Nucleus OC Hydrocarbon E

TA RG E T JEE
XII
HYDROCARBON
CONTENT
S.No Pages
1. Hydrocarbon 01 – 48
2. Exercise-1 (Subjective Questions) 49 – 51
3. Exercise-2 (Objective Questions) 52 – 62
4. Exercise-3 (Section-A) 63 – 69
5. Exercise-3 (Section-B) 70 – 72
6. Exercise-4 73
7. Exercise-5 74 – 82
8. Answer Key 83 – 91
TA RG E T JEE
XII
HYDROCARBON
HYDROCARBONS
ALKANE
INTRODUCTION
Alkanes
(i) The alkanes or the paraffins are the saturated hydrocarbons. Many occur naturally, and the chief source
of the alkanes is mineral oil or petroleum, which occurs in many parts of the world.
(ii) These are also called as ‘Paraffins’ (Parum + Affinis i.e. less reactive).
(iii) General formula is CnH2n+2 .
(iv) Hybridisation state of carbon is sp3.
(v) Geometry of carbon is tetrahedral.
(vi) Bond angle is 109º 28'.
PREPARATION OF ALKANE
From aldehydes and ketones :

Clemmensen Reduction :
The Clemmensen reduction is most commonly used to convert acylbenzenes to alkylbenzenes, but it also
works with other ketones and aldehydes that are not sensitive to acid. The carbonyl compound is heated
with an excess of amalgamated zinc (zinc treated with mercury) and hydrochloric acid. The actual reduction
occurs by a complex mechanism on the surface of the zinc.
O
||
Ph  C  CH 3 Zn ( Hg
)or Na ( Hg )
  Ph–CH2–CH3
HCl
Mechanism
O OH
|| |
Ph – C – CH3 + H Ph – C – CH3

2+
Zn Zn + 2e¯
 
Ph – C – CH3 + 2e¯ Ph – C – CH3
| |
OH OH
H
 |
Ph – C – CH3 + H Ph – C – CH3
| |
OH OH
H H H
| | |

Ph – C – CH3 + H Ph – C – CH3 Ph – C – CH3
| | –H2O 
OH  OH2
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HYDROCARBONS
H H H
| | |
+2 H
Ph – C – CH3 Zn  Zn + 2e¯ Ph – C – CH3 Ph – C – CH3 or Ph – CH2 – CH3
|
H
Wolf-Kishner Reduction.
Compounds that cannot survive treatment with hot acid can be deoxygenated using the Wolf-Kishner
reduction. The ketone or aldehyde is converted to its hydrazone, which is heated with a strong base such
as KOH or potassium t-butoxide.
O NNH2
N
2H 4
 KOH , heat
    + N2
( diethylene glycol )
Phenyl propanone Phenyl hydrazone n-propylbenzene (82%)
Mechanism
O O OH


N – NH

NH2 – NH2 NH2 – NH2 N – NH2 – H2 O
N – NH2 –OH
| –H2O
H
H N=N

N = NH N = NH
H
 H H H


+H2 O  – OH
+OH
 – N2 –H2 O +H2O
–OH
O N–NH2 +
H
N 2H 4 t-BuO¯ K H
 + N2
O
cyclohexanone hydrazone CH3—S—CH3
(DMSO, a solvent)
cyclohexane (80%)
From alkene :
By catalytic hydrogenation : Addition of H2 on alkene takes place in cis manner in the presence
of Pt or Ni or Pd to give alkane.
eg.
Ni
(i) CH2 = CH2 + H2   CH3 – CH3
HYDROCARBONS
R
R D
R D H
R Ni,  or
H
C=C + H2 D H
(cis addition) R D
(ii) D D
(cis-alkene) R
(meso) (Meso compound)
H
D R
C=C Ni
R D + H2 
(Trans alkene) (cis addition)
R D D R
R R
H D H H H D
D R R D
or H D + or D H
H R H R
Racemic Mixture
By hydroboration reduction of alkene
(i) B2H6
CH2 = CH – CH3 CH2 – CH2 – CH3
(ii) CH3COOH |
H
Mechanism
CH2 = CH – CH3 + H – BH2 CH2 – CH – CH3
H2 B H
(Four membered cyclic
transition state)
2 CH3 – CH = CH2
CH2 – CH – CH3 (CH3 – CH2–CH2)3 B
BH2 H
CH3–COOH
CH3 – CH2–CH2 + H3BO3
NOTE : Long- chain alkane may be possible by the coupling of alkyl boranes.
If (AgNO3 + NaOH) is used instead of H2O / H+
R3B R–R
HYDROCARBONS
From alkyne - by reduction :
H H H
Pt/Pd/Ni. | Pt/Pd/Ni. + H2 | |
R – C  C – H + H2 R– C =C – H R C  C H
| 200º–300ºC | |
H H H
alkene alkane
If Ni is used, it is called Sabatier - Senderen’s reaction (catalytic hydrogenation).
From Alkyl halides :

By reduction :
When alkyl halide is reduced with
Zn-Cu couple + ROH or Na + EtOH/ Na- Hg + H2O or LiAlH4, then we get respective alkane.
Zn  Cu
R–X + 2 H R RH + HX
 OH
Wurtz reaction :
When alkyl halide reacts with Sodium in presence of dry ether then we get higher alkane. Mechanism
of the reaction is based on ionic and free radical both.
R – X + 2 Na + X–R dry ether
   R – R + 2 NaX
CH3Cl + 2 Na + ClCH3  CH3–CH3 + 2 NaCl
NOTE : * This reaction is not suitable for tertiary alkyl halides
Mechanism : Two mechanism has been suggested for Wurt reaction.

Ionic mechanism
  C2H5¯Na+
C2 H5 Br + Na NaBr CH3 – CH2 – CH2 – CH3

2Na 2Na + 2 e 
 
CH3 – CH2 – Br CH3 – CH2 + Br
   
CH3CH2 + Na CH3CH2 Na
  CH3 – CH2 – Br
CH3 CH2 Na CH3 – CH2 – CH2 – CH3
– NaBr
HYDROCARBONS
Free radical mechanism

2NaBr
2C2 H5 – Br + 2Na    2C2H5•  C2H5–C2H5
Na Na+ e¯

CH3– CH 2– Br CH3– CH 2+ Br
CH3 – CH2 + CH2 – CH3 CH3 – CH 2 – CH 2 – CH 3
Corey-House Synthesis
Li CuX
R—X Ether RLi R2CuLi
R2 CuLi + 2 R—X 2 R—R + LiX + CuX

Lithium dialkyl (should be 1°)
cuprate
2 Li  2 Li+ + 2e¯
 
R–X  R+X
 
Li + X  LiX

 

R + Li  RLi
2RLi + CuX  R2 CuLi + Li X
R2 CuLi + 2R' – X  2R – R' + LiX + CuX
This method is better than Wurtz and can be used for preparing symmetrical as well as unsymmetrical
alkanes (having an odd number of carbon atoms).
Frankland’s reaction :
If alkyl halide is treated with Zn dust in closed tube then higher symmetrical alkanes will be formed.
2RX + Zn  R – R + ZnX2
This is known as Frankland’s reaction, in this reaction first Frankland’s reagent (R–Zn–R, dialkyl Zinc)
is formed. Which then react with alkyl halide to give higher alkanes. [Where R = CH3]
For Example:-
CH3 – Br + 2Zn + Br – CH3  CH3 – Zn – CH3 +ZnBr2
CH3 – Zn – CH3 + 2CH3 – Br  2 CH3 –CH3 + ZnBr2
ethane
+2
2 Zn  2Zn + 4e¯
2e¯ 
 
CH3– Br CH3+ Br
HYDROCARBONS

Zn+2 + 2CH3 (CH3)2 Zn
CH3 – Zn – CH3 + 2CH3 – Br  2 CH3 –CH3 + ZnBr2
Grignard reagents.
Alkyl halides in ether react with magnesium to form alkyl magnesium halides or Grignard reagents which,
on treatment with water or dilute acid, are decomposed to alkanes.
ether  I
(i) RI + Mg   RMgI H RH + Mg
OH
Mg  Mg+2 + 2e¯
R – I 2
e¯ R¯ + I¯
R¯+ Mg+2 + I¯  R Mg I
(Grignard Reagent)
I

RMgI H – OH R – H + Mg
(Hydrocarbon) OH
CH3MgBr H
O  H
(ii)  CH4
(iii) CH3MgBr R
O  H
 CH4
(iv) CH3MgBr CH
3CO2 H
 CH4
Preparation by Wurtz reaction, Kolbe electrolysis Ullmann reaction, Fitting reaction, Wurtz-Fitting reaction
already discussed in free radical reaction.
From Red P + HI :
It is a powerful reducing agent which will convert, aldehyde, ketone, alcohol, carboxylic acid to alkanes
with same number of carbon.
Re d P  HI
(i) R–CH3–OH     R –CH3
O
|| Re d P  HI
(ii) R  C  H     R –CH3
O
|| Re d P  HI
(iii) R  C  R     R –CH2– R
(iv) R–COOH Re

dP  HI
 R –CH3
HYDROCARBONS
KOLBE’S ELECTROLYSIS
(i) Sodium or potassium salt of acid on electrolysis gives higher alkane.
(ii) Reaction follows ionic and free radical mechanism.
(iii) 2R  C  ONa Electrolys
 is
 R–R + 2CO2 + NaOH + H2 
||
O
ANODE REACTION
2R  C  O  Na  2R  C  O ¯ + 2Na+
|| ||
O O
2R  C  O ¯  2R – C – O + 2e¯

||
O O
–2CO2
2 R·
R· + R·  R – R
CATHODE REACTION
2Na+ + 2e¯ + 2H2O  2NaOH + H2
Other products :
R  C  O· + R·  R  C  O  R
|| ||
O O
Ester
DECARBOXYLATION OF ACID:
Carboxylic acid on decarboxylation in presence of soda lime give alkane.
Rate of reaction  Stability of carbanion
R  C  O  H NaOH
 R–H + CO2
|| CaO
O
R–C–O–H  R – C – O¯ + H2O
+ OH¯
O O
R¯ + CO2
R¯ + H–OH  R – H + OH¯
HYDROCARBONS
PHYSICAL PROPERTIES
1. The first four alkanes (from methane to butane) are colourless and odourless gases. The next thirteen
(from pentane to heptadecane) are colourless and odourless liquids. And, the rest of higher alkanes
(having 18 carbon atoms or more) are colourless solids at ordinary temperature.
2. Alkanes being non-polar molecules, are soluble in non-polar solvents like benzene, ether, and chloroform.
However, they are insoluble in polar solvents like water. Their solubility decreases with increase in their
molecular weight.
3. Melting and boiling points are increases with molecular mass and decreases with No. branches. As
far as melting point is concerned the alkane having even carbons has more M.P. than odd carbons,
since the intermolecular forces in a crystal depend not only upon the size of the molecules but also
upon how well they fit into a crystal lattice.
For e.g.
C C C C C C
`
C C C C C
n- pentane n- hexane
(both methyl group are directed on (both methyl group are adversely
same side) directed)
Melting point of alkane having odd number of ‘c’ < alkane with even number of carbom atom.
4. Boiling point decreases with the increment of branches.
(n-Pentane is liquid but neo-Pentane is gas due to increase in branching, surface area decrease
therefore intermolecular forces & Vander Waals forces of attraction decreases).
5. Physical state:
Alkanes
C1– C4  Gaseous state
C5 – C17  Liquid state
(except neo pentane)
C18 & above  Solid like wax
6. Alkanes are lighter than water, so it floats over water.
CHEMICAL PROPERTIES
1. Halogenation
Alkanes react with bromine or chlorine in the presence of sunlight or UV light or in dark at high temperatures
(250°C– 400°C) forming a mixture of substituted products. For example,
Cl2 Cl2 Cl2 Cl2
CH4 h CH3Cl h CH2Cl2 h CHCl3 h CCl4
The yield of monohalogenated product can be increased by using substrate (alkane) in excess.
The reactivity of halogens follows the order: F2 > Cl2 > Br2 > I2.
HYDROCARBONS
Direct fluorination is explosive and can be achieved by the action of inorganic fluorides on bromo or iodo
derivatives.
2C2H5Br + HgF2  2C2H5 F + HgBr2
Bromination is slower than chlorination and is carried out at higher temperatures.
Iodination is reversible and can be carried out sufficiently in the presence of strong oxidising agents like
iodic acid (HIO3) or nitric acid that destroys hydroiodic acid (HI) and shifts the equilibrium towards the
right.
CH4 + I2 CH3 I + HI
5 HI + HIO3  3I2 + 3H2O
Alkyl iodides can be prepared conveniently by Finkelstein reaction which involves treating chloro or
bromoderivative with NaI in acetone or methanol solution.
acetone
R Cl + NaI RI + NaCl 
Alkyl chlorides or bromides cannot be prepared by this method of halide exchange because NaCl and
NaBr are insoluble in acetone.
h
R – H + Cl2 R – Cl + HCl
(excess)
h
R – H + Cl2 R – Cl + HCl
(excess) (mixture of
alkyl halide)
Mechanism of Halogenation :
The mechanism involves the following steps:
(i) Chain-initiation step
250-400°C
X2 or UV light 2X•
(ii) Chain-propagation step

X• + R—H  H—X + R•
R• + X2  R—X + X•
(iii) Chain-termination step
X• + X•  X2
•
R +X •  R—X
R• + R•  R—R
Radical inhibitors stop chain propagation by reacting with free radical intermediates.
R• + •O—O •• •••  R— O—O
•• ••
•• ••
•• ••
.
Peroxy radical
HYDROCARBONS
2. Nitration.
Under certain conditions, alkanes react with nitric acid, a hydrogen atom being replaced by a nitro-group,
NO2. This process is known as nitration. Nitration of the alkanes may be carried out in the vapour phase
between 150°C and 475 °C, whereupon a complex mixture of mononitroalkanes is obtained.
NO 2
HNO3
|
 CH CH CH NO + CH 3CHCH 3 + C H NO + CH NO
CH3CH2CH3 400C 3 2 2 2 2 5 2 3 2
Mechanism
HO – N O HO + NO2
||
O
OH
CH3 – CH2 – CH2 CH 3 – CH 2 – CH 2 + H 2O
|
H
NO2
CH3 – CH2 – CH2 CH3 – CH2 – CH2
|
NO2
NO2
CH3 – CH – CH3 CH3 – CH – CH3
|
NO2
Similarly we deduce other products through some process.
3. Sulphonation.
Sulphonation is the process of replacing a hydrogen atom by a sulphonic acid group, SO3H. Sulphonation
of a normal alkane from hexane onwards may be carried out by treating the alkane with oleum (fuming
sulphuric acid). It has been shown that in concentrated sulphuric acid, hydrocarbons containing a tertiary
hydrogen atom undergo hydrogen exchange (Ingold et. al. 1936). The mechanism is believed to occur
via a carbonium ion:
R3CH + 2H2SO4  R3CSO3H + H2O
This reaction is of particular interest since optically active hydrocarbons have been racemised in sulphuric
acid; e.g., Burwell et. al. (1948) have shown that optically active 3-methylheptane is racemised in sulphuric
acid.
CH 3 CH 3
| H 2SO 4
|
CH 3  C  H   CH 3  C  SO 3 H + H2O
| |
CH 3 CH 3
O
||
CH3 HO – S – OH CH3
| || |
CH3 – C – H O CH3 – C – SO3H + H2O
| – H2 O |
CH3 CH3
Imp. Rate of sulphonation 3° > 2° > 1°.
HYDROCARBONS
4 Chlorosulphonation/ Reaction with SO2 & Cl2:

The reaction is also called as Reed’s reaction. When propane reacts with SO2 and Cl2 in presence of
ultraviolet light then propyl sulphonyl chlorides are formed.
U.V. Light
CH3-CH2-CH3 + SO2 + Cl2    CH3–CH2–CH2SO2Cl + HCl
This process is used in the commercial formation of detergents.
Mechanism
S S Cl
+ Cl – Cl + Cl
S O S O
+Cl
CH3 – CH3 – CH2 + SO 2 Cl CH 3 – CH 2 – CH 2 + HCl
| –HCl |
H SO 2 Cl
O O
Alkaline
CH3 – (CH2)10 – CH2– CH2–S–Cl + NaOH       CH3 – (CH2)10 – CH2–S–O– Na+
hydrolysis
O O
(detergent i.e. sodium salt of sulphonic acid)

O O OH
||  ||
OH
CH3 – (CH3 )12 – S – Cl CH3 – (CH2)12 – S – Cl
|| ||
O O
– Cl¯
O
||
CH3 – (CH2)12 – S – OH
||
O

–H2O OH
O
||
+
CH3 – (CH2)12 – S – O¯Na
||
O
5. Isomerization : Lower alkanes are not isomerised but butane or higher number of alkanes if heated with
aluminium chloride at high temperature then they convert into stable isomers by the rearrangement reaction.
Isomerisation is also held by heating alkane with- (AlX3 + HX; X = Cl, Br, I or Al2(SO4)3 + H2SO4) at
200ºC.
AlCl 3
    CH3  CH  CH3
400 º C |
CH3
n - butane iso butane
If we take n- heptane then it converts into most stable form Triptane (trivial name).
CH3-(CH2)5 –CH3 
n- heptane 2, 2, 3- trimethyl butane

If we take n - octane, iso-octane is formed.
HYDROCARBONS
CH3(CH2)6 CH3 
n- octane iso-octane
Reaction is used in Petroleum industries, with the help of this reaction, we can convert unbranched
alkane to branched alkane (i.e. lower octane number alkane to higher octane number alkane) or bad fuel
to good fuel.
6. Combustion :
Combustion is a rapid oxidation that takes place at high temperatures, converting alkanes to carbon
dioxide and water. Little control over the reaction is possible, except for moderating the temperature and
controlling the fuel / air ratio to achieve efficient burning.
CnH(2n+2) + excess O2 heat
 nCO2 + (n+1) H2O
Example : CH3CH2CH3 + 5 O2 heat
 3 CO2 + 4 H2O
 y y
CxHy +  x   O2  xCO2 + HO
 4 2 2
7. Aromatization :
CH3
Cr2O3  Al2 O3 Cr2O3  Al2 O3
(i) n-Hexane   (ii) n-Heptane  
For converting aliphatic to aromatic.

CH3 C2 H 5
CH3
(iii) n-Octane Cr
2O
3  Al2 O3

 +
o–Xylene Ethyl benzene
HYDROCARBONS
REACTION CHART FOR ALKANES
GMP GR
H , Ni
(1) R–C  CH 2  (1) X , h or UV light or 400 C
2         
 RX
200300C
or
R–CH=CH2 Sabatier senderens
(2)  R-N
Nitration
reaction
(2) R–X Zn

 Cu
HCl
 Sulphonati on H S O
Re d P  HI , LiAlH 4 (3) 2
       2
7  Alkyl Sulphonic acid
(3) RX Na
,dry ether

Wurtz reaction Reed reaction
(4) SO2 + Cl2    RSO2Cl
h
(4) RX  Zn

Frankland 's reaction
R–H
AlCl / HCl
3 branched alkanes
(5) RX     R 2CuLi
 or (5)
Isomerisation
( Corey  House reaction 
) 

4
R–R
 HOH or ROH or
(6) R–Mg–X      CnH2n+2 (6) Pyrolysis
or NH3 or RNH2   
500 700 C
Alkenes + CH4 or C2H6
Cr or Mo or V oxide
(7) R–OH, R–CHO Re
dP / HI
 (7)        
 Al2O 3 500C Aromatic compound
R  C  R , RCOCl, RCOOH
|| CH N
22
O (8)   
step up reaction
Higher alkane
(8) R CR Zn

 Hg
/ Conc
 . HCl

Clemenson 's reduction
|| O
2
O (9) 
 CO2 + H2O

H N  NH
Combustion
2   2 
(9) R CR    
Wolf / Kishner reduction
||
O
or
(RCH2CH2)3B H O
 2
(10) RCOONa NaOH  CaO


(11) RCOONa Kolbe

 'selectrolytic synthesis
  
HYDROCARBONS
ALKENE
ALKENE
(a) General formula : CnH2n.

(b) Functional group : in alkenes is >C=C<
(c) The double bond is made up of one sigma and one pi bond.
(d) The doubly bonded carbon atoms are sp2 hybridized.
(e) Geometry of unsaturated ‘C’ carbon is trigonal planar.
(f) C = C bond length is 1.34 Å.
(g) C – H bond l ength i s 1.10 Å .
(h) C = C bond energy i s 143.1 k cal mol –1.
(i) C – H bond energy is 98.69 k cal mol–1.
(j) Alkene shows chain, position, ring chain, optical & geometrical isomerism.
METHODS OF PREPARATION OF ALKENES
Elimination reactions
Elimination reactions consist in removing the two groups (generally one being a proton and other is
leaving group from one or two carbon atoms of a substrate to form an unsaturated linkage.
Elimination reactions are classified under two general categories.
Types of Elimination reactions

1. -elimination (1, 1)
2. -elimination (1, 2)
1. -elimination : When the two atoms or groups are eliminated from the same carbon, the process is
called –elimination.
2. -elimination : When the two groups or atoms are removed from the two adjacent carbon atoms, the
process is known as -elimination.
Some important terms

(1) Substrate : That molecule or ion which undergoes change is called substrate. Substrate may be alkyl
halide, alcohol etc.
(2) Base : It is negative ion or neutral molecule which abstract the proton from the substrate.
(3) Leaving Group : It is an ion or molecule which leaves the substrate with a pair of electron. The tendency
of leaving group is inversly proportional to basic strength. Leaving group ability of different halide ions
follows the sequence
I> Br> Cl> F
-Elimination can occur by three different mechanism

(1) E-1 mechanism
(2) E-2 mechanism
(3) E1 cB mechanism
HYDROCARBONS
E-1 MECHANISM
(a) It is called unimolecular elimination reaction.

(b) It takes place in two steps.
Ist Step : Departure of leaving group from a molecule to form carbocation.
IInd Step : Carbocation formed above loses a proton to the base and forms the alkene.
H
+
Base
–C–C Fast C=C
(c) Ist step of E-1 mechanism is the rate determining step (R.D.S.)
(d) Since in R.D.S. only substrate undergoes covalency change.
i.e. it follows first order kinetics with respect to substrate
Rate = K [substrate]
(e) Since in R.D.S. carbocation is formed as an intermediate so the reactivity order of different substrate
follows the stability of order of carbocation formed.
Allylic > Tertiary > Secondary > Primary
(f) Loss of leaving group is the part of R.D.S. therefore the order of reactivity of alkyl halide in elimination
reaction is
R–I > R–Br > R–Cl > R–F
Above order is parallel to order of leaving group ability
I> Br > Cl > F
(g) E-1 mechanism does not show isotopic effect as the loss of hydrogen is not the part of R.D.S.
KH
1
KD
(h) Since the ionization take place in step I. Therefore polar solvent favors the E-1 mechanism.
(i) E-1 mechanism involves carbocation as an intermediate so rearrangement of carbocation can take place
if possible. More stable carbocation forms the major product in the reaction.
E-2 MECHANISM
(a) It is known as bimolecular elimination mechanism.

(b) It take place in single step.
(c) It involves the formation of transition state
H    B....H 
| |  | | 
Slow |
 C C    C  C   – C  C –
| | B¯  | |  |
  
L 
L 
Transition State
(d) Formation of transition state is the rate determining step.
(e) Rate of reaction depends on the concentration of substrate as well as of base i.e. it follows the second-
order kinetics.
Rate = [Substrate] [Base]
HYDROCARBONS
(f) E-2 mechanism shows the isotopic effect as the loss of hydrogen is a part of R.D.S.
KH 7

KD 1
(g) E-2 mechanism shows the halogen effect as loss of leaving group is a part of R.D.S.
 Reactivity of different alkyl halides follows the sequence
R – I > R – Br > R – Cl > R – F
Reactivity order of different substrate follows
3º > 2º > 1º
(h) The rate of reaction increases with increasing strength and concentration of the base.
(i) Non-polar solvent favors the E-2 mechanism.
(j) Since E-2 mechanism involves the transition state rearrangement is not possible.
E1 cB MECHANISM
(a) In this mechanism, the reaction take place in two steps.

(i) The first step involves rapid removal of a proton from the -carbon (carbon adjacent to the
carbon bearing halogen atom) forming a carbanion.
(ii) The carbanion formed then loses the halides ion in the second rate determining step.

B ......H 
| R  C H  C H2  B  H
R  C H  C H2 |
|
F F
R  C H  C H 2 Slow
 R–CH  CH 2  F¯
|
Br
F
(b) The overall rate of the reaction is limited to slower second step & hence the rate of reaction depends
only on the concentration of carbanion.
(c) Since carbanion is the conjugate base of the alkyl halide and rate of reaction depends on concentration
of carbanion hence the mechanism is designated as E1cB mechanism.
Mechanism of –Elimination
-elimination does not occur frequently and completes in two stages, the second of which is rate
determining.
for eq.
CHCl3 + OH– 
CCl3 + H2O

CCl3 :CCl2 + Cl–
dichlorocarbene
Another example of -elimination reaction is formation of diphenylacetylene from 2, 2-diphenyl vinyl
bromide and sodamide.

N H2
 C6H5–CC–C6H5
HYDROCARBONS
Mechanism
C6H5 H  C6H5
+ NH2
C=C C=C

– NH3
C6H5 Br C6H5 Br

– Br
C6H5 – C  C – C6H5
From Alkynes
Lindlar's Catalysts
R – C  C – H + H2 Pd – BaSO4 R–C=C–H
| |
H H
poison of catalyst such as BaSO4, CaCO3 are used to stop the reaction after the formation of alkene,
otherwise alkanes are formed.
(i) The reaction takes place at the surface of Pd, that is why it is cis addition and the product
is cis form eg.
H 2 / Pd
R – C C –R  BaSO 4
(ii) Alkyne can be reduced to trans alkene by using Na + NH3, or Li AlH4
R – C  C – R Na

NH3 liq.
From mono halides

When mono halide react with alcoholic KOH or NaOH then respective alkenes are formed
H
H H
| | |
(i) RC  C H+ Alc.KOH
– R C  C H
HX |
| |
H X H
Alkene

KOH + C2H5OH C2H5OK + H2O
H H
| | 
R – C – C – H + C2H5O R – C = C – H + C2H5OH
| | | |
H X H H
(ii) CH3 – CH2 – C H – CH3  

| NaOH alc.
Cl
HYDROCARBONS
NOTE : CH3–CH2CHX–CH3  CH3–CH2–CH=CH2  CH3 – CH =CH – CH3

Minor Major
CH3—CH = CH —CH3 (Trans) is the major product because it is more stable as having
six ‘  ’ Hydrogen in the comparison to CH3 –CH2 – CH=CH2 having only two ‘  ’ hydrogen.
This is in accordance with the saytzeff rule.
Mechanism : E2 and E1 are possible.
E 2 Mechanism :
Cl Cl
|
C —C
Slow
C— C – Cl– C= C
| – OH – H2O
H H
T.S. OH
As molecularity of slowest step is two i.e. E2 mechanism.
E1 Mechanism :-
CH2  H CH2
| ||
Cl
CH3  C  Cl  Fast
  CH3 — C

|  Slow – H |
CH3 CH3
As molecularity of slowest step is one. That is why it is termed as E1.
Remember : Possibility of E1 increases with increasing stability of carbo cation . similarly possibility
of E2 increases with decreasing stability of expected carbocation.
From Dihalides
From gem dihalides : When gem dihalide is heated with Na in ether then higher alkenes are formed.
R–CH.X2 + 2 Zn – R –CH = CH– R

2 Znx 2
CH3 – CHCl2 + 2Zn   CH3–CH=CH–CH3

 2 ZnCl2
2 – butene
Conclusion – If we take two different types of gemdihalides then we obtain three different types
of alkenes.
Note : The above reaction is used in the formation of symmetrical alkenes only, because if we take two
different types of halides then mixture of alkenes is obtained so the yield of an individual alkene is
reduced and it is improper to separate each alkene from the mixture because the difference of boiling
points in alkenes is very less.
From vicinal dihalides :

When vicinal dihalides are heated with Zn dust, alkene of same no. of carbon is obtained.
H H H H
| |  | |
R  C  C  H  Zn dust   R  C  C  H  ZnX
2
| | 300º C
X X
HYDROCARBONS
H H H H
| | | |
H  C  C  H  Zn dust  H  C  C  H  ZnCl2
| |
Cl Cl
Note : Alkene is not formed from 1,3 dihalides. Cyclo alkanes are formed by dehalogenation of it.
For eg.
Zn dust
CH2  CH2  CH2   
| |
X X
Zn  Zn+2 + e¯ + e¯
CH2 – CH2 – CH2 CH2 – CH2 – CH2
| |
X X
From Alcohols
When alcohol is heated with conc. H2SO4 at about 160º C, alkenes are formed after dehydration.
H H H H
H H | |
| | | |
R C  C H 
 R C  C H
R C  C H + H – SO4 – H | |  H 2SO 4
| | H OSO3H
H OH
(Alkyl hydrogen sulphate) Alkene

CH3 CH2 CH2 CH2 OH + H2 SO4    CH3 –CH2 – CH =CH2 + CH3 –CH=CH–CH3
160ºC
1–butene 2–butene
(major product)
H OH H
| | | 
CH3 – CH– CH  CH2 + H2SO4   CH3 – CH = CH – CH3 + H2SO4 + H2O
160ºC
2–butene
(chief product)
OH
|
CH3  C  CH3 
+ H2SO4  
 CH3  C  CH2 + H2SO4 + H2O
| 160ºC |
CH3 CH3
Iso butylene
HYDROCARBONS
Mechanism :-

OH2 OH
| + |
H
CH3 – CH2 – CH – CH3 CH3 – CH2 – CH – CH3
–H2O
H H
|  |
CH3 – CH – CH – CH2 CH3 – CH2 – CH = CH2
– H
–H+ (minor)
CH3– CH = CH– CH3

(major)
Note : Since the mechanism proceeds via- C+ ion therefore rearrangement is also possible eg.:
CH3
H2SO4 Conc. |
 
160 º + CH3 — C — CH  CH2
|
CH3
(Major) (Minor)
Negligible
Mechanism :
..
CH3:OH CH3 CH3
| | + | |
CH3 — C — CH — CH3 H CH3– –CH3  H
– H   CH3 — C — C — CH3
| 2O
CH3
Characteristics of dehydration of alcohol

(1) Since the carbocation is formed as an intermediate in the R.D.S. of dehydration of alcohol The relative
reactivity of alcohols decreases in the order.
Tertiary > Secondary > Primary
(2) Since the R.D.S. is reversible it is necessary to remove the H2O molecule produced in the reaction.
Therefore in experimental condition conc. H2SO4 is added in a regular interval.
(3) For dehydration, different dehydrating agent like Al2O3, ThO2 can also be employed.
(4) Rearrangement of carbocation can take place.
(5) –OH is not a good leaving group, in alcohols so turn it into a good leaving group, it is converted into –
H2O by protonation
(6) H2O is a good leaving group.
Rearrangement in Alcohol Dehydration

(1) Some alcohols undergo dehydration to form alkene having carbon skeleton different from those of the
starting alcohol.
(2) This is due to rearrangement of carbocation formed in the reaction to more stable carbocation.
(3) An example of alcohol dehydration that is accompanied by rearrangement is.
HYDROCARBONS
CH 3 CH 3
| |
H SO
CH 3  C  C H  CH 3 2 
4  CH 3  C CH  CH 2 + +
| | heat |
CH 3 OH CH 3
(3%)
(4) Percent yield of alkenes formed from rearranged carbocation is greater than the percent yield of
alkene obtained from unrearranged carbocation.
(5) Rearrangement of carbocations can also lead to a change in ring size, as the following example shows
OH
H3 C
CH–CH3 
H,
heat 
   H
(  H 2O )


Regioselectivity in alcohol dehydration :

1. In alcohols such as 2-methyl-2-butanol, dehydration can occur in two different directions to give alkenes
that are constitutional isomers.
2. More substituted alkene forms the major product and is called Saytzeff alkene or Zaitsev alkene.
3. Less substituted forms the minor product and is called Hofmann’s alkene.
OH
| H SO
CH 3  C  CH 2  CH 3 2 
4  +
|
CH 3
(Minor) (Major)
Kolbe’s Synthesis
When aqueous solution of K or Na succinate is electrolysed, ethylene is released at anode.
O O
||  ||
CH2  C  O K CH2  C  O . .
|  | + 2K+
CH2  C  O . .

CH2  C  O K
|| ||
O O
At Anode
2
CH COO
| 2  CH2 COO•
   | + 2e¯  CH2
CH2COO CH2 COO• + CO2
unstable CH2
CH2
CH2
HYDROCARBONS
At Cathode
2K + + 2e –  2K
2K + 2H2O  2KOH + H2
Note – If we use methyl succinic acid as reactant then propylene is formed.
From Esters
When esters are heated in presence of liq. N2 and glass wool, then alkyl part of ester converts
into respective alkene while alkanoate part of ester is converted into respective acid.
CH3 — CO — O H
| | Glass wool 450º
   CH3–COOH + CH2=CH2
CH2 — CH2 liq. N2
The reaction is called as ‘Pyrolysis of Ester’.
Mechanism : Pyrolysis of Ester is a type of E1 elimination which proceed via cyclic T.S. that is
why the product becomes ‘cis’
O
CH3– C H
|
O CH2 CH =CH–CH –CH + CH –CH – C –O–H
2 2 3 3 2
CH2 ||
Cyclic transition state O
* It is interesting to note that, in this case major product is 1- alkene in the comparision to 2-alkene.
O
||
H O — C — CH3
| |
CH3 — CH — CH — CH3  CH3 —CH2—CH =CH2 + CH3–CH=CH–CH3
(Major) (minor)
Major product is obtained by reamoval of –H from less hindered carbon.
From quaternary ammonium hydroxide

When quaternary ammonium hydroxide is heated strongly it decomposes to give alkene. eg.
+
H
(i) OH  CH2 = CH2 + CH3 – N  CH3 + H2O

CH2–CH2 |
CH3
CH3
| 
OH
H H3 C – N – CH3 CH2 = CH2 + H2O + (CH3 )3 N
| |
CH2 CH2
HYDROCARBONS
CH3
CH3 CH3
N

CH 3 – CH – CH– CH 2
| |
(ii)  H H OH 
HO
CH3– CH = CH– CH3 CH3 – CH2 – CH = CH2

(minor) (major)
This elimination is called Hoffman’s elimination. It is markable that in this reaction more acidic
H is preferably eliminated.
The wittig reaction

In this reaction methylene triphenyl phosphorane is reacted with carbonyl compound to give alkene.
eg. :
(i) (Ph)3 P = CH2 + CH – R (Ph)3 P=O + R – CH
|| ||
O CH2

O
||

R – CH
 
(ph)3 P = CH2 (ph)3 P – CH2
(ph)3 P = O + CH2 = CH – R
O CH
R
O
||
(ii) (Ph)3 P=CH –R + CH – R  (Ph)3 P =O + R – CH =CH – R
The Cope Elimination :

Tertiary amine oxide undergoes the elimination of a dialkylhydroxyamine when they are heated. This
reaction is called the Cope elimination.
CH 3 CH 3
| |
 
Re action : CH 3  CH 2  CH 2  N  CH 3 
 CH 3  CH  CH 2  N  CH 3
| |
O OH
Mechanism :
CH 3
CH3 |
+ 
CH2–N – CH3  CH 3  CH  CH 2  N  CH 3
CH3–CH 
 O 

|
H

 OH
HYDROCARBONS
PHYSICAL PROPERTIES
(i) From C2–C4 they are colourless, odourless gases, from C5–C17 they are colourless liquids, C18 onwards
alkenes are solids.
(ii) Alkenes are practically insoluble in water because they cannot form hydrogen bonds with H2O molecule.
They dissolve freely in organic solvents like benzene, chloroform, CCl4 petroleum ether, etc. ( Like
dissolves like )
(iii) B.P and M.P. decreases with increasing branches in alkene.
(iv) The melting points of cis isomers are lower than trans isomers because cis isomer is less symmetrical
than trans. Thus trans packs more tightly in the crystal lattice and hence has a higher melting point.
(v) The boiling points of cis isomers are higher than trans isomers because cis–alkenes has greater
polarity (Dipole moment) than trans one.
(vi) These are lighter than water.
(vii) The increase in branching in carbon chain decreases the boiling point among isomeric alkenes.
CHEMICAL REACTIONS
The main reactions of alkene are electrophilic addition reaction

Reaction with Hydrogen –
H H H H
| | | |
Ni
R  C  C  R  H2   R C  C R
| |
H H
Mechanism : The reaction takes place at the surface of Ni, therefore the addition is cis addition.
eg :-
CH3 CH3 Ni, 

C=C + H2
D D (cis addition)
(cis-alkene)
HYDROCARBONS
R
D
R H
D H2 R H  R D
R
Ni,  D
D R D
(cis–addition)
(cis–alkene) H H
(Meso–compound)
CH3 D Ni, 
C=C + H2
D CH3 (cis addition)
(trans-alkene)
enantiomeric pair
R
D
R H
D H2 R H  R D
D
Ni,  D
R D R
(cis–addition)
(Trans–alkene) H H
(Optically active)
H
H
D
H
R  D R
R R D
D
H
(Optically active)
Note : Hydrogenation (catalytic hydrogenation) of alkene is a cis addition and is an exothermic

reaction. Thus the heat evolved decreases with increasing stability of alkene.
Remember, Stability of alkene depends upon hyperconjugation and type of geometrical isomerism
Reduction of alkene via hydroboration

(i) Alkene can be converted in to alkane by hydroboration followed by protolysis
BH2
| H / H2O
R—CH — CH2 H–BH
 2  R—CH2— CH2  
  R—CH2—CH3
HYDROCARBONS
This reaction is also represented as

H /H2O 
H — BH2
RCH = CH2    (R – CH –CH ) B  
2 2 3
 3R – CH2 – CH3 + H3BO3
(ii) Alkene can be converted into alkane by hydroboration followed by treatment with AgNO3 + NaOH.
This method gives coupling.
CH3 –CH2 –CH2 – B

CH2 AgNO
2H6
 CH –CH –CH – CH2–CH2– CH2– CH2–CH3
3 / NaOH 3 2 2
Halogenation –
In presence of polar medium alkene form vicinal dihalide with halogen.
H H H H
| | | |
CCl4
R  C  C  H  X  X   R  C  C  H
| |
X X
Vicinal dihalide
Order of reactivity of halogens is : F2 > Cl2 > Br2 > I2
Mechanism : It is an electrophilic addition by molecular attack in which the addition takes place
in trans manner.
–Br
| Br Br
Br –Br¯ Br¯ |
Br Br C  C  C—C
C=C  
C——C |
Br
CH3 CH3 Br
C=C 2

CCl4
H H
cis
Br
2

CCl4
Note : For suitable condition

(i) Cis addition on cis form results meso
(ii) Cis addition on trans form results (±)
(iii) Trans addition on cis form results (±)
(iv) Trans addition on trans form results meso.
HYDROCARBONS
Reaction with HX (Hydrohalogenation) –
H
|
C =C + H X  C—C
|
X
alkene alkyl halide
Markovnikoff’s Rule
When an unsaturated unsymmetrical hydrocarbon reacts with HX then halogen goes on that unsaturated
carbon which has minimum number of hydrogen atom. Mechanism of the reaction is based on — C — .
|
CH3 – CH = CH2 H–X


Mechanism :

H X–
CH3 –CH=CH2  
 (Minor)
less stable

H X–
CH3 –CH=CH2  

more stable major

(i) Formation of Carbocation is Rate determining step.
(ii) Rearrangement of carbocation to more stable carbocation can occur to form a more stable product.
(iii) Regiochemistry - Markownikoff’s Addition of HX.
Addition of HX on unsymmetrical alkenes (R–CH=CH2) takes place according to Markownikoff’s rule
which states that, “the negative part of addendum is added on the carbon atom carrying lesser number of
hydrogen atoms”.
(iv) Reactivity order of different hydrogen halide towards addition
HI > HBr > HCl > HF
Anti Markownikoff’s Principle / Kharasch Effect / Peroxide Effect –

To understand antimarkownikoff’s principle let us consider the following reactions
H H
| |
CH3 – CH = CH2 + HBr  CH3  C  C  H
| |
Br H
(Markownikof f s rule)
H H H H
| | | |
Peroxide
CH3  CH  CH2  HBr     CH3  C  C  H  CH3  C  C  H
| | | |
Br H H Br
(minor) (major)
(Anti markownikoff’s rule )
It is based on free radical mechanism.
HYDROCARBONS
(a) Mechanism Concept –

(i) R – O – O – R  RO• + •OR
Peroxide
(ii) RO• + H – Br  ROH + xBr
H H H H
| | | |
(iii)   CH3  C  C  H + CH3  C  C  H
| • • |
Br Br
minor 20% major 80%
H H H H
| | | |
(iv) CH3  C•  C  H  H Br   CH3  C  C  H  xBr
| | |
Br H Br
(v) ×
Br + ×Br  Br2
Note : It is interesting to note that anti markovnikov addition in the presence of peroxide is not applicable for
HCl and HI
(i) In the case of H – Cl, the step

Cl Cl H
|  | |
CH2 – CH2 H— Cl
 CH2 — CH2 + Cl

is endothermic (as  H = + 12.6 KJ mol–1)

(ii) In the case of H – I, the step
I
 |
CH2 = CH2 + I  CH2 – CH2 is
endothermic (as H = + 46 KJ mol–1)
But in the case of HBr both of the steps are exothermic, which results spontaneous reaction.
* CCl4, CBrCl3 etc. can also be added to alkene in anti markovnikov manner.
Reaction with Hypohalous Acid –

 
R – CH=CH2 + HO – Cl 
(i) When chlorine water or bromine water is used.

Cl Cl
Cl Cl
| |
R—CH — CH2    R — CH — CH2   R — CH — CH2
 Cl ¯ | H |
 O —H OH
|
H
HYDROCARBONS
(ii) When aq. solution of HOCl is added in the presence of strong acid.
Cl
CH2 = CH–R |  H2O – H
H – O – Cl CH2 — CH — R    
| –H2O
H
Cl
| Zn dust
CH2 — CH — R    C—C
| CH 3 COOH
OH
halohydrine
Reaction with H2SO4 –

(a) With conc. H2SO4
R – CH = CH2 + H2SO4  R – CH – CH3
|
O – SO3H
alkyl hydrogen sulphate
(b) With dil. H2SO4
4 H– SO H
R–CH=CH2 
H2O

Mechanism:
–H
R — CH — CH3   R — CH — CH3
| |
O— H OH
|
H
* The hydration of alkene is not stereoselective, as in the case of HCl addition. This fact can be
explained on the basis of classical carbon cation formation.
* Since hydration proceeds via carbocation intermediate therefore rearrangement is always probable.
CH3
| H
CH3 – C – CH = CH2  
 
|
CH3
CH3 CH3 CH3 CH3

| | | |
– H
CH3 — C — C — CH3   CH3 — C — C — CH3
| | | |
H — O H OH H
|
H
HYDROCARBONS
* Rearrangement, however, may be avoided by treatment of alkene by oxymercuration-demercuration

method
OAc
OAc +
Hg
H2O
CH3CH = CH2 + Hg — OAc CH3CH — CH2 CH3CHCH2—Hg—OAc
+
OH
+ AcO¯
H
¯OAc
CH3CHCH2—Hg—OAc
OH + AcOH
Sodium borohydride (NaBH4) converts the carbon-mercury bond into a carbon-hydrogen bond. Because
the reaction results in the loss of mercury, it is called demercuration.
NaBH
CH 3CHCH 2 —Hg—OAc   4  CH 3CHCH 3 + Hg + AcO¯
HO ¯
| |
OH OH
Addition of Nitrosyl halide –
Alkene with nitrosyl bromide or nitrosyl chloride (Tilden reagent) react according to Markovinikoff’s
rule to give alkene nitrosobromide and alkene nitrosochloride respectively.
 
R – CH + O= N – Cl  
 
R–CH + O= N – Br  
 
CH3 – CH + O= N – Cl  CH3 – CH  CH2
| |
Cl NO
propelene nitrosochloride
Oxidation
Oxidation is completed by the following ways.
With Acidic KMnO4 / Hot KMnO4

H H O
| | ||
R C  C H  O acidic
 R  C  O  H  CO 2  H2 O
KMnO4
H H
| | O
H  C  C  H 
 2CO 2  2H2 O
ethene
HYDROCARBONS
H
[ O]
|
  H  C  C  O  CO 2  H2 O
| |
H OH
propenes acetic acid
H H
| |
[ O]
CH3  C  C  CH3   2CH3COOH
2-butene
[ O]


isobutylene
[ O]


With alkaline KMnO4 / Bayer’s reagent

H H
| |
Alk.KMnO
     4
R  C  C  H  O  H  OH  OH
glycol
Mechanism: Hydroxylation by alkaline KMnO4 (Bayer’s reagent) is cis addition and the mechanism
is cyclic.
H2O /H
+     
Similarly
KMnO4 / OH
  
Hydroxylation by OsO4 :
+    H / H2O
  
HYDROCARBONS
+ OsO4 OH
¯
 
Ozonolysis :-
This is the two step reaction
(i) Ozonide formation
(ii) decomposition of ozonide (reductive hydrolysis)
eg:-
O3 H2O / H / Zn
C=C  
I
  
II
 ZnO +
Remember : Ozonolysis gives oxidative cleavage of alkene to form two carbonyl group for each
. Whether it is in acyclic or cyclic or in aromatic compound. eg :-
O O O O
|| || || ||
(a) CH2 =CH – CH = CH2  Ozonolysis
 H — C — H + H— C — C —HH— C —H
(b) Ozonolysis
 
Trans
Epoxidation by O2 /Ag
(i) CH2=CH2 + ½O2  Ag


(ii) CH3 – CH = CH2 + ½ O2  Ag

 CH3—
Epoxidation by per acid
(i) CH2 = CH2
O
||
H— C — O — O —H
(ii) CH3 – CH = CH2   CH3—
R–CH = CH – R CF3 COOOH

  R– –R
HYDROCARBONS
Hydroboration
Alkene with borane hydride form an important compound called trialkyl borane.
3R–CH=CH 2 + BH3  ( R – CH2 – CH2)3B
(a) Trialkyl borane is an important compound because it gives respective alkane on acidic hydrolysis.
HCl
(R – CH2CH2)3B + 3 H2O 
(b) It gives respective alcohol on alkaline hydrolysis
(R – CH2CH2)3B + 3 H2O2 + 3NaOH 


(c) It gives 1º amine on alkaline hydrolysis with chloramine

(R – CH2CH2)3B + 3 NH2Cl + 3NaOH  3R – CH 2 CH2NH2 + 3NaCl + H 3BO3
AgNO3
(d) (R – CH2CH2)3B 3R – CH2 – CH2 – CH2 – CH2 – R
NaOH
(e) In the overall hydroboration-oxidation reaction, three moles of alkene react with one mole of BH3 to
form three moles of alcohol.
(f) Because carbocation intermediates are not formed in the reaction carbocation rearrangement do not
occur.
(g) Regiochemistry Anti-markownikoff’s Addition of water.
(h) Alkyl boranes undergo coupling by means of silver nitrate in the presence of NaOH at 25°C. Higher
alkanes are the products of this reaction.
Allylic substitution reaction –

(a) Except ethene other higher alkene having allyl hydrogen when treated with chlorine or bromine ‘’
H is substituted.
CH3 – CH = CH2 + Cl2 500

º C  600 C
    Cl–CH2– CH=CH2 + HCl
allyl chloride (3-chloropropene)
Cl – Cl 
 2Cl•
Cl + CH2 – CH = CH2 CH2 – CH = CH2

| – HCl
H Cl
CH2 – CH = CH2
|
Cl
HYDROCARBONS
(b) Allylic bromination can be easily done by NBS (N–bromo succinamide)
+ H–CH2–CH=CH2   + Br– CH2 – CH = CH2
NBS propene allyl bromide
Isomerisation :-
Alkenes isomerises when heated at high temperature or at lower temperature in the presence of
various catalysts as AlCl3
eg :-
(i) CH3 – CH2 – CH2 – CH = CH2 CH3 – CH2 – CH = CH – CH3

CH3 CH3
| |
(ii) CH2 – CH = CH2 CH2 = C — CH3
the mechanism proceeds through carbocation
HYDROCARBONS
REACTION CHART FOR ALKENES

GMP GR
H Ni
(1) 2, R–CH2–CH3
(1) R–H Pyrolysis
 200300 C
(2) X
2 R–CHX–CH2X
Ni, H
2
(2) R–C  CH 
R–CH=CH2 (3) 
HX
 R–CHX–CH3
200300C
or (4) HBr , Peroxide
C n H 2n   R–CH2–CH2Br
(3) R–CH2–CH2–X alc
. KOH
 (5) HOCl
 R–CH(OH)–CH2Cl
 HX
dil. H SO
2 4
Zn dust (6)  HO R–CH2(OH)–CH3
 
 2
(4) R–CH2–CH for higher alkene 1/ 2O2
X 2 (7) 
Ag,300C
R  CH  CH 2
(5) | | Zn
dust

 CH 2 N 2
(8)  
X X
(9) BH
3  (RCH2CH2)3B
(6) CH2=CHCl CuR 2
 R  CH  CH 3 R  CH 2  CH 2
CO  H
2 
(10)   | + |
HCo ( CO ) 4 CHO
conc. H SO CHO
(7) R–CH2–CH2–OH  24  2 O
 H 2O (11)  CO2 + H2O

R  C  O  CH 2  CH 2  R Pyrolysis R  CH  CH 2
(8) ||

(12) Os
 O4

O
| |
OH OH
RCHCH 2 COOK
(9) |
Kolbe's electrolytic synthesis
       
COOK
(13) Bayer
  R  CH
reagent
 |
 CH 2
|
1% alkaline KMnO 4
(10) (RCH2CH2)4 N+OH¯ 
 OH OH
(14) strong R  C  OH + CO + H O
 oxidant
 || 2 2
O
Per acid
(15) Priles 
 chalev 's reaction
3 2 O H O
  
(16) Ozonolysis +
2O

(17) 200 Polyalkene
C high P
Cl
2 Substitution product
(18) 500

C
Al (SO )
2  
(19) 200
4 3
 Isomerisation
300 C
(20) acetic
 anhydride
 R–CH2=CH–COCH3
Methyl alkenyl ketone
Alkane
(21)   Higher alkane
HYDROCARBONS
ALKYNE
GENERAL INTRODUCTION
(1) The chemistry of the carbon-carbon triple bond is similar to that of the double bond. In this chapter,
we see that alkynes undergo most of the reactions of alkenes, especially the additions and the
oxidations. We also consider reactions that are specific to alkynes : some that depend on the unique
characteristics of the C  C triple bond, and others that depend on the unusual acidity of the
acetylenic C– bond.
(2) Alkynes are hydrocarbons that contain carbon–carbon triple bonds. Alkynes are also called acetylenes
because they are derivatives of acetylene, the simplest alkyne.
(3) Bond angle in alkyne is 180º.
(4) Thei r general f ormul a i s C nH2n–2
(5) C – C triple bond length is 1.20 Å.
(6) C – H bond length is 1.08 Å.
Methods of Preparation
From Gem Dihalides (Dehydrohalogenation) :
H X X
| | | NaNH
2
R C C H + alc. KOH.   R  CH  C  H    R– C C– H
| | HX HX
H X

KOH + C2H5OH C2H5OK + H2O
H X X
| | 
C2H5O |
R–C–C–H R–C–C–H
| | –C2H5OH | |
H X H X
– X¯
X
|
R–C=C–H
|
H

–NH3 NH2
X

|
R–C=C–H

–X
R–CC–H
HYDROCARBONS
From vicinal dihalides :
H H H
alc. KOH NaNH2
—C—C— –HX
—C = C— —C  C—
–HX
X X X
vic-dihalide vinyl-halide alkyne
(very unreactive)
The elimination of one molecule of hydrogen halide yields vinyl halide which is very unreactive. Under
mild conditions, the dehydrohalogenation stops at vinylic halide stage but more vigorous conditions—
like the use of a stronger base like amide ion (NH2–)—are required for alkyne formation.
From Tetrahaloalkanes (Dehalogenation) :
 
+ Zn(dust)  

300ºC
 R – C  C–H
Zn dust
In the above reaction it is necessary that the four halogen atoms must be attached at vicinal carbons.
If they are attached at the two ends then the product cyclo alkene is obtained.
From Kolbe's Synthesis :
O O
|| || 
 
HCC  O K H C  C  O
||   ||  + 2K+

HCC  O K H C  C  O
|| ||
O O
Potassium Malaete
At Anode :
O
|| 

H C  C  O H–C
||   + 2e¯ 
 ||| + 2CO2
 H–C
H C  C  O
||
O
At Cathode :
2K+ + 2e–  2K•
2K• + 2H2O  2KOH + H2
Laboratory method of preparation of Acetylene :
(a) In laboratory acetylene is prepared by hydrolysis of calcium carbide.

–
2+ C CH
Ca ||| + 2H 2O ||| + Ca(OH)2
C– CH
(b) It can also be prepared from CHCl3 with Ag dust.

2CHCl3 + 6Ag   H–C  C–H + 6 AgCl
HYDROCARBONS
From Alkynes : (To form higher Alkynes)

With Na : When acetylene or 1- alkyne react with Na in presence of liq. NH3 then an intermediate
compound sodium acetylide or sodium alkynide is formed which gives higher alkyne with alkyl halide.
liq.NH X –R
3 2 H – C  C Na  

2H – C  C – H + 2 Na  
H
 H – C  C – R
2

  
H – C  C – H RMgX RH + HC  C MgX
 
R–X
H – C  C – R + MgX2
liqNH
.
3 2R – C C Na

2R – C C – H + 2Na  
H2 R R – C C –R' + NaX
' X
With Grignard reagent : When acetyline or 1- alkyne react with GR then alkane and unsaturated GR
is formed which further react with alkyl halide and form higher alkyne.
RX
 H C C MgX 
H –C CH + R MgX   
 MgX 2
H – C C –R
 RH
acetylene
R– C  C–H + R Mg X    R –C  C MgX R X

  R–C  C–R'
 RH
PHYSICAL PROPERTIES
(a) Alkynes are colourless, odourless and tasteless.
(b) Lower alkynes are partially soluble in H2O. (It is due to its polarisibility).
(c) Higher alkynes are insoluble in water due to more % of covalent character.
(d) Completely soluble in organic solvents.
(e) Melting point and boiling point increases with molecular mass and decreases with number of
branches.
(f) Upto C4 alkynes are gaseous.C5–C11 are liquid, C12 & above are solids.
(g) Pure acetylene is odourless and impure acetylene has odour like garlic. It is due to impurities of
Arsene (AsH3) & Phosphine (PH3).
HYDROCARBONS
(h) Acetylene & 1- alkyne are acidic in nature. It is due to greater electronegativity of sp hybridised
'C'.
(i) Acetylene has two acidic hydrogen atoms. It can neutralise two equivalents of base at the same time.
So it is also called as dibasic acid. But the base should be very stronger as –NH2 or –CH3 etc.
CHEMICAL PROPERTIES
The chemical behaviour of alkynes is similar to that of alkenes. Alkynes form addition products with
two or four univalent atoms or groups. They are generally less reactive than alkenes towards
electrophilic addition reactions even though  electron density is higher in alkynes. This is because
on moving from alkene to alkyne, the C—H bond has more of s character (33% in alkenes as
compared to 50% in alkynes). Therefore, the -electrons are more firmly held by carbon nuclei
in alkynes and are thus less reactive to an electrophile.
Hydrogenation
H
Ni | Ni
R–CC –H + H2 High
 R  C  CH
Temp . + H2 High
 R – CH – CH
Temp . 2 3
|
H
The above reaction is called as Sabatier Senderson's reaction.
Hydrogenation in the presence of lindlar's Catalyst :

Addition up to alkene takes place in cis manner.
(i) H–CC–H + H2 Pd BaSO 4




(ii) CH3 –C C – CH3 + H2 PdBaSO4

 
Hydrogenation by Na + NH3 (liq.) :

Addition upto alkene takes place in trans manner
Na
(i) CHCH  

NH3 (liq.)
(ii) R–CC –R Na /NH3liq.

 
Mechanism :

Na Na + e¯
HYDROCARBONS
 

R – C  C – R' + e¯ R – C = C – R'

–NH2 LiqNH3

R – C = C – R'
|
H

Na  Na + e¯

R – C = C – R'
|

H
–NH2 LiqNH3
H
|
R – C = C – R'
|
H
Reduction with the help of B2H6 :
Alkyne is first reacted with B2H6 and is follwed by acidic hydrolysis, cis alkene is obtained.
1. B2H6
R–CC–R   
2.H2O / H
Halogenation :
In presence of Lewis acid as a catalyst alkyne form tetrahaloderivative with halogen.
X X X
FeX 3 | | |
 R  C  C  H x2
R–C  C–H + X–X  
X  F,ClBr
,  R  C  C  H

| | |
X X X

FeX3 + X2  Fe X4 + X+
+
X
X–X R–C=C–H
R–CC–H
+ X¯
X
|
R–C=C–H
|
X
X – X + Fe X3
+
XX
R–C–C–H
|
X
+X¯
X X
| |
R–C–C–H
| |
X X
HYDROCARBONS
Example :
Br Br Br
Br2 Br2
—C  C— —C = C—
CCl4
—C—C—
CCl4
Br Br Br
Alkynes add two molecules of Br2 in CCl4 and decoloration of bromine water is used to detect the
presence of a double or triple bond.
Reaction with HX (Hydrohalogenation) :

Alkyne form gem dihalide with HX because reaction follows markownikoff's Ist and IInd rule both.
X X
| H X |
R – CC–H + H –X  R  C  CH2   R  C  CH3
|
X
gem dihalide
Mechanism : The reaction takes place in the presence of Hg2+ ion.
Hg2+
2 R Hg H R H
R –C C – R Hg
  R– C C –R
HX
C=C  2
 Hg  C=C
X R X R
HX
 
Note : (i) First step is faster than the second step among addition of two HX on alkyne.
X H X H
| |
/ Hg2 | | HX / Hg2
R – C  CH HX
  R — C — CH    R — C — C — H
Faster slower | |
X H
Slower rate of addition of 2nd molecule is caused by lower electron cloud density on
C = C, due to – I effect of 'Cl'.
(ii) peroxide give same effect as in alkene

H Br H Br
HBr | | HBr
| |
R–CCH   R — C — CH   R — C — C — H
Peroxide Peroxide
| |
H Br
HYDROCARBONS
R – O – O – R + H – Br Br + R – OH
R – C  C H + Br R – C = CH
|
Br
–OR R – O – H
R – C = CH
| |
H Br
Br
R – C – CH – Br
| |
H Br
–RO R – O – H
R – CH2 – CH – Br
|
Br
Reaction with Hypochlorous acid or Chlorine water :

Hypochl orous acid is broken into O HCl& ions & give addb. according to markonicoff's rule.
OH OH
| RC  O
  | |
RC RC R  C  OH  
||| +
  H O  Cl H  C  Cl
HO  Cl  ||   |  H2O
H C H C |
H  C  Cl Cl
| |
Cl Cl
unstable
Hydration : Addition of water to alkynes is carried out in the presence of acid and mercuric sulphate.
H2 O H H
HC  CH HgSO4, H2SO4
H—C = C—H Tautomerizes
H—C—C = O
H O—H
vinyl alcohol H
(enolic form-less stable) Acetaldehyde
H 2O
CH3—CH2—C  CH CH3—CH2—C = CH2 CH3CH2—C—CH3
HgSO4, H2SO4
O—H O
(enol) (ketone)
HYDROCARBONS
C  CH HO—C = CH2 O = C—CH3

H2O
HgSO4, H2SO4
Acetophenone
Addition of alcohol
O  R' O  R'
RC  
| |
 R  C
||| + H O R NaO 
   R  C  O  R'

—R || HO R |
H C
C H HC H
| |
H H
olefinic ether acetal / ketal
Addition of carboxylic acid :

In the presence of Hg2+ unioxylation of carboxylic acid takes place.
O O
|| 2 ||
H –C  C – H + H – O – C – CH3 Hg
  CH2 = CH – O – C – CH3
Adition of Boron Hydride (Hydroboration) :

(i) With mono-alkyl acetylene, R2BH gives an intermediate which on hydrolysis gives alkene but on
alkaline oxidation yields aldehyde.
R H CH3COOH
R—C  C—H + R2BH  C=C RCH = CH2
hydrolysis
Dialkyl H BR2
borane oxidation H2O2, NaOH
RCH2CHO
R – C  C – R' + BH3 R – C = C – R'
| |
H BH2
2 R – C  C – R'
R'
R R' CH3COOH |
R – (CH = C)3 – B
C=C Hydrolysis
H H
(cis-alkene) H2O2/NaOH
R – CH = C – R'
|
OH
R – CH2 – C – R'
||
O
(ii) With dialkyl acetylenes, the product of hydrolysis is cis-alkene and that of oxidation is a ketone.
HYDROCARBONS
R R
R—C  C—R + BH3  C=C B
H
3
Dialkyl acetylene vinyl borane
H2 O2 , CH3COOH
NaOH oxidation hydrolysis
R R R
C=O C=C
R H H
ketone cis-alkene
Addition of HCN :
Addition takes place in the presence of CuCl
H – C  C – H + H – CN CuCl
 CH2 = CH – CN
770º
Addition of AsCl3 :
Lewisite is obtained
R– CC –H R— C  C —H
| |
Cl AsCl2
Lewisite
Oxidation :
With acidic or alkaline KMnO4 alkyne break into two parts from triply bonded carbon and every
part forms respective acid.
R – CC –H + [O]  Acidic / Alk.KMnO4
  R  C  OH + H  C  OH
|| ||
O O
H–CC–H + [O]  Acidic

KMnO4
 2H  C  OH
||
O
CH3 – C C – H + [O]  Acidic / Alk.KMnO4
  CH3  C  OH + H  C  OH
|| ||
O O
CH3 –CC–CH3 + [O]  Acidic / Alk.KMnO4

  2CH3  C  OH
||
O
Exception : Acetylene forms oxalic acid with alkaline KMnO4 exceptionally.
Alk.KMnO4 COOH
H –C C–H + [O]    |
COOH
Ozonolysis
The ozonolysis of alkynes yields a mixture of carboxylic acids.
O
H2O H2O2
R—C  C—R + O3  R—C—C—R R—C—C—R RCOOH + R COOH
Hydrolysis oxidation
O—O O O
HYDROCARBONS
Acidic nature of 1- Alkyne or Acetylene

In 1- alkyne or acetylene, the H which is linked with sp hybridised carbon is called as acidic or
active H. It can easily be substituted by metal or alkaline species. Hence 1- alkyne or acetylene
are acidic in nature. eg.
Reaction with Na :
LiqNH
. 3
2R – CC–H + Na  
 H2
 2R – C  CNa
sodium alkynide
OR
2R – C C – H + NaNH2  
NH
 2R–C  CNa
3
H– C C – H + Na  NaC CNa

disodium acetylide
Note : Where this alkynide is treat with alkyl halide higher alkyne is obtained.
R–CCNa + X–R  R–CC–R' + NaX
Na C  CNa + 2R – X  R'C  C – R' + 2NaX
Reaction with Ammonical Silver Nitrate solution : (Tollen's Reagent)

2R – C C – H + AgNO3 + NH4OH   H O
 2R – CCAg
2
silver alkynide (white ppt)
H–C C – H + AgNO3 + NH4OH   AgC  CAg

 H2O
silver acetylide (white ppt)
Reaction with Ammonical Cuprous Chloride solution :

2R – C C – H + Cu2Cl2 + NH4OH   2R – CCCu
 2HCl
cuprous alkynide (red ppt.)
 CuC  CCu
H –CC – H + Cu2Cl2 + NH4OH  
 2 HCl
dicuprous acetylide (red ppt.)
Reaction with NaOCl :

Acidic hydrogen is substituted by 'Cl'
(i) H – CC–H NaOCl
 Cl – CC – Cl
(ii) R – CC–H NaOCl

 R – C C–Cl
Mechanism :
R–C  R – CC–Cl
HYDROCARBONS
Polymerisation Reactions : Alkyne mainly shows addition polymerisation reactions.

Dimerisation and Cyclization
(a) Dimerisation :
Two mole acetylene reacts with Cu2Cl2 & NH4Cl and forms vinyl acetylene.
Note : If acetylene would be in excess then product would be divinyl acetylene and the reaction
is called trimerisation.
H H H
| | |
+ H–C  C–H Cu2Cl2  NH4 Cl H  C  C  C  C  H
HC  C  
vinyl acetylene or butenyne
H H H H H H H
| | | | | | |
H C  C  C  C H + C  C  H    H  C  C  C  C  C  C  H
divinyl acetylene
(b) Trimerisation :
If three mole of acetylene is passed into red hot iron or Cu or quartz tube, then a cyclic trimer is formed
which is called benzene.
CH
CH
CH Re d hot Fe / Cu / Quartz
 
CH Co(CO)8  Br2
CH
(Octa Carbonyl cobalt

CH
with bromine)
benzene
CH3
| CH3
|
CH C
||| \\\ C
CH3  C CH CH CH
C  CH3 
 CH3 –C C– CH3
/// CH
HC
mesitylene (having 3-1º, 3-2º & 3-3º carbons)
Important : Mesitylene can also be obtained from acetone by condensation polymerisation.
(c) Tetramerisation : According to the name four moles of acetylene are heated with nickel tetra
cyanide, then acetylene forms a cyclic tetramer cyclo octa tetraene.
CH  CH CH=CH
CH CH CH CH
||| ||| Ni(CN)4
  
CH CH CH CH
CH  CH CH=CH
(Nonaromatic) cyclooctatetraene
Coupling:-
(a) Alkyne form respective cuprous alkynide with ammonical cuprous chloride solution. When cuprous
alkynide is reacted with pottasium ferri cyanide [K3Fe(CN)6] they converted into conjugated diyne.
R – C  CH + Cu (NH3)2Cl  R–C C.Cu
cuprous alkynide
HYDROCARBONS
2R – C  C.Cu O
2  R – C C – C C – R

diyne
(b) Coupling is also done easily by 1-alkyne in the presence of Cu2Cl2 (cuprous compound) and amine
(ie. pyridine + air) cuprous alkynide is formed (this coupling is known as oxidative coupling or glaser
coupling)
1
2R – C  CH + O Cu 2Cl2 /NH
 3  R – C C – C  C – R + H O
2 2 2
2 CH3 – CCH + ½ O2 Cu2Cl2 /NH
 3  CH – C C– C  C – CH
3 3 + H2O
2,4–Hexadiyne.
Isomerisation :–
(a) When 1-alkyne is treated with alcoholic KOH 2-alkyne is formed.
R–CH2–CCH  Alco

.KOH
 R – C  C – CH3

1–alkyne 2–alkyne
(b) When 2-alkyne is treated with sodamide then it is converted into 1-alkyne.
H2O
CH3 – C  C – CH3 NaNH
 2  CH – CH – CCNa  
 3 2   CH3 – CH2 – CCH
NH3 NaOH
HYDROCARBONS
REACTION CHART FOR ALKYNES

GMP GR
(1) CH2Br–CH2Br alc . KOH or NaNH 2 H2
  (1)  C2H4, C2H6
Ni
(2) CH3–CHBr2 alc. KOH , NaNH 2 X2
     (2)  C2H2X4
HBr
(3) CHCl3 Ag
powder
  (3)  CH BrCH Br
3 2
 Peroxide
C 2H 2
(4) CHBr2–CHBr2  
Zn dust
 HBr
(4) No   CH –CHBr
 Peroxide 3 2
CHBr (5) HOCl

 Cl2CHCHO
(5) || Zn
(6) HCN , Ba ( CN ) 2
CHBr
  2  CH2=CHCN
CH COOH , Hg
(7) 3    CH3CH(OCOCH3)2
(6) CH2=CH–Cl alc. KOH , NaNH
    2  Hg 2 , 80C , dil. H SO
(8)     2 4  CH CHO
HC  COONa Kolbe's electrolytic synthesis ( Kucherov 's reaction ) 3
(7) ||       
HC  COONa (9) Conc

. H 2SO 4
 CH3CH(HSO4)2
2 H O (10) AsCl
3  CHCl=CHAsCl2
(8) CaC2 
 
C 2 H 5OH / H 2O
electric arc ,1200C
    
 (11)     CH CHO
(9) 2C + H2 Berthelot 's process
HgSO 3
4
CO  HOH
(10) CH3–CCH (
i ) Na (ii ) R X
  (12)    CH =CH–COOH
Ni ( CO ) 2 4
(10) CH3–CCH (i ) CH MgI (ii ) R X
 3    CO  EtOH
(13)    CH =CH–COOEt
Ni ,160C 2
(14) NaNH
 2  NaCCNa
AgNO3  NH 4OH
(15) (     AgCCAg
Tollen 's Re agent )
(16) Cu Cl  NH OH
22 4   CuCCCu
Combustion
(17)     O
2  CO2 + H2O
CHO
(18) Bayer
 Reagent
 |
  HCOOH
CHO
3O

(19) Ozonolysis H O
2
  HCOOH
Trimerisat ion
(20)    benzene
(Re d hot iron tube )
Trimerisation
(21)    C8H8or 1,3,5,7-cyclo octa tetraene
[ Ni ( CN ) 2 ]
Dimerisati on
(22)    butenyne
[ Cu ( NH 3 ) 2 ]
s
(23) 


CH OH
(24)  3  methylal
( BF  HgO )
3
HYDROCARBONS
EXERCISE-1 (Subjective Questions)
Q.1 Chlorination of ethane to ethyl chloride is more practicable than the chlorination of n-pentane to
1-chloropentane.
Q.2 Why n-pentane has higher boiling point than neopentane?
Q.3 Assuming that cation stability governs the barrier for protonation in H – X additions, predict which
compound in each of the pairs in parts (a) & (b) will be more rapidly hydrochlorinated in a polar solvent.
(I) (II)
(a) CH2 = CH2 or
(b) or
H
Q.4 
 Write the mechanism.

OH
Q.5 Choose the member of the following pairs of unsaturated hydrocarbons that is more reactive towards
acid-catalysed hydration and predict the regiochemistry of the alcohols formed from this compound.
(a) or (b) or
(I)
(c) or
Q.6 Propose structures for intermediates & products A to K
Q.7 Formulate the reactions between but–1–ene in presence of small amount of benzoyl peroxide &
(i) CCl4 (ii) CBrCl3
Give your reasons.
HYDROCARBONS
Q.8 Write the structural formula of limonene from the following observation:
(a) Limonene when treated with excess H2 & Pt catalyst, the product formed is 1 isopropyl · 4 methyl cyclohexane
(b) When it is treated with O3 & then Zn/H2O the products of the reaction are HCHO & following compound
Q.9 There are six different alkene A, B, C, D, E and F. Each on addition of one mole of hydrogen gives G
which has the lowest molecular wt hydrocarbon containing only one asymmetric carbon atom. None of
the above alkene give acetone as a product on ozonolysis. Give the structures of A to F. Identify the
alkenes that is likely to give a ketone containing more than five carbon atoms on treatment with a warm
conc. solution of alkaline KMnO4.
Q.10 3, 3dimethyl1butene and HI react to give two products, C6H13I. On reaction with alc. KOH one
isomer, (I) gives back 3,3dimethyl1butene the other (J) gives an alkene that is reductively ozonized
to Me2CO. Give the structures of (I) and (J) and explain the formation of the later.
Q.11 Three isomeric alkenes A, B and C, C5H10 are hydrogenated to yield 2methylbutane A and B gave the
same 3° ROH on oxymercuration demercuration. B and C give different 1° ROH’s on hydroboration
-oxidation. Supply the structures of A, B & C.
Q.12 Two isomeric alkyl bromides A and B (C5H11Br) yield the following results in the laboratory. A on
treatment with alcoholic KOH gives C and D (C5H10). C on ozonolysis gives formaldehyde and
2 methyl propanal. B on treatment with alcoholic KOH gives only C (C5H10). Deduce the structures of
A, B, C and D. Ignore the possibility of geometrical and optical isomerism.
Q.13 An alkylhalide, X, of formula C6H13Cl on treatment with potassium tertiary butoxide gives two isomeric
alkenes Y and Z (C6H12). Both alkenes on hydrogenation gives 2, 3dimethylbutane predict the structures
of X, Y and Z.
Q.14 A organic compound A having carbon and hydrogen, adds one mole of H2 in presence of Pt catalyst to
form normal hexane. On vigorous oxidation with KMnO4, it gives a simple carboxylic acid containing 3
carbon atoms. Assign the structure to A.
Q.15 Give the product of

CH3 H 1. BD .THF
(a) 
BH
3  A H
2O 2
 B (b) C=C  3 

THF OH ¯ H 2. D 2O 2 , DO 
CH3
3 1. CF CO H
3
Q.16   


 A + B. What are A and B?
2. H 2 O / H
Q.17 Give the structure of the alkene that yields on ozonolysis

(i) CH3CH2CH2 CHO & HCHO (ii) C2H5COCH3 & CH3CH(CH3) CHO
(iii) Only CH3CO.CH3 (iv) CH3.CHO & HCHO & OHC.CH2.CHO
(v) Only OHC-CH2CH2CH2–CHO.
HYDROCARBONS
Q.18 Explain the following:

(i) 1, 2 shift does not take place during oxymericuration demercuration. Why?
(ii) Halogneation of alkene is anti addition but not syn addition. Why?
(iii) Anti markovnikov addition is not applicable for HCl. Why?
(iv) 1,4–addition takes place in butadiene. Why?
Q.19 Conversion:
(i) C2H2  racemic 2, 3 dibromobutane (ii) 2-butyne  2-pentyne
(iii) Ethyne  Acetone (iv) cis but 2 ene  Trans but 2 ene
(v) Ethene  Propionic Acid
Q.20 (a) Outline a stereospecific synthesis of meso 3, 4 dibromohexane from ethyne.

(b) Acetylene is acidic but it does not react with NaOH or KOH. Why?
Q.21 A chloro compound (A) showed the following properties :

(i) Decolourized bromine in CCl4
(ii) Absorbed hydrogen catalytically.
(iii) Gave a precipitate with ammonical cuprous chloride
(iv) When vaporised 1.49 g of (A) gave 448 mL of vapours at STP.
Identify (A) and write down the equations of reactions.
HYDROCARBONS
EXERCISE-2 (Objective Questions)
[SINGLE CORRECT CHOICE TYPE]

Q.1 BrCH2–CH2–CH2Br reacts with Na in the presence of ether to produce –
(A) BrCH2–CH=CH2 (B) CH2=C=CH2 (C) (D) All of these
Q.2 During the preparation of ethane by Kolbe’s electrolytic method using inert electrodes the pH of the
electrolyte –
(A) Increases progressively as the reaction proceeds
(B) Decreases progressively as the reaction proceeds
(C) Remains constant throughout the reaction
(D) May decrease of the concentration of the electrolyte is not very high
Q.3 The correct order of rate of Wurtz recation.

Na
(I) CH2–F  CH2–CH2
Ether
Na
(II) CH2–Cl  CH2–CH2
Ether
Na
(III) CH2–Br  CH2–CH2
Ether
Na
(IV) CH2–I  CH2–CH2
Ether
(A) I > II > III > IV (B) II > I > III > IV
(C) IV > III > II > I (D) In all rate of Wurtz reaction is same
CH 3  CH  CO 2 K 
Q.4 electrolys
 is
 (A) (Major)
|
CH 3  CH  CO 2 K 
Major product (A) of above reaction
(A) (B) (C) (D)
Q.5 Electrolysis Major product of reaction :
(A) (B) (C) (D)
HYDROCARBONS
Q.6 on electrolysis gives:
(A) (B)
(C) (D)
Q.7 HI P (Major Product)


P is
I
(A) I (B) (C) (D)
I I
Q.8 How many moles of O2 required for complete combustion of one mole of propane –
(A) 7 (B) 5 (C) 16 (D) 10
Q.9 How much volume of air will be needed for complete combustion of 10 lit. of ethane –
(A) 135 lit. (B) 35 lit. (C) 175 lit. (D) 205 lit.
Q.10 When n-butane is heated in the presence of AlCl3/HCl it will be converted into –
(A) Ethane (B) Propane (C) Butene (D) Isobutane
Q.11 Which has least heat of hydrogenation –
(A) (B) (C) (D)
Q.12 Which is expected to react most readily with bromine –

(A) CH3CH2CH3 (B) CH2=CH2 (C) CHCH (D) CH3–CH=CH2
Q.13 Anti–Markownikoff’s addition of HBr is not observed in –

(A) Propene (B) But–2–ene (C) Butene (D) Pent–2–ene
Q.14 For the ionic reaction of hydrochloric acid with the following alkenes, predict the correct sequence of
reactivity as measured by reaction rates:
(I) ClCH=CH2 (II) (CH3)2.C=CH2 (III) OHC.CH=CH2 (IV) (NC)2C=C(CN)2
(A) IV > I > III > II (B) I > IV > II > III (C) III > II > IV > I (D) II > I > III > IV
HYDROCARBONS
O
||
Q.15 Alkene A O
3 / H 2O
 CH 3  C  CH 3 + CH3COOH + CH 3  C  COOH
||
O
A can be –
C(CH 3 ) 2
||
(A) (B) CH 3  C  CH  HC  CH 3
(C) Both correct (D) None is correct
Q.16 Ozonolysis of CH3–CH=C=CH2 will give

(A) Only CH3CHO (B) Only HCHO
(C) Only CO2 (D) Mixture of CH3CHO, HCHO & CO2
Q.17 O-xylene on ozonolysis will give

O CH 3  C  O O
CHO || ||
(A) | & CH 3  C  CHO (B) | & CH 3  C  CHO
CHO CH 3  C  O
CH 3  C  O O
CH 3  C  O CHO || CHO
(C) | & | (D) | , CH 3  C  CHO & |
CH 3  C  O CHO CH 3  C  O CHO
Q.18 Which of the following carbocation is most stable?
(A) (B) (C) (D)
Q.19 Which carbocation is least likely to form as an intermediate?
 
(A) (C6 H 5 )3 C (B) (C) (D) CH 2  CH
Q.20 Which one of the following carbocation would you expect to rearrange.

(A) (B) (C) (D)
Q.21 Which will dehydrate at fastest rate by H3PO4:-

(A) 2-methyl butane-2-ol (B) 3-methyl butane-2-ol
(C) Butane-1-ol (D) 2-methyl butane-1-ol
HYDROCARBONS
Q.22 Rate of dehydration when given compounds are treated with conc. H2SO4.
(P) (Q) (R) (S)
(A) P > Q > R > S (B) Q > P > R > S (C) R > Q > P > S (D) R > Q > S > P
Q.23 How many 1,2-Shifts are involved during the course of following reaction:
conc. H SO
 24 
(A) 1 (B) 2 (C) 3 (D) 4
H
Q.24  (X).

Product (X) is
(A) (B) (C) (D)
OH
(i) O
H

Q.25  A   3  Product(s). Product is/are?
 (ii) Zn / H2O
CHO
(A) + HCHO (B) || CH = O
O
O
CHO
(C) + CH3CHO (D)
OHC
CH 2
|
conc.H PO 4
Q.26 CH 3  C  CH  CH 2 dil

.H 2SO 4
  3  ( i ) O3

|  ( ii ) Zn / H 2O
CH 3
Final product is / are
O O
|| ||
(A) CH 3  C  CH 3 (B) HCHO + CH 3  C  CH  CH 3
|
CH 3
(C) CH3CHO + (D) CH3CHO + HCHO
HYDROCARBONS

Q.27 H

(A) (B) (C) (D)
Conc
Q.28 . H 2SO 4 H Br Na / ether Product (Major)

    
H 2O 2
(A) (B)
(C) (D)
Q.29 (E)-3-bromo-3-hexene when treated with CH3O in CH3OH gives

(A) 3-hexyne (B) 2-hexyne
(C) 2,3-hexadiene (D) 2,4-hexadiene
Q.30 
 product is
(A) (B) (C) (D)
Q.31 Conc . H 2SO 4 H / Pt

    (A) 2  (B)
A and B are :
(A) Both are
(B)
(C)
(D)
HYDROCARBONS
CH 3
|
HC
|| alkaline KMnO
Q.32    4  A, which is true about this reaction?
HC
|
CH 3
(A) A is meso 2, 3–butan–di–ol formed by syn addition

(B) A is meso 2, 3–butan–di–ol formed by anti addition
(C) A is a racemic mixture of d and l, 2, 3–butan–di–ol formed by anti addition
(D) A is a racemic mixture of d and l 2,3–butan–di–ol formed by syn addition
Q.33 reagent R reagent R

  2  1 
R1 and R2 are –
(A) Cold alkaline KMnO4, OsO4/H2O2 (B) Cold alkaline KMnO4, HCO3H
(C) Cold alkaline KMnO4, CH3–O–O–CH3 (D) C6H5CO3H, HCO3H
O O (1eq )
s 4
Q.34   X.
H 2O / Acetone
Identify ‘X’.
(A) (B)
(C) (D) Reaction will not occur
Q.35 Which alkene on heating with alkaline KMnO4 solution gives acetone and a gas, which turns lime water
milky –
(A) 2–Methyl–2–butene (B) Isobutylene
(C) 1–Butene (D) 2–Butene

Q.36 H/
CO / H 2O
  P
P is
CHO COOH OH
(A) (B) (C) (D)

CHO
COOH
Q.37 Ethylene forms ethylene chlorohydrin by the action of –
(A) Dry HCl gas (B) Dry chlorine gas
(C) Solution of chlorine gas in water (D) Dilute hydrochloric acid
HYDROCARBONS
Q.38 Acetylene may be prepared using Kolbe’s electrolytic method employing –

(A) Pot. acetate (B) Pot. succinate (C) Pot. fumarate (D) None of these
Q.39 Mixture of one mole each of ethene and propyne on reaction with Na will form H2 gas at S.T.P. –
(A) 22.4 L (B) 11.2 L (C) 33.6 L (D) 44.8 L
Q.40 A mixture of CH4, C2H4 and C2H2 gaseous are passed through a Wolf bottle containing ammonical
cuprous chloride. The gas coming out is
(A) Methane (B) Acetylene
(C) Mixture of methane and ethylene (D) original mixture
Q.41 B  Lindlar Na / NH
  R–CC–R  3  A
A and B are geometrical isomers (R–CH=CH–R) –
(A) A is trans, B is cis (B) A and B both are cis
(C) A and B both are trans (D) A is cis, B is trans
BH THF
3
Q.42 B    CH3–CCH HgSO / H SO
 4 24  A
H O OH 
2 2,
A and B are –
O O
|| ||
(A ) CH 3CH 2 CHO, CH 3  C  CH 3 (B) CH 3  C  CH 3 CH 3CH 2CHO
(C) CH3CH2CHO (both) (D) CH 3  C  CH 3 (both)

||
O
Q.43 Which of the following reagents cannot be used to locate the position of triple bond in CH3–CC–CH3
(A) Br2/H2O (B) O3 (C) Cu2Cl2 (D) H/ KMnO4 , 
Q.44 In the presence of strong bases, triple bonds will migrate within carbon skeletons by the
(A) removal of protons (B) addition of protons
(C) removal and readdition of protons (D) addition and removal of protons.
Q.45 CH3–CH2–CCH CH3CC–CH3

A and B are –
(A) alcoholic KOH and NaNH2 (B) NaNH2 and alcoholic KOH
(C) NaNH2 and Lindlar (D) Lindlar and NaNH2
NH Cl
Q.46 CHCH  4 product
Cu 2Cl 2
Product is –
(A) Cu–CC–Cu (B) CH2=CH–CCH (C) CHC–Cu (D) Cu–CC–NH4
Q.47 PMA (Poly Methyl Acrylate) polymer is formed by methyl acrylate, which is prepared as follows –
CO  CH OH
(A) R – C  CH CO ROH
   3
(B) HC  CH    
Ni ( CO ) 4
2 CO  H O
(C) HC  CH      (D) None of these
Ni ( CO ) 4
HYDROCARBONS
Q.48 If octane number of gasoline sample is 70, then this sample will be similar to -
(A) 70% n-heptane + 30% n-octane (B) 70% n-octane + 30% n-heptane
(C) 70% isooctane + 30% n-heptane (D) 70% n-heptane + 30% isooctane
O
Q.49 Zn/Hg NBS alc. KOH HCl

Final Product is :
HCl
Cl Cl OH
Cl OH Cl
(A) (B) (C) (D)
Q.50 In which reaction major product is hydrocarbon?

(A) RCOOK Electrolys
 is
 (B) RCOOAg I
2 /

CH 3
Cl / hv
| C 2 H 5OH
(C) CH3–CH3 2 
 (D) CH 3  C  Cl  
|
CH 3
[MULTIPLE CORRECT CHOICE TYPE]
Q.51 Which of the following can be produced by Wurtz reaction in good yield.
(A) (B) (C) (D)
Q.52 Choose all alkane that give only one monochloro derivative upon reaction with chlorine in sun light.
(A) (B) (C) (D)
A
Q.53 Ph  C  CH 3  Ph–CH2–CH3
||
O
A could be:
(A) NH2NH2, glycol/OH– (B) Na(Hg)/conc. HCl
(C) Red P/HI (D) CH 2  CH 2 ; Raney Ni – H2
| |
SH SH
Q.54 Aqueous solution of potassium propanoate is electrolysed. Possible organic products are:
(A) n-Butane (B) C2H5COOC2H5 (C) CH3–CH3 (D) CH2=CH2
Q.55 An alkene on ozonolysis yields only ethanal. There is an isomer of this which on ozonolysis yields:
(A) propanone (B) ethanal (C) methanal (D) only propanal
HYDROCARBONS
H / Pt
Q.56 (A) C4H6 2  (B) C4H8 O
3 / H 2O
 CH3COOH
Hence A and B are
(A) CH3C  CCH3, CH3CH = CHCH3 (B) CH2 = CHCH = CH2, CH3CH = CHCH3
(C) , CH3CH = CHCH3 (D) None
Q.57 CH2 = CHCH2CH = CH2 NBS

 A, A can be
(A) CH 2  CH CH CH  CH 2 (B) CH2=CHCH=CH–CH2Br
|
Br
(C) CH2 = CH CH2 CH = CHBr (D) CH 2  CH CH 2 C  CH 2

|
Br
Q.58 Which of the following will give same product with HBr in presence or absence of peroxide.
(A) Cyclohexene (B) 1-methylcyclohexene
(C) 1,2-dimethylcyclohexene (D) 1-butene
Q.59 The ionic addition of HCl to which of the following compounds will produces a compound having Cl on
carbon next to terminal.
(A) CF3.(CH2)3.CH=CH2 (B) CH3.CH=CH2
(C) CF3.CH=CH2 (D) CH3.CH2CH=CH.CH3
Ph
H H
alc.KOH
Q.60 H Cl   Product(s), Possible products are
CH3
Ph
Ph CH3
(A) (B)
(C) Ph–CH2–CH = CH2 (D) Ph –HC = C = CH2
Q.61 Which is / are true statements/ reactions?

(A) Al4C3 + H2O  CH4 (B) CaC2 + H2O  C2H2

(C) Mg2C3 + H2O  CH3C CH (D) Me3C–H + KMnO4 H Me3C–OH
Q.62 Which reagent is the most useful for distinguishing compound I from the rest of the compounds
CH3CH2CCH CH3CCCH3 CH3CH2CH2CH3 CH3CH=CH2
I II III IV
(A) alk. KMnO4 (B) Br2/CCl4
(C) Br2/CH3COOH (D) Ammonical AgNO3
HYDROCARBONS
BH3 / THF HgSO

Q.63 C    A  4  B
H 2O 2 / OH  H 2SO 4
B & C are identical when A is –

(A) (B) (C) (D)
[MATCH THE COLUMN]
Q.64 Match List-I with List-II and select the correct answer using the codes given below the lists:
List-I (Reaction) List-II (Reagents)
(A) CH3–CH=CH2CH3–CHBr–CH3 (P) HBr
(B) CH3–CH=CH2CH3–CH2–CH2Br (Q) Br2
(C) CH3–CH=CH2BrCH2–CH=CH2 (R) HBr / Peroxide
(D) CH3–CH=CH2CH3–CHBr–CH2Br (S) NBS
Q.65 Match the column

Column I Column II
(A) RCOONa electrolys
 is
 R–R (P) Correy-House reaction
Soda lim e
(B) R–CH2–COOH   R–CH3 (Q) Kolbe electrolysis

( i ) AgNO
(C) RCOOH   3  R–Cl (R) Oakwood degradration
( ii ) Cl 2 / 
(D) R’–X + R2CuLi  R–R’ (S) Hunsdiecker reaction
Q.66 Column I Column II

( i ) BH / THF
(A) CH 3  C  CH 2  3  (P) CH3–CH2–CH=CH2
(ii ) H 2O 2 / OH
|
CH 3
2 (i ) Hg ( OAc) / HOH
(B) CH 3  C  CH 2      (Q) CH3–CH=CH–CH3
(ii ) NaBH4
|
CH 3
Cl
|
(C) CH 3  CH 2  CH  CH 3 CH ONa / 
3   (R) CH 3  CH  CH 2OH
|
CH 3
Cl OH
| ( CH 3 )3 CONa
|
(D) CH 3  CH 2  CH  CH 3     (S) CH 3  C  CH 3

|
CH 3
HYDROCARBONS
Q.67 Column I Column II

(A) CH3–CC– CH3  cis-2-butene (P) Na/NH3(l)
(B) CH 3  C  C  CH 3  trans-2-butene (Q) H2/Pd/BaSO4

(C) CH3CC–CH3 1-Butyne (R) alc. KOH, 
(D) CH3–CH3–CCH 2-Butyne (S) NaNH2 , 
Q.68 Column–I Column–II

C H3
|
(A) Ph  C  CH 2 Hg ( OAC) , H 2 O
  2—  (P) Cis
NaBH 4 ,OH
(B) (
i ) M -CPBA
  (Q) Trans
(ii ) H  / H 2O
( i ) B H  THF
(C) 2 6
   (R) Optically active
( ii ) H 2O 2 / OH —
Bayers
(D) Re
agent
 (S) Optically inactive
HYDROCARBONS
EXERCISE-3
SECTION-A
(JEE ADVANCED Previous Year's Questions)
Q.1 Alcoholic solution of KOH is a specific reagent for – [IIT ‘90]
(A) Dehydration (B) Dehydrogenation
(C) Dehydro halogenation (D) Dehalogenation
Q.2 Of the following, unsaturated hydrocarbons are – [IIT ‘90]

(A) ethyne (B) cyclohexane (C) n–propane (D) ethene
Q.3 1-chlorobutane on reaction with alcoholic potash gives – [IIT ‘91]

(A) 1–butene (B) 1–butanol (C) 2–butene (D) 2–butanol
Q.4 The hybridisation of carbon atoms in C–C single bond of HCC–CH=CH2 is – [IIT ‘91]
(A) sp3–sp3 (B) sp2–sp3 (C) sp–sp2 (D) sp2–sp2
Cl
|
Q.5 (CH 3 ) 2 C  CH 2 CH 3 alc
. KOH
 ? [IIT 1992]
alc. KOH
Q.6 C6 H 5CH 2 CHCH 3 heat ? HBr
 ? [IIT 1993]
|
Br
Q.7 C(C6H12), an optically active hydrocarbon which on catalytic hydrogenation gives an optically inactive
compound, C6H14. [IIT 1993]
Q.8 Draw the stereochemical structure of the product in the following reactions. [IIT 1994]
2 H
R–CC–R 
Lindlar catalyst
Q.9 Write down the structures of the stereoisomers formed when cis–2–butene is reacted with bromine.
[IIT 1995]
Q.10 An organic compound E(C5H8) on hydrogenation gives compound F(C5H12). Compound E on ozonolysis
gives formaldehyde and 2–ketopropanal. Deduce the structure of compound E. [IIT 1995]
Q.11 Give the structures of the major organic products from 3–ethyl–2–pentene under each of the following
reaction conditions. [IIT 1996]
(a) HBr in the presence of peroxide (b) Br2/H2O
(c) Hg(OAc)2/H2O; NaBH4
Q.12 An alkyl halide, (X) of formula C6H13Cl on treatment with potassium tertiary butoxide gives two isomeric
alkenes (Y) and (Z) (C6H12). Both alkenes on hydrogenation give 2, 3–dimethylbutane. Predict the
structures of (X), (Y) and (Z) [IIT 1996]
HYDROCARBONS
Q.13 3,3–Dimethylbutan–2–ol loses a molecule of water in the presence of concentrated sulphuric acid to
give tetramethylethylene as a major product. Suggest a suitable mechanism. [IIT 1996]
Q.14 One mole of the compound A (molecular formula C8H12), incapable of showing stereoisomerism, reacts
with only one mole of H2 on hydrogenation over Pd. A undergoes ozonolysis to give a symmetrical
diketone B (C8H12O2). What are the structure of A and B? [IIT 1997]
Q.15 Compound (A) C6H12 gives a positive test with bromine in carbon tetrachloride. Reaction of (A) with
alkaline KMnO4 yields only (B) which is the potassium salt of an acid. Write structure formulae and
IUPAC name of (A) and (B). [IIT 1997]
Q.16 The central carbon–carbon bond in 1,3–butadiene is shorter than that of n–butane. Why?
Q.17 Which of the following compounds will show geometrical isomerism? [IIT ‘98]
(A) 2–butene (B) Propene (C) 1–phenylpropene (D) 2–methyl–2–butene
Q.18 The reaction of CH3– CH=CH OH with HBr gives: [JEE 1998]
(A) CH3CHBrCH2 OH (B) CH3CH2CHBr OH
(C) CH3CHBrCH2 Br (D) CH3CH2CHBr Br
Q.19 Write the intermediate steps for each of the following reaction. [IIT 1998]

H
Q.20 Write the intermediate steps for each of the following reaction [IIT 1998]
C6H5CH(OH)CCH  C6H5CHCHCHO
Q.21 Give reasons for the following in one or two sentences. [JEE 1998]
"Acid catalysed dehydration of t-butanol is faster than that of n-butanol.
Q.22 Carry out the following transformation in not more than three steps. [IIT 1999]
O
||
CH3–CH2–CC–H  CH 3  CH 2  CH 2  C  CH 3
Q.23 Discuss the hybridisation of carbon atoms in allene (C3H4) and show the –orbital overlaps.
[IIT 1999]
Q.24 Complete the following – [IIT 1999]

1 2 3

 
 

HYDROCARBONS
Q.25 Complete the following – [IIT 1999]
4 5 6

 
 

Q.26 In the compound CH2=CH–CH2–CH2–CCH, the C2–C3 bond is of the type – [IIT ‘99]
(A) sp–sp2 (B) sp3–sp3 (C) sp–sp3 (D) sp2–sp3
Q.27 Explain briefly the formation on the products giving the structures of the intermediates. [IIT 1999]
(i) HCl
 + + etc.
But
(ii) HCl

Explain the non formation of cyclic product in (ii)
Q.28 What would be the major product in each of the following reactions? [IIT 2000]
CH 3
|
CH 3  C  CH 2 Br C 2 H 5OH 2

H
(i) |
  (ii) Lindlar's Catalyst

CH 3
Q.29 CH2=CH– is more basic than HCC– [IIT 2000]
Q.30 Propyne and propene can be distinguished by – [IIT ‘2000]

(A) conc. H2SO4 (B) Br2 in CCl4 (C) dil. KMnO4 (D) AgNO3 in ammonia
Q.31 Which one of the following alkenes will react fastest with H2 under catalytic hydrogenation condition –
[IIT ‘2000]
(A) (B) (C) (D)
Q.32 In the presence of peroxide, hydrogen chloride and hydrogen iodide do not give anti–Markovnikov
addition to alkene because – [IIT ‘2001]
(A) both are highly ionic
(B) one is oxidising and the other is reducing
(C) one of the step is endothermic in both the cases
(D) All the steps are exothermic in both cases
HYDROCARBONS
Q.33 The reaction of propene with HOCl proceeds via the addition of – [IIT ‘2001]
(A) H+ in first step (B) Cl+ in first step
(C) OH in first step
– (D) Cl+ and OH– in single step
Q.34
Hydrogenation of the above compound in the presence of poisoned paladium catalyst gives –
(A) An optically active compound (B) An optically inactive compound [IIT ‘2001]
(C) A racemic mixture (D) A diastereomeric mixture
Q.35 On reaction with 4N alcoholic KOH at 175 °C 1–pentyne is slowly converted into equilibrium mixture
of 1.3% 1–pentyne (A), 95.2% 2–pentyne (B) and 3.5% 1,2–pentadiene (C). Give the suitable
mechanism of formation of A, B and C with all intermediates. [IIT 2001]
Q.36 A biologically active compound, Bombykol (C16H30O) is obtained from a natural source. The structure
of the compound is determined by the following reactions.
(a) On hydrogenation, Bombykol gives a compound A, C16H34O, which reacts with acetic anhydride to
give an ester.
(b) Bombykol also reacts with acetic anhydride to give another ester, which on oxidative ozonolysis
(O3/H2O2) gives a mixture of butanoic acid, oxalic acid and 10-acetoxy decanoic acid.
Determine the number of double bonds in Bombykol. Write the structures of compound A and Bombykol.
How many geometrical isomers are possible for Bombykol? [IIT 2002]
Q.37 Identify X, Y and Z in the following synthetic scheme and write their structures. Is the compound Z
optically active? Justify your answer. [IIT 2002]
( i ) NaNH
H / Pd  BaSO
CH3CH2CC–H   2  X 2   4  Y alkaline KMnO
   4  Z
( ii ) CH 3CH 2Br
Q.38 Consider the following reactions – [IIT ‘2002]

H 3C  CH  CH  CH 3 + ‘X’ + HBr
| |
D CH 3
Identify the structure of the major product ‘X’
• •
(A) H 3C  CH  CH  C H 2 (B) H 3C  CH  C CH 3
| | | |
D CH 3 D CH 3
• •
(C) H 3C  C CH  CH 3 (D) H 3C  C H  CH  CH 3
| | |
D CH 3 CH 2
HYDROCARBONS
Q.39 The nodal plane in the –bond of ethene is located in – [IIT ‘2002]
(A) the molecular plane
(B) a plane parallel to the molecular plane
(C) a plane perpendicular to the molecular plane which contains the carbon–carbon –bond at right angle
(D) a plane perpendicular to the molecular plane which contains the carbon–carbon –bond
Q.40 Identify a reagent from the following list which can easily distinguish between 1–butyne and 2-butyne-
[IIT ‘2002]
(A) bromine, CCl4 (B) H2, Lindlar catalyst
(C) dilute H2SO4, HgSO4 (D) ammonical Cu2Cl2 solution
HgSO
Q.41 4  A
C6H5–CC–CH3   [IIT ‘2003]
H 2SO 4
(A) (B) (C) C6 H 5  C  CHCH 3 (D) C 6 H 5  CH  C  CH 3

| |
OH OH

Q.42 H x Br2
 H 2O ( mixture)  5 compounds of molecular formula C4H8Br2

Number of compounds in X will be: [IIT ‘2003]
(A) 2 (B) 3 (C) 4 (D) 5
Q.43 2–hexyne can be converted into trans–2–hexene by the action of : [IIT ‘2004]
(A) H2–Pd-BaSO4 (B) Li in liq. NH3 (C) H2–PtO2 (D) NaBH4
Q.44 Cyclohexene is best prepared from cyclohexanol by which of the following:

(A) conc. H3PO4 (B) conc. HCl/ZnCl2 (C) conc. HCl (D) conc. HBr
[IIT ‘2005]
Q.45 When Phenyl Magnesium Bromide reacts with tert. butanol, which of the following is formed?
(A) Tert. butyl methyl ether (B) Benzene
(C) Tert. butyl benzene (D) Phenol [IIT ‘2005]
Q.46 1–bromo–3–chlorocyclobutane when treated with two equivalents of Na, in the presence of ether which
of the following will be formed? [IIT ‘2005]
(A) (B) (C) (D)
Q.47 If after complete ozonolysis of one mole of monomer of natural polymer gives two moles of CH2O and
CH 3
|
one mole of O  C  CH  O . Identify the monomer and draw the all-cis structure of natural polymer..
[IIT 2005]
HYDROCARBONS
 (i ) O
3
Q.48 H ,
X    Y.
(ii) Zn / CH COOH
3
Identify X and Y. [IIT 2005]
Q.49 CH 3–CH=CH2 + NOCl  P [IIT 2006]

Identify the adduct.
CH 3  CH  CH 2 CH 3  CH  CH 2
(A) | | (B) | |
Cl NO NO Cl
NO
| CH 2  CH 2  CH 2
CH 3  CH 2  CH
(C) | (D) | |
NO Cl
Cl
Q.50 The number of stereoisomers obtained by bromination of trans-2-butene is [IIT 2007]
(A) 1 (B) 2 (C) 3 (D) 4
Q.51 The number of structural isomers for C6H14 is [IIT 2007]

(A) 3 (B) 4 (C) 5 (D) 6
Q.52 The reagent(s) for the following conversion, [IIT 2007]
?

 H H
is / are
(A) alcoholic KOH (B) alcoholic KOH followed by NaNH2
(C) aqueous KOH followed by NaNH2 (D) Zn / CH3OH
Q.53 In the following carbocation, H/ CH3 that is most likely to migrate to the positively charged carbon is
H H
1 2 + 4 5
H3C—C—C—C—CH3
3 [JEE 2009]
HO H CH3
(A) CH3 at C-4 (B) H at C-4
(C) CH3 at C-2 (D) H at C-2
Q.54 The synthesis of 3-octyne is achieved by adding a bromoalkane into a mixture of sodium amide and an
alkyne. The bromoalkane and alkyne respectively are [IIT 2010]
(A) BrCH2CH2CH2CH2CH3 and CH3CH2CCH
(B) BrCH2CH2CH3 and CH3CH2CH2CCH
(C) BrCH2CH2CH2CH2CH3 and CH3CCH
(D) BrCH2CH2CH2CH3 and CH3CH2CCH
HYDROCARBONS
Paragraph for Questions 55 to 56

An acyclic hydrocarbon P, having molecular formula C6H10, gave acetone as the only organic product
through the following sequence of reactions, in which Q is an intermediate organic compound.
Q.55 The structure of compound P is [IIT 2011]

(A) CH3CH2CH2CH2 – CC–H (B) H3CH2C – C  C– CH2CH3
(C) (D)
Q.56 The structure of the compound Q is [IIT 2011]
(A) (B)
OH
|
(C) (D) CH 3CH 2 CH 2 CHCH 2 CH 3
Q.57 The number of optically active products obtained from the complete ozonolysis of the given compound
is [JEE 2012]
CH3 H
CH3–CH=CH–C–CH=CH–C–CH=CH–CH3
H CH3
(A) 0 (B) 1 (C) 2 (D) 4
Q.58 In allene (C3H4), the type(s) of hybridisation of the carbon atoms is (are) [JEE 2012]
(A) sp and sp3 (B) sp and sp2 (C) only sp2 (D) sp2 and sp3
HYDROCARBONS
SECTION-B
(JEE Main Previous Year's Questions)
Q.1 The compound
H3C  C = CH– CH2 – CH3Vigorous

oxidation
 product, here product is [AIEEE-2002]
|
H3 C
(A) CH3COOH & CH3 – C – CH3 (B) CH3 – CH2 – COOH & CH3 – C  O
|| |
O CH3
(C) CH3 – CH2 – COOH only (D) HCOOH & CH3 – C – CH3
||
O
Q.2 Reaction
H – C  C – H + HOCl  product, here product will be - [AIEEE-2002]
(A) CHCl2 – CHO (B) CHO – CHO (C) CH – Cl = CHCl (D) CHCl2 – CHCl2
Q.3 Acetylene does not react with - [AIEEE-2002]

(A) NaNH2 (B) NaOH (C) Na metal (D) Ammonical AgNO3
Q.4 Butene-1 may be converted to butane by reaction with – [AIEEE-2003]

(A) Zn – Hg (B) Pd / H2 (C) Zn – HCl (D) Sn – HCl
Q.5 During dehydration of alcohols to alkenes by heating with conc. H2SO4 the initiation step is -
[AIEEE-2003]
(A) Elimination of water (B) Formation of an ester
(C) Protonation of alcohol molecule (D) Formation of carbocation
Q.6 On mixing a certain alkane with chlorine and irradiating it with ultraviolet light, it forms only one
monochloroalkane. This alkane could be – [AIEEE-2003]
(A) Isopentane (B) Neopentane (C) Propane (D) Pentane
Q.7 Which one of the following has the minimum boiling point ? [AIEEE-2004]
(A) n – Butane (B) 1– Butyne (C) 1– Butene (D) isobutane
Q.8 Amongst the following compounds, the optically active alkane having lowest molecular mass is-
[AIEEE-2004]
CH3
|
(A) CH3–CH2–CH2–CH3 (B) CH3  CH2  CH  CH3
(C) (D) CH3–CH2 – C  CH
HYDROCARBONS
Q.9 Reaction of one molecule of HBr with one molecule of 1,3–butadiene at 40ºC given predominantly
(A)1–bromo–2–butene under thermodynamically controlled conditions [AIEEE-2005]
(B) 3–bromobutene under kinetically controlled conditions
(C) 1–bromo–2–butene under kinetically controlled conditions
(D) 3–bromobutene under thermodynamically controlled conditions
Q.10 Acid catalyzed hydration of alkenes except ethene leads to the formation of – [AIEEE-2005]
(A) secondary or tertiary alcohol (B) primary alcohol
(C) mixture of secondary and tertiary alcohols (D) mixture of primary and secondary alcohols
Q.11 Reaction of trans 2-phenyl-1 bromocyclopentane on reaction with alcoholic KOH produces
(A) 2-phenylcyclopentene (B) 1-phenylcyclopentene [AIEEE 2006]
(C) 3-phenylcyclopentene (D) 4-phenylcyclopentene
Me

Me
Q.12 N
OH
n-Bu Et
The alkene formed as a major product in the above elimination reaction is [AIEEE 2006]
Me Me
(A) CH2 = CH2 (B) (C) (D) Me
Q.13 Which of the following reactions will yield 2, 2-dibromopropane? [AIEEE 2007]
(A) CH3 – C  CH + 2HBr  (B) CH3CH = CHBr + HBr 
(C) CH  CH + 2HBr  (D) CH3 – CH = CH2 + HBr 
Q.14 In the following sequence of reactions, the alkene affords the compound ‘B’
H 2O
CH3CH = CHCH3 O
3 A   B, The compound B is [AIEEE 2008]
Zn
(A) CH3COCH3 (B) CH3CH2COCH3
(C) CH3CHO (D) CH3CH2CHO
Q.15 The treatment of CH3MgX with CH3C  C – H produces [AIEEE 2008]

H H
(A) CH3C  C – CH3 (B) CH3 C C CH3
(C) CH4 (D) CH3–CH = CH2
Q.16 The hydrocarbon which can react with sodium in liquid ammonia is [AIEEE 2008]
(A) CH3CH2 C CH (B) CH3CH = CHCH3
(C) CH3CH2C  CCH2CH3 (D) CH3CH2CH2C  CCH2CH2CH3
HYDROCARBONS
Q.17 Out of the following, the alkene that exhibits optical isomerism is : [AIEEE 2010]
(A) 3-methyl-1-pentene (B) 2-methyl-2-pentene
(C) 3-methyl-2-pentene (D) 4-methyl-1-penten
Q.18 Which branched chain isomer of the hydrocarbon with molecular mass 72u gives only one isomer of
mono substituted alkyl halide? [AIEEE 2012]
(A) Isohexane (B) Neohexane
(C) Tertiary butyl chloride (D) Neopentane.
Q.19 2–Hexyne gives trans-2-Hexene on treatment with : [AIEEE 2012]

(A) Pd/BaSO4 (B) LiAlH4
(C) Pt/H2 (D) Li/NH3
Q.20 A gaseous hydrocarbon gives upon combustion 0.72 g of water and 3.08 g of CO2. The empirical
formula of the hydrocarbon is: [JEE Main 2013]
(A) C3H4 (B) C6H5 (C) C7H8 (D) C2H4
HYDROCARBONS
EXERCISE-4
SECTION-A
(CBSE Previous Year's Questions)
Q.1 Complete the following chemical equation: [CBSE 2008, 1]
CH3CH2CH = CH2 + HBr Peroxide
  ............
Q.2 Describe the following by giving a suitable example in each case: Decarboxylation[CBSE 2008, 1]
SECTION-B
(Potential Problems Based on CBSE)
Q.1 Describe the following giving a chemical equation: Markownikoff's rule.
Q.2 Write chemical equations and reaction conditions for the conversion of Propene to 1-bromo-propane.
Q.3 Complete the following reactions:

CH3–CH2–CH = CH2 + HCl 
Q.4 Write the product of the following reaction:

CH 2–CH=CH2
+ HBr Peroxide
  ........
Q.5 Identify the substances A and B in each of the following sequences reactions:
Br2
C2H5Br alc
.KOH
 A 
 B
Q.6 Complete the following reaction:

X
+ Na + RX Ether
Q.7 Identify A and B in each of the following sequences:

HBr
CH3 – CH = CH2  A aq
.KOH
 B

HYDROCARBONS
EXERCISE-5 (Rank Booster)
[SINGLE CORRECT CHOICE TYPE]
CH 3  C  NH 2
||
Q.1 Br Mg
 /
dry ether
 (X)     (Y) O
The structures of (X) and (Y) respectively are
(A) X = MgBr ; Y= OH
(B) X = ; Y=
(C) X = MgBr ; Y=
(D) X = BrMg MgBr ; Y = HO OH
Q.2 How many products will be formed excluding stereo when cis-1,3,5-trimethyl cyclohexene reacts with
NBS?
(A) 3 (B) 4 (C) 5 (D) 6
Q.3 alcoholic
  KOH  product

Major product is:
(A) (B) (C) (D)
Q.4 The addition of bromine to (3S)-3-Methyl Cyclohexene in 1,2-dichloroethane produces ____ dibromo
derivatives:
(A) 2 (B) 3 (C) 4 (D) 6
Q.5 How many 1,2-Shifts are involved during the course of following reaction:


(A) 1 (B) 2 (C) 3 (D) 4
Q.6 Which compound will yield 2-methyl-6-oxoheptanal upon treatment with ozone followed by Zn/H2O.
(A) (B) (C) (D)
HYDROCARBONS
H SO
Q.7 2 
4  X

X is
(A) (B) (C) (D)
Q.8 conc
 .H 2SO 4
 J (Major)

OH
J is
(A) (B) (C) (D) None of these
Q.9 Get the product P1 and P2 in the following reaction :

CH3
(i) BH3–THF
P1
(ii) H2O2/NaOH
D
CH3
dil H2SO4
P2
D
OH H H OH
CH3 CH3 CH3 CH3
(A) and (B) and
D D D D
H OH OH H
OH OH H H
CH3 CH3 H D
(C) D and H (D) H and OH
H D CH3 H
HYDROCARBONS
Br2 NaI
Q.10 

P(Alkene)   Q (Alkene)
 
CCl 4 Acetone
Alkene (P) & (Q) respectively are
(A) Both (B) ,
(C) Both (D) Both
A
Q.11 

A can be –
(A) Conc. H2SO4 (B) alcoholic KOH (C) Et3N (D) t-BuOK
18

(i ) CH COO OH
Q.12  3   X
(ii ) H3O
The probable structure of ‘X’ is
(A) (B) (C) (D)
Q.13 An organic compound of molecular formula C4H6, (A), forms precipitates with ammoniacal silver nitrate
and ammoniacal cuprous chloride. ‘A’ has an isomer ‘B’, one mol of which reacts with one mol of Br2 to
form 1, 4-dibromo-2-butene. Another isomer of A is ‘C’, one mole of C reacts with only 1 mol. of Br2
to give vicinal dibromide. A, B & C are
(A) CH3–CH2–CCH and CH2=CH–CH=CH2 ;
(B) CH3–CC–CH3 and CH3–CH=C=CH2 ; CH3–CC–CH3
CH 2  CH
(C) C=CH2 and | | | ; CH2 = CH–CH=CH2
CH 2  CH
(D) CH3–CC–CH3 and ; CH2 = CH–CH = CH2
Q.14 The reaction of cyclooctyne with HgSO4 in the presence of aq. H2SO4 gives
(A) (B) (C) (D)
HYDROCARBONS
Q.15 The product of reaction between one mole of acetylene and two mole of HCHO in the presence of
Cu2Cl2 –
(A) HOCH2 – C  C – CH2OH (B) H2C = CH – C  C – CH2OH
(C) HC C – CH2OH
 (D) None of these
OH OH
Q.16 P / HI
OHC OH  Product is :
OH OH
OH OH
(A) (B)
OHC
OH OH
(C) (D) OH
OHC
[MULTIPLE CORRECT CHOICE TYPE]

H / Ni
Q.17 M g2C3 D
 2O

1. BH3 .THf
   
Conc . H 3PO 4
 2      (S)
2. H 2O / O H
Product (s) are :

(A) H C  CH  CD 3 (B) H 2 C CH  CD 2
| |
D D
(C) H2C = CH–CD3 (D) H 2 C  C CH 3

|
D
Q.18 Which of the following reaction is/are not showing the correct major product ?
Na
(A) Br Cl Ether Cl Cl
Na
(B) CH3 – CH– Br Ether
CH3– CH2 – CH3 + CH3 –CH=CH2
CH3
Ag
(C) 

Cu
(D) 

HYDROCARBONS
Q.19 Select true statement(s):

(A) I2 does not react with ethane at room temperature even though I2 is more easily cleaved homolytically
than the other halogens.
(B) Regiochemical outcome of a free radical addition and an electrophilic addition reaction on propene
is identical.
(C) The rate of bromination of methane is decreased if HBr is added to the reaction mixture.
(D) Allylic chloride adds halogens faster than the corresponding vinylic chloride.
Q.20 W hich of the following elimination reactions will occur to give but-1-ene as the major product?
EtOH
(A ) CH 3.CHCl.CH2.CH3 + KOH 
(B) CH 3 .CH.CH 2 .CH 3  NaOEt EtOH

| 
NMe 3

(C) CH3.CH2.CHCl.CH3 + Me3CO¯K+  
(D) CH3.CH2.CH(OH).CH3 + conc. H2SO4 


—
Q.21 OH
The above compound undergoes elimination on heating to yield which of the following products?
(A) (B) (C) (D)
dil. H2SO4 (i) O3

Q.22 P1 (ii) Zn/H2O
P3
(gkbMªkscksjksuhdj.k vkWDlhdj.k)
P2
The realtionship among P1, P2 & P3 are:
(A) P1 and P2 are functional isomers
(B) P2 and P3 have one common functional group.
(C) P2 can also be obtained by reductive ozonolysis of 2-hexyne.
(D) P1 can also be obtained by ozonolysis of 2,3-dimethyl butene.
Q.23 Which of the following can be formed during this reaction?

H
3O

OH
OH
(A) (B) (C) (D)

OH O O
OH
HYDROCARBONS
Q.24 Ph–CH=CH2 + BrCCl3 peroxide

 
Product is:
(A) (B)
(C) (D)
[MATRIX TYPE]
Column I Column II
(A)  (P) Birch reduction
(B)  (Q)Stephen’s reduction
(C) Me – C  C – Me  (R) Wolf-Kishner reduction
(D)  (S) Clemmensen reduction
HYDROCARBONS
Q.26 Column–I Column–II


(A) HOBr
 / H
 (P) Racemic Mix.

(B) HOBr
 / H
 (Q) Meso
(C) Br / CCl (R) Diastereomer

2 4 
(D) Br / CCl (S) Enantiomer

2 4 

Column I (Reaction) Column II (Major Product)
D / D O
(A) 2
   (P)
3 1. BH .THF
(B)   
 (Q)
2. /D 2O 2 / O H
1. Hg(OCOCH ) .D O
(C)    32 
2
 (R)
2. NaBH 4 / O H
[SUBJECTIVE]
Q.28 (a) NaOH

 A. Write the structure of A.
Alc.

OH
(b)  B. Write the structure of major product A.

HYDROCARBONS
Q.29 (a) Write a reasonable and detailed mechanism for the following transformation.
conc
 . + H2O
H 2SO 4

(b) H/
HOH

Q.30 One of the constituent of turpentine is -pinene having molecular formula C10H16. The following scheme
give reaction of -pinene. Determine the structure of –pinene & of the reaction products A through E.
E(C10H18O2) A(C10H16Br2)
 H2O  Br2/CCl4
C10H16O(D)   –pinene Br
PhCO 3 H
 B (C10H17OBr)
2  H 2O
Q.31 Identify the following (A to D).
HYDROCARBONS
Q.32 Give the structure of A, B and C.

(a) A (C4H8) which adds on HBr in the presence and in the absence of peroxide to give the same product
C4H9Br.
(b) B (C4H8) which when treated with H2SO4 / H2O give (C4H10O) which cannot be resoslved into optical
isomers.
(c) C (C6H12), an optically active hydrocarbon on catalytic hydrogenation gives an optically inactive
compound C6H14.
Q.33 A hydrocarbon A, of the formula C8H10, on ozonolysis gives compound B (C4H6O2) only. The compound
B can also be obtained from the alkylbromide (C3H5Br) upon treatment with magnesium in dry ether,
followed by carbondioxide and acidification. Identify A, B and C and also give equations for the reactions.
Q.34 Compound A (C6H12) is treated with Br2 to form compound B (C6H12Br2). On treating B with alcoholic
KOH followed by NaNH2 the compound C (C6H10) is formed. C on treatment with H2/Pt forms
2-methylpentane. The compound ‘C’ does not react with ammonical Cu2Cl2 or AgNO3. When A is
treated with cold KMnO4 solution, a diol D is formed which gives two acids E and F when heated with
KMnO4 solution. Compound E is found to be ethanoic acid. Deduce the structures from A to F.
Q..35 What are A to K for the following reactions

ArCH 2 Cl
(i) PhC  CH + CH3MgX  A    B Li
/ NH 3
 C.
h
(ii)  E cold
PhCH2CH2CH3 + Br2  D alcoholic  dil. KMnO 4
  F hot
 KMnO 4
 G
KOH
(iii) H
  (iv) I 

(v) CF3 – CH = CH2 HBr

 J (vi) NBS
 K
HYDROCARBONS
EXERCISE-1
Q.2 n - pentane has larger surface area and hence stronger Vander waal’s forces.
Q.3 (a) II, (b) I

 
H –H2O –H
 H
Q.4
OH OH2
Q.5 (a) II, (b) I, (c) II
+
Q.6 OH O¯Na O
(A) (B) (C)
OH
MgBr CH3–(CH2)3–CH–(CH2)3–CH3
(D) (E) Br
(F) Br
(G)
Q.7 Free radical mechanism
Q.8
Q.9
A B C
D E F
HYDROCARBONS
Q.10
I I
I J
Q.11
B A C
Q.12
Br
A C
Br
B D
Q.13 Cl
X Y Z
Q.14
(A)
CH3 CH3
H D D H
Q.15 (a) (A) = , (B) = (b) +
DO H H OD
CH3 CH3
Q.16 A & B are two enatiomers ]
C
|
Q.17 (i) C–C–C–C=C, (ii) C  C  C  C  C  C , (iii) C  C  C  C , (iv) C–C=C–C–C=C,
| | |
C C C
(v)
Q.21 CHC–CH2–Cl
HYDROCARBONS
EXERCISE-2
Q.1 C Q.2 A Q.3 C Q.4 C Q.5 B Q.6 B Q.7 A
Q.8 B Q.9 C Q.10 D Q.11 C Q.12 D Q.13 B Q.14 D
Q.15 C Q.16 D Q.17 D Q.18 C Q.19 C Q.20 B Q.21 A
Q.22 C Q.23 C Q.24 A Q.25 B Q.26 A Q.27 D Q.28 B
Q.29 C Q.30 A Q.31 B Q.32 A Q.33 B Q.34 B Q.35 B
Q.36 B Q.37 C Q.38 C Q.39 B Q.40 C Q.41 A Q.42 B
Q.43 A Q.44 C Q.45 A Q.46 B Q.47 B Q.48 C Q.49 A
Q.50 A Q.51 BD Q.52 ABD Q.53 ABCD Q.54 ABCD Q.55 ABC Q.56 AB
Q.57 AB Q.58 AC Q.59 ABD Q.60 ABC Q.61 ABCD Q.62 D Q.63 AC
Q.64 (A) P (B) R (C) S (D) Q Q.65 (A) Q, (B) R, (C) S, (D) P
Q.66 (A) R (B) S (C) Q (D) P Q.67 (A) Q, (B) P (C) S (D) R
Q.68 (A) R (B) QS (C) S (D) PS
EXERCISE-3
SECTION-A
Q.1 C Q.2 AD Q.3 A Q.4 C Q.5 CH 3  C  CH  CH 3
|
CH 3
Q.6 alc
. KOH
 HBr

heat
H
|
Q.7 CH 3  CH 2  C  CH  CH 2
|
CH 3
(C6 H12 )
Q.8
Q.9
CH 2 CH 2
|| ||
Q.10 (E) CH 3  C  CH
Br OH
| |
Q.11 (a) (CH3–CH2)2 CH  CH  CH 3 ; (b) (CH3–CH2)2 C  CH  CH 3 ; (c) (C2H5)3C–OH
|
Br
HYDROCARBONS
CH 3 CH 3 CH 3 CH 3 CH 3 CH 3
| | | | | |
Q.12 CH 3  C  CH  CH 3 ; (Y) CH 2  C  CH  CH 3 ; (Z) CH 3  C  C  CH 3
|
Cl
C
C C | 
conc. H 2SO4
Q.13 C–C–C–C C–C–C–C CCCC
–H2O
 |
C OH + C OH2 C
H
1,2-methyl shift
 
C  C  C  C 
H
 C  C  C  C
| | | |
C C C C
Q.14 (A) (B)
Q.15 (A) CH3–CH2–CH=CH–CH2–CH3 (B) CH3CH2COOK

Q.16 Presence of partial double bond character due to resonance.
Q.17 AC Q.18 B
+ +
Q.19 H –H

H

3 H O
Q.20 C6H5CH(OH)CºCH  

OH 
C6H5CH=CHCHO C6H5CH=C= CH   C6H5CH=C= C H
|
OH
Q.21 Acid catalysed dehydration proceeds via carbocation intermediate. ALso, greater the stability of reactive
intermediate, faster the reaction:
CH 3 CH 3
| |
H
CH 3  C  OH   CH 3  C  CH 3
 H 2O 
|
3 highly stable
CH 3
t  butanol
n-butanol forms less stable (1°) carbocation.
Q.22 (1) NaNH2, (2) Me–I, (3) HgSO4 dil H2SO4
HYDROCARBONS
Q.23 H2C = C = CH2

P4 –P4
P3–P3
Q.24 1 ozonolysis ; 2 LiAlH4 ; 3 H2SO4

Q.25 (4)  HO–Cl ; (5)  CH3MgCl ; (6) H2O/H+
Q.26 D
  Cl
Q.27 (i) H   Cl
¯

OH  H 2O
 Cl¯ Stable by -resonance
Cl
 Cl ¯
(ii) H  

OH Cl
In this reaction intermediate is 2°-carbocation, which is more stable than 1°-carbocation in problem (i).
So it can not rearrange in cyclic cation.
CH3
|
Q.28 (i) CH3  C  CH  CH3 (ii)
Q.29 higher electronegativity of sp carbon

Q.30 D Q.31 A Q.32 C Q.33 B Q.34 B
alc.KOH
Q.35

H3C – CH2 – CH – C CH H3C – CH2 – CH – C CH
– H 2O
H
H 2O 
H3C – CH2 – CH = C  CH2 H3C – CH2 – CH = C CH
– H 2O alc.KOH
 
H3C – CH2 – C = C CH2 H3C – CH2 – C  C –CH2
H 2O
H3C – CH2 – C  C –CH3
HYDROCARBONS
Q.36 Bombykol :- HO–C–C–C–C–C–C–C–C–C–C=C–C=C–C–C–C

(A) :- 4 geometrical isomers are possible
Q.37 (X)  Et–CC–Et (Y)  (Z)  Z is meso so optically inactive
Q.38 B Q.39 A Q.40 D Q.41 A Q.42 B Q.43 B Q.44 A

Q.45 B Q.46 D
CH 3
|
Q.47 (a) CH 2  C  CH  CH 2 (b)
O
||
Q.48 (X) , (Y) CH 3  C  (CH 2 ) 4  CH  O
Q.49 A Q.50 A Q.51 C Q.52 B Q.53 D Q.54 D

Q.55 D Q.56 B Q.57 A Q.58 B
SECTION-B
Q.1 B Q.2 A Q.3 B Q.4 B Q.5 C Q.6 B Q.7 D
Q.8 C Q.9 A Q.10 C Q.11 C Q.12 A Q.13 A Q.14 C
Q.15 C Q.16 D Q.17 C Q.18 D Q.19 D Q.20 C
EXERCISE-4
SECTION-A
Q.1 CH 3CH 2CH  CH 2  HBr Peroxide
  CH 3CH 2CH 2CH 2 Br
But 1ene ( Anti  Mark addition ) 1 Bromobu tan e
Q.2 The process of removal of a molecule of CO2 from a carboxylic acid is called decarboxylation. It is
carried out by heating a carboxylic acid with soda-lime (NaOH + CaO) at 630 K
COOH
+ 2 NaOH CaO
 , 630 K

 + Na2CO3 + H2O
Benzoic acid Benzene
SECTION-B
Q.1 According to this rule, when addition across an unsymmetrical double bond takes place, the positive
part of the addendum goes to the carbon atom with the larger number of hydrogen atoms.
Br
|
Absence of
CH 3  CH  CH 2  HBr     CH 3  CH  CH 3
propene Peroxide 2  Bromopropa ne
Q.2 CH 3  CH  CH 2  HBr Peroxide

  CH 3CH 2 CH 2 Br
Pr opene 1 Bromopropa ne
HYDROCARBONS
Q.3 CH3–CH2–CH = CH2 + HCl  CH 3  CH 2  CH  CH 3

|
Cl
CH 2–CH=CH2 CH2–CH2–CH2–Br
Q.4 Peroxide
+ HBr  
Q.5 (A) CH2 = CH2

(B) CH 2  CH 2
| |
Br Br
X R
Ether
Q.6 + Na + RX  + NaX
Q.7 (A) CH 3  CH  CH 3 (B) CH 3  CH  CH 3

| |
Br OH
EXERCISE-5
Q.1 C Q.2 B Q.3 A Q.4 A Q.5 D Q.6 C Q.7 D
Q.8 C Q.9 B Q.10 C Q.11 A Q.12 A Q.13 A Q.14 D
Q.15 A Q.16 C Q.17 ABC Q.18 ABD Q.19 ACD Q.20 BC Q.21 BCD
Q.22 AB Q.23 ABD Q.24 AC Q.25 (A) S; (B) R; (C) P; (D) R,S
Q.26 (A) R (B) PR (C) PS (D)Q Q.27 (A) Q, (B) R, (C) P
H
D
D
Q.28 (a) (b)

D H NMe2
H
 
Q.29 (b) H  HOH
 / H
HYDROCARBONS
Br H
H Br
+ Br
Me
Q.30 Br Me
 - pinene

Br Br
H
Me
 OH C Me
OH
O OH
D Me
CC–CH3
Q.31
A B
COOH COOH
HOOC H
C D
Q.32 (a) CH3 –CH = CH –CH3 (A)

(b) (B)
H
(c) CH3–C –CH=CH3 (C)

CH3–CH3
CC COOH
Q.33
(A) (B)
HYDROCARBONS
Br
Q.34
Br
(A) (B)
OH
CC–CH3
OH
(C) (D)
CH3COOH COOH
(E) (F)
Ph  CH  Et
Q..35 (A) PhCCMgx, (B) Ph–CC–CH2Ar, (C) , (D) | ,
Br
(E) Ph–CH=CH–Me trans, (F) Ph  CH  CH  Me (threo mix.), (G) Ph–COOH

| |
OH OH
(H) cold dil. KMnO4, (I) HCO3H, (J) CF3CH2CH2Br, (K)
Bansal Quick Review Table
Instruction to fill
(A) Write down the Question Number you are unable to solve in column A below, by Pen.
(B) After discussing the Questions written in column A with faculties, strikes off them in the
manner so that you can see at the time of Revision also, to solve these questions again.
(C) Write down the Question Number you feel are important or good in the column B.
COLUMN : A COLUMN : B
EXERCISE NO. Question I am unable to Good / Important

solve in first attempt questions
Exercise # 1
Exercise # 2
Exercise # 3 (A)
Exercise # 3 (B)
Exercise # 4 (A)
Exercise # 4 (B)
Exercise # 5
Advantages
1. It is advised to the students that they should prepare a question bank for the revision as it is very difficult
to solve all the questions at the time of revision.
2. Using above index you can prepare and maintain the questions for your revision.

Nucleus OC Hydrocarbon E

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Nucleus OC Hydrocarbon E

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TA RG E T JEE

From aldehydes and ketones :

CH2 = CH – CH3 + H – BH2 CH2 – CH – CH3

CH3 – CH2–CH2 + H3BO3

From alkyne - by reduction :

If Ni is used, it is called Sabatier - Senderen’s reaction (catalytic hydrogenation).

From Alkyl halides :

NOTE : * This reaction is not suitable for tertiary alkyl halides

Mechanism : Two mechanism has been suggested for Wurt reaction.

Free radical mechanism

CH3 – CH2 + CH2 – CH3 CH3 – CH 2 – CH 2 – CH 3

R2 CuLi + 2 R—X 2 R—R + LiX + CuX

2RLi + CuX  R2 CuLi + Li X

R2 CuLi + 2R' – X  2R – R' + LiX + CuX

Zn+2 + 2CH3 (CH3)2 Zn

CH3 – Zn – CH3 + 2CH3 – Br  2 CH3 –CH3 + ZnBr2

(iv) R–COOH Re

2R  C  O ¯  2R – C – O + 2e¯

6. Alkanes are lighter than water, so it floats over water.

(ii) Chain-propagation step

4 Chlorosulphonation/ Reaction with SO2 & Cl2:

CH3-(CH2)5 –CH3 

n- heptane 2, 2, 3- trimethyl butane

CH3(CH2)6 CH3 

For converting aliphatic to aromatic.

o–Xylene Ethyl benzene

REACTION CHART FOR ALKANES

(2) R–X Zn

(8) R CR Zn

(10) RCOONa NaOH  CaO

(11) RCOONa Kolbe

(a) General formula : CnH2n.

METHODS OF PREPARATION OF ALKENES

Types of Elimination reactions

Some important terms

-Elimination can occur by three different mechanism

(a) It is called unimolecular elimination reaction.

(a) It is known as bimolecular elimination mechanism.

(a) In this mechanism, the reaction take place in two steps.

From mono halides

(ii) CH3 – CH2 – C H – CH3  

NOTE : CH3–CH2CHX–CH3  CH3–CH2–CH=CH2  CH3 – CH =CH – CH3

Mechanism : E2 and E1 are possible.

R–CH.X2 + 2 Zn – R –CH = CH– R

CH3 – CHCl2 + 2Zn   CH3–CH=CH–CH3

From vicinal dihalides :

CH3– CH = CH– CH3

Characteristics of dehydration of alcohol

Rearrangement in Alcohol Dehydration

Regioselectivity in alcohol dehydration :

Note – If we use methyl succinic acid as reactant then propylene is formed.

The reaction is called as ‘Pyrolysis of Ester’.

Major product is obtained by reamoval of –H from less hindered carbon.

From quaternary ammonium hydroxide

CH3– CH = CH– CH3 CH3 – CH2 – CH = CH2

The wittig reaction

The Cope Elimination :

(iii) B.P and M.P. decreases with increasing branches in alkene.

The main reactions of alkene are electrophilic addition reaction

CH3 CH3 Ni, 

Note : Hydrogenation (catalytic hydrogenation) of alkene is a cis addition and is an exothermic

Reduction of alkene via hydroboration

This reaction is also represented as