ORGANIC CHEMISTRY

TARGET IIT JEE 2025

HYDROCARBON
 REACTION CHART FOR ALKANES
GMP GR
H , Ni
(1) R–C  CH 2  (1) X , h or UV light or 400 C
2         
 RX
200300C
or
R–CH=CH2 Sabatier senderens Nitration
(2)  R-N
reaction

(2) R–X Zn

Cu  HCl
 Sulphonation H S O
Re d P Hi , LiAlH 4 (3) 2
       2
7  Alkyl Sulphonic acid

(3) R–Mg–X 

HOH or ROH
  
or NH3 or RNH 2 Reed reaction
(4) SO2 + Cl2    RSO2Cl
h
Na , dry ether
(4) RX   
Wurtz reaction R–H
AlCl / HCl
Zn or (5) 3  branched alkanes
(5) RX    
 Isomerisation
Frankland's reaction R–R
or
R  C  Cl or ROH CnH2n+2 (6) Pyrolysis
(6) || Re
dP / Hi
  Alkenes
500 700 C
+ CH4 or C2H6
O
or Cr or Mo or V oxide
   
R CR or RCHO (7)  Al 2O3 500C Aromatic compound
||
O
CH N
22
(8)    Higher alkane
R CR step up reaction
Zn  Hg / Conc. HCl
(7) ||     

O Clemension 's reduction
O
2
(9) 
 CO2 + H2O
R C  O 
H 2 N  NH 2
(8) |        
 Combustion
R Wolf / Kishner reduction

or
(RCH2CH2)3B H O
 2

(9) RCOONa NaOH  CaO

  

(10) RCOONa Kolbe

's electrolytic synthesis
 

HYDROCARBON [2]
 REACTION CHART FOR ALKENES
GMP GR
conc . H SO H Ni
(1) R–CH2–CH2–OH  24  (1) 2, R–CH2–CH3
H2O 200300 C

alc
. KOH
 (2) X
2 R–CHX–CH2X
(2) R–CH2–CH2–X
 HX
HX
R–CH=CH2 (3)   R–CHX–CH3
Zn dust
  or (4) HBr , Peroxide
(3) R–CH2–CH for higher alkene
C n H 2n    R–CH2–CH2Br
X2
(5) HOCl
 R–CH(OH)–CH2Cl
R  CH  CH 2 dil. H SO
Zn
dust
2 4
(4) | |  (6)  HO R–CH2(OH)–CH3
2
X X 1/ 2 O2
(7) Ag 
300C
Ni, H 2
(5) R–C  CH 
200300C
RCH  COOK
(8) 
CH 2 N 2

(6) | Kolbe 's electrolytic synthesis
    
RCH  COOK
(9) BH
3  (RCH2CH2)3B
CO  H
R  CH  CH 3 R  CH  CH
(7) (C2H5)4N+OH  2 2 2

(10)  
HCo ( CO ) 4
| + |
Pyrolysis CHO CHO
R  C  O  CH 2  CH 2  R 
(8) 2 O
||
O
(11)  CO2 + H2O

(9) R–H Pyrolysis R  CH  CH 2
 (12) O
S O4
 | |
(10) CH2=CHCl CuR OH OH
2 
Bayer reagent R  CH  CH 2
(13)   
1% alkalineKM nO | |
4
OH OH

(14) strong R  C  OH + CO + H O
 oxidant
 || 2 2

O
Per acid
(15) Pr iles  
chalev 's reaction

3 2 O H O
  
(16) Ozonolysis +
2O

(17) 200 Polyalkene
C high P
Cl
(18)  2  Substitution product
500 C

Al (SO )
2  
(19) 200
4 3
 Isomerisation
300 C
(20) acetic
 anhydride
 R–CH2=CH–COCH3
Methyl alkenyl ketone
Alkane
(21)   Higher alkane

HYDROCARBON [3]
 REACTION CHART FOR ALKYNES
GMP GR
(1) CH2Br–CH2Br alc . KOH or NaNH 2 H2
     (1)  C2H4, C2H6
Ni
(2) CH3–CHBr2 alc. KOH , NaNH 2 X2
     (2)  C2H2X4
HBr
(3) CHCl3 Ag
powder
  (3)  CH BrCH Br
3 2
 Peroxide
C2 H 2
HBr
(4) CHBr2–CHBr2 Zn
dust
 
(4) No  CH –CHBr
 Peroxide 3 2

CHBr (5) HOCl

 Cl2CHCHO
(5) || Zn
(6) HCN , Ba ( CN ) 2
CHBr
   2  CH2=CHCN
CH COOH , Hg
(7) 3    CH3CH(OCOCH3)2
(6) CH2=CH–Cl alc. KOH , NaNH
    2  Hg 2 , 80C , dil. H SO
2
(8)      4  CH CHO
HC  COONa Kolbe's electroly tic synthesis 3
( Kucherov 's reaction )
(7) ||       
HC  COONa (9) Conc
 
. H 2SO 4
 CH3CH(HSO4)2
H O AsCl

2
 (10) Ca det 3  CHCl=CHAsCl2
(8) CaC2 & Bunsen reaction
electric arc,1200C
(9) 2C + H2     
 C 2 H 5OH / H 2O
Berthelot 's process (11)   
HgSO
 CH CHO
3
4
(10) CH3–CCH ( i ) Na ( ii ) R X
   
 CO  HOH
(i ) CH 3MgI (ii ) R X (12)    CH =CH–COOH
(10) CH3–CCH      Ni ( CO ) 2 4

CO  EtOH
(13)    CH =CH–COOEt
Ni,160C 2

(14) NaNH
 2  Na–CC–Na
AgNO3  NH 4OH
(15) (    Ag–CC–Ag
Tollen 's Re agent )
(16) Cu Cl  NH OH
22 4  Cu–CC–Cu
Combustion
(17)     O2
 CO2 + H2O
CHO
(18) Bayer
 Reagent
 |  HCOOH
CHO
3O

(19) Ozonolysis H O
2
  HCOOH
Trimerisat ion
(20)    benzene
(Re d hot iron tube)

(21) Trimerisat
 ion  C8H8or 1,3,5,7-cyclo octa tetraene
[ Ni (CN ) 2 ]
Dimerisati on
(22)    butenyne
[ Cu ( NH 3 ) 2 ]
s
(23) 



CH OH
(24)  3  methylal
( BF  HgO )
3

HYDROCARBON [4]
 EXERCISE - I

Q.1 How many moles of O2 required for complete combustion of one mole of propane –
(A) 7 (B) 5 (C) 16 (D) 10

Q.2 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.3 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 the concentration of the electrolyte is not very high

Q.4 BrCH2–CH2–CH2Br reacts with Na in the presence of ether at 100 °C to produce –

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

Q.5 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

CH 3 C  NH 2
||
Q.6 Br Mg
 / dry ether
 (X)     (Y) O

The structures of (X) and (Y) respectively are

(A) X = MgBr ; Y= OH

(B) X = ; Y=

(C) X = MgBr ; Y=

(D) X = BrMg MgBr ; Y = HO OH

Q.7 When n-butane is heated in the presence of AlCl3/HCl it will be converted into –
(A) Ethane (B) Propane (C) Butene (D) Isobutane

HYDROCARBON [5]
 O
||
Q.8 Alkene A O
3 / H2O
 CH 3  C  CH 3 + CH3COOH + CH 3  C  COOH
||
O
A can be –
C(CH 3 ) 2
||
(A) (B) CH 3  C  CH  HC  CH 3
(C) Both correct (D) None is correct

CHCOOH
Q.9 CH2=CH–CH=CH2 + || 
 product X by reaction R. X and R are
CHCOOH

(A) Diels Alder (B)

(C) Diels Alder (D)

Q.10 The addition of bromine to 3-Methyl Cyclohexene in 1,2-dichloroethane produces ____ dibromo
derivatives:
(A) 2 (B) 3 (C) 4 (D) 6

Q.11 (E)-3-bromo-3-hexene when treated with CH3O in CH3OH gives

(A) 3-hexyne (B) 2-hexyne
(C) 2,3-hexadiene (D) 2,4-hexadiene

Br NaI
Q.12 

P(Alkene)  2    Q (Alkene)
CCl 4 Acetone

Alkene (P) & (Q) respectively are

(A) Both (B) ,

(C) Both (D) Both

Q.13 Ozonolysis of CH3–CH=C=CH2 will give

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

HYDROCARBON [6]
Q.14 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

Q.15 The reacting species of alc. KOH is –

(A) OH– (B) OR+ (C) OK+ (D) RO–

Q.16 Anti–Markownikoff’s addition of HBr is not observed in –

(A) Propene (B) But–2–ene
(C) Butene (D) Pent–2–ene

Q.17 alcoholic
  KOH  product


Major product is:

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

Q.18 Which is expected to react most readily with bromine –

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

BH / THF
3 H O
Q.19 B HO/ OH


3
  A
2 2

A and B are –

(A) Both (B) Both

(C) (D)

2 6 B D
Q.20 CH3CH=CH2 HO  product X
/ OH 
2 2

X is –
(A) CH 3  CH  CH 2 D (B) CH 3  CH  CH 2OH
| |
OH D

(C) CH 3  CH  CH 3 (D) none is correct

|
OD

HYDROCARBON [7]
Q.21 CH2=CH–CH=CH2 CCl Br
 3 product. The major product is –
peroxide

(A) Br–CH2–CH=CH–CH2–CCl3 (B) CH 2  CH  CH  CH 2  CCl 3

|
Br

(C) CH 2  CH  CH  CH 2  Br (D) None is correct

|
CCl 3

Q.22 Dehydration of 2, 2, 3, 4, 4–pentamethyl–3–pentanol gave two alkenes A and B. The ozonolysis products
of A and B are -
O
||
(A) A gives (CH 3 )3 C  C  C(CH 3 )3 and HCHO

O
||
B gives CH 3  C  CH 2  C(CH 3 )3 and HCHO

O
||
(B) A gives (CH 3 )3 C  C  C(CH 3 )3 and HCHO

O CH 3
|| |
B gives CH 3  C  C  C(CH 3 )3 and HCHO
|
CH3

O
||
(C) A gives (CH 3 )3 C  C  CH (CH 3 ) 2 and HCHO

O
||
B gives (CH 3 )  CH 2  C  C(CH 3 )3 and CH3CH2CHO
(D) None of these

HYDROCARBON [8]
 
Con . H SO O 3 / H 2O / Zn
Q.23 + CH3MgBr H
3O
 A  24  B    C
A, B and C are –
A B C

(A)

(B)

(C)

(D)

Q.24 Which has least heat of hydrogenation –

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

(1) Hg ( OAc ) / H O / THF

2
Q.25     2  
 A. A is –
( 2 ) NaBH 4 / NaOH / H 2O

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

Q.26 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

x
Q.27 CH3–CH=CH–CH3   product is Y (non–resolvable) then X can be –
cis
(A) Br2 water (B) HCO3H
(C) Cold alkaline KMnO4 (D) all of the above

HYDROCARBON [9]
Q.28 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

18

( i ) CH COO OH
Q.29  3   X
( ii ) H 3O 

The probable structure of ‘X’ is

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

Q.30 Compound (A) on oxidation with hot KMnO4 / OH gives two compound
O
||
CH 3  CH  COOH & CH 3  C  CH 2CH 2CH 3
|
CH 3
compound A will have structure.
(A) CH 3CH 2  C  C  CH 2CH 3 (B) CH 3  CH  CH  C  CH 2CH 2CH 3
| | | |
CH 3 CH 3 CH 3 CH 3

(C) CH 3CH  C  C  CH 3 (D) CH 3  CH  C  C  CH  CH 3

| | |
CH 3 CH 3 CH 3

O O (1 eq )
s 4
Q.31   X.
H 2O / Acetone

Identify ‘X’.

(A) (B)

(C) (D) Reaction will not occur

HYDROCARBON [10]
Q.32 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

A
Q.33 

A can be –
(A) Conc. H2SO4 (B) alcoholic KOH (C) Et 3N (D) t-BuOK

CH 3
|
HC
Q.34 || alkaline KMnO
HC
   4  A, which is true about this reaction?
|
CH 3

(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) A is 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.35 Identify (P) in the following reaction:


H / H2O
+2    (P)

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

Q.36 The reaction of cyclooctyne with HgSO4 in the presence of aq. H2SO4 gives

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

2 H SO NBS
Q.37  4  P (Major)  Q (Major)

The structure of Q is

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

Q.38 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

Q.39 Acetylene may be prepared using Kolbe’s electrolytic method employing –

(A) Pot. acetate (B) Pot. succinate (C) Pot. fumarate (D) None of these

HYDROCARBON [11]
Q.40 B  Lindlar Na / NH
 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.41 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
3
Q.42 B    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.43 Which of the following reagents cannot be used to locate the position of triple bond in CH3–CC–CH3
(A) Br2 (B) O3 (C) Cu 22 (D) KMnO4

Q.44 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 of A 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.45 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

Q.46 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.

HYDROCARBON [12]
Q.47 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.48 PMA polymer is formed by methyl acrylate, which is prepared as follows –

CO  CH OH
(A) R – C  CH CO  ROH
   3
(B) HC  CH    
Ni ( CO ) 4

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

NH Cl
Q.49  4 product
CHCH Cu Cl 2 2

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

Q.50 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

HYDROCARBON [13]
 EXERCISE - II

Q.1 Aqueous solution of potassium propanoate is electrolysed. Possible organic products are:
(A) n-Butane (B) C2H5COOC2H5 (C) CH3–CH3 (D) CH2=CH2

A
Q.2 Ph  C  CH 3  Ph–CH2–CH3
||
O
A could be:
(A) NH2NH2, glycol/OH– (B) Na(Hg)/conc. HCl
(C) Red P/HI (D) CH 2  CH 2 ; Raney Ni – H2
| |
SH SH

H / Pt
Q.3 (A) C4H6 2  (B) C4H8 O
3 / H2O
 CH3COOH
Hence A and B are
(A) CH3C  CCH3, CH3CH = CHCH3 (B) CH2 = CHCH3 = CH2, CH3CH = CHCH3
(C) , CH3CH = CHCH3 (D) None

Q.4 CH2 = 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.5 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

Q.6 CH3– CH = CH–CH3 + CH2N2 

 A
A can be

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

HYDROCARBON [14]
Q.7 Ph–CH=CH2 + BrCCl3 peroxide
 
Product is:

(A) (B)

(C) (D)

Q.8 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.9 OH

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

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

Q.10 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.11 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

HYDROCARBON [15]
Q.12 Select true statement(s):
(A) I2 does not react with ethane at room temperature even though I2 is more easily cleaved homolytically
than the other halogens.
(B) Regiochemical outcome of a free radical addition and an electrophilic addition reaction on propene
is identical.
(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.

Q.13 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.14 Which reagent is the most useful for distinguishing compound I from the rest of the compounds
CH3CH2CCH CH3CCCH3 CH3CH2 CH2CH3 CH3CH=CH2
I II III IV
(A) alk. KMnO4 (B) Br2/CCl4
(C) Br2/CH3COOH (D) Ammonical AgNO3

Q.15 C    A HgSO
BH3 / THF
 4  B
H 2O 2 / OH  H 2SO 4

B & C are identical when A is –

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

Q.16 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

HYDROCARBON [16]
Q.17 Match the column
Column I Column II

(A)  (P) Birch reduction

(B)  (Q)Stephen’s reduction

(C)  (R) Wolf-Kishner reduction

(D)  (S) Clemmensen reduction

Q.18 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

HYDROCARBON [17]
Q.19 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
2
(B) CH 3  C  CH 2      (Q) CH3–CH=CH–CH3
( ii ) NaBH 4
|
CH 3
Cl
|
(C) CH 3  CH 2  CH  CH 3 CH ONa / 
3   (R) CH 3  CH  CH 2OH
|
CH 3
Cl OH
| ( CH3 )3 CONa
|
(D) CH 3  CH 2  CH  CH 3     (S) CH 3  C  CH 3

|
CH 3

Q.20 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 , 

HYDROCARBON [18]
 EXERCISE - III

Q.1 Chlorination of ethane to ethyl chloride is more practicable than the chlorination of n-pentane to
1-chloropentane.
Q.2 Why n-pentane has higher boiling point than neopentane?

Q.3 (a) NaOH

 A. Write the structure of A.
Alc.

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

Q.4 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 products A through E.
E(C10H18O2) A(C10H16Br2)
 H2O  Br2/CCl4
C10H16O(D)  PhCO 3 H
 –pinene Br  B (C10H17OBr)
2  H2O

Q.5 Propose structures for intermediates & products A to K

HYDROCARBON [19]
Q.6 Identify the following (A to D).

Q.7 What will be the product in the following reaction

+ 
(i)  (ii) +  

CO2Me

(iii) + 
 (iv) + 


(v) + Br2  A 1

. NaNH 2 ( 3equiv .) NH 3
 B
2. CH 3I

Q.8 Write the structural formula of limonene from the following observation:
(a) Limonene when treated with excess H2 & Pt catalyst, the product formed is 1 isopropyl · 4 methyl cyclohexane
(b) When it is treated with O3 & then Zn/H2O the products of the reaction are HCHO & following compound

Q.9 There are six different alkene A, B, C, D, E and F. Each on addition of one mole of hydrogen gives G
which has the lowest molecular wt hydrocarbon containing only one asymmetric carbon atom. None of
the above alkene give acetone as a product on ozonolysis. Give the structures of A to F. Identify the
alkenes that is likely to give a ketone containing more than five carbon atoms on treatment with a warm
conc. solution of alkaline KMnO4.

Q.10 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) gives an alkene that is reductively ozonized
to Me2CO. Give the structures of (I) and (J) and explain the formation of the later.

HYDROCARBON [20]
Q.11 Three isomeric alkenes A, B and C, C5H10 are hydrogenated to yield 2methylbutane A and B gave the
same 3° ROH on oxymercuration demercuration. B and C give different 1° ROH’s on hydroboration
-oxidation. Supply the structures of A, B & C.

Q.12 Two isomeric alkyl bromides A and B (C5H11Br) yield the following results in the laboratory. A on
treatment with alcoholic KOH gives C and D (C5H10). C on ozonolysis gives formaldehyde and
2 methyl propanal. B on treatment with alcoholic KOH gives only C (C5H10). Deduce the structures of
A, B, C and D. Ignore the possibility of geometrical and optical isomerism.

Q.13 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.14 An alkylhalide, 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dimethylbutane predict the structures
of X, Y and Z.

Q.15 A hydrocarbon A, 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 by carbondioxide and acidification. Identify A, B and C and also give equations for the reactions.

Q.16 Compound A (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 from A to F.

Q.17 A organic compound A having carbon and hydrogen, adds one mole of H2 in presence of Pt catalyst to
form normal hexane. On vigorous oxidation with KMnO4, it gives a simple carboxylic acid containing 3
carbon atoms. Assign the structure to A.

Q.18 Give the product of

CH3 H 1. BD .THF
(a) 
BH
3  A H
2O 2
 B (b) C=C  3 

THF OH ¯ H 2. D 2O 2 , DO 
CH3

3 1. CF CO H
3
Q.19   
  A + B. What are A and B?
2. H 2O / H 

Q.20 Give the structure of the alkene that yields on ozonolysis

(i) CH3CH2CH2 CHO & HCHO (ii) C2H5COCH3 & CH3CH(CH3) CHO
(iii) Only CH3CO.CH3 (iv) CH3.CHO & HCHO & OHC.CH2.CHO
(v) Only OHC-CH2CH2CH2–CHO.

HYDROCARBON [21]
Q.21 What are A to K for the following reactions
ArCH 2 Cl
(i) PhC  CH + CH3MgX  A     B Li
/ NH 3
 C.
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) NBS
 K

Q.22 Explain the following:

(i) 1, 2 shift does not take place during oxymericuration demercuration. Why?
(ii) Halogneation of alkene is anti addition but not syn addition. Why?
(iii) Anti markovnikov addition is not applicable for HCl. Why?
(iv) 1,4–addition takes place in butadiene. Why?

Q.23 Conversion:
(i) C2H2  racemic 2, 3 dibromobutane (ii) 2-butyne  2-pentyne
(iii) Ethyne  Acetone (iv) cis but 2 ene  Trans but 2 ene
(v) Ethene  Propionic Acid

Q.24 (a) Outline a stereospecific synthesis of meso 3, 4 dibromohexane from ethyne.

(b) Acetylene is acidic but it does not react with NaOH or KOH. Why?

Q.25 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.

HYDROCARBON [22]
 EXERCISE - IV (A)

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

Q.5 The product obtained on acidic hydration (HgSO4 + H2SO4) of 1–butyne would be –
(A) CH 3  CH 2  C  CH 3 (B) CH3–CH2–CH2–CHO
||
O
(C) CH3–CH2–CHO + HCHO (D) CH3–CH2–COOH + HCOOH

Q.6 When cyclohexane is poured on water, it floats, because – [IIT ‘97]

(A) Cyclohexane is in ‘boat’ form (B) Cyclohexane is in ‘chair’ form
(C) Cyclohexane is in ‘crown’ form (D) Cyclohexane is less dense than water

Q.7 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.8 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.9 Propyne and propene can be distinguished by – [IIT ‘2000]

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

Q.10 Which one of the following alkenes will react fastest with H2 under catalytic hydrogenation condition –
[IIT ‘2000]

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

Q.11 In the presence of peroxide, hydrogen chloride and hydrogen iodide do not give anti–Markovnikov
addition to alkene because – [IIT S‘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

HYDROCARBON [23]
Q.12 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

Q.13

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) A racemic mixture (D) A diastereomeric mixture

Q.14 Consider the following reactions – [IIT ‘2002]

H 3C  CH  CH  CH 3 + ‘X’ + HBr
| |
D CH3
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.15 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

Q.16 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.17 C6H5–CC–CH3  4  A [IIT ‘2003]
H 2SO 4

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

| |
OH OH

HYDROCARBON [24]
 
Q.18 H x Br
 H 2O ( mixture )  2  5 compounds of molecular formula C4H8Br2
Number of compounds in X will be: [IIT ‘2003]
(A) 2 (B) 3 (C) 4 (D) 5

Q.19 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.20 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.21 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.22 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.23 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.24 The number of stereoisomers obtained by bromination of trans-2-butene is [IIT 2007]
(A) 1 (B) 2 (C) 3 (D) 4

Q.25 The number of structural isomers for C6H14 is [IIT 2007]

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

Q.26 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

HYDROCARBON [25]
 EXERCISE - IV (B)
Cl
|
Q.1 (CH 3 ) 2 C  CH 2CH 3 alc. KOH
  ? [IIT 1992]

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

Q.3 C(C6H12), an optically active hydrocarbon which on catalytic hydrogenation gives an optically inactive
compound, C6H14. [IIT 1993]

Q.4 Draw the stereochemical structure of the product in the following reactions. [IIT 1994]
2 H
R–CC–R 
Lindlar catalyst

Q.5 Write down the structures of the stereoisomers formed when cis–2–butene is reacted with bromine.
[IIT 1995]

Q.6 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.7 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

Q.8 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.9 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.10 One mole of the compound A (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.11 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.12 The central carbon–carbon bond in 1,3–butadiene is shorter than that of n–butane. Why?

Q.13 Write the intermediate steps for each of the following reaction. [IIT 1998]

H


HYDROCARBON [26]
Q.14 Write the intermediate steps for each of the following reaction [IIT 1998]
C6H5CH(OH)CCH  C6H5CHCHCHO

Q.15 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

Q.16 Discuss the hybridisation of carbon atoms in allene (C3H4) and show the –orbital overlaps.
[IIT 1999]

Q.17 Complete the following – [IIT 1999]

1 2 3

 
 


Q.18 Complete the following – [IIT 1999]

4 5 6

 
 


Q.19 Explain briefly the formation on the products giving the structures of the intermediates. [IIT 1999]

(i) HCl
 + + etc.

But

(ii) HCl


Explain the non formation of cyclic product in (ii)

Q.20 What would be the major product in each of the following reactions? [IIT 2000]
CH 3
|
CH 3  C  CH 2 Br C 2 H 5OH 2

H
(i)   (ii)
|  Lindlar 's Catalyst
CH 3

Q.21 CH2=CH– is more basic than HCC– [IIT 2000]

Q.22 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 of A, B and C with all intermediates. [IIT 2001]

HYDROCARBON [27]
Q.23 A biologically active compound, Bombykol (C16H30O) 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 compound A and Bombykol.
How many geometrical isomers are possible for Bombykol? [IIT 2002]

Q.24 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]
(i ) NaNH H / Pd  BaSO
CH3CH2CC–H   2  X 2   4  Y alkaline KMnO
   4  Z
( ii ) CH 3CH 2 Br

Q.25 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
H ,  3
Q.26  X     Y.
( ii ) Zn / Cl COOH 3

Identify X and Y. [IIT 2005]

HYDROCARBON [28]
 ANSWER KEY

EXERCISE - I
Q.1 B Q.2 C Q.3 A Q.4 C Q.5 B Q.6 C Q.7 D
Q.8 C Q.9 A Q.10 A Q.11 C Q.12 C Q.13 D Q.14 D
Q.15 A Q.16 B Q.17 A Q.18 D Q.19 D Q.20 B Q.21 A
Q.22 B Q.23 A Q.24 C Q.25 C Q.26 D Q.27 C Q.28 B
Q.29 A Q.30 B Q.31 B Q.32 B Q.33 A Q.34 A Q.35 A
Q.36 D Q.37 C Q.38 B Q.39 C Q.40 A Q.41 C Q.42 B
Q.43 A Q.44 A Q.45 A Q.46 C Q.47 A Q.48 B Q.49 B
Q.50 C

EXERCISE - II

Q.1 A,B,C,D Q.2 A,B,C,D Q.3 A,B Q.4 A,B

Q.5 A,B,C Q.6 A,B,C,D Q.7 A,C Q.8 B,C
Q.9 B,C,D Q.10 A,C Q.11 A,B,D Q.12 A,C,D
Q.13 A,B,C,D Q.14 D Q.15 A,C
Q.16 (A) P (B) R (C) S (D) Q Q.17 (A) S; (B) R; (C) P; (D) R,S
Q.18 (A) Q, (B) R, (C) S, (D) P Q.19 (A) R (B) S (C) Q (D) P
Q.20 (A) Q, (B) P (C) S (D) R

EXERCISE - III

Q.2 n - pentane has larger surface area and hence stronger Vander waal’s forces.

H
D
D

Q.3 (a) (b)

D H NMe2
H

Br H
Q.4 H Br
+ Br
Me
Br Me
 - pinene

Br Br
H
Me
 OH C Me

OH
O OH
D Me

HYDROCARBON [29]
 +
Q.5 OH O¯Na O
(A) (B) (C)
OH

MgBr CH3–(CH2)3–CH–(CH2)3–CH3
(D) (E) Br

(F) Br
(G)

C C–CH3
Q.6
A B

COOH COOH
HOOC H

C D

Me Me CO2Me
+
Q.7 (i)
CO2Me

O
NO2
O H
(ii) (iii) H
Ph
O

Br
Br CC–CH3
(iv) No Reaction (v) +
A B

Q.8

HYDROCARBON [30]
Q.9

A B C

D E F

Q.10
I I
I J

Q.11
B A C

Q.12
Br
A C
Br

B D

Q.13 (a) CH 3 –CH = CH –CH3 (A)

(b) (B)
H

(c)
CH3–C –CH=CH3 (C)
CH3–CH3

Q.14 Br
X Y Z

C C COOH
Q.15
(A) (B)

HYDROCARBON [31]
 Br

Q.16
Br
(A) (B)
OH
C C–CH3
OH
(C) (D)
CH3COOH COOH
(E) (F)

Q.17
(A)
CH3 CH3
H D D H
Q.18 (a) (A) = , (B) = (b) +
DO H H OD

CH3 CH3

Q.19 A & B are two enatiomers

C
|
Q.20 (i) C–C–C–C=C, (ii) C  C  C  C  C  C , (iii) C  C  C  C , (iv) C–C=C–C–C=C,
| | |
C C C

(v)

Ph  CH  Et
Q.21 (A) PhCCMgx, (B) Ph–CC–CH2Ar, (C) , (D) | ,
Br

(E) Ph–CH=CH–Me trans, (F) Ph  CH  CH  Me (threo mix.), (G) Ph–COOH

| |
OH OH

(H) cold dil. KMnO4, (I) HCO3H, (J) CF3CH2CH2Br, (K)

HYDROCARBON [32]
 EXERCISE - IV (A)

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

Q.8 D Q.9 D Q.10 A Q.11 C Q.12 B Q.13 B Q.14 B
Q.15 A Q.16 D Q.17 A Q.18 B Q.19 B Q.20 A Q.21 B
Q.22 D Q.23 A Q.24 A Q.25 C Q.26 B

EXERCISE - IV (B)
Q.1 CH 3  C  CH  CH 3
|
CH 3

Q.2 alc
. KOH
 HBr

heat

H
|
Q.3 CH 3  CH 2  C  CH  CH 2
|
CH 3
(C 6 H12 )

Q.4

Q.5

CH 2 CH 2
|| ||
Q.6 (E) CH 3  C  CH

Br OH
| |
Q.7 (a) (CH3–CH2)2 CH  CH  CH 3 ; (b) (CH3–CH2)2 C  CH  CH 3 ; (c) (C2H5)3C–OH
|
Br

CH 3 CH 3 CH 3 CH 3 CH 3 CH 3
| | | | | |
Q.8 CH 3  C  CH  CH 3 ; (Y) CH 2  C  CH  CH 3 ; (Z) CH 3
 C  C  CH 3
|
Cl

HYDROCARBON [33]
 C
C C | 
conc. H2SO4
Q.9 C–C–C–C C–C–C–C CCCC
–H2O
 |
C OH + C OH2 C
H

1,2-methyl shift

H  
C  C  C  C  C  C  C  C
| | | |
C C C C

Q.10 (A) (B)

Q.11 (A) CH3–CH2–CH=CH–CH2–CH3 (B) CH3CH2COOK

Q.12 Presence of partial double bond character due to resonance.

+ +
Q.13 H –H


3 H O
Q.14 C6H5CH(OH)CºCH  


OH 
C6H5CH=CHCHO C6H5CH=C= CH  C6H5CH=C= C H
|
OH

Q.15 (1) NaNH2, (2) Me–I, (3) HgSO4 dil H2SO4

Q.16 H2C = C = CH2

P4 –P4
P3–P3

Q.17 1 ozonolysis ; 2 LiAlH4 ; 3 H2SO4

Q.18 (4)  HO–Cl ; (5)  CH3MgCl ; (6) H2O/H+

HYDROCARBON [34]
   Cl
Q.19 (i) H   Cl¯ 
OH H 2O

 Cl¯ Stable by -resonance

Cl

 Cl ¯
(ii) H   
OH Cl

In this reaction intermediate is 2°-carbocation, which is more stable than 1°-carbocation in problem (i).
So it can not rearrange in cyclic cation.
CH 3
|
Q.20 (i) CH 3  C  CH  CH 3 (ii)

Q.21 higher electronegativity of sp carbon

alc.KOH 
Q.22 H3C – CH2 – CH – C CH H3C – CH2 – CH – C CH
– H 2O
H

H 2O 
H3C – CH2 – CH = C CH2 H3C – CH2 – CH = C CH
– H 2O alc.KOH

 
H3C – CH2 – C = C CH2 H3C – CH2 – C  C –CH2
H 2O

H3C – CH2 – C  C –CH3

Q.23 Bombykol :- HO–C–C–C–C–C–C–C–C–C–C=C–C=C–C–C–C

(A) :- 4 geometrical isomers are possible

Q.24 (X)  Et–CC–Et (Y)  (Z)  Z is meso so optically inactive

HYDROCARBON [35]
 CH 3
|
Q.25 (a) CH 2  C  CH  CH 2 (b)

O
||
Q.26 (X) , (Y) CH 3  C  (CH 2 ) 4  CH  O

HYDROCARBON [36]