REACTION CHART FOR ALKANES

GMP
(1) RC CH or RCH=CH2 (2) (3) (4) (5) (6) RX RMgX RX RX
R C Cl or ROH || O
2

GR
H , Ni 200 300C

(1)

2 RX

X , h or UV light or 400 C

Sabatier senderens reaction

Cu + HCl Zn Re d P Hi , LiAlH 4 HOH or ROH + or NH3 or RNH2
dry ether Na , Wurtz reaction

(2) (3) (4) RH or (5) RR or CnH2n+2 (6)

R-N

Nitration

2 2 7 Alkyl Sulphonic acid

Sulphonati on H S O

SO2 + Cl2 RSO2Cl

h AlCl / HCl

Reed reaction

Zn
Frankland 's reaction

3 branched alkanes

Isomerisation

P / Hi Re d

Alkenes

Pyrolysis

500700 C

+ CH4 or C2H6

or
R CR || O

or

RCHO

(7)

Cr or Mo or V oxide + Al 2O3 500C

Aromatic compound

(7)

R CR || O R C = O | R

(8)

Clemension 's reduction Zn Hg / Conc. HCl

2 2

CH N

step up reaction

Higher alkane

(9)

(8)

H 2 N NH 2

CO2 + H2O

Wolf / Kishner reduction

Combustion

or (RCH2CH2)3B (9) (10) RCOONa RCOONa

2

+H O

NaOH + CaO

's electrolytic synthesis Kolbe

Page 2 of 40 HYDROCARBONS

REACTION CHART FOR ALKENES

GMP (1) RCH2CH2OH (2) RCH2CH2X (3) RCH2CH (4) R CH CH 2 | | X X
4 2

GR
conc. H SO H 2O
2, RCH2CH3 (1)

H Ni

200300 C

. KOH alc HX

2 (2) X RCHXCH2X

for higher alkene X 2

Zn dust

HX RCHXCH3 RCH=CH2 (3) or , Peroxide (4) HBr RCH2CH2Br C n H 2n

(5) HOCl RCH(OH)CH2Cl

dil. H SO
2

Zn dust
Ni, H 2

2 4 RCH (OH)CH (6) 2 3 +H O

(5) RC CH (6)

200300C

(7) Ag 300C
CH 2 N 2 (8) +
3 (9) BH (RCH2CH2)3B

1 / 2 O2

RCH COOK Kolbe's electrolytic synthesis | RCH COOK

(7) (C2H5)4N+OH (8)

R C O CH 2 CH 2 R || O

Pyrolysis

(10) HCo ( CO)

4

CO + H 2 O2

R CH CH 3 R CH 2 CH 2 | | + CHO CHO

(11) CO2 + H2O

S O4 (12) O

(9) RH (10) CH2=CHCl

Pyrolysis
CuR

R CH CH 2 | | OH OH R CH CH 2 | | OH OH

Bayer reagent (13) 1% alkalineKMnO

4

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

Per acid (15) Pr iles chalev 's reaction

(16)

3 2 Ozonolysis

O +H O

2 (17) 200 Polyalkene C high P 2 (18) Substitution product 500 C 2 4 3 Isomerisation (19) 200 300 C

Cl

Al (SO )

anhydride (20) acetic RCH2=CHCOCH3 Methyl alkenyl ketone Alkane (21) Higher alkane

Page 3 of 40 HYDROCARBONS

REACTION CHART FOR ALKYNES

GMP . KOH or NaNH 2 (1) CH2BrCH2Br alc (2) CH3CHBr2 (3) CHCl3 (4) CHBr2CHBr2

alc. KOH , NaNH 2

GR
2 (1) C2H4, C2H6

(2) C2H2X4
HBr CH BrCH Br (3) 3 2 Peroxide

Ni X2

Ag powder

Zn dust

C2 H 2

HBr CH CHBr (4) No 3 2 Peroxide

CHBr (5) || CHBr (6) CH2=CHCl (7)

(5) HOCl Cl2CHCHO

Zn
2

alc. KOH , NaNH

, Ba ( CN ) 2 (6) HCN CH2=CHCN + 2 (7) CH 3COOH , Hg CH3CH(OCOCH3)2

4 2 CH CHO (8) 3 ( Kucherov 's reaction )

Hg +2 , 80C , dil. H SO

HC COONa Kolbe's electrolyticsynthesis || HC COONa

2

. H 2SO 4 (9) Conc CH3CH(HSO4)2

3 (10) Ca det CHCl=CHAsCl2 & Bunsen reaction

(8) CaC2 (9) 2C + H2 (10) CH3CCH (10) CH3CCH

H O

AsCl

C electric arc ,1200

Berthelot 's process

CH CHO (11) 3 HgSO

4

C 2 H 5OH / H 2O

i ) Na (ii ) R X (

( i ) CH 3MgI ( ii ) R X

CH =CHCOOH (12) 2 Ni ( CO )
4

CO + HOH

CH =CHCOOEt (13) 2 Ni ,160C

2 (14) NaNH NaCCNa

CO + EtOH

AgCCAg (15) ( Tollen 's Re agent )

Cl 2 + NH 4OH (16) Cu 2 CuCCCu Combustion O2 (17) CO2 + H2O

AgNO3 + NH 4OH

Re agent (18) Bayer |

3 (19) Ozonolysis

CHO CHO

HCOOH
+H O

2 HCOOH

(20) benzene
(Re d hot iron tube )

Trimerisat ion

ion (21) Trimerisat C8H8or 1,3,5,7-cyclo octa tetraene [ Ni ( CN ) 2 ]

butenyne (22) +
[ Cu ( NH3 ) 2 ]

Dimerisation

s (23)

3 (24) ( BF HgO )
3

CH OH

methylal

Page 4 of 40 HYDROCARBONS

EXERCISEI (A)
Q.1 In the given reaction C7H12 (A) HCl (A) is: (A) Q.2 (B) (C) (D) All of these

1-Methylcyclopentene can be converted into the given compound

by the use of which of the following reagents? (A) BD3 followed by HCOOH (B) BH3 followed HCOOD (C) BD3 followed by HCOOD
Q.3 Identify (P) in the following reaction: +2
H / H 2O (P)

O || (D) BH3 followed by D C O H

(A) Q.4

(B)

(C)

(D)

The reaction of E-2-butene with CH2I2 and ZnCu Couple in either medium leads to formation of (A) (B) (C) (D)

Q.5 Q.6

(E)-3-bromo-3-hexene when treated with CH3Or in CH3OH gives (A) 3-hexyne (B) 2-hexyne (C) 2,3-hexadiene

(D) 2,4-hexadiene

The reaction of cyclooctyne with HgSO4 in the presence of aq. H2SO4 gives (A) (B) (C) (D)

Q.7 amount.

h + Br2 mixture of product. Among the following which product will formed minimum

(A)

(B)

(C)

(D)

Page 5 of 40 HYDROCARBONS

Q.8

NBS 2 4 Q (Major) P (Major)

H SO

The structure of Q is

(A)

(B)

(C)

(D)

18

Q.9

3 X

(i ) CH COO OH (ii ) H3O

The probable structure of X is

(A)

(B)

(C)

(D)

Q.10

2 Q (Alkene) P(Alkene)

Br

NaI

CCl4

Acetone

Alkene (P) & (Q) respectively are (A) Both (B) ,

(C) Both Q.11

3CH=C=CH2 will give (A) Only CH3CHO (C) Only CO2
z o n o l y s i s o f C H

(D) Both

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

Q.12 O-xylene on ozonolysis will give O || CHO (A) | & CH 3 C CHO CHO
O CH 3 C = O || | (B) & CH 3 C CHO CH 3 C = O O CH 3 C = O || CHO | (D) , CH 3 C CHO & | CH 3 C = O CHO

CH 3 C = O CHO (C) & | | CH 3 C = O CHO

Page 6 of 40 HYDROCARBONS

Q.13 Identify X.

s 4 X.

O O (1eq )

H 2O / Acetone

(A)

(B)

(C)

(D) Reaction will not occur

Q.14 Identify Z. (A) (C)

2 Z.

PdCl ,HOH CuCl2 ,O 2

(B) (D) All are correct

Q.15

CH 3 CH 3 | | OsO 4 (1equiv.) A ; Identify A CH 3 C == C CH 2 CH = CH 2

( Acetone / water )

CH 3 CH 3 OH OH | | | | (A) CH 3 C == C CH 2 CH CH 2

CH 3 CH 3 | | (B) CH 3 C C CH 2 CH = CH 2 | | OH OH

CH 3 CH 3 | | (C) CH 3 CH C CH 2 CH CH 3 | | OH OH

(D) Reaction will not occur

Q.16 1-Penten-4-yne reacts with bromine at 80C to produce: (A) 4,4,5,5-Tetrabromopentene (B) 1,2-Dibromo-1,4-pentadiene (C) 1,1,2,2,4,5-hexabromopentane (D) 4,5-dibromopentyne

Page 7 of 40 HYDROCARBONS

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 | | CH 3 CH 3 (C) CH 3CH C C CH 3 | CH 3 Q.18 Consider the following reaction (A) C6H12 4 C5H10O In the above reaction (A) will be (A) CH3CH2CH2CH2CH=CH2 (B) CH 3 CH CH 2 CH = CH 2 | CH 3 (D) CH 3CH 2CH 2 C = CH 2 | CH 3
KMnO / OH /

(B) CH 3 CH CH = C CH 2CH 2CH 3 | | CH 3 CH 3 (D) CH 3 CH C C CH CH 3 | | CH 3 CH 3

(C) CH 3 CH 2 CH CH = CH 2 | CH 3

Q.19

KOH alcoholic product

Major product is: (A) (B) (C) (D)

Q.20 Number of required O2 mole for complete combustion of one mole of propane (A) 7 (B) 5 (C) 16 (D) 10 Q.21 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.22 When n-butane is heated in the presence of AlCl3/HCl it will be converted into (A) Ethane (B) Propane (C) Butene (D) Isobutane Q.23 The reacting species of alc. KOH is (A) OH (B) OR+ (C) OK+ (D) RO

Q.24 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

Page 8 of 40 HYDROCARBONS

Q.17 Compound (A) on oxidation with hot KMnO4 / OHr gives two compound

Q.25 PMA polymer is formed by methyl acrylate, which is prepared as follows

ROH (A) R C CH CO +
2 (C) HC CH 3 (B) HC CH

CO + CH OH Ni ( CO ) 4

CO + H O Ni ( CO ) 4

(D) None of these

Q.26 During the preparation of ethane by Kolbes 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.27 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 Q.28 AntiMarkownikoffs addition of HBr is not observed in (A) Propene (B) But2ene (C) Butene (D) Pent2ene

Q.29 Which alkene on heating with alkaline KMnO4 solution gives acetone and a gas, which turns lime water milky (A) 2Methyl2butene (B) Isobutylene (C) 1Butene (D) 2Butene Q.30 Acetylene may be prepared using Kolbes electrolytic method employing (A) Pot. acetate (B) Pot. succinate (C) Pot. fumarate (D) None of these Q.31
B

Na / NH 3 Lindlar RCCR A A and B are geometrical isomers (RCH=CHR) (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.32 Which is expected to react most readily with bromine (A) CH3CH2CH3 (B) CH2=CH2 (C) CHCH

(D) CH3CH=CH2

Q.33 By the addition of CO and H2O on ethene, the following is obtained (A) Propanoic acid (B) Propanal (C) 2Propenoic acid (D) None of the above Q.34 An alkyne C7H12 on reaction with alk. KMnO4 and subsequent acidification with HCl yields a mixture CH 3 CHCOOH | of + CH3CH2COOH. The alkyne is CH 3 (A) 3Hexyne (C) 2Methyl2hexyne (B) 2Methyl3hexyne (D) 2Methyl2hexene

Q.35 A compound (C5H8) reacts with ammonical AgNO3 to give a white precipitate and reacts with excess of KMnO4 solution to give (CH3)2CHCOOH. The compound is (A) CH2=CHCH=CHCH3 (B) (CH3)2CHCCH (C) CH3(CH2)2CCH (D) (CH3)2C=C=CH2

Page 9 of 40 HYDROCARBONS

(A) Br2

(B) O3

+ (C) Cu 2 2

(D) KMnO4

Q.37 CH3CH2CCH

CH3CCCH3 (B) NaNH2 and alcoholic KOH (D) Lindlar and NaNH2

A and B are (A) alcoholic KOH and NaNH2 (C) NaNH2 and Lindlar
3 Q.38 B H O / OH 2 2

BH / THF

3 A

H O+

A and B are (A) Both (C) (B) Both (D)

3 CH3CCH HgSO 4 / H 2SO 4 Q.39 B A H O OH 2 2,

BH THF

A and B are O || (A) CH 3CH 2CHO, CH 3 C CH 3 (C) CH3CH2CHO (both) O || (B) CH 3 C CH 3 CH 3CH 2CHO (D) CH 3 C CH 3 (both) || O

2 6 product X Q.40 CH3CH=CH2 H O / OH 2 2

B D

X is (A) CH 3 CH CH 2 D | OH (C) CH 3 CH CH 3 | OD (B) CH 3 CH CH 2OH | D (D) none is correct

3Br Q.41 CH2=CHCH=CH2 CCl product. The major product is

(A) BrCH2CH=CHCH2CCl3

(B) CH 2 = CH CH CH 2 CCl3 | Br (D) None is correct

(C) CH 2 = CH CH CH 2 Br | CCl3

Page 10 of 40 HYDROCARBONS

Q.36 Which of the following reagents cannot be used to locate the position of triple bond in CH3CCCH3

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 Q.43 Dehydration of 2, 2, 3, 4, 4pentamethyl3pentanol gave two alkenes A and B. The ozonolysis products of A and B are O || 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 || 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 | CH 3 O || 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
NH Cl
2

(A)

(B)

(C)

4 product Q.44 CHCH Cu Cl

2

Product is (A) CuCCCu

(B) CH2=CHCCH (C) CHCCu

(D) CuCCNH4

O || 3 / H 2O Q.45 Alkene A O CH 3 C CH 3 + CH3COOH + CH 3 C COOH || O A can be C(CH 3 ) 2 || (B) CH 3 C CH = HC CH 3 (D) None is correct

(A) (C) Both correct

Page 11 of 40 HYDROCARBONS

Q.46

reagent R

reagent R

R1 and R2 are (A) Cold alkaline KMnO4, OsO4/H2O2 (C) Cold alkaline KMnO4, CH3OOCH3

(B) Cold alkaline KMnO4, HCO3H (D) C6H5CO3H, HCO3H

Q.47

CH 3 | HC alkaline KMnO 4 || A, which is true about this reaction? HC | CH 3

(A) A is meso 2, 3butandiol formed by syn addition (B) A is meso 2, 3butandiol formed by anti addition (C) A is a racemic mixture of d and l, 2, 3butandiol formed by anti addition (D) A is a racemic mixture of d and l 2,3butandiol formed by syn addition Q.48
O3 / H 2O / Zn Con . H SO 4 + CH3MgBr H 3O B C A 2
+

A, B and C are A

(A)

(B)

(C)

(D)

Q.49

A can be (A) Conc. H2SO4

(B) alcoholic KOH

(C) Et3N

(D) t-BuOK

Page 12 of 40 HYDROCARBONS

Q.50 BrCH2CH2CH2Br reacts with Na in the presence of ether at 100 C to produce (A) BrCH2CH=CH2 (B) CH2=C=CH2 Q.51 Which has least heat of hydrogenation (A) Q.52 (B)
2 2 A. A is

(C)

(D) All of these

(C)

(D)

(1) Hg ( OAc ) / H O / THF ( 2 ) NaBH4 / NaOH / H 2O

(A)

(B)

(C)

(D)

Q.53 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) CH3CH2CCH and CH2=CHCH=CH2 ; (B) CH3CCCH3 and CH3CH=C=CH2 ; CH3CCCH3 (C) CH 2 CH | | ; CH2 = CHCH=CH2 C=CH2 and | CH 2 CH ; CH2 = CHCH = CH2

(D) CH3CCCH3 and

x Q.54 CH3CH=CHCH3 product is Y (nonresolvable) then X can be cis (A) Br2 water (B) HCO3H (C) Cold alkaline KMnO4 (D) all of the above

Q.55 Electrophilic addition reaction is not shown by (A) CH 2 = C CH 3 and Br2 | CH 3 (C) CH3CCH and CH3MgBr (B) CHCH2 and HOCl

(D) CH2=CH2and dil. H2SO4 solution

Q.56 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 Q.57 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.

Page 13 of 40 HYDROCARBONS

CHCOOH Q.58 CH2=CHCH=CH2 + | | product X by reaction R. X and R are CHCOOH (A) Diels Alder (B) Friedel-Crafts

(C)

Diels Alder

(D)

Friedel-Crafts

Q.59 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.60 The addition of bromine to 2-cyclohexenyl benzoate in 1,2-dichloroethane produces ____ dibromo derivatives: (A) 2 (B) 3 (C) 4 (D) 6 Q.61 How many products will be formed when methylenecyclohexane reacts with NBS? (A) 3 (B) 1 (C) 2 (D) 4
CH3 C NH 2 || O

Q.62

dry ether Br Mg / (X) (Y)

The structures of (X) and (Y) respectively are (A) X = MgBr ; Y= OH

(B) X =

Y=

(C) X = (D) X = BrMg

MgBr MgBr

; ;

Y= Y = HO OH

Page 14 of 40 HYDROCARBONS

EXERCISEI (B)
B A BH 3 / THF H O / OH
HgSO 4 / H 2SO 4
2 2

Q.1

B is identical when A is (A) (B) Q.2

(C)

(D)

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
CH3 CH = CHCH3 + CH2N2 A A can be

Q.3

(A) Q.4

(B)

(C)

(D)

Aqueous solution of potassium propanoate is electrolysed. Possible organic products are: (A) n-Butane (B) C2H5COOC2H5 (C) CH3CH3 (D) CH2=CH2

Q.5

Re agent R

Re agent R

R1 and R2 are: (A) cold alkaline KMnO4, OsO4 / H2O2 (B) OsO4 / NaHSO3 ; Ag2O , H3O (C) cold alkaline KMnO4, C6H5CO3H / H3O (D) C6H5CO3H ; OsO4 / NaHSO3 Q.6
2 3 / H 2O (B) C4H8 O (A) C4H6 CH3COOH Hence A and B are (A) CH3C CCH3, CH3CH = CHCH3 (B) CH2 = CHCH3 = CH2, CH3CH = CHCH3

H / Pt

(C) Q.7

, CH3CH = CHCH3

(D) None

Which is / are true statements/ reactions? (A) Al4C3 + H2O CH4 (C) Mg2C3 + H2O CH3C CH
A PhCH2CH3 Ph C CH 3 || O

(B) CaC2 + H2O C2H2 (D) Me3CH + KMnO4 Me3COH

Q.8

A could be: (A) NH2NH2, glycol/OH (C) Red P/HI

(B) Na(Hg)/conc. HCl (D) CH 2 CH 2 ; Raney Ni H2 | | SH SH

Page 15 of 40 HYDROCARBONS

Q.9

BuOK t Product

which is / are correct statements about the product: (A) (B) (C) (D)
Q.10

CH3 CH2 CH2 CH3

is an endocyclic Saytzeff product is an exocyclic Saytzeff product is an exocyclic Hoffmann product is an endocyclic Hoffmann product

CH2 = CHCH2CH = CH2 NBS A, A can be (A) CH 2 = CH CH CH = CH 2 | Br (C) CH2 = CH CH2 CH = CHBr (B) CH2=CHCH=CHCH2Br

(D) CH 2 = CH CH 2 C = CH 2 | Br

Q.11

Which are correct statements? (A) meso-2, 3-dibromo-butane on reaction with NaI / acetone gives trans-2-butene (B) d-or l- 2, 3-dibromobutane on reaction with NaI/acetone gives cis-2-butene (C) meso-2, 3-dibromo-butane on reaction with NaI / acetone gives cis-2-butene (D) d-or l- 2, 3-dibromobutane on reaction with NaI/acetone gives trans-2-butene

Q.12 PhCH=CH2 + BrCCl3 peroxide Product is:

(A)

(B)

(C)

(D)

Page 16 of 40 HYDROCARBONS

Q.13 Which of the following elimination reactions will occur to give but-1-ene as the major product? (A) (B)
EtOH CH3.CHCl.CH2.CH3 + KOH

CH 3 .CH 2 .CH.CH 3 + NaOEt EtOH | NMe3

+ CH3.CH2.CHCl.CH3 + Me3CoK CH3.CH2.CH(OH).CH3 + conc. H2SO4

(C) (D) Q.14

OH

The above compound undergoes ready elimination on heating to yield which of the following products? (A) (B) (C) (D)

Q.15 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.16 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.17 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) Stereochemical outcome of a radical substitution and a radical addition reaction 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.18 Select true statement(s): (A) Instead of radical substitution, cyclopropane undergoes electrophilic addition reactions in sun light. (B) In general, bromination is more selective than chlorination. (C) The 2,4,6-tri-tert, butylphenoxy radical is resistant to dimerization. (D) The radical-catalysed chlorination, ArCH3 ArCH2Cl, occurs faster when Ar = phenyl than when Ar = p-nitrophenyl. Q.19 Nitrene is an intermediate in one of the following reactions: (A) Schmidt rearrangement (B) Beckmann rearrangement (C) Baeyer-Villiger oxidation (D) Curtius reaction Q.20 Which reagent is the most useful for distinguishing compound I from the rest of the compounds CH3CH2CCH CH3CCCH3 CH3CH2CH2CH3 CH3CH=CH2 I II III IV (A) alk. KMnO4 (B) Br2/CCl4 (C) Br2/CH3COOH (D) Ammonical AgNO3

Page 17 of 40 HYDROCARBONS

Q.21 Indicate among the following the reaction not correctly formulated.
2 2 (A) CH2=CHCH3 CH2ClCHClCH3

+SO Cl

UV light

(B) HCCH+CH2N2
(C) (CH3)3CH + Cl2 photo (CH3)3CCl as major product
halogenati on

Na (D) CH3CCCH2CH2CH3 in NH ( liq )

3

Q.22

List I
2O3 Al 2O 3 , (A) n-Hexane Cr d (B) CH CH Re hot Fe tube

List II

(1) Substitution reaction (2) Elimination reaction

CH 3 | (C) CH 3 C X aq. | CH 3 (D) CH3CH2X alc. KOH Q.23

List I
3 (A) CH 3 C = CH 2 (ii ) H 2O 2 / OH | CH 3 2 (B) CH 3 C = CH 2 (ii ) NaBH4 | CH 3

(3) Aromatisation

(4) Cyclization
List II

(i ) BH

(1) CH3CH2CH=CH2

(i ) Hg ( OAc ) / HOH

(2) CH3CH=CHCH3

Cl | ONa / (C) CH 3 CH 2 CH CH 3 CH 3

(3) CH 3 CH CH 2OH | CH 3
OH | (4) CH 3 C CH 3 | CH 3

Cl | ( CH3 )3 CONa (D) CH 3 CH 2 CH CH 3

Codes:

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

A 4 4 3 3

B 3 3 4 4

C 1 2 2 1

D 2 1 1 2

Page 18 of 40 HYDROCARBONS

Q.24

List I (A) Walden Inversion (B) Racemic mixture

List II (1) Cis addition (2) Trans addition

(C) Alkene Baeyer

Re agent
2 (D) Alkene Br Codes: (a) (b) (c) (d)

(3) SN1 reaction (4) SN2 reaction A 3 3 4 4 B 4 4 3 3 C 2 1 1 2 D 1 2 2 1

List II
( 1 ) N a / N H

Q.25

List I (A) CH3CC CH3 cis-2-butene

3(l)

(B) CH 3 C C CH 3 trans-2-butene (C) CH3CCCH3 1-Butyne (D) CH3CH3CCH 2-Butyne Codes: A B C (a) 2 1 3 (b) 1 2 4 (c) 1 2 3 (d) 2 1 4 Q.26
List I
is (A) RCOONa electrolys RR

(2) H2/Pd/BaSO4 (3) alc. KOH, (4) NaNH2 , D 4 3 4 3

List II

(1) Corey-Housh reaction (2) Kolbe electrolysis (3) Oakwood degradration (4) Hunsdiecker reaction C 4 4 3 1 D 1 2 2 3

(B) RCH2COOH RCH3

3 RCl (C) RCOOH

Soda lim e

(i ) AgNO

(ii ) Cl2 /

(D) RX + R2CuLi RR Codes: A B (a) 2 3 (b) 1 3 (c) 2 4 (d) 2 4

Page 19 of 40 HYDROCARBONS

Q.27

List I

List II

(A)

(1) Birch reduction

(B)

(2) Stephens reduction

(C)

(3) Wolf-Kishner reduction

(D) Q.28

(4) Clemmensen reduction

List II (1) Wurtz reaction (2) Coupling of reactants is taking place

List I (A) n-Hexane Benzene (B) CHCH Benzene

) 6 CH 3 2,2,3,3 tetramethyl butane(3) AlCl3 + HCl at 300C (C) CH 3 ( CH 2 (D) CH3CH2X n-Butane (4) Polymerisation (5) Aromatic procducts is formed (6) Zn + used as reagent (7) Al2O3 at high temperature

Q.29 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) CH3CH=CH2CH3CHBrCH3 (P) HBr (B) CH3CH=CH2CH3CH2CH2Br (Q) Br2 (C) CH3CH=CH2BrCH2CH=CH2 (R) HBr / Peroxide (D) CH3CH=CH2CH3CHBrCH2Br (S) NBS

Page 20 of 40 HYDROCARBONS

EXERCISEII
Q.1 Give the product of (a)
2 2 3 B A

BH

H O

(b)

1. BD .THF

THF

2. D 2O 2 , DO

Q.2

CH 3 | LiAlH 4 ? CH 3 C Cl | CH 3 What are the ozonolysis products of

Q.3

Q.4

3 3 A + B. What are A and B?

1. CF CO H 2. H 2 O / H +

Q.5

NaOH A. Write the structure of A.

Alc.

Q.6

NH NH 2 / H 2O 2 2 A. Write the structure of A

Q.7 Q.8

OH A. Write the structure of major product A.

Q.9

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 OHCCH2CH2CH2CHO. 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 PhCO H 3 2 + H 2O C10H16O(D) pinene Br B (C10H17OBr)

Page 21 of 40 HYDROCARBONS

Q.10 Propose structures for intermediates & products A to K

Q.11

Identify the following (A to D).

Q.12 What are A to K for the following reactions / NH 3 2 Cl (i) PhC CH + CH3MgX A ArCH B Li C. (ii)
alcoholic h dil. KMnO 4 KMnO 4 E cold PhCH2CH2CH3 + Br2 D F hot G KOH

(iii)

(iv)

(v)

CF3 CH = CH2 HBr J

(vi)

NBS K

Page 22 of 40 HYDROCARBONS

Q.13 What will be the product in the following reaction

(i)

+ CO2Me

(ii)

(iii)

(iv)

(v)

. NaNH 2 ( 3equiv.) NH 3 + Br2 A 1 B 2. CH 3I

Q.14 (i) Compare the reaction of CH2 = CH2 & CF2 = CF2 with NaOEt in EtOH (ii) CCl2 = CCl2 does not decolourise Br2 solution - explain. Q.15 Account for the collowing facts (i) Ozonolysis if carried out in MeOH solvent a hydroxy peroxy ether is formed as unexpected product. (ii) When 2, 3 dimethyl 2 butene is treated with O3 in presence of HCHO in CH2Cl2 medium, an ozonide other than that expected of the starting alkene is formed. Identify the unexpected ozonide. Q.16 (i) (ii) (iii) (iv) (v) Explain the following: 1, 2 shift does not take place during oxymericuration demercuration. Why? Halogneation of alkene is anti addition but not syn addition. Why? Anti markovnikov addition is not applicable for HCl. Why? 1,4addition takes place in butadi-ene. Why? CH bond is stronger than CC bond but in chlorination CH bonds get cleaved but not CC bond. Why?

Q.17 Conversion: (i) C2H2 racemic 2, 3 dibromobutane (ii) 2 butyne 2 pentyne (iii) Ethyne Acetone (iv) Methane n Butane (v) Ethene Propionic Acid Q.18 Conversion: (i) C2H2 ethylidene diacetate (iii) C2H2 m nitroaniline (ii) C2H2 Butyne diol (iv) cis but 2 ene Trans but 2 ene

Q.19 Outline a stereospecific synthesis of meso 3, 4 dibromohexane from ethyne. Q.20 How can you convert (a) Ethane in to meso 2, 3 dimethyl oxiran (b) CaC2 into 1, 3, 5 hexatriene (c) Trimethylsecbutyl amonium hydroxide into 1,4-butan-dial (d) Cyclo hexanol into trans cyclo hexane-1, 2-diol Q.21 How will you conver (a) Hexane dial in to 1,3,5 hexatriene (b) 1-methyl propyl ethanoate into 1,4-dichloro-2-butene

Page 23 of 40 HYDROCARBONS

Q.22 Explain the mechanism of following conversion.

Me2C = CH CH 2 CH 2 CMe = CHCHO + H3O+ Citral Q.23 When citral is allowed to react in presence of dilute acid with olivetol, there is obtained a mixture of products, one of which is drug marijuana. Reaction is as follows.

Me2C = CH CH2CH2CMe=CHCHO +

(marijuana) Explain the mechanism. Q.24 The following cyclisation has been observed in the oxymercuration & demercuration of this unsaturated alcohol. Propose a mechanism for this reaction.
. Hg ( OAC ) 2 1 2 . NaBH 4

Q.25 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.26 (a)

MeCH2CCBr + CHCMe Cu A Cl | H CH 2 CHCl 2 O B OH | CH 2 = CH CH CH = CH CH 3 MeOH C

H 2SO4

(b)

(c) (d) (e)

Hg D
H 2SO4 / H 2O

2+

Cl3CCH=CH2 HOBr E
O3ZnH 2O G H F

(f)

Page 24 of 40 HYDROCARBONS

Q.27 Acetylene is acidic but it does not react with NaOH or KOH. Why? Q.28 CHCCH2CH=CH2, adds up HBr to give CHCCH2CHBrCH3 while CHCCH=CH2 adds up HBr to give CH2=C . Br . CH=CH2. Q.29 Chlorination of ethane to ethyl chloride is more practicable than the chlorination of n-pentane to 1-chloropentane. Q.30 Why n-pentane has higher boiling point than neopentane?

EXERCISEIII
Q.1 0.37 gm of ROH was added to CH3MgI and the gas evolved measured 112 cc at STP. What is the molecular wt. of ROH ? On dehydration ROH gives an alkene which on ozonolysis gives acetone as one of the products. ROH on oxidation easily gives an acid containing the same number of carbon atoms. Gives the structures of ROH and the acid with proper reasoning. An alkane A (C5H12) on chlorination at 3000 gives a mixture four different mono chlorinated derivatives B, C, D and E. Two of these derivatives give the same stable alkene F on dehydrohalogenation, On oxidation with hot alkaline KMnO4 followed by acidification of F gives two products G and H. Give structures of A to H with proper reasoning. 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. 3, 3dimethyl1butene and HI react to give two products, C6H13I. On reaction with alc. KOH one isomer, (I) gives back 3,3dimethyl1butene 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. Three isomeric alkenes A, B and C, C5H10 are hydrogenated to yield 2methylbutane A and B gave the same 30 ROH on oxymercuration demercuration. B and C give different 10 ROHs on hydroboration -oxidation. Supply the structures of A, B & C. 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. Give the structure of A, B and C. A (C4H8) which adds on HBr in the presence and in the absence of peroxide to give the same product C4H9Br. B (C4H8) which when treated with H2SO4 / H2O give (C4H10O) which cannot be resoslved into optical isomers. C (C6H12), an optically active hydrocarbon on catalytic hydrogenation gives an optically inactive compound C6H14. 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, 3dimethylbutane predict the structures of X, Y and Z. Identify a chiral compound C, C10H14, that is oxidized with hot KMnO4 to Ph COOH, and an achiral compound D, C10H14, inert to oxidation under the same conditions.

Q.2

Q.3

Q.4

Q.5

Q.6

Q.7 (a) (b) (c)

Q.8

Q.9

Page 25 of 40 HYDROCARBONS

Q.10 C7H14 (A) decolorises Br2 in CCl4 and reacts with Hg(OAC)2 in THF. H2O followed by reduction with NaBH4 to produced a resolvable compound B. (A) undergoes reductive ozonolysis to give the same compound (C) obtained by oxidation of 3hexanol with KMnO4. Identity A, B and C compound D, and isomers of A reacts with BH3. THF and then H2O2/OH to give chiral E. Oxidation of E with KMnO4 or acid dichromate affords a chiral carboxylic acid F. Reductive Ozonolysis of D, gives the same compound G which is obtained by oxidation of 2methyl3pentanol with KMnO4 identify D, E, F and G. Q.11 Three compounds A, B and C are isomers of the formula C5H8. All of them decolorises bromine in CCl4 and gives a positive test with Baeyers reagent. All the three compounds dissoslve in conc. H2SO4. Compound A gives a white ppt. with ammonical silver nitrate whereas B and C do not. On hydrogenation in presence of Pt catalyst, A and B both yield npentane whereas C gives a product of formula C5H10. On oxidation with hot alkaline KMnO4 (B) gives acetic acid and CH3CH2COOH. Identify A, B & C.

Q.12 An unsaturated hydrocarbon (A) C6H10 readily gives (B) on treatment with NaNH2 in liquid NH3. When (B) is allowed to react with 1chloropropane a compound (C) is obtained. On partial hydrogenation in the presence of lindlars catalyst, (C) gives (D), C9H18. On ozonolysis, (D) gives 2, 2dimethylpropanal and 1butanal with proper reasoning give the structures of (A) (B), (C) and (D). Q.13 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.14 An organic compound (A), C6H10 on reduction first gives (B), C6H12 and finally (C), C6H14. (A) on ozonolysis followed by hydrolysis gives two aldehydes (D), C2H4O and (E) C2H2O2. Oxidation of (B) with acidified KMnO4 gives the acid (F), C4H8O2. Determine the structures of the compounds (A) to (F) with proper reasoning. Q.15 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.16 An optically active hydrocarbon (A), C8H12 gives an optically inactive compound (B) after hydrogenation. (A) gives no ppt. with Ag(NH3)2+ and gives optically inactive (C), C8H14 with H2 in presence of Pd / BaSO4. Determine the structures, give suitable names for A, B, C & give your reasoning. 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 An organic compound A, C6H10 , on catalytic reduction first gives B, C6H12 , and finally C, C6H14. A on ozonolysis followed by hydrolysis gives two aldehydes D, C2H4O and E, C2H2O2. Oxidation of B with acidified KMnO4 gives acid F.
Q.19 A hydrocarbon has 88.89% carbon and 11.11% hydrogen. 0.405 g sample of the hydrocarbon occupies 229.54 ml at 100C and 1 atm pressure. It decolourises potassium permanganate solution and bromine water without evolving hydrobromic acid. It gave no precipitate with either ammoniacal silver nitrate or cuprous chloride solution. When it reacts with dilute H2SO4 in presence of mercuric sulphate, under appropriate conditions, methyl ethyl ketone is formed. What is the hydrocarbon. Write the structural formulae of the eight possible isomer of this compound. 6g sample of a natural gas consisting of methane (CH4) and ethylene (C2H4) was burned with excess of oxygen and 17.2g of carbon dioxide and some water was obtained as products. What percent by weight of the sample was ethylene.

Q.20

Page 26 of 40 HYDROCARBONS

EXERCISEIV (A)
Q.1 Alcoholic solution of KOH is a specific reagent for (A) Dehydration (B) Dehydrogenation (C) Dehydro halogenation (D) Dehalogenation Of the following, unsaturated hydrocarbons are (A) ethyne (B) cyclohexane (C) npropane 1-chlorobutane on reaction with alcoholic potash gives (A) 1butene (B) 1butanol (C) 2butene (D) ethene
[IIT 91] [IIT 90]

Q.2 Q.3

[IIT 90]

(D) 2butanol
[IIT 91]

Q.4

The hybridisation of carbon atoms in CC single bond of HCCCH=CH2 is (A) sp3sp3 (B) sp2sp3 (C) spsp2 (D) sp2sp2 The product(s) obtained via oxymercuation (HgSO4 + H2SO4) of 1butyne would be (A) CH 3 CH 2 C CH 3 || O (C) CH3CH2CHO + HCHO (B) CH3CH2CH2CHO

Q.5

(D) CH3CH2COOH + 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 Which of the following compounds will show geometrical isomerism? [IIT 98] (A) 2butene (B) Propene (C) 1phenylpropene (D) 2methyl2butene In the compound CH2=CHCH2CH2CCH, the C2C3 bond is of the type (A) spsp2 (B) sp3sp3 (C) spsp3 (D) sp2sp3
[IIT 99]

Q.7

Q.8

Q.9

Which one of the following alkenes will react fastest with H2 under catalytic hydrogenation condition [IIT 2000] (A) (B) (C) (D)

Q.10 Propyne and propene can be distinguished by (A) conc. H2SO4 (B) Br2 in CCl4 (C) dil. KMnO4 Q.11

[IIT 2000] (D) AgNO3 in ammonia

In the presence of peroxide, hydrogen chloride and hydrogen iodide do not give antiMarkovnikov addition to alkene because [IIT S2001] (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

Page 27 of 40 HYDROCARBONS

Q.12 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.13 The reaction of propene with HOCl proceeds via the addition of (A) H+ in first step (B) Cl+ in first step (C) OH in first step (D) Cl+ and OH in single step
[IIT 2001]

Q.14 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 carboncarbon bond at right angle (D) a plane perpendicular to the molecular plane which contains the carboncarbon bond Q.15 Consider the following reactions H 3C CH CH CH 3 + | | D CH 3

[IIT 2002]

X + HBr

Identify the structure of the major product X (A) H 3C CH CH C H 2 | | D CH 3

(B) H 3C CH C CH 3 | | D CH 3 (D) H 3C C H CH CH 3 | CH 2

(C) H 3C C CH CH 3 | | D CH 3

Q.16 Identify a reagent from the following list which can easily distinguish between 1butyne and 2-butyne[IIT 2002] (A) bromine, CCl4 (B) H2, Lindlar catalyst (C) dilute H2SO4, HgSO4 (D) ammonical Cu2Cl2 solution
4 A Q.17 C6H5CCCH3

HgSO

H 2SO 4

[IIT 2003]

(A)

(B)

(C) C6 H5 C = CHCH 3 (D) C 6 H 5 CH = C CH 3 | | OH OH

Page 28 of 40 HYDROCARBONS

Q.18

H
H 2O

x ( mixture)

2 5 compounds of molecular formula C4H8Br2

Br

Number of compounds in X will be: (A) 2 (B) 3

[IIT 2003]

(C) 4

(D) 5
[IIT 2004]

Q.19 2hexyne can be converted into trans2hexene by the action of : (A) H2Pd-BaSO4 (B) Li in liq. NH3 (C) H2PtO2

(D) NaBH4

Q.20 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.21 1bromo3chlorocyclobutane 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.22 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.23 CH3CH=CH2 + NOCl P Identify the adduct. CH 3 CH CH 2 | | (A) Cl NO NO | CH 3 CH 2 CH (C) | Cl CH 3 CH CH 2 | | (B) NO Cl CH 2 CH 2 CH 2 | (D) | NO Cl

[IIT 2006]

Q.24

Cl 2 , hv fractional distillation N(isomeric products) C5H11Cl M(isomeric products)

What are N and M? (A) 6, 6

(B) 6, 4

(C) 4, 4

(D) 3, 3

[IIT 2006]

Page 29 of 40 HYDROCARBONS

EXERCISEIV (B)
Q.1 Q.2 Cl | . KOH (CH 3 ) 2 C CH 2CH 3 alc ?
alc. KOH ? HBr C 6 H 5CH 2CHCH 3 ? heat | Br

[IIT 1992] [IIT 1993]

Q.3

C(C6H12), an optically active hydrocarbon which on catalytic hydrogenation gives an optically inactive compound, C6H14. [IIT 1993] Draw the stereochemical structure of the product in the following reactions. RCCR
2

Q.4

[IIT 1994]

Lindlar catalyst

Q.5

Write down the structures of the stereoisomers formed when cis2butene is reacted with bromine. [IIT 1995] An organic compound E(C5H8) on hydrogenation gives compound F(C5H12). Compound E on ozonolysis gives formaldehyde and 2ketopropanal. Deduce the structure of compound E. [IIT 1995] Give the structures of the major organic products from 3ethyl2pentene under each of the following reaction conditions. [IIT 1996] HBr in the presence of peroxide (b) Br2/H2O Hg(OAc)2/H2O; NaBH4 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, 3dimethylbutane. Predict the structures of (X), (Y) and (Z) [IIT 1996] 3,3Dimethylbutan2ol 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.6

Q.7 (a) (c) Q.8

Q.9

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 carboncarbon bond in 1,3butadiene is shorter than that of nbutane. Why? [IIT 1998] Q.13 Write the intermediate steps for each of the following reaction [IIT 1998] C6H5CH(OH)CCH C6H5CH=CHCHO Q.14 Write the intermediate steps for each of the following reaction.
H
+

[IIT 1998]

Page 30 of 40 HYDROCARBONS

1 2 3

Q.17 Complete the following

[IIT 1999]

4 5 6

Q.18 Explain briefly the formation on the products giving the structures of the intermediates.

[IIT 1999]

(i) But

HCl

+ etc.

(ii)

HCl

Explain the non formation of cyclic product in (ii) Q.19 Carry out the following transformation in not more than three steps. O || CH3CH2CCH CH 3 CH 2 CH 2 C CH 3 Q.20 CH2=CH is more basic than HCC Q.21 What would be the major product in each of the following reactions? CH 3 | CH 3 C CH 2 Br C 2H 5OH | CH 3
[IIT 2000] [IIT 2000] [IIT 1999]

(i)

(ii)

Lindlar 's Catalyst

Q.22 On reaction with 4N alcoholic KOH at 175 C 1pentyne is slowly converted into equilibrium mixture of 1.3% 1pentyne (A), 95.2% 2pentyne (B) and 3.5% 1,2pentadiene (C). Give the suitable mechanism of formation of A, B and C with all intermediates. [IIT 2001] Q.23 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]
KMnO 4 2 2 / Pd BaSO 4 X H CH3CH2CCH Y alkaline Z

(i ) NaNH

(ii ) CH3CH 2 Br

Page 31 of 40 HYDROCARBONS

Q.15 Discuss the hybridisation of carbon atoms in allene (C3H4) and show the orbital overlaps. [IIT 1999] Q.16 Complete the following [IIT 1999]

Q.24 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 Aand Bombykol. How many geometrical isomers are possible for Bombykol? [IIT 2002] Q.25 If after complete ozonolysis of one mole of monomer of natural polymer gives two moles of CH2O
CH 3 | andone mole of O = C CH = O . Identify the monomer and draw the all-cis structure of natural polymer. . [IIT 2005]

Q.26

3 H+ , Y. X (ii ) Zn / Cl COOH 3

(i ) O

Identify X and Y.

[IIT 2005]

Page 32 of 40 HYDROCARBONS

ANSWER KEY EXERCISEI (A)

Q.1 Q.8 D C Q.2 Q.9 B A Q.3 Q.10 Q.17 Q.24 Q.31 Q.38 Q.45 Q.52 Q.59 A C B A A D C C D Q.4 Q.11
Q.18

B D
D

Q.5

Q.6

Q.7

Q.12 A Q.19 A Q.26 A Q.33 A Q.40 B Q.47 A Q.54 C Q.61 A

Q.13 B Q.20 B Q.27 C Q.34 B Q.41 A Q.48 A Q.55 C Q.62 C

Q.14 A Q.21 C Q.28 B Q.35 B Q.42 B Q.49 A Q.56 C

Q.15 B Q.22 D Q.29 B Q.36 A Q.43 B Q.50 C Q.57 C

Q.16 D Q.23 A Q.30 C Q.37 A Q.44 B Q.51 C Q.58 A

Q.25 B Q.32 D Q.39 B Q.46 B Q.53 A Q.60 A

EXERCISEI (B)
Q.1
Q . 5

A,C
B , C

. 2

, C

. 3

, B

, C

, D

. 4

, B

, C

, D

. 6

, B

. 7

, B

, C

. 8

, B

, C

, D

. 9

, C

Q.10

A,B

Q.11

A,B

Q.12 A,C Q.16 A,B,D Q.20 D Q.23 (c)

Q.13 B,C Q.17 A,C,D Q.21 A,C,D Q.24 (c)

Q.14 Q.18 Q.22 Q.25

B,C,D B,C,D

Q.15 A,C Q.19 A,D

(A) 3,4 ; (B) 3,4 ; (C) 1,2 ; (D) 2 (d) Q.26 (a)

Q.27 (A) 4; (B) 3; (C) 1; (D) 3,4 Q.29 (A) P; (B) R; (C) S; (D) Q

Q.28 (A)5,7 ; (B) 4,5 ;(C) 3 ; (D) 1,2,6

EXERCISEII

Q.1

(a)

(A) =

, (B) =

(b)

Page 33 of 40 HYDROCARBONS

Q.2

CH 3 | CH 3 C = CH 2 O = CH | O = CH

Q.3

Q.4

A + B are two enatiomers

Q.5

Q.6

Q.7

CH 2 = CH CH 2 CH 2 CH 2 N CH 3 | CH 3
C | (i) CCCC=C, (ii) C C C = C C C , (iii) C C = C C , (iv) CC=CCC=C, | | | C C C

Q.8

(v) -pinene

Q.9

, (A) =

, (B) =

, (C) =

(D) =

, (E) =

, (F) =

ONa OH | | Q.10 (A) C C C C , (B) C C C C , (C) CCCCOCC, (D) BrMgCCCC (E) C C C C C C C C C , (F) CCCC=CCCCC , | OH
Br | (G) C C C C C C C C C , (H) CCCCCCCCC | Br

Page 34 of 40 HYDROCARBONS

Q.11

CC CC CC | | | (A) C C = C C C C C , (B) cis C C = C C C = C C , (C) HOOC C COOH , | | | | | C C C C C CC | (D) H C COOH | C

Q.12 (A) PhCCMgx, (B) PhCCCH2Ar, (C)

Ph CH Et | , (D) , Br

(E) PhCH=CHMe trans, (F) Ph CH CH Me (threo mix.), (G) PhCOOH | | OH OH

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

Q.13 (i)

, (ii)

, (iii)

, (iv) no reaction

Br | (v) (A) , (B) PhCCCH3 Ph CH CH 2 Br

Q.14 (i) II is faster , (ii) unstable intermediate

Q.25 O CH 3 | , (C) CH 2 == CH CH == CH CH CH 3

Q.26 (A) MeCH2CCCCMe, (B)

(D)

Br OH | | , (E) CCl CH CH (F) 3 3

, (G)

Page 35 of 40 HYDROCARBONS

EXERCISEIII
Q.1 Q.2 (A)
CH CH2OH CH3 | CH3CHCH2CH3 CH3 | CH3CCH2CH3 | Cl CH2CH2CH3 | CH2=CCH2CH3 CH2CH=CH2 | CH3CHCH2CH3 CH2CH2CH3 | H3CCCH2CH3 | H (I) CH3 | CH3CHCCH3 | | I CH3 (J) CH3 CH3 | | CH3C CHCH3 | I CH2=CCH2CH3 | CH3 (C) CH2=CHCH(CH3)2 (B) CH3 | H3CCHCH2CH2Cl CH3 | ClCH2 CHCH2CH3 CH3COCH3 CHCH2CH3 || CH3 CCH2CH3 CH2CH2CH3 | CH3C=CHCH3 (C) CH3 | H3CCHCHCH3 | Cl CH3 | H3CC=CHCH3 CH3COOH CH=CHCH3 | CH3CHCH2CH3 CH2CH2CH3 | CH3CHCH=CH2

(D)

(E)

(F)

(G) (B)

(H) (C)

Q.3(A)

(D)

(E)

(F)

(G)

Q.4

Q.5

(A) CH3C=CHCH3 | CH3 Br | CH3CHCH CH3CH=CCH3 | CH3 CH3

(B)

Q.6
(A)

(B) CH3

CH2BrCH2CHCH3 | CH3

(C)

CH2=CHCHCH3 | CH3

(D)

Q.7
(A) CH3CH=CHCH3 (B) (C)

CH=CH2 | CH3C* H | CH2CH3 ] (Z) CH3C = CCH3 | | CH3 CH3

Q.8

(X)

CH3CClCHCH3 (Y) | | CH3 CH3

CH2=C CHCH3 | | CH3 CH3

Page 36 of 40 HYDROCARBONS

Q.9 Q.10

(A) PhCH(CH3)CH2CH3

(B) PhC(CH3)3

OH | (A) CH3CH2CCH2CH2CH3 (B) CH3CH2CCH2CH2CH3 (C) CH3CH2CCH2CH3 || | || CH2 CH3 O (D) CH3 (E) CH3 (F) CH3 | | | CH3CHCCH2CH3 CH3CHCHCH2CH3 CH3CHCHCH2CH3 || | | CH2 CH2OH CO2H (G) CH3CH CCH2CH3 | || CH3 O

Q.11 Q.12

(A) CH3CH2CH2CCH3

(B) CH3CH2CCCH3 CH3 | (B) H3CCCC Na+ | CH3

(C) Cyclopentene

CH3 | (A) CH3CCCH | CH3 CH3 | (C) H3CCCCCH2CH2CH3 | CH3

CH3 | (D) H3CCC=CHCH2CH2CH3 | CH3 (C) (B) CH3CH2CH2CH=CHCH3 (C) CH3CH2CH2CH2CH2CH3 (E) CHO (F) CH3CH2CH2COOH | CHO (B) CH3CHCHCHCH3 | | | Br Br CH3 (E) CH3COOH (F) (C) CH3CCCHCH3 | CH3 H3CCHCOOH | CH3

Q.13 (A)
(D) CH3CHO

(B)

Q.14 (A) CH3 CH= CHCH=CHCH3

Q.15 (A) CH3CH=CHCHCH3

| CH3 (D) CH3CH CH CHCH3 | | | OH OH CH3

Q.16

H | CH 3 C = C C C C CH 3 | | | H H CH 3
CH3CH2CH = CHCH2CH3

Q.17

Q.18 (A) CH3CH=CHCH=CHCH3, (B) CH3CH2CH=CHCH2CH3,

(C) CH3CH2CH2CH2CH2CH3, (D) CH3CHO, (E) |

CHO CHO

, (F) CH3CH2COOH

Page 37 of 40 HYDROCARBONS

Q.19 Q.20

Isomer are : CCCC, C=CC=C, C=C=CC,

23.7

EXERCISEIV (A)
Q.1 Q.6 Q.11 C D C Q.2 Q.7 A,D A,C Q.3 Q.8 A D Q.4 Q.9 C A Q.5 Q.10 Q.15 Q.20 A D B B

Q.12 B Q.17 A Q.22 A

Q.13 B Q.18 B Q.23 A

Q.14 A Q.19 B Q.24 B

Q.16 D Q.21 D

EXERCISEIV (B)
Q.1 CH 3 C = CH CH 3 | CH 3 Q.2
. KOH alc heat

HBr

Q.3

H | CH 3 CH 2 C CH = CH 2 | CH 3 (C 6 H12 )

Q.4

Q.5

Q.6

CH 2 CH 2 || || (E) CH 3 C CH

Q.7

OH Br | | (a) (CH3CH2) CH CH CH 3 ; (b) (CH3CH2)2 C CH CH 3 ; (c) (C2H5)3COH | Br

Q.8

CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 | | | | | | CH 3 C CH CH 3 ; (Y) CH 2 = C C CH 3 ; (Z) CH 3 C = C CH 3 | Cl

Page 38 of 40 HYDROCARBONS

Q.10 (A)

(B)

Q.11

(A) CH3CH2CH=CHCH2CH3

(B) CH3CH2COOK

Q.16 1 ozonolysis ; 2 LiAlH4 ; 3 H2SO4 Q.17 (4) HOCl ; (5) CH3MgCl ; (6) H2O/H+ Q.19 (1) NaNH2, (2) MeI, (3) HgSO4 dil H2SO4 Q.20 higher electronegativity of sp carbon

CH 3 | Q.21 (i) CH 3 C CH 2 CH 3 | O C2H 6

(ii)

Q.23 (X) EtCCEt

(Y)

(Z)

Z is meso so optically inactive.

Q.24 Bombykol :- HOCCCCCCCCCC=CC=CCCC (A) :4 geometrical isomers are possible CH 3 | Q.25 (a) CH 2 = C CH = CH 2

(b)

Q.26 (X)

O || , (Y) CH 3 C (CH 2 ) 4 CH = O

Page 39 of 40 HYDROCARBONS