HYDROCARBON 209

LDA - 1

Alkanes - Physical Properties, Preparation, Reactions

1. Arrange the following carboxylic acids in the increasing order of the their ease of decarboxylation:

CH3CH2COOH (I), (CH3)2 CHCOOH (II), (CH3)3 COOH (III)

2. An alkane with molecular formula C5H12 forms only one monochloro product when heated with Cl2. Give IUPAC name of this
compound.

3. An organic compound has molecular formula C6H10O2(A). A on heating with soda lime yields a hydrocarbon B(C5H10). B on
monochlorination yields a single isomeric alkyl chloride C(C5H9Cl). Deduce the structures of A, B and C.

4. A chloro derivative (A) on treatment with zinc-copper couple gives a hydrocarbon with five C atoms. When ‘A’ is dissolved in
ether and treated with sodium, 2,2,5,5-tetramethyl hexane is obtained. What is the original compound ‘A’ ?

5. Write the structures of all the alkenes that can be hydrogenated to form 2-methyl pentane.

6. Give the decreasing order of boiling points of the isomeric hexane.

7. (a) What is the effect of branching on melting and boiling points of alkanes ?

(b) Out of 2-methylhexane and 2,2-dimethyl butane, which one has higher melting point and which one has higher boiling point ?

8. A hydrocarbon has molecular formula C7H16. Predict structure of this compound satisfying the following conditions

(a) Monochlorination with Cl2/hv gives six constitutional isomers.

(b) Monochlorination with Cl2/hv gives seven constitutional isomers.

(c) Monochlorination with Cl2/hv gives only three constitutional isomers.

(d) Monochlorination with Cl2/hv gives only four constitutional isomers.

9. Give the products of the following reactions

hv
(a) Br2 ? (b)

10. (a) Arrange the following alkanes in the increasing order of their boiling point explaining the reason Pentane, hexane, 2,3-
dimethyl butane

(b) Arrange the following in increasing order of melting point

I: Pentane II: Hexane III: Heptane IV: Octane

11. Which of the following is least reactive towards base catayzed decarboxylation of a carboxylic acid?

(a) CH3CH2COOH (b) (CH3)3CCOOH (c) C6H6CH2COOH (d) F3CCH2COOH

12. 2-Methyl butane on reacting with Br2 in sunlight mainly gives :

(a) 1-Bromo-2-methyl butane (b) 2-Bromo-2-methyl butane

(c) 2-Bromo-3-methyl butane (d) 1-Bromo-3-methyl butane

HYDROCARBON 210

13. Methyl bromide is converted into ethane by heating it in ether medium with :

(a) Zn (b) Cu (c) Na (d) Al

14. During Kolbe’s electrolysis of potassium butanoate, formation of propene byproduct indicates that the reaction involve

(a) a proply carbocation (b) a propyl free-radical (c) a propyl carbanion (d) a propoxy free-radical

15. Which of the following is most reactive in base catalyzed decarboxylation reaction?

(a) (b) (c) (d)

Answer Key

0 0 0
1. The order of stability of carbanion is 1 >2 >3 . Therefore, in the given question, the relative stability of carbanion is
– – –
CH3CH2 > (CH3)2 CH > (CH3)3C . Hence, the relative ease of decarboxylation is III < II < I

Since, reactivity of decarboxylation depends on stability of carbanion intermediate, any factor that stabilizes carbanion
intermediate, facilitate the decarboxylation reaction.

2. (2, 2- dimethyl propane)

8. (a) 2-methyl hexane or 2, 3 dimethyl pentane (b) 3-methyl hexane

(c) 2,2,3- trimethyl butane or 3-ethyl pentane (d) 2,2-dimethyl pentane

9. (a) (b)

10. (a) Pentane < 2, 3- dimethyl butane < hexane (b) I < III<II<IV

11. (b) 12. (b) 13. (c) 14. (b) 15. (c)
HYDROCARBON 211

LDA - 2

Alkanes - Reactions, Alkenes - Physical Properties, Preparation

1. Show the directions of individual bond dipoles and net dipole of the molecule for
(a) 1, 1- dichloroethylene, (b) cis- and trans-1,2-dichloroethylene.
2. Addition of HBr to propene yields 2-bromopropane, while in the presence of benzoyl peroxide, the same reaction yields
1-bromopropane. Explain and give mechanism.
3. How would you convert the following compounds into benzene ?
(i) Ethyne (ii) Ethene (iii) Hexane
4. Order the following alkenes in increasing order of reactivity towards addition reaction with HCl.

(I) (II) (III)

5. On being heated with a solution of sodium ethoxide in ethanol, compound A (C7H15Br) yielded a mixture of two alkenes B and
C, each having the molecular formula C7H14. Catalytic hydrogenation of the major isomer B or the minor isomer C gave only 3–
ethylpentane. Suggest structures for compounds A, B, and C consistent with these observations.
6. Aside from concentrated sulphuric acid, what other strong acid is employed in the dehydration of alcohols?
(a) Conc. hydrochloric acid (b) Conc. acetic acid
(c) Conc. phosphoric acid (d) Conc. acetone
7. Choose the answer that has the following alkenes arranged correctly with respect to increasing stability.

(I) (II) (III)

(a) I < II < III (b) II < I < III (c) III < II < I (d) I < III < II

8.

P should be

(a) (b)

(c) both of these in equal proportions (d) none of these

HYDROCARBON 212

9.

P Should be

(a) (b)

(c) (d) none of these

10.

Which of the following reactions gives better yield of this alkene ?

(a) (b)

(c) both the these (d) none of these

11. What product is formed by bromination of 2-methyl-1-pentene ?

(a) 2-bromo-2-methyl-1-pentene (b) 1,1-dibromo-2-methylpentane

(c) 1,2-dibromo-2-methylpentane (d) 1-bromo-2-methyl-1-pentene

12. The major product in the following reaction is

(a) (b) (c) (d)

HYDROCARBON 213

13. In elecrophilic addition of HX1, question of orientation stands if alkene is :

(a) (b)
(c) (d)

14.

P should be

(a) (b) (c) (d) none of these

15.

P should be

(a) (b) (c) (d) All of these

Answer Key

5. (a) (b) (c)

6. (c) 7. (d) 8. (a) 9. (b) 10. (a)

11. (c) 12. (c) 13. (c) 14. (b) 15. (b)
HYDROCARBON 214

LDA - 3

Alkenes - Reactions
1. Three different isomeric alkenes A, B and C has molecular formula C5H10 and all on hydrogenation yields 2-methylbutane. Also
heat evolved in their hydrogenation is in the order of A < B < C. Deduce structures of A, B and C.
2. Write the structural formulae for the compounds that yield the following products on reductive ozonolysis.

(a) 2 mol butan-2-one (b)

(c) Pentan-2-one + 2-Methyl butanal

3. Complete the following reaction

(a) (b)

(c)
4. Write IUPAC names of the products obtained by the ozonolysis of the following compounds :
(i) Pent-2-ene (b) 3,4-Dimethylhept-3-ene (iii) 2-Ethylbut-1-ene (d) 1-Phenylbut-1-ene
5. An alkene ‘A’ contains three C – C, eight C – H bonds and one C – C bond. ‘A’ on ozonolysis gives two moles of an
aldehyde of molar mass 44 u. Write IUPAC name of ‘A’.
6. Predict products in the following reaction mention stereochemistry where applicable

(a) (b)

(c)

7. Give the structure of alkene that would give the following products upon reductive ozonolysis.

(a) (b)

(c) (d)
HYDROCARBON 215

8. Predict the orientation in HCl addition to these alkenes :

9. Write the structure of the major organic product formed in the reaction of 1-pentene with each of the following
(a) Hydrogen chloride (b) Hydrogen bromide
(c) Hydrogen bromide in the presence of peroxides (d) Dilute sulphuric acid
(e) Bromine in carbon tetrachloride (f) Ozone-DMS
10. Identify reagents in the following reaction

11. What products are obtained in the oxidation of 2-hexene with warm concentrated permanganate solution ?
(a) Acetate and butanone (b) Acetate and butanal (c) Acetate and butanoate (d) Acetaldehyde and butanoate
12. What is the major product(s) when 2-methyl-2-butene reacts with (i) O3 (ii) Zn/CH3COOH (aq) ?

(I) (II) (III) (IV)

(a) I + II (b) II + III (c) III + IV (d) II

13.

P should be

(a) (b) (c) (d) none of these

14.

P should be

(a) (b) (c) (d) none of these

HYDROCARBON 216

15. (I) (II) (III)

Which of the following orders is correct for the ease of electrophilic addition on these alkenes ?

(a) I > II > III (b) III > II > I (c) II > I > III (d) II > III > I

Answer Key

1. (A) (B) (C)

2. (a) 2 mol butan-2-one (b) (c) Pentan-2-one + 2-Methyl butanal

4. (i) Ethanal and propanal, (ii) Butan-2-one and pentan-2-one, (iii) Methanal and pentan-3-one, (iv) Propanal and benzaldehyde
5. But-2-ene

6. (a) (b) (c)

7. (a) (b) (c) (d)

8.

9. (a) 2-chloropentane, (b) 2-bromopentane, (c) 1-bromopentane, (d) 2-pentanol, (e) 1, 2-dibromopentane, (f) Butanal + Methanal
11. (c) 12. (b) 13. (b) 14. (b) 15. (b)
HYDROCARBON 217

LDA - 4

Alkenes - Reactions, Alkynes - Physical Properties, Preparation, Reactions

1. Write chemical equations for combustion reaction of the following hydrocarbons :

(i) Butane (ii) Pentene (iii) Hexyne (iv) Toluene

2. Reductive ozonolysis of an alkene yields an equimolar amount of cyclohexancarbaldehyde and 2-butanone. Determine structure
of original alkene.

3. Why terminal alkynes are more acidic than an alkene or an alkane ?

4. Predict products in the following reactions.

HgSO4 HgSO4
(a) C6 H5 C C H H 2SO4 (b) C6 H5 C C CH3 H 2SO4

5. What alkynes gives each of the following ketones as the only product after hydration with H2O, H2SO4 and HgSO4 ?

(a) (b) (c) (d)

6. What is the major product in the following reaction ?

(a) 2-pentyne (b) 2-chloro-1-hexene (c) 1-chloro-1-hexene (d) 1-pentyne

7. The major hydration product in the following reaction is :

C6 H 5 C C CH 3 H 2SO 4 (aq) HgSO 4

(a) C6 H 5COCH 2 CH 3 (b) C6 H 5CH 2 COCH 3 (c) C6 H 5CH 2 CH 2CHO (d) Both a and c

8. The reagent which could distinguish between 1-hexyne and 1-hexene is

(a) Ag(NH 3 ) 2 (b) KMnO4 (c) Br2 in CCl4 (d) H 2SO 4

9. What is the major organic product in the reaction ?

2 mol HBr
CH3 C CH

(a) BrCH 2 CH 2 CH 2 Br (b) CH 3CBr2 CH 3 (c) CH 3CH 2 CHBr (d) CH 2 CHBrCH 2 Br

HYDROCARBON 218

10. What is the major organic product of the reaction ?

(a) (b)

(c) (d)

11. What is the product of the following reaction ?

(a) (b) (c) (d)

12. Choose the best reagent for the following transformation

2 heptyne cis 2 heptene

+
(a) H 2 / Pt (b) Na/liq. NH3 (c) H /H2O (d) H2/Lindlar’s catalyst

13.

P should be

(a) CH 3CHO CH 3CH 2 CHO (b) CH 3COOH CH 3 CH 2 COOH

(c) A mixture of (a) and (b) (d) None of these

14.

P should be

(a) CH 3 CH 2 CH 2 CHO CH 2 O (b) CH 3 CH 2 CH 2 COOH CO 2

(c) CH3CH2 – CH2 – COOH + HCOOH (d) None of these

HYDROCARBON 219

15.

Which of the following statements is correct for these reactions ?

(a) First dehydrohalogenation is slower than second dehydrohalogenation.
(b) First dehydrohalogenation is faster than second dehydrohalogenation. This is because, in vinyl bromide C-Br bond is
stronger due to resonance.

(c) both steps of dehydrohalogenations have the same rate.

(d) none of these

Answer Key

1. (i) C4H10(g) + 13/2 O2(g) 4CO2(g) + 5H2O(g) (ii) C5 H10 (g) 15 / 2 O 2 (g) 5CO 2 (g) 5H 2 O(g)

(iii) C6 H10 (g) 17 / 2 O2 (g) 6CO 2 (g) 5H 2O(g) (iv) C7 H8 (g) 9O2 (g) 7CO 2 (g) 4H 2O(g)
3. The larger s-character of carbon (sp hybridized, has 50% s character) bearing hydrogen of terminal alkyne is responsible for its
enhanced acidity.

4. (a) (b)

5. (a) 1-heptyne, (b) Propyne, (c) 1-cyclohexylethyme, (d) 3-heptyne

6. (d) 7. (a) 8. (a) 9. (b) 10. (a)
11. (b) 12. (d) 13. (b) 14. (b) 15. (b)
HYDROCARBON 220

LDA - 5

Aromatic Compounds - Preparation of Benzene, EAS - Mechanism,

Reactions, Orientation and Reactivity
1. Give the mechanism of the following reaction

CH3
AlCl3
+ CH3C CHCH3

CH3 Cl

2. Identify the final product in each reaction

CH3
(a) + HF (b) CH2 C + HF
CH3

CH3

(c) CH3 C CH2OH + HF

CH3

OH
H3PO4
(d) + (e) + D2SO4

3. Write reaction mechanism that can account for the formation of each of the following products
CH3 CH3 O
O
Cl
Cl
(a) (b)
AlCl3 AlCl 3

4. In following reaction, write the structure of the product only monosubstitution is involved in each case,
unless otherwise indicated.
HYDROCARBON 221

5. In each of the following reactions, write the structure of the product only monosubstitution is involved
in each case, unless otherwise indicate.

(a) (b)

(c) (d)

6. Draw the structure of the major product obtained from each of the following sequences

(a) (A) (B) (b) (C) (D)

7. Predict the major product (products) that would be obtained when each of the (by single nitration)
following compounds is nitrated.
(a) N-phenyl acetamide (b) methyl benzoate (c) n-propyl phenyl ether
8. Give the products of the following reactions

(a) (b) (c)

9. Give the structures and names of the principal products expected from the ring monobromination of each of the following
compounds. In each case tell whether bromination will occur slower or faster than with benzene itself.
(a) acetanilide (b) iodobenzene (c) sec–butylbenzene (d) N–methylaniline
(e) ethylbenzoate (f) acetophenone (g) phenetole (C6H5–O–CH2CH3)
(h) diphenylmethane (C6H5CH2C6H5) (i) benzonitrile (C6H5CN) (j) benzotrifluoride (C6H5CF3)
(k) biphenyl (C6H5 – C6H5)
10. (i) Classify the following substituents as activating or deactivating groups and write the structural formula of mono–substituted
products.
(a) mono–bromination C6H5CF3. (b) mono–sulfonation C6H5CH(CH3)CH2CH3
(c) mono–nitration, C6H5COOCH3
(ii) Outline a synthesis of p–bromo–nitrobenzene from benzene in two steps.
HYDROCARBON 222

11. Ph –– NO2 + Et – Cl AlCl3 (A), Product (A) of the given reaction is

(a) Ph –– NH –– Et (b) no reaction (c) (d)

12. The action of AlCl3 in Friedel-Craft’s reaction is

(a) to absorb HCl (b) to absorb HCl
(c) to produce electrophile (d) to produce nucleophile

13.

Friedel-Crafts acylation reaction can be used to obtain the compounds

(a) II, III and IV (b) I, III and IV (c) I and II (d) II and III
14. Heating benzene in a large excess of 80% D2SO4 in D2O results in what product ?
(a) C6H5SO3D (b) C6H5OD (c) C6H5D (d) C6D6
15. Which of the following organic chlorides will not give a Friedel-Craft alkylation product when heated
with benzene and AlCl3
(a) (CH3)3CCl (b) CH 2 CHCH2Cl (c) CH3CH2Cl (d) CH 2 CHCl

Answer Key

1.

2. (a) (b) (c) (d) (e)

3. (a) FC alkylation mechanism with carbocation rearrangement, (b) FC acylation mechanism.

HYDROCARBON 223

4.

5. (a) (b) (c) (d)

6. (a) (b)

7. (a) (b) (c)

8. (a) (b) (c)

9. (a) Faster, (b) Slower,

HYDROCARBON 224

(c) Faster,

(d) Faster,

(e) Slower, (f) Slower, (g) Faster,

(h) Faster, (i) Slower,

(j) Slower,

10. (i) (a) (b) (c)

(ii)

11. (b) 12. (c) 13. (c) 14. (d) 15. (d)
HYDROCARBON 225

LDA - 6

1. A compound was obtained from a natural product and had the molecular formula C14H20O3. It contained three methoxy
(—OCH3) groups and a —CH2CH = C(CH3)2 substituent. Oxidation with either chromic acid or potassium permanganate gave
2, 3, 5-trimethoxybenzoic acid. What is the structure of the compound ?

2. What are the products formed when the different isomers of xylene are treated with acidic ?
3. What combination of acyl chloride or acid anhydride and arene would you choose to prepare each of the following compounds
by a Friedel–Crafts acylation reaction ?

(a) (b)

(c)

4. Give the major product (s) of the following reaction.

5. (i) Write the products and name them :

Cl2 Cl2
(a) Toluene Boiling condition
A (b) Toluene Fe
B C
(ii) Nitrobenzene, but not benzene, is used as a solvent for the Friedel–Craft alkylation of bromo–benzene. Explain.

6. (a)

In the above reaction which product is likely to be formed and why ?

(b)

In the above reaction which is the major product and why ?

HYDROCARBON 226

(c)

Predict the major and minor product with reaction.

7. Arrange the following in decreasing order of reactivity towards ring nitration.
(a) (1) benzene (2) mesitylene (3) toluene (4) m–xylene
(5) p–xylene
(b) (1) benzene (2) bromobenzene (3) nitrobenzene (4) toluene
(c) (1) acetanilide (2) acetophenone (3) aniline (4) benzene
(d) (1) terephthalic acid (2) toluene (3) p–toluic acid (4) p–xylene
8. (a) Predict the product

(i) (ii)

(b)

9. Arrange the following groups of compounds in order of decreasing reactivity toward electrophilic aromatic substitution
(a) (1) benzene (2) ethylbenezene (3) chlorobenzene (4) nitrobenzene
(5) anisole
(b) (1) 1–chloro–2, 4–dinitrobenzene (2) 2, 4–dinitrophenol (3) 2, 4–dinitrotoluene
(c) (1) toluene (2) p–cresol (3) benzene (4) p–xylene
(d) (1) benzene (2) benzoic acid (3) phenol (4) propylbenzene
(e) (1) p–nitrotoluene (2) 2–chloro–4–nitrotoluene (3) 2, 4–dinitrotoluene (4) p–chlorotoluene
(f) (1) bromobenzene (2) chlorobenzene (3) fluorobenzene (4) iodobenzene
10. (i) Give the structural formula and name the major alkylation product

BF3 AlCl3
(a) C 6 H 5 CH 3 CH 3 2 CHCH 2 OH ? (b) C 6 H 6 CH 3CH 2 CH 2 CH 2 Cl ?
100 C

(ii) What product (or products) would you expect to obtain when the following compounds undergo ring bromination with Br2
and FeBr3 ?

(a) (b)

11. The reaction of toluene with chlorine in the presence of light gives

(a) (b) (c) (d)

HYDROCARBON 227

12.

Identify the position where E.A.S. can take place.

(a) 1 (b) 2 (c) 3 (d) 4

13.

Identify the position where electrophilic aromatic substitution (EAS) is most favorable.
(a) A (b) B (c) C (d) A and C
14. Which position will be attacked most rapidly by the nitronium ion (– NO2)+ when the compound undergoes
nitration with HNO3/H2SO4

(a) A (b) B (c) C (d) D

15. Which of the following benzene ring substituents is deactivating but ortho-para directing ?
(a) N O (b) –– OCH3 (c) –– COCH3 (d) –– NO2

Answer Key

1.

2. (Phthalic Acid) (Isophthalic Acid) (Terephthalic Acid)

HYDROCARBON 228

3. (a) C6H5CH2COCl + C6H6 (b) p-xylene + succinic anhydride (c)

4.

6. (a)

(b)

(c)

7. (a)

(b)

(c)
HYDROCARBON 229

(d)

8. (a) (i) (ii)

(b)

10. (i) (a) (b)

(ii) (a) (b) Both are deactivated rings.

11. (c) 12. (a) 13. (b) 14. (d) 15. (a)
HYDROCARBON 230

LDA - 7
1. All questions marked “M” are multiple choice questions
2. All questions marked “C” are comprehension based questions
3. All questions marked “A” are assertion–reason type questions
(A) If both assertion and reason are correct and reason is the correct explanation of assertion.
(B) If both assertion and reason are true but reason is not the correct explanation of assertion.
(C) If assertion is true but reason is false.
(D) If reason is true but assertion is false.
4. All questions marked “X” are matrix–match type questions
5. All questions marked “I” are integer type questions

1. (M) Which of the following functional groups will satisfy the following information for electrophilic aromatic substitution ?

100

5
500

O O

(a) NHC CH3 (b) C CH3 (c) NHCH3 (d) NH3

2. (M) When aqueous solution of sodium ethanoate is elecrolysed, the product(s) at anode is/are :
(a) Ethane (b) Methyl ethanoate (c) CO2 (d) H2
3. (M) Which of the following simplest alkanes with fewest number of C atom contains 1º, 2º, 3º and 4º C atoms ?
(a) 2, 2, 3- Trimethyl pentane (b) 2, 2, 4- Trimethyl pentane
(c) 2, 3, 3- Trimethyl pentane (d) 2, 2, 3- Trimethyl butane
4. (M) Which of the following molecules of alkane will give only one monohalogenated product on reaction with halogen in
presence of sunlight ?
(a) (b)

(c) (H3C)4 C (d)

5. (M) Products can be :

(a) (b) (b) (d)

HYDROCARBON 231

Comperhension
Aromatic hydrocarbon can show electrophilic substitution reaction, oxidation, and acidic nature. They are weakly acidic
and they can be oxidized by acidic K2Cr2O7 or KMnO4 into carboxylic acids.
If alkyl group attached to benzene ring has -H-atom, it is oxidized in to -COOH group.
6. (C) Which of the following aromatic hydrocarbons is the stronger acid ?

(a) (b) (c) (d)

7. (C)

Out of the given compounds, which can give this product on oxidation ?

(I) (II) (III) (IV)

(a) I, II, III (b) I, III, IV (c) I, III (d) II, III

8. (C)

Here the product formed is ?

(a) (b)

(c) (d)

9. (I) Find out number of dimerize products obtain by following reaction.

10. (I) How many different alkynes, on treatment with HgSO4/H2SO4 can give 2-pentanone as one of the product ?
HYDROCARBON 232

11. (I) Mark the following in decreasing order of reactivity towards electrophilic aromatic substitution.

OCH3 CH2CH3 O C CH3 SCH3

(1) (2) (3) (4)

12. (A) Assertion : Benzene on heating with conc. H2SO4 gives benzene sulphonic acid (used in forming detergents) which when
heated with super heated steam under pressure gives benzene.
Reason : Sulphonation is a reversible process.
(a) A (b) B (c) C (d) D
13. (A) Assertion : Friedal Crafts Acylation of benzene with acetic anhydride in presence of anhydrous AlCl3 yields acetophenone
and not poly substituted products.

Reason : It is due to stearic hindrance of bulky acyl group (CH3 C ) and also, it is a deactivating group.

(a) A (b) B (c) C (d) D

14. (A) Assertion : Benzyl chloride (C6H5CH2Cl) reacts at faster rate than benzene towards electrophilic substitution reaction.
Reason : Benzylic hydrogens exert electron donating hyper conjugation effect to aromatic ring.
(a) A (b) B (c) C (d) D
15. (A) Assertion : Nitrobenzene on treatment with CH3CH2Cl in presence of AlCl3 gives m-nitroethyl benzene.
Reason : Nitro group (—NO2) is meta directing in electrophilic aromatic substitution reaction.
(a) A (b) B (c) C (d) D

Answer Key

1. (a, c) 2. (abc) 3. (abc) 4. (acd) 5. (ab) 6. (d)

7. (b) 8. (b) 10. (0002) 11. (1324) 12. (a) 13. (a)

14. (d) 15. (d)