1 ACTIVE SITE EDUTECH-9844532971

HYDROCARBONS
INTRODUCTION
Hydrocarbons are organic compounds containing carbon and hydrogen only. As fuels, hydrocarbons
play a key role in our daily life.
The following are the familiar examples of fuels:
- LPG (liquefied petroleum gas), CNG (compressed natural gas) and LNG (liquefied natural gas)
obtained by liquefaction of natural gas.
- Petrol, diesel, and kerosene oil are obtained by the fractional distillation of petroleum found
under the earth’s crust.
- Coal gas is obtained by the destructive distillation of coal. Natural gas is found in upper strata
during drilling of oil wells. The gas after compression is known as CNG.
- LPG is used as a domestic fuel with the least pollution.
- Kerosene oil is also used as a domestic fuel but it causes some pollution.
- Hydrocarbons are also used for the manufacture of polymers like polythene, poly-propene,
polystyrene, etc. Higher hydrocarbons are used as solvents for paints.
- Hydrocarbons are also used as the starting materials for manufacture of many dyes and drugs.

CLASSIFICATION- On the basis of carbon skeleton, hydrocarbons are divided into two main classes:

Hydrocarbon

Open Chain Closed Chain or Cyclic

Open Chain or acyclic

Alicyclic
Saturated Unsaturated Aromatic
(Cyclo propane,
(Alkanes) (Alkenes & Alkynes) (Arenes)
cyclobutane etc.)

ALKANES
These are the hydrocarbons in which Carbon - Carbon contains single bond. (Saturated hydrocarbon).
• These are also called as ‘Paraffins’ (Parum + Affinis i.e. less reactive).
• In alkane if chiral carbon or unsymmetrical carbon is present, then it shows optical isomerism.
• General reagents such as dil. and conc. HCl, dil. and conc.H2SO4, dil. and conc. HNO3, acidic
and basic KMnO4 and K2Cr2O7 usually does not react with alkane.
• General formula is CnH2n+2 .(n = 1, 2, 3, 4..............)
• Hybridisation state of carbon is sp3.
• Geometry of carbon is tetrahedral.

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109.50 C 1.10Å
H
H

H
• Bond angle is 109º28’.
• Number of bond angle in methane are six, while in ethane are twelve.
H H H
H 4

3 1 2
1 6 5 5
2 3 6
2
H 1 3
4 5 4
H 6 H H H H
Methane Ethane

• C–C bond length is 1.54 Å while C–H bond length is 1.12 Å.

• C–C bond energy is 84 kcal/ mole while C–H bond energy is 98 kcal /mole.
• Alkane shows only chain, position isomerism.
• The molecules of alkanes are angular , so carbon chains in these molecules are zig- zag type
(not straight) which may be branched or unbranched as shown below.

(Unbranched) (branched)

• Isomerism - All the alkanes can be derived formally from methane by substituting hydrogen
atoms by methyl groups (CH3):
−H+CH3
CH3 − H → CH3 − CH3 or C2 H6
−H+CH3
CH3 − CH2 − H → CH3 − CH2 − CH3 or C3 H8
The next molecules will be C4H10 C5H12, etc. when the alkane contains three or more carbon atoms
substitution gives rise to isomerism. For example, propane, C3H8, can give rise to two butanes, C4H10
: n – butane (butane) by substitution at a terminal carbon atom or primary carbon atom, and isobutane
(2 – methyl propane) by substitution at the central carbon atom or secondary carbon atom.
H H H
| | |
H − C− C− C− H
| | |
H H H
0 ) -H
-H
(1 3 Propane +C (2 0)
H H3
+C

CH3− CH2 − CH2− CH3 CH - CH - CH

n-Butane 3 3
|
CH
3
iso-Butane
Similarly, substitution of H-atoms of butanes by -CH3 groups gives to three types of pentanes:
CH3 (CH2 )3 CH3 (CH3 )2 CHCH2 CH3 (CH3 )4 C
Pentane 2 – Methylbutane 2,2 – Dimethylpropane
• Note- As the number of carbon atoms in the alkane increases, the number of possible isomers
increases rapidly, e.g., the alkane C15H32 can exist in 4,347 isomeric forms.
First three members methane, ethane and propane does not exhibit any isomerism, while
butane, pentane and high members shows only chain isomerism.
CH4 CH3–CH3 CH3–CH2–CH3

Methane Ethane Propane

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CH3–CH2–CH2–CH3 CH3–CH –CH3

|
CH3
n-Butane Isobutane
CH3
|
CH3–CH2–CH2–CH2–CH3 CH3–CH –CH2–CH3 CH3–C–CH3
| |
CH3 CH3
n-Pentane Iso-Pentane Neo-Pentane
CH3
CH3–CH2–CH2–CH2–CH2–CH3 CH3–CH2–CH–CH2–CH3 CH3–C–CH2–CH3
CH3 CH3

n-Hexane 3-Methyl pentane Neo-hexane

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

Iso-hexane 2, 3-Dimethyl butane

Exp 1: Write structures of different isomeric alkyl groups corresponding to the molecular formula
C5H11. Also give IUPAC names of alcohols obtained by attachment of −OH groups to these alkyl
groups.
Solution: Remove all possible different H atoms from three isomeric pentanes, and attach −OH
groups to the carbons.
Alkyl groups derived from n-pentane and corresponding alcohols:
CH3CH2CH2CH2CH2 −− → CH3CH2CH2CH2CH2 − OH
Pentan–1–ol
CH3CH2CH2CH3 → CH3CH2CH2 CHCH3 → CH3CH2CH2 CHCH3
| |
OH
Pentan–2–ol
CH3CH2CHCH2CH3 → CH3CH2CHCH2CH3
| |
OH
Pentan–3–ol
Alkyl groups derived from isopentane and corresponding alcohols:
Alkyl group derived from neopentane and corresponding alcohol:
CH3 CH3 CH3
| | |
CH3 −C− CH3 ⎯⎯→ CH3 −C − CH2 − CH2−→ CH3 −C − CH2− OH
| | |
CH3 CH3 CH3

2, 2−Dimethylpropan-1-ol
If it is important to write the correct IUPAC name for a given structure, it is equally important to write
the correct structure from the given IUPAC name. Following steps should be noted as illustrated for
3−ethyl−2, 2–dimethylpentane.
Step 1 Write the longest continuous chain of carbon atoms corresponding to the parent alkane:
C C C C C
1 2 3 4 5
Step 2 Number the parent chain C C C C C

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CH3 C2H5
Step 3 Attach the substituents to the correct carbon atoms | |
C − C −− C − C − C
|
CH3
Step 4 Satisfy the valence of each carbon atom by putting the correct number of hydrogen
CH3 C2H5
atoms. CH | |
3 −C− CH − CH2 − CH3
|
CH3
CH3 CH 3
| |
CH3− CH − CH 2−CH 2− → CH 3− CH−CH 2−CH 2−OH
3 – Methylbutan –1–ol
CH 3 CH 3
| |
CH3 − CH− C H−CH 3 → CH 3− CH −CH−CH 3
| |
OH
3 – Methylbutan –2–ol
CH3CHCH 2CH 3
|
CH3

CH 3 CH 3
| |
CH3− C− CH 2−CH 3 → CH 3− C− CH 2−CH 3
| |
OH
2 – Methylbutan – 2–ol
CH 3 CH 3
| |
−CH 2 − CH − CH 2 − CH 3 → HO − CH 2 − CH − CH 2 − CH 3

2–Methyl butan−1−ol

Exp 2: Draw the structure of 3−isopropyl−2−methylhexane. This is the reverse of previous example
and employs a reverse strategy. First draw the carbon skeleton corresponding to the parent name
(hexane) and the identify then substituents and attach them.
Solution: Draw the skeleton of the parent compound (hexane): C − C − C − C − C − C
Hexane
Now place the substituents (3− isopropyl and 2−methyl) on the proper carbons:
CH3CHCH 3
C
1
C
2
C
3
C
4
C
5
C
6
Finally add hydrogen to complex the structure:
CH3
CH3CHCH 3

CH3CHCHCH 2CH2CH3
CH3

Exp 3: Write the correct IUPAC names of the following:

a) 3 – Ethylpentane b) 5 – Ethyl – 3- methylheptane
Solution: a) CH3− CH −CH2CH2CH3
|
C2H5
Notice that the longest continuous carbon chain is of six carbon atoms (not that of five). Thus, correct
name is 3 – methylhexane.
b) CH3 − CH2− CH − CH2− CH− CH2− CH3
| |
CH3 C2H5

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Ethyl group takes precedence over methyl group alphabetically. Thus, numbering is to be started from
the end which gives lower number to ethyl group. Hence, correct name is 3–ethyl – 5 –
methylheptane.

PREPARATION OF ALKANES

1. CATALYTIC REDUCTION OF ALKENE OR ALKYNE

(SABATIER-SENDEREN’S REDUCTION)
Reduction occur in presence of Ni or Pt or Pd also but at low temperature  150oC (even at 250oC).
Ni
Cn H2n + H2 → Cn H2n+2
Alkene heat Alkane
Ni
Cn H2n−2 + 2H2 → Cn H2n+2
Alkyne heat Alkane
Examples:
H H
| |
> C = C < + H 2 ⎯⎯→ > C C <
Ni
200−300 C
o

H H
| |
-C  C – + 2H 2 ⎯⎯→
Ni
-C-C-
200−300 C
o
| |
H H
H2 ,Ni
CH3 CH = CH2 → CH3 CH2 CH3
Propene Propane
2H2 ,Ni
CH3 − C ≡ C − CH3 → CH3 CH2 CH2 CH3
But−2−yne n–Butane
• Homogeneously Chloro-tris(triphenylphosphine)rhodium(I) in benzene solvent is used as
homogeneous catalyst.
P.T.R. : The catalyst RhCl [P(C6 H5 )3 ]3 is known as Wilkinson’s catalyst.
CH 2 CH 3
H 2 (1 atm )
⎯⎯ ⎯ ⎯
⎯→
H RhCl[ P (C6H5 )3 ]3 H
benzene ( 250o C)
Vinylcyclop rop ane ethylcyclop rop ane (85%)

It is a specific catalyst because selective reduction may take place in this case. Least
substituted portion readily hydrogenated, but the bulky portion is not hydrogenated by this
bulky catalyst.
CH3 CH3 CH3 CH3
| | | |
CH3 – C = CH CH2 CH2 – C – CH = CH2 ⎯Same⎯⎯→ CH3 – C = CH – CH2 – CH2 – C – CH2CH3
Catalyst as
| written above |
OH OH

3, 7-dimethyl – 1,6- octadien – 3 – ol 3, 7 – dimethyl – 6 – octen – 3 - ol

Note –
1. Methane is not prepared by this method
2. Both alkene and hydrogen adsorbed on the surface of the catalyst. This weakens the pi-bond of
alkene and sigma bond of hydrogen favouring the formation of products.

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3. This is an example of heterogeneous catalysis involving syn-addition.

The stereospecificity of the reaction is that the addition of hydrogen to the double bond
occurs in syn fashion without disturbing the configuration at the chiral carbon. The mechanism
of this reaction will be dealt in the topic “alkenes”.

For example,
The addition of both the deuterium atom occurs from the same side. In some molecules, the
attack is from the bottom side and in other molecules. D2 attacks from the top side leading to the
formation of two isomers called diastereomers.
2. FROM ALKYL-HALIDES
reduction R H
Alkane
R X
coupling R R'
Alkane
Alkyl halide
a) Reduction of alkyl halides
It simply involves the replacement of a halogen atom by a hydrogen atom, the carbon skeleton
remains unchanged. It can be done directly or indirectly via the Grignard reagent.
Direct reduction of alkyl halides may be done in different ways:
i) Reduction by metals dissolved in suitable solvents
1. Zinc and hydrochloric acid (dilute)
2. Zinc and acetic acid
3. Zinc and sodium hydroxide
4. Zinc – copper couple and ethanol

Zn,H+
CH3 CH2 CH2 Cl → CH3 CH2 CH3
n – Propyl chloride Propane
Zn,H+
CH3 CH2 CHCH3 ⎯⎯⎯⎯⎯ → CH3 CH2CH2CH3
|
Br
Sec – Buty lbromide n-Butane

ii) Reduction by hydride transfer reagents

Alkyl halide/Reagent Lithium aluminium Sodium borohydride Triphenyl tin
hydride (LiAlH4) (NaBH4) hydride Ph3SnH
RCH2X, primary alkyl halide ✓  ✓
R2CHX, secondary alkyl halide ✓ ✓ ✓
R3CX, tertian alkyl halide  ✓ ✓

iii) Catalytic hydrogenolysis(Reduction) It involves the addition of dihydrogen gas to sigma bonds in
the presence of a suitable catalyst.

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Primary, secondary and tertiary alkyl halides (iodides, bromides and chlorides) are converted into the
corresponding alkanes by catalytic hydrogenolysis. The best available catalyst is Pd–C, but Raney Ni
is also effective provided it is used in large amounts.
Pd−C
R − X + H − H→ R − H + HX
Examples
Pd − C
CH3 − CH− CH3 + H2 ⎯⎯⎯⎯⎯ → CH3CH2CH3 + HCl
|
Cl
Isopropyl chloride Propane
Br H
| |
Pd − C
CH3 − C − CH3 + H2 ⎯⎯⎯⎯⎯ → CH3 − C− CH3 + HBr
| |
CH3 CH3
tert – Butyl bromide Isobutane

iv) Reduction with concentrated hydriodic acid Iodides may be reduced into the corresponding
alkanes by heating with concentrated hydriodic acid at 1500C.

R − I + HI ⎯⎯→ R − H + I2
Examples:
CH3 CH3
| |
CH3 − C − CH2 − I + HI → CH3 − C − CH3 − I2
| |
CH3 CH3
Neopentyl iodide Neopentane
CH3 CH3
| |
CH3 − CH − CH2 − I + HI → CH3 − CH − CH3 + I2
Reduction with conc. HI is usually carried out in the presence of a small amount of red phosphorus
which regenerates the hydriodic acid from the iodine formed.
PI3 + H2 O → HI + I2 + P → PI3
The hydriodic acid – red phosphorus mixture is one of the most powerful reducing agents used in
organic chemistry.

Indirect reduction of alkyl halides is done via the

V) Grignard reagents.- A solution of an alkyl halide in dry ethyl ether, (C2H5)2O, reacts vigorously with
the turnings of metallic magnesium to form a solution of Grignard reagent represented as RMgX (or
ArMgX), and the general name alkyl magnesium halide (or aryl magnesium halide). It is a typical ionic
compound.
dryether
R − X + Mg → RMgX
Alkyl halide Grignard reagent
dryether
Examples: CH3 − Br + Mg → CH3 MgBr
dryether
CH3 CH2 − I + Mg → CH3 CH2 MgBr
The alkyl group remains unchanged during the preparation of the reagent. Thus n-propyl iodide gives
n-propylmagnesium iodide:
dryether
CH3 CH2 CH2 − I + Mg → CH3 CH2 CH2 MgI
n –Propyl iodide n – Propylmagnesium iodide
Grignard reagents, on treatment with compounds more acidic than an alkane, are decomposed to
alkanes:

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R − MgX + H − Z → R − H + Mg(OH)X
Stronger Weaker
acid acid
Examples
 H − OH   
   
 water   
 H − NH   Mg ( OH) X 
2
 
 ammonia   
 H − OR  → R − H +  Mg (NH2 ) X 
R−MgX +  alcohol   
 O   Mg ( OR ) X 
 ||   
 H −OCR  Mg ( OCOR ) X 
 Carboxylic acid   
For the preparation of an alkane, one acid is as good as another, so we naturally select water as the
most available and convenient.
dryether H2 O
R − X + Mg → R − MgX → R−H

b) Coupling of alkyl halides

It can be done either through the Wurtz reaction or by the Corey-House synthesis.
i) Wurtz reaction:
It involves coupling of alkyl groups when a solution of an alkyl halide (preferably the bromide or
idodide) in dry ether (free from moisture and alcohol) is treated with sodium metal:
dryether
R − X + 2Na + X − R′ → R − R′ + 2NaX
R, R are alkyl groups which may or may not be the same. The equation given above
clearly shows that in addition to the desired alkane R – R, there will also be formed, the alkanes R –
R, and R - R. Besides, unsaturated hydrocarbons are also formed.
dryether
Examples CH3 I + 2Na + ICH3 → CH3 − CH3 + 2NaBr
dryether
CH3 CH2 I + 2Na + ICH2 CH3 → CH3 CH2 CH2 CH3 + 2NaBr
Though sodium is extensively used in the Wurtz reaction, other metals such as Ag, Cu may also be
used in a finely divided state.
Limitation: The best yield of an alkane will be obtained when R and R are the same, i.e., when the
alkane contains an even number of carbon atoms and is symmetrical. Experimentally, it is found that
the Wurtz reaction gives good yields only for even carbon alkanes of high molecular mass
Application: Wurtz reaction is used to ascend the homologous series through the preparation of
higher alkanes containing even number of carbon atoms.

Note-
1. This reaction is used to increase the number of carbon atoms in a molecule.
2. Tertiary alkyl halides do not undergo Wurtz reaction.
3. Here the alkane formed will have double the number of carbon atomsthan in alkyl group.
Hence alkane containing even number of carbon atoms onlycan be prepared by this method.
4. If alkane with odd number of carbon atoms to be prepared mixture of alkyl halides should
be taken.

ii) Corey – House synthesis- It involves coupling of alkyl halides with organometallic compounds. For
this purpose, an alkyl lithium, RLi, is prepared from an alkyl halide, RX, in much the same way as a
Grigard reagent:
R − X + 2Li → R − Li + LiX

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Alkyl lithium
To it is added cuprous halide, CuX, leading to the formation of a lithium dialkylcopper, R2CuLi:
R
|
2R − Li + CuX → R − CuLi + LiX
Lithium dialkylcopper
Finally, is added the second alkyl halide, RX. Coupling takes place in the reaction between a lithium
dialkylcopper, R2CuLi, and an alkyl halide, RX (R stands for an alkyl group that may be same as, or
different from R):
R
|
R − CuLi + R′ − X → R − R′ + RCu + LiX
Alkane
For good yields, the alkyl group R in the organometallic may be primary, secondary, or tertiary but RX
should be a primary alkyl halide:
R
Li CuX | R′ X
R− X→ R − Li → R − CuLi → R − R′
may be Alkyllithium Lithium should
10, 20, 30 dialkyl copper be 10

Examples:
CH2CH3

CH3CH2 I CH 3CH2 Li CuI CH CH CuLi

3 2
CH3CH2 CH 2CH2CH3
CH3CH2CH2 I n pentane
CH3
Li
CH3 I CH3 Li CuI CH3 CuLi
CH3(CH2)5CH2I
n-Heptyl iodide

CH3(CH2)6CH3
n - Octane

iii) FRANKLAND’S REACTION :

Alkyl halide when heated with Zn metal and dry ether gives alkane.
dry ether
2R − X + Zn → R − R + ZnX 2
Δ
NOTE: The Wurtz & Frankland reactions are mainly used for the preparation of alkane
containing even no. of carbon atoms.

3) From saturated monocarboxylic acids

Reduction
R CH 3

O
Decorboxylation
R C OH R H

Coupling
R R'

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i) Reduction of carboxylic acids - Heating saturated monocarboxylic acids with HI–red

phosphorus under pressure, or with H2 gas under pressure at elevated temperature in the
presence of a Ni catalyst, produces an alkane:
O
|| redP
R − C − OH + 6HI → R − CH3 + 2H2 O + 3I2
Δ
O
|| Ni
R − C − OH + 3H2 → RCH3 + 2H2 O
Δ
HI,redP
Examples CH3 CO2 H → CH3 − CH3
Δ
Acetic acid ethane
H2 /Ni
CH3 CH2 CO2 H → CH3 CH2 CH3
Δ
Propionic acid Propane

ii) Decarboxylation
When the anhydrous sodium salt of a saturated monocarboxylic acid is heated with sodalime
[NaOH+CaO], an alkane containing one carbon atom less than the acid and other products are formed:
CaO(s)Δ
RCOONa(s) + NaOH(s) → R − H + Na2 CO3
CaOΔ
Examples: CH3 COONa + NaOH → CH4 + Na2 CO3
CaOΔ
CH3 CH2 COONa + NaOH → CH3 CH3 + Na2 CO3
This process of eliminating carbon dioxide from the carboxyl group of a carboxylic acid is known as
decarboxylation.

Limitations Only sodium acetate decomposes according to the equation given above. In rest of the
cases tested ⎯ propionate, butyrate and caproate various products are obtained. For example:
CaOΔ
CH3 CH2 COONa + NaOH → C2 H6 + CH4 + H2 + unsaturated compounds
Sodium propionate (43%) (21%) (32%)
This is therefore not a useful general method for the preparation of alkanes, since the
separation of the products is usually difficult.

iii) Coupling through Kolbe’s electrolytic method:

It involves the electrolysis of concentrated aq., solution of sodium or potassium salt of a saturated
monocarboxylic acid or mixture of saturated monocarboxylic acids:
RCOO− Na+ (aq) + R′ COO− Na(aq) + 2H2 O →H2 + 2NaOH(cathode) +R − R′ + 2CO2 (anode)
electrolysis
Example:2CH3 COO− Na+ (aq) + 2H2 O → CH3 − CH3 + 2CO2 + H2 + 2NaOH
At anode At
cathode
If R and R are different, then hydrocarbons R–R and R−R are also obtained, such mixtures can often
be separated readily. The by-products are alkenes, alcohols (in alkaline medium) and esters.
The Kolbe electrolytic method has application in the synthesis of natural compounds, particularly
lipids.
Mechanism: The reaction follows the free – radical path:
O
diasociation ||
RCOO− Na+ (aq) → R − C − O− (aq) + Na+ (aq)
At anode: The carboxylate ion discharges at the anode to form a free radical.
O O
R C R C e
O O

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The carboxylate free radical then breaks up into the alkyl free radical and carbon dioxide:
O
R C R + CO 2
O
Finally two alkyl free radicals couple together to form a higher alkane:

R +R R R
At cathode: Water has higher reduction potential than sodium, thus, water undergoes reduction to
form the dihydrogen gas:
2H2 O + 2e− → H2 (g) + 2OH − (aq)
The presence of Na+(aq) and OH−(aq) leads to the formation of NaOH (aq).
Limitation: Methane can’t be prepared by this method.
Extension: Kolbe’s electrolytic method can be extended to make alkenes as well as alkynes:
• Conc. aqueous solution of sodium or electrolysis
→ Alkene
potassium salt of a saturated dicarboxylic acid
Example:
+
CH2COO Na CH2
+
(aq) electrolysis
CH2COO Na CH2
Sodium succinate Ethene
• Concentrated aqueous solution of sodium or
potassium salt of an unsaturated dicarboxylic electrolysis Alkyne
⎯⎯⎯⎯⎯⎯⎯ →
acid
Example:
+
CHCOO Na CH
+
(aq) electrolysis
CHCOO Na CH
Sodium maleate Ethyne
or fumarate

4) From carbonyl compounds

Aldehydes and ketones may be reduced to corresponding alkanes:
RCHO RCH 3
C O CH2 Aldehyde

The following methods are employed:

i) By heating with concentrated hydriodic acid in the presence of a small amount of red phosphorus.
HI/PΔ HI/PΔ
CH3 CHO → CH3 CH3 CH3 COCH3 → CH3 CH2 CH3
Acetaldehyde Ethane Acetone Propane
ii) (Clemmensen reduction): With amalgamated zinc and concentrated hydrochloric acid
H+ ,e− H+ ,e−
CH3 CH2 CHO → CH3 CH2 CH3 CH3 COCH2 CH3 → CH3 CH2 CH2 CH3
Propanal Propane Butanone Butane
H+ comes from hydrochloric acid and e− is provided by zinc.The Clemmensen reduction does not work
well for aldehydes but is reasonably good for many ketones.

iii) [Wolff-Kishner reduction]:Heating hydrazones (or semicarbazones) of aldehydes and ketones with
sodium ethoxide at 1800C

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NH2NH2 NaOC 2H5

C O C NNH 2 CH2 + N 2
H2 O 
1. NH2NH2
Example: CH3 CHO ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ ⎯
→ CH3 CH3
2. Na+ O−C2H5 , 
Acetaldehyde Ethane
Yield of hydrocarbon is more than that obtained by the Clemmensen reduction.

5) From monohydric alcohols- 1*, 2*,3* monohydric alcohols may be reduced into the corresponding
alkanes by heating with concentrated HI in the presence of a small amount of Red P:
HI
PΔ
R − CH2 − OH → R − CH2 − H or RCH3
HI/PΔ
R 2 CHOH → R 2 − CH − H or RCH2 R
HI/PΔ
R 3 COH → R 3 C − H or R − CH − R
|
R
HI/PΔ
Examples: CH3 CH2 OH → CH3 CH3
Ethyl alcohol Ethane
HI/ P
CH3CHCH3 ⎯⎯⎯⎯ → CH3 CH2CH3
| 
OH
Isopropyl alcohol Propane
CH3
|
HI/ P
CH3 − C− OH ⎯⎯⎯⎯ → CH3 − CH − CH3
|  |
CH3 CH3
tert−Butyl alcohol Isobutane

Physical properties of the alkanes

1. Physical states: Due to the weak van der Waals forces, the first four normal alkanes (C1 to C4)
are colourless and odourless gases, the next thirteen normal alkanes (C5 to C17) are colourless
and odourless liquids, and from C18 onwards, colourless and odourless solids at 298K and 1
atm pressure.
2. Boiling points: The boiling points of the normal (unbranched) alkanes show a regular (steady)
increase with increasing molecular mass. Except for the very small alkanes (C1 to C4), the
boiling point rises 20 to 30 degrees for each carbon that is added to the chain.
3. Melting points: The normal alkanes do not exhibit the same smooth increase in melting points
with increasing molecular mass that they show in their boiling points. There is an alternation
as one moves from a normal alkane with an even number of carbon atoms to the next one
with an odd number of carbon atoms. For example, n –propane (mp – 1870C) melts lower
than ethane (mp – 1720C) and also lower than methane (mp – 1830C). n – Butane (mp – 1380C)
melts 490C higher than propane but only 80C lower than pentane (mp – 1300C). Hence there
is a saw-tooth pattern. If, however, the even-and odd-numbered alkanes are plotted on
separate curves, there is a smooth increase in melting point with increasing molecular mass.
4. Effect of branching on boiling and melting points: In a group of isomeric alkanes, the normal
compound always has the highest b.p. and m.p. Generally, the greater the branching, the
lower is the b.p. Thus n-butane has a boiling point of 00C and isobutane −120C. n−Pentane
has a boiling point of 360C, isopentane with a single branch 280C, and neopentane with two
branches 9.50C. Similarly n-hexane boils at 68.70C, and 2-methyl pentane and 3-

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methylpentane, each having one branch, boil lower at 60.3 and 63.30C, respectively. 2, 3–
Dimethylbutane and 2, 2−dimethylbutane each with two branches boil lower, at 58 and
49.70C, respectively.
The effect of chain branching on the melting points of alkanes is not easy to
predict. However, the chain-branching producing highly symmetrical structures results in
abnormally high melting points. For example, the compound 2, 2, 3, 3 – tetramethylbutane
(mp 100.70C) melts 43.70C higher than n-octane (mp − 570C) but boils 200C lower than it.
5. Solubility: Alkanes are almost completely insoluble in water. Liquid alkanes are soluble in one
another and they generally dissolve in non-polar solvents and solvents of low polarity.
Examples of good solvents for alkanes are benzene, carbon tetrachloride, chloroform and
ether. The solubility diminishes with increase in molecular mass.
6. Density: As a class, the alkanes are the least dense of all groups of organic compounds. The
density also increases with molecular mass of the alkanes, but tends to level off at about 0.79
g mL−1. Thus all alkanes are considerably less dense than water (1.00 g mL−1, the density of
water at 40C). As a result, petroleum (a mixture of hydrocarbons) floats on water.

General chemical properties of the alkanes

The alkanes are also called as paraffins. This name was suggested because alkanes were apparently
very unreactive. But reactivity depends upon the choice reagent. Under ‘ordinary’ conditions, the
alkanes are inert toward reagents such as acids, alkalis, oxidizing reagents, reducing reagents, etc., but
are reactive if the right conditions are used.
1) Substitution reactions
Alkanes mainly undergo substitution reactions in which one or more hydrogen atoms of
alkanes are replaced by suitable atoms or groups of atoms. These substitution reactions
proceed through free-radical chain reactions, which take place under vigorous conditions and
usually yield mixtures of products.
a) Halogenation It involves substitution of hydrogen of an alkane by a halogen. It takes place
either at higher temperature (250 − 4000C, thermal halogenation) or in the presence of
diffused sunlight (photohalogenation).
Relative Order of reactivity of halogens X 2 : F2 >> Cl2 > Br2 >> I2
250−4000 Corlight
R − H + X2 → R−X+H−X
Alkane a mixture of
alkyl halides
U−V light Cl2 Cl2 Cl2
Examples: CH4 + Cl2 → CH3 Cl → CH2 Cl2 → CHCl3 → CCl4
−HCl −HCl −HCl −HCl
Mechanism
• Chain–initiating step It involves homolysis of X−X bond
heatorlight
X − X→ 2X ∗
In this step energy is absorbed and a reactive particle called free radical is created.
• Chain propagating steps Many chain-propagating steps are there, each of which consumes a
reactive particle and generates another; here they involve the reaction of halogen atom with
an alkane, say methane (step 2) and of alkyl free radical, say methyl radical, with halogen (step
3).
X ∗ + H − CH3 → H − X+∗ CH3
H3 C ∗ + X − X → H3 C − X + X ∗
Then (2), (3), (2), (3), etc., until finally a chain is terminated.
The propagation steps (2) and (3) are those which directly give principal products but many other
propagation steps are possible. Two such steps given below explain how more highly halogenated
products are formed:

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X ∗ + H − CH2 X → X ⋯ H ⋯ CH2 X → H − X+∗ CH2 X

XCH ∗ 2 + X − X → XCH2 ⋯ X ⋯ X → CH2 X2 + X ∗
• Chain terminating steps – Here reactive particles are consumed but not generated. The
termination of the chain reaction may take place by adsorption of the halogen atoms on the
walls of the containing vessel, or by two halogen atoms combining with each other to form a
halogen molecule. Another termination is the combination of ∗CH3 with X ∗ or with ∗CH3 :
X ∗ + M∗ → M − X or
∗
CH3 + X ∗ → H3 C − X or
∗ ∗
CH3 + CH3 → CH3 − CH3
Under given set of conditions, about 10,000 molecules of methyl halide are formed for every quantum
of light absorbed. Each quantum cleaves one halogen molecule to form two halogen atoms, each of
which starts a chain. On the average, each chain consists of 5000 repetitions of the chain−propagating
cycle before it is finally stopped.
If we restrict the reaction to monohalogenation then,
Cl2 hυ
CH3 CH3 → CH3 CH2 Cl
Ethane Ethyl chloride
Br
Br2 |
CH3CH2CH3 ⎯⎯⎯ → CH3CH2CH2Br + CH3CHCH3
h
Propane 1−Bromopropane 2-Chloropropane
(n−propyl bromide) (Isopropyl bromide)
Br
Br2 |
CH3CH2CH2CH3 ⎯⎯⎯ → CH3CH2CH2CH2Br CH3CH2CHCH3
h
n−Butane 1-Bromobutane 2-Bromobutane
(n-Butyl bromide) (sec−Butyl bromide)
Note-
• The extent of halogenation depends largely on the amount of halogen used. A mixture of all
possible isomeric mono and polyhalides is obtained, but the isomers are not formed in equal
amounts, due to the difference of the reactivity of hydrogen atoms of alkanes.
• Reaction with fluorine is so violent that it needs to be controlled by diluting it with an inert
gas, and by using an apparatus designed to carry away the heat produced.
• Chlorination and bromination are not so vigorous.
• On the other hand, reaction with iodine is so slow that practically there is no reaction.
Moreover iodination is reversible:
R − H + I2 ⇌ R − I + HI
Thus, it needs to be carried out in the presence of an oxidizing agent, such as HNO3, HIO3 or HgO,
which oxidizes the hydrogen iodide (reducing agent) as soon as it is formed and thus drives the
reaction to the right:
5HI + HIO3 → 3I2 + 3H2 O
• The order of ease of substitution of H atom of alkane : 30 H > 20 H > 10 H > H − CH3
Chlorination of isobutane at 25°C gives a mixture of two isomeric monochlorides.
CH 3 CH 3 CH 3
| | |
CH 3 CH CH 3 ⎯⎯⎯⎯ Cl2
light, 25°C
→ CH 3 CH CH 2 Cl + CH 3 C − CH 3
|
Cl
(64%) (36%)

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The tertiary hydrogen is replaced about 5 times as fast as primary hydrogen.

b. NITRATION : Alkane on reaction with HNO3 gives nitro alkane in vapour phase at 450 to 475o. In
case of alkane containing more than one carbon atom all possible mono nitroalkanes are
formed.
Δ
CH4 + HNO3 → CH3 − NO2 .
Δ
CH3 − CH3 + HNO3 → CH3 − NO2 + CH3 − CH2 − NO2
Δ
CH3 − CH2 − CH3 → CH3 − NO2 + CH3 − CH2 − NO2 + CH3 − CH2 − CH2 −
HNO3
NO 2
NO2 |
+ CH 3 − CH − CH 3

3. SULPHONATION : of higher alkanes n-hexane and onwards occurs in presence of oleum i.e.,
fuming sulphuric acid. The ease of replacement of H–atom is given as
R R H
| | |
R -C-H >R -C-H >R -C-H
| | |
R H H
3o 2o 1o
R − H + H2 SO4 . SO3 → R. SO3 H + H2 SO4
R − H + H2 SO4 → R. SO3 H + H2 O
The reaction also occurs on heating the alkane by conc. H2SO4.
Δ
R − H + H2 SO4 → R. SO3 H + H2 O
P.T.R. : (i) In case of an asymmetric centre racemisation occurs
R' R' R'
| Conc. H 2SO4 | |
R − C − H ⎯⎯ ⎯ ⎯ ⎯⎯→ R − C − SO 3 H + HO 3S − C − R
| | |
R'' R'' R' '
(ii) It holds good for n-hexane and higher members of n-alkane.
4) Oxidation
There are two ways to oxidize alkanes:
a) Complete (or uncontrolled ) oxidation
All alkanes readily burn on heating in excess of air or oxygen and get completely oxidized to carbon
dioxide and water with the evolution of large amount of heat. This process is called combustion of
alkanes.
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2 O(ℓ); ΔC H Θ = −890kJmol−1
13
C4 H10 (g) + 2 2
O (g) → 4CO2 (g) + 5H2 O(ℓ); ΔC H Θ = −2875.84kJmol−1
The general combustion equation for any alkane is:
3n + 1
Cn H2n+2 (s, or g) + ( ) O2 (g) → nCO2 (g) + (n + 1)H2 O(ℓ)
2
Due to the release of large amount of heat during combustion, alkanes are used as fuels. For example,
the combustion of alkanes is the chief reaction occurring in the internal combustion engine. The
mechanism of combustion proceeds through a free radical chain reaction. The reaction is extremely
exothermic but requires a very high temperature (say of a flame) for its initiation.
During incomplete combustion of alkanes with limited amount of air or oxygen, carbon black is formed
which is used in the manufacture of ink, printer ink, black pigments and as filters:
Incomplete oxidation
CH4 (g) + O2 (g) → C(s) + 2H2 O(ℓ)

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b) Controlled oxidation:
On heating with a controlled amount of air or dioxygen at high pressure or temperature and in the
presence of suitable catalysts alkanes undergo controlled oxidation to give different useful products.
15000 C
6CH4 + O2 → 2HC ≡ CH + 2CO + 10H2
Ethyne
8500 CNi
CH4 + H2 O → CO + 3H2
Cu/523K/100atms
2CH4 + O2 → 2CH3 OH
Methanol
Catalytic oxidation - This is the industrial method for the manufacture of methyl alcohol.
Mo2O3
CH4 + O2 ⎯⎯⎯⎯⎯ → HCHO + H2O

Methanal
(CH3 COO)MnΔ
2CH3 CH3 + 3O2 → 2CH3 COOH + 2H2 O
Ethanoic acid
Oxidising reagents such as potassium permanganate normally do not oxidize alkanes but they readily
oxidize a tertiary hydrogen atom to a hydroxyl group(-OH).
For example:
CH3 CH3
KMnO4
CH3 C H [O] CH3 C OH
CH3 CH3
2-Methylpropane 2-Methylpropan-2-ol
(Isobutane) (t-butylalcohol)

5) Isomerization: involves conversion of n-alkanes into branched-chain alkanes carrying a methyl

group as a side-chain. It is carried out by heating the unbranched alkane with anhydrous aluminium
chloride at 3000C. For isomerisation to be feasible a trace of water (to form HCl from AlCl3) together
with a trace of alkyl halide or an alkene (to form a carbocation) is essential.
anhyd.AlCl3
CH3 CH2CH2CH3 ⎯⎯⎯⎯⎯⎯⎯ → CH3CHCH3
H2O,alkene |
 CH3
anhyd.AlCl3
CH3 ( CH2 )4 CH3 ⎯⎯⎯⎯⎯⎯⎯ → CH3CHCH2CH2CH3 + CH3 CH2− CH − CH2CH3
H2O,alkene | |
 CH3 CH3

2-Methylpentane 3-Methylpentane

6) AROMATISATION : n-Hexane on aromatisation on heating at 500oC and 15 atm. in presence of

Cr2O3 or V2O5 or MoO3 gives benzene.
CH 3
CH 2 CH 3 V2 O 5
o + 4H 2
CH 2 CH 2 500 C & 15 atm
CH 2
In same manner n-heptane gives toluene.

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CH 3 CH 3
CH 2 CH 2 CH 3 V2 O 5
o + 4H 2
CH 2 CH 2 500 C & 15 atm
CH 2

Exp 1- What are the aromatic compounds formed when n-octane is subjected to hydroforming?
CH3(CH2)6CH3 → C6H4(CH3)2 + C6H4(CH3)2 + C6H4(CH3)2 C6H5C2H5
o-Xylene p−Xylene m−Xylene Ethyl benzene
6) Steam reforming: Here the alkane is mixed with steam and a limited supply of oxygen (not air, to
avoid the entry of nitrogen). The mixture is passed over a nickel catalyst at a temperature of about
9000C and under a pressure of 30 atmospheres. This converts the alkane into a mixture of carbon
monoxide and dihydrogen gas according to the following reaction:
Ni9000 C,30atm
Cn H2n+2 + nH2 O(g) → nCO(g) + (2n + 1)H2 (g)
Dihydrogen gas is made in large amounts by the steam reforming of methane. This is the principal
method in countries possessing an abundant supply of natural gas. It is used for the industrial
production of hydrogen gas.
7) Pyrolysis (cracking): The thermal decomposition (i.e., decomposition by the action of heat
alone) of an organic compound is known as pyrolysis
The pyrolysis of alkanes, particularly petroleum, is known as cracking. In thermal cracking alkanes are
simply passed through a chamber heated to a high temperature. When heated to about 400 − 6000C,
higher alkanes are decomposed into smaller alkanes, alkenes and some dihydrogen (H2) gas:
400−6000 C
Higher alkane → Smaller alkanes + Smaller alkenes + H2
The actual products obtained from a given alkane depend on
a) the structure of the alkane,
b) the pressure under which cracking is carried out, and
c) the presence or absence of catalysts such as silica−alumina, silica−alumina−thoria,
silica−alumina−zirconia.
Example: C3 H8 → C2 H4 + CH4 or C3 H6 + H2
C3H6 + C 2H4 + CH 4

Thermal
C6H14 C4H 8 + C 2H 6
cracking

C6H12 + H 2

Note- Cracking of alkanes is a free-radical reaction as many alkanes produce alkyl free radicals of
cracking temperatures:

CH3 CH 2 CH 3  CH 3CH2 + CH 3 Disproportionation CH2 CH 2 + CH 4

Preparation of oil gas or petrol gas from kerosene oil or petrol involves the principle of pyrolysis. For
example, dodecane, a constituent of kerosene oil on heating to 973K in the presence of Pt, Pd or Ni
gives a mixture of heptane and pentene:
CatalystΔ
C12 H26 → C7 H16 + C5 H10 + Otherproducts
Dodecane Heptane Pentene

Conformations of alkanes - involves rotation about sigma bonds, and does not involve any differences
in the connectivity or geometry of bonding. Two or more structures that are categorized as

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conformational isomers, or conformers, are really just two of the exact same molecule that differ only
in terms of the angle about one or more sigma bonds. The carbon-carbon single bonds of alkanes
rotate freely. Conformers are the same molecule shown with different sigma bond rotations. Newman
projections are one way to communicate bond rotation.

Free Rotation about the Carbon-Carbon Single Bond

H H Ethane Molecule
C H
1.53Å

109.5
109.5
H C
H
H
Although there are seven sigma bonds in the ethane molecule, rotation about the six carbon-hydrogen
bonds does not result in any change in the shape of the molecule because the hydrogen atoms are
essentially spherical. Rotation about the carbon-carbon bond, however, results in many different
possible molecular conformations.

In order to better visualize these different conformations, it is convenient to use a drawing convention
called the Newman projection. In a Newman projection, we look lengthwise down a specific bond of
interest – in this case, the carbon-carbon bond in ethane. When there are multiple carbons,then we
specify the bond of interest using the carbon numbers from the IUPAC name. We depict the ‘front’
atom as a dot, and the ‘back’ atom as a larger circle.
This set of bond angles and bond lengths still does not limit the molecule of ethane to a
single arrangement of atoms, since the relationship between the hydrogens of one carbon and the
hydrogens of the other carbon is not specified. Different arrangement of atoms that can be converted
into one another by rotation about single bonds are called Conformations. Arrangement I is called the
eclipsed conformation and arrangement II is called its staggered conformation.

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H
H
H H
H
H
H
H H
H Sawhorse Representation
H H
Staggered II
Eclipsed
H
H H H
H
Newman

H H H H
H
H H Staggere II
Eclipsed I
Stability of confirmations

ALKENE

General Introduction
· These are the acyclic hydrocarbons in which unsaturation (C=C) is present.
· These are also known as olefins (i.e. oleum, oil + fines, forming) because lower alkene react
with halogens to form dihalides which are oily substances.
· General formula is CnH2n(n = 2, 3, 4, 5..........). 
· Hybridisation of unsaturated ‘C’ atoms are sp2 H H

· Geometry of unsaturated ‘C’ carbon is trigonal planar. C −−− C
· Bond angle on sp2 carbon is 120º. H H
· C=C bond length is 1.34 Å.

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· C–H bond length is 1.10 Å.

H
H
1.34Å
Å C C 117.50
110
H 1210
H
· C=C bond energy is 142 kcal/mol
· C–H bond energy is 106 kcal/mol
· Isomerism in Alkenes - Alkene shows structural (chain, position, functional or ring chain),
optical & geometrical isomerism.

(i) Chain isomers - CH3–CH2–CH=CH2 and CH3–C=CH2

|
CH3
(ii) Position isomers - CH2=CH–CH2–CH3 and CH3 – CH = CH – CH3
(iii) Functional (ring chain)isomers - CH3–CH2–CH=CH2 and CH2– CH2
| |
CH2– CH2
*
(iv) Optical isomerism - CH3CH2–CH–CH=CH2
CH3
(v) Geometrical isomers - arises due to the restricted rotation of the groups across carbon –
carbon double bond, results in different spatial arrangement of groups.
Conditions for alkenes to show Geometrical isomerism
1) There should be a carbon – carbon double bond.
2) Two different groups should be attached to each carbon atom connected by double bond.
Nomenclature of Geometrical Isomers
A Geometrical isomer containing the similar groups on the same side of the double bond is called as
cis-isomer.
The isomer with two similer groups on the opposite sides of the double bond is called as trans-isomer.
Hence geometrical isomerism is called as cis-trans isomerism.

Geometrical isomerism in But 2 ene

Formula of But-2-ene is CH3-CH=CH-CH3.It shows geometrical isomerism and its structures are cis-but-
2-ene and trans-but-2-ene.

H 3C CH 3 H CH 3
C=C C=C
H H H 3C H
CH3–C–H and CH3–C–H
|| ||
CH3–C–H H–C–CH3
(cis -2- butene ) (trans-2-butene)
Nomenclature
Longest continuous chain of carbon atoms containing the double bond is selected. Numbering of
the chain is done from the end which is nearer to the double bond. The suffix ‘ene’ replaces ‘ane’ of
alkanes.
First member of alkene series is CH2 (substituting n as 1 in CnH2n) known as methene or
methylene but it has a very short life. Thus, the first stable member of alkene series is C2H4.

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Exp 1 : Give structures or write IUPAC names of the following compounds:

a) 4−Ethyl−2, 6−dimethyldec−4−ene
b) CH2 = C(CH2 CH2 CH3 )2
c) 1, 3, 5, 7 − Octatetraene
d) (CH3)2CH CH CH CH 2 CH

CH3 CH CH

C 2H 5
Solution:
a) CH3 CH CH 2 C CHCHCH 2CH2CH2CH3

CH3 CH2CH3 CH3

b) CH2 C CH 2CH2CH3

CH2CH2CH3
2−n−Propylpent−1−ene
c) CH2 = CH − CH = CH − CH = CH − CH = CH2 or .

d) CH3 CH CH CH CH 2 CH CH CH 2 CH 3

CH3 CH3
2, 8− Dimethyl −3, 6− decadiene

EXP 2 : Count the number of sigma () and pi () bonds in the above compounds (a–d).
Solution: a)  bonds : 41,  bond : 1 b)  bonds : 23,  bond : 1
c)  bonds : 17,  bond : 4 d)  bonds : 33,  bond : 2

Exp 3 : Work out all possible structurally isomeric alkenes corresponding to C5H10 and also
give their IUPAC names.
Solution: Straight chain skeleton:
a) CH3CH2CH2CH = CH2 b) CH3CH2CH = CHCH3
Pent-1-ene Pent-2-ene
Branched−chain skeleton :
c) CH3CHC = CH2 d) CH3CHCH = CH2
| |
CH3 CH3
2-Methylbut-1-ene 3-Methylbut-1-ene
e) CH3 CH =CCH3
|
CH3

Relative Stabilities of Alkenes (Heats of Hydrogenation)

Hydrogenation provides a way to measure the relative stabilities of certain alkenes. The reaction of
an alkene with hydrogen is an exothermic reaction; The enthalpy change involved is called the heat
of hydrogenation. Most alkenes have heats of hydrogenation near -30k cal mol−1 .
For exp,
CH3CH2CH = CH2 + H2 ⎯⎯
Pt
→ CH3 CH2CH2CH3 H = −30.3 Kcal mol−1
1 - Butene

CH 3 CH 3
C=C + H2 ⎯⎯
Pt
→ CH3CH2CH2CH3 H = −28.6 Kcal mol−1
H H ACTIVE SITE EDUTECH-9844532971
cis -2-Butene
22 ACTIVE SITE EDUTECH-9844532971

H 3C H
C=C + H2 ⎯⎯
Pt
→ CH3CH2CH2CH3 H = −27.6 Kcal mol−1
H CH 3
trans-2-Butene

In each reaction the product is the same. A different amount of heat is evolved in each and this
difference is related to different relative stabilities of the individual butenes. 1-Butene evolves the
greatest amount of heat when hydrogenated, and trans-2 butene evolves the least. Hence, 1-butene
must have the greatest potential energy and be the least stable isomers. Trans - 2 butene must have
the lowest P.E and be the most stable isomer.

Preparation of Alkenes
1) Reduction of alkynes
Alkynes reacts with hydrogen in the presence of a suitable catalyst like Pd/Pt/Ni etc, the reaction
proceeds in two stages to give alkane.
H H
| |
−C  C − + H 2 ⎯⎯⎯⎯
→ − C = C− ⎯⎯⎯⎯ → − C− C−
catalyst H2
catalyst
| | | |
H H H H
Controlled reduction in presence of suitable catalysts affect hydrogenation of a triple bond, so it is
possible to isolate the intermediate alkene.
Reduction of a non-terminal alkyne to the double−bond stage can yield either a cis-alkene or a trans-
alkene depends upon the choice of reducing agent
• Predominantly trans alkene is obtained when a dialkylacetylene is reduced with sodium or
lithium in liquid ammonia. Trans−alkene is also produced by reduction with lithium
aluminium hydride.
• cis alkene is obtained by hydrogenation of dialkyl acetylene with Lindlar’s catalyst which
consists of a Pd-CaCO3 catalyst partially poisoned with lead −acetate. A better catalyst is
Pd−BaSO4 partially poisoned with quinoline or palladised charcoal partially deactivated with
quinoline. Cis−alkene is also the predominant product when reduction is carried out with
diborane (B2H6) or with di-isobutylaluminium hydride.

R R

C=C cis -alkene

Lindlar's
catalyst H H

RC  CR
R H
Na\liquid NH 3

C=C trans -alkene

2) Dehydrohalogenation of alkyl halides H R

When alkyl halides (R−X) are heated with concentrated alcoholic solution of potassium
hydroxide(potash), alkenes are obtained along with potassium halide and water:
This reaction is an example for elimination reaction and takesplace according to Saytzeff ’s rule.

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C C + KOH alcohol C C + H2O + KX

D
H X
Ease of dehydrohalogenation : 30 RX > 20 RX > 10 RX
of alkyl halides : RI > RBr > RCl
Examples
alcoholicKOHΔ
CH3 CH2 CH2 I → CH3 CH = CH2
n-Propyliodide Propene
alcoholickOHΔ
CH3 CH2 CH2 CH2 CH2 Br → CH3 CH2 CH2 CH = CH2
n-Pentylbromide Pent-1-ene
This reaction, known as dehydrohalogenation i.e., elimination of the elements of hydrogen halide, is
a typical example of the 1, 2− or − elimination reaction, in which two atoms or groups are lost from
neighbouring atoms to form a double bond. Other elimination reactions (, , etc) are also known, but
these are much less common.
Dehydrohalogenation involves removal of the halogen atom (from − carbon) and of a
hydrogen atom from a carbon (-carbon) adjacent to the one losing the halogen. The reagent required
is a strong base (like potassium ethoxide) whose function is to abstract the hydrogen as a proton.
C2 H5 OH + KOH ⇌ K + ŌC2 H5 + H2 O
R − CH2 CH2 − X + K + ŌC2 H5 → RCH = CH2 + C2 H5 OH + KX
ethanolΔ
RCH2 CH2 X + KOH → RCH = CH2 + KX + H2 O
In some cases, dehydrohalogenation yields a mixture of alkenes. This is due to the fact that an alkene
is expected corresponding to the loss of any one of the possible −hydrogens.
n−Butyl halide yields only one alkene, but−1−ene, as it can lose hydrogen only from C−2:
alc.KOHΔ
CH3 CH2 − CH − CH2 → CH3 CH2 CH = CH2
| |
H X
n-Butyl halide But-1-ene (only one product)
On the other hand, sec-Butyl bromide yields two alkenes, but-1-ene and but-2-ene corresponding to
the loss of -hydrogen either from C−1 or from C−3:

loss of
CH3CH2CH CH 2
− hydrogen
from C-1 But-1-ene (19%)
3 2 1 alc.
CH3CH CH CH 2
KOH
H Br H
loss of − hydrogen
sec - Butylbromide from C−3 CH3CH CHCH 2
But-2-ene(81%)
Notice that the preferred (or major) product, but-2-ene is a disubstituted alkene i.e., there are two
alkyl groups (two methyl groups) attached to the doubly bonded carbons of but-2-ene. The minor
product, but-1-ene is a monosubstituted alkene i.e. there is only one alkyl group (one ethyl group)
attached to the doubly bonded carbons:

CH3 − C = C − CH3 predominates over CH3 CH2 − C = C − H

| | | |
H H H H
But-2-ene But-1-ene
Disubstituted alkene Monosubstituted alkene
The following examples also show that a disubstituted alkene predominates over a monosubstituted
alkene, and a trisubstituted alkene predominates over a disubstituted alkene:

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CH 3 CH = C − CH 3 (  70 %)
Br |
| KOH / C 2 H 5 OH CH 3
CH 3 − CH 2 − C − CH 3 ( Main product )
|
CH 3
CH 3 − CH 2 − C = CH 2 (  30 %)
|
CH 3
( side product )

CH3CH 2CH 2CHCH3 ⎯⎯⎯

alc.
KOH
→ CH3CH 2CH 2CH = CH 2 + CH 3CH 2CH = CHCH 3
| disubstituted
monosubstituted
I alkene alkene
(29%) (71%)

This pattern was first observed by the Russian chemist Alexander Saytzeff who formulated (in 1875)
an empirical rule which may be stated in two ways:
In dehydrohalogenation (and also dehydration of alcohols) the predominant product is the most
substituted alkene i.e., the one carrying the maximum number of alkyl substituents.
or
In dehydrohalogenation (and also dehydration of alcohols) -hydrogen is eliminated preferentially
from that − carbon atom containing the least number of hydrogen atoms.
Since the amount of each isomer formed depends on its rate of formation, we can conclude that the
alkene with the greater number of alkyl substituents is the predominant product because it is formed
faster than alternative alkenes. Thus, Saytzeff rule gives us a sequence showing the relative rates of
formation of alkenes.
Ease of formation of alkenes:
R 2 C = CR 2 > R 2 C = CHR > R 2 C = CH2 , RCH = CHR > RCH = CH2 > CH2 = CH2
Notice that the stability of alkenes also follows the exact sequence:
Stability of alkenes:
R 2 C = CR 2 > R 2 C = CHR > R 2 C = CH2 , RCH = CHR > RCH = CH2 > CH2 = CH2
Now we can redefine the Saytzeff’s rule to state:
In dehydrohalogenation, the more substituted alkene, being the more stable, is formed faster.
Predominant formation of the more stable isomer is called Saytzeff orientation.

Kinetics of elimination- With a concentrated alcoholic solution of potassium hydroxide,

dehydrohalogenation follows second-order kinetics:
Rate = k [RX] [base]
i.e., the rate of formation of alkene depends upon the concentration of alkyl halide and base. This
behaviour is observed for all classes of alkyl halides.
If one moves along a series of substrates, 10RX to 20 RX to 30RX, and if one reduces the concentration
or the strength of the base, the dehydrohalogenation begins to follow first −order kinetics:
Rate = k [RX]

3) Dehalogenation of dihalides
Dihalogen derivatives of the alkanes undergo dehalogenation (i.e. removal of halogen) on treatment
with zinc dust and methyl alcohol to produce the corresponding alkenes:

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X
Zn
C C X C C + ZnX2
CH3 OH
Geminal dihalide Alkene

Zn
C C C C + ZnX2
CH3OH
X X
Vicinal dihalide Alkene
CH3 OH
Examples CH3 CH2 CHBr2 + Zn → CH3 CH = CH2 + ZnBr2
Propylidene Propene
dibromide
CH 3 CH − CH 2 + Zn ⎯⎯⎯⎯
CH3OH
→ CH 3CH = CH 2 + ZnBr2
| |
Br Br Propene
Propene dibromide
4) Dehydration of monohydric alcohols- A monohydric alcohol is converted into an alkene by
dehydration: 1, 2− or − elimination of a molecule of water in presence of Conc. H2SO4 at
443K.
 
C C C C + H 2O
H OH
Monohydric Alkene Water
Alcohol
Ease of dehydration of alcohols: 30ROH > 20ROH > 10ROH
Unlike dehydrohalogenation (of alkyl halides) that is catalysed (or promoted) by a base, the
dehydration of alcohols is catalysed by an acid.
Thus, dehydration requires the presence of an acid and the application of heat. It is usually carried
out in either of two ways:
i) By heating the alcohol with a Bronsted acid such as Conc. H2SO4 or Conc. H3PO4. Primary
alcohols are dehydrated by the action of concentrated sulphuric acid at about 160−1700.
oC H HSO 4
H OH ⎯100
⎯⎯ ⎯→ | | oC
| | − H 2O ⎯170
⎯⎯ ⎯→ CH 2 = CH 2 + H 2SO 4
H - C - C - H + H . HSO 4 H−C−C−H
| | (Substitution reaction ) | | ( E lim ination reaction )
H H H H
Dehydration of secondary and tertiary alcohols is best carried out by using boiling dilute
sulphuric acid, since the alkenes produced from these alcohols (particularly tertiary
alcohols) tend to polymerise under the influence of the concentrated acid.
OH CH 3 CH 2 CH = CH 2 (20%)
| 1 − Butene
dil .H SO
CH 3 − CH 2 − CH − CH 3 ⎯⎯ ⎯2 ⎯⎯
4→

CH 3 − CH = CH − CH 3 (80%)
2 − Butene
ii) by passing the alcohol vapor over heated alumina (Al2O3) which functions either as a Lewis acid or
through −OH groups on its surface, as a Lowry −Bronsted acid. 30 alcohols are dehydrated at about
1500C, 20 −alcohols at 2500C and 10 alcohols at 3500C.
Acid-catalysed dehydration of primary alcohols usually yields 1−alkenes, but 20 − and 30−alcohols yield
mixtures of alkenes due to removal of a hydrogen (as proton) from either adjacent carbon atom (to

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the C-OH group) and also due to rearrangements undergone by the different carbonium ion
intermediates.
Rearrangements may be avoided by dehydrating the alcohol over heated alumina and isomerisation
is suppressed by the addition of a small amount of pyridine to alumina.

𝑐𝑜𝑛𝑐.𝐻2 𝑆𝑂4 1700 𝐶

Examples: 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻2 = 𝐶𝐻2
Ethanol Ethene
85%H3PO4
OH
165-1700C
Cyclohexanol Cyclohexene

𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4 1400 𝐶

𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻3 𝐶𝐻2 𝐶𝐻 = 𝐶𝐻2 + 𝐶𝐻3 𝐶𝐻 = 𝐶𝐻𝐶𝐻3
Butan-1-ol Bute-1-ene But-2-ene
(n-butyl alcohol) (major product)

CH3CH 2 CH CH3 ⎯⎯⎯⎯⎯

dilute HSO 4
1000 C
→ CH3CH 2CH = CH 2 + CH3CH = CHCH3
| But-2-ene
But-1-ene
OH (major product)
Butan-2-ol
(sec-butyl alcohol)

CH3 CH3
| |
diluteH2SO4
CH3− C − OH ⎯⎯⎯⎯⎯ ⎯
→ CH3 − C = CH2
850 C
|
CH3
2-Methylpropan-2-ol 2-Methylpropene
(tert-Butyl alcohol) (isobutylene)
CH3 CH3 CH3 CH3 CH3
85% H 3PO4
CH3 C CH CH 3 CH3 C C CH + CH 2 C CHCH 3
800C 3

CH3 OH
3, 3-Dimethylbutan-2-ol 2, 3-Dimethylbut-2-ene 2,3-dimethylbutene
(major product)
Orientation of elimination is strictly Saytzeff
Where more than one −carbon is available then hydrogen attached to the − carbon atom joined to
the least number of hydrogen atoms is eliminated most easily.
For example:
CH3 CH3 CH3
CH3CH2 C CH 3 CH3CH C CH 3 + CH 3CH2 C CH 2
OH
2-Methyl-2-butan-2-ol 2-Methylbute-2-ne 2-Methylbut-1-ene
(tert-pentyl alcohol) (major product)
Thus the predominant product is the more substituted and hence the more stable one.
5) BY KOLBE’S ELECTROLYSIS METHOD:
Conc. solution of sodium or potassium salt of succenic acid on electrolysis gives ethylene &
CO2 on anode and hydrogen on cathode.

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CH 2 − COOK CH
| || 2 + CO 2 + 2 KOH + H 2
Electrolysis
CH 2 − COOK + H2O ⎯⎯ ⎯ ⎯⎯→ CH 2
Potassium succenate at anode at cathode
Physical properties of Alkenes
1) C2 to C4 are colorless and odorless gases (except C2 ie. ethylene which has light sweet smell)
C5 to C17 are colorless liquids. C18 to onwards are solids at room temperature.
2) Alkenes are less dense than water
3) Among alkenes density increases down the homologous series as molecular mass increases
4) Like alkanes, the boiling points of alkenes increases with increase in number of carbon atoms
(20 – 30° per CH2) and again branches lower the Boiling point as surface area decreases.
5) cis – isomer of a compound has higher B.P. than its trans isomer.
6) Melting points of cis – trans isomers follow opposite trend ie; cis isomer has lower M.P than
trans because trans isomer molecules are held tightly, in crystal lattice due to molecular
symmetry.

Dipole moment :
Since the loosely held  electrons of the double bond are easily displaced, alkenes are weakly
polar and hence have larger dipole moments than the non – polar alkanes cis-isomer has
relatively higher dipole moment than the corresponding trans-isomer which may have zero
dipole moment in case of symmetrical compound.
Eg : trans – 2 - Butene

In cis – 2 Butene polarity & hence dipole moment in the two bonds are equal and in the same
direction while in trans-2 – Butene dipole moments of two groups are equal in magnitude but
opposite in direction, hence they cancel each other to give net zero dipole moment.
A difference in the polarity between oils and trans isomers also leads to higher boiling point
of Cis – isomer.

Chemical properties of alkenes

The carbon−carbon double bond, the characteristic feature of the alkene structure, is the functional
group of alkenes and hence determines the characteristic reactions that alkenes undergo. These
reactions are of two types:
first, those reactions that take place at the double bond itself,
next, those reactions that do not take place at the double bond but occur at the alkyl part of the
alkene.
The double bond consists of a strong sigma () bond and a weak pi () bond. The typical reactions of
the double bond are those where the pi bond is broken and two strong sigma bonds are formed in its
place:
H
C C + AB C C
H
A B
1. ADDITION OF HYDROGEN : Alkene on reaction with H2 in presence of Ni at 2000 to 3000C (or
Pt or Pd at 1500C) gives alkane.

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Ni
CH2 = CH2 + H2 → CH3 − CH3
200−300o C
Alkenes add up one H2 gas in the presence of a suitable catalyst at the carbon−carbon double bond to
form alkanes of the same carbon skeleton. The process called catalytic hydrogenation is of two kinds:
(i) Heterogeneous (two-phase)
(ii) Homogeneous (one-phase).
Heterogeneous hydrogenation is the classical method. A solution of alkene is shaken with dihydrogen
gas under pressure in the presence of a suitable catalyst. Finely divided platinum and palladium are
effective at room temperature; nickel on a support (Sabatier−senderens reduction) requires a
temperature between 2000C and 3000C; Raney nickel is effective at room temperature and
atmospheric pressure.
H H
| | R aneyNi,PtorPd | |
−C = C − +H2 → −C−C−
| |
RaneyNi
Example CH2 = CH2 + H2 → CH3 − CH3
Ethene Ethane
RaneyNi
CH3 CH = CH2 + H2 → CH3 CH2 CH3
Propene Propane
Homogeneous hydrogenation- Here the catalysts are organic complexes of transition metals like
rhodium or iridium, for example, Wilkinson’s catalyst [Rh(Cl)(PPh3 )3 ]. They are soluble in organic
solvents; thus, hydrogenation takes place in a single phase, the solution.
Hydrogenation is exothermic as the two sigma bonds (C−H) formed are stronger than the sigma bond
(H−H) and  bond broken. The amount of heat energy released when one mole of an unsaturated
compound in hydrogenated is called the heat of hydrogenation.
Heat of hydrogenation can be used to compare the stabilities of different alkenes which
produce the same alkane on hydrogenation. Since the hydrogenation is exothermic, the smaller H
is (numerically), the more stable is the alkene to its parent alkane.
trans − CH3 CH = CHCH3 > cis − CH3 CH = CHCH3 > CH3 CH2 CH = CH2
− 115.5 kJ mol−1 −119.7 kJ mol−1 −126.8 kJ mol−1
− 27.6 kcal mol −1
− 28.6 kcal mol −1
−30.3 kcal mol−1
Heat of hydrogenation for (CH3 )2 C = CH2 is −118.8 kJ/mol
trans − CH3 CH2 CH = CHCH3 > cis − CH3 CH2 CH = CHCH3 > CH3 CH2 CH2 CH = CH2
−27.6 kcal mol−1 −28.6 kcal mol−1 −30.1 kcal mol−1
CH3 CH3 CH3
| | |
CH3 − C = CHCH3  CH2 = CCH2 CH3  CH3CHCH = CH2
−26.9 kcal mol−1 −28.5 kcal mol−1 −30.3kcal mol−1
Each set of isomeric alkenes yields the same alkane. In each case, the greater the number of alkyl
substituents attached to the doubly bonded carbon atoms, the more stable the alkene. For a pair of
geometrical isomers, the trans form is more stable than the cis form.

Order of stability of alkenes

R 2 C = CR 2 > R 2 C = CHR > R 2 C = CH2 ~RCH = CHR(trans > cis) > RCH = CH2 > CH2 = CH2
Stabilities of alkenes may also be compared by the determination of their heats of combustion.
For example
(CH3 )2 C = CH2 > trans − CH3 CH = CHCH3 > cis − CH3 CH = CHCH3 > CH3CH2CH = CH2
−2703 kJ mol−1 −2707 kJ mol−1 −2712 kJ mol−1 −2719 kJ mol−1
When the alkene is of the type R2C = CR2 or R2C = CHR, then hydrogenation at room temperature and
atmospheric pressure is difficult. The results are in accordance with the fact that the less hindered
side of an unsaturated molecule is adsorbed on the metal surface.

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P.T.R. i) It is a free radical addition reaction.

ii) It is known as catalytic hydrogenation.
iii) The reaction is called Sabitier-Senderen’s reduction.
iv) It is an example of cis addition.
v) There is a decrease in entropy occurs.
vi) A terminal double bond may be reduced by sodium in liquid NH3 in presence of alcohol
(MeOH or EtOH which is an stronger acid than NH3). This method is known as Birch
reduction

R - CH = CH2 Na in liq. NH3 R - CH2 - CH3

2) Addition of halogens Alkenes readily add up chlorine or bromine to form saturated compounds
containing two atoms of halogen attached to adjacent carbons

C C + X X C C (X2:Cl2 or Br 2)
X X
This addition reaction is the best method of preparing vicinal dihalides. The reaction is usually carried
out simply by mixing together the two reactants in an inert solvent such as CCl4.
Examples :
CCl
CH2 = CH2 + Br2 ⎯⎯⎯
4
→ CH2 − CH2
| |
Br Br
Ethene 1, 2-Dibromoethane
CCl4
CH3CH = CH2 + Br2 ⎯⎯⎯→ CH3CH− CH2
| |
Br Br
Propene 1, 2,−Dibromopropane
(propylene) (propylene bromide)

( CH3 )2C = CH2 + Cl2 ⎯⎯⎯

CCl
→ ( CH3 )2 − C − CH2
4

| |
Cl Cl
2-Methylpropene 1, 2−Dichloro-2-methylpropane
(Isobutylene)
Addition of bromine is used as a test for unsaturation.
The reddish orange colour of the solution of bromine in carbon tetrachloride is rapidly discharged
when bromine adds up to the carbon−carbon double bond:
Br Br
| | | |
−C = C − +Br2 (CCl4 ) → −C − C −
| |
colourless reddish orange colourless
Note- F2 and I2 are not used for halogenation. Because F2 decomposes the substrate molecule and I2
reacts to for, product being unstable eliminates the molecule of I2 regenerating the original reactant.
3) Addition of hydrogen halides- Alkenes add up hydrogen halides (HCl, HBr and HI) to form the
corresponding alkyl halides:

C C H X C C

H X
(HX = HCl, HBr, HI)
Alkene Alkyl halide
Exp- When ethane reacts with HBr, addition reaction takes place forming ethyl bromide.

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CH2 = CH − H + HBr → CH3 − CH2 − Br

The addition of HX to an unsymmetrical alkene could take place in two different ways to yield two
different products, depending upon the orientation of addition (i.e. depending upon which carbon
atoms get attached to the hydrogen and halogen).
It follows Markownikoff’s rule.
CH3CH = CH2 + HBr → CH3 − CH− CH3 + CH3CH2CH2Br
|
Br
Propene 2-Bromopropane 1-Bromopropane

CH3 CH3 CH3

| | |
CH3 − C= CH2 + HI ⎯⎯→ CH3 − C − CH3 + CH3 − CH − CH2−−I
|
I
2-Methylpropene 2-Methyl-2-iodopropane 2-Methyl-1-iodopropane
(isobutylene) (tert-butyliodide) (isobutyl iodide)

Markownikoff’s rule.
In an addition reaction, when an unsymmetrical molecule added to the unsymmetrical alkene,
the positive part of the molecule will attach to the carbon atom of C-C double bond contains
maximum number of hydrogen atoms.
If an unsymmetrical alkene, such as propene, undergoes addition of a hydrogen
halide, such as hydrogen bromide, then step 1 leads to two different carbocations:
The secondary carbocation is more stable than the primary carbocation and hence is formed faster.
The chief product of the reaction is thus 2-bromopropane because it is formed by the attack of
bromide ion on the more stable secondary carbocation which is formed preferentially in the first
step.
H
Br
CH3 CH CH 2 CH3 CH CH 2
0
1 carbocation
H+ H Br
(less stable)
CH3CH CH 2 (little formed)

Br
CH3 CH CH 2 CH3 CH CH 2

H Br H
20 carbocation main product
(more stable)

Order of stabilities of carbocations is 30 R⊕ > 20 R⊕ > 10 R⊕

the rate of addition of HX will be: (CH3 )2 C = CH2 > CH3 CH = CH2 > CH2 = CH2
Markovnikov’s addition of hydrogen halides are described as regioselective reactions
When a reaction that can potentially give two or more structurally isomeric products actually produces
only one (or a predominance of one), the reaction is said to be regioselective.

Solve the following –

1) Using Markovnikov’s rule, correctly predict the principal product of the following reactions.
a) But-1-ene + HI →

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b) Vinyl chloride + HI →
c) But-2-ene + HI →
d) 2-Methyl-but-2-ene + HI →
e) Pent-2-ene + HI →
I
|
Solution: a) CH3 CH2 CH = CH2 + HI → CH3 CH2 CH − CH3
2-Iodobutane
(sec-butyliodide)
I
|
b) CH2 = CH − Cl + HI → CH3 − CH − Cl
1-Chloro-1-iodoethane
I
|
c) CH3 CH = CHCH3 + HI → CH3 − CH − CH2 CH3
2−Iodobutane(sec-Butyl iodide)
2-Butene is a symmetrical alkene, thus, only one product is obtained.
CH3
|
d) H3 C − C = CH − CH3 + HI ⎯⎯→ H3C − C − CH2 − CH3
| |
CH3 I
2-Iodo-2-methylbutane
(tert-pentyl iodide)

e) CH3CH2CH = CHCH3 + HI ⎯⎯→ CH3CH2CH2 − CH − CH3 + CH3CH2CHCH2CH3

| |
I I
2−Iodopentane 3-iodopentane
2) Predict the outcome of the addition of ICl and BrCl to propene.
Solution: Chlorine being more electronegative than either iodine or bromine, is the negative
part of the addendum and thus adds in the second step:
+ −
I − Cl 
Cl
a) CH3 CH = CH2 ⎯⎯⎯⎯⎯ → CH3 − CH − CH2 ⎯⎯⎯⎯ → CH3 − CH− CH2
| | |
I Cl I
+ −
Br − Cl 
I 
b) CH3CH = CH2 ⎯⎯⎯⎯⎯ → CH3 − CH − CH2 ⎯⎯⎯→ CH3 − CH− CH2
| | |
Br Br Cl

Peroxide effect − an exception to Markovnikov’s rule:

Kharasch and Mayo found that the presence of oxygen or peroxides and hydroperoxides that are
formed when the unsymmetrical alkene stands exposed to the air, or added peroxides such as benzoyl
peroxide, causes the addition of HBr to take place in the direction exactly opposite to that predicted
by Markovnikov’s rule.
Organic peroxides or hydroperoxides are compounds containing the −O−O− linkage.

R-O-O-R R-O-O-H (C6 H5 COO)2

An organic peroxide An organic hydroperoxide benzoyl peroxide,

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Peroxides Anti-Markovnikov's
CH3CH2CH2Br
addition
HBr
CH3CH CH 2

No CH3CHCH 3 Markovnikov's
peroxides
addition
Br
This departure from the rule is known as the ‘abnormal’ reaction and this reversal of the

Mechanism for the anti-Markovnikov addition:

Mechanism of the anti−Markovnikov addition of hydrogen bromide is a free-radical chain reaction
initiated by peroxides or by light.
Step1 Chain initiation − Heat brings about homolytic cleavage of the weak oxygen−oxygen bond of
organic peroxide:
heat
R O O R 2R O
Step 2: Chain propagation – The alkoxy radical (or alkyl radical) abstracts a hydrogen atom from H-
Br, producing a bromine atom.
R − O∗ + H − Br → R − O − H + Br*
or
R∗ + H − Br → R − H + Br ∗
Step 3 Chain propagation − A bromine atom adds to the double bond to produce the more stable
secondary (20) free radical:
∗
Br ∗ + H2 C = CH − R → Br − CH2 − CH − R
Step 4 Chain propagation − The secondary free radical abstracts a hydrogen atom from H−Br. This
leads to the product formation and regenerates a bromine atom.
∗
Br − CH2 − CH − R + H − Br → Br − CH2 − CH2 − R + Br ∗
Then repetitions of steps 3 and 4 lead to a chain reaction.
In the photochemical addition, the bromine atom is produced by absorption of a quantum of light.
hυ
HBr → H ∗ + Br*
NOTE- For alkyl halide synthesis, polar, protic solvents favour Markovnikov’s addition:
H−Braceticacid
CH3 CH = CH2 → CH3 − CH − CH3
|
Br
While non-polar solvents or exposure to light or presence of peroxides favour anti- Markovnikov’s
addition:
HBrhυ
CH3 CH = CH2 → CH3 CH2 CH2 Br
Exp 1: Find the products obtained by addition of HBr to hex-1-ene
a) in the presence of peroxide
b) in the absence of peroxide
Also write their IUPAC names.
Solution: a) In the presence of peroxides, the particle that attacks the double bond first is the larger
bromine atom. It attaches itself to the less hindered carbon atom by a radical mechanism to form
the more stable free radical. The result is anti- Markovnikov’s addition.
Peroxide
CH3 CH2 CH2 CH2 CH = CH2 + HBr → CH3 CH2 CH2 CH2 CH2 CH2 Br
1-Bromohexane
a) In the absence of peroxides, the particle that attacks the double bond first is a
proton (Because, a proton is small, steric effects are not important). It attaches itself
to a carbon atom by an ionic mechanism to form the most stable carbocation. The
result is Markovnikov’s addition:

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Br
|
No
CH3 CH2CH2CH2CH = CH2 + HBr ⎯⎯⎯⎯⎯⎯ → CH3CH2CH2CH2CHCH3
peroxide
2−Bromohexane
The order of reactivity of the addition of hydrogen halides is: HI > HBr > HCl(> HF)
This is also the order of acid strength. The reactivity of HF is so low that the addition of hydrogen
fluoride is effected only under pressure.
Examples CH2 = CH2 + HI → CH3 CH2 I
Ethene Iodoethane
(ethylene) (ethyl iodide)
Br
|
CH3 CH = CHCH3 + HBr → CH3 CHCH2 CH3
But-2-ene 2-Bromobutane
4) Addition of sulphuric acid: On treatment with cold conc, H2SO4, alkenes (unlike alkanes) dissolve
because they react with sulphuric acid by addition to form compounds of the general formula
ROSO3H or RHSO4, known as alkyl hydrogen sulphates. These products are formed by a mechanism
which is similar to that for the addition of HX:
Step 1 The alkene donates a pair of  electrons to a proton from sulphuric acid to form a carbocation:
O O
C C +H O S O H C C +O S O H
+
Alkene O H O
Sulphuric acid
Step 2 The carbocation reacts with a hydrogen sulphate ion to form an alkyl hydrogen sulphate.
O

C C + O S O H C C
+
H O OSO 3H H

Carbocation Hydrogen sulphate Alkyl hydrogen sulphate

ion (soluble in sulphuric acid)
80%H2SO4
Examples CH3CH = CH2 ⎯⎯⎯⎯⎯⎯⎯ → CH3 − CH− CH3
|
OSO3H
Propylene Isopropyl hydrogen sulphate

98%H2 SO4
CH2 = CH2 → CH3 CH2 OSO3 H
Ethylene Ethyl hydrogen sulphate

Note- Alkyl hydrogen sulphates on hydrolysis using warm water gives corresponding alcohols.
Exp- In one industrial synthesis of ethanol, ethene is first dissolved in 95% sulphuric acid. In a second
step water is added and the mixture is heated
95%H2 SO4 H2 OΔ
CH2 = CH2 → CH3 CH2 OSO2 OH → CH3 CH2 OH + H2 SO4
Ethyl hydrogen sulphate

5) Addition of water (Hydration of alkene): We have just seen that alkenes may be hydrated to
alcohols by absorption in concentrated sulphuric acid followed by hydrolysis of the alkyl hydrogen
sulphate yield alcohols:

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H 3O +
C C +H OH C C
or H+
H OH
The acid-catalyzed addition of water to the double bond of an alkene (called direct hydration of an
alkene) is a method for the preparation of low-molecular-weight alcohols. The acids most commonly
used to catalyze the hydration of alkenes are dilute aqueous solutions of sulphuric acid and phosphoric
acid.
H O,H+
Examples: CH3 − CH = CH2 ⎯⎯⎯⎯
2
→ CH3 − CH− CH3
|
OH
Propene 2-Propanol
CH3
|
H
CH3 − C = CH2 + H2O ⎯⎯⎯→
0 CH3 − C − CH3
25 C
| |
CH3 OH
2-Methylpropene tert-Butyl alcohol
(isobutylene)
Since these reactions follow Markovnikov’s rule, acid catalyzed hydrations of alkenes do not yield
primary alcohols except (in the special case of) the hydration of ethene:
H3 PO4 3000 C
CH2 = CH2 + H − OH → CH3 CH2 OH
5) Oxidation of alkenes:
a) Hydroxylation (Formation of 1, 2−diols) Alkenes are readily hydroxylated (i.e., add on hydroxyl
groups), by certain oxidizing agents, to form 1, 2−diols: dihydroxy alcohols carrying the two −OH
groups on adjacent carbons. They are also called sometimes as glycols. The hydroxylation reaction
results in the addition of two hydroxyl groups to the double bond:

C C C C
HO OH
Alkene 1, 2-diol
Hydroxylation may be effected
i) By means of cold dilute alkaline (1%) aqueous solution of potassium permanganate [Baeyer’s
reagent]. The result is syn (or cis) hydroxylation. For example
CH2 = CH2 + H2O + O  ⎯⎯⎯⎯⎯⎯
Cold
→ CH2 − CH2 + KOH + MnO2
KMnO4 ,OH−
| |
OH OH
Ethylene Ethylene glycol
Decolourisation of KMnO4 solution is used as a test for unsaturation. (Baeyer test).
The mechanism of hydroxylation with permanganate proceeds via a cyclic intermediate. This results
in syn addition of the oxygen atom.
ii) By means of osmium tetroxide. This compound is widely used to synthesize 1, 2−diols (glycols). It
adds very readily to the carbon−carbon double bond of an alkene at room temperature. The
mechanism involves cyclic intermediate that results in syn addition of the oxygen atoms:

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R R
C C R R
H H
+ Pyridine
H C C H

O O O O
Os Os
O O O O
An osmate ester
These cyclic compounds, called osmic esters, on refluxing with aqueous ethanolic sodium hydrogen
sulphite or sodium sulphite are hydrolysed to 1, 2-glycols (cis−glycols)
RCH O
O
NaHSO 3/H2O C OH
Os + Os
or C OH
RCH O Na2SO 3/H2O
O
Cleavage at the oxygen-metal bonds takes place without altering the stereochemistry of the two new
C−O bonds.
b) Oxidative cleavage
Alkenes can be oxidatively cleaved using potassium permanganate or ozone. Potassium
permanganate (KMnO4) is used for strong oxidation while ozone (O3) is used for mild oxidation.
i) Cleavage with hot alkaline potassium permanganate In a cleavage reaction the carbon−carbon
double bond is completely broken and the alkene molecule is converted into smaller molecules.
Treatment of an alkene with hot alkaline potassium permanganate results in the cleavage of the
double bond. The nature of the products depends upon the structure of alkene:
Unsubstituted alkene carbons are oxidized to carbon dioxide and their hydrogens into water:
= 𝐶𝐻2 → 𝐶𝑂2 + 𝐻2 𝑂
Alkenes with monosubstituted carbon atoms are oxidatively cleaved to salts of carboxylic acids:
= 𝐶𝐻𝑅 → 𝑅𝐶𝑂𝑂−
Disubstituted alkene carbons are oxidatively cleaved to ketones:
= 𝐶𝑅2 → 𝑅2 𝐶 = 𝑂
The following examples illustrate the above results:
KMnO ,H O,OH−
CH3 −C = CH2 ⎯⎯⎯⎯⎯⎯⎯
4 2
heat
→ CH3 − C = O + CO2 + H2O
| |
CH3 CH3
2-Methylpropene Propanone

𝐾𝑀𝑛𝑂4 ,𝐻2 𝑂,𝑂𝐻 − ℎ𝑒𝑎𝑡 𝐻3 𝑂 +

𝐶𝐻3 − 𝐶𝐻 = 𝐶𝐻 − 𝐶𝐻3 → 2𝐶𝐻3 − 𝐶 − 𝑂− → 2𝐶𝐻3 − 𝐶 − 𝑂𝐻
|| ||
𝑂 𝑂
But-2-ene Acetate ion Acetic
acid
(cis or trans)
ii) Oxidative cleavage by Ozonolysis
The classical reagent for cleaving the carbon-carbon double bond is ozone. Treatment of an alkene
with ozone followed by workup with zinc and acetic acid (or dimethyl sulfide, (CH3)2S) results in
oxidative cleavage. This process is called ozonolysis (cleavage by ozone). It occurs in two stages:
Stage I; Addition of ozone to the double bond to form an ozonide. For this purpose, the ozone gas is
bubbled into a solution of the alkene dissolved in a solvent that is unaffected by ozone (e.g.

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chloroform, carbon tetrachloride, glacial acetic acid, light petrol). Evaporation of the solvent leaves
the ozonide as a viscous oil.
O O
O3
C C O O C C

C C O O
Alkene Molozonide Ozonide
Stage II Reductive hydrolysis of the ozonide to yield the cleavage products. Ozonides are very unstable
compounds, and low-molecular-mass ozonides often explode violently in the free state. Because of
this behavior, they are not usually isolated (or purified) but are reduced directly (to the carbonyl
compounds) by treatment with zinc and acetic acid (HOAc) or dimethyl sulphide:
O O
CH3COOH
C C + Zn C O + O C + Zn (OCCH 3) 2

O O
In the cleavage products a doubly bonded oxygen gets attached to each of the originally doubly
bonded carbons.
Ozonolysis results in milder oxidative cleavage of alkenes than potassium permanganate. Thus,
unsubstituted alkene carbons are oxidized to formaldehyde, rather than to carbon dioxide as with
KMnO4. Similarly monosubstituted alkene carbons are oxidized to aldehydes, higher rather than to
carboxylate salts as with alkaline KMnO4. However, disubstituted alkene carbons are oxidized to
ketones, the same as with KMnO4.
R H (1) O3,CH2Cl2 -780C R H
C C C O +O C
H H (2) Zn, CH3COOH H H

R R´ (1) O
C C 3 R R´´
R´ H (2) Zn, CH3COOH C O +O C
R´ H

A −H atom attached to the double bond is not oxidized to −OH as it was with permanganate
oxidation.
To form ozonolysis products remove the carbon −carbon double bond and attach oxygen to each of
the originally bonded carbons:
(1)O ,CH Cl −780 C
CH3 − C = CH − CH3 ⎯⎯⎯⎯⎯⎯⎯⎯
3 2 2
(2) Zn,CH3CO2H
→ CH3 − C= O + CH3 − CH = O
| |
CH3 CH3
2-Methylbut-2-ene Acetone Acetaldehyde
Besides being used to synthesize carbonyl compounds, ozonolysis can be used to determine the
location of double bonds in alkenes through structural analysis of the cleavage products.

To create the structure of the original alkene just write the cleavage products, the carbonyl
compounds, with their oxygen’s facing towards each other. Now remove the oxygen’s and join the
carbonyl carbons by a double bond.

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O
CH3 CH2 − C = O + O = C − CH3 ⎯⎯⎯
Zn
HOAc
⎯ ⎯⎯
3
⎯ CH3CH2CH = C− CH3
| | |
H CH3 CH3
2 − Methylpent − 2 − ene

O
CH3CH2 − C = O + O = C− CH2CH3 ⎯⎯⎯
Zn
HOAc
⎯ ⎯⎯
3
⎯ CH3CH2CH = CHCH2CH3
| | Hex −3−ene
H H
O
CH3CH2CH2 − C = O + O = C− CH3 ⎯⎯⎯
Zn
HOAc
⎯ ⎯⎯
3
⎯ CH3 CH2CH2CH = CHCH3
| | Hex −2−ene
H H

13) Polymerisation: Under different conditions, alkenes polymerise to form many important
materials used in our daily life. Everybody is familiar with polyethene bags and polyethene sheets.
When ethylene is heated under pressure with oxygen, a compound of high molecular mass (about
20,000) is obtained:
O ,heat,pressure
nCH2 = CH2 ⎯⎯⎯⎯⎯⎯⎯
2
→−CH2− CH2−CH2−CH2− CH2 − or ( −CH2 − CH2 )n
Polythene or polyethylene
It is essentially an alkane with a very long chain. Since this compound is made up of many ethylene
units, it is aptly called polyethylene (or polyethene). It is familiar to almost everyone as the plastic
material of packaging films.
The formation of polyethylene is a simple example of the process called polymerization : the joining
together of many small molecules to form very large molecules. The compound made up of these
very large molecules is called a polymer (Greek: poly + meros, many parts). The simple compounds
from which polymers are made are called monomers (mono, one).
Other alkenes also undergo polymerization:
nCH3 − CH = CH2 ⎯⎯⎯⎯⎯⎯⎯
High temp / press
catalyst
→( −CH − CH2 −)n
|
CH3
CH3  CH3 
| | 
nCH3 − C = CH2 ⎯⎯⎯⎯⎯⎯⎯
High temp / press
→ C − CH2 − 
catalyst | 
 
 CH3 n

ALKYNE
Alkynes or acetylenes are unsaturated hydrocarbons whose molecules contain one carbon−carbon
triple bond. The common name for this homologous series is acetylenes, after the first member, CH
 CH, acetylene.
Structure of acetylene and the carbon−carbon triple bond- The simplest and stable member of the
alkyne family is ethyne, C2H2, which is popularly known as acetylene. Completion of octet by every
atom is possible in a structure in which the carbon atoms share 3 pairs of electrons, and hence are
joined by a triple bond:
H C C H H C C H

Quantum mechanical picture - To form bond with two other atoms, each carbon atom of ethyne
makes use of two identical sp hybrid orbitals, formed by the mixing of one s and one p orbital:

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1s 2s 2p
C
(excited state)
sp hybridization
sp 2p
C
(sp hybrid state)
These sp orbitals lie along a straight line that passes through the carbon nucleus. This linear
arrangement permits the hybrid orbitals to be as far apart as possible (VSEPR theory). Thus the angle
between the two orbitals is 1800, and two linear bonds are formed through these orbitals.
1.061 Å 1.203 Å
H −−−− C  C − H
180°
Figure 1 Structure of acetylene

H IS -Csp Csp -Csp Csp -H IS

H C C H
 -electronic
Figure 2 Figure 4  -system of acetylene

· These are the acyclic hydrocarbons in which unsaturation (CºC) is present.

· Hybridisation state of triple bonded carbon in alkyne is sp.
· Geometry of unsaturated carbon is linear in alkynes.
· Bond angle in alkyne on sp carbon atom is 180º.
· Their general formula is CnH2n–2 (n = 2, 3, 4, 5 ..........................)
· C–C triple bond length is 1.20 Å, bond length is 1.08 Å.
· C–C triple bond energy is 200 kcal/mol.
· C–H bond energy is 121 kcal/mol.

Nomenclature - In common system, alkynes are named as derivatives of acetylene. In IUPAC

system, they are named as derivatives of the corresponding alkanes replacing ‘ane’ by the suffix
‘yne’. The position of the triple bond is indicated by the first−triply bonded carbon.
Exp 1: Write the structures and IUPAC names of the following compounds:
a) Methylacetylene b) Ethylacetylene c) Dimethylacetylene
Solution: a) CH3 − C  CH, Propyne b) CH3CH2 − C  CH, But-1-yne
c) CH3 − C  C − CH3 , But-2-yne
Isomerism - Alkynes exhibit structural isomerism. Ethyne and propyne have got only one structure
but for butyne two structures are possible:
CH3 − CH2 − C  CH CH3 − C  C − CH3
But-1-yne But-2-yne
(I) (II)

Exp 1 : In how many ways the structure for the alkyne with molecular formula C5H8 can be
constructed?
Solution: First arrange five carbon atoms with a continuous chain and then with a side chain.
I) CH3CH2CH2 − C  CH Pent-1-yne
II) CH3CH2 − C  C − CH3 Pent-2-yne
III) H3 C − CH − C  CH 3-Methylbut-1-yne
|
CH3

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Structures I and II are position isomers while structures I and III or II and III are chain isomers.
Exp 2: Write structures and IUPAC names of all possible structurally isomeric alkynes corresponding
to C6H10. What type of structural isomerism is exhibited by different pairs of isomers?
Solution: First, explore all possibilities for the straight−chain skeleton:
a) 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻2 𝐶 ≡ 𝐶𝐻 b) 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶 ≡ 𝐶 − 𝐶𝐻3
Hex-1-yne Hex-2-yne
c) CH3CH2C  CCH2CH3
Hex-3-yne
Now explore all possibilities for the branched−chain skeleton with one side chain.

d) HC  C − CH − CH2 − CH3 e) HC  C − CH2 − CH − CH3

| |
CH3 CH3
3-Methylpent-1-yne 4-Methylpent-1-yne
f) CH3 − C  C − CH − CH3
|
CH3
4-Methylpent-2-yne
Next explore all possibilities for the branched chain skeleton with two side chains:
Different pairs exhibit position and chain isomerism.
g) CH3
|
HC  C − C − CH3
|
CH3
3, 3−Dimethylbut-1-yne

METHODS OF PREPARATION
Acetylene or ethyne, the most important member of this series may be prepared by any of the
following methods:
1) Hydrolysis of calcium carbide
On industrial scale, ethyne is prepared by the action of water on calcium carbide:
Ca2+ [C̄ ≡ C̄] + 2H − OH → HC ≡ CH + Ca(OH)2
Calcium carbide Acetylene
Δ
Calcium carbide is prepared by heating quick lime with coke: CaO + 3C → CaC2 + CO
Δ
Quick lime can be obtained by heating limestone CaCO3 → CaO + CO2
2) Partial oxidation of methane
It is also made industrially by the controlled, high−temperature partial oxidation of methane:
15000 C
6CH4 + O2 → 2CH ≡ CH + 2CO + 10H2

Other industrial methods are:

a) The cracking of methane−ethane mixture
b) Heating a mixture of ethane (or propane) and steam to 1000−13000C.
3) Dehydrohalogenation Ethylidene dibromide and ethylene dibromide on treatment with
alcoholic potassium hydroxide undergo dehydrohalogenation. The reaction proceeds in two
steps:
CH2 − CH2 + KOH ⎯⎯⎯⎯
ethanol

→ CH2 = CH − Br + H2O
| |
Br Br
1, 2-Dibromoethane Vinyl bromide

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(ethylene dibromide)
ethonolΔ
CH2 = CH − Br + KOH → CH ≡ CH + KBr + H2 O
ethanolΔ
CH3 CHBr2 + KOH → CH2 = CH − Br + KBr + H2 O
ethanolΔ
CH2 = CH − Br + KOH → CH ≡ CH + KBr + H2 O
Under suitable conditions the intermediate product vinyl bromide may be isolated.
Sodamide in liquid ammonia can be used instead of ethanolic potassium
hydroxide.
Liq. NH3
CH2 − CH2 + 2NaNH2 ⎯⎯⎯⎯⎯ → CH  CH + 2NaBr + 2NH3
| |
Br Br
Intramoleculer dehalogenation 1, 1, 2, 2−tetrahaloethane undergo loss of halogen on heating
with zinc dust and methanol to yield ethyne:
x x
| | 
CH − CH + 2 Zn ⎯
⎯→ CH  CH + 2 ZnX 2
| |
x x
Intermolecular dehalogenation By heating a haloform with silver powder, e.g., iodoform:
heat
CHI3 + 6Ag + I3 CH → CH ≡ CH + 6AgI
4) Kolbe’s electrolytic method Electrolysis of a concentrated aqueous solution of the sodium
(or potassium) salt of maleic or fumaric acid yields acetylene:

CHCOO Na+ CH
(aq) + 2H2O ( ) + 2CO2 + 2NaOH H2
CHCOO Na+ CH
At cathode
Sodium maleate Ethyne
or
At anode
sodium fumarate

Physical properties of Acetylene

· Alkynes are colourless, odourless and tasteless.
· Lower alkynes are partially soluble in H2O.(It is due to its polarisibility).
· Higher alkynes are insoluble in water due to more % of covalent character.
· Completely soluble in organic solvents.
· Melting point and boiling point increases with molecular mass and decreases with number of
branches.
· Physical state :
C2–C4 ® Gaseous C5–C11 ® Liquids C12 & above ® Solids
Molecular weight
· Boiling point and Melting point µ
No. of branches

Acidity of Alkynes - The hydrogen in terminal alkynes are relatively acidic. Acetylene itself has a 𝑝𝐾𝑎
of about 25. It is a far weaker acid that water (𝑝𝐾𝑎 15.7) or the alcohols (𝑝𝐾𝑎 16 − 19), but it is much
more acidic than ammonia (𝑝𝐾𝑎 34). A solution of sodium amide in liquid ammonia readily converts
acetylene and other terminal alkynes into the corresponding carbanions.

RC ≡ CH + NH2− → RC ≡ C − + NH3
The reaction does not occur with alkenes or alkenes. Ethylene has a 𝑝𝐾𝑎 of about 44 and methane has
a 𝑝𝐾𝑎 of about 50. From the foregoing 𝑝𝐾𝑎′ 𝑠 we see that there is a vast difference in the stability of

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sp3 sp 2 sp
41 ACTIVE SITE EDUTECH-9844532971

the carbanions 𝑅𝐶 ≡ 𝐶 − , 𝐶𝐻2 = 𝐶𝐻 − , and 𝐶𝐻3− . This difference may readily be explained in terms of
the character of the orbital occupied by the lone-pair electrons in the three anions.

Electrons in s-orbitals are held, on the average, closer to the nucleus than they are in p-orbitals. This
increased electrostatic attraction means that s-electrons have lower energy and greater stability than
p-electrons. In general, the greater the amount of s-character in a hybrid orbital containing a pair of
electrons, the less basic is that pair of electrons, and the more acidic is the corresponding conjugate
acid.
CH 3 : CH 4
base CH 2 = CH : CH 2 = CH 2 acid
strength strength
HC  C : HC  CH
Chemical properties of acetylene - Due to the presence of a triple bond, acetylene is more
unsaturated than ethylene. It forms addition products with two or four univalent atoms or groups,
never one or three. When two univalent atoms or groups add on to a triple bond, the linear (or
diagonal) arrangement changes into the trigonal and the further addition of two univalent atoms or
groups changes the trigonal into the tetrahedral arrangement.
A B
A B H H AB
HC CH C C H C C H
A B
A B
Under suitable conditions it is possible to isolate, the intermediate alkene(s).
1) Addition of dihydrogen: Acetylene adds on dihydrogen under pressure in the presence of a Pt,Pd,Ni
catalyst, the reaction proceeding in two stages:
H2 catalyst H2 catalyst
HC ≡ CH → H2 C = CH2 → CH3 − CH3
Acetylene Ethylene Ethane
Most catalysts affect hydrogenation of a triple bond. By using suitable conditions, it is possible to
isolate the intermediate alkene one such method makes use of Landler’s catalyst which consists of a
Pd − CaCO3 catalyst partially poisoned with lead acetate. A better catalyst is Pd−BaSO4 partially
poisoned with quinoline.
Pd−CaCO3 /leadacetate(or)Pd−BaSO4 /quinoline
HC ≡ CH → H2 C = CH2

2) Addition of halogens: Acetylene adds on gaseous chlorine or bromine in the dark to form acetylene
di−and tetra−halides:
Cl Cl
CCl4 Cl2
H C C H + Cl 2 H C C H H C C H
CCl4
Cl Cl Cl Cl
1, 2-Dichloroethene 1, 2, 2, 2 -Tetrachloroethane
Similarly
Br Br
| |
CCl4 Br2
CH  CH + Br2 ⎯⎯⎯⎯ → CH = CH ⎯⎯⎯⎯ → H −C −C − H
| | CCl4 | |
Br Br Br Br

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Reddish orange colour of the solution of bromine in carbon tetrachloride is decolorized. This is used
as a test for unsaturation. The addition of halogens is catalysed by light and metallic halides.
Direct combination of acetylene with chlorine may lead to explosion. This is prevented by the
presence of a metal chloride catalyst.
Acetylene reacts with dilute bromine water to produce acetylene dibromide.
H2O
CH  CH + Br2 ⎯⎯⎯ ⎯→ BrCH = CHBr
Acetylene adds on iodine with difficulty, but if the reaction is performed in ethanolic solution
acetylene di−iodide is formed:
ethanol
CH  CH + I2 ⎯⎯⎯⎯⎯ → I − CH = CH − I
The addition of halogens to acetylene is stereoselective as the predominant product is the trans
isomer.
H X
H C C H+ X X C C
X H
3) Addition of hydrogen halides Acetylene can add on two molecules of hydrogen halides (HCl, HBr
and HI) to form gem dihalides, in which the two halogen atoms are attached to the same carbon atom:
H−X
HC ≡ CH + H − X → CH2 = CH − X → CH3 CHX2
(HX = HCl, HBr and HI)
Order of reactivity of halogen acids: HI > HBr > HCl > HF
The reactivity of HF is so low that it adds on only under pressure.
The addition of the halogen acids takes place in the dark but can be catalysed by light or metallic
halides. The addition is highly regioselective i.e. in accordance with Markownikov’s rule. For instance,
acetylene combines with hydrogen iodide to form first vinyl iodide, and then ethylidene diiodide:
H−I
CH ≡ CH + H − I → CH2 = CH − I → CH3 CHI2
Peroxides have the same effect on the addition of hydrogen bromide to acetylene as they have on
alkenes:
CH  CH + H − Br ⎯⎯⎯⎯
Organic
peroxide
→ CH2 = CH − Br ⎯⎯⎯⎯⎯⎯HBr
organicperoxide
⎯→ CH2 − CH2
| |
Br Br
4) Addition of water When acetylene is passed into dilute sulphuric acid at 600C in the presence of
mercuric sulphate as catalyst, it adds on one molecule of water to form first vinyl alcohol which
undergoes tautomerisation to form acetaldehyde as the main product:
H2 SO4 Hg2+
CH ≡ CH + H2 O → [CH2 = CHOH] → CH3 CHO
The homologues of acetylene form ketone when hydrated, example, propyne gives acetone.

OH O
H SO | ||
CH 3 − C  C − H + H 2O 2 4 CH 3 − C = C − H CH 3 − C − CH 3 ( Markovnikov addition )
HgSO 4 |
H
a vinyl alcohol Acetone
( Unstable )
C  C−H O = C − CH 3
| |
+ H 2 O ⎯⎯⎯
H 2SO 4
HgSO 4
→
Acetophenone
5) Addition of hydrogen chloride On treatment with dilute hydrochloric acid at 650C in the presence
of mercuric ions as catalyst, acetylene gives vinyl chloride:

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Hg2+
HC ≡ CH + HCl → CH2 = CH − Cl
Acetylene Vinyl chloride
6) Addition of hydrogen cyanide In the presence of cuprous chloride in hydrochloride acid as catalyst,
acetylene adds on hydrogen cyanide to form vinyl cyanide:
CuCl2 HCl
HC ≡ CH + HCN → CH2 = CH − CN

7) Combustion: Acetylene burns with a luminous smoky flame (due to the high carbon content) on
heating in excess of air or oxygen, forming carbon dioxide and water with the evolution of large
amount of heat:
2CH ≡ CH + 5O2 → 4CO2 + 2H2 O; ΔC H Θ = −1299.1kJ/mol

8) Ozonolysis
Acetylene adds on ozone to form an ozonide which on hydrolysis in the presence of zinc dust gives
glyoxal: Some amount of formic acid (HCO2H) is also formed.
O CHO + H2O
Zn
HC CH + O3 HC CH
H 2O
CHO + ZnO
O O
9) Cyclic Polymerisation Acetylene polymerises, to a small extent to benzene, when passed through
a heated iron tube:
H
C
CH
Cu or Fe H−C C−H
3H − C  C − H ⎯o⎯ ⎯ ⎯→
o
HC C
300 C or 500
H−C CH C − H

CCH
HC Benzene
H
CH

When a mixture of acetylene and ammonia is passed through a red-hot tube, pyrrole is formed,
through polymerization:
2C2H2 + NH3 → C4H5N + N2
Pyridine is formed when a mixture of acetylene and hydrogen cyanide is passed through a red-hot
tube :

2C2H2 + HCN

N
10) LINEAR POLYMERISATION OR POLYMERISATION CUM CONDENSATION:
Two mole of acetylene condenses in presence of NH4Cl and cuprous chloride gives vinyl acetylene,
which on
further condensation with one mole of acetylene in presence of same reagent on heating gives divinyl
acetylene.
Cu2 Cl2 +NH4 Cl
2H − C ≡ C − H → H − C ≡ C − CH = CH2

Cu Cl2 + NH 4Cl / 
⎯⎯2⎯ ⎯ ⎯⎯⎯ ⎯→ CH 2 = CH − C  C − CH = CH 2
H −CC− H Divinyl acetylene
Distinction between alkanes, Alkenes and Alkynes

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Property Alkane (Ethane) Alkene (Ethene) Alkyne (Ethyne)

Molecular formula CnH2n+2(C2H6) CnH2n(C2H4) CnH2n–2(C2H2)
Nature Saturated Unsaturated Unsaturated
Single bond between Double bond between two Triple bond between tw
carbon atoms. Each carbon carbon atoms. Both carbon carbon atoms both carbo
atom is sp3-hybridized atoms are sp2-hybridized atoms are sp-hybridized
C–C C=C –CC–
Bond length 1.34 Å 1.20 Å
1.54 Å 146 Kcal mol –1
200 Kcal mol–1
Bond energy : 83 Kcal mol–
1

Burning Burns with nonluminous Burns with luminous flame Burns with smoky flame
flame C2H4+3O2 → 2CO2+2H2O C2H2+5/2O2 → 2CO2+H2O
C2H6+7/2O2 → 2CO2+3H2O
Reaction with H2 – Forms alkane Forms alkene and alkane
CnH2n + H2 ⎯⎯→
Ni CAlkane
nH2n+2 CnH2n + H2 ⎯⎯→
Ni CnAlkane
H2n+2
o o
300 C 300 C

C2H4 + H2 → C2H6 CnH2n–2 + H2 ⎯⎯→

Ni
o
CnH2n
Alkene
300 C

Reation with conc. – Addition Addition

H2SO4 and hydrolysis C2H4+H2SO4 → C2H5HSO4 C2H2→ CH3CH(HSO4)2 ⎯⎯ ⎯→
H 2O

⎯⎯ ⎯→
H 2O
C2H5OH Alcohol CH3CHO Aldeh

Br2/CCl4 – Decolourises Decolourises

Dibromo derivative, Tetrabromo derivative,
C2H4 + Br2 → C2H4Br2 C2H2Br4
Baeyer’s reagent – Decolourises Decolourises
(Alk. KMnO4) Glycol is formed Oxalic acid is formed
CH 2 CH 2 OH CH COOH
|| + H 2O + O →| ||| + 4 O →|
CH 2 CH 2 OH CH COOH

Ammonical Cu2Cl2 – – Red precipitate

CH CCu
||| + Cu 2 Cl 2 + 2 NH 4 OH → | | |
CH CCu
(Red)

+ 2NH4Cl + 2H2
Ammonical silver – – White precipitate
nitrate CH C − Ag
||| + 2 AgNO 3 + 2 NH 4 OH → | | |
CH C − Ag

+ 2NH4Cl + 2H2

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AROMATIC HYDROCARBON
· These are also called arenes.
· General formula is CnH2n–6y. Where y is the number of benzene ring in molecule and n is not
less than 6.
• Arenes are cyclic and planar. They undergo substitution rather than addition reactions.
CH3 CH2CH3 CH3 CH3 CH3
CH3

CH3
Benzene Toluene Ethyl CH3
benzene

o/m/p-xylene

Aromaticity or aromatic character : The characteristic behaviour of aromatic compounds is called

aromaticity. Aromaticity is due to extensive delocalisation of -electrons in planar ring system. Huckel
(1931) explained aromaticity on the basis of following rule.

Huckel rule : For aromaticity, molecule must be planar, cyclic system having delocalised
electrons where n is an integer equal to 0, 1, 2, 3,------.
Thus, the aromatic compounds have delocalised electron cloud of 2,6,10 or 14  electrons.
Example : ; ;

Benzene 6 electrons

n=1

Biphenyl Naphthalene 10 electrons Anthracene 14 electrons

n=2 n=3
Similarly cyclolpentadienyl anion or tropylium ion are also aromatic because of the presence of 6
electrons (n=1).

H H H
H H 

.. H
H H H
−
H H H

Cyclopentadienyl anion 6ACTIVE
Tropyllium ion 6  Cyclopropenyl
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electrons (n=1) electrons (n=1) cation (n = 0)
46 ACTIVE SITE EDUTECH-9844532971

Heterocyclic compounds also have 6 electrons (n = 1).

..
.. ..
N O S N
H Pyridine
Furan Thiophene
Pyrrole

Molecules do not satisfy huckel rule are not aromatic.

H .−.

H 

Cyclopentadiene Cyclopentadienyl cation Cyclooctatetraene Cyclopropenyl anion

Illustrate example :
4 electrons 4 electrons 8 electrons 4 electrons

Benzene (C6H6)
Benzene is the first member of arenes. It was first discovered by Faraday (1825) from whale oil.
Mitscherllich (1833) obtained it by distillating benzoic acid with lime. Hofmann (1845) obtained it
from coal tar, which is still a commercial source of benzene.
(1) Structure of benzene : Benzene has a special structure, which is although unsaturated even
then it generally behave as a saturated compound.
(i) Kekule's structure : According to Kekule, in benzene 6-carbon atoms placed at corner of
hexagon and bonded with hydrogen and double bond present at alternate position.
Evidence in favour of Kekule's structure
• The elemental analysis and molecular mass determination show that molecular formula of
Benzene is C6H6
• Benzene combines with 3 molecules of hydrogen or three molecules of chlorine. It also
combines with 3 molecules of ozone to form tri-ozonide. These reactions confirm the
presence of three double bonds.

Cyclohexane
Benzene hexachloride
Benzene triozonide
• Studies on magnetic rotation and molecular refraction show the presence of three double
bonds and a conjugated system. Even though Benzene contains three double bonds like
alkenes it does not decolourise the alk.KMnO4.
This confirms the three double bonds of benzene are not free to react.
• . Kekulé proposed that the carbon atoms of benzene are in a ring, that they are bonded to
each other by alternating single and double bonds, and that one hydrogen atom is attached
to each carbon atom.

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H C H
C C
or
C C
H C H

H (I)
• Above structure gives two types of ortho disubstituted products as shown below.
Cl Cl

C Cl Cl C Cl
H Cl H
C C Cl C C Cl
or or
C C C C
H C H H H
C
H H
But in actual only one type of ortho disubstituted product is found. Hence above structure
cannot explain the practical observation.
• To overcome the above facts, Kekulé proposed that the carbon atoms in benzene were
continually in a state of vibration, and due to this vibration, each carbon-carbon pair had a
double bond half of the time and the single bond the other half.
Hence 2 structures are possible for benzene and they are in dynamic equilibrium with each
other.
H H

H C H H C H
C C C C

C C C C
H C H H C H

H H or

• According to resonance theory, whenever equivalent resonance structures can be drawn for
a molecule, the molecule (or hybrid) is much more stable than any of the resonance structures
would be individually, if they could exist.
Since resonance contributors I and II are exactly identical, and hence of exactly the same
stability they make equal contributions to the hybrid. And also, stabilization due to resonance
should be large. In this way, resonance theory accounts for the much greater stability of
benzene when compared to the hypothetical 1, 3, 5−cyclohexatriene, hence its aromatic
character. For this reason, the extra stability associated with benzene is called its resonance
energy.
The hybrid structure is represented by inscribing a circle in the regular hexagon, and it is this
new formula (III) that is most often used for benzene today.

THE MOLECULAR ORBITAL STRUCTURE OF BENZENE :

According to this theory, all of the six carbon atoms in benzene ring are in sp2 hybridised state.

By overlapping of hybrid orbitals these six carbon atoms form a planar hexagonal ring. Now

each of 'p' orbital on the six carbon atoms can overlap on either side with adjacent 'p' orbitals.

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These result in a molecular orbital which is actually made of two continuous rings, one ring

above and another below the plane of hexagon.

H H
. .
H . . H
. .
H H

H H

H H H C C H
C C
H H H H

Concept Map

Aromatic compounds

Must be Must have include have

A p-orbital at each Benzenoid aromatic Characteristic
Planar (or flat) atom of the ring compounds spectroscopic
properties
Cyclic (4n+2)-delocalized electrons:
Hückel rule for monocyclic Mono−and polycyclic
(monocyclic or
aromatic compounds and for benzenoid aromatic
polycyclic)
periphery of polycyclic aromatic compounds such as toluene,
compounds. naphthalene, anthracene,
pyrene etc.,

High degree of unsaturation Fullerenes and nanotubes

Tendency to undergo substitution Nonbenzenoid aromatic

rather than addition compounds

Atomatic anions or cations e.g.

cyclopentadienyl anion,
Unusual stability (large resonance or cycloheptatrienyl cation
delocalization energy)
Aromatic annulenes e.g. [18]
annulene

Heterocyclic aromatic
compounds e.g. pyrrole,
thiophene, furan, pyridine.

Methods of preparation of benzene

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(i) Laboratory method : Sodium salts of Benzoic acid on heating with soda lime undergoes
decarboxylation to give Benzene.
COONa
+ NaOH CaO + Na2CO3
heat
Sodium benzoate Benzene
(ii) From benzene derivatives
(a) From phenol : When phenol heated with zinc dust, reduction takesplace forming Benzene.
OH

+ Zn distill + ZnO

Benzene
Phenol Cl
(b) From chlorobenzene :
+ Ni-Al alloy
2H + HCl
NaOH
Chlorobenzene Benzene
(c) By first preparing grignard reagent of chlorobenzene and then hydrolysed
OH
C 6 H 5 Cl ⎯⎯
⎯→ C 6 H 5 MgCl ⎯⎯
Mg
⎯→ C 6 H 6 + Mg
H 2O

Chlorobenz ene dry ether Phenyl magnesium Benzene Cl

chloride

(d) From benzene sulphonic acid :

SO3H

150°-200°C +H2SO4
+ HOH
Steam HCl,press
Benzene sulphonic acid
ure Benzene

(e) From benzene diazonium chloride :

N2Cl

SnCl2
+ 2H +N2 +HCl
NaOH
Benzene

(iii) From acetylene : - When ethyne is passed through a red hot iron tube 873K, three molecules
undergo cyclic polymerisation to give Benzene.
HC
+
HC CH red hot tube
+ 1500-2000°C
HC CH
Benzene
+
HC
Three molecules of acetylene
Cr2 O3 /Al2 O3
(iv) Aromatisation : C6 H14 → C6 H6 + 4H2
n−Hexane 500°C Benzene
at high pressure
Physical properties of Benzene
· Benzene is a colourless volatile liquid. It has characteristic smell.
· Its boiling point is 80oC and freezing point is 5.5o C.
· It is highly inflammable and burns with sooty flame.
· It is lighter than water.Its specific gravity at 20oC is 0.8788.
· It is immiscible with water but miscible with organic solvents such as alcohol and ether.
· It is a non - polar compound and its dipole moment is zero.
· It is extremly poisonous substance. Inhalation of vapours or absorption though skin has a toxic

effect.

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Chemical properties of Benzene

There is a cloud of -electrons above and below the plane of the benzene ring. On account of
resonance (delocalization), pi () electrons of benzene are more involved in keeping together carbon
nuclei relative to the pi () electrons of the carbon-carbon double bond. However, with respect to the
sigma () electrons these pi () electrons are loosely held and are easily available to a reagent that is
in the need of electrons. Thus, in its typical reactions, the benzene ring acts as a source of electrons,
that is, as a (Lewis) base.
The typical reactions of the alkenes are electrophilic addition reactions while the typical reactions
of the benzene ring are electrophilic substitution reactions.
Electrophilic Aromatic Substitution
1) Halogenation: Substitution of one of the ring hydrogens by a halogen atom in presence of halogen
carrier Lewis acids like FeCl3, FeBr3 etc :
Ar − H + X − X ⎯⎯
Fe
⎯→ Ar − X + H − X
Aryl halide
2) Nitration: Substitution of one of the ring hydrogens by a nitro group in presence of nitrating
mixture.:
H SO
Ar − H + HO − NO2 ⎯⎯⎯⎯
2 4
→ Ar − NO2 + H2O
Nitro compound
3) Sulphonation: Substitution of one of the ring hydrogens by a sulphonic acid group:
SO
Ar − H + HO − SO3H ⎯⎯⎯
3
→ Ar − SO3H + H2O
Benzene Sulphonic acid
4) Friedel−Crafts alkylation: Substitution of one of the ring hydrogens by an alkyl group:
AlCl
Ar − H + R − Cl ⎯⎯⎯→
3
Ar − R + HCl
Alkyl arene
5) Friedel−Crafts acylation: Substitution of one of the ring hydrogens by an acyl group ( R C − O − )
||
O
O
||
AlCl3
Ar − H + R − C− Cl ⎯⎯⎯→ Ar − C− R + HCl
||
O
Aromatic ketone

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X2, FeX3
+ HX Halogenation
(X = Cl, Br)
NO 2

HO NO 2 + H2O Nitration
H2SO4
SO3H

SO3
+ H2O Sulphonation
HOSO 3H

RCl, AlCl 3
+ HCl Friedel-Crafts
(R can rearrange) Alkylation
O R
O C

R C Cl, AlCl 3
+ HCl Friedel-Crafts
Acylation

Examples for the mechanism of electrophilic substitution reactions of Benzene

1. Halogenation of Benzene - For the halogenation of arenes the following conditions favour
aromatic halogenation (i.e., nuclear substitution):
a) absence of light,
b) low temperature, and
c) the presence of a halogen carrier ( a Lewis acid)
Bromination and chlorination may be very conveniently carried out at ordinary temperature in the
presence of a Lewis acid. When Lewis acids are present, benzene reacts readily with bromine or
chlorine. The reactions give bromobenzene and chlorobenzene, respectively, in good yields. The Lewis
acids most commonly used to bring about bromination and chlorination reactions are the bromides
or chlorides of Fe, Al and Sb (FeX3, AlX3 and SbX3), all in the anhydrous form. Ferric bromide and ferric
chloride are usually generated in the reaction mixture by adding iron to it. The iron then reacts with
halogen to produce the ferric halide:
2Fe + 3X 2 → 2FeX 3
Thus, iron is most commonly used being converted to the Lewis acid, FeX3, by the halogen.
Br
FeBr3
+ Br Br + H Br
heat

Bromobenzene

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Cl
FeCl3
+ Cl Cl + H Cl
250 C

Chlorobenzene
The mechanism for electrophilic aromatic chlorination is as follows:
Step 1 Chlorine combines with FeCl3 to form the Lewis acid complex that dissociates to form a positive
chloride ion and FeCl4−.

+
Cl Cl + FeCl 3 Cl Cl FeCl 3 +
Cl + Cl FeCl 3
Step 2 : The positive chlorine ion (chloronium ion) attacks benzene to form an arenium ion:
+
H H H H
+ +
slow Cl Cl Cl Cl
+ Cl
+ + + +

Arenium ion
Step 3 : A proton is removed from the arenium ion by FeCl4− to yield chlorobenzene and hydrogen
chloride. At the same time, this step regenerates the catalyst, FeCl3.
H Cl
Cl Cl FeCl3 + H Cl FeCl3
+
Note-
• Aromatic fluorination requires special conditions and special types of apparatus because
fluorine reacts much readily with benzene. Moreover, it is difficult to limit the reaction to just
monofluorination.
HBF4
Fluorobenzne can be made by an indirect method Ar − NH2 ⎯⎯⎯⎯ HONO
0−50 C
→ Ar − N2 ⎯⎯⎯⎯
2) heat
→ Ar − F

.
• On the other hand, iodine is so less reactive that some special techniques are to be used to
bring about direct iodination. To avoid the reversible reaction, the reaction must be carried
out in the presence of an oxidizing agent such as nitric acid.
I

HNO3
+I I

The better method to make iodo-compounds is to use diazonium salts:

HONO KI
Ar − NH2 ⎯⎯⎯⎯⎯ → Ar − N2+ ⎯⎯⎯ → Ar − I
0−5 C
0

2. Nitration of arenes – It gives Aromatic nitro-compounds, ArNO2, are usually prepared by direct
nitration. For this purpose, any of the following reagents may be employed.
a) Concentrated or fuming nitric acid,
b) Mixed acid (a mixture of concentrated nitric and sulphuric acids(nitrating mixture) is the most
commonly employed reagent for nitration.
Exp - Benzene reacts slowly with hot concentrated nitric acid to yield nitrobenzene. Nitration of
benzene becomes much faster if it is carried out by heating benzene with a mixture of concentrated
nitric acid and concentrated sulfuric acid.

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NO2
H2SO4 +
+ HO NO2 + H3O + HSO 4
50 550 C

Concentrated sulphuric acid increases the rate of the reaction by increasing the concentration of the
electrophile, the nitronium cation,NO⊕ 2 .
Step 1 In this step the weaker nitric acid accepts a proton from the stronger sulphuric acid:
H
O O
+ fast + + + HSO4
H O N + H OSO 2OH H O N
O O
Step 2 Protonated nitric acid dissociates to form a nitronium ion.
H H
O
+ + slow +
H O N H O +O N O
O
Nitronium ion
Step 3 Water accepts a proton from another molecule of sulphuric acid:
H2O: + H-OSO2-OH H3O+ + HSO-4
The overall equation may therefore be written as:
HNO3 + 2H2 SO4 ⇌ NO+ +
2 + H3 O + 2HSO4
−

Step 4 Nitronium ion, the actual electrophile in nitration, reacts with benzene to form a resonance
stabilized arenium ion:
O H H
H +
+ Slow NO2 NO NO2
+ N 2
+ +
O
Arenium ion
Step 5 A proton is removed by a Lewis base from the arenium ion to yield nitrobenzene:
H NO2
+
NO2 O SO OH fast
+ 2 + H2SO4

3. Sulphonation of benzene – Benzene, aromatic hydrocarbons and their derivatives can be

sulphonated, with concentrated or fuming sulphuric acid or with chlorosulphonic acid.
Thus, this reaction can be used to separate alkanes from arenes (aromatic hydrocarbons) because the
alkanes are not so readily sulphonated. The normally used sulphonating agents are:
a) concentrated sulphuric acid,
b) sulphur trioxide in sulphuric acid, that is, oleum (fuming sulphuric acid),
c) sulphur trioxide in organic solvents such as nitromethane, pyridine, etc,
d) chlorosulphonic acid in carbon tetrachloride (using one molecule of reagent),
e) sulphonyl chloride (using excess of reagent).
Benzene reacts slowly with hot concentrated fuming sulphuric acid to yield benzenesulphonic acid:
heat
C6 H6 + H2 SO4 → C6 H5 SO3 H + H2 O
Sulphonation of Benzene involves the following steps:
Step 1 Formation of SO3 in concentrated sulphuric acid:
2H2 SO4 ⇌ SO3 + H3 O+ + HSO− 4
It is simply, an acid-base equilibrium, between molecules of sulphuric acid.
Step 2: Sulphur trioxide, the actual electrophile (as S atom is highly electron deficient due to being
attached with three O atoms), attaches itself to the benzene ring to form the intermediate
carbocation, an arenium ion :

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O O
slow .........
+ S + S O
H
O O O
Step 3 The arenium ion loses a proton to a Lewis base to form the benzenesulphonate ion, the anion
of benzenesulphonic acid which, being a strong acid is highly ionized:
O O
+ fast
S O + HSO 4 S O + H2SO 4
H
O O
Step 4 A proton is accepted by the benzenesulphonate ion to form benzenesulphonic acid:
O O
fast
S O +H O H S O H + OH

O O

4. Friedel-Crafts alkylation – Benzene reacts with alkyl halides in presence of Anhy.,AlCl3 catalyst gives
alkyl benzene.
H R
AlCl3
+ R Cl + H Cl

Mechanism of the Friedel-Crafts Alkylation

Step 1 It’s a Lewis acid-base reaction between the alkyl halide (Lewis base, L.B) and the ferric
chloride or AlCl3 (Lewis acid, L.A.) to form the 1:1 adduct. The complex then dissociates to form a
free carbocation and AlCl−4 .

Cl Cl
H3 C H3 C + H3 C + 
CH Cl + Al CH Cl Al Cl CH Cl AlCl3
H3 C H3 C H3 C
Cl Cl Cl
Cl
H3C +
CH + Cl Al Cl
H3C
Cl
Notice that, the AlCl−4 ion is a better leaving group than Cl−. Thus the Lewis acid, AlCl3, serves the
same purpose here that a Lowry−Brønsted acid does in the protonation of an alcohol.
Step 2 The free carbocation, behaving as an electrophile, attaches itself to the benzene ring to produce
the intermediate carbocation, the arenium ion:

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H3C CH 3

CH H
+ CH 3 +
+ CH Other resonance contributors
CH 3

Step 3 The arenium ion loses a proton to a Lewis base to form isopropylbenzene. This step also
regenerates the catalyst AlCl3 and liberates HCl.
H3 C CH3 H3 C CH3
CH CH
H Cl
+
+ Cl Al Cl + HCl + AlCl3
Cl
chloride.
The alkylating agents may be
a) alkylhalides, b) aliphatic alcohols, c) alkenes, d) ethers and e) alkyl esters of organic and
inorganic acids.
From the view point of convenience, the alkylating agent is usually confined to alkyl halides, alcohols
and alkenes.
Two types of catalysts are used in the Friedel−Crafts reaction.
(i) Lewis acid catalysts Metal halides, their general order of reactivity is :
AlCl3  BF3  SbCl5  FeCl3  SnCl4  ZnCl2
The more reactive the substrate, the weaker the Lewis acid used.
(iii) Lowry−Brønsted acid catalysts H3PO4, H2SO4 and HF.

5. Friedel−Crafts acylation The Friedel−Crafts acylation reaction is an effective method of introducing

an acyl group ( R − C − ) into an aromatic ring. A reaction which introduces an acyl group into a
||
O
compound is called an acylation reaction. Two common acyl groups are the acetyl group and the
benzoyl group:
O O
CH3 C C
Acetyl group Benzoyl group
(ethanoyl group)
The benzoyl group, C6H5CO− is not to be confused with the benzyl group, C6H5CH2− .
O
|| AlCl3
Ar − H + R − C− Cl ⎯⎯⎯⎯ → Ar − C− R + HCl
||
O

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Acyl (acid) chloride Ketone

O
O
AlCl3 C CH 3
+ CH 3 C Cl + HCl
excess
Acetyl chloride benzene
800C Acetophenone
(methyl phenyl ketone)
Besides, acid chlorides, the acylating agents may be carboxylic acid anhydrides, carboxylic acids or
esters:
O
O
CH3 C O
AlCl3 C CH3
+ O excess benzene + CH3 C OH
CH3 C 800C
O Acetophenone
Acetic anhydride
(carboxylic acid anhydride)
It involves the following steps:
Step 1 It is a Lewis acid-base reaction forming the 1 : 1 adduct:
O Cl O Cl
+
R C Cl + Al R C Cl Al Cl

Cl Cl Cl
Step 2 The Lewis acid−base complex dissociates to form an acylium ion:

+ Cl
O Cl O O
+
R C Cl Al Cl R C + R C +Cl Al Cl

Cl Cl
Step 3 The acylium ion, behaving as an electrophile, attaches itself to the benzene ring to form the
arenium ion:
R O
C
R H
+ other resonance contributiors
+C

O+ Arenium ion

Step 4 : The arenium ion loses a proton to a Lewis base to form the aryl ketone:
R O R O
C C
H
Cl
+ +
+ Cl Al Cl + HCl + AlCl3
Cl
+

Step 5 The aryl ketone, behaving as a Lewis base, reacts with aluminum chloride (a Lewis acid) to form
a complex:

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R O +
C R C O AlCl 3
Cl

+ Al
Cl Cl
Step 6 Treatment of the complex with water liberates the ketone and hydrolyzes the Lewis acid:

+ O AlCl3 O

C + 3H OH C + Al (OH)3 + HCl
R R
C6 H 5

Directive effect in substituted benzene derivatives

(1) Directive effect in mono substituted benzene derivatives : The substituent already present
on the benzene ring directs the incoming substituent to occupy ortho (2 or 6), meta (3 or 5) or para
(4) position. This direction depends on the nature of the first substituent and is called directive or the
orientation effect.
The substituent already present can increase or decrease the rate of further substitution, i.e., it
either activates or deactivates the benzene ring towards further substitution. These effects are called
activity effects.
There are two types of substituents which produce directive effect are,
(i) Those which direct the incoming group to ortho- and para-positions simultaneously
(Neglecting meta all together).
(ii) Those which direct the incoming group to meta-position only (Neglecting ortho- and para-
positions all together).

Classification of substituents
Almost all substituent groups fall into one of two classes:
Class I makes the benzene ring relatively more reactive and directs the incoming group mainly to the
o− and p− positions, that is, activating and ortho−para directors:
a) Strongly activating :
b) Moderately activating :
c) Weakly activating: −CH3 , − C2H5 , − R, − C6H5

Class II makes the benzene ring relatively less reactive and directs the incoming group mainly to the
m-position, that is, deactivating and meta-directing:
+
a) Strongly deactivating: −NO2, −NR3 , −CF3, −CCl3.
b) Moderately deactivating : −C  N, − SO3H, − CO2H, − CO2R − CHO, − COR
Ortho-para directors Meta directors
.. .. .. .. .. – Moderately deactivating
Strongly activating − NH 2 ,− NHR ,− NR2 , – .OH, – .O:.
. −C  N,−SO3 H, −COOH ,−COOR , −CHO , COR

Moderately activating
.. .. .. ..
− NHCOCH 3 , − NHCOR –, OCH3, – OR
Strongly deactivating − NO2 ,− NR3 ,−CF3 ,−CCl3
.. ..

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Weakly activating −CH3 ,−C2 H5 ,−R,−C6 H5

.. .. .. ..
Weakly deactivating – .F:. , – .Cl:
. , – Br:
. . , –.I.: ,

Theory of ortho – para directing group

S S S
:S :S

.−. .−.
,i.e.,

.−.

 S Ortho attack S S
Ortho
E
− −

+ E +

− Ortho product
E
Para attack Para product
CH3 CH3 CH3
H2SO4, SO 3 SO3H
0
+ + m - isomer
35 C
SO3H
o - Toluene
Toluene sulphonic acid p - Toluene
32%C sulphonic acid
62%C

CH3 CH3 CH3

CH3
HNO3 NO2
+ +
H2SO 4
NO2
o - Nitrotoluene
NO2 m - Nitrotoluene
(59%)
p - Nitrotoluene (4%)
(37%)

Both phenol and aniline react with bromine in water, in the absence of a catalyst, to produce products
in which both of the ortho positions and the para position are substituted. These tribromo products
are obtained in nearly quantitative yield:
OH OH NH2 NH2
Br Br Br Br
Br 2 Br2
H2O H2O

Br Br
2, 4, 6 - Tribromophenol 2, 4, 6 - Tribromoaniline
( ~ 100%) ( ~ 100%)

The above mechanism is followed when S is −OH, −NH2 , −Cl, −Br, −I, −OR, −NR 2 , −NHCOR etc

CH3 CH3 CH3 CH3

.−. .−.

.−.
In methyl or alkyl group, the +I effect of the methyl group or alkyl group initiates the resonance effect.
Thus, methyl or alkyl group directs all electrophiles to ortho and para positions.

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Theory of meta directing group : The substituent, S withdraws electrons from ortho and para
positions. Thus, m-position becomes a point of relatively high electron density and further substitution
by electrophile occurs at meta position. For example, − NO2 group is a meta directing (Electron
withdrawing). Its mechanism can be explained as :
NO2 NO2 NO2 NO2
NO2
HNO 3
+ +
H2SO4
NO2
(93%) (6%) NO2
(1%)

O−  O O−  O− O−  O− O−  O− O−  O−
N N N N N

 ..



All meta-directing groups have either a partial positive charge or a full positive charge on the atom
directly attached to the ring.
(2) Directive effect in disubstituted benzene
(i) If the directive effects of two substituents reinforce, then a single product is formed.
Example :
CH3 CH3 CH3
NO2
; Nitratio
n
+NO2
NO2 (m) NO2 NO2

Thus, both (CH 3 , NO 2 ) direct further substitution to the same position (Ortho with respect to
CH3).
(ii) If the directing effect of two groups oppose each other strongly activating groups win over
deactivating or weakly activating group. The sequence of directing power is
− NH 2  −OH  −OCH 3 −  NHCOCH 3  −C6 H 5  CH 3  meta directors

OH OH OH Directs
Directs
(Powerful
Example : activator)

CH3 CH3 CH3

Directs Directs
OH OH
Br
Br2
FeBr3

CH3 CH3

(iii) There is normally little substitution when the two groups are meta to each other. Aromatic rings
with three adjacent substituents are generally prepared by same other routes.
CH3
Too hindered position

Cl

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