Unsaturated Hydrocarbons

. 3-Chloropropene is treated witn sOQlUm in presence of (a) ClCH 2CH-:-CH z, (b) (CHjhC=CH2,
ether, i. e., undergoes Wurtz's reaction to form hexa-l ,5-diene .. (c)CH 3CH=CH2 , (d) H 2C=CHCI
Ether· (iv) . Stereochemical struc(ure ofthe reaction product of
)
Br2 with (a) cis-2-butene and (/J)trtlns-2':'butene.
H 2C=CHCH 2 CH 2CH=CH 2 (v) Why alkynes are generally less reactive than alkenes
Hexa-I,5-diene towards el~ctrophilic reagents such as H+ ? ',
(vi) The central carbon-carbon bond in buta-I,3 -diene is
(ii) Propene is first treated with bromine at 500--600°C shorter than that of n-butane.
whim 3-broinoprop-I-ene is fonned which on treatment with (vii) Arrange following alkenes in decreasing order of
alcoholic KOH yields allene (propadiene). stability towards acid-catalysed hydration.
Brz (a)' l-phenyl-l-butene; l-phenyl-2-butene; 2-phenyl-2-butene
CH 3 -CI-!--=CH2 ) CH 2BrCH=CH 2
:'r,'ene 500-600°C 3-Bromoprop-I-ene (b) 2-methylpropene; cis-2-butene; trans-2-butene
(c) l-hexene, 2-methyl-I-pentene, 2-hexene.
Ale. KOH) H C=C=CH Solution: (i) See mechanism on Page 345-346.
2 2
Allene (ii) The addition occurs at double bond because isolated
(iii) 1,3-Dibromopropane on heating with zinc forms double bond is more reactive than an isolated triple bond in
cyclopropane which is reacted with conc. HBr to yield electrophilic additions.
l-hrorilopropane. (iii) Electron releasing alkyl groups make the pi-bond
more electron rich and more reactive. While electron with-
/CH 2Br /CH 2 drawing halogen atoms make the pi-bond more electron poor
H 2C"" + Zn ~ H 2C "",I and less reactive. The order is:
CH 2Br CH2 (b) Two R>(c) oneR > (a) one R and a CI > (d) CIon a
1,3-Dibromopropane Cyclopropane double bonded carbon.
Cone. HBr (iv) 2,3:-Dibromobutane (a) racemic (b) meso.
----'--~) CH 3CH 2CH 2Br (v)-The reaction of alkyne or alkene with electrophiIic
I-Brom6propane reagent proceeds through the formation of carbocation. Since
/CH2\ CH2 the alkyl carbocation from the alkene group is more stable
H2C CH2 Cl z H2C~ "CHCI than the vinyl carbocation from alkyne group, the MI for its
(iv) I I ~
hv I I formation is less in case of alkene and hence alkene reacts
H2C",-C /CH2 H2C.......... C~CH2 . faster than alkyne ..
(vi) Buta-I,3-diene (H2C=CH-CH=CHi) has
H2 H2
Sp2 _Sp2 C--C bond length, while n-butane has sp3 _sp 3 C--C
Cyclohexane Chloroeyclohexane
bond length. More is 'i character in' hybridization, lesser is
CH2 bond length. '
Ale.KOH ·HC.,..,... -""':::CH (vii) (a) 2-phenyl-2-butene> l-phenyi-2-butene
Heat
2 I I > l-phenyl-I-butene . .
H2C.......... C~CH·· (b) ,2':methylpropene > trans~2-butene > cis-2-butene
H2 '(c) , 2-methyl-I-pentene > 2-hexene > J -hexene.
Cyclohexen.e Problem Z3. A , hydrocarbon; C 4 Hg, neither
deco(ourised bromine in carbon tetrachloride nor reacted with·
(v) CH 3CH 2CH=CH 2 HBr. When heated to 200°C 'with hydrogen in presence of a
ijut-I-ene nickel catalyst, a new hydrocarbon, C4 B 10 ' was formeq,. What
Ale.KOH
was the original hydrocarbon?
Heat) H 2C=CH-CH=CH 2 S(dution : The hydrocarbon can have the following
Buta-I;3-diene isomers:
H 0 Hz C1 · CH 3CH 2CH . CH 2, CH 3CH=ciIcH 3 ,
z C Ii
(VI.) CaC 2 ~ )C H .2) C Cl But~2-ene
2 2 Ni, 3000C 2 6 4000C 2 6 But-I-ene
(A) (B) Cyelobutane
Pro~lem 22.Explain the following: (C)
(i)' Buta-l ,3-diene gives 1,2- and 1,4-addition products. (A) and (B) are ruled,out as the compound does not react
(ii) Addition of HBr to H 2C=CHCH 2C=CH gives with Br2 and HBr~ Thus, the compound is cyclobutane.
CH 3CHBrCH 2C==CH . ' , Cyclobutane on reduction opens up the ring and forms
(iii) Alkenes in decreasing order of reactivity towards n-butane.
electrophilic addition:
D
Cyclobutane
+H2
Ni

n-Butane
...;;,348,.;;,'
:~_ _~_ _ _ _ _~_ _ _--.,_~_____________..;:;G:.:.:.R:..::.:.::B:.:..;.!?rganic Chemistry fOr Competitions

Pro"lem 24.' (i) Anorganic compound" C4 H 6 " on (b) !JP . .' ':j:rtV\:"'~ structures ofthe stereoisomersformed
ozonolysis gives formaldehyde, and glyoxal. What" is this when cis-.. <>u~~e is reacted with bromine. '
compound?' ' , . Solution: (a) Only cis-fonn of the alkene is fonned.
. '(ii) C 4 H 6 cqnrepresent various structures; identifY:
(a) Which reacts with ammoniacal AgN03" H)C=C<H
(b) Which does not react with ammoniacal AgN03 but R R
by hot alkaline KMn04 gives CH 3COOH, Cis-form
(c) Which decolourises Br2 water and by catalytic
hydrogenation (using I mol) and subsequent reaction H3C) <CH 3
with alkaline KMn04 givesCH 3 COOH and (b) C=C + Br2 ----7
(d) Which by ozonolysis using 03/H20 gives succinic H H
acid. CiS-but-2-ene
Solution: (i) The fonnula suggests that either the
compound is an. aJ.kYne or an alkadiene. The products of
ozonolysis suggest that the compound is alkadiene. It may
have the following structures~ , ,
H 2C . CH-CH=CH2 CH 3-CH=C=CH2
Buta-l,3-diene Buta-l,2-diene
(A) . (B) It exists in two optical isomers.
CH 3
Formaldehyde and glyoxal can be obtained from (A).
Hence"the compound is buta-I,3-diene. H + B ,r and
(ii) (a) C 4H 6 reacts With ammoniacal AgN03'SO it is a Br-t-H
terminal aJ.kYne (-C ' C-H). For example, CH 3 .
, CH 3CH 2-C==C!I (But-l-yne)
Problem 26. Give the structureS of the major products
'(b) C 4H 6 AIkalin: KMn0 4 ) CH 3COOH from , 3-ethylpent-2'-ene under each' of tke, following
conditions.
, Hence, it is CH3-Ci!!!!!!!C-CH3 (But-2-yne) (a) HBr in presence ofPeroXide,
(b) Bt:2/H2Q
CH3~==C-CH3 +3[O]+H 20 A1k.KMn04 ) (c) Hg(OAch/H20; NaBH 4 •
'Bu,t-2-yne ' . A Solution:
HBr
(C)C4H6 + H2 ----7 C4Hg
}>eroiU'de ) ..
(H2C=CH-CH--:-CH2 ) (CH 3CH=CHCH3 )
Buta-I,3-diene' But-2-ene
A1k,KMn04,
. 8.
) CH 3COOH
Ethanoic acid
Explanation: Buta-I,3-diene is converted into B~ ,
,but-2-ene by lA-addition. (b) CH 3CH2C=CHCH 3 ----7 CH3CH 2CBrCHBrCH 3
" () (\ + -
, I' 1
H2C=CH-cH~CH2 ----7 H 2C-GH=CH-CH2
C2 HS C2 Hs
Buta-I,3-diene H 20
. )CH3CH2r(OH)CHBrCH3
H2 .
----'~~) H 3C-CH=CH-CH 3
1,4-addition ,But-2-ene, ' C2 HS
03/H20 CH2COOH Hg(OAc)z
------"~~) I ' (c) CH 3CH 2-C=CH":"-CH 3
I H 20
)
CH 2COOH
Succinic acid C2 H S
CH 3-CH i-y.<HgOAC)-CH2-CH;l
Problem 2S. (a) Draw the stereochemical structure of
the product in the following rea,ction, ' C2 H; ,
Hz
'R-C==C-R )
Lindlar's catalyst
Unsaturated Hydrocarbons

Problem 27Jndicate.allylic, vinyl,IO, 2°,3° hydrogens. ·Only (B) gives.Camiizzaro's reaction. "
in· theJollowingcompound. Give the sequence ofreactivityfor Alkene (A) exist in following two geometrical isomers
free radical substitution. (A-l) and (A-2), ofwruch (A-2) is more stable. ' .
. . /C~3
CH3-CH. CH-:-CH 2-CHr -CH "'-CH (CH,hC)=c(CH, (CH,hC)cc/H
3 . H . H H ' "eH 3 .
. (A-1) CIs- . (A-2) Trans-

Problem 29.Give structures/configuration of the

Solution: products in the following reactions:
.C2H S
(a)H3 C ',I H+D2 Pd ) (A)+(B)
a ~ allylic, v = vinylic, 1° ~ primary, . CH CH2
, 20 ~ secondary,. 3° ~ tertiary [Roorkee 2001]
aIlylic (2 0 ) > aUylic (1 0 ) > 3° > 2° > 1° > vinylic 2
(b) 2HC==CH eu +) (C)·
Decreasing reactivity for nee radical substitution O2 (Roorkee 2001]
Problem 28Hydivcarbon (X), C,H 12 on reaction with
(c) ~ . Br2/CC4,. (V) NaNH2 to
boronhydride followed by treatment with CH 3COOHyieids
(A). On reductive ozonolysis (A) yields a mixture oj two
aldehydes, (B) and (C). Of these, only (B) can undergo . (W) HgS04 /H2S04 ) (X) NH2NHCONH2 )

Cannizzaro s reaction. (A) exists in two geometrical isomers

~tA-I) and (A-2), of which (A-2) is more stable. Give structure (y).' NaODID 20 (excess) ) (Z)
of(X), (A), (B), (C), (A-I) and (A-2) with proper reasoning.
[Roorkee 2_] (lIT 2001]
Solution: General formula of (X) indicates that it is an H
[ Hint: (a)
D'
alkyne, which on monohydroboronation with B2H 6 , followed
by protolysis with H+ gives pure cis-alkene (A).
'r I] . .
[-'-'-c=:e- ~I\ ) L-CH=C- 3B ~ -CH=CH-] or
(A)on reductive ozonolysis gives two aldehydes (B) and
(C). (B) undergoes Cannizzaro's reaction, hence, it should not
contain any a-hydrogen (i.e., at a-position, there should be
quaternary carbon. Reactions may be given as: (b) [C] =HC==C-:-C!!!!!:CH

OT~H'; ~{)-{o""'CH;
. CH) , CH3 H H
.I , . '(i) ~I\ ." I I I • (c)[I'] [WJ
CH3-C-C-C-CH3' ' ) CH3-C-C=C-CH3
I .. (ii) CH3COOH•.W I . .' Br Br
CH3 CH3
r\Jlo
'
.
(X)
4,4-Dimethylpent-2-yne .
(A)
"1--; " " [X] = "---I- -CH v 3;

Ozonolysis (1) 0 3
NNHCONH2

H
,
H CH 3
(ii) Zn/IIOH
[11= (Y...:...cH3; .
1 I. 1 .
CH3-C====O+ O=C-C-:-CH 3
(C)· I '
Acetaldejlyde CH 3
(Bt
2.2-Dimetbylpropanal
350, G.R.B. Organic Chemistry (or Competitions

MPORTANT POINTS TO REMEMBER

ALKENES [J By controlled partial hydrogenation of alkyne :
(J Unsaturated hydrocarbons with one double bond, are Hydrogenation of alkynes with Pd-CaC0 3 (Lindlar's
called' alkenes .or' olefins and are represented by the catalyst) or a nickel boride (called .P-2) catalyst yields
general fonnula C n H 2n • Their functional group is cis-alkene. Sodamide (NaJliq. NH 3 ) yields predominantly
)C = C< and are isomeric with cycloalkanes. They are trans-alkene (Birch reduction). Reduction" with
commonly named as alkylenes~ Examples are: Na/C 2 H sOH gives trans-alkene. Hydroboration of
H2C=CHi (=), CH3CH=CH2 (A..), alkynes (with B2 H 6) followed by protolysis (with H+)
Ethylene or Ethene Propylene or Propene' gives almost pure cis-alkene.
(J By pyrolysis· or cracking: Petroleum is Ii complex
CH3CH2CH CH2(~)' CH3CH~HCH3 (~) mixture of hydrocarbons which on heating at high
But~l-ene (~-Butylene1 But-2-ene (I3-Butylene). temperature (S00-700°C) decomposes to produc,e lower
alkenes and alkanes.
(J The double bond in alkenes consists of one sigma and one (J By heating quaternary ammonium compounds:
pi-bond. Each C-atom of a double bond is sp2 -hybridized. Lower alkenes are conveniently prepared by heating
>C=C< bond' length (1.34 A) is shorter than quaternary ammonium hydroxide with·the elimination of.
-;"C-C~ (I.S4 A) because the C-atoms in double bond trialkyl amine.' .
are held more tightly. (J By Grignard reagents: Alkenes can be obtained by
(J C =C are planar and H-C-C angle is 120° and reacting Grignard reagents with vinyl chloride.
H-C-H angle is 117.S A while C-:H bon.d length is (J By Wittig reaction: Any aldehyde or. ketone. on
1.09 A. treatment with (C6HSh P=CH 2 , methylene .triphenyl
(J Heats of hydrogenation can be used to estimate the relative phosphorane (Wittig reagent) yields an alkene,
stability of alkenes; The more substituted alkenes are (J By Cope elimination reaction: Tertiary amine oxide
more stable, i.e., containing at least one j3-hydrogen on heating at IS0°C,
R 2C=CR 2 >R 2C=CHR > R zC=CH 2 > RCH=CHR decomposes to fonn an alkene and a derivative of
> RCH=CH2 > CH 2 =CH 2 hydroxylamine.
General methods of preparation Physical properties
(J By dehydration of alcohols: In presence of conc. (J Lower members (C 2 -C 4 ) are gases, the next fourteen
H 2S0 4 at 170°C or A1 20 3 at 2S0°C orH 3P0 4 at 200°C or members are liquid while the higher members are solid.
heating with P20 S etc. The ease of dehydration is: They are insoluble in water but soluble in non-polar
Tert. (3°) > Sec. (2°) > Primary (10). solvents. The b.pts. increases with increasing chain length, .
(J By dehydrohalogenation of alkyl halides: On heating while m.pts. of highly substituted alkenes are higher than
at high temperature with alcoholic KOH. Stronger bases straight chain alkenes. Trans-isomers are more stable than
like NaNH z or C2 H 50Na or Et3N can also be used for cis-isomers and cis-isomers show a dipole moment.
dehydrohalogenation. When two alkenes may be fonned, Chemical properties .
the alkene which is the most substituted one predominates (J Alkenes ate reactive due to the presence of double bond
(Saytzeff's rule). and the most important reactions of alkenes .are the
(J The forination of less substituted alkene in an elimination addition reactions. At low temperature in presence of polar
reaction is called as a Hofmann elimination and that of solvents, addition proceeds by ionic mechanism whereas
more substituted alkene as a Zaitsev elimination. The at high temperature in presence of light or non-polar
ease of dehydrogenation is 3° > 2° > 1°. solvents, the addition occurs by free radical mechanism.
(J 'By dehalogenation of dihaloalkanes (vic- and (J Addition of hydrogen (Hydrogenation): Alkene adds
gem-): On heating vic-dihalides with zinc dust and one mole of hydrogen under pressure and in presence of
methanol (if sodium metal is used in place' of zinc like . catalyst Ni (200-2S0°C) or finely divided Pt or Pd
Wurtz reaction), the gem-dihalides would give alkenes (Sabatier-Senderen's reaction) or Raney Ni at room
having double the number of carbon atoms.
Dehalogenation by Nal in acetone talces place py E2
temperature to give an alkane. .
(J This reaction is exotliermic. The quantity of heat evolved
mechanism. when one mole of an unsaturated compound is hydro-
EJ By electrolysis of salts of dicarboxylic· acids (Kolbe'S genated is called the heat' of hydrogenation. The lower
method): A concentrated aqueous solution of Na or K . the heat of hydrogenation of an alkene, the more is its
salt of saturated dicarboxylic acid on electrolysis gives an stability. Trans-but-2-ene is more stable than cis-but-2-ene
alkene. and but-I-ene. .
 Unsaturated Hydrocarbons 35l1~· • ·•.•
CJ A terminal double bond may be reduced by Nalliq. NH 3 in sulphate which on boiling ,with H 20 (hydrolysis) yields
presence ofCH 30H or C2H sOH to give alkane. This is alcohol. So, this reaction is called hydration of alkenes.
called Birch reduction. a Hydroboration ox.idation: It is anti-Markowoikoff'$
a The double bond is also reduced in excellent yield by addi~on of water (hydration) to a double· bond. It
NaBH 4-PtCI 2 • involves addition of borane (B2H6) to double bond
a Addition of halogens: Alkenes give addition products followed by hydrolysis to give alcohol. '
'with Cl 2 ,and Br2 in presence of an inert solvent, CCI 4 , to aAnother convenient hydroborating agent is bor~e­
fonrivicinal dihalides. Br2 water is decolourised by tetrahydrofuran '(BH3-THF) complex. Diglyme or ether
unsaturated Jl,ydrocarbons (hence' the' te$t of can also be used in place of THF.
unsaturation). ' a Addition oJ watei': Alk.ene adds up water molecule in
a The reaction with fluorine is explosive whereas when· presence. of acid or catalyst BF3 or Mn phosphate
alkene is bubbled through alcoholic solution of iodine, a (catalytic amount) to yield alcohol in accordance witlr
mixed halide is formed. . MarkoWnikoff's rule.
a Addition of halogens is usually predominantly trans,i.e., a Oxymercuration-demercuration:With mercuric acetate
the addition' is stereoselective. With· trans-but-2-ene, the (in THF) followed by reduction with NaBHiNaOH is also
product of Br2 addition is opticallycinactive due. to the an example of hydration of alkene according to
formation of synnnetric meso compounds. Markownikoff's rule. It is a better process than catalytic
a A more substituted alkene is more reactive towards Br2 or hydration by dil. H 2SO 4, because it avoids reai:rangement.
Cl 2 than a less substituted alkene. .' a Addition of nitrosyl chloride (Tilden's
."':. R2C'CH2 <RCH=CH 2 <RCHCHR <R 2C CH 2 reagent): NOCI or NOBr adds to C=C to yield
" . . . <R 2C=CHR<R 2C=CR 2 halonitroso derivative.
a Addition of halogen acids: Alkenes add one mole' of' a Addition of alkanes: Isoalkanes . add to' isoalkenes in
;HX to form aJkyl halides~ Tlie order' of reactivity is: presence of concentrated.H 2SO 4 or HF to give branched
. ill >HBr > HCI >HF. ' . chain alkanes (alkyl~tiC)n of alkenes). .
CJ Addition of IL¥ to symnletrical alkenes gives only one a Alk~nylation of alkenes ' (Dlmerisation): 1\vo
product and to unsynnnetrical aikenes, the addition Of IL¥ . molecules of isobutene (C 4 H g) add together in presence of
can give two different products. Under normal conditions, concentrated 1I 2S0 4 0r H 3 P0 4 at about 80°C to give an
the additiqn takes place in accordance 'with. alkene, CgH16' in two 'isomeric forms, a.dimer of C4 Hg
Markowoikoff's rule. According to it, the negative part and this is calleddimerisation.
, of the unsymmetrical reagent.adds to that carbon atom of a Diels-Alder reaction: It is a diene-dienophile addition
. the unsyimnetrical alkene containing le~s· number of, reaction and forms cyclic compounds .
hydrogen atoms. "
a It is an electrophile addition and is favoured by most stable
carbocation intermediate. There may be 1,2-hydride or
1,2.-methyl shift and stability order being 1 ° < 2° < 3°.
a Peroxide effect: Kharasch obs.erved that the addition of
(
Buta-I,3-diene
+ 1\
Etbene'
-
o
Cyclohexene

", HBr only to unsynnnetrical alkenes in the presence of a Addi~on of oxygen: When mixed with air or oxidation
organic peroxides, i.e., benzoyl peroxide (C 6H sCOOh with peroxy acids (CH 3COOOH, C 6 H sC0 3H
follows anti-MarkowDikoWs addition and called as orCF3C0 3 lI) or air passed through silver catalyst at high
peroxide effect (free radical mechanism). temperature' (200-4000C), the lower alken,es form
Peroxide .
epoxides (cyclic ethers) which on hydrolysis give diols.
CH 3CH=CH 2 +HBr . ~CH3CH2CH2Br a Addition of ozon~: When. 0 3 or ozonised oxygen' is
. Propene' 'l-Bromopropane
passed through a solution of alkene in an inert solvent,
a Addition of hypohalous acid (H~X): A1k~mes form addition takes place across the double bond to form an
halohydrin with .. hypohalous acid (i.e., Cl 2 orBr2 in ozonide. Ozonides are easily decomposed on warming
presence of water). In H---O-CI or H-:-O--Br, the . with ZnlH 20 or reduction with HilPdcatalyst breaks
---O-Cl or --:...o-Br: (rather than -:-O--H bond) is )c= C( to produce two carbonyl compounds.
,broken and the molecule is polarised' in the manner a An alkene of the type RCH=CHR' gives two aldehydes'
8- 8+3- 8+' '.
Ho---Clor HO--- Br.·· , . (same or different).
a An alkene of the type R 2C=CHR' gives one aldehyde
a In these halohydrin formation reactions, a halonium ion is' and one ketone.
formed as an intermediate which' is attacked by water
a An alkene of the type R 2C=CR 2gives two keto~es (same
(nucleophile) in aqueous solution. .
or different).
a Addition of sulphuric acid:. Cold and concentrated
a The two step process of forming the ozonide,and then
HzSO 4 readily adds to alkenes and forms alkyl hydrogen
decomposing it to give a mixture' of two carbonyl
 G.R.B. Organic Chemistry for Competitions

'compoUnds is known as ozonolysis. From the ozonolysis Hydroxylation using OsO 4 :

product, the position of the double bonds can be
determined. .
R-CH O~-::?0 Ether R-CH-o ........ -::?O
1:l0zonolysis of cycloalkenes gives only a single product II + Os -- 1 Os
containing two carbonyl compounds. R-CH O-::? ~O R-CH-o/ ~O
Alkene Osmium tetraoxide An osmic ester
CH2-CHO

D
(i) 0 3
(ii) H2IPd
~
I · ·' R-CHOH
1 +H20s04
CH2-CHO
Cyclobutene Butane-I,4-dial R-CHOH
Glycol
CHO CHO

D
Cyclobuta-I,3-diene
(i) 203
(ii) 2ZnlH20
~
1
CHO
+1
CHO
Ethane-I,2-dial
I:lHydroxylation can also be done with 12 /CH 3COOAg,
peroxy acids (HC0 3H or a mixture of H 20 2 and
HCOOH).
I:lCyc1odienes on· ozonolysis give two. products each I:l Oxidation with addk KMn0 4 or addk· K2Cr207
containing two carbonyl compounds.
(Strong oxidising agent): They break the double bond
[JCyclotrienes on ozonolysis give three products each
and give ketones and carboxylic acids (because aldehydes
containing two carbonyl compounds.
formed cannot be isolated from KMnO 4 solution as they

0
CHO are easily oxidised to carboxylic acids).
1· ~
31
~ (ii) 3H2IPd CHO R 2C=CHR' KMn04, ~ R 2C=0 + RCHO ~.RCOOH
Cyclohexa-I,3,5-triene Ethane-I,2-dial Alkene [0] Ketone Acid
I:lPeriodk add (HI0 4) or lead tetra-a£etate
I:lConjugated dienes on ozonolysis yield three products, i.e., [(CH3COO)4Pb] oxidises alkene int!l glycols and finally
two monocarbonyl· compounds and one dicarbonyl gives aldehydes or ketones depending upon the nature of
compound. alkene.
. ... (i) 203
H2C~C-CH=CH2
. I . )
(ii) 2H2/Pd >r----r< .~ )=o·+o=<
CH3 Alkene OH OH Ketone
2-Methyl buta-I,3-diene Pinacol
(Isoprene)
oI 1:l0xidation of alkenes by Se0 2 affects the allylic position
CHiO +CH3-C-CHO+OH 2C and not the double bond. .
Methanal 2~Ketopropanal Se02
I:lA cumulated diene gives two monocarbonyl compounds H 2C=CHCH 2CH 3 ) H 2C=CH?HCH 3
But-I-ene
and.one mole of CO 2, . ·OH
. . (i) 203 . But-3-en-2-o1
H 2C=C--.:....CH-CH 3 .. ). CH 20 + CO 2
Buta-I,2-diene (11) 2H2/Pd· Methanal I:l Combustion: When burnt in air, alkenes are oxidised to
+OHCCH 3 CO 2 and H 20. The reaction is exothermic, because heat is
Ethanal evolved:
Oxidationreadions: Alkenes are readily oxidised. The I:l Insertion of methylene (£arbene): Phptolysis of diazo-
oxidation products depend on the nature of oxidising agent methane (CH 2N 2) and ketene (CH 2=C=0) gives·
. used: - . methylene (carbene). This adds to alkene ·to yield
I:l Oxidation or Hydroxylation with £old, dilute, alkaline cyc1oalkanes.
_KMnO 4 (Baeyer's reagent): Glycols are formed.
.......,/ Alk. KMn04....... rV
CH3-CH=CH2 + CH2N 2
,/C=C ....... +[0]+H20---~) ,/C-\...., Propene Diazomethane
Dil., cold .I I
UVLight
OHOH ~.

~'.£'':'':'ot=
This reaction is used for the detection ofunsaturation and is Methyl cyclopropane-
called Baeyer's test.
. I:lHydroxylation by KMnO 4 is always syn~additi.on. I:l Polymerisation: Two or mote molecules of an alkene
unite together to form a bigger molecule of higher
molecular mass called polyalkenes.
Unsaturated Hydrocarbons 353

Polyethene, polypropene and polybutene are "plastics" of a By rea4!ting l-alkynes with Grignard reagen"t followed
industrial importance. by treatment witb R-X : .
[J Substitution .rea4!don (Halogenadon): NBS (N-bromo CH3MgI . .
HC==C-H ) HC==C-MgI
. succinimide).is a reagent used for the'specific purpose of Ethyne ('---:CH4) . .
CH3I
brominating alkenes at the allylic position (i.e., ---7) HC==C-CH 3
replacement of H atom of the alpha carbon atom with Propyne . (-MgI2)
respect to double bond of alkyl group by th~ atom at about CH3MgI
500°C without breaking the double bond). This type of CH 3 -CFCH (-cT-f .) CH 3 -C=C-MgI
Propyne ''4
substitution is kpown as aUylk substitution. It takes place
RI
in gas phase by free radical mechanism. . --~) CH 3 -C==C-R
(-MgI2) Higher a1kyne
ALKYNES [J By oxidation of bis-bydrazone of an a-diketone :
[J Unsaturafed hydrocarbons with one triple bond are known
2NH2NH2
as alkynes or acetylenes and represented by the general . R-C-C-R' R-C--C-R'
fonnula C lI H 211 - 2 • Their functional group is -C=C-. I I I I
Alkadienes (H 2C=CH-CH=CH 2 ), cycloalkenes o 0 NNH2 NNH2
(C 4 H 6 ) D and bicycloalkanes. LSJ are isomeric with (lft-Diketone Vic-dihydrazone.

[O],2HgO . ..•.... I" .•. > •••••

alkynes containing same number of carbon atoms in their --~) R-C C-R +2N 2 +2H 20+2Hg
molecules. Heat Higher a1kyne
a The triple bond in alkynes consists of one sigma and two
Pbysi4!al properties
pi- bonds. Each C-atom of the triple bond is sp-hybridised
and -C==C- bond length (1.20 A) is shorter as a Acetylene IS a colourless gas with ether-like odour, b.pt. is
, compared with )C=c( (1.34 A) and 7C-CE (1.54 -84°C Acetylene (liquefied or when compressed) .is
explosive, burns with a luminous smoky flame, hence used
A). for lighting purpose. Oxy-acetylene flame is used for
a Monosubstituted acetyleI)es or l-alkynes. are called cutting and welding of metals. Alkynes have linear
terminal alkynes, and the H atom attached to C=C is structure and' therefore, their molecules are rather more
called acetylenic (acidic) hydrogen (R-C==C-H). closely packed in space as compared to alkanes and.
alkenes. .
General metbods of preparation
[J By debydrobalogenation (-HX) of dihalldes: On Cbemi4!alproperties
heating dihalides (vic- and gem-) with alcoholic KOH'or
[J A4!idi4! nature: The H-atoms of ethyne are more acidic
sodamide, NaNH 2 (in liquid NH 3 ) or solid KOH or KNH2 than those of ethene or ethane. The decreasing order of
etc. acidity is: H-;C==C-H> H 2C=CH2 >CH 3 -CH 3 .
[J By debalogenation (-X) of tetrabaUdes: On heating , The group -C=CH (l-alkynes) is acidic in nature due to
wi.th Zn dust in alcohol. more s-character (50%) of C==C which is sp-hybridised.
a By heating iodofonn with silver powder. Hence, proton release in -C. CH .takes place more
a By the electrolysis of Na/K salts of unsaturated readily. On account of acidic nature, ethyne and all other
dicarboxylic acids (Kolbe's method). tenninaL alkynes fomi salts with metal derivatives which
[J By the action of water on calcium carbide (Lab method). are called acetylides or. al~nides.
[J By heating methane or natural gas at I 500°C in an electric [J Formation ofsodium a4!etylides: Acetylene reacts with
arc (Manufacture method). NaNH 2 or Na/liq. NH3 fonDS sodium alkynides which is
[J By the controlled partial oxidation of methane at high utilized for the preparation'ofhigher alkynes with 10 alkyl
temperature (Manufacture method). halide (because 2° and 3° R-X give mainly alkenes).
[J By the hydrolysis of magnesium carbide, propyne is a Formation of ~oppera4!etylides: Acetylene when
fonned. passed through an ammoniacal cuprous chloride solution,
a By passing an electric arc between carbon electrodes in an a red precipitate of cuprous acetylide is formed.
atmosphere of hydrogen at 2500°C (Berthelot's [J Formation of sliver acetylides: Acetylene when passed
synthesis). through an ammoniacal solution of silver ilitrate(Tollens'
[J By reading sodium alkynides with alkyl halides : reagent), a white'precipitate of silver acetylide is fonned.
Higher alkynes are fonned. , [J Addition of bydrOg~n (Hydrogenation): Alkynes oil
treatment wjth hydrogen in presence of a catalyst (Ni, Pt or
Na/liq.NH3
HC==CH. )HC==C-Na HC==C-R Pd) fonnalkenes and finally alkanes. .
or NaNH2 Sod. alkynide . l-Alkyne

.'
 •• , • • ~F

354, G.R.B. Organic Chemistry for Competitions

[J Alkenes (cis-) can be obtained 'from aIkyne~ by partial give ethylidene acetate which on heating gives
hydrogenation with PdlCaC0 3 poisoned by quinoline or acetaldehyde and acetic anhydride.
lead acetate (Lindlar's catalyst). . [J Addition of alcobol: In presence of NaOH'Or KOH or
[J LiAlH4 or Na/liq. NH3 converts alkynes to trans' (E) mercUry salt, acetylene reacts with alcohol to form alkyl
alkenes. ' vinyl ether (vinylation) which on hydrolysis gives
[J Addition of halogens: Alkynes add two molecules of acetaldehyde and alkanol.
halogens and decolourise Br2 water (test of , o Addition of 0 3 and subsequent hydrolysis: Acetylene
unsaturation). The reactivity order of halogens is as
follows: F> CI > Br > I. Liquid bromine yields tetrabromo
°
and its homologues form ozonides with 3 and these
comp'-"lnds are decomposed by water to form diketones
derivative while BrzlH 20' or Br2ICCl4 forms dibromo which are then oxidised by H 20 2 (formed in the reaction)
derivative. Iodine reacts slowly in alcohol to fonn di-iodo to carboxylic acids.
derivative (predominantly trans- isomer). o Polymerisation: Acetylene undergoes both cyclic and
o Alkynes are less reactive than, alkenes towards addition of linear polymerisation.
halogens, because alkynes form less stable intermediate. o Cyclic polymerisation: When acetylene is passed
,0 Acetylene reacts with Cl 2 in the presence of catalyst SbCI s through a red hot metallic tube at 600°C, it is polymerised
. _to give westrOn which'on heating with BaCl 2 or lime or to benzene. Propyne on heating' trimerises to form
alc. KOH gives westrosoi; mesitylene (l,3,S-trimethyl benzene).
o Addition· of halogen acid (HX): The decreasing order . 0 Linear polymerisation: When acetylene is passed into
of reactivity is : HI> HBr > HCI > HF. Addition of one cuprous chloride solution dissolved in NH4 CI, linear
molecule of halogen acid gives vinyl halide which then ,polymerisation occurs forming monovinyl acetylene and
adds another molecule of HX to form; gem-dihalide~ The divinyl acetylene. Vinyl acetylene onreduction with H21Pt
addition follows Markownikoff's .rule. In presence of in presence of BaS04 forms buta-I,3-diene. Butadiene
peroxides, anti-Markownikoffproduct is,obtained. . and 'vinyl cyanide form polymer buna-N-synthetic
o When acetylene is passed into dilute HCI at 6O-6s o C in rubber. . Vinyl acetylene reacts with HCI to give
presence of mercuric ion (catalyst) only one molecule is chloroprene (2-chloro-buta-I,3 -diene) which polymerises
added to give vinyl chloride (vinylation). Vinyl chloride to neoprene (synthetic rubber).
(CH 2=CH-CI) is ,the monomer of PVC. IJ Addition of arsenic trichloride (AsCI 3): Acetylene
o Addition of HBr to an alkyne can be facilitated by using combines with Asa 3 in presence of anhydrous AICl 3 or
acetyl bromide (,CH 3COBr) and alUmina (Al 20 3) instead Cu 2Cl 2 or HgCl2 to form Lewisite (a poisonous gas).
of aqueous HBi. t '
o Addition of carbonyl compouncts (Alkynylation of
, . CH3COBr/Al203 '"
CsHIl-C==CH + HBr ) , )C=O compounds) : Terminal alkynes can add to
Hept-I-yne. ' I n CH2Ch solvent
)C=O group in presence ofC 2H sONa orCu2C2 to form
CSH 11 -C=CH 2 alkyndiol which is called ethinylation.
I
Br o Carbonylation: Acetylene adds to (CO + H 20) or
"i 2-Bromoh~-I-ene (CO + R-OH) in presence of catalyst nickel carbonyl,
o Addition ofhypochlo~us acid,(HO--cI): It is chloro- Ni(CO)4' and forms a,j3-unsaturated acid or ester.
hydroxylation. by chloririe water. Alkynes when passed o Formation o~ heterocyclic compounds: When acety- ,
into H{}-cl form dichloroaldehydes or ketones. lene is pass~d with sulphur over a heated tube at 300°C, it
o Addition of IhSO 4 (conc~): Acetylene gas, when forms thiophene. Acetylene combines with NH3 in red
passed through concentrated H 2S0 4, gets absorbed hot tube and forms pyrrole: With HCN in a red hot tube,
forming ethylidene hydrogen sulphate which on boiling acetylene produces pyridine.
with water gives'acetaldehyde.
o Addition of water (Hydration): \ Alkynes add on one
molecule of water when passed into dilute H 2S0 4 at 60°C
2HC=CH + H-C N
Red hot
. • ..
O·I
Acetylene ~N
in presence of HgS04 catalyst to form aldehydes or Pyridine
ketones through ketO-enol tautomerism.
o Addi~on of HCN:Ethyne adds HCN in preseJ;lceaf IJ Oxidation reactions: Different oxidation products are
, ,Ba(CN)2 or'NaCN or CuClIHClorCuCl 21NH3 cat<.):nl to obtained with different reagents.
formvinyl cyarude (acrylonitrile) which is a mon . 'ner for o Burning (combustion): Acetylene bums with ~moky
the polymer polyacrylonitrile (PAN). fla!lle in excess of air to give CO 2 and H 20 and large
• 0 Addition' of CH 3COQH: Ethyne adds tw~ moles of amount of heat is produced.
. acetic acid in presen~ of Hg 2+, or Bf.3catalyst at 80°C to o Oxidation with alkaline KMnO 4 solution: Acetylene
.- •• j'
is finally converted into oxalic acid with cold, dilute
,
" ;
Unsaturated Hydrocarbons .

alkaline KMnO 4 (Baeyer's reagent) and pink colour oftbe. [J Oxldative-hydroboratio~: Alkynes react with BH3 (in
solution is discharged. Higher alkynes under similar THF) at O°C to give an intennediate trivinyl boratie which
conditions give diketones. At higher temperature (110°C) on oxidation with alkaline H 20 2 gives an unsymmetrical
the final products are carboxylic acids, CO 2 and ketones. alcohol that tautomerises to an aldehyde or ketone.
Cl Oxidation with acidlfted KMnO .. : Acetylene is Cl Degree of unsaturatioD: The number of pairs of
converted into formic acid with acidic KMnO 4 on heating, hydrogen atoms that. a molecular ~onnula lacks to be an
while higher alkynes give R-COOH. Symmetrical . alkane (C n H2n + 2) ~ called degree of unsaturation and this
alkynes give a single product while unsymmetrical value is called the index of hydrogeli: deficiency. The
alkynes give a mixture of two products. number of degree of unsaturation'~ a hydrocarbon is
CJ Oxidation with chromic acid (K2Cr207 + H 2SO.. ): given by:
Acetylene is converted into acetic acid and the orange = --!.---=-.
colour changes to light green.
Cl Oxidation with selenium dioxide (se0 2): Acetylene is where, nl is the number of carbon atoms andn2 is the .
oxidised to glyoxal with Se02 while propyne gives keto- number of hydrogen atoms. ' •
propanal. [J Tests of UDsaturatioD: ,The tests of unsaturation
CJ Substitution reactions: When acetylene is passed (detection of double or triple bonds) are generally per-
through sodium hypochlorite (NaOCI) solution at O°C in fonned by:
absence of light, hydrogen atoms are replaced by chlorine 1. Baeyer's reagent: To an aqueous ,solution of the
atoms with the formation of 1,2-dichloroethyne. With 12 compound, a few'drops of Baeyer's'reagent (cold, dilute,
and NH3 at low temperature, acetylene formS 1,2-di-iodo . alkaline KMnO 4 soluti0'fl) is added. The decolourisation of
ethyne. pink colour indicates the presence of unsatnration.
CH. CI 2. Br2 water in CCI .. or CHCI 3 : The compound is
Low temperature
III +212 +2NH3 ) III dissolved in an inert solvent like CC1 4 or CHcl, and then a
CH CI few drops of 5% bromine. so lutiotl iIi CCl 4 are added to· it.
Ethyne 1,2-Di-iodo
ethyne If the colour of bromine disappears, it indicates the
presence of unsaturation. .
Cl lsomerisation: On heating with alcoholic KOH or [J The presence of double arid triple bonds are located by the
NaNH 2 in inert solvent, the triple bond of l-alkyne is .identification of the products of ozonolysis.
shifted towards the centre to fonn an' isomer 2-alkyne. [J l-Alkynes give a white precipitate when passed through
Similarly, on heating with sodamide (Na in liquid NH 3 ) ammoniacal AgN03 solution and also red precipitate
the triple bond (2-butyne) shifts towarqs the end when treated with ammoniacal cuprous chloride solution.
(l-butyne).

•
 (];R.B. Organic Chemistry tor Competitions

(c) An olefiruc'X'on ozonolysis gives CH 3 COCH3 and

I. Fill in the blanks: formaldehyde. The IUPAC' name of the olefm is
(a) ...... is most acidic (Ethane, Ethene, Ethyne).
(b) Tne compound having both spand sp2-hybridized (d) Acetylene is practically insoluble in, water but very
carbon atoms is ...... (propene, propane, propadiene). soluble in ...... .
, (c) Acetylene is treated with excess of sodiwn in liquid . (e): ;The 1% alkaline KMn04 solutienis known as
ammonia. The product is reacted with excess of methyl
iodide. The fmal product is . . . . . . (f) Ethylene on treatment with chlorine water gives
(d) The starting material for the manufacture of polyvinyl
chloride is obtained by reacting HCI with ...... . (g) Acetylene and formaldehyde interact in the presence
(e) The monomer of polyvinyl chloride is ...... . of copper acetylide as a catalyst to form the organic
(f) The addition of HBr on rulUruiyniirietficar alkene takes compound .......
place according to ...... rule. (h) The H-C-H bond angle in ethylene is ; ..... .
. CI (i) Alkaline KMnO4 oxidises acetylene to . . . . . . .
(g) CH3 CH=CH 2 50~~C)"" "',' (j) Carbon-carbon distance is shortest in ...... (ethane,
(h) Kolbe's electrolysis of potassium succinate gives CO2 ethene, ethyne).
and ....... (k) A hydrocarbon containing two double' bonds is
(i) Addition ofwater,o acetylenic,compounds is catalysed by named as .......
...... and.: .. ·.':.:· """" . (I) Dichloroacetaldehyde is obtained by treating
G) Unsaturation in alkenes can be tested with ...... reagent. acetylene with . . . . . . .
(k) Methane is evolved when water is added to aluminium (m) In alkenes and alkynes the electrophile adds across
carbide. The gas evolved is ...... when water is added the ...... bond.
to calciwn carbide. ' (n) Trialkylborane on decomposition by CH3COOH

)e=c<H
(I) The carbon atoms of ethene are ...... hybridized. forms ...... .
(m) The carbon atoms of ethyne are ...... hybridized.
'(n) A white precipitate is obtained by passing ac~tylehe
through ammoniacal ... . . . . sol"\ltion.
(0)
Ph

H" CH3
~ ..... .
(0) Buta-I,3-diene with bromine in molar ratio generates
predominately . . . . . . .
(P) The electrolysis of potassiwn fumarate gives . .. . . . .
(q) The position isomer of butene" 1 is ...... .
NaNH 2 CH3Br
(r)The ozonolysis product of CH3 CH=CHCH3 is (q) HC==CH ) ...... ~ ..... ".
HBr KOH(aq.)
(s) Lewisite and mustard gas are ...... in nature. (r) CH 3 -CH=CH2 .) )
, PerOXIde
(1) Alkyl halides undergo ...... reactions with alcoholic
KOH and form ...... .
Br2
(u) A compound of carbon and hydrogen used for welding (s) H 2 C=CH2 '---"-f
purposes is . .. .. . . CCl 4
(v) Carbon atoms in Ag 2C2 (silver acetylide) are ..... .
hybridized. ,
(t) HO=CH~ ~
Zn
.. ....
,
CCl 4
(w) Hydration of ethylene in presence of an,acid produces
Ph~H
(u) ~ +KNH2
(x) ...... is formed whell cthvlene is treated,with alkaline
··KMn°4 • • ,
Ph/' "'-Br
, ' (y) S2Cl2 reacts with ...... to form mustard gas.
(v) HO=CH
, (z) The' kind of delocalization involving' sigma bond
orbitals is called . . . . . . .
2. Fill in the blanks :
(a) 'The structura1 formula of the compound which yields
(x) CH 3-C==CH B2~ ) . . . . .• NaOH)
H 20 2
'ethylene upon reaction with zinc is ...... .
, AlCI)
(b) The intermediate product in the preparation of (y) HC==CH + CH3 0CH 2 CI ~
ethylene from ethanol and sulphuric acid is .. : ....
Unsaturated Hydrocarbons 357
(c) Ozonolysis (3) Alkaline potassium
(z) (CH 3 h C=CH2 + CHCl 3 (CH 3)3 C- OK; per-manganate
(d)" Mustard gas (4) But-2-ene
3. Sta~ whether the following statements are True or False:
(e) Acetylene tetrachloride (5) 2-Chlorovinyldichloro-
(a) Moist ethylene can be dried by passing it through conc.
arsenic
H 2 S04 ,
(f) Baeyer's reagent (6) Alcoholic kOH
(b) 2-Methylpropene gives isobutyl bromide with RBr.
(g) Geometrical is;)merism (7) Structure of alkene
(c) Ethyne and its derivatives' will give white precipitate
(h) Lewisite (8) Polymerisation
with ammoniacal silver nitrate solution.
[B] (a) Cn H2n ' (I) Formaldehyde
(d) The acidic nature of three types of hydrocarbons
(b) C n H 2n - 2 (2) Plastic'
follO\·'s the order,
(c) Alkyl halide + Ale. KOH (3) Allene
Alkanes < Alkenes < Alkynes. (d)Polythene (4) Thiophene
(e) Peroxide effect is effective only in the addition of HBr (e) C 2 H 4 + 03/H20 (5) Alkene
and not HCI and HI. (f) H 2C=C=CH2 (6) Pyrrole
(f) Acetylene is colourless, odourless gas. (g) C2 H 2 + S (7) Alkyne
(g) Vinyl acetate used. in plastic industry can be prepared (h) C2H2 + NH3 (8) Dehydrohalogenation
by the action of acetic acid on ethyne. 5. Complete the following equations:
(h) Bromine water can be used to distinguish ethyne and (a) H 2C=CH-CH3 + HCI ~ (A)
ethene.
(i) Decolourisation ofBaeyer's reagent is sure test ofa1kenes. (b)
G) The process of conversion of acetylene into benzene is
polymerisation. (c) H 2C=CH2 +0 H20) (A) NaOH(aq.~ (B)+(C)
(k) The reaction of ethyl alcohol with acetylene is 3

'nucleophilic addition. (d) (CH3 h C-CH=CH2 + HCI ~ (A)

(I) Propyne is more acidic than acetylene. Et. Br ) (B)
(m) In Holme's signal of the ship, the torch contains CaC2
and Al 4 C3 . I "
(n) Propene with diborane forms an additive product which
on reaction with H20 2 fonns propanol.
(0) Propene can undergo addition as well as substitution (g) HC==CH H2 , Pd(CaC0 3 » (A) ~ .
'with halogens depending upon the condition of the (CH3COO)2Pb CCl 4
reaction. (B) (Ale.) KOH) (C)
(P) Propyl bromide on reaction with alc. KOH gives acetylene.
(q) )e=C< bond length ismore'than -C==C- bond (h) HC=CH HgS04,H2_<!~ (A) H)
H2S0 4 LiAU4
length.
(r) A carbon-carbon triple bond is considerably stronger (Cone.) H 2S04 ) (C)
than that of carbon-carbon double bond. (9) 1700C
(s) Baeyer's reagent is acidified KMn0 4 solution.
(i) CH CH CH OH (Cone.) H 2S04) (A)-~~-HB)
(t) Addition of RBr to (CH3 h C=CH2 in presenct'lof 3 2 2 1700C 5000C'
benzoyl peroxide takes place according to
anti-Markownikoff's rule. G) CH CH=CH , ~'(A) (Ale.)KOH) (B)
(u) Ethene and Baeyer's reagent gives ethylene glycoL 3 2 500"C' . Heat
(v) When propene is treated with Cl 2 at 500°C,' . (k) H 2 C=CH2 + CH 2N 2 ~ (A)
substitution !,>ccurs in methyl group. (I) CH 3CH=CH2 + CH2I 2 ~ (A)
(w) Lewisite is formed by the reaction of acetylene and (m) H 2C=:CH-CH=CH2 +H 2C=CH2 ~ "
arsenic trichloride. H2
(x) But-2-yne forms white precipitate with Tollens' (A) ~ (B)
reagent.
(y) But-2-yne 011 ozonolysis forms formic acid and (n) C H CH
3 7
CH
2
, .H~OAe~) (~) NaBH4 /NaOH) (B)
propionic acid. , ~/H~
(z) Acetylene when oxidised with selenium dioxide forms
(0) CH CH=CH . BH3/1'Hl'; (A) CH3COOH), (B)
glyoxal. . 3 2
4. Match the following: . (i) NaNH2
[A] (a) Dehydrohalogenation (I) Poisonous gas (3.0,equiv.» (B)
(b) nCH2=CH 2 ~ (2) Westron (ii)CH3I
+CH 2-CH dn
 G.R.B. Organic Chemistry (or Competitions

(e) Ethylene is treated with alkaline KMn04 solution?

(f) Propene is subjected to ozonolysis and subsequently
treated with Zn/H2 0?
(B) (e) (g) Propene is treated with, hydrogen bromide in the
(r) ~~
presence of a peroxide?
(h) Acetylene is passed through ammoniacal cuprous
chloride solution?
(i) Acetylene is passed through dilute H2S04 in presence
of HgS04 ? ,
(j) Acetylene reacts with Baeyer's reagent?
, Peroxide 8. Answer the following:
(s) CH 3CH=CH2 + BrCCI 3 ) (A) (a) If the bond order (number of bonds) between two
(t) CH3CH C(CH3 h + HCI Peroxide) (A) carbon atoms increases what will happen to bond length
and bond energy?
(u) (CH3 hC--:-CH2 + isobutane 2~K) (A) (b) What type of reactions usually occur in alkenes?
(c) What type of isomerism is eXhibited by CHBr=CHBr?
CHCl 3 (A) NaOH) (d) What type ofH 2C=C=CHz diene is?
(v) CH3CH2 CH=CH2 ----"') (e) Which type of mechanism is followed in
(B) Dil. HCI) (C) Markownikoff's rule?
(f) Which type of mechanism is followed in anti-
(w) 'Markownikofrs rule?
(g) What reagent is used in the dehydrohalogenation of
alkyl halides?
(x) (h) Name two reagents which can be used to test
unsaturation?
9. (a) Arrange benzene, n-hexane and ethyne in decreasing
(y) (i) BH3, THF. (A) order of acidic behaviour. Also give reason for this
(ii) HzOz, OH- behaviour.
(b) Write the structural formulae and IUPAC names for all
(A) ,
(z) R-CH ' CH z ~ R-,--CH-CH z-CCI 3 the structural isomers of alkenes with molecular
. I formula CSHIO'
CI (c) Write the various types of isomerism shown by alkenes.
IRoorkee lOOt] Give one example of each.
6. What is the fmal product when: to. Which of the following compounds will show cis-trans
(a) Acetylene reacts with arsenic trichloride? isomerism?
(b) Acetylene reacts with acetic acid in presence of (i) (CH3hC=CH-C2H s (ii) HzC=CBr2
mercuric salt ? (iii) C6HsCH=CH-CH3 (iv) CH3 CH=CClCH3
(c) Acetylene reacts with ethyl alcohol in presence of U. Draw the cis and trans structures of hex-2-ene. Which
mercuric salt? isomer wiH have higher b.pt and why?
(d) Acetylene combines with ammonia at high U. (a) How is ethene obtained from the following compounds
temperature? in one step?
(e) Acetylene combines with nitrogen in presence of (i) Ethanol, (ii) Ethyl bromide, (iii) Ethyne, (iv) Ethylene
electric spark?
bromide.
(f) Acetylene is heated with sulphur?
(b) How is ethyne obtained from the following compounds
7. What happens when:
in one step?
(a) Ethylene reacts with hypochlorous acid?
(i) Ethylene bromide, (ii) Trichloromethane,
(b) Acetylene is passed through ammoniacal solution of
(iii) 1,1,2,2-Tetrabromoethane.
silver nitrate?
(c) Acetylene is passed through a red hot metallic tube?
(d) Ethyl alcohol is heated at 170°C with excess of conc.
H 2 S04 ?

0..,. "
Unsaturated Hydrocarbons 359

13. How wiU you synthesise?

(a) Vinyl chloride from acetylene:

lr
Hint: HC.=CH CH 3CHCl 2
(Ale.) KOH
) H2C=CHCI
1
J or
(b) But-l-yne from acetylene:
r .NaNH 2
. . CH 3CH2 Br
l Hint: HC==CH ) HC==CNa' )

(c) But-2-yne from propyne:

r ·
lHint: CH C==CH 3
NaNH
2) CH 3C==CNa
BrCH]
) CH3C==CCH 3 J
1

(d) Butan-2-one from acetylene:

~)
Hint: HC=CH
.
Chloroprene from acetylene:
HC CNa
CH]CH2Br 2 H S0 ,H 0 '
4 2
) HC=CCH2CH 3 -=--.:........::---+).
But-I-yne HgS04
?i J
CH3~C~CH2CH3
.

r.
Hint: 2HC==CH
Cu 2Ci 2
NH4 Cl
) H2C=CH~C
Vinyl acetylene
. CH

CH CH CH Br '
3 2, 2
Na I ether ) CH
Wurtz reaction 3
(~H2 )4 CH3]
(i) Cyclohexene from cyclohexane:
rHint: Ci'
Cyclobexane ~ Chlorocyclobexane ~.
c. . CyclohexeneJ
Al 1
hv, KOH
l
. (j) Vinyl ac~tate from ~thyl alcohol:
rlHint: <;H5 0H
(Cone.) H2S04 ' Br2
1700C') H2C=CH2'~ CH2Br~CH2Br

(k) Cyclohexa-1,3-diene from cyclohexene:

[Hint:
.
0.
NBS, • r'l, ~C~~H O~
~Br .' ~
]
14. How will you obtain the following from propene?
(a) n-Propyl bromide,
[Hint: Reaction of HBr in presence of peroxide]
, (b) n-Propyl alcohol,
[Hint: First convert into n-propyl bromide and then do hydrolysis with aq. NaOH or AgOR.]
(c) Isopropyl alcohol,
[Hint: First react with HBr to form isopropyl bromide and then do hydrolysis.]
(d) 1,2-0icbloropropane,' .
[Hint: Treat with Cl 2 in CCI 4 ]
360 G.R.B. Organic Chemistry [or Competitions

(e) Acetylene; . 0
[Hint: By ozonolysis propene is converted into acetaldehyde, ~ II
(k) HC CH2 CH2-CH and OHC-CHO
, 1 II .
CH3CHO CH 3CHCl 2 HC==CH J o
o
(t) Allene (propadiene). ~ II
rI Hint: CH CH =CH (1) HC CH CHr-CH
2 only
3 2 II
L o

IS. How will you differentiate the following?

(m)· [:>-1-H
o
(,)0 o

(a) Ethylene and ethane o

(b) Ethylene and acetylene
(c) Ethane and ethyne (0) (CH3 hCOand CH 3CH 2CHO
(d) But-l-ene and but-I-yne [Ans. (a) CH3CH=CH2 (Propene)
(e) But-2-yne and but-I-yne
[Hint: But-l-yne fonns white ppt. with ammoniacal silver nitrate (b) (CH3)2C=CH2 (2-Methylprop-l-ene)
while but-2-yne does not 'lis it has no acidic hydrogen.] (c) (CH3)2C=CHCH3 (2-Methylbut-2-ene)
16. (a) Agaseous mixture consists ethane and ethylene. How (d) (CH3hC=C(CH3)2 (2,3-Dimethylbrit-2-ene)
are the individual members recovered?
[Bint: Pass mixture through cone. H2S0 4, Ethylene is ab-
(e) CH3-CH2-C=C-CH 2-CH3
sorbed. The product on beating giv(', a~:1in C2H4.]
I I
CH; CH3
(b) A gaseous mixture consists of ethylene and acetylene. (3,4-Dimethylhex-3-ene)
How ]:loth are separated from each other?
[Hint: Pass mixture through ammoniacal cuprous chloride solu- (f) H2C=CH-CH-CH(CH 3)2
tion. The acetylene fonns red precipitate. It is filtered and ' I
treated with HN0 3 to recover acetylene. CH 3
Cu 2C2(red ppt.) + 2HN0 3 -7 C2H2 + Cu 2(N03)2] (3,4-Dimethylpent-l-ene)
17. Explain the mechanism of the following reactions: (g) CH 3CH 2-C=CH-CH=CHCH2CH3
(a) Bromine on ethylene. . I
(b) HBr on ethylene. ' C2H S
(c) Dehydration of an alcohol. (3-Ethylocta-3 ,5-diene)
(d) HBr on buta-I,3-diene.
(e) HClon 3,3-dimethylbut-I-ene. HC=CH
18. Deduce the structures of the compounds which yield the ~____
(b) H2C '-...... '-...... CH2
following products on reductive ozonolysis:
CH2
(a) CH3 CHOand HCHO
(Cyclopentene)
(b) (CH 3 )2C0an4 HCHO
/CH=CH~
(c)(CH~ hCOand CH 3CHO
(i) H2C, /CH 2
(dj'(CH 3 hCOonly . 'CH=CH/
(e) CHlH2 f=O (two moles) (Cyclohexa -1 ,4-diene)

, CH
3

(t) HCHO and O=CH-fH- CH(CH 3 h

me))
CH 3 (k)O
(g) CH3CH2f=O and OHC-CHO and OHCCH2CH3

C2 HS (1) (»
(h) OHC-- CH2 CH 2 CH 2 CHO only
(i), OHC-CH 2-CHO (two moles)
2)4) (m) [>-cH-CH--<:j

(,)00
. «CH
mO=C C=O only
. (CH 2 )4
Unsaturated Hydrocarbons

&~,
(0) CH3-f=CHCH2 CH3 ]

CH 3
2-Methyl pent-2-ene

19. Write short notes on:

(a) Markownikoff's rule
(b) Ozonolysis
(c) Polymerisation
(d) Anti-Markownikoff'srule or Peroxide effect
[An., &CH'; (i)

(Major)
(ii) &
(Minor)
CH
2 ....

(e) Dehydrohalogenation
(1) Saytzeff's rule
(g) Baeyer's strain theory
ZOo Explain the following:
[ill) aCH3]
(a) Why alkenes are more reactive than alkanes? (Minor)

[Ans. it-bond is weaker than a sigma-bond and is easily broken. (j) Which of the following reactions would provide a
The :rt-electrons are less firmly bound to carbon nuclei.] better synthesis of 2-pentene?
(b) Acetylene reacts with ammoniacal silver nitrate solution
. or ammoniacal cuprous chloride solution or sodamide to (i)~
form an acetylide while ethylene does not. Br
[Ans. Acetylene reacts to fonn· acetylide because it contains acidic Br

(ii)~
hydrogens.]
(c) But-2-ene shows geometrical isomerism but but-l-ene
does not show. .
[Ans. (i) is better because it gives only one product ...
[Ans. ill but-l-ene, the carbon atom linl<;ed by double bond is
~,
. attached with two hydrogen atoms (similar groups) and
thus does not show geometrical isomerism. while(ii) gives a mixture of
~and~.]
H~ /H (k) Write the major products of dehydration of:
/C=C"", OH OH
H S C2 H
But-I-ene (i) ~ (ii) + O H (iii)~
[Ans. (i) ~ (ii) ~ (iii) ~ ]
Trans-but-2-ene 2-Methyl pent-2-ene
2-Metbyl but-2-ene
.
But-2-ene ANSWERS
(d) Why has but-l-yne a larger dipole moment (0.80 D) than 1. (a) Ethyne; (b) propadiene; (c) but-2-yne
but-l-ene (0.30 D)?
[Ans. A C-C sp bond is more polarized than C-Csp 2 bond [Hint: (i) CH!!!5CH 2Na .. NaC!!!5CNa,
NH3 (liq.)
because carbon with more s-character is more (ii) NaC==CNa 2CH3I) CHP==CCH~ + 2Nal]; (d) acetylene
electronegative.] .
[Hint: C2H 2 + HCI CH 2=CHCI]; (e) vinyl chloride;
--7
(e) Why alkynes are slightly more soluble in water than
(1) Markownikoff's; (g) CICH 2CH=CH 2; (h) ethene; (i) HgS04,
alkenes and alkanes?
[Ans. Alkynes are somewhat more polar in nature and thus, their H 2S0 4; (j) Baeyer's; (k) acetylene; (I) sp2; (m) sp; (n) silver nitrate;
solubility is slightly more in water.} (0) 3,4-dibromobut-l-ene (at low temperature) or 1,4-dibromobut-
(f) Cyclopropane is more reactive than cyclobutane. 2-ene (at high temperature); (P) acetylene; (q) but-2-ene;
(g) Cyclopentane is inert like alkanes. . (r) acetaldehyde; (s) poisonous; (t) elimination;
(h) Which isomer of C4H9Br yields only a single alkene on (dehydrohalogenation), alkenes; (u) acetylene; (v) sp; (w) ethyl
alcohol; (x) ethylene glycol; (y) CH 2=CH 2 (ethene);
dehydrobromination?
(Alc.)KOH (z) hyperconjugation.
[Ans. (CH3)3C-Br ) CH 3-C CHz) 2. (a) CH2BrCH2Br; (b) C2H sHS04; (c) 2-methylpropene;
Tert. butyl bromide A I (d) acetone; (e) Baeyer's reagent; (t) ethylene chlorohydrin;
CH 3
(g) HOH 2CC==CCH20H (But-2-yn-l,4-diol); (h) 120°; (i) oxalic
2-Methyl propene
acid; (j) ethyne; (k) alkadiene; (I) HOCI; (m) :rt;(n) alIame;
(i) Write the products of dehydrochlorination of the
following: y
(0) Ph- H-CH 2CH 3 ;" (P) CH3CH2HSO~ 0I3CH 20H;

Br
 G.R.B. Organic Chemistry for Competitions

(q) CH==CNa, CH 3-C==CH; (r) CH3CH 2CH 2Br, (e) CH 3CH 2CH-CH3;
CH3CH2CH20H; (s) CI:I2Br-CH2Br, CH==CH; I
(t) CHBr2 - CHBr2' CH==CH; (u) Ph-C==C-Ph; COOH
(v) HC==C-Na, HC==C-D; (w) Na-C==C-Na, (w)(A) CJlrCH-CH-CH3 (Major);
D-C==C-D; (x) (CH 3-C=CH-hB, CH3CH2CHO; I I .
(y) CH30CH zCH=CHz; (z) (CH 3)2 \/CH 2 OH Br

/~ (x) UCI
CI Cl
3. (a) False-Ethylene combines with H 2S04; (b) False-Tert. butyl
bromide is formed; (c) False-Only R-OaCH derivatives give
white ppt. but derivatives of the type R-C=C-R' do not give
(y) VOH
white ppt. with ammoniacal silver nitrate; (d) True; (e) True; (z) CCliperoxide
(t) False-Acetylene is colourless with garlic odour gas; (g) True; 6. (a) Lewisite; (b) CHz=CHOOCCH 3, vinyl acetate;
(h) False-Both decolourise bromine water; (i) False-.-Reducing (c) C 2HsO-CH=CH2 , ethyl vinyl ether;
compounds can also decolourise Baeyer's reagent; G) True; . CH=CH"",.
(k) True; (I) False-Propyne is less acidic than acetylene; (m) False- (d) I /NfI, pyrrole;
The torch oontains CaCz and Ca3PZ; (n) True; (0) True; (P) False-
gives propene; (q) True; (r) True; (s) False-Baeyer's reagent is
alkaline KMn0 4 solution; (t) True; (u) True; (v) True; (w) True;
CH=CHr
(e) HCN, hydrogencyanlde;
. .
CH=CH"",
(x) False-It does not react with Tollens' reagent as it has no acidic (t) I /S, thiophene.
hydrogen; (y) False-forms only acetic acid; (z) True. CH=CH
4. [A] (a-{j); (b-8); (c-7); (d-I); (e-2); (f-3); (g-4); (h-5). ,
[B] (a-5); (b-7); (c-8); (d-2); (e-J); (f-3); (g-4); (h-{j).
7. See properties of ethylene and acetylene.
8. (a) Bond length decreases and bond energy increases;
5. (a) (A) CH3CHCICH3 ; (b) (A) CH 3CHO, (B) CH3COCH 3; (c) (A)
(b) Electrophilic addition reactions; (c) Geometrical or cis-trans
HCHO, (B) HCOONa, (C) CH 30H. Formaldehyde undllrgoes
isomerism; (d) Cumulated; (e) Ionic mechanism; (t) Free radical
Cannizzaro's reaction; (d) (A) 2-chloro-2,3-dimethyl butane;
mechanism; (g) Alcoholic potassium hydroxide; (h) Bromine and
(e) (A) Me-CHz-C==CNa, (B) MeCH 2C=C· Et; (t) (A)
. Baeyer's reagent.
CH==CH, (B) CH 3CH CHCOOH; (g) (A) CZH4, (B)
9. (a) The decreasing order of acidic strength is:
CH2BrCH2Br, (C) C2H 2; (il) (A) CH3CHO, (B) CH3CH 20H, (c)
C2H4; (i) (A) CH 3-CH=CH2• (B) CHzCLCH=CHz; (j) (A)' Ethyne > Benzene > n-Hexane
CH 2BrCH=CHz, (B) H 2C=C=CH 2; (k) (A) cyclopropane;
(I) (A)methylcyclopropane; (m) (A) cyclohexene, (B) eyclohexane;
(n) (A) C~7CH(OH)CH2 - HgOAc, (B) ~H7CH(OH)CH3;
(0) (A) (CH 3CH 2CHz)3B, (B) CH 3CH 2CH3;
H--C=C-H
sp 0sp2
CH3(CH2)4CH3
sl
(P) (A) CJlsCHBr-CH2Br, (B) C1;HsC==CCH3; S-character 50% 33% 25%
(q) (A)CJlsCH=CHC1;Hs (cis- and trans-);
The acidic character is linked with the percentage of S-character.
Greater the S-character, more is the electronegativity of the carbon
(r) (A) C1;HsC03H ( D)I°'c(D] , atom and more will be the acidic character.
(CH3 h C " ' - H (b) CH3CH2CH2CH=CH 2 (Pent-l-ene), CH3CH2CH=CHCH3
(Pent-2-ene), (CH3)2CHCH=CH2 (3-Methylbut-l-ene),
CH 3
I
CH)CH2-C=CHz (2-Methyl-l-butene)
(CH3)2C=CHCH3 (2-Methyl-2-butene)
(c) Position isomerism-Example: but-I-ene and but-2-ene
Chain isomerism-Example: but-l-ene and 2-methylPropene
Geometrical isomerism~Example : cis- or trans-but-2-ene
Ring chain isomerism-Example: propene and cyclopropane.
10. (iii) and (iv) will show cis-trans isomerism.
CH 3"" /CH2C~2CH3 CH 3"" /H • .
11. /C=C" /C=C,
H "H H "cH 2CH2CH 3
Cis Traru
The cis form will have higher boiling point due to more polar nature
leading to stronger intermolecular dipole-dipole· interaction, thus
requiring more heat energy to separate them.

',.
Unsaturated Hydrocarbons

PROBLEMS BASED ON STRUCTURE AND PROPERTIES

1. An organic compound [A] C6 H 10 ' on reduction fIrst gives
H2C=C-CH=CH2 Ozonolysi~ 2HCHO + O=C-CHO]
[B] C 6 H12 , and fmally [C] C 6 H 14 . [A] on ozonolysis I Formaldehyde I
followed by hydrolysis gives two aldehydes [D] C 2H 4 O, CH3 CH3
and [E] C2H 20 2· Oxid~tion of [B] witli acidifIed KMn0 4 (CsHs) (E) 2-Ketopropanal
gives acid [F] C4 H s 0 2. Determine the structures of the :i-Methyl buta-l,3-diene
compounds [A] to [F] with proper reasoning. 4. A hydrocarbon (A) adds one mole of hydrogen in presence
of Ilt caqtlyst to form n-hexane. When (A) is oxidized
[Hint: CJIIO (~? Ozonolysi: C ZH 40 + CzHzO z
(11) HydrolySiS (CH 3CHO) (OHC-CHO) vigorously with· KMn04 , a single carboxylic acid
(D) (E) (Glyoxal)
containing three carbon atoms is isolated. Give the structure
Thus, LA] is CH3CH=CH-CH=CHCH3 (Hexa-2,4-diene) of (A) and explain.

!H 2 [Hint: (A)
+ Hz(Pt)
) CH3CH2CH2CH2CH2CH3
CH3CH 2CH 2CH=CHCH3 CH3CH2CH2CH2CH2CH3 [0] ~04) 2CH CH COOH
(B) (Hex-2-ene) (C) (Hexane) 3 2
!
Acidified KMn04 So (A) is CH3CH2CH CHCH l CH3 (Hex-3-ene)]
S. A hydrocarbon (A) of the formula C 7 H l2 on ozonolysis
CH3CH l CHl COOH] gives a compound (B) which undergo aldol condensation
[F] Butanoic acid
giving l-acetylcyclopentene. Identify (A) and (B).
2. (A), (B) and (C) are isomeric heptenes. (A) on ozonolysis [liint: Since, the ozonolysis of the hydrocarbon (A) gives only one
gives ethanal and pentanal, (B) on ozonolysis gives ethanal
compound (B), the compound (A) must be a cyclic alkene.
and pentan-3-one, while ,(C) on like treatment yields Moreover since the number ofC-atoms in the product obtained
propanone and butanone. Give the structural formulae and from the aldol condensation of (B) is the same as that of (A),
IUPAC names of (A), (B) and (C). the compound (B) must have gone intra aldol condensation.
[Hint! Compound (A) gives: So, (A) and (B) are as follows:
CH3CH =f:.9~fQ+=CHCHlCH2CH2CH3
Ethanal Pentanal CH3

c5 ~~.&;
.So, (A) is CH3CH -'-CHCH2CHl CH2CH 3
(A)
f1ept-2-ene
, _______ , /CH2CH 3
Compound (B) gives: CH3CH~.Q_·LQ_TC"'-.. (A) (B)
1
&'H
Ethanal CH 2CH3
Pentan-3-one
/CH l CH3 Intra-aldol
So, (B) is . CH3CH=C"", i.,. condensation
CH 2CHj
(B) 6. Hydrocarbon (A) C6 H 10 ' on treatment with H2 /Ni,
3-Ethylpent-2-ene H2/Lindlar's catalyst and Na/liquid NH3 forms three
different reduction products (B), (C) and (D) respectively.
Compound (C ) gives: (A) does not form any salt with ammoniacal AgN03
solution, but forms a salt (E) on heating with NaNH 2 in an
inert solvent. Compound (E) reacts with CH31 to give (F).
Compound (D) on oxidative ozonolysis gives n-butanoic
acid along with other product.
So, (C) is Give structures of (A ) to (F) with proper reasoning.
[Hint:
(C)
2,3-Dimethylpent-2-ene
3. An organic compound (E) (CsHs ) on hydrogenation gives
compound (F) (C S H12} Compound (E) on ozonolysis
gilles formaldehyde and 2-keto-propanal. Deduce the CH3CH2CH2C=:::C-CH3
(A)
structure of compound (E).
[Hint: CSHg consists two double bonds as on hydrogenation, it
NalLiq.NH3
is converted into CSH I2.
Heat NaNH2
 G.R.B. Organic Chemistryfor Competitions

7. Dehydration of infonnation two isomeric structures can be proposed· for

alkene (A). Write their structures and identifY the isomer
H3COH
which on catalytic hydrogenation (H2/Pd-C) gives a
H OH racemic mixture. lilT 2001]
gives a compound which exists in two isomeric forms. Give [Hint: The given reactions are as follows :
the structure of both the isomers. 03 12 /NaOH

H3:O H3:>()]
C,Ji16 ~ CgHgO .) (1;H sCOONa
, (A) (B) Sodium benzoate
[Hint: or Alkene Only product
I. KOHlNH NH
2 2 ,
('r(CH , CsHIO
9. C 7HI2 ~
HOH
V OH
3 (C)
Since, (A) on ozonolysis gives only one product (D), the alkene
must be a symmetrical one. This reaction may be written as,
What are
the possible isomers of fonnula C 7 HI2 which give
above product?
'· D
[Hmt: f .
egree 0 unsaturation =
14 - 12 + 2 . 2
=
~IH,O > [:>c~o1
2
2
Thus, the compound should have a ring and a double bond. (A) (D)
.. Possible isomers will be . (where a + b = C7 Hg)

c5 c5
Further, (D) on treatment with 12 /NaOH (iodoiOrm test) gives
sodium benzoate, one of the group (a) and (b) may be identified
with C1;Hs and hence the other one may be CH 3 group. The given
J reactions are as follows:
9. Identify (X), (Y)and (Z) in the following synthetic scheme C1;Hs\ /{1;Hs 0 IH 0 (1;H 5\ I IN OH
and write their structures. /C=C'",- ~2 /C=O 2 a ) C6H sCOONa
CH 3 CH 3 CH 3 Sodium benzoate
CH CH C==CH (i)NaNH2 ) (X) H 2 /Pd-BaS04 ) (A) (D)
3 2 (li) CH 3CH 2Br . Acetophenone
+CHI3
(Y) AlkalineKMn04 ) (Z)
Is the compound (Z)optically active? JustifY your answer.
(liT 2002)
b
.. KOHlNH2NH 2
Wolff _Kishner
reduction
{1;HsCH2CH 3
Ethyl benzene
(C)

The alkene (A) will have two isomers, cis- and trans. The catalytic
hydrogenation (H2 /Pd-C) involves syn-addition of hydrogen.
The trans-isomer gives racemic mixture while cis-isomer gives a
meso compound.
Alkaline KMn04

Trans-isomer .
C~s
I
H-C-OH
I
H-C-OH
I
C2H S
Hexane-3,4-diot'
(Meso or inactive form)
(Z)
10. An alkene (A)C'6HI6' on ozonolysis gives one product (B)
CsHsO. Compound (B) on reaction with NaOWI2 yields
sodium benzoate; Compound (B). reacts with
KOWNH2 NH2 yielding a hydrocarbon (C)CSHIO' Write
the structure of compounds (B) and (C). Based on this
Unsaturated Hydrocarbons 365

OBJECTIVE OUESTIONS
SET I: This set contains the questions with single correct answer. (a) Me2CO+CH3CHO o
1. When ethyl iodide is treated with a!coholic potash, we get: (b) CH3CHO+CH3COOH o
(a) ethyl alcohol 0 (b) ethane 0
(c) acetylene 0 (d) ethylene D. (c) MeiCO+CH3COOH o
2. Ethylene is produced by: " (d) 2Me2CO o
(a) dehydration of acetic acid 0 12. Ethyl alcohol is heated with conc. H 2 S04 at 170°C. The
(b) electrolysis of methyl alcohol 0 product formed is: [VITEEE 2008]
(c) mixing acetic acid and c~lcium formate 0 (a) CH3 COOCH3 0 (b) C2H 6 0
(d) passing C 2 H 5 0H vapourS over hot Al 2 0 3 0
(c) C2 H 4 0 (d) C 2 H 2 0
3. A gas decolourises alkaline KMn0 4 solution but does not
13. The maximum number of isomers for an alkene with
give precipitate with silver nitrate. It is:
molecular formula C4 Hg is:
(a) CH4 0 (b) C2 H 6 0 (a) 2 0 (b) 3 o
(c) C 2 H 4 0 (d) C 2 H 2 0 (c) 4 0 (d) 5 o
4. Acetylene on treatment with dil. H 2 S04 having HgS0 4 LlIint: CH 3CH2CH =CH2 , CH 3CH =CHCH 3 (cis- and Irans-)
gives: CH 3
(a) acetaldehyde 0 (b) acetic acid 0 I
(c) ethanol 0 (d) ethylene 0 and CHr-C=CH2]
5. Which of the following reagents distinguish ethylene from 14. When ethylene is passed through alkaline KMn04 solution,
acetylene? [BHU 2006] we get:
(a) Ammoniacal cuprous chloride 0 (a) ethanol 0 (b) glycol 0
(b) Br2 water 0 (c) oxalic acid 0 (d) acetaldehyde 0
(c) Alkaline KMn0.i solution 0 15. But-2-ene can be obtained by reacting: '
(d) ChlOime dissolved in CCl 4 0 (a) 1,2-dibromopropane with zinc 0
6. Which of the following not only decolourises alkaline (b) ethyl bromide with sodium 0
potassium pennanganate but also gives red precipitate with (c) ethylidene bromide with zinc 0
ammoniacal cuprous chloride solution? (d) n-butyl alcohol with alcoholic KOH 0
[EAMCET (Med.) 2006] 16. On electrolysis of potassium succinate solution, the
(a) Ethane 0 (b) Methane 0 hydrocarbon obtained is: [JIPMER 2004)
(c) Ethene 0 "(d) Acetylene 0 (a) ethene 0 (b) ethane 0
, 7. The most reactive hydrocarbon is: [JIPMER 2003] (c) ethyne 0 (d) aU of these 0
(a) ethene [J (b) ethyne 0 17. Ethylene reacts with sulphur monochloride to form:
(c) ethane 0 (d) methane 0 (a) ethyl chloride 0 ' (b) ethylene chloride 0
8. Aqueous solution of an organic compound 'A' on (c) mustard gas 0 (d) ethylidene chloride 0
electrolysis liberates acetylene and CO 2 at anode. 'A' is: 18. Ethylene reacts with air under pressure in presence of silver
[EAMCET (Engg.) 2007) catalyst at 250°C to form:
(a) potassium citrate o(b) potassium acetate 0 (a) ethylene glycol 0 (b) formaldehyde 0
(c) potassium succinate o (d) potassium maleate 0 (c) acetaldehyde 0 (d) epoxide 0
9. Baeyer's reagent is: 19. 1,2-dibromopropane on reaction with ale. KOH yields:
(a) alkaline KMn04 solution 0 (a) acetylene 0 (b) propylene 0
(b) acidic KMnO4 solutioQ, 0 (c) propyne 0 ' (d) none 0
(c) neutral KMnO4 solution 0 20. ...... is obtained when iodoform is heated with Ag
(d) aqueous bromine solution 0 powder.
10. The negative part of the addendum adds on to the unsaturated (a) CH 4 0 (b) C2 H 4 0
carbon atom joined to the least number, of hydrogen atoms. (cl C2 H 6 0 (d) C2 H 2 0
This statement is called: [AFMC 2004)
21. Benzene is a polymer of:
(a) Saytzeffrule o (b) Kharasch effect 0 (a) methane [J (b) acetylene o
(c) Markownikoff's rule [] (d) Anti-Saytzeffrule 0
11. Products of the following reaction,
(c) ethane 0 (d) ethylene o
22. Acetylene on ozonolysis gives:
Me2C=CHCH3
(i) 0 3
' ) ? are: (a) glycol o
(ii) (CH 3 h S [AMU (PMT) 2009) (b) glyoxal and formic acid o
366 G.R.B. Organic Chemistry (or Competitions

(c) fonnaldehyde 0 33. Acetylene when treated with C1 2. in CCl 4 forms:

(d) none of the above 0 (a) mustard gas' 0 (b) lewisite 0
23 •. Chromic acid oxidises acetylene into:. (c) westrosol 0 (d) westron 0 .
(a) oxalic acid 0 (b) acetic acid 0 34. Acetylene is not used to prepare:
(c) acetaldehyde 0 (d) CO 2 + H 20 0 (a) westron 0 (b) westrosol 0
24. The. end product oftbe following sequence is:
(c) lewisite 0 (d) mustard gas 0
35. Acetylene is prepared industriaily by ..passing electric
CaO + C Heat) A H20) B _H.;;;..2S_0...;.4~) C discharge through graphite electrodes in the atmosphere of:
HgS°4 (a) air 0 (b) H2 0
(a) ethanol 0 (c) N2 0 (d) CO 2 0
(b) ethyl hydrogen sulphate 0 36. When a mixture of acetylene and nitrogen'is subjected to
(c) acetaldehyde 0 .electric discharge, the product obtained is:
(d) ethylene glycol 0 (a) ether 0 (b) ethyl amine -0
25. Addition of HOCI to ethyne gives:
(c) HCN. 0 (d) ammonia 0
(a) ethyl chloride 0 (b) vinyl chloride 0 37. A metallic carbide on treatment with water gives a
(c) dichloroacetaldehyde 0 (d) ethylidene chloride 0 colourless gas which burns readily in air and gives a
OH

~
CH . CHOH HOCI CH< CHO ] precipitate with ammoniacal silver nitrate solution. The gas
Hint: III +HOCI-/l ~I OH-I evolved is:
CH CHCl CHCh CHCl2 (a) CH4 - 0 (b) C 2H 6 0
26. Whenacetylene is reacted with HCI in presence of HgC12, . (c) C 2 H4 0 (d) C2 H 2 0
the product obtained is: 38. Which one has of the red colour?
(a) methyl chloride 0 (b) vinyl chloride 0 (a) C2Na2 0 (b) C 2Ag 2 0
(c) formaldehyde 0 (d) acetaldehyde 0 (c) Cu 2 C 2 O. (d) CH 3C==CNa . 0
21. When propyne is treated with aqueous H 2S04 in presence 39. The gas, which is used for artificial ripening of fruits, is:
of HgS04 , the major product is: [PMT (Kerala) 2010] (a) CH4 0 (b).C 2 H4 . 0
(a) propanone 0 (b) 2-propanol 0 (c) C 2 H 6 0 (d) none 0
(c) ethanal 0 (d) ~thyne 0 40. The gas, which is used for welding purposes is:
(e) propane 0 . (a) CH4 o
(b) C2 H 6 0
28. The bond between carbon atom (1) and carbon atom (2) in (c) C2 H4 0 (d) C2 H 2 0
the compound, . 41. Propane can be distinguished from propylene with:
I 2
N==C-CH CH2 (a) sodium 0 (b) bromine water 0
involves the hybrids as: (c) ammoniacal AgN03 0 (d) NaHS0 3 0
(a) s p a n d s p 2 . · p (b) sp2 and sp2 0 42. Reaction of HBr with propene in the presence of peroxide
(c)spand sp. -0 (d) sp3 and sp 0 gives: [CBSE .(Med.) 2004)
(a) isopropyl bromide 0 (b) ally~ bromide 0
29. Which of the following displaces hydrogen on reaction with
(c) n-propyl bromide 0 (d) 3-bromopropane 0
sodium in liquid ammonia?
43. The compound which is insoluble in cold H2 S04 is:
. (a) C2H 2 '0 (b) CH4 0
(c) C2 H 6 . 0 (d) C 2 H4 0 (a) n-butane 0 (b) I-butene 0
(c) 2-tmtene 0 (d) ethyl acetate 0
30. When I,I,2,2-tetrabromoalkane is heated with zinc powder 4-1. Which one of the following molecules is linear?
in alcohol, which is formed? (a) HC==CH 0 (b) H 2C=CH 2 0
(a)Alkyne o
(b)Alkene 0
(c) CH 3 -CH3 • 0 (d) H-O--H 0
(c) Alkane 0 (d) None of these 0
31. The end product of the following seqQence of operations is: 45. In the laboratory by dehydration of ethyl alcohol, ethylene
was obtained in 50% yield. The ethylene so obtained reacted
Cac2 H20) (A) H2S0 4 ) (B) . H ) (C) with bromine to give ethylene dibromide in 80% yield. If the
HgS04 LiAlH4
amount of ethyl alcohol was 0.5 mole then ethylene dibromide
(a) methyl alcohol 0 (b) ethyl alcohol 0 produced would be:
(c) acetaldehyde 0 (d) ethylene 0 (a) 0.8 mole 0 (b) 0.4 mole o
32. The name of the poisonous gas formed by the interaction of (c) 0.2 mole 0 (d) 0.1 mole o
acetylene and arsenic trichloride is: 46. Conjugated double bond is present in:
(a) phosgene 0 (b) lewisite 0 (a) propylt.;,ne 0 (b) isobutylene
(c) mustard gas 0 (d) westron 0 (c) butylene 0 (d) butadiene
Unsaturated Hydrocarbons 367

47. When alcoh~lic solution of ethylene dibromide is heated (a) zinc 0 (b) sodarni~¥ 0
with granulated zinc, the compound formed is: (c) alc. KOH 0 (d) aq. KOH 0
(a) ethylene 0 (b) ethyne 0 59. Indicate the organic structure for the product expected when
(c) cyclobutane 0 (d) butane 0 2-methylpropene is heated with acetyl chloride in presence of
48. In the reaction given belo,w, X is: anhydrous zinc chloride:
H SO (a) (CH 3 )2 CCICH 2OCCH3 0
Neo-pentylalc?hol 2 4) X (DPMT 2009]
(b) (CH 3 h CHCH 2 OCCH 3 0
(a) 2-methylpentane 0 (b) Neo-pentane 0
(c) 2-methylpent-2-ene 0 (d) 2-methylbut-2-ene 0 (c) CH 3 COCH(CH3 h 0
. 49. Which of the following will have least hindered rotation (d) none of the above 0
about carbon-carbon bond? 60. Reactions of alkenes with ...... are explosive in nature:
(a) Ethylene 0 (b) Acetylene 0 (a) Cl 2 0 (b) 12 0
(c) Ethane 0 (d) 'Hexachloroethane 0 . (c) F2 o(d) Br2 0
[Hint: Hexachloroethane has less rotation than ethane because
61. Catalyst used in dimerisation of acetylene to prepare
of greater size·of chlorine than hydrogen.~
chloroprene is:
50. The olefin which on ozonolysis gives CH3CH2CHO and
(a) HgS04 + H 2S04 o0) Cu 2 Cl 2 o·
CH3 CHOis:
(a) I-butene 0 (b) 2-butene 0
(c) Cu 2Cl 2 +NH4 0H o (d) Cu 2 C1 2 + NH4 CI o
(c) l-pentene 0 .(d) 2-pentene 0 62. Ammoniacal silver nitrate forms a white precipitate easily
51. Dilute aqueous KMn04 at room temperature reacts with with: IUPSEE (Engg.) 2008]
(a) CH3 CH=CH2 0 (b) CH3 --C=:CH 0
R-CH=CHR to give:
(a) R-CHO 0 (b) RCOOH 0 (c) CH 3 -C=C-CH 3 0 (d) H 2C=CH2 0
(c) R-CHOHCHOHR 0 (d) CO2 + H 2 0 0 63. Structural formula for lewisite is:
52. Lindlar's catalyst is: CHCI CHCI
(a) Pt in ethanol o (b) Pd + BaS04 . o (a) II 0 (b) II 0
CHAsel 3 CHAsCI
(c) Ni in. ethanol o (d) Na in liquid NH3 o CHCI CH2
53. Which of the following molecules is not linear? (c) II 0 (d) II 0
(a) H2C' CH2 0 (b) CO2 0 CHAsel 2 CHAsCl 2
(c) BeCl 2 0 (d) HC==CH 0 64. An olefm may be converted into alcohol by:
54. Butyne on reaction with hot alkaline KMn04 gives: , (a) B2H6 and H 20 2 0 (b) LiAlH4 0
(a) CH 3CH2CH 2COOH 0 (c) alkaline KMnO4 0 (d) HOCI 0
(b) CH3CH 2COOH 0 65. Propene is- more reactive than ethene towards HBr because:
(c) CH3 CH2COOH+C02 0 (a) propene can more readily undergo a free radical chain
reaction 0
(d) CH 3 CH2COOH + HCOOH 0
(b) propene gives rise to more stable carbonium ion 0
55. When C 2 H 2, CH4 and C 2H4 passes through a test tt,tbe (c) the double bond incase of propene is unstable 0
which have ammo~iacal Cu 2 C1 2, find out which gas comes (d) the' methyl group attached to double bond withdraws
out unaffected from test tube? (BCECE (Med.) 2008] electrons and facilitates the attack 0 '
(a) C 2H 2 and CH4 0 (b) C2H 2 and C2H 4 0 66. Acetylene when passed through cuprous chloride in
(c) C 2H 2 q (d) C 2H 4 and CH4 0 presence of ammonium chloride forms:
56. When propene is treated with chlorine at 500°C, allyl (a) benzene 0 (b) vinyl acetylene 0
chloride is formed as the main product. The mechanism of (c) allyl chloride 0 (d) allene 0
the reaction is: 67. Which of the following alkynes is most acidic?
(a) free radical addition 0 (a) CH3-C==CH 0 (b) CH3-C==C-CH3 0
(b) free radical substitution 0 (c) CH3-CH2-C==CHO (d) HC==CH 0
(c) electrophilic addition 0 68. Acetylenic hydroge~s are acidic because:
(d) electrophilic substitution 0 (a) sigma electron density of C-H bond in acetylene is
57. The general formula of the product formed when nearer to carbon which has 50% s-character 0
1,1, I-trichloroethane is heated with metallic silver is: (b) acetylene has only one hydrogen on each carbon 0
(a) Cn H2n+2 0 (b}Cn H2n 0 (c) acetylene contains least number of hydrogens among
(c) Cn H 2n - 2 0 (d)C n H2n+1 0 the possible hydrocarbons having two carbons 0
(d) acetylene resembles acetic acid 0
58. To prepare 2-butyne from 2,2,3,3-tetrachlorobutane, use is
69. Sample of2,3-dibromo-3-methylpentane is heated with zinc
made of: dust. The resulting product is isolated and heated with HI in
368 G.R.B. Organic Chemistry tor Competitions

the presence of phosphorus. Indicate which is the structure 78. To which class cyclopentane does belong?
that represents the fmal product in the reaction: (a) Aromatic 0 (b) Heterocyclic 0
(a) H 2 C CH-fH-CH2-CH3 0 (c) Alicyclic 0 (d) Unsaturated aliphatic 0
79. The compound 1,2-butadiene has:
CH3
(a) only sp-hybridized carbon atoms 0
(b) CH3-CH2~H-CH2-CH3 0 (b) only sp2-hybridized carbon atoms 0
CH3 . (c) both sp- and sp2-hybridized carbon atoms 0
(d) Sp_sp2_ and Sp3 -hybridized carbon atoms 0
(c) CH3-CHI--fH-CH2-CH3 o 80. A compound with molecular formula C4 H 6 may contain:
CH3 (a) a double bond 0
(d) none of the above 0 (b) two double bonds or a triple bond 0
70. Which of the following reactions will yield 2,2-dibromo- (c) a triple bond 0
propane? [CPMT 2004; AIEEE 2007] (d) all single bonds 0
(a) H 2 C=CHBr + HBr 0 81. Cyclopentene on treatment with alkaline KMn04 gives:

(b) CH3C==CCH3 + 2HBr 0 (a) cyclopentanol 0

(b) trans-} ,2-cyclopentanediol 0
(c) CH30=CH + 2HBr o (c) cis-I,2-cyclopentanediol 0
(d) CH3 CH=CHBr+ HBr o (d) mixture of (b) and (c) 0
71. How many grams of bromine will react with 21 grams of 82. A hydrocarbon of formula C 6 H IO , absorbs only one
C 3 H 6? molecule of H2 upon catalytic hydrogenation. Upon
(a) 320 0 (b) 240 0 ozonolysis the hydrocarbon yields,
(c) 160 0 (d)80 0 OHC-CH2-CH2-CH2-CH2-CHO, the compound
72. Which of the following will be the final product when C 2H2 is:
reacts with HCl? (a) cy~lohexene 0 (b) cyclohexane 0
(a) H2 C=CHCI o (b) CH3-CH2CI o (c) benzene 0 (d) cyclobutane .0
(c) CH 3-CHCI 2 o (d) CHCI-CHCI o 83. Diels-Alder reaction is used to synthesise a ring of:
(a) four carbon atoms 0 (b) five carbon atoms 0
73. The reaction, (CH3)3 C-OH H 2S04) (CH3 h C=CH 2 , is (c) three carbon atoms 0 (d) six carbon atoms 0
. Heat .
84. Terminal (ex., ro) dihalides on heating with zinc or sodium
an example of:
(a) sulphonation 0 (b) decomposition 0 forms:
(c) dehydration 0 (d) alkylation 0 (a) alkenes 0 (b) alkynes 0
74. Propene CH3 -CH=CH2 can be converted into propanol-l (c) alkanes 0 (d) cycloalkanes 0
. by oxidation. Indicate which set of reagents amongst the 85. The theory of strainless ring was exp"lill~d by:.
following is ideal to bring the above conversion? (a) Baeyer 0 (b) Sachse and Mohr 0
(a) 03/Zn dust 0 (c) Kekule 0 (d) Erlenmeyer 0
(b) B2 H 6 and alkalineH20 2 0 86. Which of the following reagents will you choose for the
given reaction? [PET (Rajasthan 2008)]
(c) Alkaline KMn0 4 0
H 2C=CH 2 + H 20+ O~ H2C--cH2
(d) 080 4 followed by NaHS0 3 /alcohoi 0 . I I
75. H 2C=CH2 + HOCI ~ ..... + ..... ~ OHOH
ethylene chlorohydrin. Fill in the blan h in the above reaction (a) Oil. KMn0 4 , 273K 0
with: (b) Alkalme KMn0 4 , high temperature 0
- + +
(a) CH20H-CH 2 +CI 0 (b) CH 2CI-CH2 +OH 0 (c). Acid andK2Cr207 at room temperature 0
+ - +-, (d) . Acid and KMnO 4 at room temperature 0 .
(c) CH 20H-CH2 + CI 0 (d) CH 2CI-GI2 + OH 0 87. In the presence of platinum' catalyst, hydrocarbo~ (A) adds
76. Acetylene is used as an anaesthetic under the name of: hydrogen to form n-hexane. When hydrogen bromide is
(a) narcylene 0 (b) pyrene 0 added to (A) instead of hydrogen, only a single bromo
(c) neopyrene 0 (d) pyroline 0 compound is formed. Which of t~e following is (A)?
77. Which one will form thiophene when heated with sulphur or (a) H2C=CH-CH2-CH2-CH2-CH3 ; 0
H2 S?
(b) CH3 -CH=CH-CH2-CH 2-CH3 0
(a) CH4 o
lc) CH3 -CH 2-CH=CH-CH2-CH3 0
(c) C2 H 4 o
(d) CH 3-CH2-CH2-CH CH-CH3 0
Unsaturated Hydrocarbons

88. Alkene RCH=CHz reacts readily with B z H6 . and the 97. All alkyne combines with a conjugated diene to give an
product on oxidation with alkaline HZ02 produces: unconjugatedcycloalkadiene. The most likely title of this
(a) R-CH-CHz n (b) R-:-CHz-CHO 0 reaction is: ..
(a) Schotten-BaUmann reaction
(JEE (Orissa) 2008]
0
I I (b) Hofmann-bromamide reaction 0
OH OH
(c) Diels-Alder reaction. 0
o (d) R-C-CH3 o (d)Pinacol-Pinacolone rearrangement 0
I 98. When cyclohexane is poured on water, it floats because
°
89. The intenitediateduring' the addition of HCI to propene in
cyclohexane is:
. (a) in boat form . 0 (b) in chair form 0
the presence of peroxide is: (c) in croWn form 0 (d)' less dense than water 0
o 99. The cylindrical shape of an alkyne is due·to the fact that it
. • . + has:
(c) CH3 CH zCHz 0 (d) CH 3 CH zCH z 0 (a) three sigma C-:-C bonds 0
90. The compound which reacts' with . HBr obeying (b) two sigma and one pi C-:-C bond' 0
Markownikoff's rule is: (c) three pi C-:-C bonds 0
(d) one sigma and two pi C-:-C bonds 0
H3e) <CH3
O (b) C=C 0 100. During debromination' of meso-2,3-dibromobutane, the
. H· . H major product formed is:
(a) n-butane 0 (b) I-butene 0
(c) H,C)CFC<H 0 (d/,C)C==e<H 0 (c) cis-2-butene 0 (d) trans-2-butene
101. Addition of bromine to buta-I,3-diene gives:
0
H· CH 3 . H3 C. . H (a) 1,2-addition product only 0
91. The number and type of bonds between two carbon atoms in (b) l,4-addition product only 0
CaC z are: (c) both 1,2 and 1,4-addition products 0
(a) one sigma and one pi (1t) bond 0 (d) no reaction . 0
(b) one sigma and two pi (1t) bonds'
(c) one sigma and one and a half pi (1t) bonds
0
0 102. The reaction 6f CH3CH=cIi-(. )-?H with ~r
(drone sigma bond 0 gives:
92. Cyclohexadiene contains how many degrees ofunsaturation?
(a) 1 -0 (b) 2 0 (a) CH3CHBrCHZ-(. )-OH 0
. (c) 3 0 (d) 6 0
93. Acetylene contains same degrees of unsaturation as: .
CH CH,CHBr-( }-OH
(aJ 0 D(bJO o
(b) 3 0

(c) 0 o (d) 0 o
(C)CH3CHBrCI:Iz-(

(d). CH3CHzCHBr-( .' )-Br

)-Br

.~
0

Q
. 94. Four degrees of unsaturati9Jl are present in which of the
compounds given below? . ~. 103. The product(s) obtained via oxymercuration (HgS04 + .
(a) But-I-yne 0 . (b) But-2-yneD H 2S04 ) of l-butyne would be:
(c) Buta-l,3-diene 0 (d) Toluene 0 ° .
95. Which one of the following alkenes will react faster with Hz II
(a) CH 3CH2-C-CH3 0
under catalytic hydrogenation condition?
(b) CH 3 CH 2 CHzCHO 0
(lIT 2000; eBSE (Med.) 2005]
(c) CH3CHzCHO+ HCHO 0
R,,---/R R,,---/H
o o (d) CH 3 CHzCOOH+HCOOH 0
(a)~H (b).
R/
r-....
"H 10-:'. The reaction of propene with HOCl proceeds via the
R,,---/R .R,,---/R addition of: [lIT (S) 2001]
(c)r-.... o (d) r-..... o (a) H+ in the first step 0
R/ . "H R/"R
(b) Cl + in the first step Q
96. Propyne and propene can be distinguished by:
(c) OH- in the first step . 0
[ItT 2000; DCE 2005)
(d) CI + and - OH in the single step D.
(a) conc. HZ S04 . 0 (b) Br2 in CCl 4 0
(c) AgN03 in ammonia 0 (d) dil. KMn0 4 0
370 G.R.B. Organic Chemistry (or Competitions

105. Which ofthese will not react with acetylene? (AIEEE 2002] (c) forms polymers 0
(a) NaOH Cl (b) Ammoniacal AgN03 0 (d) all of the above 0
(c) Nil. D. (d) HCI 0 113. Acetylene reacts with HeN in the presence of Ba(CN)2 to
106. Identify the set of reagents/reaction conditions' X' and 'Y' in yield: (UPSEAT 2004]
the following set of trans,formations: (lIT (S) 2002] (a) I,I-dicyanoethane 0 (b) 1,2-dicyaooethane 0
(c) vinyl cyanide 0 (d) none of these 0
r
. 'X' 'Y'
CH3CH2CHiBr --7 Product .---7 CH3- H-CH 3 114. Which one of the following has the minimum boiling point?
(AIEEE 2004]
Br (a) n-Butane 0 .(b) I-Butyne 0
(a) X = dilute aqueous NaOH, 20°C' (c) I-Butene 0 . (d) Isobutene 0
Y = HBr/ac;:etic acid, 20°C o 115. Which of the following alkenes will give an optically active
(b) X conc. alcoholic NaOH, 80°C alcohol when treated with H 20/H2S04? [CPMT 2004]
y' HBr/acetic acid, 20°C o (a) I-Butene 0 (b) Ethene 0
(c) X == dilute aqueous NaOH, 20°C (c) Propene 0 (d) 2-Methyl propene 0
y= Br2/CHC13,O°C o 116. CH 3COOH is reacted with HC==CH in presence of Hg2+ ,
(d) X = conc. alcoholic NaOH, 80°C the product is: (DPMT 2004; BHU'2005]
y = Bt2 /CHCI 3 ,O°C o CH2 (OOCCH 3 )
107. In presence of perOXide, hydrogen chloride and hydrogen 001 0
iodide do not give anti-MarkownikotI's addition to alkenes CH 2 (00CCH3 )
because: (lIT (S) 2001] (b) CH 3CH 2 (00C-CH3 ) o
(a) both are highly ionic 0
(b) one is oxidising and other is.reducing 0 (c) CH3CH(OOC-CH3 )2 o
(c) one of the steps is endothermic in both the cases 0 (d) none of the above 0
(d) all the steps are exothermic in both the cases 0 117. The product of acid catalysed hydration of 2-phenyl
propene is: [lIT 2004]
108. In the preparation of alkene from alcohol using AI 20 3,
(a) 3-phenyl-2-propanol 0 (b) l-phenyl-2-propanol 0
which is etIective factor? (CBSE (Med.) 2001] (c) 2-phenyl-2-propanol 0 (d) 2-phenyl-I-propanol 0
(a) Porosity of AI 20 3 0 118. Which of the following used for the conversion of2-hexyne
(b) Temperature 0 into trans-2-hexene? ' [lIT 2004]
(c) Concentration 0 (a) H2/Pd/BaS04 0 (b) H 2,Pt02 0
(d) Surface area of AI 2 0 3 0 (c) NaBH4 0 (d) Li-NH3/C2HsOH 0
109. Consider the following statements; a hydr~)Carbon of . 119. Which of the following givespropyne on hydrolysis? .
molecular fOrmula CSHIO is a; . (AIIMS 2005]
(I) mono substituted alk€me (a) AI 4C 3 0 (b) Mg 2C3 0
(Ii) disubstituted alkene (c) B4 C D' (d) La 4 C3 0
(III) trisubstituted alkene 120. When Z-butyne is treated with Pd-BaS04; the product
Which of the following statements are correct? formed wilLbe:' (DCE 2005; JEE (Orissa) 2006]
(SCRA 2001] (a) cis-2-butene 0 (b) trans-2-butene 0
(a) I, II and III 0 (b) I and II 0 (c) I-butene • 0 (d) 2-hydroxy butane 0
'(c) II and III 0 (d) I and I!I 0 12L In the reaction,
110. Identify a reagent from the following list, which can easily (i) X
. CH3C==C-CH~ . ). CH -C-C-CH3
distinguish between I-butyne and 2-butyne: (lIT (S) 2002] • ~ (ii) ZnIH20 . 3
11 II
(a) bromine, CCl 4 0
o 0
(b) H 2, Lindlar's catalyst o X is : [DCE 2005]
(c) dii. H 2 S04, HgS04 o (a) RN0 3 0 (b) O2 0
(d) ammoniacal Cu 2Cl 2 solu!ion , 0 (c) 0 3 '0 (d) KMn04 0
111. But.;.l-ene may be converted to butane bya reaction with:~ 122. Reaction of 'one molecide of JIBr with one molecule .of
• [AIEEE 2003] 1,3-butadiene at 40°C gives predominantly:
(a) Zn-HCI o (b) Sn-HCI 0 , (AIEEE 2005]
(c) Zn-Hg [J (d) PdlH 2 0 (a) 3-bromobutene under kinetically controlled conditions
112. Correct sta~emeritabout 1,3-dibutene: [UPSEAT 2003]
o
(b) I-bromo-2-butene under thermodynamically controlled
, (a) conjugated double bonds are present' 0 ,,' conditions 0
. . (b) reacts with HBr 0 (c) 3-bromobutene under thermodynamically controlled
conditions 0
.'
Unsaturated Hydrocarbons

(d) I-bromo-2-butene under kinetically controlled 131. The Markownikoff's rule is best applicable to the reaction
conditions 0 between: ' [ P E T (Kerala) 2006]
123. Which of the reagents on reaction'with cyclohexanol gives (a) C2H 4+ HCI 0 (b) C3H6 + Br2 0
best yield of cyclohexene? [lIT 2005]
(a) Conc. H 3P0 4 0 (c) C3H6 + HBr 0 «i) C3Hg + Cl 2 ~ 0
(b) Conc. HCI 0 (e) C2 H4 + 12 ' 0
(c) Cone. HBr n 132. An alkene on reductive ozonolysis giv(!s two molecules of
(d) Conc. HCl with ZnCl 2 0 CH 2(CHOh. The alkene is:' [PET (Kerala) 2006]
124. Acid catalysed hydration of alkenes except ethene leads to (a) 2,4-hexadiene ' Q
the formation of: [AIEEE 2005; JCECE (Med.) 2008] (b) 1,3-cycloliexadiene 0
(a) primary a l c o h o l [ ] (c) 1,4-cyclohexadiene ' 0
(b) secondary or tertiary alcohol 0 (d) I-methyl-l,3-cyclopentadiene 0' ,
(c) mixture of primary aDd secondary alcohols [] (e) 1,2-dimethyl cyclopropene, 0
(d) mixture of secondary and tertiary alcohols 0 133. Identify the product (Y) in the following reaction sequence:
125., Elimination of bromine from 2-bromobutane results in the [CET (Karnataka) 2006]'
formation of: [AIEEE 2005]
(a) equimolar mixture of 1- and 2-butene 0 , CH 2-CH2-C00) Heat " Zn-Hg,
(b) predominantly-2-butene [J I Ca --HX) , , ) (Y)
, CH2-CH2~00 " " HCI,Heat
,(c) predominantly-I-butene 0
(d) predominantly-2-~utyne 0 (a) cyclobutane 0 ' (b) cyclopentane 0
126. The only alcohol, that can be prepared by the indirect
hydration of alkene is: [AFMC 2005]
(c) pentane 0 (d) cyclopentanon~ 0
134. Which cycloalkane has the lowest heat of combustion per
(a) ethyl alcohol 0 (b) propyl alcohol 0
-CH2 group? [CET(Karriataka) 2006]
(c) isobutyl alcohol 0 (d) methyl alcohol 0
(a) Cyclopropane ,0 (b) Cyclobutane []
127. 3-phenyl propene on reaction with HBr gives (as a major
(c) Cyclopentane 0 (d) Cyclohexane 0
product): [AIIMS 2005]
135. HBr reacts with H 2C=CH-OCH3 under anhydrous
(a) C6Hs CH 2CH(Br)CH3 []
conditions at room temperature to give: [AIEEE' 2006]
(b) C6Hs CH(Br)CH2CH3 []
(a) CH 3CHOand CH3Br 0
(c) C6HsCH2CH2CH2Br []
(b) BrCH2CHOand CH30H . 0
(d) C6H s CH(Br)CH=CH2 []
(c) BrCH 2-CH 2-OCH 3 o
128. HO=CH HgS04 ) ,(A) CH3MgB~ (B) P/Br2 ) (C) (d) H 3C-CHBr-OCH3 []
H2S04 HOH
136. Reaction of trans-2-phenyl-l-bromocyclopentaneon
, In this reaction, the final prodl1;ct (C) is: [DPMT 2005] reaction with alcoholic KOHproduces: [AIEEE 2006]
(a) CH3CH(Br)CH3 0 (b) CH3CH 2CH2Br 0 (a) A-phenyl cyclopentene []
(c) CH 2=CHBr 0 (d) BrHC=CH-CH 3 0 (b) 2-phenyl cyclopentene o
129. One mole of an unsaturated hydrocarbon on ozonolysis (c) I-phenyl'cyclopentene 0'
gives one mole each of CH3CHO, HCHO and OHC-CHO. . (d) 3-phenylcyc1opentene o
The hydrocarbon is: , [PMT (Kerala) 2006] 137. Trans-2-butene + Br2 gives: [CET (Gujarat) 2006]
(a) CH3CH 2-C==C-CH3 0 3
CH ' "Br=t=CH3 H' .
(b) HC===C-CH 2CH 2CH3 0
(a) HH BBrr 0 (b) ,'0
(c) CH3CH ' CHCH-CH2 o =t= H . Br
(d) H2C=CH-CH2-CH CH 2 [] CH3 CH3
(e) H2C C=CHCH2CH3 [] CH3 " CH 3 '
130. Addition ofBr2 to Z-but-2-ene gives:
(c) : = t = : .0 (d) : , = t = : . .D
[PMT (Kerala) 2006]
(a)(R, R)-2,3-dibtomobutane only 0 CH 3 CH3
(bt (S, S)-2,3-dibromobutane only 0 138. Reaction of acetylen'e and propyl~Qe with HgS04 in'
(c) (R, S)-2,3-dibromobutane only ,0 presence of H2 SO 4 produces' respectively: [BHU 2006]
(d) (R,SH,2-dibromobutane 0 (a) acetone and acetaldehyde []
(e) a mixture of (R,R) and (S,S)-2,3-dibromo butanes (b) , acetaldehyde and acetone 0
,. (50% : 50%) , [] (c) propanaldehyde, and acefone. 0
(d) acetone and propailaldehyde £]
372 G.R.B. Organic Chemistry {or Competitions

139. Which of the following reagents, ~hen heated with ethyl

chloride, forms ethylene?
[EAMCET (Engg.) 2006; AFMC 2008]
(a) Aqueous KOH 0 - (b) ZnlHCI 0
(c) Alcoholic KOH 0 (d) HI 0
o
140. Ozonolysis products of an olefm are OHC-CHO and
OHC-CH 2 -CH2 ~HO, the olefin is: o
, [DCE 2006; AMU (Engg.) 2007]

(·;0 o (b) 0 o o

(e)O o (d) D o
(d) CH3 CH 2 CH 2-C-H
I
I
o
141. What is fOrnied when calcium c~bide reacts with heavy . I
water? [DCE 2006] CI
(a) C 2D 2 0 (b)CaD 2 0 ' 147. CaC 2 + H 20 ~ (X) 03/ 20) HCOOH, (X) is:
H
(c) CaD 2 0 0 (d) CD2 0
[DeE (Engg.) 2007]
142; A molecule (X) has (i) four sigma bonds fonned by the (a) C 2 H 4 0 (b) C 2 H 2 0
overlap of Sp2 and s orbitals; (ii)one sigma bond fonned by
(c) C 2 H 6 0 (d) Ca(OHh 0
, sp2, and Sp2 -orbitals and (iii) one x-bond fonned by p z and
148. In the reactions
p z orbitals. Which of the following is X?
(EAMCET (Engg.) 20061 (B) (Lindlarcatalyst R--C==C-R Na/ NH 3) (A)
o (b) C2 H 3 CI 0 , H2

(c) C2 H 2Cl 2 o(d) C 2H 4 0 (A) and (B) are geometrical isomers. Then.:
[EAl\:1CET (Med.) 2007; DeE 2008]
. Na/NH3(l)
143. RCH CH2 . ) RCH 2 CH3 (a) A is cis and B is buns 0 (b) A is trans and B is cis [J
C2HSOH (e) A and B are cis 0 (d) A and B are trans 0
This reaction is called as: [BVP 2006] 149. The reagent(s) for the following conversion,
(a) Fischer-Siper reaction o is/are: . . [lIT 2007]
(b) Clemmensen reduction o Br~ ..1.- H H
(c) Birch reduction _0 Br
(d) Arndt-Eistert synthesis o (a) alcoholic KOH , 0
144. CH3 CH==;CH2 + NOCI ~ P (b) alcoholic KOH followed by NaNH2. 0
" . Identify the adduct: [lIT 2006] (c) aqueous KOH followed by NaNH2 0
~. '. (a) CH3-r~2. 0 (b) CH 3 -CH-CH 2 0 (d) ZiIlCH3 0H 0
II 150. The compound
CI NO NO. CI
CH .
H 2 C=CH-CH 2 - N < .3, is an:
CH3
(DPMT (Med.) 2007J
145. Identify 'B' in the·following reaction: . (a) alkyne, 3° amine 0 (b) alkene, 2° amine 0
(c) alkene, 3° amine 0 (d) alkyne, 2° amine 0
. H 2 C=CH2 + HCI Anhy.d. Alel )3
~---=....---=..~- (A)+ 2H Zn-Cu j,
7
151. Identify the produJ::t/(s) in the following reaction:
~HsOH
. BH3 H 20 2I OH- .
(B) + HCI • 3CH3CH=CH 2 ~ (X) . ) Product(s)+H3B03
.. , ,[EAMCET (Engg.) 2007) [PET (KeraJa) 2007J
(a) CH4 . 0 .(b) C2 H6 0 (a) CH3 CH 2 CH 2 0H 0 (b) CH3CHOHCH3 0
(c) C2 Hs CI o
(d) CiHsOH 0 (c) CH 3 CH 2 CHO 0 (d) CH 3CH20H+CH30H 0
146. Predict the product' C'obtained in the following reaction of . (e) CH3 CHO+CH3 0H 0
. I-butyne: '. (CBSE (Med.) 20071 152. A hydrocarbon of molecular fonnula, C6HlO re~ts, with
sodamide and the same on ozonolysis followed by hydrogen
Unsaturated Hydrocarbons 373·

. peroxide oxidation gives two molecules of carboxylic acids, Br

one being optically active. Then the hydrocarbon may be: I
[PMT (Kerala) 2007; Punjab CET(Engg.) 2008] (d) 'CH3 -C-CH2 CH3 o
(a) I-hexyne 0 (b) 2 - h e x y n e D
. I
CH3
(c) 3-hexyne 0 (d) 3-methyl-l-pentyne 0
(e) 3,3-dimethyl-l-butyne 0 161. The hydrocarbon which can react with sodium in liquid
153. The hydrocarbon which does not decolourise alkaline ammonia is: [AIEEE 2008]
KMn04 solution and also does pot give any precipitate with (a) CH 3 CH 2 C==C-CH2 CH 3 0
ammoniacal silver nitrate is: [AIIMS 2007] (b) CH3 CH=CHCH 3 0
(a) benzene 0 (b) acetylene 0 (c) CH 3 CH 2C==CH 0
(c) prop~e 0 (d) I-butyne 0
(d) CHjCH2CH2C==CCH2CH2CH3 0
154. Which of the following is the most stable alkene?
. [AFMC 2007; Ludhiana CMC (Med.) 2008] 162. Oxidation of I-butene with hot KMnO4 solution produces:
(a) R2 C=CR 2 • 0 (b) RC:H. CHR 0 , [UGET (Med.) 2008]
(c) RCH CH 2 · 0 (d) H 2C=CH2 D· (a) CH3 CH 2COOH+ HCOOH· 0
(b) CH 3 CH 2COOH + CO 2 0
155. 'Which of the following compoundS yields acetone on
.ozonolysis followed by hydrolysis? [BHU (Mains) 2008]
(c) CH3 COOH+C02 0
(a) 2-Metbyl-2-butene 0 (b) 3-Methyl.!.1-butene 0
(d) (CH3 )2 C=O + CO 2 0
,(c) Cyclopentane 0 (d) 2-Methyl-I-butene 0 163. From which one of the following, both ethylene and
156. The angle strain in cyclobutane is: acetylene could be prepared D:t 'a single step reaction?
[CET (Karnataka) 2008] [PMT (Kerala) 2008]
(a) 19"22' 0 (b) 9"44' 0 (a) CH3 CH 20H 0 (b) Br-CH2 -CR2 -Br 0
(c) 24°44' 0 (d) 29°16' . 0 (c) CH3 CH 2Br 0 (d) Br-CH2-CH2':"OHD
157. A mixtUre of I-chlorobutane and 2-chlorobutane when (e) CH]'COOH 0
treated with alcoholic KOH gives: [GGSIP (Engg.) 2008] 164. A compound 'X' on ozonolysis foUowed by reduction gives
(a) I-butene 0 an aldehyde, C2H4 0and 2-butanone. Compound 'X' is:
(b) 2-butene 0 [UPSEE (Engg.) 2008)
(c)isobutylene 0 (a) 3-methyl pent-2-ene 0 (b) 3-methyl pent-3-ene 0
(d) mixture of I-butene + 2 butene 0 (c) 3-methyl hex-3-ene 0 (d) 3-ethyl pent-3-ene D·
158. Acetylene and HCHO react in presence of copper acetylide 165. The number of possible alkynes with molecular formula
catalyst to form: [nCE 2008; PMET (Moo.) 2008] CSHg is: . [UPSEE (Engg.) 2008]
(a) I-butyne-I,40diol 0 (b) 2-butyne-I,2-diol 0 (a) 6 0 (b) 5 ,.0
(c) 2-butyne-l,4-diol 0 (d) none ofthese 0 (c). 4 0 (d) 3 D
159. The major product formed when a 3,3-dimethyl butan-2-o1 166. Hydration of which one of the following yields a ketone?
is heated with concentrated sulphuric acid is: . . [CET (J&K) 2009]
[lIT 1996; Punjab CET (Engg.) 2008] (a) Propyne 0 (b) Ethene 0
(a) 2,3-dimethyl-2-butene 0 (c).Propene 0 (d) Ethyne 0
(b) 2,3-dimethyl-I-butene 0 167. One moiecule of alkene 'X' on ozonolysis gave one mole of
(c) 3,3-dimethyl-I~butene 0 acetone. The IUPAC name of 'X' is:
(d) cis- and trans-isomers of 2,3-dimethyl-I-butene 0 [EAMCET (Engg.) 2009]
160. ,,(;H3 -CH-CH=CH2 + HBr~ <A' , (a) 2-methyl-I-butene 0 (b) 2-methyl-2-butene 0
I . (c) 2-butene 0 (d) I-butene 0 .
CH 3
168. The order of reactivity of the alkenes,
'A' (predominantly) is: [CBSE (Med.) 2008] (CH3 )2 C=CH 2 , CH3CH=CH2, H 2 C CH 2
(a) CH3 -CH -CH-CH3 o I II ill ,
I I when subjected to acid catalyzed hydration is:
Br CH3 [AMU (P~fT) 2009, 1(1]
(b) CH3 ---YS-F-CH3 o (a) I>II>m 0 '(b) I>m>II 0
(c) m>II>I 0 (d) D>I>m 0
CH 3 Br 169. Identify thealkyne in the following sequence of reactionS:
(c) CH 3 -CH-CH2 -CH2 Br
I. . o Alkyne
H
2) (A) Ozonolysis) (B) ( Wacker
Lindlar'scatalyst Only . Process
. CH
3
H 2 C, CH2,
[EAMCET (Engg.) 2009)
314ii G.R.B. Organic Chemistry for Competitions

(a) H3C-C==C-CH3 o (a) 2-butene 0 (b) I-butene []

(b)' H3C-:-CHz -C==CH o (c) propene 0 (d) l-hexene 0
(c) HzC=CH--'-C==CH o (e) 2-methylpropene 0
177. Among the given· compounds, one which can be
(d) HC==C-CHz-C. eH -0 distinguished by AgN03 is: [AFMC 2010]
170. In the following reaction, (a) ethane 0 (b).ethylene 0
RCH;CH=CHz + ICI ~ (A) . (c) acetylene 0 (d) diethyl ether 0
Markownikoff's product (A) is: [AMU (Engg.) 2009] 118. 'iiitlie following reaction, the product 'R' is :
(a) RCHzr-,-CH21 0 (b) RCHz-r-CH2CID
CaC ~ P Q CH3Cl) R
hot iron)
2
CI I tube A1CI 3 [AFMC 2010]
(a) benzene 0 (b) ethylbenzene 0 .
(c) RCH2-CH CH2 0 (d) RCH=CHCH 21 0
·. I (c) toluene 0 (d) n-propyl benzene 0
I 179. Name the reagent used to bring about the following
transformation; but-2-ene to ethanal: [AMU (Mec:l.) 2010]
171. The addition of HBr to 2-pentene gives:
' ( J E E (WB) 2009] (a) K2Cr207 in acidic medium 0
(a) 2-bromopentane only o (b) Cr0 2 CI 2 /H 3 0+ 0
. (b) 3-bromopentane only o (c)PCC 0
(c) 2-bromopentane and 3-bromopentane o (d) 03/H20-Zn dust 0
(d) I-bromopentane and 3-brQmopentane o 180. The major product formed when 2-bromobutane is tr~ated
1n. Which of the' followmg haS lowest boiling point? with alcoholic KOH is : [PMT (Kerala) 2010]
[AFMC 2009] (a) 2-butanol 0 (b) trans-2-butene 0
· (a) CH3c:H2CH=CIlCH3 o . (c) I-butanol 0 (d) I-butene 0
(b) CH3CH2CH2CH2CH3 o (e) iSO-butyl alcohol 0
(c) H 2C==CH-CH2CH=CHz o 181. Identify the product in the reaction
(d) CH,J-C=C-CH3 o Ph-C==C-Me --=---~ ? . [DUMET 2010}
" I I . (a) PhCH 2CH 2CHO. 0 (b) PhCOCH2CH3 0
CH3 CH 3
173. One per cent composition of an organic compound A is (c) PhCH2COCH 3 0 (d) PhCOCOMe 0
carbon 85.71% and hydrogen:;: 14.29%. Its vapour 182. The synthesis of 3-octyne is achieved by adding a •
density is 14. Consider the following reaction sequence: bromoalkime into a mixture of sodium amide and an alkyne.
CI2/H zO. B . (i) KCN/EtOH C Identl'fy C' • The bromo alkane and alkyne respectively are :
A. >
7 ) ;
[lIT 2010]
(ii) H 30+ .
(a) BrCH2CF{zCH2CH2CH3 and CH3CH2C==CH
. .
0
(EAMCET (Engg.) 2009]
.(a)CH3 -CH-C02H o (b) BrCH2CH2CH3.and CH3CH2CH2 C==CH 0
. I .. ·· . . (c) BrCH2CH2CH2CH2CH3 'and CH3C==CH 0
OH (d) BiCH2CH2CH2CH3 and CH3CH2C==CH 0
(6) Hb-CHi -CHz'-COzH
. .
o set II: This set contains the questions with two or more correct answers.
(c) H~CHz-C02H o
183. Which ·Of the following reagents can be used to distin~ish
(d) CH3CHz -C02H o between propene 'and propyne?
174. One mole of a symmetrical alkene on ozonolysis gives two (a) Schiff's reagent 0 (b) Lucas reagent 0
moles of an aldehyde having a molecular mass of 44u. The (c) Grignard reagent 0 (d) Ammoniacal AgN03 0
alkene is : [AIEItE 2010]
184. The reaction,
(a) ethene 0 (b) propene 0
(d) 1:butene 0 (d) 2-butene 0 CH3-CH=CH-C2 H s
G;lisCOOOH
)
175. The 'deCreasing order of acidic character among ethane (I),
ethene (II), ethyne (Ill) and propyne (IV) is ~ .~
o
[PET (Kerala) 2010] CH3-CH-CH-C2Hs is called:
(a) 1>11 > III> N 0 (b) II> III > I > N 0 (a)" hydroxylation o
(c) III> IV> II> I 0 (d) IV> III > II > I 0 (b) ozonolysis o
(e) Ill> N > I > II 0 (c) Prileschaiev's reaction o
176. The alkene that will give the same product with HBr in the (d) epoxidation o
as
absence well ~ in the presence of peroxide is':
· [PET (Kerala) 2010]
Unsaturated Hydrocarbons 375

185. The reagent used for the following reaction is/are: (c) In the second step NaB~ reduces--Hg (OAch group
CH3-CH=CH-C2 H s ~ CH 3CHO+C 2 Hs CHO to hydrogen 0
(d) Th~ net reaction is addition, of water. according to
(a) 0 3 and Zn/steam 0 (b) Baeyer's reagent 0 Markowniko:tI's rule q
(c) KMn0 4/H 2 S04 0 (d) Lemieux reagent 0 191. Hexa~2,4-diene on ozonolysis by using 03/CC14 followed
186. Which of the following on reductive ozonolysis give only by ZnlHz 0 gives :
glyoxal? (a) acetaldehyde 0 (b) glyoxal 0
(a) Ethylene 0 (b) Benzene 0 (c) formaldehyde 0 (d) propanaldehyde 0
(c) Toluene 0 (d) Acetylene 0 192. Alkenes can be prepared by:
187. Aqueous solution of which ofthe following compounds is (a) dehydrohalogenation of alkyl halide D
electro lysed, when acetylene gas is obtained? (b) Sabatier-Sanderen's reduction of alkynes 0
(a) Sodium fumerate 0 (b) Sodium maleate 0 (c) dehydration of alcohols with conc. H 2 S0 4 at 443K 0
(c) Sodium acetate 0 (d) Calcium carbide 0 (d) treatment 0:f3° alkyl halide at 573K '0
188. Anti-Markowniko:tI's addition of HBr is/are observed in : 193. The compound(s) which will give propylene on
(a) propene 0 (b) but-I-ene 0 dehydration with conc. Hz SO4 at 440 K is/are. :
(c) but-2-ene 0 (d) pent-3-ene 0 (a) isobutyl alcohol 0 (b) n-propyl alcohol 0
189. What product(s) results when two moles of hydrogen (c) isopropyl alcohol 0 (d) n-butyl alcohol. 0
chloride react with 4-methyl-2-pentyrie? 194. Which of the following alkynes show acidic charact~r?
(a) 3,3-Dichloro-4-methyl pentane 0 (a) 0 (b) CH3-Cs=C-H; 0
(b) 2-Chloro-4-methyl pentene 0
(c) 2,2-Dichloro-4~methyl pentane
(d) 3-Chloro-4-methyl pentene
0
0
(c) 0
~C .C-H .
.0 (d) CH3 -C==C-CH3 0
190. Which is/are' correct statements about oxymercuration
demercuration? 195. Presence of unsaturation in organic compounds can be
(a) The rearrangement takes place 0 tested with: .
(b) In the fIrst step (OAc)zHg and H 2 0 are added to the . (a) Brz water 0 (b). Baeyer's reagent, O'
double bond 0 (c) Tollens'reagent 0 (d) Grignard reagent 0

!#ASSERTION-REASON TYPE QUESTIONS

The questions given below consist Assertion (A) and (R) It is an example of 'anti' addition.
Reason (R). Use the following keys to select the appropriate 6. (A) Properie is more rea.ctive, than ethene towards
answer: ele.ctrophilic addition reactions. .
(a) If both (A) and (R) are correct and (R) is correct (R) Electron density' of double .bond increases due to
explanation of (A) hyperconjugation of methyl group. .
(b) If both (A) and (R) are correct but (R) is not correct 1. (A) 1,-chlorobutane on heating with alcoholic KOH
explanation of (A) ·undergoes dehydrohalogenation to yield but-: I-ene.
(c) If (A) is correct but (R) is incorrect (R) It is elimination reaction involving carbonium ion
(d) If (A) is incorrect but (R) is correct intermediate.
(e) Both (A) and (R) are incorrect. 8. (A) Moist ethylene can be dried by passing it' through
1. (A) Addition of HBr to I-butene gives two optical isomers. concentrated H ZS04.
(R) The product contains one asyrn.metric carbon. (R) Addition ofsulphuric acid takes place on alkene.,
2. (A) Dimethyl sulphide is commonly used for the reduction of in
9. (A) Acidity of C-H bOlJd lies following sequence: .
an ozonide of an alkene to get the carbonyl compounds. · HC=CH> CHz=CHz > CHr -:-CH3
(R) It reduces the ozonide givmg water soluble dinlethyl (R) Perc.en~ge character of ''S- orbital in these compounds
sulphoxide and excess of it evaporates. [lIT (8) 2001] · lie in following sequence.
3. (A) Addition of HCI to propene in presence of peroxide H-CSECH>CH 2 =CH 2 >CH3 -CH 3
gives l-chloropropane.
10. (A) Addition of bromine to' trans-but-2-ene yields
(R) The reaction occurs by carbonium ion intermediate.
meso-2,3-dibromo butane..
4. (A) Addition of HBr to I-butene in presence of peroxide
(R) Bromine addition to an alkene is an. electrophilic
produces I-bromobutane.
addition. ' [lIT (8) 2001]
(R) It involves the fotmation of primary radical.
[lIT (8) 2000] 11. {A) 1.3-Butadiene is the monomer for natural rubber.
5. (A) Reduction of but-2-yne by Nalliq. NH3 gives 'trans' (R) Natural rubber is formed through anionic addition
but-2-ene. • polymerization. [AIIM8 2006]
··.·316 G.R.B. Organic Chemistry for Competitions

12. (A) Addition of HBr on 2-butene gives two isomeric 13. (A) C-H bond in ethyne is shorter than C-H bonds in
products. ethene.
(R) Addition of HBr on 2-butene follows Markownikoff's (R) Carbon atom in eth,ene is sp hybridised while it is Sp2 in
rule. [AIIMS 2006] ethyne. [AIIMS 2007)

'ANSWERS'
..
OBJECTIVE QUESTIONS c

1. (d) 2. (d) 3. (c) 4. (a) 5. (a) 6. (d) 7. (a) 8. (d) . 9. (a) 10. (c)
11. (a) 12. (c) 13. (c) }'\t (b) 15. (c) 16. (a) 17. (c) 18. (d) 19. (c) 20. (d)
21. (b) 22. (b) 23. (b) 24. (e) 25. (c) 26. (b) 27. (a) 28. (a) 29. (a) 30. (a)
31. (b) 32. (b) 33. (d) 34. (d) 35. (b) 36. (c) 37. (d) 38. (e) 39. (b) 40. (d)
41. (b) 42. (e) 43. (a) 44. (a) 45. (c) 46. (d) 47. (a) . 48. (d) 49. (c) : 50. (d)
51. (c) 52. (b) 53. (a) 54. (d) 55. (d) 56•. (b) 57. (c) 58. (a) 59. (a) 60. (c)
61. (d) 62. (b) 63. (c) . 64. (a) 65. (b) 66. (b) 67. (d) 68. (a) 69. (b) 70. (c)
71. (d) 72. (e) 73. (e) 74. (b) 75. (d) 76. (a) 77. (d) 78. (e) 79. (d) 80•. (b)
81. (e) 82. (a) 83. (d) 84. (d) ·85. (b) 86. (a) ~7. (c) 88. (e) 89. (b) 90. (d)
91. (1) 92. (e) 93. (b) 94. (d) 95. (a) 96. (c) 97. (c) 98. (d) .99. (d)' 100. (d)
101. (c) 102. (b) 103. (a) 104. (b) 105. (a) . 106. (b) 107. (c) 108. (d) 109. (a) 110. (d)
111. (d) 112. (d) 113. (c) 114. (d) 115. (a) 116. (c) 117. (c) 118. (d) . 119. (b) 120. (a)
121. (c) 122. (b) 123. (a) 124. (b) 125. (b)- 126. (a) 127. (b) 128. (a) 129. (c) 130. (e)
131. (c) 132. (c) 133. (b) 134. (d) 135. (d) 136. (d) 137. (a) 138. (b) 139. (c) 140. (e)
141. (a) 142. (d) 143. (c) 144. (a) 145•. (b) 146. (b) 147•. (b) 148. (b) 149. (b) 150. (c)
151. (a) 152. (d). 153. (a) 154. (a) 155. (a) 156. (b) 157. (d) 158. (c) 159. (a) 160~ (d)
161. (c) 162. (b) 163. (b) .164. (a)' 165. (d) 166. (a) 167. (b) 168. (c) 169. (a) 170. (a)
171. (e) 172. (d) 173. (b) 174. (d) 175. (c) 176. (a) 177. (c) 178. (c) 179. (d) 180. (b)
181." (b) 182. (d) 183. (c;d) 184. (c,d) 185. (a,d) 186. (b,d) 187. (a,d) 188. (a,b,d) 189. (a,c) 190. (b,c,d)
191. (a,b) 192. (a,c,d) 193. (b,c) 194. (a,b,c) 195. (a,b)

ASSERTION-REASON TYPE QUESTIONS

1. (a) 2. (a) 3. (d) 4'. (c) S. (a) 6. (a) 7. (a) 8. (d) 9. (a) 10. (b)
11. (e) 12. (e) 13. (c) .
Unsaturated Hydrocarbons

.
1: Write down the products when following compounds are dehydrated:
CH3

. (a)A
CHzOH
~.H3OR H 3C-C
I
X H

/LJ (b)U (c) V

Due to
Hydride shift

Q-LO Cyclohexene .

~OH
(b) ~
"""" ",so,
--H~-4-(~~H-2-m·~
0+0+6
Major Minor

H3C'-.,/CH3
Rare amount

CH
(c)

Major
+
6
Minor
(These products are according
to Saytzeff's rule)

(d) c5C;:7:;i c5 +0 +c5] Major

2. Write down dehydration products of the following compound:

HoHzOH

[Hint:
-H+·
~~~'.
6
CH

,rn, +
..]
H

"'6CH-C 3

3° Oubocation
(More stable)
 G.R.B. Organic Chemistry for Competitions

3. Complete the following reactions:

(i) 1'r Znlalcohol

L1
?
...

[Ans.
H Br
(i) 0
4. Complete the following reactions:

')-
(1

~ (iii)
_

cr
0
-
CH2
•
CoHsCOOOH I> ?
CHCl3 at 25"C _

C6H sCOOOH
CHCl3 at 25"CI> ?
•

[Hint: (i) Fonnation of epoxide takes place.

U CH
'
C6HsCOOOH"
CHCll at 25°C

C
C=O
(iii) I
OH
- ?=O
OH

(iv) Since, C;:-":'C bond in ring is more substituted than that in open chain, epoxide will be fonned at the unsaturation of ring.
~H=CH2

~]
5. Give the structures of (A) and (B) in the following reaction:

According to which rule, above addition takes place?

[Hint: (A) ~ C 2Hs CHCH 2HgOAc; (8) ~
I
OH
The reaction is according to Markownikoff's rule and is better acid catalyzed hydration as it avoids rearrangement.]
6. Give the structures of compounds which give following produc~s on hydroboration-oxidation:
_ OH
- I

~
.. - CH3 ,. ~CH'-.CH / CH2'-.CH /CH3
(i) (n) ~ 2 2 (iii)
0-·· H

- o-
[Hint: (i) _ .
CH
3 (ii)

7. An unsaturated compound C6 H12 (A) decolourises Br2 water and on oxidation by -acidified KMn04 gives optically active
carboxylic acid C 4 H9 COOH (B). Give the structure of (A) and (B),
[Hint: Compound is unsaturated because it is decolourising Br2 water. On oxidation it gives a carboxylic acid with one carbon atom less than
alkene; it shows that compound is tenninal alkene. Thus, structure of terminal alkene with chiral carbon can be given as:
Unsaturated Hydrocarbons
H H
I [0] I
CH2 =CH-Y--CH3 • HOOC.-:..c-CH3]
CH2-CH3
I
CH CH 2 3
(A) Optically active
(B) .

8. A compound CSH9Br (A) does not decolourise Baeyer's reagent or Br2 water. (A) on treatment with alcoholic KOH forms
(B)CsHs which reacts with Baeyer's reagent and Br2 water. Ozonolysis of (B) forms (C) C SH S 0 2. Identify (A), (B), (e) and
explain reactions. .
(Hint: CsH9Br is not deoolourising Baeyer's reagent or Br2 water hence. it should be cyclic compound. Possible structure for (A) can be given as:

(i)~
r-v Br
(U)
Bru
.

CH3
(iii) A
CH3
Br

CH3
'>,

Reactions involved may be given for above compounds as:

o
II
(i)U Br
Alc.KOH
.. Ozonolysis .. ('HI HC=O

(A) (B) (C)

(ii) B r u Ale. KOH

.. Ozonolysis ..

. CH ·
3
(A)

Ozonolysis
(iii) Alc.KOH
.. d'>. "'- ..
/'
CH3 CH 3
(B)

9. Give the structnre of polyisoprene (natural rubber). Write down the ozonolysis of polyisoprene.
-. CH
3
I
[Ans. Monomer of natural rubber is isoprene CHz-C-CH=CH2• General structure of polyisoprene will be:

10. Limonene (C IO HI6 ) is a naturally occurring hydrocarbon. It absorbs·2 molecules of hydrogen for each molecule during
hydrogenation. On ozonolysis followed by zinc dust and steam hydrolysis, it gives one mole of fon;naldehyde and one mole of
tricarbonyl compound of following structure. . . .

o °
CH3 +HCHO

Give probable structure of limonene if it has a six tnembered ring.

°
[Hint: Contpound has a six membered ring. Therefore, its structure will be cyclic unsaturated. There will be two double bonds in the iimonene
because it absorbs two molecules of Hz. ' .
 G.R.B. Organic Chemistry/or Competitions

. r 2

-' C
H3 - C D -
#
(Probable sttucture of
CH3]

limonene)

11. Hydrocarbon (A) (C =87.2%) on hydrogenation forms (B) (C =84.1 %). Ozonolysis of (A) fonns acetic acid, acetone and pyruvic
•
" 'II0 1
acid [ CH3-C-COOH' What are (A) and (B)?
{Hint: Percentage composition shows that (A) and (B) has empirical fOIDlula (A) C4H7 and (B) C4Hg.

Compound (A),
Ozonol~s ) W
CH 3-C-OH + CH3-C-CH3 + CH 3-C-C-OH
~'. ~ ~
Thus, compound (A) should have eight carbons.
:.Molecular fOIDlula of (A) will be CSHI4 and that of (B) will be CsH ls .
Degr~ ofunsaturation in compound (A) = + 2 = 2 x 8 -14 + 2= 2
-
2 2
Thus, compound (A) should have two double bonds. On the basis of ozonolysis products structure of (A) can be guessed as,
CH~-.:oH CH3
\I CH3 CH3-C-H C<
+0 + C< - 1\ II CH3
WW II CH3 CH~--C-H
CH~-C-OH 0 Probable sttucture of
(A)
. CH3 <CH3
CH3-C-H C< 82 CH:r-CH2 CH
Reactions may be summarized as: II II CH3 - I, I CH)
CH3-C--C-H CH~H--CH2
(A) (B)

,' 1 Ozonolysis ,

H
[CH3 A'j[O] ] + [CHjJJ-H) + CHLH3

j[O] 0 0
" II II
CH3-COOH CH3-C-C-OH]
Acetic acid Pyruvic acid
f~ 12. CII Hl6 (A) reacts with two equivalent ofH2 and on reductive OoZOnolysis gives two equivalents fonnaldebyde and (B) offollowing
structure:

Identify structure of (A).

[Hint: Structure of compound (A) can be guessed as,
Unsaturated Hydrocarbons 381

Involved reaction may be given as,

It
(i) Ozonolysis
(ii) ZnlSteam •
(Xc,- c,/CH2 ,+ lHC.HO]

13. Complete the following reaction:

·f

W
~CCH~Ha
(B) ~

14. Identify the product in the following reaction:

o{)=o + 2C1H1 CH10Na. (.4)

[Hint: (A) HC==:CllC==:CH] . .

HO OH
 G.R.B. Organic Chemistry for Competitions

(c) Deduce the structural fonnula of a compound, ClOH10 (A) that gives (~) on oxidation:

HOOC-CH~H-Car-COOH
(B) I .
CHr,:'-eOOH

y=OONa
C=C-CH)

(b) (i) Q-c=c-Q

(0) Degr~ ofunsaturation' = 2nl - "2 + 2,= 20-10+ 2._ 6
,2 2
Thus, there may be 61t bonds. Presence of three carboxylic acids confirm that there are three triple bonds in .'A'.

(A) - HC=C-CH:r-CH-CH:r-C=C-H]
, I
. CH:r-C=C-H
16. Explain why the addition of ill to 3,3-dimethylbut-I-ene gives 2-iodo:-2,3-dimethylbiltane as the major product and not the
l-iodo-3,3-dimethyl-butane. . [Roorkee 2001]
CH) CH) CH) CH3
. I r... (HI) I + 1,2 M~':yl sht'ft I +1- I
[Htnt: CH)-C-CH:::bCH2 ----to- CH)-C-CH-CH) - CUI • CH~H-CH) ___ CH,-<:-CH-CH3]
I +H+ I j I. I t
CH) CH) CH3 I eH3
3,3-Dimethylbut-I-ene 2° Cll!bocatiOD 3°Cll!bocation 2-Iodo-2.3-di-
(More stable) methylbutane
17. In which case the product fonned is in accordance of anti
Markownikoff's rule? 20. ( ) • on reaction wub HBr and peroxide gives:

o
or
(a) CH -CH=CH HCI Peroxide)
3 z

CXCH2~ D~)
HBr
(b) CH3-CH=CH-CH 3 ..) .
PeroXlde
o
(a)
o
o .CH2Br
(d) (CH3 h C=CH2 0

cb
HBr/Peroxide)
n-<Br
. 18. In which of the following cases, the correct product is not
written? (C)W o (d) o
. CI Br
. '.
(a) CH3-CH=CH2'~ CHr :-CH-CH2
BrCI I· I 0 . 21. A hydrocarbon has the formula C 3H 4 • To find out whether it
contains two double bond or a triple ~()fid, the following test
(b) (CH 3 )2 CH' CH! ~~~)' (OI3 )2 CH(OH)CH 2CI 0 is preferred:
(a) passed ~ough anunoniacal AgN03 0
Hydroboration (b) treated witl;t Fehling's solution 0
(c) (CH 3 )3 C-CH=CH2 )
(c) treated with Baeyer's reagent . 0
(CH~ h e--;CH 2CH20H 0 (d) treated with Br2 water 0
. HCl .
(d) CCl 3CH CH2 ~ CCI 3-CH2-CH 2-Cl 0 22. Which among the following alkenes will be, oxidised .by
se02 ? .
19. Cis-2-butene. on reaction }Vith Baeyer's reagent gives:
(a) CH 2=CH 2 . 0
(a) meso-geminal diol 0 (b) racemjc-viCiIial diol 0
(c) meso-vicinal diol . 0 (d) none of these 0 0
,(b) CH3-CH-CH=CH
I . 2
CH)
 .~

Unsaturated Hydrocarbons 383

CH 3
I
.(c) CH3-C-CH=CH2
. I o
CH3
CH 3 CH 3
I . I
(d) CH3 -C-CH=CH-C-CH3 o
I, I
CH3 CH)
[Hint: Only CH 3-CH-CH=CH2 has bydrogen ata-carbon.]
I o
CH 3
23. Match List-I with List-IT and select the correct answer from
the codes given below the lists:
List-l List-II o
Reaction Product
A. CH3CH=CH2 (i)BH 3-THF) '1. n-propylamine
(ii) HCOOH

2. n-propylbromide
27. Alkyne (A) on catalytic hydration gives only one ketone
while alkyne (B) gives only aldehyde. (A ) and (B ) may be:
(a) pent-2-yne, acetylene 0 (b) oct-3-yne, propyne 0
4. n-propane (c) pent-2-yne, 'but-I-yneO (d) but-l-yne, propyne 0
28. The catalyst used in the manufacture of polythene by
Codes: Zeigler-Natta method is:
ABC D (a) TiCI 4 ,(C6Hs )3Al 0 (b) TiCl4,(CH3)3Al 0
(a) I 2 3 .4 ' (c) Ti0 2 0 (d) Titanium metal 0
(b) 2 I 4 3 29. Intermediate in hydration of alkene is:
(c) 3 4 2 I
(d) 4 3 1 ,2'
(a)fJ:ee radical 0 .(b) carbene 0
(c) carbonium ion 0 (d) carbanion 0
24. A hydrocarbon of formula C6HIO absorbs only one
'30. Order of reactivity of given four alkenes for hydrogenation
molecule of H2 upon catalytic hydrogenation. Upon , reaction will be:
ozonolysis, the hydrocarbon yields a compound of the , I. CH2=CH2
following structure,
CH3)
H 0 III. . C=CH2
I , I CH)
O-:-C-CH2-CH 2-CH 2-CH 2--:-C-:-H
(a) III> IV> II > I 0 (b) I> U > IV > ill 0
The hyilrocarbon is: (c) I> II > III > IV 0 (d) II> I > III > IV 0
(a)cyclohexane 0 (b) cyclohexyne 0 31. In the given reaction,
(c) cyc1oh~xene 0 (d) cyclobutane P
25. Match List-I with List-II and select the correct answer using ' C==£"' CH NaINH3(liq~ X
CH 3 - ~-) . )
the codes' given below the lists:
List-] , List-II 'Compound (X) will be:
Reaction Reagent , (a) ,butane 0 (b) trans~2-butene '0
,A. CH3-CH=CH2 ~ (c) cis-2-butene 0 (d) I-butene 0
CH3-CHBr-CH3 ' 1. HBr 32. 3,S-dimethyl cyc1opentene, on ozonolysis, yields: .
B. CH) -CH-CH 2 ~ (a) onlyan aldehyde 0
CH3-CH2-CH2Br 2. NBS (b) only a ketone 0
C. CH 3-CH==CH2 ~ (c) an aldehyde and a ketone 0
BrCH2-CH==CH2 3. Br2/CCl4 (d) a dialdehyde 0
D. CH3-CH=CH2 .~
. CH3 "":"'CHBr.:..-CH2Br 4 .. HBr (peroxide)

I'
384 G.R.B. Organic Chemistry for Competitions

33. A compound C4HS decolourizes a KMn0 4 solution. How Compounds [X] and [Y] are respectively:
many structures are possible for this compound?
(a) 3
(c) 2
0 (b) 4
0 (0)5
0
0
(a) ~-CH
I I 2
D-e' CH 0

34. An organic compound decolourises Br2 in CCl 4 and can be Br Br

rednced catalyticaUy. Also, it gives a precipitate with
ammoniacal cuprous chloride. The compound will be:
(a) CH3 -CH=CH-CH3 0 (b) CLu CH-Br' '; D-c=CH 0
(b) CH3CH2 C=i=CH 0 (c) n =-CH
LLc n . 0
(c) CH3-CH=CH2 · o LLcHr-CH3

o
(d) CH3 -C=CH2
I .
CH3
(d) ~=CH2
;' I
D-e H3 0

35. The relative stability of the compounds, Br

CH CH CH 39. The number of structural and configurational isomers of a .
I 3 I 3 .: I 3
. bromocompound, C~H9Br formed on addition of HBr to
CH3-C=C-CH3; CH3 -C=CH-,-:CH3 .

<Ii
(I) (II)
2-pentyne respectively are:
. (a) 4 and 3 0 (b) 2 and 4 0
H
3
) ..
c=C ; (c) 4 and2 o
(d) 2 and 7 0
40. H2 C=CH-C==CHon reaction with one mole DBr gives:
. CH3
(III) (a) CH z . CH-CBr=CHD 0
I (b) CHz (Br}-CHDC==CH 0
(c) DCH 2-CHBrC==CH o
. is of the order:
(a) I>II>III>IV>V>VI 0
(d) CH 2=CH-CD=CHBi o
41. Which of the following reactions are expected to give
(b) VI> V> IV> III> II> I 0
(c) I>III>V>II>IV>VI 0 CH)
(d) II> 1;> IV> III> V> VI . O. I
CH 3-C-CH=CH2
36. Alkenes can be converted to carbo.nyl cOmpound in one step
by:
I
CH .
3
(a) Wacker process 0
(b) Oxylnercuration;'demercuration .0 in yields of more tha.J;l50%?
(c) Hydroboration oxidation 0 . CH3
(d) Wittig reaction 0 c . I
,(a) CH1-C- CH-CH3
. o
37. Unknown COl'QP9und (A) on oxidation with hot basic .
KMnb 4 'gives only one'compound whose structure is given I I
below, CH3 0H

CH
. I 3 ..
(b) CH3 -C-CH-CH3

.
I
CH3 Br
I
Compound (A) will be:.
(a) CH3-C C-(CHz k-=-C=:C-CH3, o CH3
(b) CH3-:-CH=CH~(CHz )4-CH . CHz o I
(c) CHJ-C-CH-CHj Zn) .. o
(c) CH3-CH-CH-(CHz )4-CH=CH-CH3 o I I· Acetone

(d) 0 o
CH3 Br

(d) None of the above

42. Addition polymerisation can be brought about by:
o
~.' ~ 0 (b) cations o
"
38. [X] NaNH2 • [y] (a) free radicals
CC4 (c) anions 0 (d) none of these o
.
Unsaturated Hydrocarbons '385

43. Which of the following contains acidic hydrogen? 47. Which of the following ~ll reach with sodium metal?
(a) Ethene 0 (b) Ethane 0 (a) Ethyne D (b) 'But':'l-yne ' 0
(c) Ethyne 0 (d) But-I-yne 0 (c) But-2-yne 0 (d) Ethane 0
44. Which are the possible intennediate8 in the' following 48. Which of the following will give cis,-di(lls'!
reaction?
(a) )C=C< ' LKMn04 ) 0
CH CH CH=CH 1. Br2/CCI4 ) CH CH C==CH , 2. H 20
3 2 2 2. NaNH 2 (1l0-1600 C) 3 2

(a) CH3 CH2 CH-CH2 Br 0

, I
Br
(b) CH3 CH 2 CH-CHBr 0 0
(c) o
, (c) CH3 CH2 0=CH2
I
Br
(d) None of the above
'
0

0
(d)O 35%,H~2
. o
45. Which of the following statements are not correct. for 49. Ionic addition of bromine to clS-2-butene yields:
alkanes? (il) meso-:2,3-dibromobutane 0
(a) All C~H and C-:-C bonds have a length of 1.112 A and (b) racemic-2,3-dibromobutane 0
1.54 A respectively ,0 (c) d-2,3~bromobutane 0
(b) All bond angles are tetrahedral, having a value of, (d) 1-2i3-dibromobutane 0
109.5° 0 SO. The exacts representation(s) of molecular formula C6HS
(c) The C-C chain is linear and not zig-zag 0 containing sp, Sp2 ,and sp3 -hybrid-states of carbon atoms
(d) All alkanes exhibit isomerism 0
is/are:
46. What are the products obtained by the ozonolysis of
RCH-CR 1R 2 ? ' (a) H2 C=CH-CH=CH-CH=CH2 ' o
(a) RCHO 0 (b) R 1R 2 CO 0 (b) H 2 C=CH-O==C--':CH2-CH3 o
o (c) CH3-CH-:-C=CH-CH CH2 o
(d) H();;;;;;C-CH2 -CHr ':-CH=CH2 o

IANSWERS: BRAIN STORMING PROB~EMSI

17. (d) 18. (c) 19. (c) %0. (c) %1. (a) U. (b) %3. (d) 24. (c) %5. (c) %6. (a)
%7. (a) %8. (b) %9. (c) 30. (b) 31. (b) 3%. (d) 33. (b) 34. (b) 35. (a) 36. (a)
37. (d) , 38. (a) 39. (b) 40. (a) 41. (b,c) 4%. (a,b,c) 43. (c,d) 44. (a,b,e) 45. (c,d) 46. (a,b)
47. (a,b) 48~ (a,b,e) 49. (b) SO. (b,e,d)
 G.R.B. Organic Chemistryfor Competitions

LINKED CO ION TYPE ESTIONS

Passage 1 o
Hydrogenation of alkenes and alkynes takes pla¢e in
presence of certain catalysts. In Sabatier Senderen's reaction, the . (a) (b)
addititm ·of·hydrogen takes·· place in presence of Raney nickel·
catalyst. Platinum and palladiwn can also be used as catalyst in
these reactions. These are heterogeneous catalyst and used in OH OH
. fmely .divided state. Experimentally, it is observed that less
.crowded alkenes adsorb H2 with faster rate. Controlled (c) (d)
hydrogena~ion of alkyne in presence of Lindlar's catalyst yields
cis product i.e., 'cis' alkene. Thus, in presence of Lindlar's
catalyst 'syn' addition takes place. The relative rate of 5. ,Powaered nickel is more effective than grantlular nickel
hydrogenation follows the order: .. because:

»c C > )C 0 > C6H6 <

Non-tet:minal alkynes an reduce4 in presence ofNa or Li
. (a) Surface area of powdered nickel is maximum
(b) Free valencies are large in number
(c) powdered nickel increases the activation energy of the
metal dissolved in liquid ammonia. In this reaction, anti-addition ·reaction
of hydrogen results into the trans-product. . (d). powdered nickel increases the Intermolecular collision
Answer the following questions: of reactant molecules.
1. The relative rate of catalytic hydrogenation of following
Passage 2
. alkenes is:
Oxidation without cleavage of sigma bond takes place in
alkenes. .

I II III IV
(a) II>III>IV>I (b) I>fV>I1I>II or
A~O
(c) I1I>IV>I>II (d) II>IV>I>I1I
Pd/CaC0 3 . Presence of unsafuration· -in alkenes is detected by using
2. H3C-G-C-CH3 + H2 ----"'--7) (A) Baeyer's reagent. Alkenes decolourise pink colour of Baeyer's
Boiling Quinoline .r
. reagent.· In presence of Baeyer's reagent, 'syn' addition of-OH
groups takes place on bOth carbons· of double· bond. The net
reaction <;an be given as,
OH OH
KMn04
I . I
R-CH=CH-R OW ) R-'---CH-CH-R

(c) HC> <H

3

H
C=C·..·
. CH3
.,
Ozonolysis of· alkenes gives ozonide, which on further
hydrolysis gives aJdehyde and/or ketone.
H H
(d) CH3-CH 2-CH=CH2 Rl) I (CH Cl) . RI
)c·\P, I
\ "C-
I 3. In which of the following cases, the;:.r~action is most C=C- R3 + 0 3 . 2 i. R3
. exothermicf ... . ( . ... . Rz . .. R2 a+o'
(a)()~ o 0
Znduststeam. RI-1-R3 +'R3-1-H

.(C)(Y". Answer the following questions:

1. Linear polyenes on .ozonolysis gives two moles of
acetaldehyde and one mole of propanedial. Linear polyene
will be:
4. The product of the following r~action is: (a) alkadiene (b) . alkatriene
o (c) _alkate.traene . (d) alkapentaene

cY
2. Ort~o' xylene on reductive ozonolysis will give:

I ,./ +H2
PdtCaC03
... o
'v" Boiling Quinoline
(a) CHO-,-CHO and CH3-C-CHO
I
Unsaturated Hydrocarbons '387

o 0 0 . / C I I3
I I . I +O=C~ .
(b) CH3-C-C-CH3 and CH 3-C-CHO
. , .. , CH
o 0 .
Propanone
3
I I .
(c) CH3- C - C-CH3 and CHO-CHO Oxidation ofalkenes with 080 4 followed by alcoholic
000 NaHS0 3 or Na2S0J yields glyCols.
. I I I .' '.CH 2 - · ° . 0
(d) CH3-C-C-CH3' CH3-C-CHOand
CHO-CHO
3. Which of the following will give only formaldehyde on
CH 2 +080 4
II·
---1 I. /"'0<'
CH 2 - 0 ' ~O
CHz
ozonolysis? '
Ethylene

(b) CH03CH=CH2 NaHS03 CHzOH ".

- _ . : . . . .4) I +H 080 4
(c) CH3-CH=CH-CH3 (d) ~ Alcohol CHzOH z
Glycol
4. Which of' these cotnpCl1JIlds give glyoxal only on
ozonolysis?
.I Answer the following questions:
1. Which of these compounds on oxidation with hot KMti0 4

V
CH3
(a)
0-:7'
"'"
I'
.
'(b) ,
~.'

2.
gives only butanoic acid?
(a) Oct-3-ene
(c) Oct-2-ene
(b)Oct-4-ene
(d) 3-Methyl-hept-3-ene
Which of these compounds. on treatment with 0s0 4.'
followed by Na2 S03 will give cis-2-methylbutan-2,3-diol?
(d) All of these (a) 2-Methyl-2-pentene (b) 4-Methyl-2-pentene
(c) 2,3-Dimethyl-2-butene . Cd) '2,2-Dimettiyl.. 2~butene
3. An alkene I-methyl cyclohexene on oxidation ,with hot
5. Product of ozonolysis gives information about: basic KMnO4 gives:
(a) configuration (b) conformation (a) heptanoic acid
(c) both of these, (d) none of these (b) 2-methyl hexanoic acid
(c) 6-keto heptanoic acid
Passage 3 (d) butanoic acid and acetone
Oxidation of alkenes by cleavage with acidic or alkaline 4. Which of the following alkenes on oxidation with hot .
KMn04 or acidic K2Cr207 at higher temperature yields products KMn0 4 gives .cyclopentanone? . '.
depending upon the nature ofaIkene. A hot solution ofKMn04 is (a) 2-Methyl cyclopentene (b) Cyclopentene
a strong oxidising agent which gives only ketones and carboxylic . (c) Methylene cyclobutane (d) Methylerie cyclQpentane
acids and not aldehydes (as they cannot be isolated). 5~ An alkene 1,2-dimethyl cyclobutene on oxidation With. hot
KMn0 4 gives: . ,
o
. H 3 C, ~. /. CH3 [0] I (a) 4-ketopentanoic acid
",-,-c(\
.
----4) CH3'~C-OH (b) 2,3-diketo cyclohexane
(c) hexane-2,5-dione .' . .
H/ CH3 Hot KMn04 Ethan' 'd
OlcaCl
2-h{ethylbut-2-ene
(d) ethanoic acid and butanoi(; .acid

ANSWERS: LINKED COMPREHENSION TYPE QUESTIONS 1 1 - - - - - - - - - - - - - - - - - .

Passage 1•. 1. (a) 2. (b) 3. (b) 4. (a) 5. (a,b)

Passage 2. 1. (a) 2. (d) .3. (a) 4. (a) 5. (d)
Passage 3. 1. (b) 2. (a) 3. (c) 4. (d) 5. (c)