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 Hydrocarbons
HYDROCARBONS
Organic compounds composed of only carbon and hydrogen
Saturated Hydrocarbon (Al Kanes)
Represented by CnH2n + 2 (n = no of C-atoms)
Called paraffins (parum = little; affinis = affinity)
Bond angle is 109.5° or 109°28'
General methods of Preparation of Alkanes

1. Decarboxylation of carboxylic acids (Laboratory preparation)

An alkane is prepared by heating strongly the anhydrous sodium or potassium salt of a carboxylic acid with
sodalime (NaOH + CaO).

 R  H  Na 2CO3
R  COONa  NaOH 
CaO


 CH3CH3  Na 2CO3
CH 3CH 2COONa  NaOH 
CaO
Sodiumpropionate Ethane
Note :
(i) The alkane prepared contains one carbon atom less than that of the original acid.
(ii) CaO increases the porosity of the mixture and acts as a dehydrating agent and catalyst.
2. Sabatier-Senderen’s Reaction
Alkane may be obtained by the catalytic hydrogenation of alkenes or alkynes is presence Ni catalyst at 200°C –
300°C.
Ni
R  CH  CH 2  H 2  R  CH 2CH3
Alkene 
Alkane

Ni / 
CH3C  CH  2H 2  CH3CH 2CH3
Pr opyne Pr opane

Note :
(i) Platinum or Palladium or Raney nickel may also be used as catalyst at ordinary temperature.
(ii) Methane cannot be prepared by this method.

3. By the Reduction of Alkyl Halides :

Alkyl halides are directly reduced by either of the following reducing agent to form alkanes.
(a) Zn/Cu + (C2H5OH)
(b) Zn + HCl
(c) Zn + Acetic acid (CH3COOH)
(d) LiAlH4

[1]
 (e) Red phosphorous and hydrogen iodide
(f) H2 + nickel or palladium or platinum
Zn  Cu
RX  2H 
 RH  HX
Alkyl Ethanol
halide

4. Wurtz Reaction :
An ehterial solution of alkyl halide when treated with sodium metal forms alkane.
dry Ether
R  X  2Na  X  R 
 R  R  2NaBr


dry ether
H3C  Br  2Na  BrCH3  CH3CH 3  2NaBr

Methyl Bromide Ethane
Note :
(i) Wrutz Reaction is useful only for the preparation of symmetrical alkanes containing even number of carbon
atoms.
(ii) When a mixture of two different alkyl halides are used a mixture of three alkanes are
obtained.
(iii) Methane cannot be prepared.
(iv) This reaction fails with tertiary alkyl halides.
5. Clemmensen’s Reduction :
Carbonyl compounds like aldehydes and ketones are reduced by amalgamated zinc and conc. HCl to produce the
corresponding alkanes having the same number of carbon atoms.
R Zn-Hg + HCl
R
C =O CH2
R' R'
Zn  Hg  HCl
 CH3CH 2CH 3
CH3COCH3 
Acetone Pr opane

6. Wolf-Kishner Reduction :
Carbonyl compounds can be reduced to hydrocarbons in presence of excess of hydrazine or semicarbazide and
sodium alkoxide on heating.
R R EtONa
C =O C = N – NH2
R' R'
180°C
R
CH2
R' Alkane

7. Kolbe Reaction (Electrolytic Method) :

An alkane is prepared by the electrolysis of a concentrated aqueous solution of sodium or potassium salt of a
saturated monocarboxylic acid using platinum electrodes.
 Electrolysis
2RCOOK  2H 2O  R  R  2CO2  2KOH  H 2
144244 3 14243
Anode Solution Cathode

Electrolysis
2CH3COOK  2H 2O  CH3CH3  2CO 2  2KOH  H 2
Ehtane

8. Frank Land Method :

The alkyl halide is heated with zinc in inert solvent.
RX  Zn  XR 
 R  R  ZnX 2

C2 H5Br  Zn  BrC 2 H5 
 C 4H10  ZnBr2
Ethyl Butane
bromide

9. By the reduction of alcohols, aldehydes, Ketones and Carboxylic acids, by red phosophorus and HI

Re d P
R  OH  2HI 
 RH  I2  H 2O
Alcohol 150C Alkane

Re d P
 RCH3  2I 2  H 2O
R  CHO  4HI 
200C

Re d P
CH3COCH3  4HI 
 CH3CH 2CH3  2I 2  H 2O
250C

Re d P
R  COOH  6HI 
 R  CH3  3I2  2H 2O
250C

10. By the Decomposition of Grignard Reagents :

A Grignard reagent can be decomposed by active hydrogencontaining compound to produce alkane.
Ether
RMgX  HOH  R  H  Mg  OH  X
Alkane

Ether
RMgX  R   OH  R  H  Mg  OR   X
Zerewitnoff reaction

11. Corey-House Alkane Synthesis :

Symmetrical as well as unsymmetricalalkanes can be prepared by the action of alkyl halides with an etherial
solution oflithium dialkyl cuperate (LiR2Cu)
Ether
RX  2Li  2RLi  LiX

2RLi  CuI 
 LiR 2Cu  LiI
Lithium
dialkyl Cuprate

LiR 2Cu  R Br 

 R  R  R  Cu  LiBr
Alkane
Note : R ' should be mainly 1°.
 Examples :
Ether
CH3Br  2Li  CH3Li  LiBr

 Li  CH3 2 Cu  LiI
2CH 3Li  CuI 

Li  CH 3 2 Cu  C2 H5Br 
 C2H 5  CH3  CH3Cu  LiBr
Propane

12. Hydroboration of Alkenes :

Diborane (B2H6) reacts with alkenes to form trialkyl-boranes which on treatment with acetic acid or propionic
acid yields corresponding alkane.
B H
2 6  R  CH  CH 3 CH COOH
R  CH  CH 2   2 2 3 B  R  CH 2  CH3

13. By Cycloalkane :
Cycloalkanes can be reduced to alkanes by cleavage of C — C bond which minimises the strain.
H2-Ni
120°C propane
cyclopropane

H2-Ni
20°C
cyclobutane Butane

14. Hydrolysis of Metal Carbides :

H O
2  Al OH  CH
Al4C3   3 4

H O
2  Be OH  CH
Be 2C   2 4
N.B. :
This method is applied only for methane.

PROPERTIES

A. Physical Properties
First four members are gases, next 13 members are colourless liquids and rest are solids.
The alkanes are insoluble in water but soluble in organic solvents like ether, carbon tetrachloride, benzene etc.
The density and boiling points increase with the increase of molecular weights. The boiling points of isomeric
branched chain alkanes, are generally lower than those of straight chain alkanes.

B. Chemical Properties
Alkanes are generally stable and chemically inert.
The C — H and C — C bonds in alkanes are almost non-polar, attacking reagents find no reaction sites to
 which they could be attacked.
Under suitable conditions the alkanes undergo two types of reactions
(a) Free radical substitution Reaction
(b) Thermal; and Catalytic Reaction

(a) Substitution reaction

1. Halogenation :
In presence of diffused sunlight or in ultra violet light or at relatively high temperature (300°C – 500°C) the H-
atoms (1°, 2°, 3° H) of alkanes are replaced by equal number of halogen atoms yielding a mixture of halogenated
alkanes.
(i) Chlorination : (Free Radical Substitution)

UV  light
CH 4  Cl 2   CH3Cl  HCl
or 
Excess Chloromethane
 Methylchloride 

UV  light
CH3Cl  Cl2 
 CH 2Cl2  HCl
or 
Dichloromethane

UV  light
CH 2Cl2  Cl2 
 CHCl3  HCl
or 
Trichloromethane
 Chloroform 

UV  light
CHCl3  Cl2   CCl4  HCl
or 
Carbon tetrachloride
 Pyrene 
Note : Methyl Chloride is the major product if an excess of methane is used.
(ii) Bromination : Bromine reacts with alkanes in a similar manner but less vigorously.
(iii) Iodination : The reaction between iodine and alkane is reversible. Iodination can be done in the presence
of an oxidising agent such as HIO3 (or HNO3) which removes the hydroiodic acid (HI).

ˆˆ† CH3I  HI
CH 4  I 2 ‡ˆˆ

5HI  HIO3 
 3I2  3H 2O
(iv) Fluorination : Fluorine reacts with alkanes at ordinary temperature explosively. So fluorination can be done
by diluting fluorine with an inert gas or indirectly.

 2C2H5 F  HgBr2
2C2 H5Br  HgF2 
2. Nitration : A mixture of an alkane and nitric acid vapours is heated at 400°C – 500°C, one hydrogen atom of the
alkane is replaced by a nitro group. This reaction is also free radical substitution.

R  H  HO  NO2 
 R  NO2  H 2O
Nitric Acid Nitroalkane
 400C 500C
CH 4  HNO3  CH3  NO2  H 2O
 VapourphaseNitration  Nitromethane

N.B. : This temperature (400°C – 500°C) is sufficient to break C–H as well as C–C bond homolytically and thus
mixture of products are obtained.
400C 500C
CH3CH3  HONO2  CH3CH 2 NO2  CH3 NO2  H 2O
Nitroethane Nitromethane

3. Sulphonation : Sulphonation is carried out with fuming H2SO4.


R  H  HO  SO3H 
 R  SO3H  H 2O
Fuming AlkaneSulphonic
Acid

Note : R = C6H13 or larger alkyl group

4. Oxidation :
(i) Complete Combustion :
In the presence of excess oxygen alkane burn to form carbon dioxide water.

CH 4  2O 2  CO2  2H 2O  212.8 Kcal/mole


Methane

3n  1 Flame
Note: Cn H 2n  2  O 2   nCO 2   n  1 H 2O  Heat
2
 4CO2  6H 2O  745.6 Kcal/mole
2CH3CH3  7O2 
(ii) Incomplete Combustion :

2CH 4  3O 2 
 2CO  4H 2 O

CH 4  O 2 
 C  2H 2O
Carbon
black
(iii) Catalytic Oxidation :

Cu  tube
I.  2CH3OH
CH 4  O2 
200,100 atm.
Natural Methyl alcohol
gas
II. Alkane having 3° H on oxidation with KMnO4 gives 3°-alcohol.
CH3 CH3
| |
KMnO
4
CH3  C  H  CH3  C  OH
| |
CH3 CH3
tert  butylalcohol
III. Higher alkane on oxidation with manganese acetate gives carboxylic acids.
 CH3COO 
2
Mn
R  CH3  R  COOH
 Mo O
2 3  HCHO  H O
IV. CH 4  O 2  2
275C

5. Isomerisation : Normal alkanes are converted to their branched chain isomers in the presence of aluminium
chloride and HCl at 25°C.

CH3
|
3 AlCl
CH3  CH 2  CH 2  CH3  CH3  CH  CH3
HCl
Isobu tane
(2  Methylpropane)

6. Prolysis (Cracking) : Decomposition of higher alkane into amixture of lower alkanes, alkenes and hydrogen on
heating at high temperature in the absence of air.
500C
3CH3CH3 
 2CH 2  CH 2  2CH 4  H 2
Absence of air
Ethylene Methane

N.B. : In the presence of finely divided silica-alumina as catalyst, this reaction can be carried atless high
temperature. This is called catalytic cracking.

7. Aromatisation :

2 3 2 3 Cr O  Al O
CH 3CH 2CH 2CH 2CH 2CH 3   + 4H2
600C,10 atm

CH3
2 3  Pt  Al O
CH3CH 2CH 2CH 2CH 2CH 2CH3  + 4H2
600C,10atm

Ni on alu min a
8. CH  H O   CO  3H 2
4 2 1000C 14243
 Steam  synthesis gas

1500C
9. 2CH 4   2HC  CH  3H2
Acetylene

2 3 Al O  Cr O
2 3
CH3CH3   CH 2  CH 2  H 2 
10. 500C  600C
Ethylene

11. Reaction with Alkenes

CH3 CH3 H
| | |
CH 3  CH  CH 2  C  CH 3 
 CH 3  C  CH 2  C  CH 3
| | | |
CH3 CH3 CH3 CH3
Iso  oc tan e
Uses :
C1 to C4 alkanes are used as domestic fuels.
In the manufacture of fuels.
Gasoline (petrol) is a mixture of alkanes alkenes and aromatic hydrocarbons. The quality of gasoline is determined
by the amount of iso-octane (2, 2, 4-trimethyl pentane) present in it.
Methane is used in the manufacture of carbon black used in printer’s ink, black paints etc.

ALKENE
H – C – C or H – C – H bond angle in ethylene is 120°.

C = C bond distance in ethylene is 1.34 A
Alkenes are generally very active and due to the presence of pie-bond they exhibit addition reactions.
°
9A H
H 1 . 0
120° C °
C
H 1.34A H
Generally represented by the general formula CnH2n.

Preparation
1. By the dehydration of alcohols :
Conc.H SO
2 4  CH  CH  H O
CH3CH 2OH  2 2 2
160C 180C

Syrupy Phosphoric acid

CH2= CH2 + H2O
Al2O3
CH2 = CH2 + H2O
350°-400°C

Note :
(i) Here conc. H2SO4 acts as a dehyderating agent as well as catalyst.
(ii) The ease of dehydration of alcohols is
Tertiary alcohol > Secondary alcohol > Primary alcohol
Conc. H2SO4
OH 180°C
CH3CH = CHCH3
But-2-ene
CH3CH2CHCH3 (saytzeff's product major)
2-Butanol Conc. H2SO4
CH3CH2CH = CH2
180°C But-1-ene
(Minor)

Note : Saytzeff’s Rule :

During the dehydration of unsymmetrical alcohols the hydrogen atom is preferentially
eliminated from that carbon atom which contains lesser number of hydrogen atoms
(Dehydrohalogenation)

2. By the Removal of Hydrogen Halides from Alkyl Halides :

 Alc.KOH
R  CH 2CH 2 X 
 R  CH  CH 2  KX  H 2O
Alkyl halide

MECHANISM

H H
OH– R – C — C – Cl R– CH = CH2 + H2O + Cl–

H H
For unsymmetrical alkyl halide.

CH3CH = CHCH3
Major (saytzeff's product)
Alc. KOH
CH3CHBrCH2CH3
CH2 = CHCH2CH3
Minor

CH3
|
Note : If base taken in above reaction is highly hindered like CH3  C  O major product is
|
CH3

CH2 = CH – CH2 – CH3 and it is Hoffmann’s product.

Ease of reactivity is R – I > R – Br > R – Cl

3. By Kolbe’s Electrolytic Method : When concentrated aqueous solution sodium or potasium salt of vicinal
saturated dicarboxylic acid is electrolysed, the alkene and CO2 liberate at anode where as alkali and H2 at
cathode.
R  CHCOOK
| ˆˆ† R  CH  CH  R ' 2CO 2
‡ˆˆ
R ' CHCOOK
4. By the Partial Hydrogenation of Alkynes :

Pd  CaCO
3  R  CH  CH  R 
R  C  C  R   H 2 
Quinoline
or, Ni 2  B(P  2)

Note :
(i) Lindlar’s Catalyst : Finely divided palladium or platinum deactivated by poisons like BaSO4, CaCO3 or
quinoline. Partial reduction with Lindlar’s catalyst gives cis alkene
(ii) P-2 Catalyst = Nickel boride also gives cis-alkene.
(iii) Birch Reduction : Partial hydrogenation with Na and liquid NH3 produces trans alkene.

Na / Liq.NH
R H
3
R  C  C  R   H   C =C
H R
(iv) B2H6 followed by treatment with CH3COOH will give cis-alkene
4. By the dehalogenation of vicinal di-halides with Zn-dust in alcohol or NaI in acetone
Zn-dust
R – CH – CH – R' R – CH = CH – R' + ZnBr2
Alcohol,
Br Br
Nal/Acetone
R – CH = CH – R' + NaBr + IBr

7. By Dehydrogenation of Alkanes :

Cr O Al O
2 3 2 3  CH  CH  CH  CH  H
CH3  CH 2  CH 2  CH3  3 3 2
500C
n  Butane But  2 ene

Properties

At room temperature, C2  C4  Gases

C5  C13  Liquids

C13 Onwards  Solids

Gaseous alkenes are colourless and odourless. Only ethylene has a sweet smell.
All the alkenes are soluble in organic solvents like ether, benzene, etc.
The densities and boiling points increase with the increase of molecular weights. Their b.p. and m.p. are higher
than corresponding alkanes. Cis-isomer has a higher boiling point than trans-isomer due to higher polarity whereas
trans alkene has higher melting point than cis alkene.
Chemical :
Following types of reactions are given by alkenes
1. Addition Reaction (Electrophillic & radical addition)
2. Oxidation
3. Ozonolysis
4. Isomerisation
5. Substitution at   carbon
6. Polymerisation

1. Addition Reaction

(a) Addition of HX(HCl, HBr and HI)

Electrophilic addition reaction.
Product of formation takes place according to Markovnikov’s rule.
 I
|
CH 3  C  CH 2  HI 
 CH3  C  CH3
| |
CH3 CH3

Note : Monosubstituted and disubstituted alkenes whose   carbon is 4° give addition reaction through
rearrangement.

CH3 Br
| |
CH3  C  CH  CH 2  HBr 
 CH3  C  C H  CH3
| | |
CH3 CH3 CH3

Mechanism :

CH3 CH3
slow
CH3 – C – CH = CH2 + H+ CH3 – C – CH – CH3
..–
CH3 CH3 1,2-CH 3 shift
Br
– +
Br
CH3 – C – CH – CH3 CH3 – C – CH – CH3
CH3 CH3 CH3 CH3

Product according to Anit Markownikoff’s rule. (Free radical addition)

 C6 H5COO 
2  CH CH CH Br
CH 3CH  CH 2  HBr  3 2 2
Benzoyl peroxide

(b) Addition Reaction of Water : (Catalysed by acid) (Electrophillic addition)

OH
|
H SO
2 4  R  CH  CH
R  CH  CH 2  HOH  3
Mechanism is exactly same as that of previous reaction.

 O 
 || 
(c) Addition Reaction of Conc. H2SO4  H - O - S- O - H  (Electrophillic addition)
 || 
 O 

OSO3H
|
Conc.H SO
2 4  R  CH  CH
R  CH  CH 2  3
Alkyl hydrogen
Sulphate

OSO3 H OH
| |
R  CH  C H3  HOH 
 R  CH  CH3  H 2SO 4
 (d) Addition of Hydrogen (Hydrogenation) :
Ni, Pt or Pd
 R  CH 2CH3
R  CH  CH 2 
Heat, pressure
(e) Addition of Halogens : (Electrophillic addition)
4 CCl
R  CH  CH 2  Br2  CH 2Br  CH 2 Br
Brown  Inert
solvent 
Ethylene bromide
 colourless 
 Test for Unsaturation 
This reaction proceeds via cyclic intermediate that’s why their no chance of
rearrangement and it is anti addition.
(f) Addition of hypohalous acids :

 CH 2OHCH 2Cl
CH 2  CH 2  HOCl 
Ethylene Chlorohydrin
Follow electrophillic addition via cyclic intermediati as in previous reaction.
(g) Hydroboronation oxidation :

 2  CH3CH 2CH 2 3 B
6CH 3  CH  CH 2  B2 H6 

OH 
 CH3CH2CH2 3 B  3H2O2   3CH3CH 2CH 2CH 2OH  H 3BO3
Overall result of above reaction is anti Markonikoff addition of H2O with Syn Stereochemistry.
(h) Oxy-Mercuration demercuration :

3 2 2  CH COO  Hg / H O
 CH3 3 C  CH  CH2 
THF
  CH3 3 C  CH  CH 2  HgOOCCH3
|
3,3 Dimethylbut 1 ene
OH  NaBH 4 ,NaOH

 CH3 3 C  CH  CH3
|
OH
3,3 Dimethyl  2  bu tanol

Overall result of above reaction is Markonikoff’s addition of H2O without rearrangement chance and with
anti stereochemistry.

2. OXIDATION
(a) Addition of Oxygen :
+
1 Ag H2O/H
R – CH = CH2 + 2 O2 200°C-400°C
R – CH – CH2 R – CH – CH2
O OH OH
oxirane
(b) Reductive ozonolysis :
O
CCl4 Zn / H O
2 
 C  C  O3  > C C >   C  O  O  C 
Carbonyl
O O Compounds
Ozonide
 Note Zn-dust is added to prevent the oxidation of aldehyde into carboxylic group by H2O2

O
CCl 4
R – CH = C – R' + O3 R – CH C – R'
Zn + H2O
O O or
Zn + CH3COOH
or
(CH 3)2S

R – CHO + R'COR''
(c) Oxidative Ozonolysis :
O
||
1.O
3  CH  C  OH  CH  C CH
CH3  CH  C  CH3  3 3 3
| 2.H 2O
CH3

(d) Hydroxylation :
OH OH
| |
Hydroxyllating
R  CH  CH  R   R  CH  CH  R
agent
Hydroxylating agent
1. Cold dilute alkaline KMnO4
2. OsO4/H2O2
O
||
3. R  C O  OH / H3O
(e) Wacker Process :

O
2 | ||
2PdCl / HOH
CH3  CH 2  C H  C H 2 
 CH3  CH 2  C CH3
air / Cu 2Cl2

(f) Oxidation with hot basic KMnO4.

In this reaction = CH2 part gets oxidised to CO2 and H2O, = CHR part gets oxidised to
R
RCOOH and = CR2 part gets oxidised C=O
R

4 KMnO / OH / 
CH3  CH  CH  CH3 
 CH3COOH  CH3COOH
(g) Combustion :
3n
Cn H 2n  O2 
 nCO 2  nH 2O
2

C2 H 4  3O 2 
 2CO 2  2H 2 O
3.SUBSTITUTION AT α - CARBON
(a) Allyllic oxidation :

OH
|
SeO
2 CH  CH  CH
CH3  CH  CH 2  2 2
Allyl alcohol

OH
|
SeO
2 CH  CH  C  CH  CH
CH3  CH 2  CH  CH  CH 2  3 2 2
| |
CH3 CH3

(b) Allylic halogenation :

Br
|
NBS / CCl
4  CH  CH  CH
CH3  CH  CH 2  2 2
or X 2 / 
Allyl bromide

U ses
Ethylene is used in the preparation of polythene and also used in the manufacture of synthetic rubber, ethylene di
chloride and mustard gas.
Ethene is used for artificial ripening of fruits.
Ethene is used as a general anaesthetic.

ALKYNES
General formula – CnH2n–2
The C – H bonds are formed by the overlapping of sp hybrid orbital of one carbon atom and s-orbital of
180°
hydrogen atom H °
C °
C H
1.06A 1.2A

 
C  C distance is 1.20 A and C – H bond length is 1.08 A
H – C – C bond angle is 180°

General Methods of Preparation of Alkynes

1. By the reaction of calcikum carbide with water :
Room Temp.
C C  H  C   H  Ca  OH  2
2HOH 
Ca Acetylene
Calcium carbide
2. Dehydrohalogenation of Vicinal Dihalides
H Br
| |
(i) Alc.KOH / 
R  C  C  H  R  C  H  2HBr
| | (ii) NaNH 2 / 
Br H
 H Br
| |
NaNH / 
2  R  C  C  H  2HBr
R  C  C  H 
| |
Br H
3. Dehalogenation of Tetrahalides :
X X
| |
Alcohol
R  C C R  2Zn  R  C  C  R  2ZnX 2
| |  Alkyne
X X
Tetrahalide

4. Reaction of sodium acetylides with primary alkyl halides :

H  C  C  Na  CH3Br 
 CH3  C  CH  NaBr
5. Kolbe’s Method :
CHCOONa 2H 2O, Current
||   HC  CH  2CO2  2NaOH  H 2
CHCOONa
Sodium Salt of
maleic acid or
fumaric acid

6. By heating Iodoform with Silver

 CH  CH  6AgI
CHI3  6Ag  I3CH 

Properties
A. PHYSICAL
The first three members are gases. The next 8 members are liquids and the rests are solids.
Alkynes are slightly soluble in water but dissolves in organic solvents like acetone, benzen,
ethanol.
B. CHEMICAL
Alkynes give two types of chemical reaction
1. Reaction due to acidic hydrogen and
2. Reaction due to   bonds.
1. Reaction due to Acidic Hydrogen
NaNH 2 1
(a) R  C  C  H   R  C  C  Na   H 2
NH3  l  2
 (i) CO2(solid)
R–C C – COOH
(ii) H2O/H+

R – CH2 – X
R–C C – CH2 – R'
O
OH
(i) R' – C – R''
R–C CNa R–C C – C – R'
(ii) H2O/H+
R''
(i) CH2 – CH – R'
O
R–C C – CH2 – R'
(ii) H2O/H+
Cu2Cl2/NH4OH
R – C C – Cu
Red
AgNO3/N4OH
(b) R–C C–H R – C C – Ag
White ppt.

AuCl/N4OH
R – C C – Au
Golden ppt.

(c) Reaction with Grignard reagent and alkyl lithium :

CH3MgBr
R – C C – MgBr + CH4
R–C C–H
CH3-Li
R – C C – Li + CH4
Organolithium

2. Reaction due to π - bonds (Addition Reaction of Alkynes)

Alkynes generally gives electrophilic addition reaction and are less reactive than alkene for electrophilic
addition reaction due to following reason

R  CH  CH 2  H  
 R  C H  CH3
Alkene (I)
Alkyl carbocation


R  C  C  H  H  
 R  C  CH 2
(II)
Vinyl carbocation
less stable than (I)

They also give nucleophilic addition reactions with HOH, HCN, ROH, RCOOH etc.

I. Electrophilic Addition Reaction

(a) Addition of HOX :
 OH OH
| |
HO  X
R  C  C  H  HO  X 
 R  C  C H 
R  C CH  X
| | |
X OH X

 H2 O
O
||
R  C  CHX 2

(b) Addition of HX :
X
R X |
R  C  C  R  HX 
 C =C HX

 R  CH 2  C R
X R |
X
gem dihalide

Note : order of reactivity of HX is HI > HBr > HCl

(c) Addition of X2 (Cl2, Br2 and I2) :
X X
R X | |
4CCl X / CCl
2 4  R  C C R
R  C  C  R  X 2  C =C 
H R | |
X X

Note : The reactivity order of Halogen is Cl2 > Br2 > I2

II. Nucleophilic Addition Reaction

(a) Addition of water

O–H
HgSO / H SO
4 2 4
R  C  CH  HOH  R – C = CH2

Tautomerism

O
R – C = CH3

(b) Addition of HCN :

CN
Ba  CN  |
2  R  C  CH
R  C  C  H  HCN 
Pr essure 2

O
||
(c) Addition of CH3  C OH :
3. Other Reactions :
I. Oxidation of Alkynes
(a) Baeyer’s Test :

4 KMnO / OH / HOH

R  C  C  R 
 R  C C  R
Cold & dil || ||
O O
(b) Oxiation by SeO2 :
SeO
2 R  C C  R
R  C  C  R 
|| ||
O O

KMnO4 / OH /  
(c) R  C  C  R   R  COOH  R COOH

4 KMnO / OH  / 
CH 3  C  C  H 
 CH 3COOH HCOOH
 O
CO2  H 2O

II. Coupling Reaction (linear polymerisation)

Cu Cl
2 2  H C  CH  C  CH
H  C  C  H  H  C  C  H  2NH 4Cl
Vinylaccetylene
III. Isomerisation
alc.KOH
(a) CH 3  C  C  CH3  CH3  CH 2  C  CH
 NaNH 2

CH3  CH 2  C C N a

IV. Oxidative ozonolysis

O –– O
O3 H2O
R–C C – R' R – C — C – R' R – C – C – R'
O O O
H2O2
R – COOH + R'COOH

 i  O3
e.g. CH 3C  C  H   CH 3COOH   HCOOH 
 ii  H O2 Acetic Acid Formic Acid
 O
CO 2  H 2 O

V. Reductive ozonolysis
O –– O
O3 H2O + Zn
R – C = C – R' R – C — C – R' R – C – C – R'
O O O
 O –– O
O3 Zn + H2O
CH3 – C CH CH3 – C — CH CH3 – COCHO
Propyne Methyl glyoxal
O

Uses :
(a) It is used for the production of oxy-acetylene flame, which is employed for cutting a n d
welding of metals. it provides the temperature above 300°C.
(b) Acetylene on electrical decompositionproduces finely divided carbon and hydrogen.
Hydrogen is used in air ships. C2 H 2  2C  H2
(c) It is used for the preparation of Westron and Westrosol (solvents).
CH CHCl 2 CHCl
Alc.KOH
 |
|||  Cl2  
 ||
 HCl
CH CHCl 2 CCl 2
 Western   Westrosol

AROMATIC HYDROCARBON

Methods of Preparation :
1. Hydrofroming or Catalytic reforming :

2 3 2 3 Cr O  Al O , 500C
CH 3CH 2CH 2CH 2CH 2CH3  
10  20 atm
n  Hexane
 H2  Cyclohexane Benzene

2. High Temperature Cracking :

Metal Oxide -2H2

H 2C  CH  CH  CH 2  CH 2  CH 2 
600C  700C
Cyclohexane Benzene

3. Laboratory Method :
COONa

CaO
+ NaOH heat + Na2CO3
Sod. Benzoate

4. From Chlorobenzene :
Cl

Ni-Al alloy
+ 2[H] NaOH + HCl
Chlorobenzene

5. From Benzenediazonium Chloride :

 N2Cl

+ H3PO2
Benzene diazomium chloride

6. From Phenol :
OH

Zn-dust
+ H3PO2 red P + HI

Phenol Benzen

CHEMICAL PROPERTIES
A. Electrophilic Aromatic Substitution -
1. Nitration
NO2
Conc. HNO3 + Conc. H2SO4

( Electrophile NO ) 2
+
Nitrobenzene
2. Sulphonation
SO3H
Fuming H2SO4

Benzene-sulphonic Acid

ˆˆ† SO3  H3O   HSO4

2H 2SO 4 ‡ˆˆ
Electrophile
3. Friedal Craft’s Reaction

CH3
CH 3Cl
Anhy.AlCl3
+ HCl
Toluene
COCH3
CH 3COCl(Acetyl Chloride)
+ HCl
Acetophenone

COC6H5
CH 6COCl(Benzoyl Chloride)
+ HCl
Benzophenone

COCl COOH

COCl2 H 2O
Anhy. AlCl3 Boil

Benzoyl Chloride Benzoic Acid

 4. Halogneation :
Cl

FeCl3
+ Cl2
Chlorobenzene

 FeCl4  Cl
FeCl3  Cl2 
Electrophile

B. Addition Reaction
1. Addition of Hydrogen :

Ni
+ 3H2 150°, Pressure

Benzene Chlorohexane
2. Addition of Halogens :
Cl
Cl Cl
UV
+ 3Cl2 Light
Cl Cl
Benzene
Cl
Benzene hexachloride
(BHC)

3. Oxidation Reaction :
(a) Ozonolysis :
O H
O C H
3O3 Zn + H 2O
H–C O C O 3 CHO

H–C–O O C O CHO
H
O C
O H
(b) Vapour Phase Oxiation :
O

V2O5 CH — C
+ 9O2 450°C
O + 4H2O + 4CO2
CH — C
Benzene
O
Maleic anhydride
 OH

1 V2O5
(c) + 2 O2 350°C

Phenol

Other Reaction
1. Gattermann Koch Aldehyde Synthesis :
CHO
AlCl3
+ CO + HCl
Benzaldehyde

2. Gattermann Aldehyde Synthesis :

CH = NH CHO

ZnCl2 H2O
+ HCN + HCl Boil
+ NH3
Aryl imine Benzaldehyde

H H
(i) Na/NH 3 (l)
(ii) C2H5OH
3.
H H
1,4-cyclohexadiene

Uses of Benzene :
It is used as a solvent for oils and fats.
As synthethic liquid by mixing with petrol.
For the manufacture of toluene, nitrobenzene, acetophenone, etc.

TOLUENE OR METHYL BENZENE

PREPARATION :
1. From Benzene
CH3

AlCl3
+ CH3I

2. Wurtz Fittig Reaction

Br CH3

dyr
+ 2Na + CH3Br ether
+ 2NaBr
3. Aromatisation Reaction
CH3
2 3 2 3  Al O / Cr O
CH 3CH 2CH 2CH 2CH 2CH 2CH 3  
500C, High pressure
n  heptane

4. From Grignard Reagent

MgI CH3
dyr
+ CH3I reflux
+ MgI2

Phenyl magneisum
iodide

CH2MgCl CH3

dil.HCl
+ MgCI2

Benzyl magneisum chloride

5. From Tolueic Acid

CH3 CH3

CaO
+ NaOH + Na2CO3

Toluene
COONa
Sodium Salt of
para toluic acid

Properties
Toluene gives three types of Reaction
(a) Side Chain Reaction (b) Nuclear Chain Reaction
(c) Reduction Reaction
A. Side Chain Reaction
1. Chlorination
 CH3 CH2Cl CHCl2 CCl3
Cl2/hv Cl 2/hv Cl 2/hv

Benzyl Chloride Benzal Chloride Benzo Trichloride

Ca(OH2) Ca(OH 2) Ca(OH2)

CH2OH CHO COOH

Benzyl alcohol Benzyl dehyde Benzoic acid

2. Side Chain Oxidation

CH3 COOH
–
KMnO 4/OH /
(a)
Benzoic acid

OCOCH3 OH
CH3 CH CH
OCOCH3 OH
(b) (CH 3CO) 2O HOH/H
+

CH3COOH

–H2O
OCrCl2OH OH
CH CH CHO
OCrCl2OH OH
+
CrO 2Cl 2 H2O/H
Etard's Reaction –H2O

Benzaldehyde

CH3 CH2OH

SeO2
(c)
Benzylalcohol

B. Reduction :
1. Total Reduction
CH3

H 2/Ni/

2. Birch Reduction :
 CH3 CH3 CH3

(i) Na/NH3(l)
(ii) C 2H5OH
+
Major Minor

C. Nuclear Chain Reaction :

1. Nitration :
CH3 CH3 CH3
NO2
HNO3/
+

o-nitrotoluene
NO2
p-nitrotoluene

CH3 CH3
O2N NO2
Conc.HNO3/Conc H2SO4

TNT
NO2
2. Reaction with Halogen :
CH3 CH3 CH3
Cl
Cl2/Fe
Low temp., Dark
+

Cl
3. Friedal Craft’s Reaction :
CH3 CH3 CH3
CH3
Anhy.AlCl3
+ CH3Cl +
o-xylene
CH3
p-xylene

4. Sulphonation :
CH3 CH3 CH3
SO3H
Conc. H2SO4/
+

SO3H
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