Hydrocarbon

1.
Alkane
General methods of preparation :
(1) By catalytic reduction of alkenes and alkynes :
H , 25 C
R – C  C – R  2  
 R – CH2 – CH2 – R
Ni, Pt or Pd
2 H , 25C
R – CH = CH – R    
 R – CH2 – CH2 – R
Ni, Pt or Pd
Hydrogenation  Addition of H2 to unsaturated bond.
Hydrogenation is of two kinds
(a) Heterogeneous (b) Homogeneous
(a) Heterogeneous : It is two phase hydrogenation the catalyst is finely devided metal like Ni, Pt or Pd and
a solution of alkene.
(b) Homogeneous : It is one phase hydrogenation both catalyst and alkenes are in solution. In this
hydrogenation catalyst are organic complex of transition metal like Rh or Ir.
Hydrogenation is exothermic, quantitative and during the hydrogenation, total heat evolved to hydrogenate
one mole of unsaturated compound is called heat of hydrogenation. Heat of hydrogenation is the measurment
of stability of isomeric alkenes.
1
stability of alkene  Heat of hydrogenat ion
Note : Hydrogenation of alkene or alkyne in presence of metal catalyst is syn addition
Pd Pd
(a) + H2 
 (b) + H2 

CH3 COOH CH3 COOH
(Meso) (Racemic mixture)

(2) From alkyl halide :
(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  +
R  X + 2e¯ 
(1 , 2)
S 2 R–R
N
 NaX
(b) Free radical mechanism
Na 
R–X +  R  +
R  + R   R – R
JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 343
Note : The alkyl halide should be 1° or 2°, with 3° R – X SN2 and free radical coupling is not possible due to
steric hinderence so in that case elimination or disproportionation is possible.
In the ionic mechanism alkyl sodium gives strong base as well as nucleophile which gives SN2
with R – X, ether should be dry otherwise if moisture is present than forms R – H instead of R – R with H2O.
Na
(a) CH3 – CH2 – Br  CH3 – CH2 – CH2 – CH3
Na
(b) CH3 – Cl + CH3 – CH2 – Cl  CH3 – CH3 + CH3 – CH2 – CH3 + CH3 – CH2 – CH2 – CH3
(ii) By reduction of alkyl halides :
(A) with metal-acid
RX R – H + HX
1
Reducing agent
Zn / HCl , Zn – Cu / H2O or Zn – Cu + CH3COOH
Zn – Cu / C2H5OH, Na – Hg / HCl, Al – Hg / H2O etc.
(B) With metal hydrides
(a) TPH (Ph3SnH) Triphenyltin hydride : It reduces 1°, 2° & 3° R – X
3Ph SnH
R–X    R – H

1º / 2º / 3º
4 NaBH
(b) NaBH4 : R  X    R – H
2 & 3
4 LiAlH 4 LiAlH
(c) LiAlH4 : R  X    R–H ; R  X    Alkene
1 & 2 3
(3) From organometallic compound :

(i) By Grignard Reagent.
Mg
RX   RMgX
ether
1, 2 3
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) X
RSH
R–H + Mg (SR) X
R – COOH
R–H + Mg (OCOR) X
(ii) By Corey House alkane synthesis ;

R  X
2Li CuX R 2CuLi (1  2)
RX 
      R – R
Lithium dialkyl
(1, 2, 3)
cuprate (Gilman ' s reagent )

Mechanism
R2CuLi is the source of R
R – R
R2CuLi does not reacts with – NO2, – CN, etc.
(iii) By Franklands reagent :

Ether
R – X + Zn + R – X  
 R – R + Zn X2
(4)From carboxylic acids:

(i) By soda lime :
Fatty acids are good source of hydrocarbon, continuous heating of sodium salt of carboxylic acid (R –
COONa) with soda lime (NaOH – CaO) gives hydrocarbon, this process 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.
NaOH CaO
R  C  OH     R – H + Na CO
 2 3
||
O
(ii) By Kolbe’s electrolysis :
Electrolysis
2RCOOK + 2HOH   
 R – R + 2CO2 + H2 + 2KOH
Mechanism
R CO2K R CO2– + K+
At Anode: - R CO2–  R CO 2 + e– (oxidation)
(I)
R CO 2  R  + CO2
(II)
 
R + R  R – R
If n is the number of carbon atoms in the salt of carboxylic acid, the alkane formed has 2(n–1) carbon atoms.
Electrolysis
e.g. 2CH3 – COOK + 2H2O   
 CH3CH3 + 2CO2 + H2 + 2KOH.
(5) By Reduction :
(i) By Clemmensen’s reduction (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  C 2H5 + 4[H]      CH3CH2C2H5 + H2O

Clemmensen reduction is not used for compounds which have acid sensitive group.

(ii) By Wolff-kishner reduction (NH2NH2 / KOH) :
2 2 NH NH / KOH
RCHO     RCH3


NH2NH2 / KOH
RCO – R    
 RCH2R

Wolff-kishner reduction is not used for compounds which have base sensitive groups.
eg.     

Clemmemsen’s reduction can be can be used to reduce the given compounds.

(iii) By Red P & HI :
Red P & HI is a strong reducing agent
Re d P  H I Re d P  H I
(a) R – COOH     R – CH3 ; (b) R  C  Cl      R – CH
3
||
O
Re d  H I
(c) R  C  OEt  P  R – CH ; (d)
Re d P  H I
R – X     R – H
3
||
O
Re d  H I
(e) R – OH  P  R – H
Physical Properties of Alkanes :

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.
Boiling points :
The boiling points of n-alkanes increase regularly with the increase in the number of carbon atoms.
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 molecule more compact and brings it close to a
sphere, so the magnitude of vander wall forces decreases.
Melting Point :
It is 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.

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.
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.
Chemical Reactions of Alkanes :
Characteristic reaction of alkanes are free radical substitution reaction, these reactions are generally
chain reactions which are completed in three steps.
(i) chain initiation (ii) chain propagation. (iii) chain termination
Halogenation :
UV Light or temp
R – H + X2          R – X + HX
250  400C
Mechanism :
(i) Chain initiation  it is an endothermic step.
UV or temp. •
X2        2 X
250   400 C
(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
Steps of halogenation, Value of H for each step. (Kcal/mole)

F Cl Br I
•
(i) X2  2 X + 38 + 58 +46 +36
• •
(ii) X + CH4  C H3 + HX – 32 +1 + 16 + 33
• •
(iii) C H3 + X2  CH3X + X – 70 – 26 – 24 – 20
Reactivity of X2 : F2 > Cl2 > Br2 > I2
Reactivity of H : 3°H > 2°H > 1° H
With F2 alkanes react so vigorously that even in the dark and at room temperature, reactant is diluted with an
Inert gas. Iodination is reversible reaction, since HI formed as a by product and It is a strong reducing agent
and reduces alkyl iodide back to alkane. Hence iodination can be done only in presence of strong oxidising
agent like HIO3, HNO3 or HgO.
R – H + I2 R – I + HI
5HI + HIO3  3H2O + 3I2
2HI + HgO  I2 + H2O + Hg

2HI + 2HNO3  I2 + 2H2O + NO2
Formation of alkyl free radical is rate determining step.

Order of stability of Free radical 
• • • •    •
Ph 3 C > Ph2 C H > Ph  C H2 > CH2  CH  C H2 > (CH3)3 C > (CH3)2 CH > CH3 CH 2 > C H3
Cl2 Cl Cl Cl
eg. CH4   CH3Cl 2
  CH2Cl2 2
  2
CHCl 3   CCl4
h  h h h 
 
HCl HCl HCl HCl
When equimolar amount of methane and Cl2 is taken, a mixture of four possible products are formed, but
when we take excess of CH4 then yield of CH3Cl will be high.
Each photon of light cleaves one chlorine molecule to form two chlorine radicals, each chlorine atom starts
a chain and on an average each chain contains 5000 repeatitions of the chain propagating cycle so about
10,000 molecules of CH3Cl are formed by one photon of light.
In a chain reaction following reagents are involved -
(i) Initiators  they initiate the chain reaction, Initiators are peroxide (R2O2), Perester's etc.
•
h
R – O – O – R 
 R O
or 
•
h
R C O O C R  R  C  O
|| || or  ||
O
O O
(ii) Inhibitors  A substance that slows down or stops the reaction is 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 stops for a period of time.
Relative reactivity of halogen towards methane 
Order of reactivity is F2 > Cl2 > Br2 > I2 which can be explained by the value of H (enthalpy change)
Halogenation of higher alkane :

2 Cl
(a) CH3 – CH2 – CH3    CH3  CH  CH3 + CH3  CH2  CH2  Cl
light , 25 C
|
Cl 45%
55%
2 Cl
(b) CH3 – CH2 – CH2 – CH3  CH3  CH2  CH  CH3 + CH3  CH2  CH2  CH2  Cl
light , 25C |
Cl 28%
72%
CH3
Cl2 |
(c) CH3  CH  CH3  CH3  CH  CH2  Cl + CH3  C  CH3
light , 25C
| | |
CH3 CH3 Cl
64% 36%
Br 2
(d) CH3 – CH2 – CH3     CH3  CH2  CH2  Br + CH3  CH  CH3
heat, 127C
|
3% Br
97%

CH3
|
2 Br
(e) CH  CH  CH     CH3  CH  CH2Br + CH3  C  Br
3 3 heat, 127C
| | |
CH3 CH3 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 a mixture in which one isomer dominates greatly (97% – 99%),
Factors affecting the relative yields :
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 3° > 2° > 1° the relative rate per hydrogen atom is
found to be
(iii) Reactivity v/s selectivity principle 

The more reactive is halogen less selective it will be, so the more reactive chlorine free radical is less
•
selective and more influenced by the probability factor and the less reactive B r is more selective and less
influenced by the probability factors.
Based on relative reactivity of different types of H, percentage of each in the product mixture can be calculated.
e.g.
6 15.2
% yield A = × 100 = 28.3 % ; % yield B = × 100 = 71.%
21.2 21.2
Sulphonation :
Lower alkanes are not easily sulphonated but hexane & higher members are sulphonated on heating with
oleum (conc. H2SO4 + SO3) at 400°C
400C
C6H14 + H2SO4   C6H13SO3H + H2O
Isomerisation :
Anhyd . AlCl / HCl
3
CH3CH2CH2CH3     
 CH3  CH  CH3
300C
|
CH3
Isobu tan e
CH3
|
AlCl3 / HCl
CH3 – (CH2)3 – CH3 300
   CH3  C  CH3
C
|
CH3
Neopentane

Alkylation :
Isoalkanes add to isoalkenes in presence of conc. H2SO4 or HF to give higher branched alkane
CH3 CH3
| |
CH3  C  H + H C  C  CH conc. H SO4
2 3   2  CH3  C  CH2  CH  CH3
| | | |
CH3 CH CH3 CH3
3
Isobu tane Isooc tan e
Isobutene
Aromatisation :
Alkanes containing 6 or more number of C atoms are oxidised (dehydrogenate & cyclised) in presence of
oxidising agent at higher temparature and form benzene or its derivatives.
Cr O  Al O
CH3 – (CH2)4 – CH3 23 
2 3
 + 4H2
600C
High P
Cr O  Al O
CH3 – (CH2)5 – CH3 23 
2 3

600C
High P
Cr O  Al O
CH3(CH2)6CH3 23 
2 3
 +
600C
High P
CH3
| Cr O  Al O
CH3  (CH 2 ) 4  CH  CH3 23 
2 3

600C
High P
CH3
| Cr O  Al O
CH3  (CH 2 )3  CH  CH2  CH3 23 
2 3

600C
High P
Pyrolysis / Cracking :
CH3 – CH2 – CH3 CH3CH3 + CH3CH = CH2 + CH2 = CH2+ CH4 + H2
Higher alkanes are heated in absence of air so these compounds break down into smaller alkanes which are
better fuel. Mixture of products contains all lower alkanes, alkenes & hydrogens.
Combustion :
 3n  1  combustion
CnH2n+2 +   O     nCO2 + (n + 1) H2O (Hcombustion = -ve)
 2  2 
exothermic reaction
 y combustion y
CxHy +  x   O2     xCO2 + HO
 4  2 2
combustion
C5H12 + 8O2     5CO2 + 6H2O


Heat of combustion :
Amount of heat liberated when 1 mole of hydrocarbon is completely burnt into CO2 & H2O.
 H of combustion is a measurement of stability of alkane :
Combustion is used as a measurment of stability.
More branched alkanes are more stable and have lower heat of combustion.
CH3
|
e.g. CH3 – CH2 – CH2 – CH3 CH3  C  CH3
|
I H
II
Hcomb. : I > II
Stability : II > I
Points to remember for H of combustion :
Homologes : Higher homologes have higher heat of combustion.
CH4 < C2H6 < C3H8
Isomers : Branched isomer has lower heat of combustion.More branched alkane has more no. of primary
C – H bonds. (therefore it has more bond energy).
> >
Cyclo-alkanes : More strained ring has higher heat of combustion per – CH2 – unit.
> > > (Hcomb. per ‘CH2’ unit)
Octane Number :
It is a scale of fuel efficiency when the fuel burns during combustion, more branched alkanes have lower
knocking (cracking sound). so are better fuels. On commercial scale iso-octane has been alotted a rating
i.e. octane no. of Isooctane is 100 & n-heptane is - ‘0’
If the octane no. of a fuel is 80, it means that the efficiency of the fuel is equivalent to the efficiency of mixture
of 80% isoctane and 20% n-heptane.

Miscellaneous Solved Problems
1.
Sol. In all cases product is
2. Arrange the following alkenes in decreasing order of their stability

R2C = CR2, CH2 = CH2, R2C = CH2, R – CH = CH – R (cis, trans), R2C = CHR, RCH = CH2
Sol. R2C=CR2 > R2C = CHR >R2C = CH2 > R  CH  CH  R > RCH  CHR > R – CH = CH2 > CH2 = CH2
trans cis
3. What is the order of stability of following alkene
CH3
|
CH3  CH  CH  CH2 , CH2  C  CH2  CH3 , CH3  C  CH  CH3
| |
CH3 II CH3
I III
Ans. III > II > I
Sol. Stability of alkene  Hyperconjugative Structure.
Na
4. C2H5Cl   products
Ether
Write all possible product
Sol. CH3 – CH2 – Cl  CH3  CH2  CH2  CH3

major

CH3 – CH2 – Cl CH3  C H2
coupling
   CH3 – CH2 – CH2 – CH3
disproportion
    CH3 – CH3 + CH2 = CH2
5. Wurtz reaction will not be observed in
(A) (B) (C) CH3  CH  Br (D) none of these

|
CH3
Ans. B

Sol. Na + H2 gas

Li CuI Y
6. CH3 – Br  A  B  C
if C is CH3 – CH2 – (CH2)5 – CH3, than what is Y.
Ans. CH3 – (CH2)6 – Br
Li CuI
CH3 – (CH2 )5 – CH2 – X
Sol. CH3 – Br  CH3Li  (CH3)2CuLi     CH3 – CH2 – (CH2)5 – CH3
 NaOH
7.  A   B
CaO / 
What are A and B
Sol. A is , B is
8. Explain why the chain initiating step in thermal chlorination of CH4 is

• • •
 
Cl2  C l and not CH4  C H3 + H
Sol. Because Eact of Cl2 is less than Eact of CH4
9. Chlorination of CH4 involves following steps :

•
(i) Cl2  2 Cl
• •
(ii) CH4 + C l  C H3 + HCl
• •
(iii) C H3 + C l  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
Sol. Formation of alkyl free radical is Rds step.

2. Alkene & Alkynes
1. INTRODUCTION
(A) Alkenes
Alkenes are hydrocarbons with carbon–carbon double bonds, Alkenes are also called as olefins, a term
derived from olefiant gas, meaning "oil forming gas". Alkenes are among the most important industrial
compounds 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.
Alkenes polymerise to give many important polymers.
(B) Alkynes
A triple bond gives an alkyne four lesser hydrogen atoms than the corresponding alkane. Therefore, 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

(A) Alkenes
(1) Alkenes are unsaturated hydrocarbons having at least one double bond.
(2) These 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) These 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
1.34A
117.2°
1.10A
(b)
121.2°
(a)
Note : That angle a > b since repulsion due to  electrons (double bond - single bond repulsion > single bond
- single bond repulsion according to VSEPR theory.
(B) 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 (180°) structure.
(8) Two  bonds result from overlap of the two remaining unhybridized p orbitals on each carbon atom. These
orbitals overlap at right angles (90°) 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
Note : Any type of stereoisomerism does not arise in acetylenic bond due to linearity of C  C bond.
3. IUPAC NOMENCLATURE
(A) Alkenes and Alkadienes

(B) Alkynes :
4. ISOMERISM
(A) Alkene

(B) Alkyne
5. Laboratory Test
(A) Alkenes
(B) Alkynes
(C) Laboratory test of terminal alkynes

When triple bond comes at the end of a carbon chain. The alkyne is called a terminal alkyne.

6. ACIDITY OF TERMINAL ALKYNES
Terminal alkynes are much more acidic than other hydrocarbons due to more electronegative sp hybridised
carbon. The polarity (acidity) of a C – H bond varies with its hybridization, increasing with the increase in
percentage s character of the orbitals :
sp3 < sp2 < sp.
The hydrogen bonded to the carbon of a terminal alkyne is considerably more acidic than those bonded to
carbons of an alkene or alkane. The pKa values for ethyne, ethene & ethane illustrate this point
The order of basicity of their anions is opposite to that of their relative acidity :
Relative Basicity : CH3 CH2 :  H2C  CH :–  HC  C :–

If we include in our comparison hydrogen compounds of other 2nd period elements of the periodic table, we
can write the following orders of relative acidities and basicities :
Relative Acidity :
pKa 15.7 16–17 25 38 44 50
- - - - - -
Relative Basicity : OH < OR < C CR < NH2 < CH CH2 < CH2CH 3
Ex.1 Acetylene hydrogens are acidic because:-

(A) Acetylene contains least number of hydrogen atoms.
(B) Acetylene has only one hydrogen atom at each carbon atom.
(C) Acetylene belongs to the class of alkynes with formula CnH2n – 2.
(D) Sigma electron density of C – H bond in acetylene is nearer to a carbon which has 50% s-characler.
Ans. D
7. STABILITY OF ALKENES
Overall relative stabilities of Alkenes
Studies of numerous alkenes reveal, pattern of stabilities that related to the number of alkyl groups attached
to the carbon atoms of the double bond. The greater the number of attached alkyl groups (i.e., the highly
substituted the carbon atoms of the double bond), the greater is the alkene’s stability. This order of stabilities
can be given in general terms as follows.

Relative stabilities of alkenes
R H R R
> > C=C > > C=C > >
R H H H
Another way of measuring the stability of an alkene is the determination of its heat of hydrogenation or
the heats of combustion. Both are exothermic reactions. (H = – ve)
1
H  (– ve sign indicates the exothermic nature of reaction)
stability
Heat of Hydrogenation of Alkenes :
Heat of hydrogenation,
Alkene Heat of
kcal/mol
Alkene combustion
kJ / mol
Ethene 32.8
1-Butene 2719
Propene 30.1
Isobutene 2703
1-Butene 30.3
cis-2-Butene 2712
1-Pentene 30.1
trans-2-Butene 2707
Isobutene 27.2 All four butenes may be compared,
since all give the same products on
cis-2-Butene 28.6 combustion viz. 4CO2 + 4H2O.
trans-2-Butene 27.6
2-Methyl-2-butene 26.9
8. COMPARATIVE STUDY OF ALKANES, ALKENES, ALKYNES
Properties Alkanes Alkenes Alkynes

1. Bond length Å 1.54 (C – C) 1.32 (C = C) 1.20 (C  C)
2. Bond energy(KJmol-1) 415 (C – C) 615 (C = C) 835 (C  C)
3. Hybridization sp3 sp2 sp
4. % s character 25% 33% 50%
5. pKa 50 44 25
6. Electronegativity of ‘C’
7. Polarity
8. Rate of hydrogenation – less more
9. Rate of electrophilic
addition reaction – more less
10. Heat of combustion C2H6 (– 373 kcal) C2H4 (– 337 kcal) C2H2 (– 317 kcal)
11. Density (g/cm3) C3H8 (0.50) C3H6 (0.52) C3H4 (0.67)
H 121.2° H
C=C
H H
12. Structure
1.08Å
ethene
13. Shape Tetrahedral Planar Linear

9. PREPARATION
(A) General 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 :)
(i) Lindlar’s catalyst : Metallic palladium deposited on calcium carbonate conditioned with lead
acetate and quinoline.
(ii) P-2 catalyst (Ni2B nickel boride)
H2 ,Pd / CaCO 3
(Lindlar 's catalyst )
General Reaction R–CC–R       
quinoline
H2 / Ni2B(P 2)
2 3 or H / Pd / CaCO
Ex.2 CH3 CH2 C  CCH2CH3 
( syn addition )
3  Hexyne
(b) Birch Reduction : (Anti Addition of Hydrogen: Synthesis of trans-Alkenes)

Na / Li R H
General Reaction R C C R C C
Liq. NH3 H R
Na / NH (  )
Ex.3 CH3 – CH2 – C  C – CH2 – CH3   3
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 – C  C¯ Na+ + H
(II) By Dehalogenation 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 effected either by NaI in acetone or zinc in the presence of acetic
acid or ethanol.
General Reaction
Br
| |
CC NaI
C C
| | or Zn, CH3COOH
Br
NaI
Ex.4 CH3 – CHBr – CHBr – CH3    CH – CH = CH – CH
Acetone 3 3
(III) By Dehydrohalogenation of alkyl halides

Dehydrohalogenation is the elimination of a hydrogen and a halogen from an alkyl halide to form an alkene
when heated with strong base.

(i) Hot alcoholic solution of KOH (EtO¯ / EtOH ) (ii) NaNH2 (iii) t-BuO¯ K in t-BuOH

CH3
| Heat
Ex.5 CH3  C  Br + alc. KOH  CH3  C  CH2  KBr  H2 O
| |
CH3 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.
Ex.6 +
(IV) By 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 / 160°C (ii) H3PO4 / 
(iii) P2O5 /  (iv) Al2O3 / 350°C undergo loss of water molecule and form alkenes
General Reaction
CH2
CH2 OH
Ex.7 +
(I)
Minor
(V) By Kolbe's Electrolytic synthesis :
CH2
Electrolysis
+ H2O     || + 2CO2 + 2KOH + H2
Current CH2
(B) General methods of preparation of Alkynes :

(I) By Double Dehydrohalogenation of gem and vic dihalide :
H H
| |
2 NaNH
General Reaction : 2
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.
Br2 NaNH2
Ex.8 CH3 CH2 CH  CH2  CH3 CH2 C HCH2Br    CH3CH2C  CH
CCl4 | mineral oil
Br 110 160 º C
CH3CH2CH  CHBr 
   NaNH - +
Ex.9  CH CH C  CH    2
 CH3 CH2C  CH   CH3CH2C  C Na
NaNH2
3 2 2 mineral oil
 |  110 160 º C
 Br 
CH3 CH2C  C   Na  

4NH Cl
 CH3 CH2C  CH  NH3  NaCl

Ex.10
(II) By Dehalogenation of tetrahaloalkane :
General Reaction R – C  C – R + 2Zn X2
(III) By Kolbe's electrolytic synthesis :

R
|
Electrolysis C
+ H2O Current
   ||| + 2CO + 2KOH + H
2 2
C
|
R
If R = H, product will be CH  CH
If R = CH3, product will be CH3 – C  C – CH3.
(IV) By Hydrolysis of carbides
CaC2 + 2HOH  C2H2 + Ca(OH)2
Mg2C3 + 4HOH  CH3 – C  CH + 2Mg(OH)2
10. CHEMICAL REACTIONS OF ALKENES & ALKYNES

Due to presence of weak  electrons in alkene and alkyne, it well go for electrophilic reaction. Now question
is electrophilic addition or electrophilic substitution ?
In electrophilic substitution reaction, one  bond is broken and a new - bond between one of the doubly
bonded carbon atoms and the electrophile is formed. Since the bond energies of the  bond broken and the
new  bond formed are not much different therefore electrophilic substitution reaction are not accompnied by
large energy changes.
On the other hand in electrophilic addition reactions one weak -bond (251 KJ mol–1) is broken and two
strong  bonds (2 × 347 = 694 KJ mol–1) are formed. The overall reaction is accompnied by a release of about
694-251 = 443 KJ mol–1 of energy. In other words electrophilic addition reactions are energetically more
favourable than electrophilic substitution reactions Thus the typical reactions of alkenes are electrophilic
addition reaction and not the electrophilic substitution reactions.
Electrophilic addition reaction (Mechanism, Remarks, Reactivity order)
(A) Electrophilic Addition to Alkenes :
(a) Orbital Diagram :
The electrons in the pi bond are spread farther from the carbon nuclei and are more loosely held than the
sigma electrons.

The pi bond acts as a nucleophile. A strong electrophile attracts the electrons out of the pi bond to form a
new sigma bond, generating a carbocation. The curved arrow shows the movement of electrons, from the
electron-rich pi bond to the electron-poor electrophile.
(b) General Reaction of electrophilic addition :
............. Addition product.
(c) Mechanism :
(d) Remarks :
Alkenes, Alkynes and Alkadienes are electron rich species. So they function as Nu: species (due to loosely
bound  – electrons)
These compounds mainly give electrophilic addition reactions. Due to nucleophilic nature of alkenes / alkynes
having affinity for E.
The reaction is initiated by an attack of E.
(e) Reactivity of an Alkene:
Factors :
(1) Presence of e– releasing groups (+m, +I) at C = C increases nucleophilicity and reactivity.
(2) Presence of ERG stabilises the intermediate carbocation.
(3) More stable C  , more is reactivity..
(f) Examples of Reactivity Orders:-
(i) > > > > > >

..
(ii) G – CH = CH2 >> CH2 = CH2 (reactivity)
( m )
..
 NH2 – CH = CH2 (enamine)
..
R – .O. – C = C – (vinyl ether)
–
–
(iii) ERG – CH = CH2 > CH2 = CH2 > EWG – CH = CH2 (Reactivity)
(a) CH3 – O – CH  CH2 > CH2 = CH2 > CH2  CH – CN (Reactivity)
(vinyl ether ) (acrylonitrile)
(b) – CH = CH2 > CH2 = CH2 (Reactivity)
(c) < CH2 = CH2 (Reactivity)
CH = CH2 CH = CH2 CH = CH2

–
–
(d) > > (Reactivity)

–
ERG EWG
(B) Electrophilic Addition to Alkynes :

Many of the reactions of alkynes are similar to the corresponding reactions of alkenes. Like the pi bond of an
alkene, the pi bonds of an alkyne are electron-rich, and they readily undergo addition reaction. The bond
energy of the alkyne triple bond is about 226 kJ (54 kcal) more than the bond energy of an alkene double
bond.
Since sigma bonds are generally stronger than pi bonds, the reaction is usually exothermic. Alkynes have
two pi bonds, so upto two molecules can add across the triple bond.
We must consider the possibility of a double addition whenever a reagent adds across the triple bond of an
alkyne. Some conditions may allow the reaction to stop after a single addition, while other conditions give
double addition.
 
ENu ENu
General Reaction : – C  C –  
 
Common Reagents :
(i) + X2 (ii) + HOX
(iii) + HX (iv) + H2O/H+
Major Types of Addition Reaction :

1. ADDITON OF HALOGEN (HALOGENATION)
(A) Alkenes
Alkene + X2  Vicinal dihalides
Halogen add to alkenes to form vicinal dihalides.
+ X2 
(X2 = Cl2, Br2, but not F2 and I2)

EXAMPLE : Addition of Br2 to propene.
Step 1 : Electrophilic attack forms a bromonium ion.
Step 2 : Bromide ion opens the bromonium ion
Chlorine and bromine commonly add to alkenes by the haloninum ion mechanism. Iodination is used less
frequently because diiodide products decompose easily. Any solvents used must be inert to the halogens;
methylene chloride (CH2CI2), chloroform (CHCI3), and carbon tetrachloride (CCI4) are the frequent choices.
Stereochemistry of halogen addition
The addition of bromine to cyclopentene is a stereospecific anti addition.
Halogen addition is another example of a stereospecific reaction, in which different stereoisomers

of the starting meaterial give different stereoisomers of the product.
Ex.11
Ex.12

Ex.13
(B) Alkynes (– C  C –)
Alkyne + 2X2  Tetrahalide
Br Br Br
– –
– –
–
(a) Br2 (1eq.)
R – C  C – R  Br2 (1eq.)
   R – C = C – R      R – C – C – R
–
Br Br Br
(Trans-dihalide) (Tetrahalide)
(b) Nature of Addition:- Anti in both step
X (leq.) D
R – C  C –R 2  2
(1) Anti ( 2) Syn.
D / Pd / CaCO 3
R – C  C –R 2     
(1) Syn.
[lindlar , catalyst ]
2. ADDITION OF HOX
(A) Alkene
Alkene + HOX  Halohydrin
OH
| | | |
(a) General Reaction  C  C  + HOX   C  C 
| |
X
(b) Reagents
(i) X2 + H2O  HOX + HX or (ii) HOX
(c) Mechanism : Halohydrin formation from an alkene :
Step 1 : + X
This step is the same as for halogen addition to an alkene.

Step 2 : fast H

 
Here, a water molecule acts as the nucleophile and attacks a carbon of the ring from back side.

(d) Remarks : Anti adition
No rearrangement
No carbocation
Bridged Carbocation
Cl , H O
Ex.14 CH3CH=CH2 2 
2
 CH3 CH  CH2
Propylene | |
(Propene) OH Cl
Pr opylene chlorohydr in
(1  Chloro  2  propanol )
(B) Alkynes
Alkynes + HOX  , -dihaloketone + -haloketone
(90% major) (10% minor)
X
HOX
–
HOX(leq.)
(a) R – C  C – H     R – C = CH   
–
(1 eq.)
OH enol
–H2O
R – C – CH2X R – C – CHX2
O O
10% (minor) 90% (major)
[-Haloketone] [-Dihaloketone]
(b) Remakrs :
# Two molecules of HOX can be added, the end product is -Dihaloketone.
# The intermediate product is an enol which gives a minor product -haloketone.
Extention :
KOH – H2 O
R – C – CHX2    R – C – CH(OH)2    R – C – CHO
O O O
(major product)
3. ADDITION OF HYDROGEN HALIDES (+ HX)
(A) Alkene
Alkene + HX  Alkylhalide
(a) General Reaction + H – X 
(b) Mechanism :
slow


(c) Markovnikov’s Rule :
When reagent (asymmetrical HX, H2O) adds to asymmetrical alkene eg, propene isobutene etc. the
addition occurs such that the nucleophifile attaches itself to the carbon atom of the alkene bearing
the least number of hydrogen, or electrophifile adds to the sp2 carbon that is bonded with the greater
number of hydrogen.
(d) Remarks :
(i) Non stereoselective (ii) Markovnikoff additon
(iii) Intermediate carbocation (iv) Rearrangement may take place
(v)
(e) Regioselective Reaction : A Reaction in which two or more constitutional isomers could be formed
but one of them predominates is called a regioselective reraction.
HI
Ex.15 CH3 CH  CH2  CH3 CHICH3
 + CH3 CH2CH2 I
Pr opene 2  Iodopropane 1  Iodopropane
(Isopropyl iodide) (minor )
(major )
Ex.16    +
Ex.17 + HI  +
(major) (minor)
(B) Alkyne
Alykne + 2HX  Geminal Dihalides
Hydrogen halides add across the triple bond of an alkyne in much the same way they add across
the alkene double bond. The initial product is a vinyl halide. When a hydrogen halide adds to a
terminal alkyne, the product has the orientation predicted by Markovnikov’s rule. A second molecule
of HX can add, usually with the same orientation as the first.
Br Br
– –
HBr
–
HBr (dark )
(a) General Reaction R – C  C – H     R – C = C – H     R – C – CH 3
–
H Br
(MK)
(b) Remarks :
(1) Markovnikov’s Addition in both steps.
(2) If two moles of HX are added the final product is Gemdihalide.
(3) Electrophilic addition to terminal alkyne is regioselective.
Cl
|
Ex.18 HCl HCl
CH3 CH2  C  C  H   CH3 CH2  C  CH3
|
1  Butyne Cl
2, 2  Dichlorobu tane

H CH2CH2CH3 H Br
| |
Ex.19 HBr C C HBr
H  C  C  CH 2CH2 CH3   H  C  C  CH2CH2CH3
H Br | |
H Br
4. FREE RADICAL ADDITION OF HBr : KHARASCH EFFECT OR PEROXIDE EFFECT
| | | |
peroxides
(a) General Reaction :  C  C  + Y – Z      C  C 
or light
| |
Y Z
HBr / R O 2 / h
R – CH = CH2   2   R – CH2 – CH2 – Br
(b) Mechanism :
(c) Remarks :
(1) When HBr is added to an unsymmetrical alkene in presence of sunlight and peroxide. Then an
Anti Markovnikov's Addition Product is obtained.
(2) It is a free radical chain reaction.
(3) In presence of peroxide and sunlight Brº is formed in chain initiation step.
(4) Brº forms more stable alkyl radical by homolysis of C = C  bond.
(5) In the last step alkyl radical abstracts Hº from HBr and Anti markownikov's product is obtained.
HBr / R O
2 2
Ex.20 n  C 6H13 CH  CH2     nC6H13CH2 – CH2 – Br
1  Octene
Ex.21 Why do we get Anti markownikov's product ?

Ans. In the chain propagation Step (3), more stable alkyl radical (3º > 2º > 1º) is formed which gives the major
product.
Ex.22 Some Reactions :
CH3
HBr
–
(a) CH3 – C = CH2   (Carbocation is intermediate)

( dark )
CH3
–
HBr
CH3 – C = CH2   (Light can also cleave HBr bond)
(light )
(free radical is intermediate)

CH3
– –
HBr
(b) CH3 – C – CH = CH2   (R2O2 accelerates cleavage of HBr bond)
CH3 (R 2 O 2 )
(free radical is intermediate)
CH3
– – HBr
CH3 – C – CH = CH2   Carbocation is intermediate)
CH3 (Dark )
HBr(R O )
(c) Ph – CH = CH2   22 Ph – CH2 – CH2
–
Br
HBr
Ph – CH = CH2  
CH3 CH3
HBr
– –
(d) CH3 – C – CH = CH2   CH3 – C – CH – CH3

–
–
CH3 Br CH3

–
H
(e) 

HCl
(f) 
Cl
(g) + HCl 
Cl
HCl(leq.) HCl(leq.)
– –
(h) H – C  C – H    H – C = CH 2    H – C – CH3

–
Cl Cl
Vinyl Chloride gem dihalide
HCl(leq.)
(i) CH2 = CH – CH2 – C  CH    CH3 – CH – CH2 – C  CH
–
Cl
(Double bond is more reactive)
HCl(leq.)
(j) CH2 = CH – C  CH    CH2 = CH – C = CH2 Conjugated product.
–
Conjugated System Cl
Neoprene
(When double bond and triple bond is in conjugation, triple bond is more reactive)

5. ADDITION OF H2O (HYDRATION REACTION)
(A) Hydration in Alkenes
Alkene + H2O  alcohol
(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.
(a) General Reaction : + H2O
(b) Mechanism :
Step 1 : Protonation of the double bond forms a carbocation
Step 2 : Nucleophilic attack by water
Step 3 : Deprotonation to the alcohol
Ex.23 CH3 CH  CH2 H O, H

2  
 CH3CHCH3
Pr opene |
OH
Isopropyl alcohol
CH3 CH3 H
| | |
Ex.24 CH3  C  CH  CH2 50% H2SO 4
    CH3 – C – C – CH3
| | |
CH3
3,3  Dimethyl  1  butene OH CH3
2, 3-Dimethyl-2-butanol
(major product)
(ii) 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
(a) General Reaction :
OH O
 O  | | ||
  THF
+ H2O + Hg  ||    –C–C– + CH COH
 OCCH  O 3
 3 2 | | ||
Hg – OCCH3
OH
| | | |
–C–C– CC
O + + NaBH4  | | + Hg + (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 it with hydrogen. The net addition of H–
and – OH takes place with Markovnikov regioselectivity and generally takes place without the complication
of rearrangements.
Advantage over acid hydration :
(1) No requirement of acidic condition, which is harmful to many organic molecules.
(2) No rearrangement occur.
(iii) Alkoxymercuration - demercuration

If solvent taken is alcohol product will be ether & process is called alkoxymercuration
demercuration.
OR
| | NaBH4
General reaction : ROH
+ Hg(OAc)2    
  C  C 

| |
HgOAc
Ex.25 CH2  CH  CH2  CH3

1  butene
(iv) Hydroboration-oxidation (SYN - Addition)

General Reaction :
| |
ROH
+ BH3.THF    C  C 

| |
H B 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. Hydroboration-oxidation
therefore, serves as a useful regiochemical complement to oxymercuration demercuration.
Ex.26

CH3 CH3 CH3
| +
H (dil. H2SO4) | + CH3 ¯ shift + |
Ex.27 CH3 – C – CH = CH2 CH3 C CH CH3 CH3 – C – CH – CH3
| | | 3°carbocation
CH3 CH3 CH3
2°carbocation (– H + ) H2 O
CH3
Hydroboration | OH CH3
CH3 – C – CH2 – CH2OH | |
oxidation | CH3 – C – CH – CH3
CH3 |
CH3 OH CH3
Hg(OAc)2 | |
NaBH4 CH3 – C – CH – CH3
|
CH3
(i) Hydration with dil. H2SO4 proceeds via carbocation rearrangement
(ii) Hydration with Hg(OAc)2, H2O, followed by NaBH4 proceeds via Markovnikov’s rule (no rearrangement).
(iii) Hydration with (BH3)2 followed by H2O2 / OH¯ proceeds via Anti Markovnikov's rule.
(B) Hydration of Alkynes :

(i) Mercuric ion catalyzed hydration :
Alkynes undergo acid–catalyzed addition of water across the triple bond in the presence of mercuric ion as
a catalyst. A mixture of mercuric sulfate in aqueous sulfuric acid is commonly used as the reagent.
H
|
General Reaction R  C  C  H  H2O R C C H
|| |
Markonikoff rule) O H
(
ketone
( stable )
O
||
Ex.28 CH3  C  C  H  H2 O CH3  C  CH3
propyne Pr opanone (acetone )
HgSO ,H SO
4 2 4
Ex.29 CH 3 – C  CH + H 2O  X
Identify the (X) in the above reaction
Sol. (X) = CH 3C CH3
O
Acetone (a ketone) stable
(ii) Hydroboration Oxidation of Alkynes :
Alkynes react with BH3 or B2H6 + THF to give trivinyl borane which upon subsequent treatment with alkaline
H2O2, gives alcohols corresponding to anti-markovnikov's addition of H2O to alkynes, which on tautomerisation
give corresponding aldehydes or ketone. Terminal alkynes give aldehyde whereas internal alkynes give
ketone.
CH2  CH
(1) BH3  THF
Ex.30 3CH  CH      | 
CH3 – CH = O (Ethanal or acetaldehyde).
– 
( 2) H2O2 OH  OH 
( Vinyl alcohol )
Me – CH  CH
(1) BH3  THF
Ex.31 3Me – C  CH (Terminal alkyne)      |  MeCH2CHO
– 
( 2) H2O2 OH  OH 
(Pr opan  1  al )

Me – CH  C – Me
(1) BH3  THF
Ex.32 3Me – C  Me (Internal alkyne)      |  Me – CH2 – C – Me
–
( 2) H2O2 OH  OH  ||
O
Bu tan 2  one
6. CATALYTIC HYDROGENATION
(A) Alkenes (Heterogeneous hydrogenation)
Hydrogenation of an alkene is exothermic reaction ( Hº  –120 kJ mol–1):
There is usually a high free energy of activation for uncatalyzed alkene
hydrogenation, therefore, the uncatalyzed reaction does not take place at room temperature. Hydrogenation
will take place readily at room temperature in the presence of a catalyst because the catalyst
provides a new pathway for the reaction that involves lower free energy of activation
Heterogeneous hydrogenation catalysts typically involve finely divided platinum, palladium, nickel, or rhohdium
deposition on the surface of powdered carbon ( charcoal). Hydrogenation actually takes place at the surface
of the metal, where the liquid solution of the alkene comes contact with hydrogen and the catalyst. Hydrogen
gas is adsorbed into the surface of these metal catalysts and the catalyst weakens the H – H bond. In fact,
if H2 and D2 are mixed in the presence of a Pt catalyst, the two isotopes quickly scramble to produce a
random mixture of HD, H2 and D2. (No scrambling occurs in the absence of the catalyst.)
Hydrogenation is an example of heterogeneous catalysis, because the (solid) catalyst is in a different phase
from the reactant solution. In contrast, homogeneous catalysis involves reactants and catalyst in the same
phase, as in the acid-catalyzed dehydration of an alcohol.
| |
Catalyst
General Reaction C=C + H2    C  C 
| |
H H
(syn addition)
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.

Ex.33 Pt
CH3–CH = CH – CH3 + H2 
 CH3 – CH2 – CH2 – CH3
H

2
Ex.34
Pt
Ex.35 Complete the following reactions :

Pd, Pt or Ni
CH3CH = CH2 + H2    
 ?
Sol. CH3CH2CH3
(B) Catalytic Hydrogenation of Alkynes

(i) Reduction to Alkenes
(a) By Lindlar's reagent : Hydrogenation of an alkyne can be stopped at the alkene stage by using a
“poisioned” (partially deactivated) catalyst made by treating a good catalyst with a compound that makes the
catalyst less effective. Lindlar’s catalyst is a poisioned Pd catalyst, composed of powdered barium sulfate
coated with pd, poisoned with quinoline.
Pd / BaSO4, quinoline
General Reaction R – C  R + H2         (syn addtion)
(b) By Birch reduction
3 Na  NH
General Reaction R – C C – R’     (anti addtion)
H2 , Pd / BaSO
4
Ex.36 CH3 CH2  C  C  CH2 CH3    
quinoline
 
3  Hexyne
(c) By hydroboration reduction
(i) BH3 - THF R R

General Reaction R – C  C – R C=C (syn addtion)
(ii) CH3COOH H H
7. MISCELLANEOUS REACTIONS OF ALKENE

(A) Alkylation
| | | |
acid
General Reaction  C  C  + R – H   C  C 
| |
H R
CH3 CH3 CH3 CH3

| | | |
e.g. CH3  C  CH2 + CH3  C  H H2SO 4
  CH 3 C  CH 2  C  CH3
Isobutylene | | |
CH3 H CH3
Isobu tane 2, 2, 4  Trimethylpen tan e

(B) Polymerisation reactions of alkene
(a) Polymers are compounds which consist of very large molecules made up of many repeating subunits.
The molecular subunits that are used to synthesize polymers are called monomers, and the reactions
by which monomers are joined together are called polymerization reactions.
(b) Propylene (propene), for example, can be polymerized to form polypropylene. This polymerization
occurs by a chain reaction, and as a consequence, polymers such as polypropylene are called
chain-growth or addition polymers :
(c) Alkenes are convenient starting materials for the preparation of chain-growth polymers. The addition
reactions occur through radical, cationic, or anionic mechanisms depending on how they are initiated.
The following examples illustrate these mechanisms. All of these reactions are chain reactions.
Radical polymerization

Cationic polymerization
etc.
Anionic polymerization
etc
Stereochemistry of polymerism : Natural rubber is an all cis-isomer of isoprene units.

Note* : Neoprent, Polybutadiene, Buna-s and Buna-N are synthetic rubbers.

(C) Halogenation. Allylic substitution
General Reaction X2 = Cl2, Br2
NBS = N-Bromosuccinimide ; NCS = N-Chlorosuccinimide
Ex.37 Cl2 , 600C

CH3 CH  CH2     Cl  CH2 CH  CH2
Pr opylene Allyl chloride
(Pr opene ) (3  Chloro  1  propene )
(D) Addition of NOCl
O N Cl
CH3 – CH = CH2  
3. Alkadienes
Dienes
1. Dienes are of three types :
(a) Isolated dienes : eg. CH2=CH–CH2–CH=CH2
(b) Conjugated dienes : eg. CH2=CH–CH=CH=CH3
(c) Cumulated dienes : eg. CH3–CH=C=CH–CH3
2. Stability Order : Conjugated > Isolated > Cumulene
3. Heat of Hydrogenation :
Cumulated > terminal alkyne > nonterminal alkyne > isolated diene > conjugated diene
4. General Reaction :
Reaction take place at two position (1, 2) and (1, 4), major product depends on reaction temperature.

5. Mechanism :
Step 1 :
Step 2 :
Note :
(1) Kinelocally controlled process (KCP) is governed by stability of intermediate, faster reaction.
(2) Thermodynamically controlled process (TCP) is governed by stability of products.

Preparation and Properties of alkenes

Preparation and Properties of alkynes

MISCELLANEOUS SOLVED PROBLEMS (MSPS)
1. Write IUPAC names of .

Ans. 1-(but-2-enyl) cyclohex – 1–ene
Sol. IUPAC based.
2. Give the structure for each of the following

(a) 4-Methyl-1, 3-hexadiene (b) 1-Isopropenylcyclopent-1-ene
Ans. (a) (b)
Sol. IUPAC based.
3. What is the configuration (E or Z) of the given stereoisomer of 3-methyl-pent-2-ene.
Ans. E
Sol. According to CIP rule.
4. There are ............... stereocentres in

Ans. Two
Sol. Two double bond show geometrical isomerism.
5. Cis-trans isomerism is not possible in alkynes because of:

Ans. 180o bond-angle at the carbon-carbon triple bond.
Sol. Self explanatory.
6. Draw the geometrical isomers of hept-2-en-5-yne ?
Ans. MeC CCH2 H ,

C=C
H Me
(trans)
7. In the following compounds there are three (C = C) bonds. Arrange them in increasing stability.
CH3 CH3
b a H
C C C C
CH3
CH3
c
H
H
Ans. c<a<b
Sol. Stability of alkene (C=C)  Number of -Hydrogen in Hyperconjugation.

8. Match the heat of combustion with type of alkene
-1
Alkene Heat of Combustion (Kcal mol )
(i) Pent-1-ene (A) 804.03
(ii) cis Pent-2-ene (B) 806.9
(iii) trans Pent-2-ene (C) 805.3
Ans. (i) – (B), (ii) – (C), (iii) – (A)

Sol. Greater the value of H , smaller the stability..
9. Which has a longer carbon-methyl bond, 1-butyne or 2-butyne. Explain ?

Sol. 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
3 3
sp sp sp3 sp
10. Arrange the following bond-lengths in increasing order.

(e)
H3C (c) C C – CH3
(a) (d)
C=C
(b)
H H
Ans. (d) < (b) < (c) < (e) < (a)
1
Sol. Bond length  % s  character
11. Identify the reagent for following synthesis.
?

Ans. H2 / Lindlar’s catalyst.
H
Sol.  2 

Lindlar 's catalyst
12. Identify the product in the following reaction :
Na / NH
3
   
Na / NH
3
Sol.    
this is known as Birch reduction.

13. Identify the product in the following reactions :
(a) NaI / acetone (b) NaI / acetone

         
H CH3
Sol. (a) NaI / acetone
    
H3C H
(b) NaI / acetone

    
14. Which 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) CH3  CH2  C  CH2
|
CH3
CH3
|
Ans. (i) CH3  C  CH3 (ii) CH3CH2CH2CH2CH2Cl (iii) CH3 CH2CHCH2Cl
| |
Cl CH3
CH3 CH3
| |
Sol. alc. KOH
(i) CH3  C  CH3   CH3  C  CH2
|
Cl
alc. KOH
(ii) CH3CH2CH2CH2CH2Cl   CH3 – CH2 – CH2 – CH = CH2
alc. KOH
(iii) CH3 CH2CHCH2Cl  CH3  CH2  C  CH2
| |
CH3 CH3
15. What are the various producs formed due to loss of HBr from
CH3
CH3
Ans. , ,
(minor)
Sol. This is E1 reaction.

16. Write the intermediate species as indicated :

H
3, 3 – Dimethylbutan-2- ol  H O Migration
 .................. 2 ....................    .....................
(A) (B) (C)
oxonium ion 20 carbocation 30 carbocation
-H+ -H+
.......................................................
(E) (D)
Alkene Alkene
CH3 CH3 CH3 CH3
Ans. (A) = CH3 C CH CH3 (B) = CH3 C CH CH3 (C) = CH3 C CH CH3
+ +
CH3 OH2 CH3
+
CH3 CH3 CH3

(D) = CH3 C C CH3 (E) = CH3 C CH CH2
CH3
Major product is (D)
Minor product is (E)
CH3 CH3 CH3 CH3
H H O Migration
Sol. 3, 3 – Dimethylbutan-2- ol
 CH3 C CH CH
3 2 CH3 C CH CH
3    CH C CH CH3
+ 3
+
CH3 OH2 CH3
+
(A) (B) (C)
oxonium ion 20 carbocation 30 carbocation
-H+ -H+
CH3 CH3 CH3

CH3 C CH CH2 CH3 C C CH3
CH3
(E) (D)
Alkene Alkene
17. Predict the major product of dehydration of each reactant :
(A) (CH3)2C (OH) CH2CH3 (B) (CH3)2 CHCH (OH)CH3 (C) (CH3)2C (OH) CH (CH3)2
CH3 CH3 CH3

Ans. (A) and (B) = ; (C) = C C
CH3 C CHCH3 CH3 CH3
Sol. This is E1 reaction of alcohol.
18. Give the structure of three isomeric dibromides that could be used as starting materials for the preparation of
3, 3-Dimethylbut-1-yne.
CH3 CH3 CH3 Br

CH3 C CH2 CHBr2 CH3 C CH CH2 CH3 C C CH3
Ans.
CH3 CH3 Br Br CH3 Br
(I) (II) (III)
19. Show the product in the following reaction
CH3
CH CH2 EtOK
?
EtOH
Br Br
CH3 CH3
CH CH2 EtOK C  CH
Sol.  + 2HBr
EtOH, 
Br Br
20. Show how to synthesize Dec-3-yne from acetylene along with necessary alkyl halides.
Sol. Another name for Dec-3-yne is Ethyl n-hexylacetylene. It can be made by adding an ethyl group and a hexyl
group to acetylene. This can be done in either order; we begin by adding the hexyl group.
H C C H H3C–(CH2)5–CC–H
Oct-1-yne
H3C – (CH2)5 – C  C – H CH3 – (CH2)5 – C  C – CH2CH3
Oct-1-yne Dec-3-yne
21. Give the product of the following reaction.

Me2C = CH2 + ICl  ?
Sol. Cl is more electronegative than I making I the E+, according to the Markovnikov's rule, E+ adds to the C with
the greater number of H's. The product is 2-chloro-1-iodo-2-methylpropane, (Me2CClCH2I).
22. What are the products and (type of isomers) when Br2 adds to:-
(a) Br 2 (b) Br 2
   
Ans (a) Br 2 & enantiomer

 
(Anti-addition)
(b) Br 2 & enantiomer

 
(Anti-addition)
23. Explain why alkynes are less reactive than alkenes toward addition of Br2 .
Sol. The three membered ring bromonium ion formed from the alkyne (A) has a full double bond causing it to be
more strained and less stable than the one form the alkene (B).
(A) HC CH (B) H2C CH2 (A) less stable than (B)
+ +
Br Br
Also, the C’s of A that are part of the bromonium ion have more s–character than those of B, further making
A less stable than B.

24. Predict the product in the following reactions
Br H2O + Br2 H

(a) 2 (b) 2O
    
Anti addition Anti addition
Sol. (a) 2Br H2O

   
Anti addition
CH3
H2O OH
(b) + Br2   
Anti addition Br
H
25. 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 + H3 C  C  O  O  C  CH3 
| |
CH3 CH3
CH3
CH3
| Br
Ans. (A) H3 C  CH  CH2Br (B) (C) H2C – CH – CH3
|
Br
Sol. Based on kharas effect (anti Markovnikov's rule).
26. Identify the major 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 CH2CH3
Ans. (a) F3C–CH2–CH2Cl (b) O2N–CH2–CH2Cl (c) CH3 O – CH – CH3
|
Cl
(d) Ph – CH – CH2 – CH3 (e)

|
Cl

27. Identify the product when one equivalent of HBr reacts with Pent-1-ene-4-yne.
Ans. CH3CHCH2C CH
Br
 
H 
Sol. CH2  CHCH2C  CH  Br
 CH3 C HCH2C  CH 
stable 20
alkyl carbocation
 
H
CH2  CHCH2C  CH  CH2  CHCH2 C  CH2
less stable vinyl carbocation
(It is not formed)
Note : When double bond and triple bond are not in the conjugation, double bond is more reactive.
2HBr
28. CH3 C  CH   (X) + (Y)
Identify (X) and (Y) in the above reaction.
Ans. X= , Y = CH3CH2CHBr2
+
Sol. After first HBr molecule is added, product is CH3C CH2 ; Second addition forms intermediates CH3 C CH3
Br Br
0
(2 )
Br
+
0 0
and CH3 C CH2 . Since 2 carbocation ion is more stable than 1 , hence final product is CH3 C CH3
Br Br
0
(1 ) (X)
Y is CH3CH2CHBr2
29. If HF, HCl, HI are used even in sunlight electrophilic addition takes place. Why only HBr give free radical
addition ?
Sol. In chain propagation (iii) steps:-

R – CH = CH2 + X R – CH – CH2 – X + HR

R – CH = CH2 + F R – CH – CH2 – F exo
 
R – CH = CH2 + Cl R – CH – CH2 – Cl exo

R – CH = CH2 + Br  R – CH – CH2 – Br exo

R – CH = CH2 + I  R – CH – CH2 – I endo
B.E.:- C – F > C – Cl > C – Br > CI
In step (iv)

R – CH – CH2 – X + H – X R – CH2 – CH2 – X + X  + HR

R – CH – CH2 – X + H – F R – CH2 – CH2 – X + F + endo

R – CH – CH2 – X + H – Cl R – CH2 – CH2 – X + Cl + endo

R – CH – CH2 – X + H – Br R – CH2 – CH2 – X + Br  + exo

R – CH – CH2 – X + H – I R – CH2 – CH2 – X + I  + exo
B.E.:- HF > HCl > HBr > HI
Chain propagration steps indicate that addition of I is endo. is step 3 and is unfavourable.
Addition of F, Cl is endothermic, unfavourable in step 4.
Addition of HBr is energetically favourable [in both chain propagation steps-3 & 4]
30. Identify the product in following reaction
CH3

D O/ D
CH3 C C CH3 2  
H
CH3 H
Ans. CH3 C C CH3
OD D
Sol. Based on stability of carbocation.
CH2
0
83 C
31. CH3 C + H2SO4  deliquescent white solid  H O (B). Give the structure of A and B.
2
(A)
CH3
CH3 CH3
Ans. (A) CH3 C OSO3H (B) CH3 C OH
CH3 CH3
t–Butyl hydrogen sulphate t–Butyl alcohol
Sol. Based on stability of carbocation.
32. Write the structures for (X) and (Y) in the following two – step reaction :
NaBH 4 / NaOH
C3H7CH = CH2 (X)       (Y)
NaBH 4 / NaOH
Ans/Sol. C3H7CH = CH2 C3H7CH(OH)CH2 – HgOAC       C3H7CH(OH)CH3
(An organomercurial alcohol)
(X) (Y)
33. Identify final product in the following :
NaBH4
(a)    
OH
Hg(OAc )
NaBH4
(b) 2


NaOH
Ans (a) (b) O
OCH3
NaBH
4
Sol. (a)    
OCH3
OH
Hg(OAc )
(b) 2



34. Give the structural formulas for (X), (Y) and (Z) in the following sequence :
H (Y)
COO
CH 3
BH3 / THF
CH3CH = CH2 (X)
H2 O
2 /O
H-
(Z)
Ans (X) (CH3CH2CH2)3B (Y) (CH3CH2CH3) (Z) CH3 –CH2 –CH2 –OH
Sol.
35. (a) Give the structure of product obtained from the hydroboration-oxidation of 1-Methyl cyclopentene.
(b) Classify the mode of addition.
H 
Ans/Sol. (a) BH / THF H O / OHO
3
   2 2   

Me
1-Methylcyclopentene trans-2-Methylcyclopentan-1-ol
(b) Syn (Cis, addition)
36. When 2-heptyne was treated with aq. H2SO4 containing some HgSO4, two products, each having the molecular
formula C7H14O, were obtained approximately in equal amounts. What are these two compounds ?
O
H SO / HgSO 4
Ans/Sol. CH3CH2CH2CH2C  CCH3 2 4     +
2-Heptanone
O
3-Heptanone
37. Compare the results of hydroboration oxidation and mercuric ion-catalysed hydration for
(a) 2-butyne (b) Cyclohexylacetylene
Ans/Sol. Product by
Reactant
Hydroboration oxidation Hg2+ ion-catalysed hydration
(a) CH3C CCH3 O O
CH3CCH2CH3 CH3CCH2CH3
O
(b) –C CH –CH2CHO –CCH3

38. Identify (X) and (Y) in the following reaction
BH3.THF CH3COOD
(Y)
CH3 – CH2 – C  C
BH3.THF CH3COOH
(X)
Ans/Sol.

Type (I) : Very Short Answer Type Questions : [01 Mark Each]
1. What is Wurtz reaction ?
2. How many monochlorination products are possible for (only structural)

(i) Neo-pentane (ii) n-Pentane ?
3. Give the structure of the alkene (C4H8) which adds on HBr in the presence and in the absence of peroxide to
give the same product, C4H9Br.
4. How can ethylene be converted into ethane ?
5. Arrange the following : HCl, HBr, HI and HF in order of decreasing reactivity towards alkenes.
6. How will you distinguish between1-butyne and 2-butyne ?
7. How will you detect the presence of unsaturation in an organic compound ?
8. How can ethylene be converted into propane nitrile?
9. What is mercuration- demercuration product of 3-Methyl but-1-ene.
10. How will you carry out the following conversions?

H3CCCH  H3C–COCH3
Type (II) : Short Answer Type Questions : [02 Marks Each]

11. How can, we get
(i) Ethene from 1, 2-Dibromoethane
(ii) 2, 3-Dimethylbutane from iso-propyl iodide
12. Write chemical equations for combustion reaction of the following hydrocarbons.
(i) Butane (ii) Pentene
(iii) Hexyne (iv) Toluene
13. For the following compounds, write structure formulas and IUPAC names for all possible isomers having the
number of double or triple bond as indicated :
(i) C4H8 (one double bond)
(ii) C5H8 (one triple bond)
14. Give two reactions to show acidic nature of acetylene. What explanation can you offer for its acidic behaviour ?
15. How many monochlorination products are possible for (Only structural)
(i) Methyl cyclopentane
(ii) Isobutane
16. Why acetylene is more acidic than ethene ?
Type (III) : Long Answer Type Questions: [03 Marks Each]
17. Addition of HBr to propene yields-2-bromopropane, while in the presence of benzoyl peroxide, the same
reaction yields 1-bromopropane. Explain and give mechanism.
18. Give two methods of preparation of each of the following :

(i) Methane (ii) Ethane (iii) Ethyne
19. How does propene react with

(i) HBr
(ii) Water in the presence of sulphuric acid
Name and state the rule which you use while writing the products in above reactions.

20. Carry out the following conversions :
(i) Acetylene to propyne
(ii) Ethanoic acid to methane
(iii) n-Hexane to benzene
Type (IV) : Very Long Answer Type Questions: [05 Marks Each]
21. Explain the following :
(i) Boiling points of n-alkanes are higher than their branched chain isomers.
(ii) Melting point of cis-2-butene is lower than that of trans-2-butene.
22. How does acetylene react with :

(i) H2O (ii) H2
(iii) Ozone (H2O2) (iv) HCl (one mole)
23. Give a chemical test to distinguish between

(a) Ethylene and acetylene
(b) But-1-ene and but-2-ene
(c) 2-Butyne and acetylene
(d) butane and butene
24. (i) Explain hydroboration-oxidation of alkene ?

(ii) Why electrophilic addition reaction is more favorable to double bond as compared to triple bond.
25. How is acetylene prepared by (i) Kolbe's electrolysis (ii) Dehydrohalogenation of 1, 2-dihaloalkanes
(iii) Double Dehydrohalogenation of tetrahaloalkanes ?
26. Discuss the stereochemistry of the reduction products obtained when but-2-yne is reduced with (i) Lindlar's
catalyst (ii) Na in liquid NH3.
27. Complete the following reactions :

Hg  / H SO
2 4
(i)    
 
Hg  / H SO
2 4
(ii)    
 
Hg  / H SO
2 4
(iii)    
 

PART - I : SUBJECTIVE QUESTIONS
Section (A) : Prepartion of Alkane
A-1. Sodium salt of which acid will be needed for preparation of propane ? Write chemical equation for the
reaction.
A-2. Prepare butane from chloroethane using the Corey-House synthesis.
A-3. Write the major product of following reactions.

(i) CH3 – CH2Br
(ii)
(iii) Ph–Br + CH3–Br (report mixture)
Section (B) : Chemical reactions of alkanes

B-1. How do you account for formation of ethane during chlorination of methane.
B-2.
What is the correct order of removal of hydrogen atom from the given molecule in the free radical halogenation
reaction.
B-3. How many structural mono chloro products obtained by propane.
Section (C) : Stability and preparation of Alkenes/ Alkynes

C-1. Compare the C – H bond lengths and bond dissociation enthalpies of an alkyne, alkene & alkane.
C-2. The same alkane is obtained from the catalytic hydrogenation of both alkene A and B. The heat of hydrogenation
of alkene A is –29.8Kcal/mol and alkene B is –31.4Kcal/mol. Which alkene is more stable.
C-3. Predict the more stable alkene of each pair I & II.
I II
(A) 2-Methylpent-2-ene 2,3,-Dimethylbut-2-ene
(B) cis-Hex–3–ene trans-Hex-3-ene
(C) Hex-1-ene cis-Hex-3-ene
(D) trans-Hex-2-ene 2-Methylpent-2-ene
C-4. Which isomers of C4H9Br yield only a single alkene on dehydrohalogenation ? Give the structure of that alkyl
bromides.
C-5. Give the major elimination product obtained from an E2 reaction of each of the following alkyl halide with
hydroxide ion.
(A) CH3CH(Br)CH2CH3 (B) (CH3)2CHCH(F)CH2CH3
(C) CH3CH(F)CH2CH3 (D)
(E) (CH3)2CHCH(Cl)CH2CH3 (F) CH3CH(Cl)CH2CH=CH2

C-6. Write major product in each step :
(i) or P Q
(ii) CH3–CH=CH–CH3 R S T
C-7. Find out the product of following reactant by dehydration.
(a) and (b)
Section (D) : Rate of reaction of Alkenes / Alkynes

D-1. The acid catalysed hydration follows following order (CH3)2C=CH2 > CH3CH=CH2 > CH2=CH2
Explain this order of reactivity.
D-2. What will be order of reactivity of following compounds towards addition of HBr ?
CH3 Ph
| |
CH3  CH  CH  CH3 Ph  C  CH  CH3 Ph  C  CH  CH3
I III IV
Section (E) : Electrophilic addition reaction of alkenes (X2, HOX, HX, H2O)
E-1. Write the structures of But-2-ene and 2-Methylpropene and show addition of HBr in the absence of peroxide.
E-2. What will be the reagent for the preparation of following from (CH3)3CCH=CH2.
(P) (CH3)2C(OH)CH(CH3)2 (Q) (CH3)3CCH(OH)CH3 (R) (CH3)3CCH2CH2OH
(S) (CH3)3CCH(Cl)CH2Cl (T) (CH3)3CCH(OH)CH2Cl (U) (CH3)3CCH(OR)CH2Cl
E-3. Identifiy (X) and (Y) in the given sequence of reaction :
CH3
|
H3 C  C  CH  CH2 dil. aqueous H SO H , 
|      2 
4
 (X)  
 (Y)
CH3
3,3  dim ethyl  1  butene
Section (F) : Free radical addition /Allylic substitution reaction of alkenes

F-1. Predict the product of the reaction below :
HBr
CH3–CH=CH2 
Peroxide
or light
F-2. During addition of HCl over propene in the presence of peroxide, what will be the intermediate?
F-3. Predict the product(s) of the reaction below :
HBr

Peroxide
or light

F-4. In the reaction sequence,
HBr
 B
What is the relationship between A & B :
F-5. Synthesize Buta-1, 3-diene from But-1-ene.
F-6. Prepare Benzene from cyclohexane.
Section (G) : Addition reaction of alkynes

G-1. List the products formed when But-1-yne reacts with one equivalent of
(a) HBr , (b) HBr with peroxides and (c) Br2 (1 equivalent)
G-2. What reagents would be required to carry out the following synthesis ?
G-3. Give the equation for the reaction of one equivalent of HBr with Pent -1-en-4-yne
Section (H) : Reactions of alkadiene (1,4-and 1,2-addition).

H-1. Why 1,2-addition reaction of 1,3-butadine with HBr occurs faster than 1, 4-addition. Explain it.
Section (I) : Stereochemistry involved in reactions of alkane/alkene/alkyne

I-1. How many alkanes of molecular weight 100 are chiral ?
I-2. Give the total isomers formed when one equivalent of HBr is added to Buta-1, 3-diene.
I-3. What will happen when Br2/CCl4 react with (a) Cis But-2-ene (b) Trans But-2-ene.
PART - II : OBJECTIVE QUESTIONS

* Marked Questions may have more than one correct option.
Section (A) : Prepartion of Alkane
A-1. Successive alkanes differ by
(A) CH2 (B) CH (C) CH3 (D) C2H4
A-2. Which of the following compounds will form a hydrocarbon on reaction with a Grignard reagent ?
(A) CH3CH2OH (B) CH CHO (C) CH3COCH3 (D) CH3CO2CH3.
3
A-3. Methane is formed when

(A) Sodium acetate is heated with soda-lime (B) Iodomethane is reduced
(C) Aluminium carbide reacts with water (D) All of these

A-4. Sodium propionate on decarboxylation with soda-lime gives
(A) Propane (B) Ethane (C) Butane (D) Pentane.
A-5. Which of the following reactions can be used to prepare an alkane from an alkyl halide ?
(A) Wurtz reaction (B) Kolbe electrolysis
(C) Hoffmann reaction (D) Fittig reaction
A-6. Which one of the following cannot be prepared by Wurtz reaction ?

(A) CH4 (B) C2H6 (C) C3H8 (D) C4H10.
A-7. Which of the following alkanes can be synthesized by the Wurtz reaction in good yield ?
(A) (CH3)2CH – CH2 – CH (CH3)2 (B) (CH3)2CH – CH2 – CH2 – CH (CH3)2
(C) CH3 – CH2 – C(CH3)2CH2 – CH3 (D) (CH3)3C – CH2 – CH2 – CH3
A-8. Which of the following alkanes cannot be produced by Kolbe electrolysis of sodium or potassium salts of
carboxylic acids ?
(A) Methane (B) Ethane (C) Butane (D) Hexane
A-9. Which of the following reaction can be employed for getting unsymmetrical alkanes in good yield?
(A) Wrutz reaction (B) Corey-House reaction (C) Both (D) None
A-10. When water vapours are passed over aluminium carbide, we get:
(A) acetaldehyde (B) ethylene (C) methane (D) methyl alcohol
A-11. A mixture of two organic compound was treated with sodium metal in ether solution. Isobutane was obtained
as product. The two chlorine compounds are
(A) Methyl chloride and propyl chloride (B) Methyl chloride and ethyl chloride
(C) Isopropyl chloride and Methyl chloride (D) Isopropyl chloride and ethyl chloride
A-12. Which of the following reaction is correct ?
(A) + (CH3)2CuLi  + CH3Cu + LiI
(B) ( CH CH ) CuLi

3 + CH3CH2 Cu + LiBr
   22 
O O
( CH3 )2 CuLi
(C) CH3 – CH – C – CH3    CH3 – CH – C – CH3+CH3Cu + LiBr
Br CH3
(D) All of these
A-13. Which among the following reagents convert alkyl halide into alkane?
(A) Bu3SnH (B) Na/dry ether (C) R2CuLi (D) All of these
A-14. C6H12 (P) has only two types of alkenes that can be reduced to only one type of alkane C6H14 (Q). Q is:
(A) (B) (C) (D)
Section (B) : Chemical reactions of alkanes

B-1. The homolytic fission of hydrocarbon results in the formation of
(A) Free radicals (B) Carbocations (C) Carbanions (D) Carbenes.
B-2. In the free radical chlorination of methane, the chain initiating step involves the formation of
(A) Chlorine radical (B) Hydrogen chloride (C) Methyl radical (D) Chloromethyl radical.

B-3. Halogenation of alkanes is an example of
(A) Free radical addition reaction (B) Free radical substitution reaction
(C) Nucleophilic substitution reaction (D) Nucleophilic addition reaction.
B-4. Chlorination of an alkane involves the attack of

(A) An electrophile (B) A nucleophile (C) A base (D) A free radical
B-5. The reactivity of hydrogen atoms attached to carbon atom in the halogenation of an alkane has the order :
(A) tertiary > primary > secondary (B) secondary > primary > tertiary
(C) tertiary > secondary > primary (D) primary > secondary > tertiary
B-6. In which of the following pairs, the bromination of first member is easier than the second member ?
(A) Isobutane, n-butane (B) n-Butane, isobutane
(C) Methane, ethane (D) None of these
B-7. Which of the following cannot be considered as a step of mechanism in chain reaction of methane with CI2?
(A) Cl2  CI · (B) CH4 + CI·  CH CI + H·3
·
(C) CI + CH4  CH3 + HCI · (D) CI· + CH ·  CH CI
3 3
B-8. During chlorination of methane to methyl chloride, the propagation step is represented by
   
h
 CI  CI
(A) CI — CI  (B) CH3  CI  CH3CI
   
(C) CH4 + CI  CH3 + HCl (D) CI  CI  CI — CI
B-9. Methane reacts with excess of chlorine in diffused sunlight to give the final product as
(A) Chloroform (B) Carbon tetrachloride
(C) Methylene chloride (D) Methyl chloride.
B-10. A gaseous hydrocarbon ‘X’ on reaction with bromine in light forms a mixture of two monobromo alkanes and
HBr. The hydrocarbon ‘X’ is :
(A) CH3–CH3 (B) (C) (D)
B-11. The number of monochloro derivatives of isohexane is (Only structural isomers)

(A) 3 (B) 4 (C) 5 (D) 6
B-12. lodination of an alkane is carried out in presence of

(A) Alcohol (B) P + I2 (C) HNO3 or HIO3 (D) A reducing agent
B-13. The maximum ease of abstraction of a hydrogen atom by a chlorine atom is shown by
(A) (CH3)3 C–CH3 (B) (CH3)2 CH2 (C) C6H5CH3 (D) CH2 = CHCH3
B-14. Which of the following statement is correct in relation to the halogenation of alkane ?
(A) The reactivity of chlorine is less than bromine towards alkanes.
•
(B) For photochemical chlorination of methane, C l is formed in slowest step.
(C) Free radicals are pyramidal intermediate, stabilised by hyperconjugation and resonance.
(D) Bromine has much higher regioselectivity than chlorine in abstracting 30 hydrogen.
B-15. Which statement is incorrect about free radical halogenation of alkanes.

(A) The number of product molecules formed by one photon is very high.
(B) If O2 is added, initially the rate of reaction decreases, then increases.
(C) Inhibitors combine with free radical and terminate the chain reaction.
(D) presence of C 6H5  CO  OC  C6H5 inhibits the free radical reaction.
|| ||
O O

B-16. Which of the following is correct potential energy diagram for the given chain propagating step.
 
CH3 – H  F  C H3  H – F Ho  –134 kJ / mol
B.E.  435 B.E.  569
(A) (B)
(C) (D)
Section (C) : Stability and preparation of Alkenes/ Alkynes

C-1. sec-Butyl chloride on boiling with alc. KOH gives .......as the main product.
(A) 1-Butene (B) 2-Butene (C) 1-Butanol (D) 2-Butanol
C-2. An alkene is formed from a carbocation by
–
(A) Elimination of a H+ ion (B) Elimination of H ion
–
(C) Addition of a H+ ion (D) Addition of a H ion.
C-3. Alcoholic solution of caustic potash is a specific reagent for
(A) Dehydration (B) Dehydrohalogenation
(C) Dehydrogenation (D) Hydration.
C-4. When two alkenes may be formed by dehydrohalogenation of an alkyl halide, the alkene which is more
substituted is the major or preferred product. This generalisation is known as
(A) Markownikoff’s rule (B) Anti-Markownikoff’s rule
(C) Saytzeff rule (D) None of these is correct.
C-5. Ethyne can be prepared in a single step from

(A) Calcium carbide (B) Ethylidene bromide (C) Ethylene bromide (D) All of these.
C-6. Which is the correct increasing order of the stability of isomers of pentene ?
(1) CH3–CH2–CH2–CH=CH2 (2) (3) (4)
(A) 1 < 2 < 3 < 4 (B) 1 < 3 < 2 < 4 (C) 4 > 3 > 2 > 1 (D) 4 < 2 < 3 < 1
C-7. Which is the correct order for heat of hydrogenation ?

(A) Hept-1-ene < Hept-3-ene < 2-Methylhex-2-ene
(B) 3-Methylcyclooctene < 1-Methylcyclooctene < 1,2-Dimethylcyclooctene
(C) 3-Ethyloct-1-ene < 2-Ethyloct-1-ene < Oct-2-ene
(D) Ethene < ethyne
C-8. Predict wrong option for stability

(A) 2, 3-Dimethylbut-2-ene > 2-Methylpent-2-ene (B) trans-Hex-3-ene > cis-Hex-3-ene
(C) Cis-Hex-3-ene > Hex-1-ene (D) trans-Hex-2-ene > 2-Methylpent-2-ene

C-9. To prepare But-2-yne from 2, 2, 3, 3-Tetrachlorobutane, reagent used is :
(A) Zinc dust /  (B) Sodamide (C) Alc. KOH (D) aq. KOH
C-10. Which of the following compounds on hydrolysis gives propyne ?

(A) CaC2 (B) Mg2C3 (C) Al4C3 (D) Cu2Cl2
C-11. Acetylene may be prepared by electrolysis of
(A) potassium oxalate (B) potassium acetate
(C) potassium maleate (D) potassium succinate
C-12. Which gas is obtained when iodoform is heated with Ag powder ?

(A) CH4 (B) C2H4 (C) C2H6 (D) C2H2
Section (D) : Rate of reaction of Alkenes / Alkynes

D-1. To which of the following compounds Br2 adds most readily.
(A) CH2 = CH2 (B) CH3 – CH = CH2
(C) CH3 – CH = CH — CH3 (D) CH3 – C = CH – CH3.
CH3
D-2. What is correct order of acid catalysed hydation of following alkene ?

(I) CH2=CH2 (II) CH3–CH=CH2 (III) (CH3)2C=CH2 (IV) CH3–CH=CH–CH3
(A) III > I > II > IV (B) III > IV > II > I (C) II > IV > III > I (D) I > II > III > IV
D-3. What is correct order of electrophillic addition of following alkene ?

(I) Ph2C=CH2 (II) Ph–CH=CHPh (III) Ph–CH=CHMe
(A) I > III > II (B) III > II > I (C) I > II > III (D) I = II > III
D-4. What is correct order of electrophillic substitution of following alkene ?
(I) (II) (III) (IV)
(A) II > IV > I > III (B) IV > III > II > I (C) III > I > IV > II (D) I > II > III > IV
D-5. The correct order of alkene reactivity towards an electrophile is mentioned in-
(A) CH2=CH–Cl > CH2=CH–OCH3 (B) CH2=CHCl < CH2=CCl2
(C) ethene > propene (D) CH2 = CH – OCH3 > CH2=CH–
D-6. Identify the incorrect statement / statements :

(i) Alkynes are more reactive than alkenes towards electrophilic addition reaction
(ii) Alkynes are less reactive than alkenes towards electrophilic addition reaction
(iii) Alkynes decolourise Br2 water
(iv) Addition of HBr to alkynes in presence of peroxide proceeds via Markownikoff’s rule
(A) (i) & (ii) (B) (ii) & (iii) (C) (i) & (iv) (D) (ii) & (iv)
Section (E) : Electrophilic addition reaction of alkenes (X2, HOX, HX, H2O)
E-1. Markownikoff rule is applicable to :
(A) CH2 = CH2 (B) CH3 – CH2 – CH3
(C) CH3 – CH = CH – CH3 (D) (CH3)2 C=CH–CH3
E-2. Anti Markownikoff addition of HBr is not observed in
(A) Propene (B) 1-Butene (C) But-2-ene (D) Pent-2-ene.

E-3. Which of the following is the predominant product in the reaction of HOBr with propene ?
(A) 2-Bromo-1-propanol (B) 3-Bromo-1-propanol
(C) 2-Bromo-2-propanol (D) 1-Bromo-2-propanol.
E-4. Ethene is shaken with aqueous solution of Br2 and NaCl. Which of the following is not the possible product?
(A) CH2 – Br (B) CH2 – Br (C) CH2 – Cl (D) CH2 – Br
CH2 – Br CH2 – Cl CH2 – Cl CH2 – OH
E-5. A hydrocarbon of formula C6H12 on ozonolysis gives only one carbonyl product which does not reduce
Fehling’s solution. The hydrocarbon is
(A) 2-Hexene (B) 2, 3-Dimethyl-2-butene
(C) 2-Methyl-2-pentene (D) 3-Hexene.
E-6. Which of the following is wrong statement about oxymercuration-Demercuration -
(A) In the Ist step oxymercuration occurs i.e. water & Hg(OAc)2 add to double bond
(B) In the IInd step demercuration occurs i.e. NaBH4 reduces –HgOAc group to hydrogen
(C) The net reaction is addition of water according to Markonikoff rule
(D) Rearrangement takes place
E-7. In which reaction the product following antimarkovnikoff rule is observed :
HCl HCl
(A) CF3CH=CH2 
 (B) ClCH=CH2 

HCl
(C) CH3OCH=CH2 
 (D) None
E-8. + Br2 P, P will have configuration :
(A) (B) (C) both true (D) none is true
dil. H SO
E-9. Ph – CH2 – CH = CH2  2 
4
 X,
Identify product 'X' is :
H H
| |
(A) Ph – CH2 – CH2 – CH2 – OH (B) Ph  C  C  CH3
| |
H OH
H H
| |
(C) Ph  C  C  CH3 (D) Ph – CH2 – OH
| |
OH H
E-10. X,
Identify product X is :
(A) (B) (C) (D)

E-11. RCH = CH2
In this sequence of reactions, product A, B, C and D are :
(A) B, RCH2 OH, RCH2 , + Red P

(B) (RCH2CH2)3B, , RCH2CH3, HI + Red P
(C) B, , RCH2CH3, HI + Red P
(D) None of these
E-12. Ph–CH=CH–CH3 X, X is : (X %)
(A) (B)
(C) Ph–CH=CH–CH2Cl (D)
E-13. P,,
Identify major product 'P' is :
(A) CCI3CHCH2CI (B) CCI3CHCH2OH (C) CCI3CHCH2 (D) CCI3CHCH2
OH CI CI CI OHOH
Section (F) : Free radical addition /Allylic substitution reaction of alkenes

F-1. Allylic bromination of an olefin is :
(A) Nucleophilic substitution (B) Electrophilic substitution
(C) Free radical substitution (D) Electrophilic addition.
F-2. When HBr adds to 1-butene in the presence of benzoyl peroxide, the products is
(A) 1-Bromobutane (B) 2-Bromobutane (C) 1-Bromobutene (D) 2-Bromobutene.
F-3. In the presence of peroxide, hydrogen chloride and hydrogen iodide do not give anti-Markovnikov addition to
alkenes because :
(A) both are highly ionic.
(B) one is oxidising and the other is reducing.
(C) one of the steps is endothermic in both the cases.
(D) all the steps are exothermic in both the cases.
Section (G) : Addition reactions of alkynes

G-1. Which will form 2, 2-Dibromopropane with HBr ?
(A) CH2 = CH – CH3 (B) CH3 – C  CH (C) (D) Both B & C

G-2. HOBr ( excess )
   
O O Br
|| ||
C C CH
(A) CHBr2 (B) CH2Br (C) (D) CHO
G-3. A H – C  C – CH2 – CH3 B
A & B are :
(A) Positional isomers (B) Functional isomers (C) Metamers (D) Homologs
G-4. Find incorrect product in following reactions :
(A) Ph – C  CH HBr

HBr
(B) Ph–C  CH peroxide

(1) BH .THF
(C) CH3 – CH2 – C  CH  3

( 2) CH3COOD
(1) BD .THF
(D) CH3 – CH2 – C  CH  3

( 2) CH3COOH
Section (H) : Reactions of alkadiene (1,4-and 1,2-addition).
H-1. CH2=CH–CH=CH2
At given temperature, these reaction tell about control of reaction which is :

(1) (2)
(A) Kinetic Thermodynamic
(B) Thermodynamic Kinetic
(C) Kinetic Kinetic
(D) Thermodynamic Thermodynamic
H-2. What is the product of 1, 4-addition in the reaction shown below ?
HBr
Ph–CH=CH–CH=CH–Ph 
(A) Ph–CH2–CH=CH– CH –Ph (B) Ph–CH2– CH –CH=CH–Ph

| |
Br Br
(C) CH2–CH=CH–CH2 Br (D) CH2–CH=CH–CH2
H-3. The reaction of one equivalent of HBr with CH2=CH–CCH gives :

(A) CH2=CH–CCBr (B) CH2=CH– C  CH2 (C) CH3– CH –CCH (D) CH2=CH–CH=CHBr
| |
Br Br
Section (I) : Stereochemistry involved in reactions of alkane/alkene/alkyne
I-1. Number of isomers which can be theoretically obtained on monochlorination of 2-methylbutane is :
(A) 1 (B) 2 (C) 3 (D) 4
I-2. Which statement is correct about photochemical bromination of Butane ?
Br2 , h
CH3 – CH2 – CH2 – CH3  
(A) 1-Bromobutane and 2-Bromobutanes are formed in equal amounts.
(B) 2-Bromobutane is formed with faster rate than 2-chlorobutane in the other experiment of chlorination.
(C) The major product is an equimolar mixture of two compounds
(D) Homolysis of C – H bond has lower activation energy than homolysis of Br – Br bond.
I-3. The number of possible enantiomer pairs that can be produced during monochlorination of 2-methylbutane is :
(A) 2 (B) 3 (C) 4 (D) 1
I-4. For the given reaction how many products are optically active (all isomers) :
CH3 CH3
| |
Br2 / h
CH3  C  CH2  CH  CH3  
|
CH3
(A) 1 (B) 2 (C) 3 (D) 4
CH3
|
I-5*. Ph  CH2  CH  CH3
Which statements is/are correct about photochemical chlorination of the above compound ?
(A) The major product will have chiral carbon atom but is optically inactive.
(B) The intermediate free radical of the major product is resonance stabilised.
(C) The intermediate free radical is tertiary for major product.
(D) The intermediate free radical is planar, and stabilised by only hyperconjugation.
I-6. The correct statement about the following reaction is :
CH2 – CH3
|
C – CH2 – CH3 + Cl2 + C–O–O–C h
| || ||
H (excess ) O O
(excess) ( II)
(III)
(I)
(A) By absorption of one mole of photon of light only one mole of product (racemic mixture) is obtained.
(B) In total 6 optically active isomers are obtained on monochlorination of side chain.
(C) Homolysis of III takes place in chain propagation step.
(D) Homolysis of II takes place in the slowest step.
Cl , heat or
I-7. 2    Products
light
Sec-butylchloride
Which statement is incorrect ?
(A) One of the product exist as three stereoisomers
(B) Two pair of diastereomers are obtained only
(C) Only one meso stereoisomer is obtained
(D) Two pair of enantiomers are obtained

I-8. Br / h
2  Product, major product will be
(A) (B) (C) Both A and B (D)
I-9. An isomer of C5H12 gives total six isomeric products on monochlorination. Calculate the percentage yield of
the primary monochloride which is chiral. Consider the following relative reactivity of C – H bonds for chlorination.
Degree of C – H 1° C – H 2° C – H 3° C – H
Relative reactivity
1 3 5
for chlorination (RR)
(A) 26.8% (B) 25% (C) 30% (D) 50%
4 CCl
I-10. + Br2   ? Product is :
(A) (B) (C) (D)
H 2 4 Br , CCl
I-11.   F   G (C4H8Br2)
OH (H2O)
How many stereo isomers are possible for G :

(A) 2 (B) 3 (C) 5 (D) 6
HOBr
I-12. cis-2-Butene  P,,
Identify product 'P' is :
(A) (B) (C) (D)
I-13. The products of the following I and II sequence are related as
(A) Diastereomers (B) Identical (C) Enantiomers (D) Geometrical isomers

PART - III : ASSERTION / REASONING
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) STATEMENT-1 is true, STATEMENT-2 is true and STATEMENT-2 is correct explanation for STATEMENT-1
(B) STATEMENT-1 is true, STATEMENT-2 is true and STATEMENT-2 is not correct explanation for STATEMENT-1
(C) STATEMENT-1 is true, STATEMENT-2 is false
(D) STATEMENT-1 is false, STATEMENT-2 is true
(E) Both STATEMENTS are false
1. Statements-1 : CH3 – CC–CH3 is more reactive for electrophilic addition reaction than CH3CH = CH – CH3
Statements-2 : Carbocation intermediate formed in alkene is more stable than the alkyne
2. Statements-1 : Addition of HBr in the presence of peroxide on 1-methylcyclopentene gives two optical
isomers as major product.
Statements-2 : The major product contains two chiral carbon atom .
3. Statements-1 : Stability of alkene is governed by hyperconjugation.

Statements-2 : Hyperconjugation involves delocalisation of  electron with sp2 hybridised orbitals.
4. Statement-1 : When double and triple bonds are in conjugation, addition takes place at triple bond.
Statement-2 : When double and triple bond are not in the conjugation, addition takes place at double bond
alco KOH BrCl

5. Statement-1 : CH3 – CHBrCH3     CH3 – CH = CH2  CH3CHCl CH2Br

Statement-2 : In above reaction product formed, is based on the principle of E2 & electrophilic addition
reaction by markownikov's rule.
6. Statements-1 : Reaction of HCl with But-2-ene in the presence or absence of peroxide will give same
products.
Statement-2 : Above reaction is regioselective reaction.
7. Statement-1 : Addition of bromine to trans-2-butene yields meso-2. 3-dibromobutane.

Statement-2 : Bromine addition to an alkene is an electrophilic addition.
PART - I : SUBJECTIVE QUESTIONS
NaOH
1.   [X].
Electrolysis
2. Identify the unknown compounds in the following reaction sequence.

Br / h CH MgBr Br / h Na / ether
CH3 – CH3   A    B   C   
 D
2 3 2
(a)
Li CuI C
(b)  A  B 
NaOH
Electrolysis 2 Br / h
(c) CH3CH2CH2COOH  A    B   C

3. An organic compound (A) (m.f. = C7H12O2) on heating with sodalime produces (B) (m.f. = C6H12). (A) on
reduction with P/HI produces (C) (m.f. = C7H14) (C) has six membered ring, on monobromination it can
produce five structural isomers products. Find out structure of (A), (B) and (C).
4. The final product D of the following sequence of reactions :
A B C D
5. (a) A halide C5H11X on treating with alc. KOH gives only pent-1-ene. Identify halide ?
(b) A halide C5H11X on reacting with alc. KOH gives only pent-2-ene. Identify halide ?
6. Which reaction gives 2, 3-Dimethylbut-1-ene in the better yield
(a) Dehydration of 2,3-Dimethylbutan-1-ol in acidic medium or
(b) Dehydrohalogenation of 2, 3-Dimethyl-1-bromo butane with alc. KOH. Explain ?
7. Describe how a mixture of But-1-yne and But-2-yne can be distinguished chemically into two pure components?
8. (a) Predict strucutre of A & B in the following two step reaction.
Hg (OAc )2 NaBH4 / NaOH
C3H7CH=CH2     A   B
THF / H2O
(b) What is the net regiospecificity of this hydration reaction.

(c) Why is this hydration procedure superior to acid catalysed hydration of most alkenes ?
(d) What is the final state of mercury ?
9. From what alkene and by which method would you prepare each of the following alcohols free of constitutional
isomers (structural isomers).
(a) (C2H5)3C – OH (b) (c)
10. Give the structure of the major organic products from 3-Ethyl-2-pentene under each of the following reaction
conditions.
(a) HBr in the presence of peroxide (b) Br2 / H2O (c) Hg(OAc)2 / H2O ; NaBH4
11. Complete the following reactions with appropriate structures of products
2 Br 2 (i) NaNH (3.0 equiv .)
C6H5CH = CH2 
  [A]        [B]
(ii) CH3 I
12. How to form Acetone from acetylene.

13. Write the intermediate step for the following reaction :
H O
C6H5CH(OH)C  CH 3  C6H5CH =CHCHO
PART - II : OBJECTIVE QUESTIONS

Single choice type
1. The product formed in the reaction.
is :
(A) (BrCH2)3CCH2CH2C(CH2Br)3 (B)
(C) (D)

2. Which of the following will form cyclohexane on reaction with two moles of Na in ether.
(A) CH3 CH2 – Br (B)
(C) Br–CH2–CH2–CH2–CH2–CH2–CH2–CI (C)
3. CH3CH2Cl CH3CH2Li X n-Nonane
(A) The compound ‘X’ is (CH3CH2)2CuLi. (B) The compound ‘X’ is CH3(CH2)5CH2Br.
(C) The compound ‘Y’ is (CH3CH2)2CuLi. (D) The compound ‘Y’ is CH3(CH2)5CH2Br.
4. Write correct reactivity order towards photochemical chlorination.
CH3
|
(X) CH3 – CH2 – CH2 – CH2 – CH3 (Y) CH3  CH  CH2  CH3
CH3
|
(Z) CH3  C  CH3 (W) CH3 – CH3
|
CH3
(A) X > Y > Z > W (B) Y > X > Z > W (C) X > Z > W > Y (D) Z > W > Y > X
5. What is the chief product obtained when n-butane is treated with Br2 in the presence of light at 130°C ?
(A) CH3 – CH2 – CHBr – CH3 (B) (CH3)2CHCH2Br
(C) (CH3)3CBr (D) CH3 – CH2 – CH2 – CH2 – Br
CH3
| R O
6. CH3  C  H  CCl4 2
2
 (P) + (Q)
|
CH3
major products (P) and (Q) will be :

CH3
|
(A) CH3  C  Cl (B) CHCl3 (C) Both A & B (D) None of these
|
CH3
7. Arrange in increasing order of heat of hydrogenation of following dienes.
(i) (ii) (iii) (iv) (v)
(A) iii < v < i < iv < ii (B) v < i < iv < ii < iii
(C) iii > v > i > iv > ii (D) iii > v > iv > i > ii
8. Match the heat of combustion with the appropriate diene.
Dienes Heats of combustion
(1) Penta-1,2-diene (P) 761.6 kcal/mol
(2) Penta-1,3-diene (Q) 768.9 kcal/mol
(3) Penta-1,4-diene (R) 777.1 kcal/mol
(A) 1–P, 2–Q, 3–R (B) 1-Q, 2–P, 3–R (C) 1–R, 2–P, 3–Q (D) 1–R, 2–Q, 3–P

9. A sample of 2,3-dibromo-3-methylpentane is heated with zinc dust. The resulting product formed is isolated
and heated with HI in the presence of phosphorus. Identify which is the structure that represents the final
organic product formed in the reaction ?
(A) CH3  CH2  C H  CH2  CH3 (B) CH2  CH  CH  CH2  CH3

| |
CH3 CH3
(C) CH3  CHI  C H  CH 2  CH3 (D) CH2  CH  CI  CH2  CH3

| |
CH3 CH3
10. But-2-ene can be obtained by electrolysis of an aqueous solution of

(A) 2, 3-Dimethyl maleic acid (B) 2, 2-Dimethyl butanedioic acid
(C) 2-Methylbutanedioic acid (D) 2,3-Dimethylbutanedioic acid
1. excess NaNH , NH
2 3
11. BrCH 2CHCH 2CH 2CHCH 2Br         
2 . H 2O
| |
Br Br
(A) H – C  C – CH2 – CH2 – C  C – H (B) H – C  C – C  C – H
(C) H – C  C – CH2 – C  C – H (D) H – C  C – H
KOC (CH ) , DMSO

12.  3 
3
 , Identify the product ?
heat
(A) (B) H – C  C – H (C) (D)
13. The correct reactivity order of following C=C / CC bonds towards Br  is :
(A) 4 > 3 > 2 > 1 (B) 3 > 2 > 1 > 4 (C) 1 > 3 > 4 > 2 (D) 1 > 3 > 2 > 4
14. Observe the following compounds,
CH3–CH=CH2 CF3–CH=CH2
(1) (2) (3) (4)

The incorrect order of reactivity towards electrophilic addition reaction :
(A) 1 > 2 (B) 3 > 1 (C) 4 > 2 (D) 4 > 3
15. Br2
  P,,
Identify product 'P' is :
(A) (B) (C) (D)

16. Br2
 P
Identify major product 'P' is :
(A) (B) (C) (D)

H O
17.  P ; Identify major product 'P' is :
3 
(A) (B) (C) (D)
HCl
18.* In the given reaction, 
Structure of X can be :
(A) (B) (C) (D)
19.
X, Y, Z reaction are :
(A) Simple hydration reaction
(B) Hydroboration oxidation, hydration and oxymercuration demercuration
(C) Hydroboration oxidation, oxymercuration demercuration and hydration
(D) Oxymercuration demercuration, hydroboration oxidation and hydration
(1) HBr (2moles ) (2) Zn

20.        P  Q
R 2O 2 Ether
Give the molecular weight of Q :
(A) 135 (B) 140 (C) 138 (D) 133

21. The product(s) via-oxymercuration (HgSO4 + H2SO4) of 1-butyne would be :
O
(A) || (B) CH3 – CH2 – CH2 – CHO
CH3  CH2  C  CH3
(C) CH3 – CH2 – CHO + HCHO (D) CH3 – CH2 – COOH + HCOOH
22. Propyne and propene can be distinguished by : [JEE-2000, 1/35]

(A) Conc. H2SO4 (B) Br2 in CCl4 (C) Dil. KMnO4 (D) AgNO3 in ammonia
23. Identify a reagent from the following list which can easily distinguish between 1-butyne and 2-butyne.
(A) bromine, CCl4 (B) H2, Lindlar catalyst
(C) dilute H2SO4, HgSO4 (D) ammonical Cu2Cl2 solution [JEE-2002, 3/90]
24. Identify the set of reagents/reaction conditions ‘X’ and ‘Y’ in the following set of transformations.
X Y
CH3 – CH2 – CH2Br  product  CH3  CH  CH3
|
Br
(A) X = concentrated alcoholic NaOH, 80°C ; Y = HBr acetic acid, 20°C
(B) X = dil. aq. NaOH, 20°C, Y = HBr / acetic acid, 20°C
(C) X = dil. aq. NaOH, 20°C, Y = Br2 / CHCl3 , 0°C
(D) X = conc. alc. NaOH, 80°C, Y = Br2 / CHCl3 , 0°C
More than one choice type

25. Photochemical fluorination is explosive while iodination is too slow to occur. The reason for this is
(A) Bond dissociation energy of I2 is minimum
(B) Formation of CH3 – F is most exothermic
(C) Formation of H – F is most exothermic while formation of H – I is endothermic
(D) F2 has lower bond dissociation energy than Cl2 or Br2
26. Which of the following compounds will give same major product on acid catalysed hydration
(A) (B)
(C) (D)
27. The correct products have been reported in reactions.

HCl( g)(–10º C )
(A) CH2 = CH – CHO        CH2 – CH2 – CHO
Cl
H2O / H2SO 4
(B) CH2 = CH – COOH      CH2 – CH2 – COOH
OH
CH3
CH3
CH3OH / H2SO 4
(C) CH3 – C = CH – C – CH3       CH3 – CH – CH C – CH3
O OCH3 O
CH3OH / H
(D) CH3 – CH = CH – OCH3      CH3 – CH2 – CH – OCH3
OCH3
28. Which of following will react with But-1-yne ?
(A) AgNO3 + NH4OH (B) Cu2Cl2 + NH4OH (C) Na (D) KMnO4/KOH cold
29. Acetone (CH3COCH3) is the major product in :
I CH2 = C = CH2
II CH3C  CH
III CH3C  CH
(A) I (B) II (C) III (D) none
30. Which of the following statements is/are correct.

(A) Addition of HBr to Buta-1, 3-diene occurs at a faster rate than But-1-ene.
(B) Addition of one mole of HBr to Buta-1, 3-diene at room temperature gives 1-Bromobut-2-ene as the major product.
(C) When double and tripple bond are in the conjugation tripple bond is more reactive.
(D) When double and tripple bond are in the conjugation, tripple bond is less reactive.
31. The correct statement(s) is/are.
HBr / R O / h 
2 2
   
(A) It is a regioselective addition reaction, which forms Anti Markownikov's addition product.
(B) The reaction intermediate is paramagnetic.
(C) It is a chain reaction. (D) The product has two chiral C* atoms
PART - III : MATCH THE COLUMN

1. Column-I Column-II
DilH2SO4
(A) 1-Phenylbut -1-yne   (p) 1–phenylbutan-1-one
Hg 2
(1) BH3  THF
(B)1-Phenylbut -1-yne    (q) 1–Phenylbutan-2-one
( 2 )H2O 2  O H
Br CCl
(C) But-2-ene (cis) 2
4
 (r) Syn addition
Br2  CCl 4
(D) But-2-ene (trans)     (s) Antiaddition
(t) Optically inactive
2._ Column-I (Reactions) Column-II

(Reactant) (Major Product) (Intermediate involve)
(A) (p) Free Radical
(B) (q) Carbanion
(C) (r) Carbocation
(D) (s) Two isomers are formed

PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
When alkyne passed into dilute sulphuric acid at 330 K in the presence of HgSO4 (catalyst), alkynes add
one molecule of H2O to form carbonyl compound.
H2SO4 ,HgSO4
H—C  C—H + H2O  CH3—CH=O.
   
H2SO4 ,HgSO4
CH3—CCH + H2O     
In fact, enols are formed in the hydration of alkynes. An alcohol contain OH group on a double bonded carbon
is called an enol. Enols can not be isolated because they are unstable and are rapidly converted into
corresponding aldehydes or ketones.
Based on above passage answers the given questions.
1. In the sequence of reactions :

H2SO4 ,HgSO4 [O]
H—CC—H + H2O      [A]   [B]
The compounds A and B are :
(A) Acetone and acetic acid respectively. (B) Acetaldehyde and acetic acid respectively.
(C) Acetaldehyde and ethyl alcohol respectively. (D) Ethyl alcohol and acetaldehyde respectively.
2. The reagent required to convert But-1-yne to Butanone and Butanal respectively are :
(A) dilute H2SO4 and BH3 – THF + H2O2. (B) ZnCl2 + conc. HCl and BH3 – THF + H2O2.
(C) Hg2+ + H2SO4 (dilute) and BH3–THF + H2O2 (D) BH3 – THF + H2O2 and Hg2+ + H2SO4 (dilute).
3. 3-Methylbut-1-yne reacts with mercuric acetate in presence of water to form a product, which on reduction
with NaBH4 yield.
(A) 2-Methylbuten-2-ol (B) 3-Methylbutanone (C) 3-Methylbutan-2-one (D) 2-Methylbutan-2-ol
Comprehension # 2
alc. KOH Br2 NaNH2 AgNO3
X(C4H9Br)     Y   Z (Dibromide)   
 W (gas)    White ppt
Solution
4. X, Y and Z are :
X Y Z
(A) CH3 – CH2CH2CH2Br CH3 – CH = CH – CH3
(B) CH3 – CH2CH2CH2Br CH3 – CH2 – CH = CH2
(C) CH3 – CH = CH – CH3
(D) CH3 – CH2 – CH = CH2
5. Reductive ozonolysis of Y yields

(A) 2 moles of CH3CHO (B) CH3CH2CHO & HCHO
(C) CH 3 – C – CH 3 & HCHO (D) CH3CH2COOH & HCOOH
O
6. Which of the following statement is correct
(A) Y and W distinguish by bromine water test (B) Y & W are functional isomers
(C) W can be converted into Y with Lindlar's catalyst (D) W can be converted into Y with H2/Pt
PART - I : IIT-JEE PROBLEMS (LAST 10 YEARS)
* Marked Questions may have more than one correct option.
Hg2 / H
1. Ph – C  C – CH3   A, A is : [JEE-2003, 3/84]
(A) (B) (C) (D)
2. The major product obtained on acid–catalysed hydration of 2–phenylpropene is [JEE-2004, 3/84]

(A) 2-Phenylpropan-2-ol (B) 2-Phenylpropan-1-ol
(C) 3-Phenylpropan-2-ol (D) 1-Phenylpropan-1-ol
3. An organic compound (P), C5H10O reacts with dil. H2SO4 to give (Q) and (R). Both (Q) and (R) give positive
iodoform test. The reactivity of organic compound (P) is 1015 times more than ethylene with respect to dil.
H2SO4.
(i) Identify the compounds (P), (Q) and (R).
(ii) Give reason for the extraordinary reactivity of compound (P). [JEE-2004, 2/60]
4. The number of chiral compounds produced upon monochlorination of 2-methylbutane is :

[JEE-2004, 3/84]
(A) 2 (B) 4 (C) 6 (D) 8
5. 1-Bromo-3-chlorocyclobutane will react with two moles of Na in ether producing ? [JEE-2005, 3/60]
(A) (B) (C) (D)
Cl h  / Fractional
6. (CH3)2CH – CH2CH3 2 [N]       [P] [JEE-2006, 5/184]
distillati on
The number of possible isomers [N] and number of fractions [P] are :
(A) (6, 6) (B) (6, 4) (C) (4, 4) (D) (3, 3)
NOCl
7. CH2 = CH – CH3  
 X , X is : [JEE-2006, 3/184]
CH 2  CH  CH3 CH 2  CH  CH3
(A) | | (B) | |
Cl NO NO Cl
(C) ON – CH2 – CH2 – CH2 – Cl (D) ON  CH  CH2  CH3

|
Cl

8. The reagent(s) for the following conversion, [JEE - 2007, 3/162]
Br ?
Br  H H
is/are
(A) alcoholic KOH (B) alcoholic KOH followed by NaNH2
(C) aqueous KOH followed by NaNH2 (D) Zn/CH3OH
9. The number of stereoisomers obtained by bromination of trans-2-butene is : [JEE - 2007, 3/162]

(A) 1 (B) 2 (C) 3 (D) 4
10. The maximum number of isomers (including stereoisomers) that are possible on monochlorination of the
following compound, is : [JEE-2011, 4/160]
11. The structure of compound P is [JEE - 2011, 3/180]

(A) CH3CH2CH2CH2–CC–H (B) H3CH2C–CC–CH2CH3
(C) (D)
12. The structure of the compound Q is [JEE - 2011, 3/180]
(A) (B)
(C) (D)
13. The number of optically active products obtained from the complete ozonolysis of the given compound is:
[JEE - 2012, 3/136]
(A) 0 (B) 1 (C) 2 (D) 4
PART - II : AIEEE PROBLEMS (LAST 10 YEARS)

1. But-1-ene may be converted to butane by reaction with : [AIEEE-2003]
(1) Zn – HCl (2) Sn – HCl (3) Zn – Hg (4) Pd / H2
2. On mixing a certain alkane with chlorine and irradiating it with U. V. light, it forms only one monochloroalkane.
This alkane could be : [AIEEE-2003]
(1) Propane (2) Pentane (3) Isopentane (4) Neopentane

3. But-1-ene may be converted to butane by reaction with : [AIEEE-2003]
(1) Zn – HCl (2) Sn – HCl (3) Zn – Hg (4) Pd / H2
4. Acetylene reacts with hypochlorous acid to form : [AIEEE-2003]

(1) Cl2CHCHO (2) ClCH2COOH (3) CH3COCl (4) ClCH2CHO
5. Which one of the following is reduced with Zn/Hg and hydrochloric acid to give the corresponding hydrocarbon?
[AIEEE-2004]
(1) Ethyl acetate (2) Acetic acid (3) Acetamide (4) Butanone
6. Which one of the following has minimum boiling point ? [AIEEE-2004]

(1) n-butane (2) 1-Butyne (3) 1-Butene (4) Isobutene
7. Reaction of one molecule of HBr with one molecule of 1, 3-butadiene at 40°C gives predominantly :
(1) 1-Bromo-2-butene under kinetically controlled conditions [AIEEE-2005]
(2) 3-Bromobutene under thermodynamically controlled conditions
(3) 1-Bromo-2-butene under thermodynamically controlled conditions
(4) 3-Bromobutene under kinetically controlled conditions
8. Acid catalyzed hydration of alkenes except ethene leads to the formation of [AIEEE-2005]
(1) Mixture of secondary and tertiary alcohols (2) Mixture of primary and secondary alcohols
(3) Secondary or tertiary alcohol (4) Primary alcohol
9. 2-Methylbutane on reacting with bromine in the presence of sunlight gives mainly ? [AIEEE-2005]
(1) 1-Bromo-3-methylbutane (2) 1-Bromo-2-methylbutane
(3) 2-Bromo-3-methylbutane (4) 2-Bromo-2-methylbutane
10. Which of the following reactions will yield 2,2-dibromopropane ? [AIEEE-2007, 3/120]
(1) CH3 – C  CH + 2HBr  (2) CH3CH = CHBr + HBr 

(3) CH CH + 2HBr  (4) CH3– CH = CH2 + HBr 
11. The hydrocarbon which can react with sodium in liquid ammonia is: [AIEEE-2008, 3/105]
(1) CH3CH2 CCH (2) CH3CH = CHCH3
(3) CH3CH2CCCH2CH3 (4) CH3CH2CH2CCCH2CH2CH3
12. In the following sequence of reactions, the alkene affords the compound ‘B’ [AIEEE-2008, 3/105]
O3 HO
 A 2 B, The compound B is :
CH3CH=CHCH3 
Zn
(1) CH3COCH3 (2) CH3CH2COCH3 (3) CH3CHO (4) CH3CH2CHO

13. One mole of a symmetrical alkene on ozonolysis gives two moles of an aldehyde having a molecular mass
of 44 u. The alkene is : [AIEEE-2010, 4/144]
(1) propane (2) 1-butene (3) 2-butene (4) ethene
14. Ozonolysis of an organic compound gives formaldehyde as one of the products. This confirms the presence
of :
(1) two ethylenic double bonds (2) a vinyl group [AIEEE-2011]
(3) an isopropyl group (4) an acetylenic triple bond
15. How many chiral compounds are possible on monochlorination of 2- methyl butane ? [AIEEE-2012]
(1) 8 (2) 2 (3) 4 (4) 6
16. Which branched chain isomer of the hydrocarbon with molecular mass 72u gives only one isomer of mono
substituted alkyl halide ? [AIEEE-2012]
(1) Tertiary butyl chloride (2) Neopentane
(3) Isohexane (4) Neohexane

PART - III : CBSE PROBLEMS (LAST 10 YEARS)
1. State Markownikov's rule. [1 Mark, CBSE 2007]
2. Complete the following reaction.
O3/ Zn
(a) [2 Mark, CBSE 2008]
H2O
CH2–CH3 KMnO,Hot
4
(b)
3. Describe how the following conversions can be brought about : [2 Mark, CBSE 2010]
(i) Cyclohexanol to Cyclohexan-1-one (ii) Ethylbenzene to Benzoic acid
4. How would you convert the Propene to propan-2-ol [1 Mark, CBSE 2010]
5. How would you obtain 2-Methylpropene from 2-methylpropanol? [1 Mark, CBSE 2011]
6. How would you convert ethanol to ethene? [1 Mark, CBSE 2011]
7. What happens when bromine attacks CH2 = CH – CH2 – C  CH ? [1 Mark, CBSE 2012]
8. Explain the mechanism of acid catalysed hydration of an alkene to form corresponding alcohol.
[2 Mark, CBSE 2012]
9. How will you bring about the following conversions [2 Mark, CBSE 2013]
(i) Propanone to propane
(ii) Propene to propan–1–ol

BOARD LEVEL EXERCISE : HINT & SOLUTIONS
1. When alkyl halide react with sodium metal in presence of dry ether then formation of higher alkane is known
as Wurtz reaction.
Na
R– X   R–R
dry ether
2. (i) one monochloro product (ii) three monochloro product

3. But–2–ene give same product with HBr in the presence and in the absence of peroxide.
HBr
CH3CH = CHCH3  CH3–CHBr–CH2CH3
(Marke. rule)
HBr
CH3CH = CHCH3 R
O
 CH –CHBr–CH CH
3 2 3
2 2
(Anti Marke. rule)
4. By catalytic hydrogenation (H2/Ni) ethylene can be converted into ethane.

5. HI>HBr > HCl> HF
6. Cu 2Cl2 / NH 4 Cl
CH3CH2–CCH  – +
   CH3CH2CC Cu
red ppt
Cu 2Cl2 / NH 4 Cl
CH3CCCH3     No. ppt formation.
7. Either by Baeyer's reagent or by Br2 in CCl4.
8. KCN
CH2 = CH2 + HCl  CH3CH2Cl   CH3CH2CN
Hg( OAc )2 / H2O

9. (CH3)2 CH–CH=CH2     (CH3)2 CH–CHOH–CH3
NaBH 4
2
Hg / H 2O
10. H3CCCH     H3C–COCH3

Zn / CH3 OH
11. (i) BrCH2–CH2Br    CH2=CH2

(ii) Na / dry ether

   

13
12. (i) C4H10 + O  4CO2 + 5H2O
Butane 2 2
15
(ii) C5H10 + O  5CO2 + 5H2O
Pentene 2 2
17
(iii) C6H10 + O  6CO2 + 5H2O
Hexyne 2 2
(iv) C7H8 + 9O2  7CO2 + 4H2O

Toluene
All combustion reactions are highly exothermic .

13. (i) Isomers of C4H8 (one double bond) :
CH3–CH2CH=CH2 , CH3–CH=CH–CH3 , (CH3)2C=CH2
But–1–ene, But–2–ene, (cis+trans), 2-Methyl propene
(ii) Isomers of C5H8 (one triple bond)

CH3CH2CH2CCH, CH3CH2CCCH3, (CH3)2CHCCH
pent-1-yne, pent-2-yne, 3-Methyl Butyne
Na 1
14. (i) CHCH Metal

 CHC– Na++ H 
2 2
(ii) CHCH + CH3MgBr CH4 + CHC– MgBr
Acidic H reacts with alkali metals and bases.
15. (i) Four (ii) two
16. Because of greater ‘s’ character ‘sp’ hybridised ‘C’ is more electronegative hence bonded electrons between
‘C’ and ‘H’ atoms are shifted towards carbon as a result proton is being accepted, using proton acceptor.
Following reactions show acidic property of acetylene.
Metal   1
(i) CH  CH + Na  
 CH  C Na + H
2 2
(ii) CH  CH + NaNH2  CH  CNa + NH3
17. HBr add to propene through electrophilic addition reaction via the formation of more stable carbocation
intermediate. While is presence of peroxide, reaction proceed via free radical addition mechanism. So,
products are different according to stability of intermediate.
18. (i) For Methane (CH4)

( i) Mg / ether
(1) CH3Cl ( 
ii) H O
 CH
4
2
(2) CH3Cl  Zn / HCl

 CH4
(ii) For Ethane (C2H6)
Na / ether
(1) CH3Cl    CH3–CH3
H2 / Ni
(2) CH2=CH2   CH3–CH3
(iii) For Ethyne
(1) CaC2 + 2H2O  CHCH + Ca(OH)2
(2) 2CHCl3 + 6Ag  CHCH + 6 AgCl
19. HBr
(i) CH3–CH=CH2  CH3CHBr–CH3
(ii) CH3–CH=CH2  H2O / H2 SO 4
   CH3–CHOH–CH3
Electrophilic addition reaction follows Markownikov's rule.
Na CH3 I
20.  CHC–Na+  
(i) CHCH   CHC–CH3
SN 2
NaOH / CaO
(ii) CH3COOH   CH4

Cr2O3 or V2O5 or Mo 2O3

(iii)       
773 K 10  20 atm

21. (i) Branched chain isomers have less surface area in comparision of n-alkanes, so boiling point decreses on
increasing branching.
(ii) trans-2-butene gives more symmetrical, close packing in crystaline solid state than cis-2-butene, so have
more melting point.
22. (i) CHCH + H2O  CH2 = CH–OH  CH3–CHO

Ni Ni
(ii) CHCH + H
2 CH2 = CH
2  CH3– CH3
H2
H2 O 2
(iii) CHCH + O3   2 HCOOH
(iv) CHCH + HCl  CH2 = CH–Cl
23. (a) On reaction with sodium metals acetylene releases H2 gas while Ethylene does not.
(b) On ozonolysis But-1-ene give one mole propanal and one mole methanal while but-2-ene give two mole
of ethanal .
(c) On reaction with excess sodium metals acetylene release one mole H2 gas while 2-Butyne does not
release H2 gas.
(d) Bayer's reagent.
BH3
24. (i) Hydroboration : CH3–CH=CH2  CH CH –CH BH  (CH CH –CH ) B
BH H 3 2 2 2 3 2 2 3
2
H2O2 / OH
Oxidation : (CH3CH2–CH2)3 B   3CH3CH2CH2OH
Result : addition of H2O by Anti Markovnikoff Rule.
(ii) Though former one is having 2 e– only and latter one is having 4 e–.
In case of () C-atom is in sp hybridized state which is more electronegative and thus  electron are being
held by this more electronegative C–atom i.e. they are not free to be attacked by electrophile.
25. (i)
alc.KOH, 
(ii)    CHCH
– 2HX
Zn, Powder
(iii) Br2CH –CHBr2    HC CH

26. (i) CH3– CC–CH3 cis but-2-ene (ii) CH3 –CC–CH3 Trans-But-2-ene
27. (i) Hg  / H SO

 
2

4

(ii) Hg   / H SO
2
   
4


Hg / H2 SO 4
(iii)   

EXERCISE - 1
PART - I
CaO
A-1. CH3CH2CH2 – COONa + NaOH  CH3CH2CH3 + Na2CO3
630K
CaO
+ NaOH 630
 CH – CH – CH + Na CO
K 3 2 3 2 3
A-2. (i) Ether

CH3 CH2 Cl + 2Li   CH3CH2Li + LiCl
(ii) 2CH3 CH2 Li + CuI  (CH3CH2)2 Li Cu + LiI
Lithium diethyl cuprate
(iii) Li (CH3CH2)2 Cu + CH3 CH2 Cl  CH3 CH2 CH2 CH3 + CH3 CH2 Cu + LiCl
Butane
A-3. (i) Butane (ii) (iii) Ph–Ph + CH3–CH3 + Ph–CH3
B-1. Chlorination of methane is a free radical reaction which occurs by the following mechanism
Homolytic Fission
Initiation      2
Propagation  + HCl
 CH3 – Cl +
Termination  CH3 – CH3
 CH3 – Cl
 Cl – Cl
B-2. x > y > z.
B-3. 2.
C-1. The more s character in the hybridised orbital used by an atom will may more closer bonding electrons to the
atom which make shorter and stronger  –bonds. The decreasing order of C–H bond lengths is
–C–H > = C–H >  C–H
sp3 sp2 sp
The decreasing order of bond enthalpies is  C–H > = C–H > –C–H
C-2. A is more stable.
C-3. (A) II (B) II (C) II (D) II
C-4. 1º halides : BrCH2CH2CH2CH3, BrCH2CH(CH3)2

3º halides : (CH3)3 CBr
C-5. (A) CH3CH=CHCH3 (Saytzef's Product) (B) (CH3)2CHCH=CHCH3 (Hoffmann's Product)
(C) CH2=CHCH2CH3 (Hoffmann's Product) (D)
(E) (CH3)2C=CHCH2CH3 (Saytzef's Product) (F) CH3CH=CH–CH=CH2

C-6. (P) (Q) R–CC–R (R) (S)
(T) CH3–CC–CH3-
C-7. (a) (b)
D-1. 3º carbocation > 2º carbocation > 1º carbocation (stability order)
D-2. IV > III > II > I
HBr
E-1. CH3CH  CHCH3  CH3CHBrCH2CH3 (2-Bromobutane)
But  2  ene
HBr
 (CH3)2CBrCH3 (2-Bromo-2-methylpropane)
E-2. (P) dil. H2SO4 (Q) (a) Hg(OAc)2 + H2O (b) NaBH4 + OH–
–
(R) (a) BH3 + THF (b) H2O2 + OH (S) Cl2 + CCl4 (T) Cl2 then H2O
(U) Cl2 then ROH
H CH3
| |
E-3. (X) = H3 C  C  C  CH3 (Y) = H3 C  C  C  CH3
| | | |
CH3 OH CH3 CH3
2, 3  dim ethyl  2  bu tanol 2, 3  dim ethyl  2  butene
F-1. 1-bromopropane
F-2.
F-3. +
F-4. Positional isomers
(1) NBS
F-5. H2C=CH–CH2–CH3     H2C=CH–CH=CH2
( 2) alc . KOH / 
(1) Cl2 h

( 2) alc . KOH / 
F-6.     

(3 ) NBS
( 4 ) alc . KOH / 

G-1. (a) CH3CH2CBr = CH2 a Markownikov's electrophilic addition.
(b) CH3CH2CH = CHBr (trans) an anti-Markownikov's radical addition.
(c) CH3CH2CBr = CHBr an electrophilic addition.
G-2. (A) (i) H2 / Pd / BaSO4 (ii) HBr / peroxide (B) (i) H2 / Pd / BaSO4 (ii)+HBr
(C) HgSO4 / H2SO4 (D) BH3 + THF / H2O2 + OH–
(E) 2 mole HBr (F) 1 mole HBr
G-3.
H-1. Addition of the proton gives the resonance hybrid of .
Since (I) is more stable so it contributes more to the resonance hybrid and reacts faster with the bromide ion.
I-1. 2
I-2. 4
I-3. (a) Racemic mixture of 2,3-dibromobutane obtained.

(b) Miso 2,3-dibromobutane obtained.
PART - II
A-1. (A) A-2. (D) A-3. (D) A-4. (B) A-5. (A)
A-6. (A) A-7. (B) A-8. (A) A-9. (B) A-10. (C)
A-11. (C) A-12. (D) A-13. (D) A-14. (B) B-1. (A)
B-2. (A) B-3. (B) B-4. (D) B-5. (C) B-6. (A)
B-7. (B) B-8. (C) B-9. (B) B-10. (C) B-11. (C)
B-12. (C) B-13. (C) B-14. (D) B-15. (D) B-16. (C)
C-1. (B) C-2. (A) C-3. (B) C-4. (C) C-5. (D)
C-6. (A) C-7. (D) C-8. (D) C-9. (A) C-10. (B)
C-11. (C) C-12. (D) D-1. (D) D-2. (B) D-3. (A)
D-4. (C) D-5. (D) D-6. (C) E-1. (D) E-2. (C)
E-3. (D) E-4. (C) E-5. (B) E-6. (D) E-7. (A)
E-8. (B) E-9. (C) E-10. (B) E-11. (A) E-12. (B)
E-13. (B) F-1. (C) F-2. (A) F-3. (C) G-1. (D)
G-2. (A) G-3. (B) G-4. (C) H-1. (A) H-2. (A)
H-3. (B) I-1. (D) I-2. (C) I-3. (A) I-4. (D)
I-5*. (A,B) I-6. (B) I-7. (D) I-8. (C) I-9. (C)
I-10. (B) I-11. (C) I-12. (B) I-13. (B)

PART - III
1. (D) 2. (D) 3. (C) 4. (B) 5. (A)
6. (C) 7. (B)
EXERCISE - 2
PART - I
1. X=
2. (a) A = CH3CH2Br , B = CH3 – CH2 – CH3 , C = , D=
(b) A = , B = [(CH3)2CH]2CuLi , C =
(c) A = CH3CH2CH2 – COONa , B = CH3 – CH2 – CH2 – CH2 – CH2 – CH3
C = CH3  CH2  CH  CH2  CH2  CH3 + CH3  CH  CH2  CH2  CH2  CH3
| |
Br
Br
3. (A) (B) (C)
4.
5. (a) CH3CH2–CH2–CH2–CH2–X (b)
6. Dehydrohalogenation is preferred because dehydration in acidic medium is accompanied by a hydride shift

leading to an intermediate 3º carbocation, which forms 2,3-Dimethylbut-2-ene.
7. (a) Addition of AgNO3 and NH3 converts But-1-yne to the insoluble silver acetylide which is filtered, leaving
the unreacted But-2-yne in solution But-1-yne is regenerated by treating its Ag acetylide with HCl.
CH3CH2CCAg + HCl  CH3CH2CCH + AgCl(s)
8. (a) (A) = (B) =
(b) MarkowoniKoff's addition (c) It avoids rearrangements (d) Hg (atomic state)

9. Alcohol Alkene Method
(a) (C2H5)3C–OH Oxymercuration demercuration
(b) Hydroboration oxidation
(c) acid hydration or any of (a) and (b)
10. (a) CH3  CH2  C  CH  CH3  HBr  Peroxide

  CH3  CH2  CH  CH  CH3
( Anti markowniko ff )
| | |
C 2H5 C 2H5 Br
OH
|
(b) CH3  CH2  C  CH  CH3  HOBr  CH3  CH2  C  CH  CH3
| | |
C 2 H5 C 2H5 Br
OH
(1) Hg( OAc )2 / H2O |
(c) CH3  CH2  C  CH  CH3       CH3  CH2  C  CH  CH3
(  AcOH) | |
|
C H C2H5 Hg(OAc )
2 5
OH
|
AcOH + Hg + CH 3  CH 2  C  CH 2  CH3
|
C 2H5
2 Br (1) NaNH
2
11. 
     
(3 eq )
NaNH2 MeI
12. H – C  C – H    H – C  C – Na  H – C  C – CH3

13. C 6H5 CHC  CH 
|
OH
Tautomerise
C6H5CH = CHCHO    
 C6H5CH = C = CHOH
PART - II
1. (D) 2. (C) 3. (A, D) 4. (B) 5. (A)
6. (C) 7. (A) 8. (C) 9. (A) 10. (D)
11. (A) 12. (D) 13. (D) 14. (D) 15. (D)
16. (B) 17. (C) 18.* (B) 19. (C) 20. (C)
21. (A) 22. (D) 23. (D) 24. (A) 25. (B,C)
26. (A,B,C,D) 27. (A,B,D) 28. (A,B,C,D) 29. (A,B) 30. (A,B,C)
31. (A,B,C,D)
PART - III
1. (A) p, t (B) q, t (C) s,t (D) s, t 2._ (A – p, s) ; (B – r, s) ; (C – p, s) ; (D – s)
PART - IV
1. (B) 2. (C) 3. (C) 4. (B) 5. (B)
6. (C)
EXERCISE - 3
PART - I
1. (A) 2. (A)
3.
+ 
CH3 – CHO
(P) (Q) CH3 – CHO (R)
4. (B) 5. (A) 6. (B) 7. (B) 8. (B)
9. (A) 10. 8 11. (D) 12. (B) 13. (A)

PART - II
1. (4) 2. (4) 3. (4) 4. (1) 5. (4)
6. (4) 7. (3) 8. (3) 9. (4) 10. (1)
11. (1) 12. (3) 13. (3) 14. (2) 15. (3)
16. (2)
PART - III
1. Negative part of addendum or acid reagent will go to that carbon atom of C=C which has less number of H-
atom or where carbocation is more stable.
2. (a) O3/Zn
2
H2O
CH2–CH3 KMnO4 ,Hot COOH

(b)
K Cr O
3. (i) 2 2
7
Conc . H2SO 4
6 [O]
(ii)  
KMnO4 / KOH
heat
OH
H O |
4. CH3 – CH  CH2 2 CH3 – CH – CH3
Pr opene H2SO 4 Pr opan  2  ol
CH3 CH3
H2SO4 (Conc.)
5. CH3 — C — CH2OH CH3 — C = CH2 + H2O
H 2-Methyl propene
(Isobutylene)
2-Methyl propanol
Conc. H2SO4
CH3CH2OH 
6.     CH2  CH2  H2O
(Ethanol ) 443 K (Ethene )
7. is formed when Br2 is used in excess.
Br
|
If only one mole of Br2 is used then will be formed.
|
Br
8. Step 1 : H2O + H+  H3O+
Step 2 :
Step 3 :
Zn-Hg/HCl
9. (i) CH3–C–CH3 CH3–CH2–CH3
O
CH3–CH=CH2 CH3–CH=CH2
(ii) CH3 –CH=CH2+ (H–BH2 )2 CH3–CH–CH2 (CH3–CH2–CH2)2BH (CH3–CH2–CH2)3 B
H BH2
H2O
3CH3–CH2–CH2 –OH + B(OH)3 3H2O2OH
–
Propan-1-ol

PART - I : OBJECTIVE QUESTIONS
Single choice type
1. Observe the following compounds :
CH3–CH=CH2 CF3–CH=CH2
(1) (2) (3) (4)
The incorrect order of reactivity towards electrophilic addition reaction.
(A) 1 > 2 (B) 3 > 1 (C) 4 > 2 (D) 4 > 3
2. The correct order of reactivity of following alkenes towards acidic hydration is :
(1) Ethene (2) Propenoic acid (3) Butenedioic acid
(A) 3 > 2 > 1 (B) 2 > 1 > 3 (C) 1 > 2 > 3 (D) 1 > 3 > 2
3. Arrange in decreasing order of reactivity with HCl :
(A) II > III > I (B) III > II > I (C) III > I > II (D) none of the above
H O
4. 3 
 P (major), P is :
(A) (B)
(C) (D)
5. The major product of the following reaction is :

H


(A) (B) (C) (D)

6. Which of the following alkene will give (P) on oxymercuration reduction reaction, .
(A) (B) (C) (D)
7.
Which is correct statement about X and Y.

(A) X is product of ionic reaction and Y is product of radical reaction.
(B) X and Y both are product of ionic reaction.
(C) X and Y both are product of radical reaction.
(D) X is radical reaction and Y is ionic reaction.
8. + ICI  P (major product), Here 'P' is :
(A) (B) (C) (D)
9. Br , X may be :
2
  X
CCl4 (stereoisom er )
()
(A) (B) (C) (D)
10. Which is wrong statement

(A) Addition of halogen to double bond is stereo selective and stereospecific
(B) Elimination of X2 from dihalide is stereo selective and stereospecific
(C) Addition of X2 to > C=C < is of anti addition
(D) Elimination of X2 from dihalide is of syn elimination
11. cis-but-2-ene product, product of the reaction is :

(A) Racemic (B) Diasteriomers (C) Meso (D) E & Z isomers
Cl , 500 C
12. CH3CH = CH2 2  
 P, Product P is :
(A) CH3  CH  CH2 (B) CH2  CH  CH2 (C) CH3  C  CH2 (D) CH3 – CH = CH – Cl
| | | |
Cl Cl Cl Cl

NBS
13. CH2 = CHCH2CH = CH2  
 X (Major), (X) is :
(A) (B) CH2 = CH – CH = CH – CH2 – Br
(C) CH2 = CHCH2CH = CHBr (D)
14. HCC–CH=CH2 + HCl  ‘X’, ‘X’ is :

(A) (B) (C) (D) HCC–CH2–CH2–Cl
15. A. The product A in the above sequence of reaction is :
(A) (B) (C) (D)
16. Consider the following reactions :
H5 C2 C2 H5
C=C
H H
R1 R H C2 H5
2
C=C
H5 C2 H
H5C2 C C C2H5 R3
H5C2 C CH 2 C 2H 5
R4
O
2CH3 CH2 COOH
The correct set of reagents for these reactions is

(A) R1 : H2/Lindlar catalyst R2 : Na/liq. NH3
R3 : (i)O3, (ii)H2O R4 : H2O,H2SO4,HgSO4
(B) R1 : H2/Lindlar catalyst R2 : Na/liq. NH3
R3 : H2O,H2SO4,HgSO4 R4 : (i)O3, (ii)H2O
(C) R1 : (i)O3, (ii)H2O R2 : H2O,H2SO4,HgSO4
R3 : Na/liq. NH3 R4 : H2/Lindlar catalyst
(D) R1 : H2O,H2SO4,HgSO4 R2 : H2/Lindlar catalyst
R3 : (i)O3, (ii)H2O R4 : Na/liq. NH3
17. Which one of the following will be the major product when is treated with dil. H2SO4 in the
presence of HgSO4. HO CH2

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

HO OH CH3 HO CH3 O CH3
HO CH3

18. Alkynes are less reactive than alkenes towards adition of Br2 because :
(A) CH = CH is less stable than CH 2 – CH 2 (B) CH = CH is more stable than CH 2 – CH 2
+
Br +
Br Br+ Br+
(C) Both are equaly stable (D) Orginal statement is incorrect
19. Which of the following statements is correct ?

(A) Alkynes are more reactive than alkenes towards halogen addition.
(B) Alkenes are more reactive than alkynes towards halogen addition
(C) Both alkynes and alkenes are equally reactive towards halogen addition
(D) Primary vinylic cation is less reactive than secondary vinylic cation
BH , THF H O / OH ¯
3
20. CH3CH2CH2C  CH   2 2  
 'X'
Identify the product 'X' :
(A) CH3CH2CH2CH2CHO (B) CH3CH2CH2C CH2
||
O
(C) CH3CH2CH2CHO (D) CH3 CH2CCH2 CH3

||
O
21. + a  HCHO + b d
a. (i) OH b. (ii) O c. (iii) Conc. H2SO4 d. (iv) LiAlH4 e. (v) O3, Zn/H2O
Which of the following is correctly matched ?
(A) a-ii, b-iii, c-iv, d-v, e-i (B) a-v, b-ii, c-iv, d-i, e-iii
(C) a-i, b-ii, c-iii, d-iv, e-v (D) a-v, b-iv, c-iii, d-ii, e-i
22. The compound which reacts with HBr obeying Markownikoff's rule is :
(A) CH2=CH2 (B) (C) (D)
23. Major products of the following reaction :
(A) (B) (C) (D) All

CH3
H Br 
Nal
 ? Product is :
24. Br H acetone
CH3
CH3
H 
(A) (B) (C) (D)
 H
CH3
25. Br / h  Product (major)

2 
Identify the major product.
CH3 CH3
| |
(A) CH3  C  CH2  Br (B) CH3  C  CH3 (C) CH3 – CH2 – CH2 – Br (D) CH3  CH  CH3
| | |
H Br Br
26. (X) , The end product (X) is
(A) (B)
(C) (D)
More than one choice type

27. What are the possible intermediates in the following reaction ?
(1) Br  CCl
CH3–CH2–CH=CH2  2  
4
 CH3–CH2–CCH
(2) NaNH2 
(A) (B) CH3CH2–CH = CHBr
(C) (D) CH3– CH –CH=CH–Br


28. Which of the following has dipole moment ?

(A) cis But-2-ene (B) trans But-2-ene
(C) cis-1, 2-Dibromoethene (D) trans-1,2-Dibromoethene
29. When is reacted with Br2 (1-equivalent) would give ;
(A) (B) (C) (D)

30. Which of the following reactions are correct ?
Br
2 (i) C H COOH  CH Cl
(A)  (B)  6 
5 2 2
    

CCl4
(ii) OH– / H2O
H / H O
2 H / H O
2
(C)    (D)   
31. Which of the following reactions are correctly represented .
(A) R – CH = CH2 + HCl  (B) R–CH=CH2 + HI
(C) R–CH=CH2 + HBr (D) R–CH=CH2 + HI
32. The reagents used to convert (E) – 2, 3 – dibromo – 2 – butene to 2 – butyne

H 3C Br
C C  CH3  C  C  CH3
Br CH3
(A) Zn dust /  (B) Mg,  (C) NaI / Acetone /  (D) alc. KOH
33. In which of the following reactions Hoffmann elimination product is major products ?
Potassium
Conc.H SO t butoxide
(A)  2 
4
 (B)    


1.Ag OH alc .KOH

(C)  
 (D)   
2.  
PART - II : SUBJECTIVE QUESTIONS

1. Give steps involved in the synthesis of following compounds :
(a) Hex-2-yne from acetylene (b) 5-Methyl-2-hexyne from acetylene
(c) Propyne from propene (d) But-2-yne from but-2-ene
2. Give reaction involved in conversion of But-2-yne to

(a) Meso-2,3-dibromobutane (b) Racemic -3-chloro-2-butanol
(c) Meso - 2,3-butanediol (d) Racemic-2,3-butanediol
3. Convert the following molecule in given product :

a. CH3CH2CH2CH2I to CH3CH2CH2CH2Br
b. Cyclohexyl acetylene to ethylcyclohexylacetylene.
c. CHCH to (a) 2-butanone and (b) butanal
d. Cyclohexane to cyclohexene and 1,3-cyclohexadiene

e. 2-bromobutane to cis and trans-2-butene
f. 1-Butyne to (a) 1-butanol and (b) 2-butanol
g. 1-butene to 1,3-butadiene
HBr
Y
4. (A) HBr (X) (B)

HBr / R2O 2
Z
Identify X, Y and Z.
5. Draw the structures for (X, Y and Z) in the following reaction scheme.

H O/H
2
(W) (optically inactive)  

6. Arrange the following bond-lengths in increasing order.
7. Explain which of these reactions would provide a better synthesis of this ketone.
H2O
(I) CH3 CH2C  CCH2 CH3     
H2SO 4 , HgSO 4
3  hexyne
H2O
(II) CH3 C  CCH2CH2 CH3
H2SO4, HgSO4
2  hexyne
8. Give the products of the following hydroboration oxidation (HBO) reactions :

HBO
(a) CH3 (CH2 )2 C  CH  
 X
HBO
(b) CH3 CH2C  CCH2 CH3  
 Y
HBO
(c) CH3 CH2C  CCH3  
 Z
HBO
(d) CH3C  CCH(CH3 )2  
 W
9. When gas A is passed through dry KOH at low temperature, a deep red coloured compound B and a gas C
are obtained. The gas A, on reaction with but-2-ene, followed by treatment with Zn/H2O yields acetaldehyde.
Identify A, B and C.

PART - I
1. (D) 2. (C) 3. (B) 4. (C) 5. (D)
6. (C) 7. (A) 8. (B) 9. (A) 10. (D)
11. (A) 12. (B) 13. (B) 14. (A) 15. (C)
16. (B) 17. (D) 18. (A) 19. (B) 20. (A)
21. (B) 22. (D) 23. (A) 24. (C) 25. (B)
26. (D) 27. (A,B,C) 28. (A,C) 29. (A,B) 30. (A,B,C)
31. (A,C,D) 32. (A,B,C) 33. (B,C)
PART - II
1. (a) (1) Na (2) CH3–Br (3) Na (4) CH2 – CH2 – CH2 – Br
(b) (1) Na (2) CH3–Br (3) Na (4)

(c) (1) Br2 (2) alc KOH (3) NaNH2
(d) (1) Br2 (2) alc. KOH (3) NaNH2
2. (a) (1) Na / liq. NH3 (2) Br2
(b) (1) Lindlar (2) HOCl/H+
(c) (1) Lindlar (2) Beyer’s reagent
(d) (1) Birch (2) (i) HCOOOH (ii) H3O+
3. a. (i) alc. KOH (ii) HBr / peroxide

b. (i) NaNH2 (ii) CH3CH2Br
c. (a) NaNH2 / CH3CH2Br, HgSO4 / H2SO4 (b) NaNH2 / CH3CH2Br, BH3.THF / OH–, H2O2
d. (i) Br2 / , (ii) alc. KOH, (iii) NBS, (iv) alc. KOH
e. (i) alc. KOH, (ii) Br2, (iii) liq. NH3 + NaNH2 / , (iv) Li/NH3 - trans or (v) H2 lindlar catalyst - cis
f. (a) H2 / Lindlar catalyst , BH3 / THF , H2O2 / OH– , (b) HgSO4 / H2SO4 , LiAlH4
g. (i) NBS , (ii) alc. KOH
4. (X) = ; (Y) = CH3 ; (Z) =
Br CH3 Br
H
5. (X) : (Y) : CH3CH2 C CH2CH3
CH3
H OH
(Z) : CH3CH2 C C*H CH3 (W) : CH3 CH2 C CH2 CH3
CH3OH CH3
(hydration without rearrangement)
6. (d) < (b) < (c) < (e) < (a)
7. 3-hexyne is symmetrical hence, by hydration using HgSO4/H2SO4, we get 3-hexanone as the single product
but 2-hexyne by similar reaction will give 2-hexanone and 3-hexanone. Hence 3-hexyne is a better source.
8. X = CH3(CH2)2 CH2CHO Y=
Z = CH 3CCH 2 CH 2 CH3 + CH3 CH2 CCH2CH3 W = CH3 CCH2 CH(CH3 )2 + CH3 CH2 CCH(CH3 )2
|| || || ||
O O O O
(i ) gas A
9. CH3  CH  CH  CH3   
 2CH3CHO
(ii ) Zn / H2O
But  2  ene
Hence gas A is ozone because in above reaction, ozonolysis of but-2-ene takes place.
Low
Gas A + KOH (dry) temp
 ' B' + ' C'
( deep red coloured )
(gas )
 4O3 + 4KOH  4 KO 3 + 2H2O + O 2

' B' ' C'
Thus Compound A = Ozone (O3)
Compound B = Potassium ozonide (KO3)
Compound C = Oxygen (O2)

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1.

(Meso) (Racemic mixture)

Mechanism  Two mechanisms are suggested

(3) From organometallic compound :

(ii) By Corey House alkane synthesis ;

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 344

R2CuLi is the source of R

R2CuLi does not reacts with – NO2, – CN, etc.

(iii) By Franklands reagent :

(4)From carboxylic acids:

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 345

Clemmemsen’s reduction can be can be used to reduce the given compounds.

Physical Properties of Alkanes :

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 346

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

5HI + HIO3  3H2O + 3I2

2HI + HgO  I2 + H2O + Hg

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 347

Halogenation of higher alkane :

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 348

(iii) Reactivity v/s selectivity principle 

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 349

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 350

> > > (Hcomb. per ‘CH2’ unit)

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 351

Sol. In all cases product is

2. Arrange the following alkenes in decreasing order of their stability

3. What is the order of stability of following alkene

Sol. CH3 – CH2 – Cl  CH3  CH2  CH2  CH3

5. Wurtz reaction will not be observed in

(A) (B) (C) CH3  CH  Br (D) none of these

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 352

What are A and B

8. Explain why the chain initiating step in thermal chlorination of CH4 is

9. Chlorination of CH4 involves following steps :

Which of the following is rate determining ?

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 353

2. STRUCTURE AND BONDING

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 355

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 356

(C) Laboratory test of terminal alkynes

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 357

Relative Basicity : CH3 CH2 :  H2C  CH :–  HC  C :–

Ex.1 Acetylene hydrogens are acidic because:-

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 358

8. COMPARATIVE STUDY OF ALKANES, ALKENES, ALKYNES

Properties Alkanes Alkenes Alkynes

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 359

(b) Birch Reduction : (Anti Addition of Hydrogen: Synthesis of trans-Alkenes)

(II) By Dehalogenation of vicinal dihalides

(III) By Dehydrohalogenation of alkyl halides

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 360

(IV) By Dehydration of alcohols

(B) General methods of preparation of Alkynes :

CH3 CH2C  C   Na  

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 361

(II) By Dehalogenation of tetrahaloalkane :

General Reaction R – C  C – R + 2Zn X2

(III) By Kolbe's electrolytic synthesis :