxide on reacting with sodium bicarbonate. It exists in two
forms neither of which is optically active. It yields compound (B) (C5H10O2) on hydrogenation. Compound
(B) can be separated into enantiomorphs. Write the structure formulae for (A) and (B) giving reasons.
4. A compound (A) with molecular formula C5H10 reacts with dilute alkaline potassium permanganate to
form compund (B) (C5H12O2). (A) on reduction yields 2-methylbutane and on ozonolysis forms acetone
and acetaldehyde. Deduce the structural formula of (A) and (B). Write equation for the above reactions.
5. 448 ml of a hydrocarbon (A) having C, 87.80%; H, 12.19% has a mass of 1.64 g at STP. On hydrogenation
it gives 2-methyl pentane. Treatment of (A) with acidic HgSO4 gives a new compound (B) (C6H12O).
Compound (A) does not react with ammonical AgNO3. Find out the structure of (A) and explain the
reactions involved.
6. The hydrocarbon (A), adds one mole of hydrogen in the presence of a platinum catalyst to form
n-hexane. When (A) is oxidized vigorously with KMnO4, a single carboxylic acid, containing three
carbon atoms, is isolated. Give the structure of (A) and explain.
7. Shown below is the final step in a synthesis of the important perfume constituent, cis-Jasmone. Which
reagents would you choose to carry out this last step?

o o

CH2 — C  C – CH2CH3
(A)
cis - Jasmone

8. Deduce the structural formula of a compound, C10H10(A), that gives as the only organic compound,

HOOCCH2CHCH2COOH (B) on oxidative cleavage.

|
CH2COOH
Chemistry : Hydrocarbons

9. Identify the products of 1, 2 and 1,4 addition reactions of

1eq. Br
(a) 2
    

(b) 1eq. HCl

  


Li. NH3 dil. KMnO 4

10. n – BuC  CMe   A  420


C

H2 H CO / H O

Lindlar's catalyst
 B 
2 3 2


Identify A, B and C with proper explanation.

 LEVEL - III
1. cis-2-butene on treatment with Baye’s reagent gives meso diol whereas trans-2-butene on same
treatment results in formation of racemic mixture. Accounts for the difference.
2. 2-Butyne undergoes following reactions in steps indicated. Identify A to H.
H2 D 2 / Pt
CH3 — C  C — CH3  
Ni B(P  2)
 A  B
2

Na / EtOH D 2 / Pt
  C  D
H2 Br2

NiB(P  2)
 E  F

Br2 H2
  G 
Ni
H
3. Identify
(a) the chiral compound C, C10H14, that is oxidized with alk. KMnO4 to Ph COOH and
(b) the achiral compound D, C10H4 inert to oxidation under the same condition.
4. Write the structures of (CH3)3N and (me3Si)3N. Are they isostructural? Justify your answers.
5. An organic compound E (C 5H8 ) on hydrogenation gives compound F(C 5 H12 ). Compound (E) on
ozonolysis gives formaldehyde. Deduce the structures of compound (E).
CH3

HCO3H
 X
6. KMnO 4 , 
 Y . Identify X, Y, Z.
O3 , H 2 O
  Z (mix)
7. 3, 3-dimethyl-1-butene and HI react to give two products, C6H13I. On reaction with alc. KOH one
isomer, (I) gives back 3, 3-dimethyl-1-butene the other (J) give an alkene that is reducatively ozonised
to Me2C=O. Give the structure of (I) and (J) and explain the formation of the latter.
8. (a) Give reason for the following :
When 1-pentene-r-yne is treated with HBr in equmolecular proposition, the addition takes place
on double bond and not on triple bond yielding thereby the product CH3CH(Br)CH2CCH.
(b) Prove a suitable mechanism for the following reaction

OH CH3
CH3
Chemistry : Hydrocarbons

9. Complete the following reaction :

1 2 3
(i) CH2      

CH3

H2
(ii) 
landlar catalyst
 major product

CH3

(iii) CH3 C2 H 5OH

 
 major product.
CH3 Br

10. Draw newman projection of relatively less stable staggered from of n-butane. The reason fo low
stability of this form is Vander Waal’s repulsion, torsional strain, or both.
 SECTION - II
SINGLE CHOICE QUESTIONS
1. (CH3)3C—MgCl on reaction with D2O produces
(a) (CH3)3CD (b) (CH3)3OD
(c) (CD3)3CD (d) (CD3)3OD
2. Consider the following reaction:
•
CH3 – CH – CH – CH3 + Br  X + HBr
| |
D CH3

Identify the structure of major product X:

(a) H3C CH CH CH2 (b) H3C CH C CH3

D CH3 D CH3

(c) H3C C CH CH3 (d) H3C C CH CH3

D CH3 D CH3

3. The compound 1, 2-butadiene has

(a) only sp-hybridized carbon atoms
(b) only sp2-hybridized carbon atoms
(c) both sp- and sp2-hybridized carbon atoms
(d) sp-, sp2 and sp3-hybridized carbon atoms
4. The compound which reacts with HBr obeying Markownikoff’s rule is
CH3 CH3
(a) CH2 = CH2 (b) C=C
H H
CH3 H H3C H
C=C C=C
(c) (d)
H CH3 H3C H

5. Which one of the following alkenes will react faster with H2 under catalytic hydrogenation condition?

R R R H

(a) (b)

H H R H

R R R R
(c) (d)

R H R R
Chemistry : Hydrocarbons

6. The reaction of CH3CH = CH — —OH with HBr gives

(a) CH3CHBrCH2— —OH (b) CH3CH2CHBr— —OH

(c) CH3CHBrCH2— —Br (d) CH3CH2CHBr — —Br

7. The major product for the reaction,

CH3 O
3 H O+
CH2 = C – CH2 – CH 2 – CH – CH2 

will be
CH2OH
CH3 O
I
(a) CH3 – C – CH2 – CH2 – CH – CH2 (b) CH3
I
OH OH

CH3 CH2OH

(c) CH3 (d)

OH CH3

8. Which of the following is most stable conformation?

CH3
CH3
HO H
H CH3
(a) (b)
H OH
H OH
CH3
OH

CH3 OH
H OH H CH3

(c) (d)
H OH H CH3
CH3 OH

9. The product obtained via oxymercuration (HgSO4 + H2SO4) of 1-butyne would be

H3 C
(a) CH3 (b) H C O
3
O
O
O
(c) H3 C
+ CH2O (d) H3C + HCO2H
OH
10. Point out (A) in the given reaction sequence:
O /H O Δ
( A ) 3 2(B )  2CH3COOH  CO 2

(a) (b)

(c) (d)

11. CH3 – CH – CH = CH2 + HBr  A (predominant), A is

|
CH3
(a) CH3 – CH – CH – CH3 (b) CH3 – CH – CH2 – CH2Br
| | |
CH3 Br CH3
Br
|
(c) CH3 – C – CH2 – CH3 (d) None is correct
|
CH3
12. Stability of CH3 – CH = CH – CH3 CH3 – C = C – CH3
(I) | |
CH3 CH3
(II)
CH3 – C = CH2 CH3 – C = CH—CH3
| |
CH3 CH3
(III)
(IV)
In the increasing order is
(a) I  III  IV  II (b) I  II  III  IV
(c) IV  III  II  I (d) II  III  IV = I

CH3
|
H–C
alkaline KMnO 4
13. ||     A
H–C
|
CH3

Which is true about this reaction?

(a) A is meso 1, 2-butan-di-ol formed by syn addition
(b) A is meso 1, 2-butan-di-ol formed by anti addition
(c) A is a racemic mixture of d and l, 1, 2-butan-di-ol formed by anti-addition
(d) A is a racemic mixture of d and l, 1, 2-butan-di-ol formed by syn-addition.
Chemistry : Hydrocarbons

CH3
| CH3
14. H–C H Br
|| Br2
 H Br
C–H
CH3
|
CH3
(A)
Which is true statement?
(a) A is formed by anti addition and is meso (b) A is formed by syn addition and is meso
(c) A is formed by anti addition and is racemic (d) A is formed by syn addition and is racemic
HCO 3H HCO H
15. (A) cis-2-butene   I (B) trans-2-butene   
3
 II
Correct statements are
(a) I is racemic mixture by anti addition (b) II is meso compound by anti addition
(c) I is meso compound by syn addition (d) II is racemic compound by syn addition

BH3 / THF 
H O
16. B    CH2 3  A
H2O 2 / OH

A and B are

(a) both CH2OH (b) both CH3

OH

(c) CH2OH, CH3 (d) CH3 CH2OH,

OH OH ,

17. 10 mL of a certain hydrocarbon requires 25 mL of oxygen for complete combustion and the volume of
CO2 product is 20 mL. What is the formula of hydrocarbon.
(a) C 2H 2 (b) C2H4
(c) CH4 (d) C2H6
18. The treatment of C2H5Mgl with water produces
(a) Methane (b) Ethane
(c) Ethanal (d) Ethanol
19. The order of reactivity of halogens towards halogenation of alkanes is
(a) F2 > Br2 > Cl2 (b) F2 > Cl2 > Br2
(c) Cl2 > F2 > Br2 (d) Cl2 > Br2 > F2
20. In presence of peroxide, hydrogen chloride and hydrogen iodide do not give anti-Markownikoff’s addition
to alkenes because
(a) both are highly ionic
(b) one is oxidising and other is reducing
(c) one of the step is endothermic in both the cases
(d) all the steps are exothermic in both the cases.
 SECTION - III
MULTIPLE CHOICE QUESTIONS
1. The product obtained in the reaction
Cl 2 , hv
C6 H5 CH 2 — CH 3 
273 K

is
(a) C6H5CHCl—CH3 (b) C6H5CH2CH2Cl
(c) C6H5CCl2—CH3 (d) C6H5CHClCH2Cl
2. Which of the following reactions will give an alkyne?
(a) electrolysis
Potassium fumarate  Zn / alcohol
(b) CH3CBr2CHBr2 

(c) alc./ KOH
CH3CH2CHBr 2  NaNH 2
(d) CH3CHBrCH2Br 
 
3. Alkenes undergo
(a) substitution reactions (b) addition reactions
(c) ozonolysis (d) none of these
4. Which of the following statements are correct for geometrical isomers?
(a) The cis-isomer is more polar than the trans-isomer
(b) The boiling point of the cis-isomer is higher than that of the trans-isomer
(c) Geometrical isomers have different physical poperties but their chemical properties, though similar,
are not identical.
(d) The stability of trans-isomers is greater than that of cis-isomers.
5. Which of the following contains acidic hydrogen?
(a) Ethene (b) Ethane
(c) Ethyne (d) Butyne-1
6. Which of the following reactions can be used to prepare methane?
(a) Clemmensen reduction
(b) Wurtz reaction
(c) Catalytic hydrogenation of methyl iodide
(d) Reduction of methyl iodide by using a zinc-copper couple
7. Methane is obained when
(a) sodium acetate is heated with soda lime (b) iodomethane is reduced
(c) aluminium carbide reacts with water (d) potassium acetate is electrolysed
8. Which of the following compounds cannot be prepared by the Wurtz reaction?

(a) CH3CH3 (b) CH3 CH — CH3

|
CH3

(c) CH3CH2CH2CH2CH2CH3 (d) CH3CH2CH2CH3

Chemistry : Hydrocarbons

9. The nitration of propane with concentrated HNO3 gives

(a) CH3CH2CH2NO2 (b) CH3 CHCH 3

|
NO2

(c) CH3CH2NO2 (d) CH3NO2

10. Which of the following compounds exhibit geometrical isomerims?
(a) CH3CH=CH—COOH (b) Br—CH=CH—Br

(c) C6H5CH=NOH (d)

 MISCELLANEOUS QUESTIONS
SECTION - IV
COMPREHENSION TYPE QUESTIONS
Write up - I
Free radical substitution is main initiated by HELPR [Heat, Electricity, Light (U.V.), Peroxide or Radical].
The most common example of free radical substitution is the halogenation reaction Halogenation
reactions are mainly given by those hydrocarbons which have atleast one hydrogen on sp3 hybrid
carbon.

1. The major product obtained when isobutane is treated with chlorine in the presence of diffused sun
light is
(a) isobutylchloride (b) n-Butylchloride
(c) tert-Butylchloride (d) sec-Butylchloride
2. An alkane by molecular weight 72 upon chlorination gives one monochlorination product. The alkane is
(a) 2-M ethylbutane (b) n-Pentane
(c) 2, 2-Dimethylpropane (d) all the three above
3. The percentage of 1-bromo-2-methyl propane obtained in the photochlorination of isobutane is about
(a) 46% (b) 64%
(c) 56% (d) 1%

Write up - II
Alkenes undergo electrophilic addition reaction with Hg(OAc)2, BH3 and H2O. In all these cases
reaction is regioselective reaction. BH3 gives addition reaction via formation of four centred cyclic
transition state. Hg(OAc)2 gives addition reaction via formation of bridge carbocation as reaction
intermediate whereas water gives addition reaction via formation of classical carbocation.

4. In the given reaction

CH3 OH
| |
[X]
CH3 —C — CH  CH 2  CH3 —C — CH — CH 3
| | |
CH3 H3C CH3

[X] is :
(a) H2O/H2SO4
(b) Hg(OAc)2 followed by NaBH4
(c) BH3 followed by H2O2/NaOH
(d) all of these
Chemistry : Hydrocarbons

5. In the given reaction

(i) BD 2 / THF
CH3 —C  CH 2 (ii) Br2
[X]
|
CH3
[X] is :
D
|
(a) CH3 —C — CH 2 — Br (b) CH3 —CH — CH 2 — Br
| |
CH3 CH3
Br Br
| |
(c) CH3 —C — CH 2 D (d) CH3 —C — CH 2 — Br
| |
CH3 CH3
6. The compound X in the following reaction
C CH
Dil. H 2SO4 / HgSO4
  X is

CH2 CHO COCH 3

(a) (b)

CH CH3 COCHO
(c) OH (d)

MULTIPLE MATCHING TYPE QUESTIONS

Match the following

7. Match List-I with List_II and select the correct answer from the codes given below the lists :
List-I (Reaction) List-II (Product)
OH
|
(i) Hg(OAc) / HOH
(P) CH3—CH2—CH=CH2  2
(ii) NaBH
 (A) CH3 — CH 2 —CH — CH 2 D
4

OH
|
(i) Hg(OAc) / CH OH
(Q) CH3—CH2—CH=CH2  2
(ii) NaBH
3

 (B) CH3 — CH 2 —CH — CH 3
4

OCOCH3
|
(i) Hg(OAc) / CH COOH
(R) CH3—CH2—CH=CH2  2
(ii) NaBH
3
 (C) CH3 — CH 2 —CH — CH 3
4

OCH3
|
(i) Hg(OAc) / H O
(S) CH3—CH2—CH=CH2  2
(ii) NaBD
2
 (D) CH3 — CH 2 —CH — CH 3
4
 (P) (Q) (R) (S)
(a) B D C A
(b) D B C A
(c) B D A C
(d) B D C A
8. Column A Column B
Cl
Cl 2
(P) 
light
 (A)

CH3 CH3

Cl 2
(Q) 
light
 (B)

Cl
Cl
Cl Cl

(R) Cl 2
  (C)
FeCl3

Cl Cl
Cl
CH3 CH 2Cl

Cl2
(S) 
FeCl
 (D)
3

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

(a) C D A B
(b) D C A B
(c) C D B A
(d) C A D B
 Chemistry : Hydrocarbons

ASSERTION-REASON TYPE QUESTIONS

The question given below consist of an ASSERTION and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.
9. Assertion : 2-Butyne changes to trans-2-butene by Li/NH3.
Reason : 2-Butene has cis- and trans-isomers.
10. Assertion : Alkyl shift in a carbocation is a Lewis acids-base reaction.
Reason : Carbocation is an electrophile and can accept lone-pair from Lewis-base (alkyl).
.
 SECTION - V
(PROBLEMS ASKED IN IIT-JEE)

A. Only one option is correct (Objective Questions)

1. The reagent(s) for the following conversion,

Br ?
Br   H H

is/are
(a) alcoholic KOH (b) alcoholic KOH followed by NaNH2
(c) aqueous KOH followed by NaNH2 (d) Zn/CH3 OH
2. The number of structural isomers for C6H14 is
(a) 3 (b) 4
(c) 5 (d) 6
3. Cyclohexene on ozonolysis followed by reaction with zinc dust and water gives compound E. Compound
E on further treatement with aqueous KOH yields compound F. Compound F is

(a) CHO (b) CHO

CO2H
(c) COOH (d)
CO2H

4. The number of stereoisomers obtained by bromination of trans-2-butene is

(a) 1 (b) 2
(c) 3 (d) 4
5. CH3—CH=CH2 + NOCl  P
Identify the adduct :

(a) CH3 —CH — CH 2 (b) CH3 —CH —CH 2

| | | |
Cl NO NO Cl

NO
|
(c) CH3 — CH 2 — CH (d) CH 2 — CH 2 —CH 2
| | |
Cl NO Cl
Chemistry : Hydrocarbons

6. What would be the poduct formed when 1-bromo-3-chloro cyclobutane reacts with two equivalents of
metallic sodium in ether?

Cl

(a) (b)
Br

(c) (d)

7. 2-phenyl propene on acidic hydration gives :

(a) 2-phenyl-2-propanol (b) 2-phenyl-1-propanol
(c) 3-phenyl-1-propanol (d) 1-phenyl-2-propanol
8. 2-hexyne gives trans-2-hexene on treatment with
(a) Li/NH3 (b) Pd/BaSO4
(c) LiAlH4 (d) Pt/H2
9. How many chiral compound are possible on mono chlorination of 2-methyl butane?
(a) 2 (b) 4
(c) 6 (d) 8
10. The nodal plane in the -bond of ethene is located in :
(a) the molecular plane
(b) a plane parallel to the molecular plane
(c) a plane perpendicular to the molecular plane which bisects the carbon-carbon -bond at right
angle
(d) a plane perpendicular to the molecular plane which contains the carbon-carbon -bond
B. More than one options are correct (Objective Questions)
1. Which one of the following has the smallest heat of hydrogenation per mole?
(a) 1-butene (b) trans-2-butene
(c) cis-2-butene (d) 1, 3-butadiene

CH3

2. Cl 2 , hv fractional distillation
H3C  N (isomeric products) C5H11Cl   M (isomeric products).

CH3

What are N and M?

(a) 6, 6 (b) 6, 4
(c) 4, 4 (d) 3, 3
SUBJECTIVE QUESTIONS
1. 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. (1995)
2. Give the structure of the major organic products from 3-ethyl-2-pentene under each of the following
reaction conditions : (1996)
(a) HBr in the presence of peroxide
(b) Br2/H2O
(c) Hg(OAc)2/H2O, NaBH4
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 gives 2, 3-dimethyl butane. Predict the
structures of X, Y and Z. (1996)
4. Complete the following, giving the structures of the principal organic proudct : (1997)

Ph H
 KNO 2 
A
Ph Br

5. The hydrocarbon A, adds one mole of hydrogen in the presence of a platinum catalyst to form
n-hexane. When A is oxidized vigorously with KMnO4, a single carboxylic acid, containing three carbon
atoms, is isolated. Give the structure of A and explain. (1997)
6. Give reason for the following in one or two sentences : (1998)
“The central carbon-carbon bond in 1,3-butadiene is shorter than that of n-butane”.
7. Complete the following reaction with appropriate structures of products/reagents: (1998)
Br2 (i) NaNH 2 (3.0 equivalent )
C6 H 5 CH  CH 2  [A]  (ii) CH I
[B]
3

8. Give reason for the following : (2000)

CH2=CH– is more basic than HCC–
9. What would be the major product in the following reaction? (2000)

H2

Lindlar catalyst

CH3

10. Monomer A of a polymer on ozonolysis yields two moles of HCHO and one mole of CH3COCHO.
(a) Deduce the structures of A.
(b) Write the structure of “all cis”—form of polymer of compound A. (2005)
Chemistry : Hydrocarbons

ANSWERS

SECTION - I
(Subjective Questions)

Answers are given in the separate booklet (Level – I to Level – III)

SECTION - II
(Single Choice Questions)
1. (a) 2. (b)
3. (b) 4. (d)
5. (a) 6. (b)
7. (b) 8. (a)
9. (a) 10. (c)
11. (c) 12. (a)
13. (a) 14. (a)
15. (c, d) 16. (d)
17. (a) 18. (b)
19. (b) 20. (d)

SECTION - III
(Multiple Choice Questions)
1. (a, c) 2. (a, b, c, d)
3. (a, b, c) 4. (a, b, c, d)
5. (c, d) 6. (c, d)
7. (a, b, c) 8. (b)
9. (a, b, c, d) 10. (a, b, c)

SECTION - IV
(Comprehension Type Questions)
1. (c) 2. (c)
3. (d) 4. (a)
5. (a) 6. (b)
 (Multiple Matching Type Questions)

8. (A) (R) (B) (S)

(C) (P) (D) (Q)

(Assertion Reason Type Questions)

9. (b) 10. (a)

SECTION - V

A. Only one option is correct (Objective Questions)

1. (b) 2. (c)
3. (a) 4. (a)
5. (a) 6. (d)
7. (a) 8. (a)
9. (b) 10. (a)

B. More than one options are correct (Objective Questions)

1. (b) 2. (b)

SUBJECTIVE
Answers are given in the separate booklet