7

UN.SATURATED HVDR·OCARBONS
[Alkenes (Olefins) and Alkynes (Acetylenes)]

7.1 INTRODUCTION n,~,y, etc., are written to indicate the carbon atoms having
The open chain hydrocarbons which ~ontain lesser number of double bond.
hydrogen atoms than the corresponding alkanes containing H 2C=CH 2 (Ethane - ane + ylene) Ethylene
same number of carbon atoms are called unsaturated CH 3-CH ,CH 2 (Propane - ane + ylene) Propylene
a
hydrocarbons. The members which contain two hydrogen CH 3-CH 2 -CH=CH 2 (Butane - ane + ylene) a~Butylene
atoms less than the corresponding saturated hydrocarbons are
~
known as olefins* and are represented by the general formula CH 3-CH=CH - CH 3 (Butane - ane + ylene) ~Butylene
C n H 2n • These are characterised by the presence of a double
bond between two adjacent carbon atoms,)C=C<' in the CH 3-C=CH 2 (lsobutane -:- ane + ylene) . ISo-butylene

molecule. In IUPAC system, the olefins are termed as alkenes.**

, I
CH 3
The unsaturated hydrocarbons which are characterised by
a
the presence of a triple bond between two adjacent carbon CH 3CH 2CH 2CH=CH 2 a-Amylene
atoms, -C=C-, in the molecule and contain four hydrogen
~
atoms less than the corresponding saturated hydrocarbons are CH 3CH 2CH=CH-CH 3 ~Amylene
termed alkynes. These are represented by a general formula
C n H 2n - 2 • '(ii) As derivatives of ethylene: Olefms are named as
Alkenes seldom occur free in nature. Lower alkenes occur substituted derivatives of ethylene. The names are derived by
in coal gas in minute quantities. Ethylene is present in natural adding the name of alkyl groups replaCing the hydrogen
gas. However, alkenes are produced in large amounts by atom/atoms of the ethylene to the parent name ethylene. The
cracking of petroleum. dialkyl derivatives are of two types, symmetrical or
unsymmetrical; depending u~on whether the alkyl groups are
7.2 NOMENCLATURE OF ALKENES attached to the same carbon atom or to diffe{ent carbon atoms.
There are three ways of naming the alkenes or olefms. CH 3-CH=CH 2 Methyl ethylene
(i) The common system: The common names of fIrst CH3-CH=CH-CH3 Sym..,dimethyl ethylene
three members are derived from the corresponding'alkanes by
changing the ending -ane to -ylene. Greek letters are used to CH 3-i=CH 2 Unsym-dimethyl ethylene
distinguish isomers as to indicate the position of double bond.
CH 3

* The tenn olefin has its origin from an old Dutch name of ethylene 'Olefiant gas' (oil fonning gas) which refers to the oily nature of the product
(ethylene chloride) fonned by the combination of ethylene and chlorine.
** Alkenes containing two carbon-carbon double bonds are called dienes or alkadienes.'
 Unsaturated Hydrocarbons 299·

(iii) IUPAC system: The name is obtained by dropping Butene has two position isomers.
the suffix -ane from the name of the corresponding alkane and CH 3CH 2CH=CH 2 ; CH 3CH=CHCH 3
adding the suffix -ene. . '. But-I-ene But~2-ene
Alkane - ane +ene = Alkene (b) Chain isomerism :. This is. due to the difference in
The position of the double bond' is indicated by the the nature of carbon skeleton:
number of the first carbon atom (lowest numbered) involved CH 3CH2CH=CH 2 "
in the double bond. Alkyl groups are numbered, named and But-I..:ene
.. placed as prefixes in alphabetic order. When there are two or
three double bonds in the molecule, the ending -ane of the 2-Methylpropene
corresponding alkane is replaced by -adieneor -atriene.
H 2C=CH 2 CH 3CH=CH 2 Chain isomers
Etbene . Propene
CH 3CH2CH=CH 2 .., CH 3CH=CHCH 3
But-I-ene But-2-ene
CH34=CH2 CH 3CH 2CH 2CH=CH 2

CH 3
Pent-I-ene rIf3
2-Methylprop-l-ene
CH 3 -CH 2 -C-CH2
2-Methylbut-l-ene
CH 3CH 2CH=CHCH 3 ; . CH 3CH 2C=CH2
Pent-2-ene . I Chain isomers
CH 3 (c) Geometrical isomerism : Due to restricted rotation
2-Methylbut-l-ene about the double bond, the alkenes (with the exception of
ethene and propene) show geometrical isomerism. But-2-ene
H 2C. CH-CH-CH 2 shows geometrical. isomerism.
Buta-I,3-diene

3-Methylbut~l-ene .
Alkenyl groups: The monovalent groups obtained by .
. H3)C c~j\~;:ut:<~J
the removal of one hydrogen atom from alkenes are called H H H~ H
alkenyl groups. Cis-form Trans-fonn
H 2C=CH- H 2C=CH-CH 2- Pent-2-ene also shows geometrical isomerism.

H)C <~,~~;>ent:<~.
Etbenyl (Vinyl) 2-Propenyl (Allyl)
CH 3-CH=CH- . CH 3-CH=CH-CH 2-
I-Propenyl 2-Butenyl (Crotyl)
HC C- CH 3CH 2-C=CH-CH 2- C2HS . CH 3 . H CH 3
2 I .' I. Cis-form Trans-form
CH 3 CH 3 Besides. the above three types, alkenes show ring-chain
lsopropenyl 3-Methylp~nt-2-enyl . isomerism with cycloalkanes.
( I-MetJIylvinyl)
Alkylidene groups:
H3C- CH= ; CH 3-CH 2-CH=
Ethylidene Propylidene
CH 3 -C= H2C-CH2
I CH3CH2CH=CH2
But-l-ene
.I I
CH 3 H 2C-CH2
lsopropylidene Cyclobutane

7.3 ISOMERISM IN ALKENES 7.4 STABILITY OF' ALKENES

Alkenes can show the followmg types of isomerism. Ethene
and propene do not show structural isomerism.
(a) Position isomerism: This is due to the position of
double bond in the same molecular formula.
(HEATS OF HYDROGENATION)
. '
The relative stability of alkenes can be determined by
comparing their enthalpies of hydrogenation, (i.e,. the heat
evolved when one molecule of alkene reacts with hydrogen).
·300 G.R.B. Organic Chemistry (Or Competitions

So;' heats of hydrogenation have been used to assess the I 1 .1 1

relative stabilities of alkenes in much the same way as was C-C- ~ -C=C-+XY
described for heats of combustion as catalytic hydrogenation rJ--J-.
ofbut-l-ene, cis-but-2-ene or trans-but-2-ene yields the same •X y.
1 _______ <1

product, butane in presence of catalyst such as Pd or Pt.

1. By dehydration of alcohols: An alcohol is
H)C) <C1l3 H ' . converted into' an alkene by dehydration, i. e., elimination of a
C=C '. .-4 CH 3CH 2CH 2CH 3 molecule of water.
H . . H . Pd
. · "Butane
Cis-b~t-2-ene r· . ,II-H20
. -e-c- ~ + H 20
H3 C H2 Pd H J . _.L __ Alkene
....... ',>'C=C< :_IJ_'j~IJJ
H CH 3 Alcohol
Trans- but-2-ene The dehy'di-ation' of alcohols is generally carried out in
It has been. observed that enthalpy of hydrogenation of either of two ways:
cis-isomer is 120.0 kJ/mol and that of trans-isomer is (a) heating . the alcohol witl} acid catalyst like
115.0 kJ/mol. Thus, the measured heats of hydrogenation concentrated sulphuric acid or phosphoric acid H 3 P0 4 or
reveal that trans-but...2-ene is 5 kJ/mol (1.2 kcaVmol) lower in p-toluene sulphonic acid or P2 0 S to temperatures as high as
energy than cis-but-2-ene and that cis-but-2-ene is 7 kJ/mol 200°C. or
(1.7 kcaVmol) lower in energy than but-I-ene; In otherwords, (b) passing the vapours of alcohol over alumina (A1 20 3 )
the trans-isomer is 5 kJ/mol more stable than the cis-isomer. at 350 400°C, (A1203 serves as a Lewis acid). .
The energy differences between the isomeric butenes as The ease of dehydration follows the following order:
measured, by their ,heats of hydrogenation are, within Tertiary (3°) > Secondary (2°) > Primary (10)
experimental error,. equal to the differences in their heats of
combustion. CH 3
Heats of hydrogenation can be used to, estimate the I
stability of double bonds as structural units, even in alkenes, CH3-C-OH > CH 3-CH-CH 2CH 3
that are not isomers and also depends upon the position of I I
CH 3 OH
double bonds. For example,
CH 3CH 2CH 2CH=CH 2
Pent-I-ene
(Monosubstituted)
MI = - 126 kJ/mol
2-Metbylbut-l-ene
(Disubstituted)
MI = - 119.5 kJ/mol

CH 3 -C=CH-CH 3 CH 3-C=C-CH 3 (This sequence of reactivity is due to conjugate

1 ' ,I I stabilization in the ring.)
CH 3 CH 3CH 3
2-Metbylbut-2-ene 2,3-Dimetbyl
(Trisubstituted) but-2-ene
(Tetrasubstituted)
75% H 2S04
MI = 112.5 kJ/mol MI = - 111.5 kJ/mol CH 3CH 2CH 2CH 20H CH 3CH=CHCH 3
140°C )
The more substituted alkenes, (i.e., greater the number Butan-I-ol But-2-ene
(n-Butyl alcohol) 1° (Unexpected chief product)
of alkyl groups attached to the double bond) are more stable.
Thus, the order of stability of alkenes is:
R 2C=CR 2 > R 2C=CHR > R 2C=CH z > RCH=CHR
CH3CH2). '
CHOH
60% H2S04 ..
lO00C ) CH 3CH=CHCH 3
> RCH=CH 2 >.H 2C=CH 2 CH 3 But-2-ene
(Chief product)
Butan-2-o1
7.5 GENERAL METHODS OF PREPARATION (Sec. butyl alcohol) 2°
OF ALKENES CH 3 CH 3
Alkenes containing upto five carbon atoms can be obtained in I 20%H,S04 I
pure form from the petroleum. More complicated alkenes and CH 3 -C-OH -8-5--9.....::~:.....oC~) CH 3-C=CH 2
also the simpler ones can be prepared by the application of any
one of the general methods. Most of the methods involve
I lsobutylene
CH 3 (2-Methylpropene)
elimination of atoms or groups. from two adjacent carbon 2-Metbylpro~-2-o1
atoms from the molecules having only single bonds. (Tert. butyl alcohol) 3°
Unsaturated Hydrocarbons

In the dehydration of secondary and tertiary alcohols, result, the protonated ethanol breaks with the elimination of a
when there is a possibility of formation of two isomers, the water molecule to form ethyl carbocation. .
hydrogen atom is preferentially eliminated from the adjacent (1-+-H~
Slow +
carbon atom with the fewer number of hydrogen atoms. CH 3 CH 2 -O CH 3 CH z + H20
This is Saytzeff's rule. I Carbocation
H
CH -CH -CH-CH 60% H 2SO\ CH 3CH 2C. H=CH 2.
3 2 I . 3 100°C
But-l-ene (20%)
This step is slow and hence is the rate-determining step of
the reaction. .
OH 3rd step: Finally the carbocation being unstable and a
Butan-2-o1 (Sec. alcohol)
+CH 3CH=CHCH 3 reactive' chemical speCies, readily loses a hydrogen ion to
But-2-ene (80%) yield an alkene.
H H . • . . .
Dehydration of alcohols are stereoselective reactions in
which a single starting compound can yield two or more
(Main product)
I I
H-y-C-H~
.H) . H C=C<· + H+ .
stereoisomeric products and proceeds in the. direction that [J + H H Taken up by new
H alcohol molecule
produces the most highly substituted alkene and the more
stable one is formed in greater am.ounts. A carbocation As alkene is more volatile than alcohol, it is easily driven
intermediate is involved and sometimes' rearrangements take out from the reaction mixture and thus the reaction is
place during elimination. For example, butan-2-01 gives completed inspite of the reversible nature.
but-2-ene (80%) and more stable trans-stereoisomer [The formation of ethylene from ethyl alcohol c~m also be
predominates. Pentan-3-01 gives 75% trans-pent-2-ene and explained in the following manner.]
25% cis-pent-2-ene and so on. 1st step: When ethyl alcohol is reacted with H 2S0 4 at
Cone. H 2SO,,>
CH3CH2-iH-CH2CH3 Heat 170°C, it forms ethyl hydrogen sulphate.
C 2 H sOH + H-HS0 4 ---4 C 2H sHS0 4 + H 20
. OH 2nd step: Ethyl hydrogen sulphate decomposes to form
Pentan-3-ol alkene.
3 2 2 C 2H sHS0 4 ~ C 2H 4 + H 2S0 4
CH CH )C=c(CH 3 + CH 3CH )C=C<H
A controlling factor in the dehydration is the formation of
H H H CH 3 carbocation. The alcohol is dehydrated more easily which
Pent-2-ene (25%). Pent-2-ene (75%) foons a carbocation more easily. The more stable the
(Cis) (Trans) carbocation, the more easily it is formed. Thus, the ease of
H+ dehydration follows the same sequence as the ease of
R 2CHCR'2 ~ R 2C=CR '2 + H 20 formation of carbo cations, i.e., the stability· of the
I Alkene carbocations.
OH Tertiary (3°) > Secondary (20) > Primary (10)
Alcohol
OH (The detailed mechanism is given in chapter 5),
~.' '. The same sequence is observed when vapours of alcohols
~ are passed over alumina for dehydration.. Some . other
2-Methyl hexan-2-ol 2-Methyl hex-I-ene dehydrating agents are P20 S , BF3 , conc. H 3 P0 4 , dry ·HCI,
(20%) CaCl 2 and KHS0 4 , etc.
Al 20 3
+~ Primary alcohol --"":7)
350°C
Alkene +H 20

2-Methyl bex-2-ene Al 20 3 .
(80%) 3500C) H zC=CH 2 + H 20
Ethylene
Mechanism: The mechanism of acid catalysed
dehydration involves the formation of carbocation as an
intermediate. The reaction is believed to occur in three steps:
1st step: Due to the presence of two lone pairs of
electrons on oxygen, alcohols act as weak bases. Therefore,
they react with strong mineral acids (H 2S0 4 or HCI etc.) to
form a protonated alcohol (oxonium ion).
"..---"..
•• + +
CH 3CH 2 0H+H CH 3CH 2 0H CH 3 CH 3
•• ••
Ethyl alcohol H I I .
Protonated alcohol CH 3 -C-OH CH 3-C=CH 2
2nd step: The presence of positive charge' on highly
electronegative oxygen atom weakens the C-O bond. As a
I 2-Methylpropene
CH 3 (Isobutylene)
Tert. butyl alcohol
302 G.R.B. Organic ChemistrYjor Competitions

Cyclohexanol'
Conc.H3P04
100-130°C

.
o
Cycblhexene
In the case of secondary and tertiary alcohols, the
3 2
CH3
CH -6-CH OH- Conc. H2S0,\
I
CH
.6., -H20
3
CH 3-C=CHCH 3
fH 3

2-Methyl but-:-2:-ene (Major)

Saytzeff's _rule is followed when dehydration is done with the 2,2-Dimethyl propan-l~ol
help of alumina. . 2. By dehydrohalogenation of alkyl bandes .: Dehydro-
~etropinacolrearrangement (Wagner rearrangement) : halogenation involves removal of the halogen atom together
It' is the rearrangement in open chain compounds in which with . a hydrogen atom from a carbon adjacent to the one
shifting of C6HS (Ph -) ; CHi and H- takes place to form bearing the halogen. Alcoholic KOH - is used for
dehydrohalogenation.
more stable. carbocation and hence more stable products.
Shifting of these groups takes place in following sequence: . ,I I Alc. KOH 0 I I
-C-C- --=--:-.~) -C=C"":"" +HX
- C6~S (Ph-) > CHi.> H- / ..t---L Heat Alkene
LtLX!

3,3-Dimethyl pentan-2-ol 2,3-Dimethyl pent-2:-ene

Mechanism:
1st step :CH CH H
3 3 CH 3-CH-CH 3 Alc. KOH) CH -CH= CH i
3
I _ -OH- I I. - .- I: .6. Propene (Propylene)
CH 3CH 2-C-jH-CH 3 ------*H+ CH 3CH 2-C-C-CH 3 CI
I
CH3~ @J+' Isopropyl chloride

2° Carbocation CH 3CH 2CH 2CH 2CI Ale. KOH ) CH CH CH=CH

3 2 2
(Less stable) n-Butyl' chloride .6. But-l-ene
. (a-Butylene)
CH 3 H
1,2-Methyl shift I I CH 3CH 2CHCH 3 Alc. KOH) CH 3CH=CHCH 3
- - - - .~), CH3CH2-C-C~CH3 1-. .6. But-2-ene (J3-Butylene) (80%)
+ I CI (Main product)
CH 3 (2-Chlorobutane)
.,3° Carbocatidn (More stable) Sec. butyl chloride
+ CH 3CH 2CH=CH 2
But-l-ene (20%)
Br

~ Ale.KOH
.6. ,,~-+~
2-Bromopentahe Pent-2~eDe Pent-l-ene
(Major) (Minor)

~
Alc.KOH
.. +
.6.
ar 2-Methyl but-2-ene 2-Methylbut-I-ene
2-Bromo-2-methyl-butane (70%)' - (30%)

So, in strong bases (pKa =- 16) hydroxide ions (OH-) cause

a proton and a halide to be lost from adjacent carbons of an
alkyl halide to yielO an alkene,
R 2CH-C-R'2 +':B- ------*R 2C=CR'2
CH3 C~ CH3
. 'I ' . Base Alkene

CH3-b~-CH3
I X
S0 Alkyl halide
CH 3 -C--CH-CH3 COIl-c. H2 4) + H~B + X-
, I- I ' a,-H 2 0
2,3-Dimethyl but-2-ene
Conjugated . Halide
CH3 0H acid of base .
3,3-Dimethyl butan-2-ol
 '~

Unsaturated Hydrocarbons 303

This is an example Qf eliminatiQn (E 2 ) reactiQB as it CH3CH 2 Br + C 2 H 50- ----7 H 2CCH2 +C 2 H 50H + Br~
fQllQWS the secQnd Qrder kinetics. EthOxide ion Ethene'
AccQrding to, the SaytzetT's rule, when twO, alkenes may The reactiQn dQes nQt take place in stepwise manner but
be fQrmed; the alkene which is mQSt substituted Qne invQlves a cQncerted mechanism. It is an example. Qf E2
predQminates. reactiQn and represents abimQlecular \>-eliminatiQn reactiQn.
The fQrmatiQn Qfless substituted alkene in an eliminatiQn . The energy required fQr the cleavage Qf C-H and C~X
reactiQn is called as a Hofmann eliminatiQn and that Qf mQre bonds is provided by; . .
substituted alkene as a Zaitsev elimination. RegiQselectivity (i) fQrmatiQn Qf bond between H+ and OH- iQns,
. is in accQrdance with the Zaitsev rule.
(ii) fQrmatiQn Qf x-bQnd and
The ease Qf dehydrQhalQgenatiQn in alkyl halide is in the
. (iii) sQlvatiQn Qfhalide iQn in alcQhQl. All these release a .
Qrder: .,
cQnsiderable amQunt of energy.
Tertiary> SecQndary > Primary Let us' cQnsider eliminatiQn . Qf HBr· from
The ease Qf dehydrQhalQgenatiQn fQr differenthalQgens is l-brQmQ-I-methyl cyclQhexane. There are twO, possibilities Qf
in the Qrder: dehydrQhalQgenatiQn.
IQdide > Bromide> ChlQride
The yields are very gQQd in the case Qf tertiary and
secQndary alkyl halides but Qnly fair QrlQw in the case Qf
primary alkyl halides, Saytzeff's rule i,s fQllQwed in these
0~Hl
I-Bromo-l-methyl-
Endoeyelie
• o
rY. CH +HBr
I-Methyleyelo-
3

cyelohexane hexene (94%)

reactiQns. This is in accQrdance with the stability Qf alkenes, a
mQre substituted alkene is more stable. than less substituted
alkene Qwing to, higher number Qf resQnating fQrms.
This methQd is preferred because Qfless cQmplicatiQns in
Exoeyclie ..
cQmparisQn to dehydratiQn Qf alcohQls which is accQmpanied
by a hydride shift leading to, the fQrmatiQn Qf an intermediate
mQre stable carbQcatiQn. Methyleneeyclo-
Further greater the cQnjugatiQn, greater the stability (due hexane (6%)
to resQnance) hence easier the debydrQhalQgenation.
Mechanism
CH r --'CH-CH=CH 2 Ale. KOH) H 2C=CH-CH CH 2
. I Heat Buta-I,3-diene ('r(Br
Br
5-Bromobut-I-ene
(b), (i) V CH3
(a)

CH 3-CH-CH2CH 3 Ale. KOH ) CH -CH=CH-CH -H+(From

3 3
I Heat But-2-ene (Major)
(d)
methylene)
II
Br (Fast)
2-Bromobutane
(c)
FQrmatiQn Qfthis prQduct is accQrding to, SaytzetT's rule.
Since the product (b) is mQre stable than (d) hence,
dehydrQhalQgenatiQn Qf (a) is easier than that Qf (c).
Stronger bases like NaNH 2 Qr C 2H 50Na in ethanQI.Qr
triethyl amine, (C2H5)3N, can also' be used in place Qf
alcQhQlic KOH fQr dehydrQhalQgenatiQn (Et3Nis a bulky
(ii) ·0· . r3
CH
B. - - Br-·rHCl~Cc'<ES~l H
H
H

base and PQQr nucleophile, minimising SN2 reactiQn).

ChlorocyeloheKane
o
Cyclohexene
The fQrmatiQn Qf less substituted alkene in an eliminatiQn
Mechanism: The functlQn Qf hydrQxide iQn is to, pull
reactiQn is called as Hofmann elimination.
the hydrQgen iQn away frQm carbQn atQm; simultaneQusly the
The increasing Qrder Qf dehydrQhalQgenatiQn is:

o-r-{;H,
halide iQn separates and the dQuble bQnd fQrms. .
. CH
OH-:-~
•• I
-C-C
·I~
----7 > <
C=C +X- +HzO
~2CH,Br < < OBr '
 G.R.B. Organic Chemistry (Or Competitions

In addition to bemg regio~lective, dehydrohalogenation Stereo selectivity: Elimination of halogen from

of alkyl halide is stereoseleetive and favours the formation of dihalides give dominant trans-product.
more stable isomer. Me
1 Me'-./H
Br ~ -H~-Br C
~ ~'- ~
Nal
_E_tO....,;H.....
t + . 1
Acetone
• II
EtONa H~-Br C
3-Bromo hexane Cis-hex-3-ene. Trans-hex-3-ene 1 H/'-.Me
(Minor) (Major) Me . Trans

3. Debalogenation of vicinal dihalides (Two halogen Me

atoms are attached to adjacent carbon atoms): When 1 H'-./Me
H~-Br C
vicinal dihalide is heated with ZnlCu couple in methanolic Nal
solution, pure alkene is formed. . I Acetone
t II
. Br--<[c-:--n C
i.x:---X-: H/'-.Me
'r---r
--:- c~ C - + Zn Alcohol) -c=c- +ZnX2
Me Cis
CJIs
I I Heat I I I H'-./CJIs
H~-Br C
CH 2Br Methanol
CH 2
I
Nal
. II
I +Zn
Heat
) II. + ZnBr2 H~-Br Acetone C
CH 2Br CH 2 CJIs/'-.H
1
1,2-Dibromoethane Ethylene CJIs Trans
(Ethylene bromide)
4. Electrolysis of salts of dicarboxylic acids: When
Methanol sodium or potassium salt of saturateddicarboxylic acids of
+ Zn --~) CH 3CH +.ZnBr2
Heat II succinic acid type are subjected to electrolysis in ~eous
CH 2 solution, alkenes are formed.
1,2-Dibromopropane Propylene CH2COONa CH2COO- ' , ~
(Propylene bromide) 1 _ ·1·, +2Na
CH2COONa CH2CO~r / . .
Gem-dihalides have also been used in the preparation of
ttlktmes. Anode / Cathode

CH3CH2CHBr2 + Zn Methanol) [CH 3CH2CH(] + ZnB;~ CH2COO- -2e- CH2 2Na+ + 2e-- 2Na
l,l-Dibromopropane
(Propylidene bromide) .
1 I ; . - I I +2C02
CH2COO- CH2· 2Na + 2H 0 - 2NaOH + H
Ethene 2 2
CH 3CH=CH2
Propylene The method is an extension of Kolbe's method for the
preparation of alkanes.
If sodium metal is used in place of zinc (like wurtz S. Controlled partial hydrogenation (reduction) of
reaction), then higher alkenes can be obtained. alkynes :. Alkynes react with hydrogen when passed over
r-----------------~
/:Br Br heated catalyst (Lindlar's eatalyst)-Palladium poisoned
CH3CH~
I
Ether with CaC0 3 or BaS04 and partially poisoned by addition of
+4Na+ )cHCH3
.Br·------------~
I ______
I,l-Dibromoethane
Br I

I PbC0 3 , S or quinoline to fOrin predominantly cis-alkenes (as

high as 98%).
R-C=C-H + H2 Lindlar's) R~H=CH2
CH 3CH=CHCH 3 + 4NaBr Alkyne catalyst Alkene
But-2-ene
Ether CH3~==C-H + H2 Lindlar's) CH r -:--CH=C:H2
CH3CH2CHBr2 + 4Na + Br2CHCH 2CH 3 Propyne catalyst Propene
l,l-Dibromopropane .,', 1 HC==CH + H2 Lindlar's) H 2C=CH2
CH 3CH2CH=CHCH2CH 3 + 4NaBr
Hex-3-ene Acetylene . catalyst Ethylene (Ethene)

In place of Zn dust, NaI in acetone can also be used by E 2 (a) Hydrogenation ofalkynes with Lindlar's catalyst or a
mechanism. nickel boride called P-l catalyst yields only cis-alkene.

Nal Lindlar's catalyst R~-H

BrCH 2-CH 2Br .) H 2C=CH 2 + NaBr + IBr
Acetone
R-C==C--'-R + H2
Alkyne
.
orNI-B(P- )
2)
R~-H
I
. I,2-Dibromoethane Ethylene
Cis-alkene
 . i-'-'- ;.' . '-:~~'~"-:"'- ~'-::"

t.~..;~::
_. .', .. _,,'~.' __ ,
~ .<:-.>,-.\'O:,:~_>-~_

.;;;u._n_sa_tu_n~'ll_te_d;.;H_y~di_n_oc_a_r_b_ons_____..,..._ _ _ _ _ _ _ _ __ _....._ _ _ _.....______.-._..,..._ _...i-

..t=;~~.~:·'{i.-.'~;..···
(PJ But reduction of alkynes with lithiuin or sodium in "CuR
liquidNH3 (Birc:b: redudioD) yields ' predominantly H 2C=CHCl . 2) H 2C . CHR'
Vinyl chloride
trans~a",ene ..
R-C-H ;' .. (CH3 )2 Cu . .

R'--C==C-R+ H2
Li, NalLiq. NH3
)
I H 2C=CHC1 . ) H 2C=CH-CH3·
Propene
Alkyne H--C'-R
9. By GrigDardreageDts : . Alk:enes can be obtained by
Trans-rukene
,reacting Grignard
.
reagent with vinyl chloride.
.
.
So. R . . . . . "',

Lindlar's
.--..,.....--~
H 3) "
C=c
. ( "CH 3 Mg<. +X~CH=CH2'~ MgX2 +RCH'·~·-:-tH~
catalyst
, ,X Vinyl halide .' _ . AU<.ene .
H .' H
.Cis-but-2-ene " CH "',' .'
CHjO=CCH3 + 1I2
'+CI'--CH,-:-CH2'~ MgCI~ +CH 3CH
3
But-2-yne " Mg< 'CH 2
Na/Liq. NH3 CIVinyl chloride '. Propene
Birch reduction
10. By Wittig reactioD: ConverSion of aldehydes and
Trans-but-2-ene ketones to alkenes with the help of alkyUdene (methylene)
(c) Hydroboronation of alkynes (with B2Ho) followed by triphenyl phosphorus (Willig reagent) is .known as Wittig'
protolysis (with H+) gives almost pure cis-alkene. reaction, e.g. " . . .
. ." I ' . .' '. . '. , . ' . Heat'
CH 3C" , o + (C 6 H sh P =CH2 ~CH3CH=CH2
~ .
~~" .... H.j.·, ~.
'--C==C- ) (-CH=C-)3B -=-j'--CH CH- . Acetaldehyde " . Propene
'+(t.(jHshP . 0
6•. Pyrolysis or c:racking: Higher alkanes when heated ;Triphenyl
at high temperature (50o-700~C) decompose to produce a pho~hine Qxide
lower alkane and an alkene (C'--C fission).

. 3CH 2CH2CH 3 .Cracking

.CH . ,)'.·CH 3'CH'-CH
-
.
. 'CH 4 .
2 -+.
H3 C )c .' ".
. ....
Heat·
.
'.' •
.'. =0 + (Phh P-CH2 .~ CH 3-·C-:-CH 2
n-Butane· . Propene,. -'. Methane . ' " j '
H3 Acetone' . '. :; ., . CH .
or 3
2~Methyipropene
"2C=CH2 + CH 3-:-CH3
·+(Phh P.:...... O
CH3CH2CH2CH2CH2CH3 Cracking) CH 3CH=CH 2 .' '.. . Heat . ' ..
·~-Hexarie. Propene C 6 H sCH=0 + (Ph) 3 P==CH2~C-6HSCH=CH2
Benzaldehyde. . Styrene
. +CiI~CII2CH3
' . Propane- . +(PhhP .. 0
. I
. The presence of catalyst (like oxides of Cr. vanadium· and '.

C~)+~h)~2 Hw~8·+~h)3PO
Mo)~ h()wev~r, accelerates the C-H.linkagefission.
. . . . . Cracking . . . . . .
CH3'--Cl;I2-CH 3 . . .) .CH 3ClI-:-CH 2 + H2
. Propane' .. (Catalyst) . '. Propene ,
,'. .,. PyfoIysiS ofquatemary ammODiumeompoilnds:'
Many alkenes are conyeniently prepared by lieating quatetnary Now, ',carbonyl compound is ad~ed, din';~tly to ether
ammonium compounds.::..:.... . ' . . solution of Wittig reagent. " .'
+ -' Heat' 11. PetersoD reac:ti9D: . (3-Hydroxy alkyl silane gives
(C 2Hs )4NOH ) (C 2H s h N +C 2H 4 + H 20 elimination reaction in presence of acid as well as.base. It is
.Tetraethylammonium . Triethylamine Ethene
hydroxide (ten. amine) .
.stereosefective of E- and Z- iSOl;ners of alkene. .

(C 2 8 s )4 Heat) (C 2H ShN +C ZH 4 + ~
NX '.' H"c ' c/H ~. BF3,e~er Si(CH3~~c(~jf7
It is called HofmaDn eliJilinatioD with ,the fonnatioti of .' C3117/ "C3H7 (Anti-eliniination) C3H7 / ~iI
on
'an amine having smaller alkyl groups the x-bonded carbon. Z~alkene .
. This reaction is E2 elimination with an all}ine 'as leaving
/C==c,/~~7
.- group:. ,. ' .,. . Kil, THF
""
. 8. AdioD' of c:opper alkyl Oil' 'Vioyl-eblorides: ~lkyl
.J>. . .
(Syri-elimination) C3H?' .... . "-H
derivatives of ethylene can be conveniently prepared by the ....:{CH3hSi-DH· E-alkene
action of copper alkyls on vinyl chloride..

. .
-:Ail
--,,--.
 306
12. Cope reaction or cope elimination: When a
3°-amine oxide containing at least one j3-hydrogen is heated at
150°C, it decomposes to fonn an alkene and a derivative of
hydroxylamine {Thennal elimination} " stronger than carbon-carbon single bond.
Transition state
R-CH
+ ' R2NOH
- II
CH Djalkyl
2
Alkene hydroxylamine
This reaction may also be carried out in dimethyl
sulphoxide or THF at room temperature.
7.6 GENERAL CHARACTERISTICS
Physical' properties: (i) The first three memb'ers are
gases, the next fourteen members are liquids while' alkenes
with more than 17 carbon atoms in the molecule are solids at
room temperature.
(ii) Except ethene, all are odourless. Ethene has pleasant
odour. All are colourless.
(iii) Like alkanes1 alkenes are insoluble in water but
dissolve freely in organic solvents.
(iv) The boiling points, melting points and specific
gravities show a gradual increase with the increase of
molecular mass in the homologous, series. They are less
volatile than alkanes, i. e., their boiling and melting points are
higher than corresponding alkanes. Cis-isomer has a higher
boiling point than trans-isomer due to higher polarity.
For example, cis-but-2-ene has boiling point 277 K and
trans-but-2-ene has boiling point 274 K.
However, trans-alkenes have higher melting points than
their corresponding cis-isomers. For example, cis-but-2-ene
(m.pt. = 134 K) and trans-but-2'-ene (m.pt. = 167 K). This is
due'to the fact that the trans-alkene molecules are symmetrical
ap.d therefore, they can pac~ more closely in the crystal lattice
than the cis-alkene molecules. So, larger amount of energy is
required to break the crystal lattice 'of trans-a.lkene than the
corresponding lattice of cis-alkene, i.e., trans-isomers are
more stable than the cis-isomers.
(v) They are weakly polar. The values of dipole moment
for alkenes are pretty close in the rang\.: of 0.35 to 0.40 D.
> However, trans-isomers have zero dipole moment and are
non-polar.
(vi) The double bond in alkenes consists one sigma and
onepi-bon<J.
, 'Carbon-carbon double bond (C=C) is shorter than the
, cali'on-carbon singlehond.
>~34 i< 7~54 ~
, , .
. .;.
G.R.B. Organic Chemistry tor Competitions
The total bond dissociation energy of double bond
(146 kcal) is greater than carbon-carbon single bond
dissociation energy (83 kcal). Hence, the double bond is
Chemical properties: ,The most important reactions of
alkenes are the addition readlons. Alkenes are reactive due to
the presence of double bond. The double bond consists of a
strong a-bond and, a weaker 1t-bond. The 1t-electrons are
loosely held, and are, therefore, easily polarisable. In addition
reactions, the 1t-bondis broken and ,two new a-bonds are
fonned. The fission of the bond may be heterolytic or
homolytic as shown below.
C-C< .(Heter~lytic >C=C< 'HO~lytic) >c-c<
> fiSSlon fiSSlon. .
Charged species Drradical
In polar solvents, addition proceeds by ionic mechanism
(i.e., at low temperature), whereas in the presence of light or
non-polar solvents, the addition occurs by free radical
mechanism (i.e., at high temperature).
Ionic mechanism involves three steps:
1st step: The reagent E-Nu ionises to give an
electrophile and nucleophile.
E-Nu ----7 E+ + :Nu-
2nd step: The electrophile attacks the carbon-carbon
double bond and fonns a covalent bond with one ofthe carbon
atoms by utilising the 1t-electrons. The other carbon atom
acquires positive charge, i. e., fonnation of carbocation occurs.
E+ + >[\Alkene
C< SlOW) >C-c<
I
E
Carbocation
3rd step: The nuc1eophile now attacks the carbocation
to fonn an addition product.
>C-e(+ :Nu- Fast) >C-C<
I~ I I
E E Nu
Addition product
As the addition reaction is initiated by an electrophile,
the reaction is termed as electropliilic addition. '
The addition of electrophilic reagents relieves the strain
of >C=C< (bond angle 120°) by changing itto 7C-C~
(bond angle 109.5°). The r~ctivity order for alkenes hail been
given on the basis of heat of hydrogenation as,
H 2C-CH 2 > R--CH=CH2 >R 2C=CH 2 ""
, R-CH=CHR > R 2C=CHR > R 2C=CR 2
The reactivity of alkenes is, however, also related to the
following factors: '
(i) Steric effect, ' (ii) Hyperconjugation and (iii) Heat
'of combustion.
Alkenes (except ethene) also contain' alkyl groups. Alkyl
part is very stable. Like alkanes, this part can show
substitution reactions with difficulty.
Unsaturated Hvdrocarbons 307

1. Addition reactions: The important addition (b) AdditiOn of halogens: Halogens (chlorine and
reactions of alkenes are described below: bromine only) add at ordinary temperatures to alkenes in
(a) Addition of hydrogen (Hydrogenation): Alk~nes presence of an inert solvent, (e.g., CCI 4 ) to form vicinal
combine with hydrogen under pressure and in presence of a dihalides. Br2 water is decolourised by unsaturated hydro-
catalyst (Ni, Pt, Pd or Rh) to form corresponding alkanes carbons (hence the test of uusatoration).
(Sabatier-Senderen'sreaction). CCl 4 .
Catalyst Br2 + H 20=CH 2 ------~~) CH 2Br--CH2Br
Hp CH 2 +H 2 ---=~) CH 3 -CH 3 + Heat (Brown Ethylene (Inert solvent) Ethylene bromide
~ Ethene Ethane colour) (Colourless)
Catalyst Inert
CH 3 -CH=CH 2 + H2 ----=~) CH 3 CH 2CH 3 + Heat Br2 + CH 3CH=CH 2 --~)' CH 3CHBrCH2Br
Propene (Brown Propylene solvent .
Propane Propylene bronude
colour) (ColoUrless)
The reaction with fluorine is explosive whereas iodine
reacts very slowly. When alkene is bubbled through alcoholic
solution of iodine (12 solution in CCI 4 ), a mixed halide is
formed.
H 2C=CH 2 + I+Cr ~ CH 2I-CH 2CI
CH 3CH=CH 2 + I+Cr ~ CH 3 -CH-CH 2I
Cis-cyclododecene Cyclododecane (100%) Propene I
CI
When nickel is used as a catalyst, the reaction is carried
2-Chloro-l-iodopropane
out at 200-300°C and in presence of Pt or Pd, the
hydrogenation can occur even at room temperature. With trans-but-2-ene, the product ofBr2 addition is optically
Hydrogenation follows free radical mechanism. inactive due to the formation of symmetric meso compounds.
Hydrogenation is exothermic. The heat of hydrogenation CH 3 CH 3
of every alkene is fairly close to an approximate' value of
30 kcaVmol. The heat of hydrogenation of ~ alkene is an
H-C-CH 3
I +Br2
~H+Br + Br+H
index of its stability. The lower the heat of hydrogenation of H3 C--C-- H H+Br Br+H
an alkene, the more stable it is. Trans-but-2-ene Trans-but-2-ene CH 3 CH 3
(Meso)
(27.6 kcaVmol) is more stable than cis-btit-2-ene
(28.6 kcaVmol) and but-I-ene (30.3 kcaVmol). In general, for symmetrical alkenes and symmetrical
A terminal double bond may be reduced by sodium in reagents, the addition takes place as:
liquid ammonia in the presence of an alcohol (MeOH or cis-alkene + syn-addition ~ meso
EtOH). This is called Birch reduction.
trans-alkene +syn-addition.'~ racemic
RCH=CH 2 +2H Na/Liq. NH3 ) RCH CH cis-alkene + anti-addition ~ racemic
EtOH 2 3
trans-alkene + anti-addition ~ meso
Cyclohexene can also reduce olefinic bond, and itself is This re&ction provides a useful test for unsaturation, the
oxidised to benzene. .

0'1
brown colour of the bromine being rapidly discharged as the

O 2CH3~H3
colourless dibromoderivative is formed. The reaction is.
+ 2H2C=CH2 - + stereospecific, anti-addition is observed. A stereospecific
Ethene ::::,... , ,Ethane reaction . is that where stereoisomeric starting substrate
Cyclohexene Benzene produce products which are stereoisome~ of each other.
The double bond is also reduced in excellent yield by Mechanism
NaBH 4 -PtCI 2 • 1st step: . The Br2 molecule ionises on interactio~ with

q
Me Me
~.
H
Me Me
1t-bond.
Br2~· . Br+ +
Bromoniurn ion
(Electrophile)
.
:Br-
Bromide ion
(Nucleophile)
[Meso ()r syn addition product] 2nd step: Bromonium ion attacks the double bond to
form a carbocation.
The rate of hydrogenation of olefmic bonds at room
temperature is -CH=CH 2 > -CH=CH-' 'or a ring .. , Br
, I
double bond. . )c·rt< +Br+
Alkene .
Slow)
)C--C< '
Carbocation .
 ..
G.R.B.Orf!;.anic Chemistry for Competitions

. ,jrd step: Nucleophile (Br -) attacks the carb~ation to ' . Thus, ionjc . addition of
unsyminetrical reagents .to
. form addition product ' ,.,' unsymmetrical alkeQes is regioselective reaction. '
Br.,. Br Hi . ,. The order of reactivity of the hydrogen halides is:
," , + ,'I , . . I' ,I' '. ,. t.
HI> HBr :;> HCl >HF
, )c-e< + :Br- Fast) )C::-e( Mechanism
. ~., ,lststep : HXionis~s;' HX ~ 'H+ +:X-
'Mechanism-was proved by following addition reac~(m.
'.. ' ~ H"~;'H:.' . 'B ' NaCi (aq,) ~ . '. 2nd step :,' ElectroiJhile (H+)'attacks the double bond to'
:; " '. '.' ,2""'-"" 2 + r2 . - .) form carbocl!tion.
" CH z'-CH 2 ,+ CH 2-CH 2 +tH2~CHi
I ,t ·1,
Br OH Br
I" I
Br ' Br
. I '.
. CI
H+.+
,
C< ~ ,>c~~
)C,.
'.' R·

3rd step: Nucleophileattacks the carbocatiorrto forin

,
Mechanism th~ alkyl halide. . .
", H " ' R
>C~X .~ >r-c~,
X
. '. .-
2nd step: . Markownikoff's Rule:" The negative part, of the
"CH:z-CH2 unsymmetrical reagent ad4s .to less hydrogenated (more'
I' I . sU,bstituted) carbon atom etf the double bond. The modern
Br.· Br , version of the rule 'is that electrophilic addition to a
1,2-DibtOmoethane carbon-carbon double bond involves the rearrangement
'(1,2-hydride or 1,2-methyl shift)'leading to the
. CHz-CH2
I '·1,' ilJtermediate formation 'of' a. more' stable. carbocation
Br" Cl (c~rbonium ~on). The, order of stability is:
"1-Br°Dt°:2-chloroethane +
oft-from water· 3.0 >" 2°> 1° > C1h
CHi-CH2
. '. I·, :1\, For eJl,ample, an addition of HBr to propene is ap. Ionic
BI: OH electrophilic IJdditioil reaction, in }Vhich the electrophile in
2-~romQethanof , the step 1 isH+. . ' , , " ..,. ' , .

.~
Mechanism:
Step 1: HBr' -""-'-4 H+ + :Br-
, Attacking eleCtrophil~
Cyclopentene,
Br 'Br Step 2: The proton (H+) attacks the 1t-b()nd to give a
i
.l,2-Dibromocyclopenjane, stable carbo<;ation. .
-+
(Trans)' .
. .
. , ~CH3-CR-CH3
. (c), Additi~n of : halogen acids: . Alken:es react ,with 20 Carboeation
, halog~'acids (HCI~, H.Br or HI) to foi"Iri alkyl halides .. ' CH 3--r-C'H =nC~H
2 + H + Slow . ' . (More stable)
." '
Propene
., . r,.,.j.'
'+
CH 3 -CH 2,-CH2
. 10 Carbocation
(Less stable)
. .~ , Step 3: ' The nucleQphile bromide ion attacks the·,more
A protbn. 'ltnd 'a halogen add to the doubie ,bond of an stable 2~ carbocation togive2-bromopropane (major product).
alkene' ,to form an aU<yl Mlide 'in accordance With . , . + . . Fast '. . "
. ¥ar~o~ikoff's rule'undernonniil qoridition. ' ' . CH3-C.iI-CH:; +:Br~ ) CH 3--,-CH-CH 3
. " or
-
,RCH" CR z ' . '"
+ ,HX'; RCH2~C.R2 l' , I3r'
, Alkene:, " ,Hydrogen ',' , I, , 2-BrQmopropane ,
, ,halide,' X': '
. A.J.kylli.a1id«: , In another .example, an addItion' ofHBl' to isobutyl<:?ne
Uns~etrichlalkenes give ~o diff~rent products with forms tlirt., butyl bromide (2-bromo-2,-methyl propane) as .
unsymmetricalteagents; .These prOducts are constitu~ional major product It is a completely regioselective reaction, as
isot)1eis: the one ~duct y.rhichptedomi1ui:tes in the reaction, 'one ofthe possibl€: product'(1~bromo-2-methylprQPane)'is not
is ,called aregiosel~tive reaction, "" .' ) . . .' ., formed at alL '

;
(
,', \ :
.
~.
 . . '. :

. Unsaturated Hydrocarbons '309

CH 3 ' CH3 CH3

· 1
CH3 -C=CH 2 + HBr ~ CH3 -C-CH3
. 1+
or CH1 · +
3 -CH-CH 2 .
2-Metbyl propene A '3!>'<:arbocation A I" caIbocation
(Isobutylene) (MoIestable) (Less stable) .' ,

. "·.lsr-
CH .
I 3
CH 3...::.cc-CH 3
, . '!i . , .
'i-BroiOO~2-methyl propane
orTen: butyl bromide (Majorproduci)
Other examples are:
CH 3 · CH 3 Ca3
1 " . .
CH 3-CH-CH=CH2
+HBr I , I '
) CH 3 -,-CH 2CH 3 +CH 3-CH-'.
3-Methyl but-I-ene
Br
r-CH
Br .
3

2-Bromo-2-methyl 2-Bromo-3-methyl
. butane (Major) butane (Minor)

CH 3 CH 3 CH3
I ,+HBr I I',
CH 3 -C-CH=CH 2 ~ CH 3-C-'. CHCH 3 +CH 3-C-,.-CH-CH 3
I , ,l 1 . '. , 'I . I '",-
CH 3 . Br 'CH 3 'CH3 Br
3,3-Dimetbyl but~l~ene ..' 2-Bromo-2,3-dimethyl butane ,2-Btomo-5,3-<limethyl
(Major) butane '(Minor)
The addition of fIX to 2-i>entene V$'.notregioselective as both alkyl halides CZ-Bromopentane and 3~Bromopentane)'~ formed in
comparable amoun~s. . . . .

) CH3CHitH2'H~'. '
+
CH 3CH 2CH 2CHCH3
2° Carbo cation .
..:- '
, .
'. . ' Br
CH 3CH 2t:H==CHCH 3 H
, 2-Bromopentane
. Pent-2-ene + Br...·· .'."
CH3CH2CHCH2CH3 ." ) CH 3CH 2CHCll2CH 3
2°. Carbocation'
.. ',
I·
. Br
. ".
,J

3-Btomopentane
. Addition occurs rapidly ina variety ofsolvents~ mduding Peroxide effect :. Kharascb observed tbatthe addition
cblorofo~ benzene, acetic aCid and dicbloromethane; etc. of HBr totmsYnunetrical alkenes in the presence of organic "
CH3CH~'>'..... . <.'CH;CH3 . . . '. . peroxides [(C 6H sCOOh , Benzoyl peroxide] follows an .

.' -r::'
,. . C=C'. + HBr • Solvent )' . opposite course' to that. suggested by Markownikoff.This is
, . H·' . H~'
.
..
. termed anti-Markownikoff or peroxide effect.
. .
Peroxide . .
Hex-3-ene (cis)
. .', ." . CH3CH2CH2Br
I-Bromopi'opane'
';:;H3CHzCHCH2CH2CH3
· . I' . . . CH3~CH2 +HBr . . . ' .(l1-PrOPYlbrO~~e)
. Br .
opene . ' .No ~oxide CH CHBrCH
3-BromOhexane . ,3 ,3
(75%) . 2-Bromopl"9JJane
acc ~.'
. CH3 .r .... (Isopropylbromide)
. . .
~

+ HCl ~.~-CI
..
I-Methyl cyclopentene · .:~ I-Chloro-I-methyl-
, cyclopeptane (100%)
310·. G.R.B. Organic Chemistryfor Competitions

In presence of benzoyl peroxide, the reaction is free radical

H 2C=CH-N(CH 3 h +HBr) BrCH 2-CH2.N(CH 3 h
eleetropbilic addition reaction, in which the electrophile here is
Br· free radical which is obtained by the action of benzoyl (d) Addition of bypobalous acids: Alkenesfonn
peroxide on RBr. halohydrins withhypohalous acids, (i.e., chlorine or bromine
in aqueous solution). In place of HOCI or HOBr, chlorine or
Meebanism: bromine in presence of water can be used.
Step 1: Peroxide undergoes fission to give free radicals - +. CI 2 ,H20
H 2C=CH 2 + HOCI ) . CH 20H-CH 2CI
(initiation).
Ethylene Ethylene chlorohydrin
C6H5C~O~COC6H5 Heat) 2C H Coo----7 (2-Chloroetbailol) .
(Homolytic 6 5 .
Benzoyl peroxide . ) Benzoyl radIcal
fi SSlOn (Unstable)
• Propylene chlorohydrin .
[2C 6Hs + 2C0 2] ( I-Chloropropan-2-o1)
Phenyl free radical
R
Step 1: RBr combines with free radical to fonn
bromine-free radical.
I
RCH=CR~ .+ X 2 + H 20 ----7 X-CH-C-OH
.~
C6HS +H-Br
0n Alkene Halogen Water I I
R R'
• Vicinal halohydrin
Step 3: Br attacks the double bond of alkene to fonn a
more stable free radical (propagation). + HX
CH 3 -C =1....H + Br
C\H~· Slow .•
) CH 3 -CH-CH2Br
Hydrogen
halide
2
2° Free radical

(termination). .
(More stable)
Step 4: More stable free radical attacks the RBr O CH

Methylene cyclohexane
2
O CH2Br
OH
I-Bromomethyl
.~ ~
CH 3CH-CH 2Br + H-Br
Fast
) CH 3CH 2CH 2Br + Br
• cyclohexanol (90%)
I-Bromopropane
Br2
• • (CH 3 hC=CH 2 H 0) (CH 3 h,-,H2 .
Step 5: Br + Br ----7 Br2 2
2 .. Methyl propene
Free radical chain reaction can also be initiated OHBr
photochemically either with or without adding peroxides. I-Bromo-2-methyl-

~CH2+ RBr ~
propan-2-ol(77%)
[)<H
~ CH2Br
Oxygen is more electronegative than bromine (or chlorine
Methylene
cyclopentane
Bromomethyl
cyclopentane (60%)

Note: Peroxide effect is effective only in the case ofHBr and not.effec-
tive in the case of HCI and HI. This is due to the following rea-
o
or iodine) and so the HO-Br bond is polarized.

+ el, H,o.
CycIopentene
H
et° CI
sons: 2-Chlorocyclo-
pentanol m'ans)
1. H-CI bond (103 kcal/mol) is stroIlger than H-Br bond
(87kcal/mol).H-Clisnotdecomposedbyperoxide-:fi:eeradical. In these halohydrin fonnation reactions, a halonium ion is
2. Iodine-free radical formed as H-I bond is weaker but fonned as .an intennediate which is attacked by water in
iodine-free radicals readily combine with each other to form aqueous solution. .
iodine molecules rather than to attack the double bond. The order of reactivity of different X 2/H 20 (H0-X) is:
3. InH-Br both the chain propagation steps 3 and 4 are exother- CI 21H20(HOCI) > Br 2/H 20 (HOBr) > I 2/H20(I-OH)
mic while in HCI step 3 is exothermic and step 4 is endother- Mechanism: The addition of halogens in presence of
mic. In HI, step 3 is endothermic. water occurs through the intennediate formation ofhal onium
ion as shown below:
The abnonnal addition ofHBr in presence of peroxide can
be ~revented by the addition of an inhibitor such as diphenyl 1st step: CH3CHVcH2 + 8~~~ ~ CHl:H-CH2CI + cr
anune or catechol, etc. .
An . M·
u- arkownik0 ff addItIon
..
is observed if the alkene
Propylene
~
bears a powerful electron withdrawing gl'llUp (-/ group) 1nd step: CH3-rn-CH2Cl + H--O: ~CH3-CH-CH2Cl
attached directly to the doubly bonded carbon. I I.
H H-o+
I
H
Unsatu.rated /fydrocarbQns .311

CH -ClI-CH + H+ Note: To obtain alkan-l-ol from alk-l-ene, the following procedure

3 I I Z should be adopted. Alk-I-ene is treated first with diborane, the
HO CI boron compound formed is then reacted with H20 2 to get the
Propylene chlorohydrin desired alcohol. Thi~ addition of: borane followed by oxidation
is known as llydroboration'Oxidation reaction.
For example,
(e) Addition ofsulphuric acid: Cold and concentrated CH 3CH=CH 2 + (BH 3)2 --+ CH 3CH2CH2BH 2 '
sulphuric acid or fuming sulphuric acid readily adds upto Propene Diborane
alkenes to fonn alkyl hydrogen sulphate. In the case of
CH 3CH=CH2) (CH3CH2CHzhBH CH 3CH=CH 2 )
unsymmetrical alkenes, Markownikoff's rule is followed:
HzC=CH2 + H+HS0 4 ~ CH 3CH2 HS0 4 (CH 3CH 2CH zhB H20 2 , OH~CH3CH2CH20H + B(~Hh
Ethylene Ethyl hydrogen sulphate Propan-I-ot • Boric acid
This reaction involves two steps, i.e., addition ofborane (BH3)
CH 3-CH=CH 2 + H+HS0 4 ~ CH 3 --CH-CH 3 to double bond called hydroboration and oxidation followed by
Propylene , I hydrolysis to give alcohol. '
, HS0 4 6CH3-CH 2 -CH=CH2 + B2H6--+
But-l-ene
Isopropyl hydrogen sulphate
2(CH3-CH2-CH2-CH2)3B ,
Ethyl hydrogen sulphate on heating at 160 -170°C yields Tributylborane '
ethylene again. Hence, this reaction is used in the (CH3 CH 2CH2CH 2 )3 B + 3HzOz --+
separation of ethylene or alkene from a gaseous mixture of 3CH 3CHzCH 2CH20H + H3B03
alkanes and alkenes. Butan-I-ol
With diborane .B2H6 alkenes undergo addition reaction
CH3CH 2 HS0 4 ~ H 2C=CH 2 + H2S0 4 (Hydroboration) to yield trialkyl boranes, which are used for
Ethanol is obtained when alkyl hydrogen sulphate (an the synthesis of primary alcohols by the reaction with alkaline
ester) is boiled with ,water. aqueous solution of hydrogen peroxide (oxidation).
6(R-CH=CH2 ) + B2H6 --+ 2(R-CH2CH2 )3 B (OH-»
CH 3CH 2 HS0 4 + HOH Hydrolysis) CH 3CH 2 0H + H 2S0 4 Alkene + 6HzOz
Trialkyl borane
Hence, the reaction is used for the preparation of 6(R-CH2CH 20H) + 2H 3B03
Primary alcohol
alcohols as alkenes are readily available from the cracking
of petroleum. RCH=CRi
Conversion of alk-l-ene. to alkan-2-o1 (reaction with cold Alkene
and conc. H2S0 4),
HOH The overall result of the above reactions, appears to be
CH 3CH=CH 2 + H-HS04 Cold) CH 3CHCH 3 Warm)
Propene (Cone.) I
HS0 4

CH 3fHCH 3
2 S
CH )
HH
bond (Hydroboration oxidation).

C=C <C H

Hex-3-ene
2 s

,
2 s
B2 H6 '(ether») C H
H20 2 ,OH H
>
anti-Markownikoff's addition of water (hydration) to a double

C-C,<CzH
I I H
H OH
s

OH Hexan-3-QI
Propan-2-ol '+ Enantiomer

CH3-CH z-CH=CH 2 + H-HS04 Cold)

But-I-ene (Cone.)
Methylene cyclopentane , Cyclopentylmethanol
HOH
CH3-CH 2 --CH-CH3 ---+) CH 3-CH 2 -CH-CH 3
, I Warm I Addition of -H and -OH is syn. addition.
HS0 4 OH
Butan-2-01
Acid catalysed hydration to alkenes with Markownikoff's
rule are regioselective reactions. The order of hydration is:
i f
H
H3
OH

CH 3--C=CH z >CH 3-CH=CH 2 > H 2C=CH z Another convenient hydroborating agent is the
borane-tetrahydrofuran (BH3 - TIfF) complex. It is very reactive
I and the reaction is carried out in THF (tetrahydrofuran), ether or
CH 3
diglyme (diethylene glycol methyl eth~,
CH30CH2CH2OCH2CH2OCH3)'
 G.R.B. Organic Chemistryfor ComBetitions

BHr-THF ' , "

(CH3)iC=CH-CH3 ' H 0 OH~ ) (CH3)z--CH-CH- CH3
2~Methyl b1!1-i -ene
2 h
6H , r
3 - Methyl butan - 2 - 01(98%)

(CH3hCH-'-CH=CHzBH1-THF) (CH3)2CH-CHzCHzOH
• 3-Methyl but+ene .' H 20 2 ,OH '3.Methyl butan·l·ol
, ", __ ,'B2He (diglyme) , "
CH3(CH z)7 qr--CH z ' Hil2'0& ), ~H3(CHz)7 CHz:Hz()H,
, , Dec-l-~ " ,Pecan-l-ol(93Y..) , , " ,
The hydroboratiotl reaction was discoyetedby H.,C, Brown, ~ho was 'awarded Norn;IPrize in 1980 for the synthetic Uses of the reaction.
Trialkyl bOtaDe on decomposition,by aceti~ acidfomis alkane. '
~ 'Trialkyl borane reacts with organic acid, generally ~cetic acid, to give alkane corresponding-to alkanes.

Trialkyl borane Alkane

, ,

, "BH3 " ,, GH 3COOH

, 3CH3CH=CH 2 ---'7 (CH3CH2CHih B ") 3CH 3CH 2CH 3 '
Propelle Tripropylborane Propane

(i) BD3/THF
CH 3- 'CH=CH 2 -----=---~) CH 3-CH-CH 2
~CH3COOHI I
D H
BD /THF
(i) 3 ) CH -CH-CH
(ii) CH3COOD 3 I I 2
D D
Tpalkyl b9raries undergo coupling reactiop. in presence of AgN03/NaOl:{.
(i) BH3/THF . ' '
CB3CB--:'CH 2 .. " ')CH3- ' (CH 2 )4-CH 3
Propene (u).AgN°3/NaOH ',' n-Hexane'·
, ' ~ "

(f) Addition of water (Hydration) : Alkenes add up water !ll0lecule in presence of aCids or catalyst BF3 or Mn phosphate,
etc.~ to yield alcQhQ\g., This' additi9n also follows Markownikoff's rule. A carbocation is an interme4iate and is captUred by a
molecule of water acting ,as, ~ npcleophile. For ~synthetic purposes, this reaction ordinarily' works well for the preparation of
secondary 'or tertiary alcohol. For example,
',.'
'
. * . .
" , ' .

(i) CH3CH=CH 2 + H 20Dil H2S04 ) CHicH-CH 3

, Pro~ (MR.) , t
Oll
Propan~2-QI

Mechanism: ' 'The mechanism of acid catalysed addition of water (hydration) to alkenes involves the following three steps:
Step 1. Electrophilic attack by hydroniuin ion (H30+) on alkene gives an intermediate, carbocation. "
(H~S04 ,.....---72H+ +SO~-') ,
H
I
..O-':a +
• •• _<

H+ ~ H-O+-H(H30+)
H-,
'.. H~oni~ion '
,

1 '

H
," ~'I .+
0'
'
,'"
CH 3CH CH 2 +HT 8,-H Slow)" CH 3 - 'CH-,CH + H 2 ••
Propene V ,3
2° Carbocation
Step 2. Nucleophilic attack by water on carbocation to yieldprotonated alcohol.
 Unsaturated Hydr.ocarbons

+~. Fast ..
CH 3-CH-CH 3 + :O-H --.....) CH 3-CH-CH 3
Isopropyl . . \ \

/ ..\
carbocation (2°) H 0 +

H a-··
Protonated alcohol
Step J. Deproronation (lossQf proton) to form an alcohol.
•• Fast' +
CH3-rH-CJH3+:Y-'H . ) CH3-rH-:-:-CH3+FhO:

19.\•. . . H P~~2~1
llrotonateda)cohol

Other examples a,re,

OH
\
(a) CH 3-C-CH 3
. \
:
CH 3
2-Methyl propene 2-Methylpropan-2-o1
(Lsobutylene) (Ten. butyl alcohol)
. . /
(55:-00%)

Meehanism:
··CH 3 . . CH 3 · ~.. CH3
CH 3 .
. \ \~ !I-R-H\ \ -H+
CH 3-C-"::"'CH 2 + H+ --.....) CH 3--'-C-CH3 . ) CH 3-CH-CH j ~=-~) CH3-y~H3
2-Metliyl propene . . (Slow) .+ (Fast) I +.
Ten. butyl
car~cation 9\ OH·
2-Metbylpropan-2-o1
H .. H·

(b) RCH=CR2+ H 20 ~ RCH1C"-:R;

Alkene. . .\
OH
,Alcohol
. CH3
I' .:

Oi
~ I. I-CH-CH
I .
3

'H OH
. 3-Phenylbutan-2-o1
(by Mark,ownikotf's rule)
(c)
CH3 .
I
3~Phenylbut-l-ene
~H~H3
VbH
2-Phenylbutan-2-o1
(by 1,2-hydride shift)
(Ii) Oxymercuration-demercura~on: With mercuric aCetate (in THF) followed by reduction with NaBHiNaOH is also
an example of hydration of alkene according to Markownikoff's rule. The ~gioselectivity of this reaction is identical with that
. of acid-catalysed hydration.
314~ G.R,B. Organic Chemistry for Competitions

3 H NaBH4
(CH3hC-CH. CH 2 0) (CH COO)2 g) (CH ) C-CH-CH HgOOCCH --~) (CH 3hC-CIH-CH 3
(ii) THF, H 0
3,3-Dimethyl but-I-ene
3 32 2 3 NaOH I.
OOCCH 3 OH
3,3-Dimethyl butan -2-01

Cyclopentene
(ii) NaB}4, mr
•
~OH
Cyclopentanol

Experimentally, it has been found that the product of the reaction is a result of the anti-addition reaction. For example,
CH3 (i) Hg(OCOCH3hIHO~ rY~Ifl
(XI D (ii) NaBH4 . ~g
Anti-addition can only be obtained if product formation takes place by the formation of cyclic intennediate.
Oxymercuration-<iemercuration is a better process of hydration of alkene than catalytic hydration by dil. H 2S0 4 , because it
avoids rearrangement (due to the absence of free carbocation involvement in this mechanism).
(i) Hg(OAch .
R-CH=CH2 ) R-CH-CH2-HgOAc
Alkene (ii) THF/H 20 I
OH .
If alcohol is used in place of water as nucle()phile, then this reaction is called alkoxy mercuration-demercuration and the
product of the reaction is ether. Addition of alcohol works better in the presence of mercuric trlfiuoroacetate.
OCH 3
(i) Hg(OCOCF3h/THF-CH30H . I
(ii) NaBH4, OH ) CH3CH-CH 3 + CF3COO
2-Methoxy propane
CH3 .

(i) Hg(OCOCF3hIC2H50~ ~OC2H5

(ii) NaBH4 . U
(g) Addition of nitrosyl chloride (Tildens Reagent): Nitrosyl chloride (NOCI) or bromide adds to a carbon-carbon
double bond to yield halonitroso derivatives. '7

(NOCI ----? -CI +N=O); (NOBr ----? -Br +NO)

NO
. I
)C=C< + NOCI ----? ) c - c <
I
CI
+
CI-N=O
CH 3CH=CH 2 CH 3-CH-CH 2NO
(NOCI)
Propylene I
CI
Propylene nitrosochloride
The product is stable when the C3roon atom bearing -NO group does not contain hydrogen. However, if hydrogen is attached to the .
carbon atom, the product changes to more stable oxime.
NO

)c-1<H ~ )I~I=NOH
I
Cl Cl
Oxime
Unsaturated Hydrocarbons 3j5

(h) Addition of alkanes: Highly branched alkanes add to alkenes in the presence of cone. H 2S0 4 or HF (Alkylation of
alkenes).
CH 3 CH 3 CH 3 CH 3
I I Cone. H2S04 I I
CH3-C-H + H 2C=C-CH 3 0-5°C )
CH 3-C-,CH 2-CH-CH 3
I 2-~e~lpropene . I
CH 3 (Isobutene) CH 3
2-~ethylpropane Iso-octane (2,2,4-Trimethyl pentane)
(Isobutane)
.This reaction is used in the manufacture of iso-octane. .
CH 3
I
CH 3-C-H + H 2C=CH 2
I Ethylene
O-~d CH 3 -TH-1~H-CH3
CH 3 CH 3 CH 3
2-~ethyl propane 2,3-Dimethyl butane
(Isobutane)
(I) Alkenylation ofalkenes (Dimerisation): Two molecules ofisobutene (C 4 Hg) add together in the presence of H 2S04
or H 3 P0 4 at about 80°C to give an alkene, CgH16 in two isomeric forms, a dimer ofC 4 Hg and this is called dfmerisation.
CH 3 CH 3
I I
H 2C=C-CH 2-C-CH 3 +CH 3-C=CH-C-CH 3
I I I I
CH 3 CH 3 CH 3 CH 3
2-~ethylpropene (A) Major (B) ~inor
(Isobutene) (C SH I6 ) (C SHI6)
(C4Hs)
Products (A) and (B) are position isomers and on hydrogenation form the same alkane, 2,2,4-trimethyl pentane.
Similarly, styrene (Vinyl benzene) on dimerisation gives 1,3-diphenylbut-I-ene. .

!(5\-rH
~s~
CH2 + H2C=CH--fc:5\
V.nYlbe_~
~
Hou © ©. CH=CH-CH-CH3

.There are different types of dimerisation of alkenes in presence of sunlight forming cycloalkane.
H2C--CH2
2H2C=CH2 hv .. I I
Ethene H2C--CH2
Cyclobutane
(j) Diels-Alder reaction:. It is a diene-dienophile addition reaction. It forms cyclic compounds.
~CH2 ,../CH2........
CH CH2 CH CH2
I + II -II I
CH CH2 CH· CH2 ·
~CH Ethylene ........CH ,../
2 2
Buta-l,3-diene Cyclohel'ene

0 0-
~CH2 Il II
CH
CH
,.
~CH2
+
H-C-C-OH
II
H-C-C-OH
II·
0
- CH~-OH
II
CH II
0
-OH

~aleic acid
 G,R.B. Organic Chemistry (or Competitions .

(k) Addition of oxygen:· Wherimixed with i:>xygen or oxidation with peroxy a~ids (CH3C03H~ C 6 H sC0 3 H or CF3C0 3 H)
or air and passed through a silver catalyst at high temperature (200':"400°C) and pressure, lo~er alkenes add atom of oxygen to an
. form epoxides, (i.e., cyclic ethers, jn which the ether oxygen atoin is a part of three membered ring). The·reaction is a stereo-
specific syn-addition.

·c
H 2C= H2 + 2 0 2 --~
I Ag
.~H2
Ethylene .
o
Ethylene oxi!1e (Oxirane)
(1,2-Epoxyet~) .

RCH=CHR
..
+1.0
2 .2

o o
I I
RtzC=CR 2 + R'-C-oOH ~R2C-CR2 +' R'-C-OH
Alkene Peroxy acid, ,V Carboxylic acid
o . '
Epoxide

CJ
CHj
I . +CH3-C~H
, .
o
'II·
. Peroxyacetic .
-
.O
..

.
.
..
CH
0
3 ..
+ CH3-C-OH
0
11

Acetic acid .
..

I-Methyl cyclci- acid I-Methyl-l,2-epoxy

hexene cyclohexane

These epoxides on hydrolysis form diols or glycols. .

(I) Addition of ozone (Ozonolysis) : When a stream of ozone or oz6nised oxygen is passed through a solution of alkene in
an in~ solvent (ether or CH2Cl z or CRCl 3 . or CCI 4 ), at low temperature (196-200 K), the molecule adds up to form ozonide.
Ozonide is unstable, explosive compound and easily decomposes either by reduction [with ZnlH 20 or ZnlCH 3COOH or H2IPd or'
(CH 3 hS]or hydrolysis in presence of reducing agent and formscoinpounds ha~ing :)C-:-O group. This process is known"as
ozonolysis.

.I .I
. -C=C-+03
. CH2CI2
..
.
>c\I.:-01.fC<
: 1
ZnIH20 I..
-C=O+ 'O=C-
I
..
Alkene· 196-200 K 0HO· ,...ZnO Products
(Reductive cleavage) (Aldehydes or ketones o.r mixture)
Ozonide

Zinc dust is' added. to Ilreveht the formation ofH 20 2 produced by the reaction ofH 2Q and 0 (Reductive ozonolysis); .
-0 1

, CH2Ch H cY, r-CH ZnIH20

H2C=CH2 + 0 3 .. ~ I : : ,I 2 ----~--. 2HCHO
Ethylene 19~200 K O~O . - Zno Fonnaldehyde
(Reductive cleavage) (2-niolecules)
Ozonide

H
'- -0r-C
CH~Y,
1
<H ZrtIH20 .
H
I .
. H
. I
3 1 \I :I 1 H . -----...... CH~=O + O=C-H
Of--!;-O ... -ZnO . Acetaldehyde. Formaldehyde
(Reductive cleavage)
Unsaturated Hydrocarbons

196-200K

Knowing the number and arrangement of carb~n atoms in these aldehydes and ketones, the structure of the original alkene
can be worked out. . .
Note: (a) All a1kene9!typeRCH .. CHR'gives aDnxtllre of two aldehydes..
(b) ~ alkerie'6ftype R2C CHR'givesllmiXtute of aldehyde and ketone." ' . .' ..... .
.' (c) .~alkene ofth.e· type R2(;--:-Clf.2. gives a. mi?tt].lre of two ,ketones.,~ lind R'cntaY. be·.sanie;nr;difrerept,
(d)EtP¢n~(H2Cc,CI:l2)giVeson1Y.fomia1aehYde;'i; '. i ., . , ; .... ' . .

(e) Bqt-2~ne/qI~CH==CHCH3)gives~onlf''acetaldehyde. . '. ' .

(t) (CH3)2C.C(~H:ih·(2,3-cJimethYlput-2-eneJgives only~cefone(propanone).
(g) CYClobu(ene.gives,.;the product containing equal number of cinbQnatoms.
,\·!1t;·;(,;,ro?':~J":l~:~.. .' ~ '.~~) 03 .:. <[H:r-CHO

. (1l)ZnlCH3COOH .;;,·elf2~HO
Butane-l,4-dial

Butany.} ,4-dioic acid

Absence of Zn/CH 3COOH will oxidise.::.::cliOhtto -COOH~

". ":;;'~.~.·.;8
. '.'~.·'.'.' ~ "',:(i:~'~k~d~ ..OHC~Hr-CH~~~IIO' ..' .
;.i. '.:· •". .•
. '. " .
Cyclopeniene :
".':'.:' >
. . .·.•.•..•
. ; ;Pen~e-l ;5.,dial .;

So, ozonolysis of cycloalkene gives one molecule of dialdehyde. Cycloalkfidiene on ozonolysis gives two molecules (,)f ,
dialdehyde. .
HC~H2--:-CH2--:-CH (I') 203 CH~--:-CHO
'\I" II " 2 I" ,
HC-CH~H~H. (ii) 2ZnlH20 CHz---CHO
Cyclo-octa-l ,5~diene But;me-l,4-dial

CHO
(i) 203 .2H2 C<·
" I'
(ii),2ZrilCH3COOH . . CHO
Cyclohe:xa-I,4-diene Prop,ane-l,3-dial

While conjugated diene and.triene gives mainly glyoxal (dialdehyde) ~i1d formaldehyde.

H~C=CH-CH:-:-CH2 .(~:203) 2HCHO +OHC~CHO'

. Buta-l,3-diene (11) 2Zn/H20 Formaldehyde Glyo:xal '.

H2C=CH~CH .CH~CH=CH2 (i) 303 ) 2HCHO

Hexa.t,3,5-triene (ii) 3Zn/H20 Formaldehyde
.' .... ~

. (01) .Addition "f HN03 ':, Nitric acid (funung) .adds to a~arbbn:caibon doubl~ bond to yield nitro alcohol.
+
, Fl 2C ,CH 2 HO~N02 .~ CH20HCH2NO~
, . Bthene .)' . ,. .' 2·Nitroethatiol ". ' . ' . •• .
(n) Addition 'of aietyl ~hloride: 'A molec~le of ace~l chloride adds ,to a carbon-carbon double bond in prest;nc.e of AlCI 3.
to form chiaro substituted ketone,' ., ',\ . ,'.. .' ..' .
J
 G.R.B. Organic Chemistry tor Competitions

H 2C=CH 2 +CH 3COCI ----? CH~CICH2COCH3

Ethene 4-Chlorobutan-2-one
(0) Self addition or polymerisation: Alkenes in the presence of acid catalysts at high temperature (473 K) under a
pressure of 1500 atmospheres and in presence of a trace of oxygen (0.001- 0.1 %) undergo self addition. Two or more molecules
of an alkene link together to fonn a new bigger molecule of higher molecular mass. The small molecules are called monomers
while the bigger (new) molecules are called macro-moleCules or polymers and the process is called polymerisation. In such a
polymerisation no atom breaks off and the molec1!les unite by the change in the position of double bond.
CH 3
I
H 2C=CH 2 + H 2C=CH 2 H 2C=CH-CH 2-CH 3 ; C-CH2
Ethylene
(Monomer)
Isobutylene I
CH 3
IH'C=CH' n
Polybutylene or polybutene
+CH 2-CH 2 -1n
Polyetbylene (polytbene)

nCH 3 -CH=CH 2
Propene
.
Peroxides, a
or Zlegler-Natta catalyst
,
)
f CH 2 -CH
I
CHt.

. Polypropene
Polythene. polypropene and polybutene are "plastics" of industrial importance and squeeze plastic bottles
n

ate moulded from high density polyethylene. Polypropene is a harder and stronger polymer than polythene and its fibres are used
in carpets and automoblIe tyres. Polystyrene -( C 6 H sCH=CH 2 + n is used in television cabinets, housewares luggage and
packaging, etc., cis~polyisoprene fH2 =f-CH=CH! is a natural rubber.
CH 3
n. ,

[Polymer and the original alkene have the same empirical mass but different molecular masses. The molecular mass of the
polymer is generally very high. The derivatives of alkenes of the type H 2C=CHX (X may be Cl, Br, I~ CN, COOR, C 6 H s , etc.)
are also used as monomers and undergo polymerisation to fonn useful plastics.]
,
nH 2C=CH I
CI
Polymerisation
in presence of
benzoyl peroxides
) t CH 2 -CH
I
CI
tn
Vinyl chloride Polyvinyl chloride (PVC)

PVC is used for making plastic bottles, sheets, pipes, raincoats, hand bags, table mats, records, etc.
Polymerisation
I
nH 2C=CH in presence
.) of tCH2-C~Ht
CN (FeS04 + H:P2)
Acrylonitrile Polyacrylonitrile (PAN)
Polyacrylonitrile is used for making Orion and Acrilan fibres used for making clothes, carpets and blankets, etc.
(N~nS:P8
nF2C CF2
High pressure
+CF2-::-CFftn
Tetra fluoroethene Polytetra fluoroethene (PTFE)
(Teflon)
Teflon is chemically inert and a heat resistant polymer. It is very tough, electrical resistant and is used for making non-stick
surfac,e coating particularly for cooking utensils. It is also used in the manufacture of pipes and surgical tubes.
2. Substitution reactions (Halogenation): The alkyl group of the alkenes undergo substitution at high temperature.
Chlorine or bromine replace hydrogen of the alpha carbon atom with respect to the double bond of alkyl group at about 500°C
wit~out breaking the double bond (allylic substitution). The substitution proceeds by free radical mechanism. If the alkyl group
contains more than one carbon atom, then the substitution occurs at the a-carbon to the double bond.
Unsaturated Hydrocarbons

CH 3CH=CH 2 +C1 2 500°C •

Heat) CICH 2-CH=CH 2 + HCI
Propene Allyl chloride
(3-Chloroprop-I-ene)
. 500°C
CH 3CH 2CH=CH 2 +C1 2 ) CH 3CHCICH=CH 2 + HCI
But-I-ene Heat 3-Chlorobut-I-ene
NBS (N-bromosuccinimide) is a reagent used for the specific purpose ofbrominating alkenes at the allylic position.
CH 2-CO> CH2-CO~
CH 3CH=CH 2 + I N-Br' --7 CH2-CH=CH 2 + I NH
Propene CH 2-CO I CH 2-C
NBS Br Succinimide
Allyl bromide
Bond energy of C-H bond in the different environment:
". '. .. <,,". " .' ."C, / "'/,., .~ .. ::> .'
.'. .',"
Type ofHydr~en
.,
Eumple
.J ',.
(Hydroearbqll)' " ' ......
Bond Energy kcallmol(~
, :'.,'
"'.

Methyl (H3C-!1) 103.8

: 1-----.
H-:C __ H:
I
H
Vinyl (H 2C=CH-!O 108
He=:C~~if'
2 -"-_ ...... ..l

Allyl (H 2C=CH-CH:r-H) H 88
J------,
H2C=CH~T-_-HJ
,

H
Primary (0) (CH 3-CH 2-H) H 97.9
J------.
CH "'-:f-- Ji:
3

H
1--"
[(CH3)2 CH-H1 1H,:
·'I'..
Secondary (2°) 95
'

e,;;.,
CH3-i l-CH
r
H
3

Tertiary (0) [(CH3hC-Hl

Iii: 90
·: I:'
CHr--lC+-CH3
'

I
CH3

On the basis of bond dissociation energy data, abstraction reactivity for different types of hydrogen may be given as:
Allylic > 3° > 2° > 1° > methyl> vinyl
3. Oxidation reactions: Alkenes are readily oxidised. The oxidation products depend on the nature of the oxidising agent
used. ,
(i) Oxidation with cold dilute alkaline potassium permanganate (Hydroxylation): Alkaline potassium perrnanganate
(Mn0 4 +OH-) is known as Baeyer's reagent. When alkenes are treated with dilute alkaline KMn0 4 (1%) solution at low
temperature, dihydroxy (glycol) compounds are fonned. The pink colour of KMn0 4 solution disappears during the reaction.
Thus, this reaction is used as a test of unsaturation. '
. CH 2 CH 0H
I + H20+O Alk. KMn04 ) I 2
CH ' ' (Cold) CHzOH
2
Ethene Etbane-l,2-diol
(Glycol)
 G.R.B. Organic Chemistry {Or Competitions

. ' 'CH 20 H '

3H 2C=.CH2 +2KMn0 4 +4H 20 ~ II '+ '2Mn0 2i +2KOH
' C H20H (Brown ppt.)

CH 3CH, Alk. KM.ti0 CH 3CHOH "-

I~ + H20 +0
4
.CH2·
(CQld» , I
CH 20H
Propene Propane-I,2-diol
(Propylene glycol)

CH
\
I 3 ,
CH 3-C-H H-C-OH
Alk.KMn04
, II ,

(Cold)
) I
CH 3 -C-H H-C-;--OH
~But-2-ene (cis)
I'
CH 3
(Mesofonn)

CH3 CH 3

CH 3 -C..:....-H '
I HQ..:....-C-H
I ,
H-C-OH
I Alk. I04nO4
.I + I,
H-C-CH3 HO-C-H ,H~C..:....-QH
But-2-ene (trans) 'I' ' I,
CH 3 CH 3
(dl) mixture
Hydroxylation by KMn0 4 is always syn-addition.

P ~H' H'o/.
Alk:. KMn04
..
(Syn-addition)
,, ,
,.
CH3 , CH3 OH OH
1,2-Dimethyl cyclohexene 1,2-0imethyl cyclohexanediol (cis-)
[Glycols are Iillso fanned when alkenes are treated with osmium tetraoxide (OsO 4) and the product is ret1uxe~ with NaHSO 3
(ate.) or Na2S03 or H20 2. ' ' " ,

/ ' CH2 CH2-O)' , , 0 , NaHS0 ' CH 20H .

I :+O&O 4 ~' I, Os, ---~ 3
+ H 20s0 4 ] I
CH 2. . CH2..:....-Q. ',.Al!Zohol CH 20H

Hydroxylation using 080 4 is syn:'addition but witli H 20 2IHC0 2H is anti-addj.tion.

o
Cyclopentene
H~~H" A
.
,
)--{
OH 'OH"
C2~>~ C<~2~S, ~:~: ..
C2Hs~
H7 c-c"H
HO ",
LC2Hs '
"OH
(Meso)
'l ~2-Cyclopentanediol (trans-)
(Anti-addition)
can also be used for diols fonna~on. ,
, '

Hydroxylation using I2 /CH 3COOAg

.H Ii H H
F11 . NaOH ~ , R~~-R'
R-C;-'---\C-'-R "
J. ,', J ,. . . . ' I I.
Alkene PCOCH3 . OCQCH3 ' OHOH
' ..,).
Alkanediol
, UnsaJurated Hydrocarbons '321

(ii) Oxidation with aei~le potassium pennanganate or p«!tassium dichromate: When alkenes are treated with acidic or .
hot KMn0 4 0r acidic K2Cr207' glycols are fU'St formed which are further oxidised to aldehyde~, ketones or acids. Terminal
fon;nic ,acid isoxidised to CO 2 and H 20 ; . . .
CH 3CH' .' CH CHOH' '.' .
3
(a) I (H20 + 0),) I [0]) CH CHO +HCHO [0]) HCOOIl
3
CH2 · . CH20H ~[O]" Formic acid
Propene CH C O O H t [0]
3
Acetic acid CO 2. + H 20

or CH 3CH=C,H2 ,+. 4[0]' . Hot, aIk.KMn0 4 )

373-383K
cn3COOH .+CO 2 + H 20
. . R R '
. CH 3CH=CHCH 3 KMnO... .1 ) . 2CH3~0<?H; )c=C<' KMn0 4
• ~) 2R-CO-,-R
But-2-ene [0] . AcetIc aCId R' R [0] Ketone .

(HzO+ 0)
)

2-Methyl propene Acetone

(Isobutylene)
(b) Same products are obtained when oxidation is done with periodicaeid (HI0 4) or lead tetra-acetate (CH3COO)4Pbor
sodium pedodate (NaI0 4 ) . .-
The aqueous solution of sodium periodate and a trace of potassium permanganate (Lemieux reagent) isa better method both
for determining the position of double bond and for preparing carbonyl compounds.
HzO z 4 HI0
R-CH=CH-R' . )' R-CH-CH-R') RCHO + R'CHO .
(HzO+O) I I
OR OH,
Cis-diol
Formaldehyde is usuaUyobtained from a terminal alkene. Instead of permanganate, a trace ofOsO 4 has also bel,m used by .
Lemieux. . .
(c) By passing a mixture ~f ethene' and oxygen under pressure into an aqueous solution ofPd and CuCI 2 (cupric chloride)at ,
SO°C, the product is acetaldehyde. '. . .."
50°C
H 2C=CH2 + PdCl 2 + H 20 ----; CH 3CHO + Pd + 2HCI
Ethene Acetaldehyde
Pd +2CuC1 2 ----; PdCl 2 +Cu 2Ch 1
[ Cu 2Cl 2 +2HCl+t[Oh----;2CuC1 2 +H 20 .

With propene, acetone is formed.

CH 3CH=CH2+ PdCl 2 + Hi0----? CH~C.OCH3' + P~ +2HCI
. Propene . A:~one ..
(d) Oxidation of alkenes by selenium dioxide (Se02) readily affects the allylic :position and not the d4:)Uble bond.,
, Se02', .
H 2C=CH-CH 2CH 3 -"---7.) H 2C. CH-CH-' CH 3
. But-i-em: . .~ '6H '0' .

But-3~en-2-o1

. '. /.8 e02 ..

CH 3CH . CHCH2CH 3 ) CH 3CH=CHCHCH g
Pt;lnt-2-ene . I.
OH
Pent-3-en -2-01
But the following types of alkenesare oxidised to (X~diketones, i.e.,
·~a.22 G.R.B. Organic Chemistry (or Competitions

R'-CH=CH-· R".~ Rl-C-C-R"

. I I
o 0
(iii) Hydtoxylationusing peroxy acids: A mixture ofH20i and formic acid, (i.e:, HC.o3H) on allowing to stand with an
alkene yields glycol atld the addition of two -OH gr9ups in anti~position. .
. .
,,(
CH3
I
H-C
..H-1I
Hi0 2,HCOOH
or HC03H
..
(anti-addition)
CH3
But-2-ene Trans-(racetnic)

If perbenzoic acidi(C 6 H sC0 3H) or peroxyacetic acid, (CH 3C0 3H) is used then ftrstly glycols are fo~ed and ftmdly yields
oxirane (epoxide). Peroxy. formic /ilcid forms only glycol, ids strong to decompose epoxy link.

R-CH=CH-R _QI~5_C_O_~~) R-CH-CH-R H 20) R-CH-CH-R

orCH 3C03H I I .. ~.

OH OH o
Epoxide
. .

Ep? xi4e formation (EpoxldadoD) aIsonam;:;;;.v,c:2:

is

·
O
Cis-meso
-I
Cyclohexene ,---=.H=-=C-=.O-=.O-=.O.;;;.:.H~
Anti-addition
..... ~OH + Bnan.tiomer
It!g)-H
Racemic mixture·

Reactivity of alkenes for peroxy acids: More is. in the substitution at double bond, gteateris the reactivity.
Me Me Me Me
I :I. I I ,
Me-,-C ,. C-CH2-CH=CH2 . Me-C-C-CH2-CH CH2 ·
'---..--' '--:-----' V -
More reactive site . Less reactive ·0
(Highly substituted) . . .site

(iv) Combustion: .. · When: bumt in air, alkenes are oxidised to carbon dioxide and water. The ~action is exothermic because
heat is evolved;

Burn
C 2H 4 + 30 2 . ) 2CO z + 2H 20 + Heat
They bum irith luminoiIs flame and fonn explosive mixture ~th air or oxygen.
4. InsertioD,'of methylene (Carbene): Photolysis of diazomethane and ketene gives methylene. Alkenes react with
methylene in presence of light to fonn cyc1oalkanes.
CH 2N 2 .l!:4 :CH z +N 2
.Diazomethane

H 20=C=0 ~:CH2 + CO
Ketene •
". ,~. ...
Qnly si11~let carbene (CH ) is involved in alkene addition reaction.
..
.,
2
 . . " .

.' lTnsatur,ated f9vkocarhpnt ·323"

.: \ '.

.. <•.... /. . . . . CH
..' " ' ':. I 3
.... . . (eH) C--'-OK: '. ............... '..' . . . '., ' . . ' . . .." .
CH3~_2.;~~CH~+CHC13 , 3 3 ..••. ·..~.C:{I3~II~H3 + CH3-?~H +KCl:
.. ~:. ':A . '.' .CH 3 .: .
.CI .Ct . ':Tert.buty1alcohol~

SO, when an alkene reacts with chlorofoJ1}l in :p£eseq<:e:£tfPitassimntert.;'b~toxid~~ ·thereiiaddiqon of dioh1orojn~hyleiie .

(dichlorooarbene : CC1i); Methylene can also.·1)e ad~d\1V1i~'rtail-B:~erier¢'actsWitli QthI:2,ln presenoe of catalYst (Cu;..Zri) to form
cycloalkane, ' . . ' .', . .. '. . . " ' .

This reaction is known as Simmons-Smith reaction.

.. Uses ofalkenes: Etheneisused:.'· .' . , .
(i) for the manufacture ofpolythen~a:plastio:rna~rial:,Substituted.aIkeJ.1es ttpon'polymerisationfornls a number of useful
polymers such as polypropene, PVC,: teflon and natural ru~etc.:
(ii) for artificial ripening of fruits;" . ,'., .,
(iii) as a general anaesthetic; " . "., .:. . . ' . .'. ........; ..... '" .. '. . ... .'. '. . ' . ' . . . . "
(iv) as a starting material for a Iargenumberof compoundSsuclias. giycol;'ethyl ha.lides,~ethylalCohol,/ethylene oxide, etc;
(v) for making poisonous mustard gas (War gas); " . " . . ..' .
• (vi) for making ethylcne-oxygeuflame.for cutPng,andw~ldirtgtt;leials.' '. . "',

7.7 ALKYNES
Alkynescontain four hydrogen atonis less thim the coirespondingallolriegand ~echar~cteri~.edby.fu~presence of airiplebond in.
the molecule. The first and the most important member of this .seiies~s acetylene; He. CH, He,nce,;tn<? alkynes (C';H2~"':2) are '
also called acetylenes.. . .' ." _. _ . . . . . ... ! . . .'
. Nomenclature: There are, three systems for naming. alkyrtes.':·.: . ' ." .' ". . •. .' ,
(i) The common name system: '. The c9DllllonnamesofalkYtt--e$dQilot bear any relationshfp and are based onthe names-
.ofrelatedoorupounds. . .. ' .... . . ....... .-"i" ":""'. ';,', '" .,....... -'.' '. . '. .'
Formula (C H - ) _ . . . . • C(nn~onntin.e .... - . .
II 2n Z

C2 H 2 (gC-CH)' ,-A¢,ctyHlne'-
C3H 4 (CH 3C .. GH) ··-AUylene •
. C4 H6 (CH 3C==CCH 3 r croionylen~ .
.Except acetylene, other names ar~.nci 10ngeruSed~
,.;" ·'·3
..201014_·_..;......;.;...~~_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~G~.R'-l...""B~.J..Qa.r~gp.wnwi~c,..!.Cd.hloSOe:.u.mu.i,.uS'tu'£.t.fi.LIoQ~r,..!.C..sQaJmW1J;ae<!Jtlw·tii.!.:Qwns

(ii) Derlyed system: In this' system, the higher alkynes CH 3" " , .
are'regarde~ as allryl derivatives of acetylene; CH 3CH 2CH 2C==CH /CH-C=CH
.... forinula Derived name Pent-I-yne CH 3
3-Methyl 'but-I-yne
\. 'HC==CH Acetylene
(U) Position isomerism: . It is due to 1he difference in
CH 3C==CH Methyl acetylene
the position of triple bond in the carbon chain.
CH 3CH 2C-CH Ethyl acetylene
CH sCH 2C-CH ; . CH 3 -C==C-CH 3
CH;C-CCH 3 Dimethyl acetylene But-I-yne But-2-yne

H~C"", . CH 3 CH 2CH 2C,=CH; CH 3CH 2C==CCH 3

/CH-C==CH '. Isopropyl acetylene Pent-I-yne Pent-2-yne
H3C . (iii) Functional isomerism: Alkynes and dienes have
same molecular formulae. Alkynes contain one triple bond .
(iii) IUPAC system:. Names are obtained by dropping
while dienes contain two double bonds in their molecules.
-ane of the parent alkane and adding the suffix -yne. . C 4 H 6 represents butyne and butadiene.
. Alkane - ane + yne =Alkyne _
Wh~n the triple bond can take up more than one position
CH 3CH 2C=CH ; H 20=CH- CH=CH 2
But-I-yne ' Buta-I,3-diene
in the molecule, the carbon chain is numbered in such a way as
to give minimum number to carbon atom bearing triple bond. CH;-C=CH H 2C=C=CH 2
. Formula . IUPAC name Propyne' Propa-l,2-diene (Allene)
(iv) Ring chain isomerism: Alkynes and cyc10alkenes
HC=CH Ethyne
having same molecular formulae are ring chain isomers .
.' CH 3C' CH Propyne
CH 3CH;C=CH But-I-yne CH 3-C .CH;
Propyne .
CH 3.t==CCH3 . 'But-2-yne Cyclopropene .

o
.Alkynyl groups :

HC . CH ,-H) HC==C- CH3CH 2C==CH;

(-e + yl) Ethynyl
But-I-yne
) -H" . . ~ .' Cyclobutene
H3C-C-CH ~ H3C-C=C-(-e+yl) = I-Propynyl
Reactivity ofalkynes: Inspite of the fact that the two 7.9 GENERAL ME'rHODS OF. PREPARATION OF
1C-bonds .are present in alkynes, these are less reactive than. ALKYNES
alkenes) towards addition reactions (due, to symmetrical
(i) By heating ethylene bromide or ethylidine bromide
cylindrical nature ,of 1C-e1ectron cloud of alkynes). Further,
with •. alcoholic potash 'followed by sodamide (NaNH 2) in
. alkynes do not showgeometricalisomensm due to their linear
liquid ammonia (Dehydrohalogenation of dihalides).
structure. " . .' '. . .
, . Due ,to' greaterelectronegativity ofsp-hybridizedcarbon H Br [R~~B~
atoms ofa triple bon!} than Sp2 -hybridized carbon atoms Of a
H-C-C~H
I I Al KOH
c.
I·' I. NaNH2) HC==CH
)H-C=C-H
". doule, bond, the 1C-electrons' of alkyne are more tightly •. r - ~ - - - L A Vinyl bromide Acetylene
. attached to the carbon' atoms than 1C-electrons in alkene and LBcH
hence are less easily available for additioQ reactions with
1,2-Dibromoethane
electrophiles. As. a result, alkynes are less reactive than (Ethylene bromide)
alkenes .towards electrophilic addition. reactions. A
majority of addition reactions of alkynes are catalysed by H Br H Br
2
heary.metal ions stich as Hg2+ apd Ba +, etc., while t:I0 such I . I 1 I
H-C-C-H Alc. KOH) H-C=C-H
. catalysts. are needed in case of electrophilic addition reactions ··1 1 . A Vinyl bromide
to alkenes.. . . . H' Br
I, I, Dibromoethane
7.8 ISOMERISM IN ALKYNES (EthyJidine bromide)
Ethyne does not show any type o(1somerism. Oth~r alkynes
NaNH2) HC----CH
can exhibit the following types of structural isomeriSm:.
. '. (i) Chain isomerism: It is due to the difference in the AcetYlene
type of ~arbon skeleton. .
. (i) Heat of combustion of alkanes is great\!f than corresponding alkene and alkyne.
(ii) 'Cis' ~isomer has greater heat of combustion than 'trans' -isomer because cis~isomer is destabilized by sterlc hindrance..
 ~ ,/.

Unsaturated Hydrocarbons 325

Sodamide (NaNH 2 ) in liquid NH3 can be used instead of 2PH 3 +3CuS04 ---7 CU3P2' + 3H 2S0 4
alcoholic KOH. ' Cupric phosphide '
H Bi.- (Black ppt:) ,
I I Li uid NH
q 3) R-C==CH +2NaBr
'
(vi) Manufacture: (a) Laboratory method of prepara-
R-C-C-H +2NaNH 2
, I I 196K Alkyne tion of acetylene is also used 'on a large scale ·for its
Br H manufacture. The start is made with limestone (CaCOi). It is
heated at IOOO°C to fonn.quick lime, (C'hO). A mixtUre of
quick lime and coke is then heated in an electric furnace when
Note: By this method, ethene can be ~onverted mto acetylene.
calcium carbide is fonned.
Br2/CCI4' Ale. KOH ' . Heat
H2C=CH 2 ) CH2Br-CH2Br ----,-7) H2C=CHBr ~=.-4) CaO + CO 2
Ethene 1,2-Dibromoetharie Vinyl bromide
lNaNH 2
CaO + 3C 2000-3000°C) CaC + CO
2
HC=CH (b) Acetylene is manufactured by heating methane' or
Acetylene natural gas at I SOO°C in an electric arc. .
(ii) By heating 1,1,2,2-tetrachloroethane with zinc in
2CH Electric arc) HC ' CH + 3H
methanol (Dehalogenation of tetrahaJides): 4 2
CHCl 2 ' CH (c) A recent method for the manufacture of acetylene is
I +2Zn Alcohol) III +2ZnC1 2 the controlled partial oxidation. of methane at high
CHCl 2 Heat CH temperature.

.Note: This method can be used for the punhcatlOIi of ethyne and 6CH4 + 02 1500°C) 2HC=CH + 2CO + IOH 2
higher alkynes can also be prepared.
X X (d) Propyne can be prepared by the hydrolysis of
I I ,gnesium carbide. ,_; , . - \

R-C-C-H + 2Zn Alcohol) R-C=CH+. 2ZnX2 Mg 2C 3 + 4H 20 ---7 CH 3C=CH +7Mg(OH}z

I I
X X (vii) Synthesis (Berthelot): Acetylene is synthesised
by striking an electrIC arc between, carbon electrodes in the
(iii) By heating halo form . (CHX 3) with" silver 'atmosphere of hydrogen. . '
powder: Pure acetylene is obtained when iodofonn or '
chlorofonn is heated with silver powder. 2C+H22000-2500°C) HC' CH

cHfr;--·V6Ag-·H;1 CH ~ HC=CH +6AgI .

IodofoI-iii------------' Ethyne 7.10 GENERAL CHARACTERISTICS OF ALKYNES
~hysical properties : .,'.'
(iv) By·the electrolysis of aqueous solution of sodium or (1) The first three members (C 2, C 3 andC 4).are colourless
potassium maleate or fumarate (Kolbe's method): gases, the next eight are liquids while the higher one are solid. ,).
CH<::QOKElectrolysis CHCOO-' (ii) Acetylene has a garlic odour due to the presence of
II ' . II
CHCOOK
~
CHCOO-
+ 2K+
.
C th d
aoe
1 phosphine as impurity. '
(iii) Alkynes are weakly 'polar, lighter than water and
immisible with water but highly soluble in organic solvents
like ether, acetone, benzene and carbon tetrachloride.
CHCOO- -2e CH 2K+ + 2e - - 2K Acetylene is transpo)1:ed under high pressure in' acetone .,
II -III +2C0 2
soaked on porous material packed .insteel cylinders ..
CHCOO- CH 2K + 2H20 - - 2KOH + H2
(iv) The melting and boiling points of alkynes are slightly
(v) Laboratory method: Acetylene is prepared in the higher than those of correspqnding members, of alkane and
laboratory by the action of water on calcium carbide.' alkene series. This is du,e to' the fact that alkynes have ,a linear
CaC 2 + 2H 20 ---7 HC==CH + Ca(OH}z '> Structure and therefore, their molecules are rather more
Calcium carbide Acetylene closely packed in the crystal lattice as compared to alkanes
and alkenes.
Acetylene prepaI 'd by this method is contaminflted with
(v) Their melting poiI1t, boiling point anq density increase
small amounts of phosphine, hydrogen sulphide, arsine,'
with increase in molar mass.
ammQnia, etc. The evolved gas is thus, passed through
acidified copper sulphate solution. There should be no flame, Chemical properties: (1) Acidic nature: Acetylene
is.acidic in nature. The acidity can be explained on the basis of
in the vicinity of the apparatus because acetylene catches fire as
percentage of s-character of the hybrid atomic Qrbital. The
it forms explosive mixture with air.
amount of s-character in various hybrid orbitals is as follows:
H 2S +CuS0 4 ---7 CuS + H 2S0 4
(Black ppt.)
326. . ,:G.R..B.. 0r.ganic Chemistry (oF Competitions

aY~Orbital'J'e;cei>la:~~~~i;i; ~C+!l+~N~f~J4~~~~~
s p 2 ; ' : ' } } ; : . " ' ; 'Ethyne .' Sod.$JIide'··. Pisodiwut:tbyDide ... '

The Nh:cter of C,M bQ~6f.~~~iw~2';;;B#1If:t.'~~~"fi:~~

comparison to <:>-H bOll<l9fetheneandethane,>'I'b.er¢.fOre;' ~a.r.8U.10ns (aceryhdelOns). ,,'
the release of H+ ionfrotnl.analk.e~e'~datkari;;tnol~ei;.ri .~7'7"~±~~j-T:":;#;c7i#-;&~~-:-'=--:"':~~"";::;';:;;'-~
difficult and they do not ·showacidi~charac;ter. .'<," '•.,.'.,.,.' .•.•..
. +NsX'
HC==CH >HgC. CH1 >H3 6Cil;
K a= 10 - 26 '-:·K····~f l' O'~36'
..
','
..'< a... . . , '. .
K····:' " ':'1"'0:4:4'
.:"""%:i' . '',.-:'
'11":' . : . <
:..:
- "'. '-.'': "<".-,~,<,-">,-~.
::-,:-~±~~~~--'-:---.::.~----~---"-~----~.::......;,.~---'-
..••......
The hybridisation ~q4.eatotn.bOrid~dt~'!lJe:~yqiogeti~~~: ;,::',~~)~=Cf8Nai+BrCH3'~ HC .•' C-CH3 + NaBr
a large effect on the acldl:ty ofthathydrogeii~ssho'W:l1:itlthe>; .,§~di~!iCetylide .. ' . 'Pl."opyne.. . , ..

following examples: . '. ' "..·':·,·j:;. . ~r:.c.'.'.• '.H,<!.,:3~, ·., ~~.:

. .• •. ~.".'.".'.~.'.p.,~,.~.'.':H+Na·Liq.NH~)CH3--c'.
.• ""... '. C-Na .
HI HI' ,,,,':' ,."'. ,.:,:;." ',,':<"'"
..; .",: .,-
r'h, "..,v
H-C---.C-H IIC~' c~ij.~» •.,.>'·.•,:~5~:(·~C==c-Na •. +ICH3 +-+~CH3~==c~CH3
'. '.
kk (pi::n~);."·~i~~~{;y{,;t> •.' . . ..' .'
E t h a n e : : , - c1fiC.;C·Na+BrCH;CH3~C.H3C==G-CH2CH3
. . IM·2~yrie .
(PKa = 5~) .'. . , ; ' , / : , ' "Ethyl bromide. . . 'Peht-2~yne, . .
'DIe hybridisation changes fronisp3.··in~h~e't6~Ji2in .'.......•. c'1'he'.acetylinicand tertnin~l H.ar~ reactivehenfe;'salt : ....
ethene andto~p ~n ethyne, the acitlitYincoofiSes atldthepK ' fOpnatiQIlis easier. c··· '. .... .···c . ' . ..'
a
decreases, Thls IS because of the relative stability oftl!t< '. . •. .•. . . . . ......, .... Liqml ., ....•.... ' ..... '.,
unshared electronS' in .the conjtigatepasesofca6li o{fhese<: ·.··.R~~~H·· " l)R~C::::i5C,--,:Na
compounds. .'. .' . '. '. .' ···.···c:.'·· i./..~'·aIkyne . "
An's' orbital has alow~ energy .~aq;~'p>orl:ii~t'.. .•. . .' .·XK. R ' . Cl..-r' 'R' ,.
Therefore, the energy ofa hybrid ot'Qital deeteaseswitl{tbe:,;: .; ";. ~ "~~; .
Increase in's' character. The energy of hybrid orbitals 'istnthe' . ',', ..... ". HighetaIkYrt
.'0 ....' .' '.'
e'
order sp < sp2 < sp3 . . . '. ,.,... : " ,.;;,:.fIIg}ieia;Ikynesareformed when R":::":X and R' X should .
The electr?ns of the C-H bQn,d.' ~n. . · aC¢.tyle.fiJ.'a.re Str.o~~lY'.· ···])e.·?ti1tlar~r (l OJ alkyl halides, since higher 2° and 3°, alkyl
held by .car60n nucJeh This . facilit~te$therem(jvat\QLb.~l<i~sgiv¢; 'maillly alkeneswhetl they react with sodium
hydrogen as proton. . ." . c . . . . > alky'riides.·· . ...... . . . . . .' . .
. ...• ". . •........ \ . . , > . . ····'·"9H3d==C-Na+ ClCH--CH 2CH3 . ~ .
.'A cidic nature is HOH>ROH>Hc;~g~~3c~RH;. . . . . I
Conversely, th~ relative basicitiesfollow11leoid~r:'·,{··'·:· . . . '. q1 3 . ". '.'

Ii. > NH2 > !1C~C'" >RO~.>lib~;:· .. (2Q) See.. butylchloride;

On accouttt of'a~idic~ature,acciylene,fo~~t8;'~h~c~:: .'. CH3~C==CH +CH 3CH. CHCHl +NaCl

'are called acetylides oralkynid¢s~ " ' . ........... .' ." .But~2~eile'
. (a)For~atio.n~( ,sodium"a.cetyUdes'.; AcetYl~e. ;(\..(b)"For~ation c~pper
of acetyHde.: Acetylene when '..
reacts WIth SOdlUffi. mhqUld ammofllaorsodamt4e(NaN1I:l}.·pass~d through an ammomacal cuprous chloride solution, a
to form SOdciuHm a c e t y l i d e s . , .•,. .• . . •. . < . red, precipi1ate of cuprous acetylide is: fornied:This a test of .
CNa . . . '. acetylene,' '. .'.
is
~H +Na Liq.NH
3
)·· . ~H .' +~FIit'WH~+c;u2th +2NFi40H~ . W-Gu+2NH4CI
Acetylene · . M o n o s o d i u m '. CR,. ',.... ..' 'c-en
acetylide' AcetYlene . OJprousaeetylide
. CNa CNa 1" .'. .•... (Red ppt)
III· +Na Llq. NH3>111 +~R2t . , . : .
c' . . . ' ." .+2H 20
CH· CNa ,2,' ·2C.Hj~C==CfI+QI2C12 +2NRf OH ~ .
Disodium' · P r o P Y . l 1 e .. . . . . ' '. .
acetylide

,.
 ,./

Unsaturated Hydrocarbons ,·327

(a) Addition of hydr9gen. (Hydtogenation):

R-C=CH +[Cti(NH3)2tOH----7R-C C-'Cu Acetylene reacts with hydrogen in the presence~'~fa catalyst'
(Terminal aIkyne) , Copper alkynide
, , (Redppt.) , (Ni, Pt or Pd). The reaCtion occurs ip two stages~, '
-
+H 20+2NH 3 'flH ,H2) ~~2. Hi .) ~
?1I-3.. __ :
(c) Forination of silver acetyl ide : Acetylene when
eH Catalyst ' CH 2 Catalyst' CH ••
3
passed through an ammoniacal solution of silver nitrate (Tollens'
AcetYlene , Ethylene Ethane
reagent), a white precipitate of silver acetylide is formed. This is '
also a test of acetylene. ' , Ethylene can be obtained ii:J. very good yield if Lil).dlar's
CH C-Ag catalyst is u~ed. "
III +2AgN03 +2NH 40H ~ III , 'R . R
CH C-Ag Lindlar:~ catalyst) i ~C=C/
Silver acetylide Pd/CaC03 ,,'. / ' ~
(White ppt.) (Boilingquinoliile) H H
Cis-alkene
R-C=CH +[Ag(NH3>ztOH----7R-C C-Ag
(Terminal aIkyne) ToIlens' reagent Silver alkynide
, (White ppt,)
-I:" H 20 + 2NH 3
Note : Copper and silver acetylides are very sensitive to shock when, ',aut-2-ene (cis) 95%
,dry and may explode yiolently.' However, ,these c'an be This reaction is an eX:~ple of stereoselective reaction.
decomposed by acids to regenerate acetylene.' , Thus rea~tion that generates a C~double'bond or chiral
, Cu--':'C==C-Cu + 2HCI ~ HC==CH + 2CuCI,j, carbon in a product leading to 'the preferential formation of
Cuprous acetylide Acetylene
one stereoisomer over another is known as a ,stereoselective
2HN0 3 ; ,:
Ag-C==C:"""'Ag ~ HC==CH + 2AgN03 reaction.
, , (Oil,)' \.' , For 'trans' product we, take Nalliq. NH3 or Li-
Hence,tbese reactions can be'utilised for"tbe separation of ,NH3 /C 2H 50HorLiAlH 4 as a redu(:ing agent (anti::.arldition).
;acetyl~nefrom'a mixture ~ontaining etbane, etbylene and
, 'R\.. ./R
acetylene. Na/Liq. NH3 "" /.
R-C=C-R +H2 ) . C=C" '
(d) Reaction with Grignard reagent: (Alkylation of orLiAlH4 ' R/,;~ "H
acetylene and terminal alkynes). Tz'an.~-alkene

HC CH+CH 3MgI Dry) CH 4 + HC=C-MgI

ether ' R-C~G--R + 2H2 ~02 or [(CJI5)3 h), 'RCI;IiCH2~R ' P
Higher aIkyne' ' , " ,Catalyst, Higher alkane '
D
HC==C-MgI HCH 3 , ry ) HC=C-CH 3 +MgIi
ether Propyne
Iristeid of H2 , the D 2 canbe us~d to fOrin ·;ans-alkene.
H3C~ ~ / D '
R '-C.......CH RMgX
Terminal aIkyne '
+ Dry,)
ether
R '-C=CMgx + 'RH
AIkynyl G.R.
'
. Alkane'
H 3C-C=C---:CH3 + O2 ----7
But-2-yne .
D ' .( C-C", '
/' '" CH
3

Alkynyl Grignard reagents like usual Grignard reagents But-2-ene (trans)

can be used t9prepare'a varietyoiorganic compounds. (b) Addition' of halogens: Acetylene combines with
(e) Reaction with ammoniacal 12:. gaSeous chlorIDe or bromine in the dark to form di or tetraha:lides.
HC=CH+I 2 +2NH 40H ----7 IC=CI+2NH~ +2H 20 CH CCI 'H", . / /CI
c((c=k~I:I
4
(2) Addition reactions: Carbon-carbon triple ,bond is mH' +C1 2 , )
a combination of one sigma-bond arid two pi-bonds. D~e to
Ethyne,
the presence of excess of 1t-electrons, acetylene, should, be (Acetylene) 1,2-Dichloro-
very reactive and should undergo addition reactions very, ethene (trans)
readily but acttially it is not so. Ethylene has been found to be (Acetylene dichloride)
more reactive than acetylene towards electrophilic reagents. This " CHCl 2'"
, , is quite unexpected. • I '
'However, acetylene, undergoes electrophilic additi011 ~CHCI2
reactions. The addition occurs in tWo stages. In fIrst stage, , 1,1,2,2-Tetrachloro-
acetylene is converted into ethylene compound and in the ethane (Westron)
(Acetylene t~tr.achloride)
second stage, into ethane derivative, i.e., two molecules ofthe
reagent are used; Besides electrophilic addition reactions, Mechanism(See unit 5, problem 6'on page ,220)
nucleophilic addition reactions are also observed.
 , G.R.P. Organic Chemistry for' Competitions

CC" H 3C",,- ' /Br CH CH 2 , CH 3

CH3 -C==CH + Br2 4) /C=C"" II ' + HEr ~II HBr ) , I'
'Propyne Br, H 'CH CHBr CHBr2,
1,2-Dibr.omopropene 'Acetxlene Vinyl , l,l-Dibromoethane
bromide ' (Ethylidene bromide)
(trans)
Br ,Br Mechanism (See unit 5, problem 5 on page 220)
I I CH 3 -C=CH + iIei Maik. addu. ) CH -C=CH
H3C- C -C-H 3 2
I , Propyne I
Br Br . CI
1,1,2,2-TetrabromO propane 2-Chloropropene
Thus, ' a1kynes also decolourise bromine water and this I
reaction'gives a useful test for unsaturation. , +HI I
Liquid ,bromine yields tetrabromo derivative while CH 3-C-CH 3
Mar\c. addn.
bromine water or Br2/CCI~ forms;dibromo derivative. I
CI
C H B r C H ,Liquid CHEr2 2-ChIoro-2-iodopropane
" (Bromine' ,III ' ) I" "
CHEr Waiet' CH' Bromine CHEr2 In presence of peroxides, anti-Markownikoff product is
1,2-Dihromo ' Ethyne 1,1,2,2-Tetrabromo ol;>tained. '
ethene' (Acetylene) " ethane CH CH 2
(Acetylene (Acetylene HBr )
dibromide) , tetrabromide) III
. CH
+HBr~ I Peroxide
CHBr
Iodine ~eacts slowly in alcohol to formdi-iodo derivative. Acetylene 1,2-Dibromoethane
CH CHI , By passing acetylene into dilute hydrochloric add at
- ,III, + 12 Alcohol) I 6(),.,65°C in presence of mercuric ion (catalyst), only one
CH CHI molecule is added to give vinyl chloride. ' ,
Acetylene 1,2-Di"iodoethene
(Acetylene ill-iodide) ~H., ~ H~l Hg2+) rH2
Dihalid~derivati:ves are trans-isomers and the addition of CH CHCI
halogens to acetylene is,stereoselective reaction. , Acetylene , Viilyl chloride
Alk:yi:tes are less reactive than alkenes towards addition of . Vinyl chloride polym~rises' to ,yield polyvinyl chloride
'halogens becausealkynes form less stable intenrtediate. ' , (PVC), an addition polymer used in making PVC sheets, water
" 'Br2' " pipes: hoses and hand bags, etc. '
H-C==C-H ~ H-C=C-H (Less stable)
The order of reactivity of halogen acids is HI > HBr> HCI
, , ", '\/ ,Intermediate
Br > HF,butHF adds only under pressure.
+ , (d) Addition of hypochlorous acid (Chlorohydroxyla-
tion by chlorine water): Acetylene when passed into
(More stable) hypochiorous acid solution forms dichloroacetaldehyde.
Intermediate , OH
+
'CH 3- 3+' CHOH CH/
Alkynesuridergo addition of halogens, as well as other
electr~philic'addition more slowly than alkenes.

HC=C-CH 2 -CH=CH2"
Br2 (1 mole)
, )
IIICH
Acetylene
+ HOCI ~ II,
. CHCl
HOCl) I , OH
CHCl 2
""
, Unstable

Pent-I-en-4-yne CCI 4 • -20·C /H

HC==C-CH 2-CH(Br)-CH 2 (Br) r'O
4,5-Dibromopent-I-yne (90%) CHCl 2
This reaction clearly shows that alk:yi:tes are less reactive 2,2~Dichloroethanal
than alkenes towards electrophilic reagents. (a,a-Dichloro-
Thus, the order ofreactivity of halogens is: acetaldehyde)
C1 2 > Br2 > 12
(c),Addition of halogen acids: Addition of one CH 3 -C==CH + HOCI ~ CH 3 -C=CH
molecule of halogen a<;id gives vinyl halide which then adds
,Y Propyne " I I
" OHCl
another'molecule of hydrogen halide to form gem-dihalide.
The addition follows Markownikoff's rule.
Unsaturated Hydrocarbons , 329'
,
o important reagent f.or making polymers such as Orion (Poly

HOCI)
I
CH -C-CHCI
acrylonitrile or PAN) and Buna-N rubber.
3
1,I-Dichloroacetone
2
flH + I Ba(CNh) ~H2
(e) Addition of sulphuric acid: Acetylene gas when CH CN CHCN
passed through conc. H 2S0 4, it gets absorbed fonning Acetylene Vinyl cyanide,
(Acrylonitrile)
ethylidene hydrogen sulphate.
CH' ,CH 2 H SO ' CH 3 (h) Addition of acetic acid: Acetylene combines with
II +H2S0~~ II, 2 4} I acetic acid in presence of mercuric sulphate or zinc acetate or
CH (Conc.) CHHS0 4 Conc. CH(HS0 4h , BF3 (as catalyst) at 160°C. It first forms vinyl acetate and then
, Acetylene Vinyl hydrogen Ethylidene ethylidene acetate.
sulphate hydrogen sulphate H
CH
E~} :.idene hydrogen sulphate on boiling with water
produces acetaldehyde.
III +100CCH 3
CH
>~jCH3 ao CH3 CH 3 Acetylene Vinyl acetate
I 2)I<OH~ I, (Vinyl ethaooate)
CH(HS0 4 h CH CHO
OHAcetaldehyde
Unstable
H()()CCH 3 ) TH 3

(f) Addition of water (Hydration): Alkynes cannot
be hydrated more easily than alkenes because of their low
reactivity tc:>wards electrophilic addition reactions. Further
when acetylene is passed through 40% H 2SO 4 containing 1%
HgSO 4 at 80°C, a water molecule adds upto give
acetaldehyde.
CH(00CCH 3 h'
Ethylidene acetate
Vinyl acetate on polymerisation fomis polyvinyl acetate
(PVA), used in' plastic industry and ethylidene acetate on
heating at 300-400°C yields acetaldehyde and acetic'
anhydride.

fiR
,CH
+'HOH 40%H 2S04 )
1% HgS04
[112) 1
CHOH
TautOmerises)
H

CHO
T3 /
CH3CH"" '
00CCH 3
Heat
) CH 3CHO'
"OOCCH 3 300-400"C Acetaldehyde
, Acetylene Vinyl alcohol Acetaldehyde
(Unstable) Ethylidene acetate

R~Cli + HOH H':~~L) [R1~ ),] (i) Addition of alcohol : In presence ofNaOH or KOR
+ (CH 3COhO
Acetic anhydride

(Enolic) , or a mercury. salt, acetYlene reacts' with alcohol (AlcoQolation

! Tautomerises
of alkynes) to form ethyl vinyl ether.

R-C-CH 3 CH 3
I ',' I
o CHO
, Ketone' Ace,tyiene Ethyl vinyl ether Acetaldehyde
This is called keto-enol tautomerism. '
+CzHsOH
However, if the unsymmetrical alkyne is non-tern;rinal, a
mixture of two isomeric ketones is obtained in which methyl BF3
HC===CH ,+ CH 30H HgO) H 2C=CH-0-CH 3
ketone predomina~es. For example, Acetylene 'Methanol Methyl vinyl' ether
H 2 S04 (dil.)
CH 3CH 2 --C=C-CH 3 + HOH-----~ e a!'
Pent-2-yne HgS04, 70" C CH10H
)
, (Non-terminal alkyne)

~ ~
CH 3CH 2CH 2 -C-'CH 3 +CH 3CH 2-C--CH 2CH 3 Such a reaction is termed vinylation.
Pentan -2-one Pentan-3-one (i) Addition of ozone (Ozonolysis): Acetylene
(Major product) (Minor product) combines with ozone in presence of some inert solvents such
(g) Addition of hydrogen cyan~de: The addition of a asCC1 4, CHCl 3 orCH2Cl 2 at low temperature (196--200 K) to
form an ozonide which on decomposition with zinc dust and
molecule ofHCN occurs in the presence of barium cyanide or
CuClIHCI (catalyst). Vinyl cyanide is formed. This is an water or H2IPd (reductive cleavage) yields glyoxal.
330· G.R.B. Organic Chemistry for Competitions

CH CCl4' " /' CH~O, ,CHO' (iii) Linear polymerisation: When acetylene" is
II '+0 3 ~ ,/ ,"I I, Zn!lI2q, I" + H 2,0' 2
0,' passed into cuprous chloride solution containing NH 4 Cl,
CH 'CH-O -Zno CHO linear polymerisation occurs forming monovinyl acetylene
Acetylene Ozonide Glyoxal and divinyl acetylene.
~ 2HCOOH CU2Cl2
HC===CH + HC===CH --~~ H 2C=CH-C==CH
Glyoxal is further converted into formic acid. Formic acid Acetylene NH4CI Monovinyl acetylene
0, (Two molecules)
1\ Zn/H20 HC-CH 1300. molecule
CH 3 - .~-:-CIH )
I (-znO) H 2C=CH-C==C - C;fI=CHi
0-0 Divinyl acety16iie' .
Propyne ozonide
Vinyl acetylene on reduction with H 2 /Pt in:presence of
CH3-C-C-H BaSO 4 forms buta:-l,3-diene.
! A
Methyl glyoxal
H 2C=CH-C==CH
H2 /Pt
) H 2C=CH-CH...:-CH 2
Vinyl acetylene (Ba804) , Buta-I,3-diene
(2-Oxopropanal)
[Higher alkynes form diketones which are further Butadiene and vinyl cyanide form polymer Buna
oxidisedto carboxylic acids. N-syntbetic rubber:
o Butadiene adds to acetylene (Diels-Alderreaction)to
CCl 4 /, form addition product.
R-C===C-R' +0 3 ~'R-H-R'
Alk:yne Reductive ~CH2 /CH2"
" cleavage

-'
·0-0 CH CH HC CH
Ozonide
I + III II II
CH CH HC CH'
~CH2 Ethyne "CHr'
R-C~C-R' + H 20 2 ~ R-COOH + HOOC-R']
Buta-l ,3~diene Cyclohexa-I,4-diene
II I A~ids' ' ' ,
o 0 But if 1~alkynes react with Cu 2Cl2 con~ining NH 4CI and
. Dia1ky1 glyoxal air, oxidative coupling takes place and dimerised products are
formed.
(k) Self addition or polymerisation: Acetylene .
Cu 2Cl 2
undergoes polymerisation yielding different types of HC==CH + HC==CH . ) HC=C-C==CH + H2
polymeric compounds under different conditions : ' NH4CI,air
,(i) ,Cyclic polymerisation: When, acetyle~e is passed, CU 20 2
2R~=CH, ) ,R-C==C-C===C-R +H2
through a red-hot metallic tube at 600°C, cyclic polymeri- ~CI,air

'0
sationtakes place with the formation of benzene.'
When monovinyl acetylene is treated with HCI. it forms .
3HC==CH
Acetylene
Red hot
(~g!~)
I
~.
chloroprene which is used for making synthetic rubber like
substance; neoprene.
. , Benzene, Cl '
Propyne on heating trimerises under similar, conditions
and formsmesitylene (1 ,3,S-trimethyl benZene). H 2C-:-CH-C==CH
HCI
) H 2C-.:-CH-C=CH 2
I

3CHr-C==CH Red hot iron tubi

Propyne
, Heat
CH3

HC
3
0'"
~ CH3
Vinyl acetylene 2-Chlorobuta-l,3-dJ.ene

copper or its oxides, a cork like substance cuprene is

(Chloropr~ne)

(iv) When acetylene is heated in presence of spongy

, . Mesitylene produced. This is'used in the manufactUre of linoleum.

(ii)Acetylene dissolved in tetrahydrofunin polymerises , (I) Addition of arsenic trichloride: . In the presence of
into cYclo-octa-l,3,S,7-tetrene in presence of Ni(CNh and a11hydrous aluminium chloride, acetylene combines with AsCI 3
under ~igh pressure. to yield,Le\.vii;ite, a powerful poisonous gas. -
CH-:-CH
He CH +CI-AsCl 2 ~ CICH=CHAsCl 2"
HC' / "-cn Acetylene 2-Chlorovinyldichloroarsenic
, 4HC-CH
Acetylene Tetrahydrofuran II II (Lewisite) ,
(Solvent) HC CH
High pressure "-CH=CH /
Cyclo-octatetrane
 Unsaturated Hydrocarbons 331'
It is more poisonous than mustard gas and was u800jn .(0) Som~ other addition reactions rim be sumrnemed as: .
World War~II.The British chemists developed an antidote for .• . '. .... . .. ..... '.' NaNH .. ' . . . ' '. . .
2
Lewisite and natIled it·as BAL (British Anti Lewisite) . (i}'HC~H+CH2~fh ' H 0)HC .··C-CH 2CH 20H
'CH2~H-CH2 . .. '
.....•..... '.~ ..... 2

I . I' I . .' 'Ethyleneoxide .... . .;

8H 8H OH
BAL O' OR
';. ....... ·.11 NaNH · · . 1
. .... (m) Alky,!ylation of carbo'}yl compounds :. Terrnm.·al.. ' (it) CH3C~CH+CH3CC2Hs ···.H()2) CH C==C-C-C H
aJkynes (contalQUlg -:-:-CH, a methme hydiogenatom) can add . 3
I 2 s
>
... on to. c=o gro.up in presence of sodiuq1 alk~xide or·'
Ethylmethyf 2 .· ..
ketone . CH 3 .
copper acetyli(l~ catalyst and. formalkyndiol (along with small.
atIlount of alkyneol),' This is called alkynylation or .(iii) Propargylicbromination .'
ethinylaticu. . . ............... •........... .....~.'
' : .. ' . '.

H
,8$ I 0._ RONa. .... . ' .'. .' . • . . .CH2 --:C ""
(1) HC==C-H + H-C . 0 ........,-4. HC==CCH20H (:Hr-C==CH+ I. .' /NBr
Propyne" . CH 2-C/.
., '. Ethyne" Formaldehyde . Prop~2~yn~1-ol
. .'. . I
H o
. ··1.··· ....... '.. ' ."; N-Bromosuccinilllide .
HC==C-CH 20H+H--,-CO ~ HOCH 2C==CCH 20H o
. ." But-2-yn-l,4-di'ol .'
.' '. '.' ..... '....... CH 2 -C
I
(ii) CH 3--"C=CH+ H-'-C~Hj CH 30Na)
Propyne '. . .' I .. ' .
. BrCH2-c~H+1
, '. Propargyhc..
.'
CH 2-C
)NH
.. ' O' . . . . .' . bromide'· .' I .'. .
Acetaldehyde '...... ; . " ...... O. .
(3) ~ea~don$with$illphur, 'ilitrogenand ammonia:
. . '. . .
. CH r ":C=C-.-:.CH 2-CH 3 ·· '. ..'. •'(a)Wben acetyleoeispassed .oVerheated iron pyrites at
.. . r . ,.' .
. . OIl .. 300°C. ifoornbines with stllphur to form,tbiQpb~Jie.

.
.

. .... \,'
..
V CH 3 .
. ".' .
. ·······~2+s'S·~!L~~-
'·'(iii)CH3~~-~i +O==='C( .•.. ' ...~~
'., CI:I 3 . rhloPhette '
'. Acetone·
(tl)'Wb~~ari:el¢ctric SP~ki$"pas~ed througpa.rmxmte 'of .
.' .. ' ..... '.. .... . ' '. ···ac~tYletiemld!Ilittqgen,hydtQcyanieaciid is form~.
·CH r -.C' C , ' / .. ,.CH3>.· .... :.:, ....:... '. '.. ". ...
.'. '. . )c«.> ' + LtCl .. ' II1'+,Ni E~:~c)2HCN .' . 'ci
. ',' ..•... ' .... .'/... ..... . . { HO
3
CH . . ..... (c)~cetyletie:~ombine!?Witharrimonia
at high
. '...• (iv)Terrilin:~ralkyne(R~C-H) on reaction with temperatnreto· fol1l1Pyrrolew
certainhydroxy compounds can also undergo, ethiny1ation . . ~Ii ". '. .' p <. CH~H
. "2111' +NH3 ... e-Pyrite) 'II '11 +lIi··
. 'witbtheremoval ofHiO
, . CH '... ,Heat CH CH
H--C==C-JI +H.oCH t l\JR 2~ H-C-C~CH2N~2
+lIo···
Acetylene
. ....
" ¥ .H
.
. (nJ CarbonylatiQn :Acetyl~ereactswit1i(CO +I-I~~) .•. . .' .... '.. ' . .. .....':. . pyrroie
'or (CO R0H)~n~esence of
+ nickel<:atalyst~ndfo:rins(4)OXidati6n'::DifferentoXidation' pn>ductsare.
. a.~Wlsaturatedacid o:r estet.. '.. ' . obtained with differentreagents:. ....
. . '.. . .... . . (a).BunJing (CQm~ust,oQ):A(:etylene burps'. with
.. a~===CH+CO+Hi) .'. Ni\. lItC 'CHCOOH .. slJ1okyflameirlexCessofaitUndercontrolledstipplyofair, it
..... ..' '. .'. .• '. •..... Prop-2-erioic acid ; ·bwns;WitIia brig)lt lighfwhi~h:is;ilijuriQuS· to eyes> The
. . ..... '.' . . burning'isrughlY.· exothenmc'ait& al&ieaniount heat is . of
. 'HC==CH +CO+HOCH 3 Ni·).· H 2C=CHC()OCH3 ptoduced;TheoxY~aeetylene;flanie(blue.flatne)is used for
. Ester
 G.R.B. Organic' Chemistry for Competitions

welding and cutting purposes and gives a temperature of about (e) With SeOz (Selenium .dioxide) : Acetylene is
3500°C.. oxidised to glyoxal (ethane-I,2-dial) with se0 2.
2C2H 2 +50 2 ~ 4C0 2 +2H 20; AH=-1300k) CH CHO
(b) With alk. KMn04 solution: Acetylene is finally III + 2[0] se02 ) I
CH CHO
converted into oxalic acid with cold, dilute alk: KMnO 4 Ethyne Glyoxal
is
solution and pink colour of the soluti9n dischargoo.
Se02
CH Alk. KMn04 COOH CH3 -C==CH +2[0] -~)CH3COCHO
1\1 + 4[0] ) I Propyne 2-Ketopropanal
CH COOH
. Ethyne Oxalic acid (I) With chromic acid (K ZCrZ0 7 + HzSO 4): Acetylene
Alk.KMn04
is converted into acetic acid and orange colour of the dilute
CH 3C==CH +[0] . ) CH3-C-C---OH acidified dichromate changes to light green.
Propyne 25-30"C . AA
CI1IH
+ H 20+[0] ~
cI H 3
. 2-0xopropanoic acid .
(Pyruvic acid) CH COOH
Acetylene Acetic acid
Alk. KMn04
CH 3 -C==C-CH 3 + 2[0] 30"C) CH 3-C-C-CH 3 Oxidation of alkyne is slower than that of alkene. Thus,
But-2-yne 11 11 only double bond can be oxidised leaving behind triple bond.
o 0
B\ltan -2.3-dione

10 + H 20]) 2CH COOH

3 CH 3C=CCH 2COOH +C 2H sCOOH
EthaD.oic acid
Peroxy formic acid (HC0 3 H) hydroxylates'C=Cwithout
(c) With acidified KMn04: ,Acetylene is converted affecting C=C bond.
into formic acid with a rupture of triple bond at high
HCOOOH
, temp~ature. C2HS-C C-CH=CH2 )
CH
C 2H s-C==C-CH-CH 2
III + 3[0] + H 20 ~ 2HCOOH
CH Fonnic acid
I I
OH OH.
Acetylene
(5) Substitution reactions: When acetylene is passe9.
R-C==CH+3[0]+H 20 Heat) RCOQH+HCOOH through sodium hypochlorite solution at O°C in absence of
(d) With hot acidic or alkaline KMli0 4 : light, hydrogen atoms are replaced by chlorine atoms with the
formation of 1,2-dichloro~thyne. •
•
CH 3 ......,...C=CH +[0]' lOO-llO"C) CH COOH +CO CH CCI
KMn0 3 2
Propyne 4 III NaOCI ) III
CH O°C CCI
In contrast, non-terminal alkynes on oxidation with hot
Ethyne 1,2-Dichloroethyne
alkaline KMnO 4 gives only carboxylic acids.
For example, (6) Isoinerisation: (a) On heating with alcoholic
KOH or NaNH 2 in inert solvent, the triple bond of l-alkyne is
Alk. KMn04 shifted toward~ the centre to form an isomeric 2-alkyne.
CH 3 -C==C-CH 3 +4[0]
.But~2-yne
lOO-110°C )
CH CH -C=CH AlcoholicKOH) CH -C===C-CH
3
3 2 3
CH 3COOH + HOOCCH 3 But-l-yne (Heat) . . But-2-yne
Ethanoic acid (2 moles)
(b) On heating with sodamide (NaNH 2 in liquid NH 3 ),
Alk. KMn04 the triple bond shifts towards the end.
CH 3CH 2C-C-CH 3 +4[0]
Pent-2-yne 100-110"C NaNHa · H 20
CH 3-C=C-CH 3 ' ) CH 3CH 2-C==CNa )
CH 3CH 2COOH + HOOCCH 3 But-2-yne (-NH 3) Sodium alkynide
Propanoic acid Etbanoic acid
CH 3CH 2 -C-CH
So, it is possible to detennine the position of triple bond But-l-yne
in an alkyne molecule by alkaline oxidation with KMn0 4 .
Unsaturated Hydrocarbons

(7) Oxidative-Hydroboratio.. : Alkynes react with BH3 (in THF) and fmally converted into carbonyl compounds.

3C~3-C==CH BH3 , THF ) . (CFi3~H'-:""CH-hBHP2' OH; 3CH 3-CH ~ Tautomerise\· 3CH CH CHO
3 2
Propyne Propanal
Thus, this method is useful for preparin,g aldehyde from terminal alkyne, which is otherwise not possible by hydration.
o
H 2S04
.------.....::....-.:...--+
Ie

CH -C-CH
3 3
HgS04 Propanone
CH 3-C==CH
. Propyne (i) BH3> TIIF .
' - - - - - - + CH 3CH 2CHO
(ii) H20 2, OH- Propanal
Higher ketones can also be prepared by this method.
rHO
~. I ·
Tautomenses) ?!
R-CH=C-CH 3 R-CH2--':"C-CH 3
(enol) . Ketone
o o
CH 3-C==C-CH 2CH 3
(i) B2H6, THF
------''--'--~)
I
CH3-C-.CH 2CH 2CH 3 +CH 3CH 2-C-CH 2CH 3
I
.. Pent-2-yne (ii) H20 2• OH- . Pentan-2-one . Pentan-3-one
(Major) (Minor) .
Aldehydes can likewise be prepared from terminal alkynes, but to avoid complications due to double addition.of diborane,
bulky sterically hindered boranes such as (1,2-dimethylpropyl) borane commonly known as disiamylborane (R2BH) is used in
place of ~H6'
(i)R2BH
CH 3C==CH ----=----"7) CH 3CH 2CHO
Propyne (ii) H20 2 , mr Propanal

Here, R2BH (abreviated as Sia2BH) is disiamylborane, i.e., [(CH 3 hCH-CH-hBH.

. . . . .I
CH 3
Uses: (i) Acetylene is used as an illuminant.
(ii) It is used for the production of oxy-acetylene flame. The temperature of the flame is above 3000° C.1t is employed for
cutting and welding of metals.
(iii) Acetylene is used for artificial ripening of fruits.
(iv) It is used as a general anaesthetic under the name Naracylene.
(v) Acetylene has synthetic appliCations in synthesis of cis and trans alk~nes and methyl ketones. It serves as a starting
material for the manufacture of a large variety of substance like acetic acid, ethyl alcohol, vinyl plastics, synthetic rubbers such as
Buna N and synthetic· fibres such as Orion.
(vi) On electrical decomposition acetylene produces finely divided carbon' and hydrogen. Hydrogen is used in airships.
7.11 . TESTS OF UNSATURATION
Unsaturation means the presence of double or triple bondlbonds in the molecule of the compound. The tests of unsaturation
are actually the tests for the detection of double or triple bond. The following two tests are generally performed for unsaturation..
.1. Baeyer's reagent: It is 1% KMnO 4 solution containing sodium carbonate. It has pink colour. To an aqueous solution .of
the compound a few drops ofBaeyer's reagent are added. The pink colour of the solution disappears on shaking and a brown
precipitate of Mn0 2 appears. The decolourisa,non of pink colour indicates the presence of unsaturation in the compound.

[:> <:1
Note: . (a) This test is also given by aldehydes qr primary and secondary alcohols which are readily ox!.dised. . .

. (b) AJk_ wiiliohy hydroge. atom on ... =tOn £0.-"" double bo.d c do 001 ,oow ""..,,'

2~ Bromin~arbon tetracbloride test: The compound is dissolved in carbon tetrachloride or chloroform and then a few .
drops of5% bromine solution in carbon tetrachloride are added to it. If the colour of the bromine is discharged, i.e., disappears, it
indicates the presence of unsaturation in the compound.
 334' G.R Ii. Organic ChemistQ?for CO'Ppeiitious

Note : This test also fails in the case of alkenes of f!!e type

Besides the above two tests, l~al.k)'nesgive a white precipitate when passed through allllri6niacal silver nitrate solution
(Tollens' reagent). . ., ..
The double and triple bonds are located by the identification of the products of ozonolysis .
. Degree 01 Unsaturation
The number of pairs of hydrogen atoms that a-molecular formula lacks to be an alkane (CnHZn+Z) is called degree of
unsaturation and this value is also called the index of hydrogen deficiency.
For example, amolecularformula, C 4 H 6 has 2° ofunsaturation, because a molecule with four carbon atom needs IOH atoms
to be an alkane. It has 4Hatoms (or two pairs of hydrogen atoms) less than alkane.
. (C~H6 +2H z ~C4HIO)
So, C 4H6 with 2° of unsaturation can· have the following possible isomers:
(i) H 2C=CH-,CH=CH 2, or :H 2C=C=CH-CH 3 ;
(ii) HC-C-CH 2-CH 3 , or H 3C-C==C-CH 3 ;

(iij) 1: l or or 1
The number of degree ofunsaturation in a hydrocarbon is given by:
or D; (iv) LSJ
2nl +2-n2
= 2
where, nl is the number of carbon atoms; n; is the number of hydrogen atoms.
F·or exampIe, m
. C H h d f . ' . 2 x6+2-12
6 12' t e egree 0 unsaturatlon IS =, 2 =1

So, C 6H12 with 1° ofunsatuiatiol1 can have different arrangements.

(i)~ or'~ ,or ~

(ii)~. or '

(iii) >=< or or

(iv) 0 or or

Other examples have the following degree of unsaturation:

(i) C6H6 ---t 4° (ii) CSHg ---t 2°
(iii) C7HlO ---t 3° (iv) CgH12 ---t 3°
(v) ClO H16 ---t 3° (vi) C 12 H lO ---t 8°
(vii) C 3 H 3Cl 3 (It is like C 3 H 6 ) ---t 1° (viii) C 3 H 40 (It is like C 3 H 4 ) ~ 2°
(ix) C4H sN (It is like C 4 H 4 ) ---t 3° . (x) CsH9CI (It is like CSHlO) ---t 1°
Hence, degree of urisaturation induces double bonds, triple bonds and rings.

ILLUSTRATIONS OF OBJECTIVE QUESTIONS

J. The shape of but-2-ene is:
(a) planar (b) . tetrahedral
(c) linear (d) pyramidal
~ns. (a)]
Unsaturated Hydrocarbons 335

2. The molecule that will have dipole moment is; (a) cis-l,2-dichlorobutane
(a) trans-3-hexene (b) trans~2,3-dichloro-2-nexene
(b) trans-2-pentene (C) cis:l,2-dichloro-l-hexene
(c) 2,2-dimethyl propane (d) trans: r,2-dichloro-I-hexene
(d) 2,2,3,3-tetramethyl butane t\ns. .(d)] .
~ns; (bH 5. I-Pbenyl-2-chloropropane on treatment with alcoholic
3. Which of the following cannot be obtained by oxidation of KOH /sives.mainly:
alkenes with potassium pennanganate followed by acid (a) l-phenylpropan-l-ol . (b) I-phenyl prop~-2-o1
hydrolysis? . (c) I-phenyl propene (d) 2-phenyl propene. '
(a) Carboxylic acid (b) Aldehyde~ t:\ns. (c)l
(c) Ketones (d)C0 2 ' 6. Allene' (C 3 H4 ) contains:
~DS. (b)] , (a) one triple' and two double bonds
4. Find the identity of compound [B] in the following reaction (b) two double and four single bonds
sequence; (c) two triple and one double bond
(d) . one double bond and one triple bond
HC-C-r--:Na + CH3CH2CH2CH2Br ----? [AJ,
t:\ns. (b)]
[A] + C1 2. ----? [BJ
11l1Ole 11l1Ole

7.12 INTEACONVEASIONS
(i) Conversion of ethane into ethene : (Alkane into alkene)

CH 3-CH 3
,Ethane

(ii) Ethene into ethane: (Alkene into alkane)

.. (iii) Ethane into ethyne (acetylene) : i.e., alkane into alkyne

Ale. KOH) HC eM
or NaNH2 Ethyne

(iv) 'ltthyne into ethane: . (Alk:yi1e into alkane)

(v) Ethene into propene: Ascending in alkene series.

HI KCN [H] HN02
H 2C=CH 2 ~ CH 3CH 21 ~---+) CH 3CH 2CN
Ethene Iodoethane . Propane nitrile
(Ethyl cyanide)
Reduction
. ) CH 3CH 2CH 2NH 2
Propan-l-amine
I
) . CH 3CH 2CH 20H
Propan-l-ol .

PBr3
. Ale.
CH 3CH==CH 2 (KOH CH 3CH 2CH 2 Br
Propene l-sromopropane

H2C=CH z ~ CHjCH 21 Li(CH3h

Cu
Or ) CH 3CH 2CH 3 .Alc. ) CH CH=CH 2
3
Ethene Iodoethane . Propane KOH Propene
. . ::'l:'<~

"'336 G.R.B. Organic Chemistry for Competitions

Or H 2= HI CH CH I CH 3I1Na' CH CH CH
C CH 2~ 3 2' ) 3.23
Propane

(vi) Propene into ethene: Descending an alkene series.

H0
CH 3-CH=CH 2 03/ 2 ) CH CHO
3
Propene Ethanal

(vii) Acetylene into propyne (methyl acetylene): (Ascent)

HC==CH Na)' HC==CNa CH 3I) HC===C-CH 3

Acetylene Monosodium Propyne
acetylide

(viii) Propyne into acetylene: (Descent)

CH~CH
~~)
.Lindlar's catalyst C OJ/H 20 PCls ) CH CHCl
CH 3C=CH ) H3 - 2 ---7) CH 3CHO 3 2 HC=CH
Propyne Propylene Acetaldehyde Ethylidene Acetylene
chloride
(ix) I-Butyne into 2-pentyne : (Ascent)

f " ' l l NaNH2

CH 3CH 2C-==\..-ll· ) CH 3
CH 2C -r<'
~-Na CH31 ) CH 3CH 2-C-r<CH
~ 3
But-l-yne . Pent-2-yne

(x) l-:Butyne into 2-pentanone: (not more than three steps)

7.13 SEPARATION OF ALKANE, ALKENE AND ALKYNE OR SEPARATION OF ME"rHANE

OR ETHANE, ETHYLENE AND ACETYLENE
The gaseous mixture is passed through ammoniacal cuprous chloride solution. The alkyne (acetylene) reacts with Cu 2Cl2 and forms a
red precipitate. It is ftltered. The aIkyne or .acetylene is recovered by decomposition of .the precipitate with an acid.
C2H2+Cu2CI2+2NH40H~ C2CU2 +2NH 4CI +2H 20 .
(Red ppt.)
C 2CU 2 +2HN0 3 ~ C 2H 2 + Cu i(N°3h
The remaining gaseous mixture is passed through concentrated sulphuric acid. Alkene (ethylene) is absorbed. The hydrogen
sulphate derivative is heated at 170°C. .
. Heat.
C 2 H 4 + H 2S0 4 ~ C 2 H s HS0 4 1700C) C 2H 4 + H 2S0 4,

The methane or ethane is left behind.

Unsaturated Hydrocarbons

7.14. DISTINCTION BETWEEN ALKANES;' ALKENESAND ALKYNES OR DISTINCTIOt:4 BETWEEN

ETHANE, ETHENE AND ETHYNE '

1.

2. Nature Unsaturated.. . Unsa~ted.

Single bond between carbon atoms.· D6uble bond between tWocarbo~ Triple bond between two carbon atoins.
Each carbon atom is sp3.hybridized. a(oms. Bothcarbpnat()msate sl:
Both,carbonatoms are sp-hybridized..
~C-C~ hybridized.
.·.:.·>C·c(
Bond length : 1.54 A . L34A' 1.20A
Bond energy: 83 kcal mql-I 192 kcal mol~1

3. Burning Burns'with nonluniip.ousflame. Burns with lUminous flame.

~H6 + ~. oi ----:-7 2C02 + 3H20 HC 2H4 + 302 2C0 2 + 2H 20

4. Reaction with H2 Forms alkane forms alkene and alkane;

C"H2n + H2'~
.. 300°C
CIIH 2n+£
Alkane' .
CJ.f . +H .~ CH
U
IT 2n-2 . 2 .. 3.00°C Aike~

C2H.i + H2 ~ C2H6- .
C,jH2n + H2 ~ C"H2n+2
300°C Alkane

5. Reaction with cone. Addition. Addition.

H 2S04 and hydrolysis . ~H4 + H,2S04 ~C2H5H804 ~H2 ~ CH 3CH(HS0 4)2

~ ~H50H H20) CH3CHO

. Alcohol Aldehyde

Decolourises. . Decolourises.
Dibromo derivatives,. Tetrabromoderivatives,
, ~H4 + Br2 . ~ C2H4Br2 ~H2Br4:
7: Baeyer's reagent Decolourises. Decolourises..
(Alk. KMn0 4 ) Glycol is formed. Oxalic acid is fonned. -
C~. . CH 20H CH COOH
~. +H20+0~. I .... III +40·~·1··
CH 2 ' . . ···CH20H CH· COOH'

8. Ammoniacal Cu 2C12 ' .Red precipitate

. Cli. ) CCu
III + Cu 2C12. + 2NH40H. ~ III"
CH. . ceu
(Red)
+ 2NHi::1 :- 2H 20
9. Ammoniacal silver . White precipitate
nitrate CH .', .C-Ag.
III + 2AgN03 + 2NH40H.~ III ~. '. .
CH . . C-J,\g
. ,. (White) .

+ 2NH4N0 3 + 2H20
,338,' . G.R.B. Organic Chemistry (or Competitions,

hOME-SOLVED PROBLEMS (b) Ethyneand its derivatives will give white precipitate
with ammoniacal silver nitrate solution. ldention the-
Problem 1. Write the structures of all the isomers of condition under which this statement is true. '
dichloroethene. which one of them will have zero dipole Solution : (a) 2~Methylpropene . reacts with HBr in
moment? presence of peroxide as' the addition '. occurs . through
Solution: There are three isomers of dichloroetherie. anti-Markownikoff's rule.
CI-C-Cl H-C-CI H-C-CI CH 3 CI:I3
· I , I , I . I Peroxide' '. I '.
H-C--'-H H-C-CI CI-C-H CH 3-C=CH 2 + HBr ) CH 3-:-CHCH 2Br
I,I-Dichloroethene' Cis-f,2-Dichloroethene Trans-! ,2-Dichloroethene 2-Methy!propene . Isobutyl bromide
',.(i)·' '(ii) (iii)
(b) Only those derivatives of ethyne will give white
The'structure (iii); i.e., trans,;,isomer has zero dipole precipitate with ammoniacal sHyer nitrate which possess
moment. . . acidic hydrogen atom, i.e., R-C!:1!5!!CH. The derivatives
'f'roblem2.Propene reacts with HBr to give isopropyl ,R tC==C-R 2 do not give precipitate with ainmoniacal silver
bromid~ Qut does not give n-propyi bromide.. nitrate. "
.. ' Solution: The addition of HBr on propene takes place Pro~lem 7. 36.4 g of 1,1,2,2-tetrachloropropane was'
in accordance to Markownikoff's rule, i. e., negative p.art ofthe . heated with zinc dust- and the product was bubbled through
additive goes to that carbon atom which is linked with lesser ammoniacal AgN03' What is th~, mass. of. preCipitate
nJ.1ll1ber of hydrog~n atQms. The addition of an electrophile obtained? Give equations for the reactions involved. .
involves the intermediate' formation of a more stable Solution:
· ,',. +.'. . +.
carbonium ion. (CH 3hCH is mo~e stable, than CH 3CH 2CH 2. CI Cl
. carbonium ion; , I I
CH 3-C-C-H
Problem 3. Acetylene is acidic but it does not react with , I I Propyne
NaOH or KOH. Give reason. CICI (Mol; mass 40)' .
Solution :~cetylene.is very weak acid. The value of Ka is 1,1,2,2-Tetrachloropropane
. near about 10:-25 . Thus, it does notreact with NaOH or KOH but (Mol. mass 182)
·.reacts with very strong base such as NaNH2' . " . Mass of propyne obtained from 36,4 g of
. '. Problem 4;Ethene'01z:treating with Br2 in presence of , " 40 '
.$odium "chloride forms i:l mixture' of CH 2CICH 2Br and 1,1,2,2-tetrachloropropane == 182 x 36.4= 8 g
CH 2BrCH 2Br. Give reason.
Solution: The . ,addition . of Br2 follows ionic CH 3C==CH + AgN0J + NH 40H ~ ~H3C=C-Ag
,mechanism.. 'The intermediate carbonium ion formed is Ag-salt
, (Mol. mass 147)
attacked by Br- as well as byCl- given by NaCl: .
+ NH 4 N0 3 -+ H 20
+.
H 2C=CH 2 · - '---'-"::"::---'-"'-:"'~ HiC-CH:i Mass· of precipitate obtained from 8 g of propyne
. (NaCI ~ + cn '. . . 147
=-x8=29,4g
40 ..
· +.' -c:+
H 2C-CH 2Br . .
.
Br
- BrH 2G-CH2Br
1,2-DibromOethane
Problem 8. Compound .
(A) contains only carbon and
'.

:.. hydrogen. It decolourises bromine in CCl solution and reacts

4
(Carboniumion) . '.+Cl- .' slowly with concentratedH 2 SO,4- Compound (A) reacts with
, ,ClH 2C-CH 2Br
HBr tolorm (B). (B) reacts with NaOH to form (C)~ On
1-BromO.'2-chloroethane
oxidation (C) gives hexanone.,.3; Write the, structural formulae
~roblem 5.How can you prepare qenzene from lime? of (A), (B), (C) and explain the reactions involved
Solution :CaO + 3C .Electric " 'C' C' +CO . Solution: (A) is an alkene as it decolourises bromine in
Lime Cok~
fUrnace .) " a 2 . CCl 4 and reacts with'H 2S0 4 •
CaC 2 +2H 20 ~ Ca(OHh + C2 H 2 (C) is a !!econdary alcohol a'S it forms hexanone-3 on '
Acetylene o~idation. The structure of (C) sho\lld be

Red hot tube C H 'CH3CH2THCH2CH2CH3 (Hexan-3-ol)

, ) 6 6
Polyineriz!)tion .' 'Benzene OH .
Problem 6.(a) 2-Mf!thylpropene can be converted into (B) on hydrolysis with NaOH gives (C) thus, (B) should
. isobutyl bromide by hydrogen ~romide. Write the condition. , be
Unsaturated Hydrocarbons 339

should be kept in mind while deciding the ,structUre of the

. ,
CH3CH2CHCH2CH2CH3 (3-Bromohexane) .
alkene: . ,
Br H
(A) on HBr addition gives (B) hence, (A) is r
1. -:-CH 2 gs:oup gives formaldehyde, O=C~H
CH 3CH 2CH=CHCH 2CH 3' (Hex-3-ene)
H
Reactions:
. ' I,
Br2 =CHR group gives aldehyde, Q=C-R
CCl 4 )
R
CH 3CH 2CHBrCHBrCH 2CH 3 . ' \
=CR 2 group gives ketone, O=C~R
H 2S0 4
CH3Cij:2Ca-CHCH2CH3 ) 2. When only one aldehyde or one ketone is obtained, the
alkene is symmetrical with respect to double bond. '
.3. The structures of carbonyl compoUnds are wr;ittenin
such a way that the carbonyl groups face each other.

HBr
-:---7 CH3CH2CH2THCH2CH3
,
R2 R4
,
Rj-C=Q '. 0= C-R3'
Br (A) . (B)
Ni:tOH . , 4. The '-:".0 of both the compounds is removed and linked,
, ,
CH3CH2CH2CHCH2CH3 - - '~) CH 3CH 2CH 2C,HCH 2CH 3 through a double bond. This is the structure of unknown'
alkene.
Br OH

CH · CH CH Oxidation CH CH CH CCH CH
, 3 CH 2CH 2\
CH 2 3 ) . 3 2: '21\' i, 3
OH 0 R j , Ri, R 3 , R4 are either hydrogen atoms or alkyl groups
Problem 9. Anorganic compound (A), having carbon or both.
and hydrogen, adds one mole of hydrogen in the presence of Problem 11. An olefin was treated with ozone and the
platinum catalyst to form normal hexane. On vigorous resulting ozonide' on . hydrolysis gave 2..pentanone and
oxidation with KMpO 4' it gives a single carboxylic acid acetaldehyde. What is the structure of the original olefin?
containing three carbon atoms. Assign structure· to the Write equations for the reactions involved, .
compound (A). Solution : 'The products of ozonolysis are .2-poo.tanone ,
Solution: The compound.combines with hydrogen to and acetaldehyde. Writing the structure of both the carbonyl
form· normal hexane by conswning one mole of hydrogen, compounds.
hence the hydrocarbon is n-hexene. . H
C 3 H7"'- _
C 6 H!2 + H2 -:---7 C 6 H14 /C-O. Q=C/
n-Hexene n-Hexane CH 3 ,'. "'-CH '
3
. The position of double bond is indicated by its oxidation Pentan-2-one Acetaldehyde
to propanoic acid. Thus, the double bond is_ pr.~sent in the .
middle of the chain (a symmetrical alkene). Removing =.0 of the compoUnds· and linKing both
,through double bond, we get the alkene.,
CH 3CH 2CH=CHCiI 2CH3
Hex-3-ene C3H7,~, /H

.~~. C=C
CH3/~CH3
2CH 3CH 2COOH CH3CH2CH2CH2CH:zCH3 Thus, the alkene is3-methyl hex-2~ene.
Propanoic acid n·Hexane . . Reaction :,
P~obJem 10. How is the structure. of an. at/rene C H7 -H,
' '. CR' C I
determined? .. ' 3 ". ". ../
. ", 2 Z
·Solution: Ozonolysis is the best method for locating " . /C=G"" CH3+ .03 -
CH3' ,.
the double, bond position in 'unknoWn alkene. An alkene is
treated with ozone in an inert solvent to form an ozonide. The
ozonide is treated with Zn/H 20 to obtain the carbonyl
compounds., The structure of' the carbonyl compounds
depends upon the structure of the alkene. The following points' , Acetaldehyde, ,Pentan-2-one
 Pr~blem 12.. Writfi! the strUcture and give ·the ]UPAC 'name of the alkene which gives only pent'dn-2-one onreductive
ozonolysJs:'Give equations, '
· :Solll~iori: As the alkene gives only pentan-2-one, it is symmetrical. Writing the structure of pentan-2-one,
C3H 7 " , ' "
'. /C=O.
CH 3 '
, ,".
,C 3H 7 "", . / C 3H 7
Hence, the alkene is, /C=C",
CH 3 "CH 3

Problem i3. Write the structure oj the isomeric butenes and name them. Give the products obtained on reductive
ozonolysis. ,
Solution : Butene exists in three isomeric fonns:
CH 3
I
CH 3-CH 2-CH=CH 2 CH3-CH=CH-CH3 CH 3-C=CH 2
But-I-ene But-2-ene , 2-Methylprop-I-ene
But-I-ene on reductive .ozonolysis gives propionaldehyde and formaldehyde.

But-2-~ne on reductive ozonolysis gives only a~etaldehyde;

2-Methylprop-l-ene on reductive ozonolysis gives acetone and formaldehyde .
. Probiem 14. Effect the following transformations:
~...
, (a) CH~CH2CH2CH21 to CH 3CH 2CH 2CH 2 Br
'

(b) CH 3CHBrCH 3 to CH 3CHCICH 3

,'(c) CH 3CH 2CH 20H to CH 3CHOHCH 2CI
,Solution :'
AI ' HBr
(a) 'CH 3CH2CHitH21 KO~) CH 3CH2CH=CH 2 'R-O-O-R) CH 3CH 2CH 2CH 2Br
(Peroxide)

:(h.) , ' C H3CHBrCH 3 ~~) CH~--:-CH CH 2 HeI) CH 3CHCICH 3

.(cf CH3CH2CH 20H H~:~4) CH 3-CH=CH2 HOCl) CH 3CHOHCH2CI

, . . \

Problem 15. Account for the following: . ,

· (aJtheC1tii5C distance is shorter thanC=C and C-;C distan'Ce.
(b)Thi? stability of alkenes is in decreasing order of substitution by R. , .
. Solution: (a) .The carbon-~arbon distance depends upon the shielding of carbon. nuclei by bonded electrons. In the .
carbon nuclei i,s,sh~elded by six electrons while in C=C andC-C by four and two electrons respectively. As a result of this, th~
, ,'carbon atoms' come closer and undergoing more of overlapping of atomic orbitals and thus form stronger bonds.
· Itcm also be explained on the basis -of hybridization concept. Iii C=c, each carbon, atom is sp-hybridized while in C=C and
C~"each carbon atom is sp2_ and sp3 ~hybridized respectively. More the. s-character of the orbitai, shorter will be bond formed,
f( :by~e orbitafIn sp, thes-character is maximum, hence CC distance is minimum.-:-·

'.- ',. :.
.....;.,u._ns_a..;.,tu;.;..r...;.,a..;.,te_d_H""'y_d_ro..;.,c_a_rb_o_n_s-=-_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _.3.;...,41 ... ·.
•
(b) According to Saytzeff's rule, stability of alkenes
depeflds upon the substitution in CC bond. More of
. substitution by R, the more stable is the alkene. Hence, the BH3!TIlF
.. order of stability is: (H) CH 3CH 2CH 2CH=CH 2 . ')
R 2C---':CR 2 > R 2C=CHR > RCH=CHR >
(CH3CH2CH2CH2CH2hB DOAc). (B)'
RCH= H 2C > H 2G-CH2
Problem 16. .Write the structural and steredisomers of BD~!TIlF
(iii) )
pentene, CSHIO and compare their stabilities. ,
Solution : .Pentene exist in the following isomeric forms:
CH3~H2CH2-CH=CH2;· CH r .......CH 2-C-H ..
Pent-l-ene II Problem 19. Write the expected products formedfraw'
H3C- C:........H hot KMn0 4 oxidation o/{i) alkenes"C 4 H s',(ii)cyclobutene"
(iii) l-methylt:yclobutene, (iv) l,2~dimethylcyclobutene.. ,
Pent-2-ene (cis)
Solution:
CH 3 -CH 24-H ; CH 37'-CH 2-C=CH 2 0'
.
I
CH3'
.11 '
H-C~H3 (i) . But-I-ene ~ CH 3CH i C-OH +C0 2
Pent-2-ene (trans) 2~Methylbut-l-ene
, . o 0
CH 3-C . CHCH 3 ' CH 3 -CH-CH-:-CH2 ~ ~
, I' I . But-2-ene ~ CH 3-C-:-OH + HO'-G-.:cH3
CH 3 ,CH~
2-Methylprop-'1-ene ~ CHr~1 . 0 + CO2
2-Methylbut-2-ene 3-Methylbutc l-ene
and the stability order is: CH 3
Pent-l-ene < pent-2-ene (cis) <' pent-2-ene (trans)
< 2-methylbut-2-ene (ii) _ ICHr-COOH. J

(since, stability increases ~ith increasing numbet of CH2-C00H

Cyclobutene
electron releasing alkyl groups.)
CH3
Problem 17. What are the possible pr.oducts, in order of ...... CH3 1

D. -
t/ecreasing yield, obtained from the reaction of3-bromo-2,3- CH 2-C· O'
dimethylpentane with alc. KOH? ' (Hi) ·1.
Solution: CH~dH
1. -Methykyclobutene
CH 3-C=C-CH 2CH 3 >CH 3-CH-C=CHCH 3 CH3
,I I I I ' 1.
CH 3 CH 3

> CH 3CH-C-:-CH 2
CH 3 CH 3
(RzC=CHR, trisubstituted) (iv)
DC"' - CH3 ·
1,2-!?imethylcyclobiitene .
CH2-C=0
I
CH2-C-0
t
I I ' CH3
CH3 CH 2-CH 3
(RzC=CH z disubstitnted) Problem 20. Predict the product of the reaction,

Problem 18. Prepare the following from I-pentene : Ph>'.C=c<H . . HBr ) produci
H . CH 3
(i) CH 3CH 2CH2,CHDCH 3 (A), . .
[AIPMT (Mains) 2008]
(ii) CH3CH2CH2CH2CH2D (B), Solution:
(iii) CH 3CH 2CH 2CHDCH 2D (C). In the first step of electrophilic addition reac;tion: H+ idd~'
to that carbon atom of the· double bond whicbcarriesCH1 "'.
Solution:
group since, it produces carboc~tion (I} which is stabilized by
+R-effect of the Ph group. In the second step, the micleophile.;
Br- attacks the carbocation (I) to give l-bromo-l-phenyl~
propane (II). .
 G.R.JJ.. Organic Chemistry fo~ Competiti(Jn8

"~<H
Ph)C=C "
H+
)
Ph)C-CH2CH3
+
CH2

H "CH 3 (Slow) H Hzc6 cH2 +2NaCI

(1)
Cycl,opropane

Br-) PhCHCH 2CH 3

(Fast) I This reaction can
be regarded. as intramolecular wurtz
Br " reaction. It is useful for the preparation of three to six membered
(II) rings.
I-Bromo-I-phenylpropane " (U) From calcium salts of dicarboxylic acids: When
calcium salts ofdicarboxylic acids are heated, cyclic ketones
ISUPPLEMENTARY READING are formed which yield cycloalkanes by Clemmensen
reduction.
7.15 CYCLOALKANES o . . ',
'Cycloalkanes are carbocyclic saturated hydrocarbons in II // i
which ~bon atoms are joined by single covalent bonds to form CH2CHz
I :'
C4"
"Caz~
! Heat . CH 2CH2""-.
a ring."" They form a homologous series of general formula I /C=O
C n Hzn . They are also tenned alicyclic because of their
CH2CHk C-O-/ i CH2CH2
: II : Cyclopentanone
similarity to aliphatic compounds. Some of the members of 0 .:. __________ 1~
:, ___
this series are: Calcium adipare "
ZnJHg
CH2 "
HCI
..
HzCDCHz Cyclopentane
Cyclopropane Cyclobutane (iii) Dieckmann cyclization-From esters of
(Trimethylene) {Tetramethylene) dicarboxylic ,acids: Esters of dicarboxylic acids undergo
H2 "intramolecular Claisen condensation in presence of sodium or .
Hz
/C"",-" C sodium ethoxideyielding cy:clic j)-ketoesters. The j)-ketoesters
H2C CH2 H2~ 'L:Hz on subsequent hydrolysis and heating (decarboxylation) give
"I I I I " cycloketones. These onreditction yield cyclic. alkanes.
HzC--CHz HzC" C-.. . . . CH2 A
COOCzH 5
Cyclopeiitane '( I
Hz
(Pentarilethylene)
H2C........- CH
C2 s9 ~ ~C=O
Cyclohexane H Na
I
Note:" For nomenclature see Chapter3. "
Cycloalka'ites are, usually represented" by simple
HC"c( .
2

:Diethyl adipate
geometrical figures: a triangle (D.) represents
cyclopropane; a square ( ) cyclobutane, a.pentagon

( ) cyclopentane; a hexagon ( 0 tcyclohexane and Heat

-:--+
so on. Each corner of the geometrical "figure represents a
-CH 2- (methylene) group.
Hydrocarbons havip.g medium'size rings (C s or C 6 ) are .
quite stable and closely resemble alkanes. But the compounds
ZnJHg HZC-CHZ)
having rings with carbon atoms fewer than five show chemical, .. I CHz
properties somewhat intermediate between alkanes and alkenes. HC1 H2C-CH2 "
Methods of preparation : Cycloalkanes are Cyclopentane
synthesised from aliphatic compounds by using ,suitable
reactions which bring ilbout cyclization. They are also (iv) From alkenes: Cyclopropane derivatives are
obtained" from aromatic compounds: Some of the common formed when alkenes are treated with methylene iodide
methods used are: (CH 212 ) in the presence of Zn-Cu couple or diaiomethane
(i) From dihalogen compounds (Freund reac~on): (CHzN 2) and ultraviolet light.
a.,ro-Dihalides when treated with sodium or zinc form
cycloalkanes.
 " ,

Unsaturated Hydrocarbons" "343

Zn-Cu alloy (2) Addition reactions: Like alkenes cyclopropane

CH 3-CH=CH 2 +CH212 " "") CH 3 -CH-CH 2 undergoes electrophilic addition reactions with ring fission.
Propene " V Some of the examples are:
CH 2
Metbylcyclopropane
BrH2CCH 2CHiBr
(CC4) dark
Zn-Cu aHoy 1,3-Dibromopropane
CH 3CR " CHCH 3 +CH 21z " ) CH3~HCH3 HBr
But-2-ene CH3CH2CH2Br
CH 2 I-Bromopropl\ne '
(v) From aromatic compounds: Six membered (i) Conc. H2 S0 4
CH3CH2CH20H
cycloalkane compounds are conveniently prepared by the "(ii) H 20
Propan_l-ol
catalytic reduction of benzene and" its derivatives.
CH3CH 29H 3
"0::-...
"" I
"'-"'-
+ 3Hz Ni,200°C.
Under pressure
0 " Propane

Cyclobutane is not as reactive as cyclopropane as it does

Benzene Cyclohexane

0
"~
" "I OH
+3H2
",
Ni,200°C
Under pressure
•
not undergo addition reactions under ordinary conditions.
However, it can be hydrogenated to n-butane at 120°C.
CH2-CH2
I I +H2
Phenol , Cyclohexanol CH 2-CH2 n-Butatie"
Cyclobutane
Physical properties: (a) First two members are gases, (3) Oxidation : Cyc10alkanes are oxidised by alkaline
next three members are liquids and higher ones are solids. potassium" permanganate to dicarboxylic acids with ring
(b) They are insoluble in water but soluble in alcohol and fission.
ether. '
H2
(c) Their boiling points show a gradual increase with C
increase of molecular mass. Their boiling points are higher H 2C"""""" '"'cH2 CHz-CH2COOH
Alk.
than those of isomeric alkenes or corresponding alkanes. I I + 5[0] I"" '
(d) Their density increase gradually with increase of H 2C""C........-CH2 CHz-CH2COOH
molecular mass. " Adipic acid
, Chemical properties: Cycloalkanes resemble alkanes H2
in their chemical properties. However, the first two members, "Cyclohexane
i. e., cyclopropane and cyc10butane are exceptions which are
comparatively less stable and tend to break open like a double 7.16 BAEYER'S STRAIN THEORY
bond and give addition reactions. The similarity of
cyc10alkanes with alkanes can be attributed to the fact that all In 1885, Adolf Baeyer proposed his famoustheQry in order "to
the carbon atoms in cycloalkanes are sp3 -hybridized forming explain the relative stability of cycloalkanes. The theory is
sigma bonds with two neighbouring carbons and, two based,ona purely mechanical concept of bonding._Th~ main
hydrogens. It has been observed that cycloalkanes from assumptions of the theory are:
cyclopentane onwards show hi!$ degree of stability and are (i) Since carbon atom is "tetrahedral in nature with aIr the
not affected by acids, alkalies and corinnon oxidising agents four valencies directed towards four comers of a regular
under usual conditions. tetrahedron, the angle between any two bonds should be
(1) Free radical substitution with C1 2 , and Dr;!: 109°28', Any deviation from'thisi,mgle would result in internal
"Cyc10alkanes undergo halogenation in presence of sunlight or strain in the molecule.
ultraviolet light. (ii) All cydoalkanes are planar, i. e., cyclopropane ring is'
equilateral" triangle; "cyclobutane ring is a square and other
CH 2-CHCl + HCl
~/ cyc16alkane rings are polygons. In the formation of these
CH 2 rings, there is deviation from the normal bond angle causin~ a
Chlorocyclopropane
lot of strain in the molecule. This stiain"commonly referred to' '
H2 as angle strain, would depend up~n the, extent. of sU9h
____C'---
H 2c CHC1" . deviation, "
I"" I ' .. (iii) The deviations from normal tetrahedral angle can be
H2C"" C ....."CH2 calculated as follows: _.
H2 D~viation =~ [109°28' bond angle in the planar ring]'.
Chlorocyclohexane 2
34A G.R.B. Organic Chemistry (or Competitions

1 (109628' 60°) = 24 °44'

2
Cyclooutane 1 (109°28' _ 900) =9°44'
2
, ", <::ydoPerJ.tane .!.(109°28' 108°)=0°44'
2.' ,
Cyciohexane
, " 1 (109028'- 1290) = _ 50 lt)'"
2 ' '
Cycloheptap.e
!2 (109°28'
""
,-'-128°34') - 9°33'

"

, The positive values of deviation mean that the bond , 6

angles are compressed whlIe negative vaiues in~an expansion
of the bond angle from the tetrahedral angle. In bQth the cases
the molecule has been strained. '
It is Qbserved that the angle strain is maximum in the case Qf
Q 0:0: , .3 ,
CyClobutene Cyclopentene Cyclohexene Cyclohexa-l,4-diene
.cyclopropane.Thus, Gycloprop~e molecule is a highly strained
. CyclQalkenes can be easily obtained by Diels-Alder
molecule and consequently most unstable. ,The ring. open!) up on 'reactiQn. These cQmpQunds undergo. the electrQphilic addition
slight provoCatiQn and thus releasing the strain. The angle strain reactiQns Which are characteristic Qf alkenes, while the ring
iricyClobutane .is less than thatincyclQPropane.Thus, it nas remains intact. Cycloalkenes decolourise the purple CQIQur of
higher stability than cyclQpropane. It undergoes ring Qpening dUute CQldKMn0 4 Qr redcQIQur Qf bromine in carbQn

y-Br
reactiQns Qnly under drastic conditiQns ,;18 expected. The angle tetrachloride.
strairi is minimum in cyclQpentane and thus, it is 'mQststable and
dQes not undergo. ring opening reactiQns.
From cyclQhexane Qnwards the angle strain CQntinuously . CJ:clopentene
increases. AccQrding to" Baeyer's ,strain theQry, higher, Br
cyclQalkanes ,shOuld' become incFeasinglyunstable and hence' 1,2-Dibromo-cyclopentane .
mQre reactiv'e,But, cyclQhexane 'and higher members are
0+
fQund to be quite stable. Thus, it is concluded that the'theo,ry is '
valid fQr first three members Qnly, "
In Qrder to. aCCQunt fQr the stability Qfcyclohexane and
higher members, Sachse and Mohr (1918) prQPosed that such'
' .
Cyclopent-l-ene
0 + H 20 KMn04 (aq.),.

OH
YaH
Cycfopentane-l,2-diol
rings can becQme free from strain if all the ring carbQns are nQt
forced into' Qne plane but assume a, strain-free' puckered
cQnfiguration in which each carbQn atQm retains its nQrmal
7.1ffOIENES
valency angle. Onthis basis Sachse proPQsed two. models fQr These are hydrQcarbQns with two. carbon-carbQn dQuble
cyclQhexane-called the bQat and chair forms. MQhr bonds. Dienes ,are of three types:
, supported .this prQPQsal and'the theQry."became knQwn as, (i) Conjugated dienes : Double bonds are separated by
Sachse-Mohr theQryQf strafuless rings. ' , , one single bQnd. FQrexampie,

~.
Buta-l,3-diene H 2C==:!CH----CH =CH 2
, (H) Cumu'ative dienes: Double bonds are adjacent to.
, Boat form' . Chair form 'each other. FQr example,
The reactivity. of unsaturated hydrocarbQns (alkenes and Allene (PrQpadiene). H 2C=C=CH2 .
alkynes) is explained with the help QfBaeyer's strain theory. Buta-l,2-diene CH 3 ----CH=C=CH 2
When carbon atQms are linked by dQuble bQnd, the valen~y
bQnds undergo bendirig and are distQrted from their nQrmal (iii) Isolated or Non--conjugated dienes: DQuble bonds
directiQns. This bending produces strain in the molecule with are separated by mQ~ than Qne single bond. FQr example,
the result that it becQmes unstable and hence mQre reactive. In - Penta-I,4-diene H 2C=CH-CH 2 ----CH=CH2
, acetylene, there is greater strain and hence is reactive. The . The general fQrmula of dienes is Cn H 2n - 2 • Dienes are
strain disappears when addition QCcurs. .
iSQmeric -with alkynes. The most impQrtant class of dienes is
7.17 CYCLOALKENES that Qf conjugated dienes. Their chemical properties are
Carbocyclic cQmpQundswith dQuble bonds in the ring are , different frQm those of Qrdinary alkenes. Thepredominent
called cyclQalkenes. SQme,Qf the CQmmQn cyclQalkenes are> . ,member Qf this class is Buta-l,3-diene.
 '.
Unsaturated Hydrocarbons

Delocalisation of electrons and stability of conjugated Buta-l,3-diene, H 2C=CH-CH==CH 2

dienes : In, buta-! ,3-diene, a11 the carbon atoms are in a state Buta-l,3-diene may be prepared:
ofsp 2-hybridization. The three sp2-hybrid orbitals of each (i) From acetylene: Acetylene in presence ofCuzCl z
carbon lie in the same plane and'are atangle of 120° to each and NH 4CI dimerise to form, vinyl acetylene which on
other. Each carbon atom in buta-l ,3-diene has anunhybridised reduction with Lindlar's catalyst yields buta-l,3~diene.
p-orbital ofC I or that ofC 3 • Similarly, the orbital at C3 can
overlap with that ofe 2 orC 4 to form X-bonds. Therefore, the CU2Cl2 , H2
2HC=CH ) HC==C-CH=CH z )
four x-electrons of buta-l ,3-diene are delocalised over all the Acetylene' -NH4Cl Vinyl acetylene Pd/BaS04
four carbon atoms. This delocalisation of x-electrons makes '
the molecule more stable. H 2C=CH-CH=CH z
" Buta-I,3-diene

,
Parti.81 double
bond character (ii) From 1,4·dichlorobutane: 1,4-Dichlorobutane is
heated with alcoholic KOH when dehydrohalogenation occurs
H>VV-fJfJ<H with formation of buta-! ,3-diene.
C-C-C-C
or H M.61J H
CI
I
CHzCHzCHzCH2
CI
I Ale. KOH ) HzC=CH-CH=CH z
Delocalisation of 1t-electrons
1,4-Dichlorobutane Buta-I,3-diene
or
H>VVVV<H
C-C-C-C C> <J (iii) From 1,4-butanediol: Acid-catalysed dehydration
H 8--(J 8--(J H HzG-CH-C.H-CHz is done by heating 1,4-butanediol with cone. H ZS04 •
Overlap ofp-QrbitaIs in a C> <J OH' OH
conjugated diene to fonn ,I I H S04
2
two double bonds " . CHzCHzCHzCH z heat) H zC=CH-CH=CH2
The central carbon atoms in this molecule are close to 1,4-Butanediol Buta~I,3·diene

each other and there is a possibility of overlapping between (iv) From butane: Buta-l,3-diene is obtained by
p-orbitals of C2 and C 3 • Tliis gives the partial double bond passing the butane vapours overheated catalyst (CrZ03 on an
character to the central bond. Rotation of the molecule about alumina support) at 600°C., '
atoms C 2 and C3 requires only about 5kcaVmoi whereas that
about the double bond in ethylene, the barrier is 60 kcaVmol.. CH 3CH zCH zCH,3 Catalyst ) HC=CH-CH=CH
~
2
The stability of conjugated dienes are supported by bond n-Butane 600°C· Buta-I,3-diene
length measurement and study of heat of hydrogenation and (v) From cyclohexene: Buta-l,3-diene may be
heat of combustion, etc. prepared by passing cyclohexene over a heated nicbrOme wire.
The heat of hydrogenation of monosubstituted alkenes
(R -CH=CH2) is 30.3 kcaVmol (or 126 kJ/mol); The heat of,
hydrogenation of butadiene, having two double bonds, should
,.'0'I ~ HzC=CH-CH, . CH2 +HzC ,', CHz
." Buta-l,3·diene Ethene '
be 2 x 30.3= 60.6 kcaV mol (or 252 kJ/mol). The experimental Cyclohexene
(observed) value is 57.1 kcaVmol (or 236 kJ/mol). Thus
butadiene is more stable by about 3.5 kcal (15 kJ/mol). This is Properties : Buta-I,3-diene is a gas. It shows the
foUowing reactions:
reSOnance energy of butadiene. These values support that
(I) Addition of ,halogens: Buta-l,3-diene reacts with
conjugateddienes are !Dore stable.
halogens (Brz or Clz) in ~e presence of an inert solvent (CCI 4 )
• The CZ-C 3 bond length in butadiene, is 1.48 A and for to yield a mixture of 1,2- and 1,4-addition products.
Cj"-"":'C 2 andC 3-C4 bond length is 1.37 A. TheC 2-C 3 bond
, , { CH2BrCHBrCH=CHz
length is i shorter than the C-C :bond ~ength in ethane (1.54 , 3,4-Dibromobut-l-ene (l,2-Addition)
A). ' , H 2C=CH-CH= CHz + Br predominates (62%) in non-i9nising
The resonance struotures ofbuta-I ,3-diene are;as follows: Buta-l,3.dien~ i solvent (hexane) ,

H>'
H
C=C,'
H
C=C
5' H> +
<H - -
H
5H
C-C,-
C-C
_<' H,
CHzBrCH=CHCH2Br
1,4-Dibromobut-2-ene (1,4Add~tion)
predominates (70".4) in an ionising
; H 'H' H H solvent (acetic acid)
, HH The mechanism of the above reaction involves the
--
c
H>c- 5c_c<H
following steps: "
lststep: The halogen molecule (Br2) undergoes
H H
heterolytic fission.
 G.R.B. Organic Chemistry for Competitions

Br2 ~ Br+ + :Br-' , The presence of electron attracting groups such as ---{;N,
BromoniUIll 'Bromide ---{;HO, ~OR. ---{;OOH, ---{;OOR, etc., oil., dienophile
, ion 'ion
facilitates the reaction. This reaction is widely used in the,
, 2nd step: ,The bromonium ionattacks the double bond ' synthesis of six membered ring compounds. ' "'
to give' a resonance stabilized carbocation.'
(vii) Ozonolysis: Dienes undergo ozonolysis to give
, ' BrCHr-CH~CH2{A) three molecules. Buta-I,3-diene yields formaldehyde and
glyoxal on ozonolysis.
Br++ H2C=CH---{;H= CHz{ 't ,+'
.' Zn/H 20 .
Buta-l,3-diene BrCHz-CH= CH-CH2(B) HzC=CHCH=CH z +20 3 ) 2HCHO+OHCCHO
Buta-1 ,3-diene
, 3rd step: The bromide ion combines with (A) to form,
3,4-dibromobut-I-ene (l,2-addition). It combines with (B) to Problem 20. How will you distinguish between:
form I,4-dibromobut-2-ene (l,4-addition). (i) Cyclop~pane and propene,
(ii) Cyclopentane and pent-2-ene,
(il) Addition of halogen acids: A mixture ,of two
(iii) Buta-I,3-diene and but-I-yne,
compounds is formed when buta-l,3-diene reacts with
(iv) Buta-I, 3-diene and butane?
halogen acids (HX). Solution: (i) Propene decolourises dilute KMnO 4
CH 3 CHBrCH=CHz
(1,2~Addition)
solution whiie cy~lopropane does not give this test.
3-Bromobut-l-ene KMn° 4(aq·) )
(Major yield at low temp.) CH 3CH=CH z +[0]+ H;>O
HzC=CH-CH=CH2 + HBr
Buta-l,3-diene 'Propene
H3C-CH=CH-:-CH2Br
(l,4-Addition) , 1,2-Propanediol
I-Bromobut-2-ene
(Major yield at high temp.) (ii) Pent-2-ene decolourises the purple colour ofKM:it0 4
solution. It also decolourises red colour of bromine in CC1 4 •
, (iii) Addition of water: ' Buta-I ,3-diene reacts with These tests are not given by cyclopentane.
water in the presence of H 2SO 4 to give a mixture of 1,2- and
l,4-addition products. CzH sCH==CHCH 3 +[0] + HzO
KMn° 4(aq·) )
' CH3CHOHCH= CHz
OH OH
H2C "-:'CH-CH=CH2+ H20 ' But-3-en~2-ol
. Buta~Ii3-diene,
{
CH3CH CHCH20H
I I
CzH s CH-CHCH 3
But~2-en-l-ol 2,3-Pentanediol

(iv) Addition of hydrogen:,' A mixture of but-I-ene CCl'} ,

and but-2-ene is formed when buta-l,3-diene reacts with Hz, CzHsCH=CHCH 3 + Brz C zH sCHBr-CHBrCH 3
2,3-Dibromopentane ..
in the preserice of a catalyst(Pt). ,', '
, (v) Polymerisation: ,It undergoes polymerisatioIi in (iii)But-I-yne forms a white precipitate with
the presence of peroxides to form polybutadiene (Buna anlmoniacal silver nitrate solution, while this reaction is not
rubber). ' observed 'with buta-l,3-diene.
CH 3CH zC=CH + Ag(NFi3 h N0 3 ~
CH 3CH zC=C-Ag + NH 4 N0 3 + NH3
" (iv) Buta-I,3-diene decolourises red colour of Brz in
(vi) Diels-Alder reaction: This is' a reaction ~etwee:n a CC1 4 solution. It also decolourises purple colour of KMnO 4
conjugated dieneand an alkene or alkyne called dlertophIle. solution. These tests are not observed with butane.
This reaction does not require any catalyst. It involves the Problem 21. How will you synthesise the following?
formation of two sigma-bonds and a pi-bond at the expense of (i) Hexa-l,5-diene from propene. '
three original pi-bonds. The product is called adduct, a six (ii) Allene from propene. '
membered aromatic ring and involves an addition at '(iii) I-Bromopropane from I,3-dibromopropane.
positions 1,4. (iv) Cyclohexene from cyclohexane:
(v) Buta-l,3-diene from but-l-ene
, ~CH2. CH2 (vi) Hexachloroethane from calcium carbide.
H~.J + \...11
'CH2 2000C
•
HC/-:::""'CH2
II I Solution:
H---{; ~ CHz HC .......... __ CH z ell
(i) CH 3CH. CH z 600 od CH zCICH=CH 2
~cHi Ethene CH z Propene 3-Chloroprop-l-ene
Buta-l,3-diene (Dienophile) Cyclohexene (Allyl chloride)
(Adduct)
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