Hydro Carbons Theory

HYDROCARBON Page # 3
ALKANE
Alkane are the saturated non polar hydrocarbon having general formula CnH2n+2.
Hydrocarbon – Those organic compounds which contain only carbon and hydrogen atoms are known as
hydrocarbons.
1.2 General method of preparation
1.2.1 By catalytic reduction of alkenes and alkynes

H2,25ºC
R – C  C – R’ R – CH2 – CH2 – R’
Ni,Pt or Pd
H2,25ºC
R – CH = CH – R’ R – CH2 – CH2 – R’
Ni,Pt or Pd
Hydrogenation  Addition of H2 to unsaturated bond.
Hydrogenation is of two kind

(a) Heterogeneous and (b) Homogeneous
(a) Heterogeneous  It is two phase hydrogenation the catalyst is finely divided metal like Ni, Pt
or Pd and a solution of alkene.
(b) Homogeneous  It is one phase hydrogenation both catalyst and alkenes are solution. In this
hydrogenation catalyst are organic complex of transition metal like Rh or Ir.
Hydrogenation is exothermic, qualitative and during the hydrogenation, total heat evolved to hydrogenate
one mole of unsaturated compound is called heat of hydrogenation. Heat of hydrogenation is the
measurement of stability of isomeric alkenes.
1
stability of alkene 
Heat of hydrogenation
1.2.2 From alkyl halide
(A) From organometallic compound  compound having bond. (M  metal)

(i) By wurtz reaction
dry ether
2R – X + 2Na R – R + 2NaX
Na
R – X + R’ – X R – R, R– R’, R’ – R’’
ether (dry)
Mechanism Two mechanisms are suggested

(a) Ionic mechanism
2Na 2Na + 2e
–
R – X + 2e R+X
(1º, 2º)
2
R+R–X SN R–R
(1º or 2º)
Na + X NaX
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Page # 4 HYDROCARBON
(b) Free radical mechanism
Na Na + e
R–X+e R+X
R +R R–R
Note : The alkyl halide should be 1º or 2º, with 3º R – X SN2 and free radical coupling is not possible
due to steric hinderance so in that case elimination or disproportionation is possible.
In the ionic mechanism alkyl sodium (R Na) gives R strong base as well as nucleophile which gives SN2
with R – X, ether should be dry otherwise, if moisture is present then R forms R – H instead of R – R
with H2O.
R–X Mg
(ii) By G.R. RMgX
1º,2º,3º ether
all active
RMgX + H containg R–H
compound
H2O
R–H + Mg (OH) X
ROH R–H + Mg (OR) X
RMgX NH3
R–H + Mg (NH2) X
R' – C = CH
R–H + Mg (C = CR')
RSH R–H + Mg (SR) X
R – COOH R–H + Mg (OCOR) X
(iii) By corey house alkane synthesis
R' – X
R–X 2Li CuX (1º > 2º)
R Li R2CuLi R – R'
(1º,2º,3º) + Lithium dialkyl
LiX cuprate
(Gilman Reagent)
Mechanism
R2CuLi is the source of R

2
SN
R + R' – X R – R'
1º >> 2º
R2 CuLi do not reacts with –NO2, – CN, > C = O etc.
Ex.1 CH3 – Br Li CuI B Y

A C
if C is CH3 – CH2 – (CH2)5 – CH3, than what is Y.
Ans. CH3 – (CH2)6 – Br
CH3 CH3
Li CuI R'X
Q.1 CH3 – C – Cl A B CH3 – C – CH2 R' is ?
CH3 CH3
(iv) By Franklande reagent

Ether
R – X + Zn + R – X R – R + Zn X2
Mechanism
R
Zn R–X
R–X R Zn X R–R
+
Organozinc ZnX2
compound
(B) By reduction of alkyl halides
(i) with metal-acid
e/H
R–X R – H + HX
1º Metal / acid
Reducing agent
Zn / acid, Zn – Cu / H2O or Zn – Cu + acid

Zn – Cu / C2H5OH, Na – Hg / acid, Al – Hg / H2O etc.
Mechanism
Metal M+e
e M
R–X R + X MX
1º
acid
R–H
(ii) With Metal hydrides
(a) TPH (Ph3SnH) : It reduces 1º, 2º & 3º R – X

R–X Ph3SnH R–H
NaBH4
(b) NaBH4 R–X R–X
1º & 2º
LiAlH4 LiAlH4
(c) R–X R – H, R–X Alkene
1º & 2º 3º
1.2.3 By red P & HI

Red P & HI is strong reducing agent
Red P + HI
R – COOH R – CH3
Red P + HI
R – C – Cl R – CH3
O
Red P + HI
R – C – OEt R – CH3
O
Red P + HI
R–X R–H
Red P + HI
R – OH R – H + H2O
1.2.4 By soda lime  Fatty acids are good source of hydrocarbon, correction, heating of sodium salt of
carboxylic acid (R – COONa) with soda lime (NaOH – CaO) gives hydrocarbon, which is known as
decarboxylation (e.g. replacement of – COOH group by –H) decarboxylation also takes place on heating
only, when compound is gem dicarboxylic acid or there is keto group or double bond on  carbon.
CaO/NaOH
R + Na 2CO3
–H2O
H–OH
R–H
COOH NaOH
Ex.2 A B
COOH
What are A and B
Ans. A is COOH , B is
O
H3C COOD
Q.2
Opticallyactive
Write the structure of A and mention its stereochemistry
1.2.5 By Kolbe’s electrolysis
Electrolysis
2RCOOK + 2HOH RR + 2CO2 + H2 + 2KOH
Electrolysis
e.g. 2CH3 – COOK + 2H2O CH3CH3 + 2CO2 + H2 + 2KOH.
If n is the number of carbon atoms in the salt of carboxylic acid, the alkane formed has 2(n – 1) carbon
atoms.
1.2.6 Reduction of aldehydes, ketones :
(a) By Clemmensen’s reduction : with Zn – Hg / conc. HCl
Zn – Hg /conc. HCl
R – CHO RCH3 + H2O
O
R – C – R' RCH2R’ + H2O
e.g. CH3 – CHO CH3CH3 + H2O
O
CH3 – C – C2H5 + 4[H] CH3CH2C2H5 + H2O
Clemmensen reduction is not used for compound which have acid sensitive group.
(b) By Wolff-kishner reduction with NH2NH2 / KOH
NH2NH2 / KOH
RCHO RCH3
NH2NH2 / KOH
RCO – R’ RCH2R’
Wolff-kishner reduction is not used for compounds which have base sensitive groups.
1.3 Physical Properties of Alkanes :
3.3.1 Physical State :

The first four members (C1 to C4) are gases : the next thirteen members, (C5 to C17) are liquids while
the higher members are waxy solids.
1.3.2 Boiling points :
The boiling points of n-alkanes increase regularly with the increase in the number of carbon atoms
650 Bolling point
500
Temperature, K
350
200
50
0 4 8 12 16 20
Number of carbon
atoms per molecule
Among the isomeric alkanes, the branched chain isomers have relatively low boiling points as compared
to their corresponding straight chain isomers. Greater the branching of the chain, lower is the boiling
point. This is due to the fact that branching of the chain makes the molecules more compact and
brings it close to a sphere, so the magnitude of vander wall forces decreases.
1.3.3. Melting Points
It is the evident that the increase in melting point is relatively more in moving from an alkane having
odd number of carbon atoms to the higher alkane with even no. of ‘C’ while it is relatively less in moving
from an alkane with even number of carbon atoms to the higher alkane.
Explanation : The alkanes with even no. of ‘C’ atoms are more closely packed.
320
260
Temperature, K
200
140
80
0 7 11 15 19 23
Number of carbon
atoms per molecule
1.3.4 Solubility
In keeping with the popular rule “like dissolves like” hydrocarbons are insoluble in polar solvent like
water because they are predominantly non-polar in nature.
1.3.5 Density
The densities of alkanes increase with increasing molecular weight but become constant at about 0.8
g cm–3. This means that all alkanes are lighter than water so they floats over water.
1.4 Chemical Reaction of Alkanes :
Characteristic reaction of alkanes are free radical substitution reaction, these reaction are generally
chain reactions which are completed in three steps mainely.
(i) chain initiation (ii) chain propagation, (iii) chain termination
Examples of free radical substitution reaction 

UV Light or
R – H + X2 R – X + HX
250º – 400ºC
Cl2 Cl2 Cl2 Cl2

Exp. CH4 CH3Cl CH2Cl2 CHCl3 CCl4
hv hv hv hv
+ + +
HCl HCl HCl
When equimolar amount of methane and Cl2 are taken, a mixture of four possible products are formed,
but if we take excess of CH4 then yield of CH3Cl will be the major product.
Reactivity of X2 : F2 > Cl2 > Br2 > I2
Reactivity of H : 3ºH > 2ºH > 1ºH
with F2 alkanes reacts so vigorously that, even in the dark and at room temp, reactant diluted with an
inert gas.
Iodination is reversible reaction, since HI formed as a by-product is a strong reducing agent and
reduces alkyl iodide back to alkane. Hence iodination can be done only in presence of strong oxidizing
agent like HIO3, HNO3 or HgO
R – H + I2 R – I + HI
HI + HIO3 H2O + I2
Mechanism of halogenation of CH4
(i) Chain initiation  it is a endothermic step

UV or temp •
X2 2X
250º – 400ºC
(ii) Chain propagation 
• •
X+R–H R + HX
• •
R+X–X R–X+X
(iii) Chain termination  it is always exothermic
• •
X+X X2
• •
R+R R–R
• •
R+X R–X
Each photon of light cleaves one chlorine molecule to form two chlorine redicals, each chlorine atom
starts a chain and on an average each chain contains 5000 repetitions of the chain propagating cycle
so about 10,000 molecules of CH3Cl are formed by one photon of light.
Some reagent affects the rate of halogenation : For example
Q.3 In the given ways which is feasible

•
CH 3 + HCl (1)
•
CH4 + Cl
•
CH 3Cl + H (2)
Q.4 Which of the following reaction has zero activation energy

• •
(A) CH4 + Cl CH3 + HCl (B) Cl2 2 Cl
• • • •
(C) CH + CH CH3 + CH3 (D) CH3 + Cl – Cl CH3 + Cl + Cl
3 3
Q.5 If the Eact for a forward reaction is given

• •
CH3 – H + Cl CH3 + HCl
the Eact for backward reaction will be
(A) 1 kcal (B) 4 kcal (C) –4 kcal (D) 3 kcal
Halogenations of higher alkane :
Cl2
(i) CH3 – CH2 – CH3 CH3 – CH – CH3 + CH3 – CH2 – CH2 – Cl
light, 25ºC
Cl 45%
55%
Cl2
(ii) CH3 – CH2 – CH2 – CH3 CH3 – CH2 – CH – CH3 + CH3 – CH2 – CH2 – CH2 – Cl
light, 25ºC
28%
Cl
72%
CH3
Cl2
(iii) CH3 – CH – CH3 CH3 – CH – CH2 – Cl + CH3 – C – CH3
light, 25ºC
CH3 Cl
CH3
64% 36%
Br2
(iv) CH3 – CH2 – CH3 CH3 – CH2 – CH2 – Br + CH3 – CH – CH3
light, 127ºC
3% Br
97%
CH3
Br2
(v) CH3 – CH – CH3 CH3 – CH – CH2Br + CH3 – C – Br
light, 127ºC
CH3 CH 3 CH3
trace over 99%
Relative amounts of the various isomers differ remarkably depending upon the halogen used from the
above reaction, it is observed that chlorination gives mixture in which no isomer greatly dominates
while, in bromination gives mixture in which one isomer dominates greatly (97% – 99%).
Factors determining the relative yields of the isomeric products.

(i) Probability factor  This factor is based on the number of each kind of H atom in the
molecule.
(ii) Reactivity of hydrogen  The order of reactivity is 3º > 2º > 1º
Aromatisation:
CH3
CrO3 + Al2O5
CH3 – (CH2)5 – CH3 + 4H2
600ºC
Toluene
CH2 – CH3 CH3

CH3
CH3 – (CH2)6 – CH3 + + 4H 2
ortho-xylene
CH3
CH 3
CH3 – (CH2)4 – CH – CH3
CH 3
meta-xylene
CH3
CH3
CH3 – (CH2)3 – CH – CH2 – CH 3
CH3
para-xylene
1.4.8 Combustion : (i.e. complete oxidation)
 3n  1  combustion
CnH2n  2    O nCO2 + (n + 1) H2O (Hcombustion = –ve)
 2  2
 y combustion y
C xH y   x   O xCO2 + HO
 4 2 2 2
combustion
C5H12 + 8O2 5CO2 + 6H2O
Heat of combustion : Amount of heat i.e. liberated when 1 mole of hydrocarbon is completely burnt into
CO2 & H2O.
Heat of combustion as a measure of stability of alkane :

Combustion is used as a measurements of stability.
More branched alkanes are more stable and have lower heat of combustion.
CH3
e.g. (I) CH3 – CH2 – CH2 – CH3 (II)
CH 3 – C – CH 3
H
stability : II > I
Hcomb. : I > II
More branched alkane has more no. of primary C – H bonds. (therefore it has more bond energy).
Homologues : Higher homologues have higher heat of combustion.
Isomers : Branched isomer has lower heat of combustion.
(i) Initiators  they initiate the chain reaction, initiators are R2O2, Perester’s etc.
hv •
R–O–O–R RO
or
temp
hv •
R–C–O–O–C–R R–C–O
or
O O temp
(ii) Inhibitors  A substance that slow down or stop the reaction are known as inhibitors
For example O2 is a good inhibitor
• • •
R + O2 R–O–O+R R–O–O–R
all reactive alkyl free radicals are consumed so reaction become stop for a period of time.
Relative reactivity of halogen toward methane

Order of reactivity is F2 > Cl2 > Br2 > I2 which can be explained by the value of H (energy change)
Steps of halogenation, value of H for each step. (Kcal/mole)

F Cl Br I
(i) X2 2X + 38 + 58 + 46 + 38
• •
(ii) X + CH4 CH3 + HX –32 + 1 + 16 + 33
• •
(iii) CH3 + X CH3X + X – 70 – 26 – 24 – 20
Ex.3 Explain why the chain initiating step in thermal chlorination of CH4 is
Cl2 • • •
Cl and not CH4 CH3 + H
Ans. Because Eact of Cl2 is less than Eact of CH4
Potential energy
Eact of Cl2 Eact of CH4
Progress of reaction
Ex.4 Chlorination of CH4 involves following steps :

•
(i) Cl 2 Cl
2
• •
(ii) CH + Cl CH3 + HCl
4
• •
(iii) CH 3 + Cl
CH3Cl
Which of the following is rate determining ?
(A) Step (i)
(B) Step (ii)
(C) Step (iii)
(D) Step (ii) and (iii) both
Ans. (B)
Reactivity of hydrogen  3º > 2º > 1º
Because formation of alkyl free radical is Rds so, that H is more reactive which produce more stable
free radical (less Eact)
order of stability of F.R. 

• • • • •
Ph3C > Ph2CH > Ph – CH2 > CH2 = CH – CH2 > 3º > 2º > 1º > CH3
ALKENE
1. INTRODUCTION
Alkenes are hydrocarbons with carbon–carbon double bonds, Alkenes are sometimes called olefins, a
term derived from olefinic gas, meaning “oil forming gas”. Alkenes are among the most important
industrial compound and many alkenes are also found in plants and animals. Ethylene is the largest –
volume industrial organic compound, used to make polyethylene and a variety of other industrial and
consumer chemicals.
2. Structure and bonding in Alkenes
(1) Alkenes are unsaturated hydrocarbons having at least one double bond.
(2) They are represented by general Formula (G.F.) CnH2n (one double bond)
(3) In Ethene C = C bond length is 1.34 Å
(4) Its bond energy is 146 kcal.mol–1
(5) The hybridization of (C = C) alkenic carbon is sp2
(6) The e– cloud is present above and below the plane of –bonded skeleton.
(7) They are also known as olefins since ethene, the first member of the homologous series forms
oily liquid substance when treated with halogens.
(8) Compounds may exist as conjugated polyenes or as cumulated polyenes or as isolated polyenes
Note : That angle a > b since repulsion due to  electrons (double bond - single bond repulsion > single
bond single bond repulsion according to VSEPR theory.
Ex.1 Write IUPAC names of
CH3
CH3
(a) (b)
Ans. (a) 2, 3-Dimethylcyclohexene

(b) 1-(2-butenyl) cyclohex –1–ene
Ex.2 Give the structure for each of the following

(a) 4-Methyl-1, 3-hexadiene
(b) 1-Isopropenylcyclopentene
Ans. (a) (b)
5. Physical Properties of Alkenes / Hydrocarbons

Table : III
Physical properties Homologus series Isomers
1. Physical state C1 – C3 gases

C4 – C20 liquids
>C20 : solids
2. cis > trans
3. Polarity – cis > trans (for Cab = Cab type of alkenes
4. Melting point increases with M.W. trans > cis

(due to more packing capacity)
5. Boiling point increases with M.W. cis > trans
# branching decreases B.P.
C
C–C=C<C–C=C–C
Polarity increases, boiling point
increases
6. Solubility Practically insoluble cis > trans
in water but fairly Polarity increases, solubility in polar
soluble in nonpolar solvents increases.
solvents like benzene
petroleum ether, etc.
7. Stability trans > cis

(cis isomers has more Vander Waals
repulsion)
6. Laboratory test of Alkene

Table - IV
8. Methods of preparation of alkenes

(I) BY PARTIAL REDUCTION OF ALKYNES
(a) By Catalytic Hydrogenation of Alkynes in presence of poisoned catalyst (A Syn Addition
of Hydrogen : Synthesis of cis-Alkenes : This is performed by)
(i) Lindlar’s catalyst : Metallic palladium deposited on calcium carbonate with lead acetate
and quinoline.
(ii) P-2 catalyst (Ni2B nickel boride)
H 2Pd / CaCO3
(Lindlar's catalyst) R R
General Reaction R–C=C–R C=C
quinoline H H
Mechanism of hydrogenation :
(1) (2) C=C

H–H+–C=C–+H–H H–H – C=C– H–H H H
H H
metal surface
adsorption desorption
Steps : The reactant alkyne molecules and hydrogen molecules get adsorbed at the surface of metal
catalyst. It is chemical adsorption (chemisorption).
In this state, the reactants lie very close to each other and so the hydrogen atoms start forming
bond with carbon. Two hydrogen atoms are added to two triply bonded carbon atom from the same
side of  bond and a cis or syn addition product is formed. The product alkene now escapes away
from the surface of the catalyst. Quinoline occupies the metal surface inhibiting further reduction to
alkanes Quinoline therefore is called catalyst poison and palladium is called deactivated catalyst or
poisoned catalyst.
H2/Ni2B(P-2) CH3CH2 CH2CH3

or H2 /Pd/CaCO3 C=C
e.g. CH3CH2C = CCH2CH3
(syn addition) H H
3-Hexyne (Z)-3-Hexene
(cis-3-hexene)
(97%)
(b) Birch Reduction : (Anti Addition of Hydrogen : Synthesis of trans-Alkenes)
R H
Na / Li
General Reaction R–C C–R C=C
Liq. NH3 H R
+ –
Mechanism : Reagents Na(or Li, K) + liq NH3 Na + e (solvated electron)
R R H
Na H – NH2
R–C=C–R C=C C=C
R R
Na
R H R H
H2N – H
NaNH2 + C=C C=C
H R Na R
(–100%)
(trans alkene)
Na / NH3 ( l) CH3CH2 H
e.g. CH3 – CH2 – C = C – CH2 – CH3 C=C
H CH2CH3
trans
hex-3-ene
Note : This process of reduction is not eligible when terminal alkynes are taken. (R – C  CH)
because terminal alkynes form sodium salt with Na metal.
CH3 – C = CH + Na / NH3  CH3 – CH = C– Na+ + [H]+
Ex.3 Identify the reagent for following synthesis.
O O
?
CH2 – C C – CH2CH3
(A)
cis Jasmone
Ans. H2 / Lindiar’s catalyst.

H2
A cis - Jasmone
Lindlar's catalyst
Ex.4 Identify the products in the following reaction :
Na / NH3
CH2 – C CCH3
CH2 H
Ans.
C=C
H CH3
(II) BY DEHAL OGENATION OF VICINAL DIHALIDES
There are two types of dihalides namely gem (or geminal) dihalides in which the two halogen atoms
are attached to the same carbon atom and vicinal dihalides in which the two halogen atoms are
attached to the adjacent carbon atoms.
Dehalogenation of vicinal dihalides can be effect either by NaI in acetone or zinc in presence of
acetic acid or ethanol.
General Reaction
Br
NaI
(i) C–C C=C
or Zn. CH3COOH
Br
Br
Zn
Mech. C–C :
– C –– C – – C = C – + ZnBr2
Br Br
Zn dust
(ii) CH3 – CHBr – CH2Br CH3 – CH = CH2
CH3COOH or
C 2H5OH as solvent
Mech.
With NaI in acetone :
–
I X:
–C–C– C=C + IX
It involves an antielimination of halogen atoms
Remarks
(1) Both are E2 elimination.
(2) Both are stereospecific anti elimination.
(III) DEHYDRO HALOGENATION OF ALKYL HALIDES
Dehydro halogenation is the elimination of a hydrogen and a halogen from an alkyl halide to form an
alkene.
Dehydro halogenation can take place by E1 and E2 mechanism.
(i) Hot alcoholic solution of KOH EtO– / EtOH (ii) NaNH2

(iii) t-BuO–K+ in t-BuOH
(i) Dehydrohalogenation by the E2 mechanism : Second-order elimination is a reliable synthetic

reaction, especially if the alkyl halide is a poor SN2 substrate. E2 dehydrohalogenation takes place in
one step, in which a strong base abstracts a proton from one carbon atoms as the leaving group
leaves the adjacent carbon.
General reaction :
alcohol
– C – C – + KOH C = C + KX + H2O
H X
B:H
–C–C– C=C +B–H +X

Mechanism
X
Undergo elimination of hydrogen halide (HX) leading to the formation of alkenes.
CH3
Heat CH3 – C = CH2 + KBr + H2O
e.g. CH3 – C – Br + alc. KOH
CH 3 CH3
Here  – H is eliminated by base hence called  elimination following Saytzeff rule.

i.e, (Highly substituted alkene is major product). It also involves an anti elimination of HX.
e.g.
(minor)
Br
(less stable alkene)
Cl CH3 CH3
CH3
e.g. alc. KOH +
(major) (minor)
Cl H
H (CH3)3CO K
e.g. H
H H
Chlorocyclooctane Cyclooctene
CH 3
CH3
e.g. CH3 – C – Br + OH H 2C = C + H 2O + Br
CH3
CH3
(ii) Formation of the Hoffmann product

Bulky bases can also accomplish dehydro halogenation that do not follow the saytzeff rule.
Due to steric hindrance, a bulky base abstracts the proton that leads to the most highly
substituted alkene. In these cases, it abstracts a less hindered proton, often the one that
leads to formation of the least highly substituted product, called the Hoffmann product.
H CH 3
OCH2CH3 H3C CH3 CH 3 – H 2C H
CH3 – C – C – CH2 C=C + C=C
CH3CH2OH H CH3 H 3C H
H Br H 71% 29%
Saytzeff product
H CH 3
OC(CH3)3 H3C CH3 CH 3 – H 2C H
CH3 – C – C – CH2 C=C + C=C
(CH3)3COH H CH3 H H
H Br H 28% 72%
less
hindered
Stereospecific E2 reactions
The E2 is stereospecific because it normally goes through an anti and coplanar transition state. The
products are alkene, and different diastereomers of starting materials commonly give different
diastereomers of alkenes.
Ph Ph Base H
Ph Ph H
Br S H
H R CH 3
H CH3 Ph
Ph CH 3
Br H
Br
Ph H CH3
Ph Ph
CH3 Ph
H
Ex.5 What alkyl halide would yield each of the following pure alkene on reaction with alcoholic KOH ?
CH3
(i) CH3 – C = CH2 (ii) CH3 – CH2 – CH2 – CH = CH2 (iii) CH 3 – CH 2 – C = CH 2
CH 3
CH3
Ans. (i) CH 3 – C – CH 3 (ii) CH3CH2CH2CH2CH2Cl(iii) CH3CH2 CHCH2Cl

Cl CH3
CH3
CH3
Ex.6 What are the various product due to loss of HBr from
Br
CH3 CH3 CH3

CH3 CH3 CH2
Ans.
(major) (minor) (minor)
(IV) DEHYDRATION OF ALCOHOLS
Alcohols when heated in presence of following reagents undergo loss of water molecule and form
alkenes. The elimination is  elimination.
(i) H2SO4 / 160ºC
(ii) H3PO4 / 
(iii) P2O5 / 
(iv) Al2O3 / 350ºC undergo loss of water molecule and form alkenes
P2O5 or conc. H2SO4 or Al2O3

General Reaction RCHCH2OH R – CH = CH2 + H2O
CH2OH CH 2 CH3
P2O5 or conc. H2SO4 or Al2O3

e.g. +
(I) (II)
Minor Major
Q.1 If the starting material is labelled with deuterium as indicated, predict how many deuterium will be
present in the major elimination product ?
HO CD3 HO CD3
D D
(a) (b) D D
H2SO4 H2SO4
CH3 CH2OH CH3 CH2
Conc. H2SO4
Q.2 +
Major Minor
Explain the mechanism ?
(V) BY PYROLYSIS OF ESTERS

Thermal cleavage of an ester involves formations of a six membered ring in the transition state
leading to the elimination of an acid leaving behind an alkene.
H H H
R2C O R2C O R2C o
500ºC +
H2C C c
H2C C H2 C
Me o Me
O Me O
As a direct consequence of cyclic transition state, both the leaving groups namely proton and
carboxylate ion are eliminated from the cis position. This is an example of syn elimination.
(VI) BY HOFMANN ELIMINATION METHOD
Alkenes can be prepared by heating quaternary ammonium hydroxide under reduced pressure at a
temperature between 100ºC and 200ºC.
Less substituted alkenes are formed as major product in this case, which are defined as Hofmann
alkenes.
CH3
CH3 – N – CH2 – CH 2 – H + OH (CH 3)3N + CH 2 = CH 2 + H2O
CH 3
CH 3 CH 2 – CH2 – CH3 CH3 CH 2 – CH2 – CH 3

–
OH
CH3 – CH – CH2 – N – CH2 – CH2 CH 2 = CH 2 + CH 3 – CH – CH2 – N
CH3 H CH3
less crowded 'H'
(VII) BY WITTIG REACTION

The aldehydes and ketones are converted into alkenes by using a special class of compounds called
phosphorus ylides, also called Wittig reagents.
The Triphenyl group of phosphorane has a strong tendency to pull oxygen atom of the aldehyde or
ketone via a cyclic transition state forming an alkene.
R'' R''
C=O C–O
R'' R'' R
R''
C=C + Ph3P = O
R – C – PPh3 R'' R'
R – C – PPh3
R'
ylide
R'
(R, R’, R” and R”’ may be hydrogen or any alkyl group)
Me
C=O
Me
e.g. Ph3P: + CH3 – Br [Ph3P – CH3] Br Bu-Li
Ph3P – CH3
Methyltriphenyl Ylide
phosphorium salt
Me
Ph3P = O + C = CH2
Me
Product alkene
Ex.7 Complete the following reaction :
H (i) Ph3P
C = PPh3 + O=C
H CH = CH 2 (ii) :B
Ans.
H
C=C H
H C=C
H H
1-Phenyl-1, 3-butadiene
Ex.8 Identify the (X), (Y), and (Z) in the following reactions
O
(i) Ph3P
(i) PhCH2Br + CH3 – C – CH3 (X)
(ii) :B
(i) Ph3P
(ii) CH3I + PhCOCH3 (Y)
(ii) :B
(i) Ph3P
(iii) PhCH2Br + PhCH = CHCHO (Z)
(ii) :B
Ans. (X) = Ph – CH = C(CH3)2
(Y) = Ph – C(CH3) = CH2
(Z) = Ph – CH = CH – CH = CH – Ph
Q.3 Complete the following reactions
(i) Ph 3P
(i) CH3I +
(ii) :B
(i) Ph3P
(ii) C2H5Br +
(ii) :B
9. Chemical reactions of alkenes

(I) CATALYTIC HYDROGENATION OF ALKENES : (HETEROGENEOUS HYDROGENATION)
Hydrogenation : The function of catalyst
Hydrogenation of a alkene is exothermic reaction (Hº = – 120 kJ mol–1)
Ni
R – CH = CH – R + H2 R – CH2 – CH2 – R + heat
As a consequence ,both hydrogen atoms usually add from the same side of the molecule. This mode
of addition is called a syn addition.
Hydrogenation of an alkene is formally a reduction, with H2 adding across the double bond to give
an alkane.
The process usually requires a catalyst containing Pt, Pd or Ni.
Pt
e.g. CH3 – CH – = CH – CH3 + H2 CH3 – CH2 – CH2 – CH3
D H
H2 D
e.g.
Pt D
D H
Ex.9 Complete the following reactions :

Pd,Pt or Ni
CH3CH = CH2 + H2 ?
Sol. CH3CH2CH3
(II) ELECTROPHILIC ADDITION REACTIONS :

Mechanism
Step 1 : Attack of the electrophile on  bond forms a carbocation.
C=C +E –C–C
E
Step 2 : Attack by a nucleophile gives the product of addition
–C=C + Nu: –C–C–

E E Nu
(i) Acid-Catalyzed Hydration of Alkenes

Alkenes add water in the presence of an acid catalyst to yield alcohols. The addition takes place
with Markovnikov regioselectivity. The reaction is reversible, and the mechanism for the acid-
catalyzed hydration of an alkene is simply the reverse of that for the dehydration of an alcohol.
The carbocation intermediate may rearrange if a more stable carbocation is possible by hydride or
alkanide migration. Thus, a mixture of isomeric alcohol products may result.
H –C–C–
General Reaction C=C + H2 O
H OH
(Markovnikov
orientation)
Mech.
Step 1 : Protonation of the double bond forms a carbocation
H H
:
C=C +H–O–H –C–C+ + H2 O :
Step 2 : Nucleophilic attack by water

H
H
H
+
O–H
C–C + H 2O
–C–C–
Step 3 : Deprotonation to the alcohol
H
:
H H
O–H :OH
:
–C–C– + H2O: –C – C – + H3O
+
H2O, H
e.g. CH3CH = CH2 CH3CHCH3
Propene
OH
Isopropyl alcohol
CH 3 CH3 H
50% H2SO4
e.g. CH 3 – C – CH = CH2 CH3 – C – C – CH3
CH 3 OH CH3
3, 3-Dimethyl-1-butene 2, 3-Dimethyl-2-butenol
(major product)
Ex.10 Identify the product in following reaction
CH3
D 2O / D
CH3 – C = C – CH3
CH3 H
Ans. CH3 – C – C – CH 3
OD D
(ii) (a) Oxymercuration - Demercuration

Alkenes react with mercuric acetate in a mixture of water and tetrahydrofuran (THF) to produce
(hydroxyalkyl) mercury compounds. These can be reduced to alcohols with sodium borohydride and
water :
Oxymercuration
OH O
O
THF
General Reaction C=C + H 2O + Hg OCCH –C – C– O + CH3COH
3
2
Hg – OCCH 3
OH O
–C – C– O + OH + NaBH4 –C – C– + Hg + CH3CO (Demercuration)
Hg – OCCH3 HO H
In the oxymercuration step, water and mercuric acetate add to the double bond; in the
demercuration step, sodium borohydride reduces the acetoxymercury group and replaces in with
hydrogen. Then net addition of H –and –OH takes place with Markovnikov regioselectivity and
generally takes place without the complication of rearrangements.
OH
Hg(OAc)2 NaBH4
e.g. H2C = CHCH2CH3 CH3 – CHCH2 CH3
H2O
1-butene 2-butanol
(b) Alkoxymercuration - demercuration
OR OR
General reaction C=C ROH NaBH4
+ Hg(OAc)2 –C – C– –C – C–
HgOAc H
(Markovnikov
orientation)
e.g. CH2 = CH – CH2 – CH3 (i) Hg(OAc)2, CH3OH

CH3 – CH – CH2 – CH3
1-butene (ii) NaBH4
OCH3
2-Methoxy butane
Ex.11 Supply the structures for (X) and (Y) in the following two – step reaction :
Hg(OAC)2 NaBH4 / NaOH
(X) (Y)
C3H7CH = CH2
THF / H2O
Sol. (X) = C3H7CH(OH)CH2–HgOAC (Y) = C3H7CH(OH)CH3
(An organomercurial alcohol)
Ex.12 Identify final product in the following :
Hg(OAC)2 NaBH4
(a)
CH3OH
OH
Hg(OAC)2 NaBH4
(b)
NaOH
Ans. (a) (b) O
OCH3
Q.4 Identify the product in the following reaction
CH3
Hg(OAc)2, H2O NaBH4
CH3 – C – CH = CH2
CH3
3, 3-Dimethyl - 1- butene
(iii) Hydroboration-oxidation (SYN ADDITION)
ROH H2O2, – OH
General Reaction C=C + BH 3.THF –C – C– –C – C–
H B–H H OH
anto-Markovanikov
orientation
H (syn stereochemistry)
An alkene reacts with BH3 : THF of diborane to produce an alkylborane. Oxidation and hydrolysis of
the alkylborane with hydrogen peroxide and base yields an alcohol.
CH3
BH3 ; THF H
e.g. CH3 + enantiomer + dialkyl-and trialkylborane
anti-Markovnikov and
syn additon
H
B
H H H
Oxidation
CH3 H2O2, HO CH3

H H
Boron group is + enantiomer
replaced with
H retention of H
B configuration OH
H H
In the first step, boron and hydrogen undergo syn addition to the alkene in the second step,
treatment with hydrogen peroxide and base replaces the boron with –OH with retention of
configuration. The net addition of –H and –OH occurs with anti Markovnikov regioselectivity and syn
stereoselectivity. Hydrogboration –oxidation therefore, serves as a useful regiochemical complement
to oxymercuration demercuration.
CH3
(i) BH3, THF H
e.g. H
(ii) H2O2, OH
OH
e.g.
CH3 CH3 CH3

+ –
H (dil. H2SO4) CH3 shift
CH3 – C – CH = CH2 CH3 – C – CH – CH3 CH3 – C – CH – CH3
3º carbocation
CH3 CH3 CH3
H2O
2ºcarbocation (–H )
CH3 OH CH3
Hydroboration
CH3 – C – CH2 – CH2OH CH3 – C – CH – CH3
oxidation
CH3 CH3
CH3 OH
Hg(OAc) 2
CH3 – C – CH – CH3
NaBH4
CH3
(i) Hydration with dil. H2SO4 proceeds via carbocation rearrangement

(ii) Hydration with Hg(OAc)2, H2O, following by NaBH4 proceeds via Markonikov’s rule
(ii) Hydration with (BH3)2 followed by H2O2 / OH– proceeds via Anti Markonikov’s rule
Q.5 Identify x, y, z and w in the following reaction :
HBr H2SO4 (i) BH3/THF HBr

(W) z (X) (Y)
(ii) H 2O2/OH
Also select pair of isomers if any
(iv)Addition of hydrogen halides
General Reaction C=C + H–X –C – C –

(HX = HCl, HBr, or HI) H X
Markovniko
orientation
(anti-Markovnikov with
HBr and peroxide)
HBr (dark)
CH3CHBrCH3 Markovnikov addition
2-Bromopropane
(Isopropyl bromide)
CH3CH = CH2
peroxides
CH3CH2CH2Br
HBr (light) 1-Bromopropane Anti - Markovnikov addition
(n-Propyl bromide)
Note : (1) Anti Markovnikov addition is valid only for HBr in presence of
peroxide and light only.
(2) HF, HCl and HI give only polar addition and give Markovnikov product only.
HI CH3CHICH3
e.g. CH3CH = CH2
Propene 2-Iodopropane
(Isopropyl iodide)
CH3 CH3 CH3 CH3

H Br
H – Br H Br H
H H H H
product
positive charge
on less substituted carbon
less stable ; not formed
H H
CH2 C
H
e.g. + HI I
+ HCl
H
Cl H
H
Ex.13 Predict the major products of the following reactions and propose mechanism to support your
predictions.
CH3 O O
(A)
H3C – C = CH2 + HBr + CH3 – C – O – O – C – CH3
CH3
(B) + HBr + CH3 – CH2 – O – O – CH2 – CH3
CH3 CH3
(C) HC = CH – CH3 + HBr + H3C – C – O – O – C – CH3
CH3 CH3
CH3
CH3
Br
Sol. (A) H3C – CH – CH2Br (B) (C) H2C – CH – CH3
Br
Ex.14 Identify the products in the following reactions :

(a) F3C – CH = CH2 + HCl
(b) O2N – CH = CH2 + HCl
(c) CH3O – CH = CH2 + HCl
(d) PhCH = CHCH3 + HCl
(e)
+ HCl
H3C CH 2CH3
Q.6 Give the products of the following reactions : –
CH3
CH3 – C – CH = CH2 HBr
CH3
3, 3-dimethyl - 1 - butene
Q.7 Give the reactant (alkene) of the following products.
CH3
Br CH3
Br
X Y
1-bromo-1-methyl 2-bromo-1-methyl
cyclohexane cyclohexane
(v) Addition of halogen

Halogen add to alkenes to form vicinal dihalides.
X
C=C + X2 –C – C–
General Reaction X
usually anti addition
(X2 = Cl2, Br2)

The nucleophile attacks the electrophilic nucleus of one halogen atom, and the other halogen serves
as the leaving group, departing as halide ion. Many reactions fit this general pattern.
Note : (i) F2 is not added because F+ is never generated. Morever reaction is explosive giving CO2 &
H2O
(ii) I2 is not added because reaction is reversible with equilibrium in backward direction.
(iii) Reaction with bromine is basis for test of alkenes.
(iv) Halogen addition is stereospecific anti addition
(v) Halogens can also be added in presence of sun light and give free radical addition.
(Reactivity of halogen addition in sunlight is F2 (explosive) > Cl2 > Br2 > I2)
Mech.
Step-1 Formation of a halonium ion
: :
: :
: :
C=C + : X – X: –C – C– + :X:
Halonium ion
Step-2 Opening of the halonium ion

:
: :
X :X:
–C – C– –C – C–
:X:
:
: :
:X:
X attacks from the back side of halonium ion.
Br2 in CCl 4
e.g. CH 3CH = CH 2 CH3CHBrCH2Br
Propene 1,2-Dibromopropane
(Propylene) (Propylene bromide)
–
:Br back side
e.g. H attack H Br + enantiomer
+
H H Br Br H
trans
Br – Br
Ex.15 Give the product of the following reaction.

Me2C = CH2 + ICl  ?
Sol. Cl is more electronegative than I making I the E+ that, according to the Markovnikov rule, adds to
the C with the greater number of H’s. The product is 2-chloro-1-iodo-2-methylpropane,
(Me2CClCH2I).
Ex.16 What are the products and (type of isomers) when Br2 adds to : -
Br2
(a) (b) Br2
Br
& enantiomer & enantiomer
Ans. (a) (b)
Br Br
Q.8 Account for the acid-catalyzed isomerization of cis-2-butene to trans-2-butene
(vi) Hydroxylation of Alkenes

(a) Syn Hydroxylation : (Reaction with Bayer’s reagent, (cold dilute alkaline KMnO4 solution).
Both OH groups are added from same stereochemical side. This addition is example of syn addition
General Reaction C=C + KMnO4 + OH, H 2O

–C – C–
(or OsO4, H2O2)
OH OH
(syn addition)
e.g.
–
OH + MnO2 + H2O
H H H H
H2O
H H O O OH OH
cis-glycol
O O Mn
O O–
Mn
O O–
The same function of syn addition of 2 - OH groups is performed by OsO4 / H2O2
O O
2H2O H H + H2OsO4
+ Os H H
O O OH OH
H H O O
Os
O O
H
OsO4.H2O2 OH
e.g.
OH
H
Cyclohexene Cis-Cyclohexane-1,2-diol
(b) Anti hydroxylation
OH
+
H , H2O
General Reaction C=C + R – C – OOH –C – C– –C – C–
O O
OH
(anti addition)
O H
+ OH
e.g. H – C – OOH, H3O
H
OH
Cyclohexene
Trans-Cyclohexane-1,2-diol
Ex.17 Identify the product in the following reaction :
KMnO 4
(x)
Cold
OH
Ans.
OH
Ex.18 Identify the product (X) in the following reaction :
CH = CH2
C6H5CO3H
CHCl3 at 298K
CH = CH2
Ans. (x) : O
Since C = C bond in ring is more substituted than that in open chain.
(vii) Addition of carbenes to Alkenes :

Methylene is the simplest of the carbenes : uncharged, reactive intermediates that have a carbon
atom with two bonds and two nonbonding electrons. Like borane (BH2), methylene is a potent
electrophile because it has an unfilled octet. It adds to the electrons rich pi-bond of an alkene to
form a cyclopropane.
C H C H
General Reactions + :C C
C H C H
Heating or photolysis of diazomethane (CH2N2) gives nitrogen gas and methylene.
H
Heat or ultraviolet light
N = N = CH2 N = N – CH2 N2 + C
H
diazomethane Methylene
There are two difficulties with using CH2N2 to cyclopropene double bonds. First, it is extremely toxic
and explosive. A safer reagent would be more convenient for routine use. Second, methylene
generated from CH2N2 is so reactive that it inserts into C – H bonds as well as C = C bonds.
H 3C H
C=C CH2 – N = N; shv
e.g.
H H
Propene
H 3C H H 3C H H – CH 2 – H3C H
C–C + C=C + C=C
H H H CH2 – H H H
CH2
H 3C H
+ C=C
H – CH2 H
Ex.19 Identify the product in the following reactions

light
CH3CH = CHCH3 + CH2N2
(a)
2-Butene Diazomethane
(b) + CHBr3 NaOH /H2O
Br
Ans. (a) CH3CH – CHCH 3 + N2 (b)
Br
CH2
1,2-Dimethylcyclopropene
(III) EPOXIDATION OF ALKENES :

An alkene is converted to an epoxide by a peroxyacid, a carboxylic acid that has an extra oxygen
atom in a –O – O – (peroxy) linkage.
O O
O
General Reaction C=C +R–C–O–O–H C C + R – C – O – H (acid)
Epoxide (Oxirane)
The epoxidation of an alkene is clearly an oxidation, since an oxidation, since an oxygen atom is
added Peroxyacids are highly selective oxidizing agents. Some simple peroxyacids (sometimes called
per acids) and their corresponding carboxylic acids are shown below :
O O
R–C–O–O–H C–O–O–H
a peroxyacetic acid
Peroxy benzoic acid
Mech.
O R R O R
C O C C O C C
O C
H O O +
C O C H O
C
H
transition state Acid
Alkene peroxyacid
e.g.
O H
O
Cl C O
O H3C CH3
MCPBA Cl C H
CH3 CH3 O O
C=C +
H H
Cis CH2Cl2
H H
Cis
H CH3
CH3 H O
C=C
H CH3
Trans
H3 C H
Trans
Ex.20 Complete the following reaction
+ C – OOH (X) + (Y)
Cyclohexene O
Cl
Ans. (X) O (Y) C – OH
Epoxycyclohexane Cl O
Ex.21 Predict the product, including stereochemistry where appropriate, for the m-chloroperoxy-benzoic
acid expoxidations of the following alkenes.
H H H CH 2CH2CH3
(a) CH C = C (b) C=C
3 CH2CH2CH3 CH3 H
(c) Cis-cyclodecene (D) Trans-cyclodecene
(IV) HALOHYDRIN FORMATION
General Reaction –C = C– + X2 + H2 O –C = C– + HX (X2 = Cl2, Br2 )
X OH
X’ and H2O are generated as attacking species from X2 + H2O
Cl2, H2O
e.g. CH3CH = CH2 CH3CH – CH2
Propylene OH Cl
(Propene)
Propylene chlorohydrin
(1-Chloro-2-propanol)
Ex.22 Predict the product in the following reactions
H
Br2 H2O
(a)
Anti addition
H (Markovnikov Orientation)
Cyclopentene
H2O
(b) + Br2 Anti addition
(Markovnikov Orientation)
H CH3
Br OH
Ans. (a) (b)
Br Br
H
H
trans-1,2-dibromocyclo
pentane (92%)
(V) OXIDATIVE CLEAVAGE OF ALKENES
(i) Cleavage by permanganate
In a KMnO4 hydroxylation, if the solution is warm or acidic or too concentrated, oxidative cleavage
of the glycol may occur. Mixtures of Ketones and carboxylic acids are formed, depending on whether
there are any oxidizable aldehydes in the initial fragments. A terminal = CH2 group is oxidized to CO2
and water.
R R' KMnO4 R R'

General Reaction C=C C=O + O=C
R H Warm R H
conc.
Glycol Ketone Aldehyde
(Stable) (Oxidizable)
R'
O=C
OH
O OH
e.g. KMnO4
+
Warm C
O
conc.
KMnO 4
e.g.
Warm + CO2
conc. COOH
O COOH
Ex.23 What is the main utility of this reaction and why is it superior to KMnO4 cleavage for this purpose
Sol. It locates the position of C = C’s in molecules. KMnO4 cleavage is more vigorous and can oxidiz
other groups, i.e., OH.
Ex.24 Give the products of the following reactions : -
H H
or KMnO4 (aq.)
+ KMnO4 X C=C Y
(i) (aq.base) OsO 4 in (ii) or
H 2O 2 H3C CH3 OsO4 in H2O 2
H3C H
KMnO 4 (aq.)
C=C Z
(iii) or
H CH3 OsO4 in H2O2
Sol. X = Cis-1, 2-Cyclopentanediol Y = meso - CH3 – CHOH – CHOH – CH3

Z = rac – CH3CHOHCHOHCH3
Q.9 Complete the following reactions
CH3
hot KMnO4 hot KMnO4
(a) (X) (b) Y
(or K2Cr 2O7) (or K2Cr 2O7)
CH3
1,2-dimethylcyclobutene
(ii) Ozonolysls : Like permanganate ozone cleaves double bonds to give ketones and aldehydes.
However, ozonolysis is milder, and both ketones and aldehydes can be recovered without further
oxidation.
R R'
R R' C C
General Reaction C=C + O3
R H R H
Ozonide
(CH3)2S
R R'
C=O + O=C
R H
Ketone
Mech.
C O C
O
C O C
Monozonide (Primary ozonide)
C
C
O O
O
C C
Ozonide
O
R' R R'
R
CH3 – S – CH3 C=O + O=C + CH – S – CH
C C 3 3
H dimethyl sulfide R H
R Dimethyl sulfoxide
(DMSO)
H H
O3 H2O, Zn
e.g. CH3CH2CH = CH2 CH3CH2C = O + O = CH
1-Butene
(i) O3
e.g. CH3CH2CHO + CH3(CH2)4CHO (65%)
3 - nonene (ii) (CH3)2 S
CH 3 CH3 H
O3 H2O, Zn
e.g. CH3 – C = CH2 CH3C = O + O = CH
(IX) HALOGENATION, ALLYLIC SUBSTITUTION
(500-600ºC)
X – C – C = C–
General Reaction H – C – C = C– X2 = Cl2, Br 2

NBS or NCS
X – C – C = C–
(allyl halide)
O
NBS = N-Bromosuccinimide N – Br
O
NCS = N-Chlorosuccinimide N – Cl
Cl2, 600ºC
e.g. CH3CH = CH2 Cl – CH2CH = CH2
Propylene allyl chloride
(Propene) (3-Chloro-1-propene)
Ex.25 CH2 = CHCH2CH = CH2 NBS (X), (X) is
(A) CH 2 = CH – CH–CH = CH2 (B) CH2 = CHC = CHCH2Br
Br
(C) CH2 = CHCH2CH = CHBr (D) CH2 = CHCH2C = CH2
Br
Ans. A
Ex.26 Assertion (A) : Propene (CH3CH = CH2) undergoes allylic substitution.
Reason (R) : CH2 = CHCH2 (allylic) free radical is stabilised by resonance.
Ans. (A)
Q.10 Identify the product (X) in the following reaction
+ NBS (X)
Cyclohexene
Ex.27 Identify the product in the following reactions

H
(i) O3
(i) O3
(a) (ii) (CH3)2 S (b)
(ii) (CH3 )2 S
H
H
H
C
Ans. (a) O (b) CHO
H C CHO
H O O
Ex.28 Identify the products (x, y) of following reaction : -
CH3 CH3
O3 /H2O, Zn
CH3 – C = CHC – CH3 (X) + (Y)
CH3
CH3 O CH3
Ans. (X) : CH3 – C = O (Y) : H – C – C – CH 3

CH3
Q.11 Predict the major product of the following reaction
(i) O3
+
(ii) (CH3)2 S
10. (a) CH3 – (CH2)3 – CH = CH2 < CH3 – (CH2)2 – CH = CH – CH3 < H3C – (CH2)2 –C = CH 2
CH3
H H H3C H
(b) C=C < C=C < H3C – C = CH2
H3C CH3 H CH3
CH3
cis-2-butene trans-2-butene
(c) CH2 – CH = CH – CH3 < CH = CH – CH 2 – CH 3 < H 3C – C = CH – CH3
(Greater the stability of carbocation (intermediate), greater the hydration.)
(VIII) ADDITION OF FREE RADICALS
peroxides
General Reaction – C = C – + Y – Z –C–C–
or light
Y Z
BrCCl3 peroxides
e.g. n – C6H13CH = CH2 n – C6H13CH – CH2 – CCl3
1-Octene Br
3-Bromo-1,1,1-trichlorononane
HBr/R2O2
n – C6H13CH – CH2 – Br
Ex.29 Which of the following reactions are correct ?
peroxides
(a) C6H13CH = CH2 + BrCCl3 C6H13CHCH 2CCl3
Br
peroxides
(b) RCH = CH2 + CCl4 RCHCH2CCl3
Br
(A) only (a)

(B) only (b)
(C) both are correct
(D) None of these
Ans. HYDROCARBON
(C) Page # 41
+HBr
Ex.30 Isobutylene product is :
peroxides
(A) Tertiary butyl bromide (B) Isobutyl bromide

(C) Tertiary butyl alcohol (D) Isobutyl alcohol
Ans. (B)
ALKYNES
1. Introduction
A triple bond gives an alkyne four fewer hydrogen atoms than the corresponding alkane. There fore the
triple bond contributes two degree of unsaturation (DU).
Alkynes are not as common in nature as alkenes, but some plants do use alkynes to protect themselves
against disease or predators. Acetylene is by far the most important commercial alkyne. Acetylene is
an important industrial feedstock but its largest use is as the fuel for the oxyacetylene welding torch.
2. Structure and Bonding in Alkynes

(1) Alkynes are hydrocarbons that contain carbon -carbon triple bond.
(2) Alkynes are also called acetylenes because they are derivatives of acetylene.
(3) The general formula is : CnH2n–2. (one triple bond)
(4) In alkyne C  C bond length is 1.20 Å.
(5) Its bond energy is 192 kcal. mol–1
(6) The hybridization of carbon atoms having triple bond (C  C) in alkynes is sp
(7) Overlapping of these sp hybrid orbitals with each other and with the hydrogen orbitals gives the
sigma bond framework which is linear (180º) structure.
(8) Two  bonds result from overlap of the two remaining unhybridized p orbitals on each carbon atom.
These orbitals overlap at right angles (90º) to each other, forming one  bond with electron density
above and below the C – C sigma bond, and the other with electron density in front and in back of the
sigma bond. This result in a cylindrical  electron cloud around  bonded structure
1.20Å 1.06Å
180º
H C C H H–C–C–H
Note : Any type of stereoisomerism does not arise in acetylenic bond due to linearity of C  C bond.
Ex.1 Cis-trans isomerism is not possible in alkynes because of :

Ans. 180º bond-angle at the carbon-carbon triple bond.
Ex.2 Draw the geometrical isomers of hept -2-en-5-yne?
MeC CCH2 H MeC CCH2 Me

C C C C
Ans. H Me H H
(trans) (Cis)
Q.1 C6H10 (alkyne) is optically active. What is its structure?
Q.2 C5H8 (alkyne) has three-degree of unsaturation. What is the structure ? What is the isomerism show?
4. Physical Properties of Alkynes

(1) Alkynes are relatively nonpolar (w.r.t. alkyl halides and alcohols) and are nearly insoluble in water
(but they are more polar than alkenes and alkanes). They are quite soluble in most organic solvents,
(acetone, ether, methylene chloride, chloroform and alcohols).
(2) Acetylene, propyne, and the butynes are gases at room temperature, just like the corresponding
alkanes and alkenes. In fact, the boiling point of alkynes are nearly the same as those of alkanes and
alkenes with same number of carbon atoms.
Table
Relative density
Name Formula M.p.,ºC B.P., ºC
(at 20ºC)
Acetylene HC CH – 82 – 75
Propyne HC CCH3 – 101.5 – 23
1-Butyne HC CCH2CH3 – 122 9
1-Pentyne HC C(CH2)2CH3 – 98 40 0.695
2-Butyne CH3C CCH3 – 24 27 0.694
2-Pentyne CH3C CCH2CH3 – 101 55 0.714
3-Methyl-1-butyne HC CCH(CH3)2 29 665
TABLE - COMPARATIVE STUDY OF ALKANES, ALKENES, ALKYNES
o.
.N Properties Alkanes Alkenes Alkynes
S
1. Bond length 1.54 (C – C) 1.32 (C = C) 1.20 (C C)
-1
2. Bond energy (KJmol ) 415 (C – C) 615 (C = C ) 835 (C C)
3 2
3. Hybridization sp sp sp
4. % s character 25% 33% 50%
5. pKa 50 44 25
6. Electronegativity of 'C' Increases
7. Polarity Increases
8. Rate of hydrogenation less more
9. Rate of electrophilic more less

addition reaction
10. Heat of combustion C 2H 6(-373) C 2H 4(-337k cal) C 2H 2(-317kcal)
3
11. Density (g/cm ) C 3H 8(-373) C 3H 6(0.52k cal) C 3H 4(0.67)
109º28'
121.2º
H H H H 180º
C–C C C
12. Structure H–C C–H
H H
H H H
H 1.06Å
1.09Å 1.08Å
ethene ethyne
ethane
13. Shape Tetrahedral Planar Linear
Ex.3 Which has a longer carbon-methyl bond, 1-butyne or 2-butyne. Explain?

Ans. The bond from the methyl group in 1-butyne is to an sp3-hybridised carbon and so is longer than the
bond from the methyl group in 2-butyne, which is to an sp-hybridised carbon.
CH3–CH2–C  CH CH3–C  C – CH3
sp3 sp3 sp3 sp
Ex.4 Arrange the following bond-lengths in increasing order.
(e)
H3C (c) C C – CH3
(a) (d)
C C
H H (b)
Ans. (d) < (b) < (c) < (e) < (a)
Q.3 Arrange C – H bond -lengths (,,) in increasing order as shown : –

H H H
H–C C–C=C–C–H
H
6. Laboratory test of Alkyne
Table-V
Functional Reagent Observation Reaction Remarks

Group
(1) Bayer's HC CH + H2O + O alk. KMnO4

Pink Colour
Reagent OHC – CHO Hydroxylation
disappears
alk.dil.cold KMnO4
–C C– (2) Br2/H2O Red Colour Br2 + HC CH Bromination

decolourises
(3) O 3 (ozone) O3
Acid Formed R – C C – R' RCOOH + Ozonolysis
RCOOH
7. Laboratory test of terminal alkynes

When triple bond comes at the end of a carbon chain. The alkyne is called a terminal alkyne.
acetylenic hydrogen
H–C C – CH2CH 3
1-Butyne, terminal alkyne
Table-VI
Functional Reagent Reaction

Group
(1) Cuprous chloride R–C CH + CuCl NH 4OH

+NH4OH Red ppt. R – C C Cu (red)
+
R–C CH + Ag
R–C C–H (2) AgNO3 + NH4OH White ppt
R – C C Ag (white)
(3) Na in ether Colourless HC CH + 2Na

gas
Na – C C – Na + H2
8. Acidity of Terminal Alkynes

Terminal alkynes are much acidic than other hydrocarbons due to more electronegative sp hybridised
carbon. The polarity (acidity) of a C – H bond varies with its hydridization, increasing with the increase
in precentage's character of the orbitals.
sp3 < sp2 < sp
Weakest
acid
.
o
—
.N
Compound Conjugate Base Hybridization of C %Character

S
1. H H H H
3
– sp 25% 50
H–C–C–H H–C–C
H H H H
–
H H H 2
sp 33% 44
2. C C C C
H H H H
–
3. NH3 NH 2
sp 50% 25
4. H–C C–H H–C C
16-18
5. R – OH R – O–
Stronger
acid
The hydrogen bonded to the carbon of a terminal alkyne is considerably more acidic than those bonded
to carbons of an alkene and alkane (see section). The pKa values for ethyne, ethene & ethane
illustrate this point
H H
H H
H–C C–H C C H–C–C–H
H H
H H
pKa = 25 pKa=44 pKa=50
The order of basicity of their anions is opposite to that of their relative acidity:
Relative Basicity
CH3CH2: > H2C = CH:– > HC  C:–
Relative acidity
H – OH > H – OR > H – C CR > H – NH2 > H – CH=CH2 > H – CH2CH3
pKa 15.7 16-17 25 38 44 50
Relative Basicity
OH < OR < C CR < NH2 < CH = CH2 < CH2CH3
9. General methods of preparation :

(I) By dehydro halogenation of gem and vic dihalide:
H H
2 2NaNH
General Reaction: RCH = CHR + Br2  R – C – C – R R – C  C – R + 2NaBr
Br Br
A vic - dibromide
The dehydrohalogenations occur in two steps, the first yielding a bromoalkene and the second alkyne.
Mechanism :
Step 1
H H
+ R H
H–N+ R–C–C–R C C + H – N – H + Br
Br R
H Br Br H
Amide ion Vic-Dibromide Bromoalkene Ammonia Bromide
(The strongly ion
basic amide ion
brings about an
E2 reaction.)
Step 2
R H
C C + N–H R–C C – R + H – N – H + Br
Br R
H H
Bromoalkene Amide ion Alkyne Ammonia Bromide
(A second E2 reation ion
produces the alkyne)
Br2 NaNH2
e.g. CH3CH2CH = CH2 CCl4
CH3CH2CHCH 2Br CH3CH2C  CH
mineral oil
110-160ºC
Br
CH3CH2CH=CHBr
+
CH3CH2C = CH2 NaNH2 NaNH2
e.g. [CH3CH2C  CH] CH3CH2C  CNa
mineral oil
110-160ºC
Br
NaNH2
CH3CH2C  C:–Na+ CH3CH2C  CH + NH3 + NaCl
O Cl
CH
C C CH3 C
CH3 PCl5 PCl5
Cl
General Reaction 0ºC 0ºC
(-POCl3) (-POCl3)
Cyclohexyl methyl A gem-dichloride Cyclohexylacetylene
Ketone (70-80%) (46%)
Ex.5 Give the structure of three isomeric dibromides that could be used as starting materials for the
preparation of 3,3-dimethyl-1-butyne.
CH 3 CH3 CH 3 Br
Sol. (I) CH3–C–CH2–CHBr2 (II) CH3–C – CH – CH2 (III) CH3–C – C – CH3
CH 3 CH3 Br Br CH 3 Br
Ex.6 Show the product in the following reaction

CH3
EtOK
CH – CH 2 ?
EtOH
Br Br
CH 3
C CH
Sol.
Q.4 1,1-dibromopentane on reaction with fused KOH at 470 K gives 2-pentyne

Br
fused KOH
Br-CHCH2CH2CH2CH3 CH3CH2C CCH3
470 K
1,1-dibromo pentane 2-pentyne
Give the mechanism of this rearrangement.
(II) By Dehalogenation of Tetrahaloalkane:

X X
2 Zn dust
General Reaction R – C – C – R' R–C C – R' + 2Zn X2
Alcohol,
X X
(III) Replacement of The Acetylenic Hydrogen atom of terminal Alkynes.
NaNH2
General Reaction R – C CH R–C C + R' – X R–C C – R'
Sodium ethynide and other sodium alkynides can be prepared by treating terminal alkynes with sodium
amide in liquid ammonia.
liq. NH3 +
H–C CH – H + NaNH2 H–C C Na + NH3
liq. NH3 +
CH3 – C CH – H + NaNH2 CH3C C Na + NH3
R–C C: Na + R'CH2 – Br R–C C – CH2R' + NaBr

Sodium Primary Mono or disubstituted
alkynide alkyl halide acetylene
(R or R' or both may be hydrogen)
The following example illustrates this synthesis of higher alkyne homologues.
liq. NH3
CH3CH2C C: Na + CH3CH2 – Br CH3CH2C CCH2CH3 + NaBr
6 hours 3-Hexyne
(75%)
2
SN
R–C C + R'–X R–C C–R' + X
(R'–X must be an unhindered primary halide or tosylate)
The unshared electron pair of the alkynide ion attacks the back side of the carbon atom that bears the
halogen atom and forms a bond to it. The halogen atom departs as a halide ion.
2 eq. + – – + 2 moles (CH3X)
e.g. H–C=C–H Na C = C Na CH3–C = C – CH3
NaNH2
R' MgX R' X
e.g. R–CC–H R–C C Mg X R – C  C – R'
+ R' H
(i) NaNH2
C C–H (ii) ethyl bromide
C C – CH2CH3
e.g.
Ethynylcyclohexane 1-Cyclohexyl-1-butyne
(ethylcyclohexyl acetylene)
Addition of acetylide ions to carbonyl groups
Nu C=O Nu – C – O
R' R'
R' H2O (or H3O)
R–C C + C=O R–C C–C–O R–C C – C – OH
R'
R' R'
O OH
e.g. H2 O
H–C C + CH3CH2 – C – H H–C C – CH – CH2CH3
Sodium Propanal 1-Pentyn-3-ol
acetylide
CH 3 CH3 Ph
(i) NaNH2
e.g. CH3 – CH – C C–H CH3 – CH – C C – CH – OH
(ii) PhCHO
+
(iii) H 3O
3-Methyl-1-butyne 4-Methyl-1-Phenyl pent-2-yne-1-ol
O OH
(i) Na–C C–H
e.g. +
C C–H
(ii) H 3O
Cyclohexanone 1-Ethynylcyclohexanol(3º)
Ex.7 Show how to synthesize 3-decyne from acetylene along with necessary alkyl halides.
(i) NaNH2
Sol. H–CC–H (ii) CH3(CH2)5Br H3C – (CH2)5 – C  C – H
1-Octyne
(i) NaNH2
H3C – (CH2)5 – C  C – H (ii) CH3(CH2)5Br CH3 – (CH2)5 – C  C – CH2CH3
1–Octyne 3–Decyne
Q.5 Show how you would synthesize the following compound, beginning with acetylene and any necessary
additional reagents.
OH
CH–C C–CH2CH3
(IV) By Kolble's Electrolytic synthesis.

– +
CH–COO K CH
Electrolysis
–
+ H2 O + 2CO2 + 2KOH + H2
+ Current
CH–COO K CH
(V) By Hydrolysis of carbides
CaC2 + 2HOH  C2H2 + Ca(OH)2
MgC2 + 2HOH  C2H2 + Mg(OH)2
Mg2C3 + 4HOH CH3 – C  CH + 2Mg(OH)2
10. Chemical reactions of Alkyne

(I) Reduction to alkenes
(a) By Lindlar's reagent
R R
Pd/BaSO4, quinoline C=C
General Reaction R – C  R' + H2 (syn addition)
H cis H
(b) By Brich reduction
R H
Na + NH3 C=C
General Reaction R – C  C – R' (anti addition)
H Trans R
CH3CH2 CH2CH3
H2Pd/BaSO4
CH3CH2–C C–CH2CH3 quinoline
C C
H H
cis-3-hexene
e.g. Na + NH3
CH3CH2 H
C C
H CH2CH3
trans-3-hexene
(c) By hydroboration reduction

R R'
(i) BH3–THF
General Reaction R – C  C – R' (ii) CH3COOH
C C
H H
Ex.8 Identify (X) and (Y) in the following reaction
BH3.THF CH 3COOD
(Y)
CH3–CH2 – C  CH
BH3.THF CH3COOH
(X)
CH3CH2 H CH3CH2 H
Ans. (X) : C C (Y) : C C
H H H D
Q.6 Use two methods to convert 2-butyne to (z) – 2,3-dideutero-2-butene
Q.7 From 1–butyne, synthesize

(a) (E) –1-deutero-1-butene and
(b) 2-deutero -1-butene
Q.8 Write the equation for the reduction of 2-butyne with Na with EtOH.
(II) Addition of Halogen (X2=Cl2, Br2)

X X
X2 X2
R – C – C – R' (Anti-addition)
General Reaction R – C  C – R' R – CX = CX – R'
X X
Ex.9 Explain why alkynes are less reactive than alkenes toward addition of Br2.
Sol. The three memebered ring bromonium ion fromed from the alkyne (A) has a full double bond causing it
to be more strained and less stable than the one from the alkene (B).
HC = CH H2C – CH2
(A) (B)
Br Br
(A) less stable than (B)
Also, the C's of A that are part of the bormonium ion have more s-character than those of B, further
making A less stable than B.
(III) Addition of Hydrogen halides (Were HX = HCl, HBr, HI)
H X
H–X
General Reaction R – C  C – R' H–X R – CH = CX – R' R – C – C – R'
(Markovnikov addition)
H X
CH3-CH2 H Cl
HCl HCl
e.g. CH3CH2 – C C–H C C CH3CH2–C–CH3
1-Butyne Cl H
2-Chloro-1-butene Cl
2,2-dichlorobutane
Br H H Br
e.g. CH3–C  C – CH2CH3 + HBr  CH3–C = C – CH2CH3 + CH3–C = C – CH2CH3
H H Br
CH 2CH 2CH 3
HBr HBr
e.g. H – C  C – CH2CH2CH3 C C H – C – C – CH 2CH 2CH 3
H Br
H Br
Ex.10 Identify the product when one equivalent of HBr reacts with 1-pentene-4-yne
H
Ans. CH2 = CHCH2C  CH CH3 C HCH2C  CH Br
CH3CHCH2C CH
Br
stable 2º
alkyl carbocation
H
CH2 = CHCH2C  CH CH2=CHCH2 C =CH2
less stable vinyl carbocation
(It is not formed)
Ex.11 CH3C  CH 2HBr (X) + (Y)

Idntify (X) and (Y) in the above reaction.
Ans. After first HBr molecule is added, product is CH 3C = CH2 : Second addition CH3–C–CH3 and CH3–C–CH2.
Br Br Br
(2º) (1º)
Br
Since 2º carbocation ion is more stable than 1º, hence final product is CH3–C–CH3 Y is CH3CH2CHBr2
Br
(X)
(IV) Addition of water

(a) Mercuric ion catalyzed hydration:
Dil. HgSO4
General Reaction R – C  C – H + H2O Tauto.
Dil. H2SO4
(Martkovnikov rule) Vinyl alcohol Ketone

(unstable) (stable)
Electrophilic addition of mercuric ion gives a vinyl cation, which reacts with water and loses a proton to
give an organomercurical alcohol. Under the acidic reaction condition, Hg is replaced by hydrogen to
give a vinyl alcohol, callled an enol.
OH OH H
+2 + H H + O
Hg H2O/H H H
Mech. R–C C–H R–C=C–H C C C C C–C–H
+
Alkyne R Hg R H H
+2 Vinyl alcohol H
Hg methyl Ketone
(enol)
Vinyl cation (Keto)
O
Dil. HgSO4
e.g. CH3 – C  C – H + H2O CH3 – C – CH3
Dil. H2SO4
Propanone (acetone)
Dil. HgSO4
Ex.12 CH3 – C  CH + H2O Dil. H2SO4
X
Identify the (X) in the above reaction
Sol. (X) = CH3CCH 3 Acetone (a ketone) stable
Ex.13 When 2-heptyne was treated with aq. H2SO4containing some HgSO4, two products, each having the
moleuclar formual C7H14O, were obtained approximately in equal amounts. What are these two
compounds?
O
Dil. HgSO4
Ans. CH3CH2CH2CH2C  CCH3 Dil. H2SO4 +
2-Heptanone O
3-Heptanone
Q.9 From which alkyne could each of the following compound be prepared by acid-catalysed hydration?
O O O
(a) CH3CCH2CH2CH3 (b) (CH3)3CCCH3 (c) CH3(CH2)3C(CH2)4CH3
(b) Hydroboration-oxidation
In alkyne, except that a hindered dialkylborane must be used to prevent addition of two molecules of
borane across the triple bond.
General Reaction
H2O2 NaOH
O
(1) BH3, THF
e.g. CH3–C  C – H (2) H2O2, NaOH
CH 3–CH2–C–H
Propanal
Ex.14 Compare the results of hydroboration oxidation and mercuric ion-catalysed hydration for
(a) 2-butyne (b) Cyclohexyl-actylene
Ans.
Product by
Reactant 2+
Hydroboration oxidation Hg ion-catalysed hydration
O O
(a) CH3C CCH 3
CH3CCH2CH3 CH3CCH2CH3
O
(b) C CH CH 2CHO
CCH 3
(V) Formation of Alkylide anions (Alkynides)

Sodium, lithium and magnesium alkynide
General Reaction R – C  C – H + NaNH2  R – C  C:— +Na + NH3
R – C  C – H + R' – Li  R – C  CLi + R' H
R – C  C – H + R'MgX  R – C  CMgX + R'H
(VI) Alkylation of alkylide ions

General Reaction R – C  C:— + R' – X  R – C  C – R'
(R' – X must be an unhindered primary halide or tosylate)
e.g. CH3CH2 C  C– + Na + CH3CH2CH2 – Br  CH3CH2–C  C – CH2CH2CH3
sodium butynide 1-bromopropane Hept-3-yne
(VII) Reactions with Carbonyl Groups

General Reaction
R – C  C:— +
e.g.
Ex.15 Give the products of the following reactions.

(a) CH3C  C: + CH3CH = O H2 O X
 H2 O
(b) CH3C  C : + (CH3)2C = O Y
(c) CH3C  C: + O H2O Z
Sol. (a)
(b)
(c)
Q.10 What are the products of the following reactions:
(a)
(b) CH3C  CH +
(c) HC  CD + CH3CHO
Q.11 Identify 'X' in the following reaction
(VIII) Oxidation of -Dlketones

If an alkyne is treated with aqueous KMnO4 under nearly neutral conditions, an -diketone results.
General Reaction
KMnO 4. (neutral)
e.g. CH3– C C – CH2CH3 CH3– C – C – CH2CH3
(or, O3 & Zn/H2O)
2-Pentyne
O O
Pentane-2,3-dione
Ex.16 Give the product of the following reactions.

KMnO4
H3C – H2C – C  C – CH2CH2CH3 X
Neutral
KMnO4
H3C – H2C – C  C – CH2CH2CH3 acidic higher temp
Y
Sol. X = CH3CH2C – CCH2CH2CH3 Y = CH3CH2COOH + HOOCCH2CH2CH3
|| ||
O O
( diketone)
(IX) Oxidative Cleavage

If the reaction mixture becomes warm or too basic the diketone undergoes oxidative cleavage. The
products are the salts of carboxylic acids, which can be converted to the free acids by adding dilute
acid.
General Reaction
e.g.
e.g.
Ex.17 Give the products of the following reactions

KMnO 4
(i) (CH3)2CHC  CCH2CH2CH3 X
KMnO 4
(ii) CH3CH2C  CCH2CH3 Y
KMnO 4
(iii) HC  CCH2CH2CH3 Z
KMnO 4
(iv) CH3C  CCH2CH2C  CCH2CH3 W
Sol. X: (CH3)2CHCOOH + HOOCCH2CH2CH3
Y: 2CH3CH2COOH, symmetrical internal alkynes give one acid
Z: CH3COOH + HOOCCH2CH2COOH + HOOCCH2CH3
Q.12 C5H8 on KMnO4 oxidation gives CO2 and isobutyric acid. Identify C5H8.
(X) Ozonolysis
(i) O3
General reaction R – C  C – R' (ii) H2O R – COOH + R' – COOH
(i) O3
e.g. CH3 – C  C – CH2CH3 (ii) H2O CH3–COOH + CH3CH2–COOH
Ex.18 C8H10 (A) O3.H2O Acid (B) Identify (A) and (B) in the above reaction
Sol. (A) C C (B) COOH
Ex.19 A certain hydrocarbon has the formula C16H26. Ozonation followed by hydrolysis gave CH3(CH2)4CO2H
and succinic acid as the only product. What is hydrocarbon
Sol. DU = 4
Hydrocarbon C16H26 is
CH3(CH2)4  CCH2CH2C  C(CH2)4CH3
Solution Unsolved problems

1. It means there is chiral carbon, hence structure is
H
CH3CH2 C CH
CH 3
2. Alkyne (–C  C–) has unsaturation hence C5H8 has also one ring of three or four carbon atoms.
(a) (b)
HC C CH 3 C CH
(a) Exists as cis-and trans-isomer
H H HC C H
HC C CH3 H CH3
(cis) (trans)
3. ( C – H) < ( = C – H) < ( – C – H)
Hence  <  < 
4. As the S-character of the orbital that binds carbon to another atom increases, the pair of electrons in
that orbital is more strongly held and it requires more energy for homolytic cleavage of both the C – H
and C – C bonds.
5. Mech.
6. We need to add two groups to acetylene and ethyl group and a six-carbon aldehyde (to form the
secondary alcohol). If we formed the alcohol group first, the weakly acidic – OH group would interfere
with the alkylation by the ethyl group. Therefore, we should add the less reactive ethyl group first, and
add the alcohol group later in the synthesis.
(i) NaNH2
H–CC–H (ii) CH3CH 2Br H – C  C – CH2CH3
The ethyl group is not acidic and it does not interefere with the addition of the second group
H – C  C – CH2CH3 NaNH2 Na C  C –CH2CH3
Reason : Electron donating groups such as R's make the -bond more electron - rich and more reactive.
Conversely, electron - withdrawing groups such as halogens make the -bond more electron-poor and
less reactive.
CH3 CH3
D2/Lindlar's catalyst BD3
7. CH3– C C – CH3 C C CH3– C C – CH3
CH3COOD
D D

Hydro Carbons Theory

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HYDROCARBON Page # 3

1.2 General method of preparation

1.2.1 By catalytic reduction of alkenes and alkynes

Hydrogenation is of two kind

1.2.2 From alkyl halide

(A) From organometallic compound  compound having bond. (M  metal)

Mechanism Two mechanisms are suggested

(b) Free radical mechanism

(iii) By corey house alkane synthesis

R2CuLi is the source of R

R2 CuLi do not reacts with –NO2, – CN, > C = O etc.

Ex.1 CH3 – Br Li CuI B Y

(iv) By Franklande reagent

(B) By reduction of alkyl halides

(i) with metal-acid

Zn / acid, Zn – Cu / H2O or Zn – Cu + acid

(ii) With Metal hydrides

(a) TPH (Ph3SnH) : It reduces 1º, 2º & 3º R – X

1.2.3 By red P & HI

Write the structure of A and mention its stereochemistry

1.2.5 By Kolbe’s electrolysis

1.2.6 Reduction of aldehydes, ketones :

(a) By Clemmensen’s reduction : with Zn – Hg / conc. HCl

(b) By Wolff-kishner reduction with NH2NH2 / KOH

1.3 Physical Properties of Alkanes :

3.3.1 Physical State :

1.3.2 Boiling points :

650 Bolling point

1.3.3. Melting Points

1.4 Chemical Reaction of Alkanes :

Examples of free radical substitution reaction 

Cl2 Cl2 Cl2 Cl2

Mechanism of halogenation of CH4

(i) Chain initiation  it is a endothermic step

(ii) Chain propagation 

(iii) Chain termination  it is always exothermic

Some reagent affects the rate of halogenation : For example

Q.3 In the given ways which is feasible

Q.4 Which of the following reaction has zero activation energy

Q.5 If the Eact for a forward reaction is given

Halogenations of higher alkane :

Factors determining the relative yields of the isomeric products.

CH2 – CH3 CH3

Heat of combustion as a measure of stability of alkane :

Relative reactivity of halogen toward methane

Steps of halogenation, value of H for each step. (Kcal/mole)

Eact of Cl2 Eact of CH4

Ex.4 Chlorination of CH4 involves following steps :

order of stability of F.R. 

2. Structure and bonding in Alkenes

Ex.1 Write IUPAC names of

Ans. (a) 2, 3-Dimethylcyclohexene

Ex.2 Give the structure for each of the following

Ans. (a) (b)

5. Physical Properties of Alkenes / Hydrocarbons

Physical properties Homologus series Isomers

1. Physical state C1 – C3 gases

2. cis > trans

3. Polarity – cis > trans (for Cab = Cab type of alkenes

4. Melting point increases with M.W. trans > cis

7. Stability trans > cis

6. Laboratory test of Alkene

8. Methods of preparation of alkenes