HYDROCARBON

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ALKANES [C nH2n+2]

Alkanes, also known as paraffins, are chemical compounds that consists only of the elements
carbon (C) and hydrogen (H) (i.e., hydrocarbons), wherein these atoms are linked together
exclusively by single bonds (i.e., they are saturated compounds) without any cyclic structure (i.e.
loops).

Each carbon atom must have 4 bonds (either C-H or C-C bonds), and each hydrogen atom must
be joined to a carbon atom (H-C bonds). A series of linked carbon atoms is known as the carbon
skeleton or carbon back-bone. In general, the number of carbon atoms is often used to define the
size of the alkane (e.g., C2-alkane).

An alkyl group is a functional group or side-chain that, like an alkane, consist solely of singly-
bonded carbon and hydrogen atoms, for example a methyl or ethyl group.

PHYSICAL PROPERTIES

Conformations of Alkanes

The carbon-carbon bonds in alkanes result from sigma overlap of two tertrahedral carbon sp3
orbitals. Sigma bonds result from the head-on overlap of two atomic orbitals, and that they are
cylindrically symmetrical. The cross section of a sigma orbital is circular. Due to this sigma bond
symmetry, there is free rotation around the carbon single bond. Bond overlap is exactly the same
for all geometric arrangements of the hydrocarbons. The different arrangements of atoms caused
by rotation about a single bond are called conformation, and a specific structure is called a
conformer (conformational isomer).

HH H
H H

H H
H H H
H

Newman projections of the two conformations of ethane : eclipsed on the left, staggered on the
right.

Staggered form is more stable than eclipsed as more repulsions are experienced between the alkyl
group in eclipsed form.

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Example 1

Compare the torsional strain in the gauche conformer of butane with the anti conformer.
Draw Newman projections of both and indicate the values of the dihedral angles between
MeÊs.
Solution :
The gauche conformer has the Me groups on adjacent CÊs closer to each other, leading to greater
torsional strain than in the anti conformer where they are separated as much as possible.

Me Me

H Me H H

H H H H

H Me
Gauche 60Ĉ Anti 180Ĉ

PREPARATION OF ALKANES

1. Hydrogenation of alkenes

C=C +HăH Catalyst

C C
(Pt/Pd/Ni)
H H

Hydrogenation is the chemical reaction that results from the addition of hydrogen (H2). The
process is usually employed to reduce or saturate organic compounds. The process typically
constitutes the addition of pairs of hydrogen atoms to a molecule. Catalysts are required for the
reaction to be usable; non-catalytic hydrogenation takes place only at very high temperature.
Hydrogen adds to double and triple bonds in hydrocarbons.

Ć Alkenes can be reduced to alkanes with H2 in the presence of metal catalyst such as Pt, Pd,
Ni or Rh.

Ć The two new C-H  bonds are formed simultaneously from H atoms absorbed on to the metal
surface.

Ć The reaction is stereospecific giving only the ÂsynÊ addition product.

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Catalytic Hydrogenation

Step 1 : Hydrogen gets absorbed onto the HăH

metal surface.

H H
Step 2 : Alkene approaches the H atoms
absorbed on the metal surface.

Step 3 : C=C reacts with the atoms on the H H

surface forming two new C-H  bonds.

H H

Note : Since hydrogenation is ÂsynÊ addition, hence we can observe the following :

CH3 CH3 CH3

D2 /Ni H OH H OH
H OH +
H D D H
CH = CH2 CH2 D CH2 D

Diastereomers

2. Wurtz reaction

Wurtz reaction, is a coupling reaction whereby two alkyl halides are reacted with sodium to
form a new carbon-carbon bond :

dry
2R  X  2Na 
 R  R  2NaX
ether

Note : Methane is not formed by this method.

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M echanism :

This reaction involves the radical species RĆ

One electron from sodium is transferred to the halogen to produce a sodium halide and an alkyl
radical.
+
R ă X + Na  R Ć + Na X
The alkyl radical then accepts an electron from another sodium atom to form an alkyl anion and
the sodium becomes cationic.
R Ć + Na  Ră Na+
The alkyl anion then displaces the halide in an SN2 reaction, forming a new carbon-carbon
covalent bond.
R ă Na+ + RX   R ă R + Na+ X

Example

anhydrous
2CH3I  2Na 
 CH3CH3  2NaI
ether
ethane

anhydrous
2CH3 CH2 Cl  2Na 
 CH3 CH2 CH2CH3  2NaCl
Sodium ether Sodium Chloride
n  butane

Here methyl iodide and ethyl chloride are reacted with powered sodium metal in anhydrous
ether. Alkanes containing double the number of carbon atoms are formed, i.e., methyl iodide gives
ethane, and ethyl chloride gives n-butane.
The solvent, ether in this case, must be anhydrous (free of moisture) become the alkyl anions are
so basic they readily deprotonate water to hydroxide ion, forming alcohols, and reducing the yield
of the desired product.

Limitations

(1) The wurtz reaction is limited to the synthesis of symmetric alkanes. If two dissimilar alkyl
halides are taken as reactants, then the product is a mixture of alkanes that is, often,
difficult to separate.
(2) Tertiary alkyl halides do not give wurtz reaction. (Since it follows SN2 mechanism)

Illustration

Br Cl + 2Na Cl Cl

This is formed because C-Br bond is weaker than C-Cl bond.

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3. Clemmensen reduction

The Clemmensen reduction is a chemical reaction described as a reduction of ketones (or

aldehydes) to alkanes using zinc amalgam and hydrochloric acid.

H H
O
Zn(Hg)
C
HCl
R1 R2 R1 R2

The Clemmensen reduction is particularly effective at reducing aryl-alkyl ketones.

With aliphatic or acyclic ketones, zinc metal reduction is much more effective.
Ć The substrate must be stable in the strongly acidic conditions of the Clemmensen reduction.
As a result of Clemmensen Reduction, the carbon of the carbonyl group involved is converted
from sp2 hybridisation to sp3 hybridisation. The oxygen atom is lost in the form of one
molecule of water.

4. Wolff-Kishner reduction

The Wolff-Kishner reduction is a chemical reaction that fully reduces a ketone (or aldehyde) to
an alkane.

NH2
O N H H
NH2 NH2
HOH
R1 R2 R1 R2 R1 R2

Reaction mechanism

The most probable mechanism involves the elimination of an alkyl anion as the final step :
H H
ă ă
H2N N N
O N N N
ăH2O OH ă
+ H2 NNH2
R R´ R R´ R R´ R R´

ă
OH
N
H2O N H H
ăN2 ă H2O

R ăH2O ă
H R H R H + OH
R´ R´ R´

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The mechanism first involves the formation of the hydrazone in a mechanism that is probably
analogous to the formation of an imine. Successive deprotonations eventually result in the evolution
of nitrogen. The mechanism can be justified by the evolution of nitrogen as the thermodynamic
driving force.
Ć Wolff-kishner reduction, utilizes strongly basic conditions.

5. Kolbe electrolysis

The Kolbe reaction is formally a decarboxylative dimerisation and proceed by a radical reaction
mechanism. Generally, the reaction can be observed as :

2RCOOă  R ă R + 2CO2

As an example, electrolysis of acetic acid yields ethane and carbon dioxide :

CH3COOH  CH3COOă  CH3COOĆ  CH3Ć + CO2

2CH3Ć  CH3CH3

A concentrated solution of sodium or potassium salt of a carboxylic acid or mixture of carboxylic

acids is electrolysed.

Current
RCO2 K + R´ CO2 K + 2H2O   R ă R´ + 2CO2 + H2 + 2KOH

Current
2CH3 CO2 K + 2H2O   CH3 ă CH3 + 2CO2 + 2KOH + H2
  
anode cathode

Ć If R and R´ are different, then hydrocarbons R ă R´, R ă R, R´ ă R´ are also obtained.

Ć Esters, lower alkane and alkenes are also obtained as side products.

ă +
C2H5CO2K 

 C2H5CO2 + K

C2H5CO2ă ă eă  C2H5CO2Ć (I)

C2H5CO2Ć + C2H5Ć  C2H5CO2C2H5

(I) (II) ester

Intermolecular
C2H5Ć + C2 H5Ć 
Hydrogenation
 C H + C H
2 6 2 4

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6. MAZINGO METHOD
In this method carbonyl compound is converted into its dithio-acetal or Ketol using ethanedithiol
in the presence of a lewis acid, dithio-acetal is hydrogenlysed over Raney Nickel.

R R S CH2
CH2SH Et2O+ăBF3
ă
C=O+ C
20Ĉ C
R CH2SH R S CH2

H2 ă Ni

R
CH2
R

7. Using orgnometallic compounds

Organometallic compounds react as electron rich or anionic carbon atoms i.e. as carbanions, which
means they will function as either base or nucleophiles.
It is reasonable to think of these organometallic compound as RăM+.

Basicity :
The following equation represents the loss of a proton from a generic hydrocarbon forming a
carbanion :

ă
RăH R H+
hydrocarbon carbanion

Ć Organolithium and organomagnesium compound are strong bases since the negative charge
is on carbon.
Ć Simple carbanions are strong bases, since the C is not very electronegative (compared to N
or O)
Ć In the presence of weak acid, RLi and RMgX protonate giving the hydrocarbon.

(a) Decomposition of Grignard Reagent

Grignard reagent (an organametallic compound) on treatment with water or dilute acid, or alcohol
is decomposed to alkanes.

X
R ă Mg ă X + H2 O RH + Mg
(Grignard
Reagent) OH

(R is alkyl or aryl X is Cl, Br, I)

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It is the R part of the Grignard Reagent that is converted into RH.
If heavy water D2O is used, then product is

X
R ă Mg ă X + D2 O  RD + Mg
OH

X
+ D2 O + Mg

MgX D OH

RMgX + NH3  R ă H + Mg(NH2)X

RMgX + CH3OH  RH + Mg (OCH3)X

( b) Coupling of alkyl halides with organometallic compounds corey–House Synthesis

R ă CuLi + R´X R ă R´ + RCU + LiX

Lithium Dialkylcopper

Li
RX R ă Li RCuLi + R´ X R ă R´
Alkyl Lithium
Lithium dialkyl copper

For good yields R´X should be a primary halide, the alkyl group R in the organametallic may be
primary, secondary or tertiary, for example.

Li Cul
CH3 Br CH3 ă Li CH3 ă CuLi

(CH3)CH2)6CH2I

CH3 ă CH2(CH2)6CH3

NOTE : Unlike wurtz Reaction, this reaction can be employed to prepare unsymmetrical alkanes

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8. Reduction by dissolving metals :

Reduction by dissolving metals e.g. zinc and acetic or hydrochloric acid, zinc and sodium hydroxide,
zinc-copper couple and ethanol, etc. In this reaction, earlier ÂnascentÊ hydrogen was considered to
be reducing agent. Now it is believed that there is an electron-transfer from the metal to the
substrate leading to the formation of carbanion, which is followed by the abstraction of a proton
from the solvent. Thus, reduction with a zinc-ethanol couple may be formulated as
Zn  Zn2+ + 2eă

e
RX + eă  Xă + R  ă
 R:

R:ă + C2H5OH  R ă H + ăOC2H5

9. Reduction by reducing agents like LiAlH4, NaBH4 etc.

Primary and secondary alkyl halides are readily reduced to alkanes by lithium aluminium hydride
LiAlH4 while reduction of tertiary halides with LiAlH4 gives mainly alkenes. On the other hand,
sodium borohydride NaBH4 reduces secondary and tertiary, but not primary, whereas triphenyltin
hydride Ph3SnH reduces all three types of alkyl halide. So each reducing agent is specific in its
action.

(a) 4R ă X + LiAlH4  4R ă H + LiX + AlX3 (X  F)

or R ă X + H :(ă)  R ă H + Xă (Hă comes from LiAlH4)

(b) R ă X + (n ă C4H9)3SnH  R ă H + (n ă C4H9)3SnX

LiAlH4 is not useful for 3Ĉ alkyl halide which is converted into alkenes. In such cases NaBH4 or
TPH is used.

LiAlH4
CH3 ă CH2 ă CH3 CH3 ă CH2 ă CH3

Cl

CH3
LiAlH4
CH3 ă C ă Cl CH3 ă CH2 ă CH3

CH3 CH3

Cl NaBH4
X (No Reaction)

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Cl

TPH
1Ĉ, 2Ĉ, 3Ĉ alkyl halide 
 TPH  Ph3SnH 
 Alkane

1 0. Reduction of alcohols, carbonyl compounds, acids and acid derivatives :

Alcohols, aldehydes, ketones, carboxylic acid their derivatives like acid halides and acid amides
can be reduced by HI and red phosphorous to alkanes.

red P
R ă CH2OH + 2HI   R ă CH3 + I2 + H2O

red P
R ă CHO + 4HI   R ă CH3 + 2I2 + H2O

red P
R ă CO ă R´ + 4HI   R ă CH2 + R´H + 2I2 + H2O

red P
R ă COOH + 6HI   R ă CH3 + 3I2 + 2H2O

red P
R ă COCl + 6HI   R ă CH3 + 3I2 + + HCI + H2O

red P
R ă CONH2 + 6HI   R ă CH3 + 3I2 + NH4OH

Reduction of esters with red phosphorus and HI gives two alkanes

O
|| Red Phosphorus
R  C  O  R´  HI   RH  R´H

We can use other reducing agents also reduce alkyl halide to alkanes.
P  HI
R ă X  CH3 CH3
or
Zn + HCl
or
Zn + CH3OH
or
C2H5OH + Na

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Example 2

Prepare
(i) Butane from chloro ethane using the Corey ă House synthesis.
(ii) Deuteropropane from isopropyl bromide.
Solution :
(i) 1. Li
CH3CH2Cl (CH3CH2)2LiCu
2. Cul
Chloro ethane Lithium diethyl cuprate

CH3 CH2 Cl

CH3 CH2 CH2 CH3

1. Li
(ii) CH3CH2Cl (CH3CH2)2LiCu
2. Cul
Chloro ethane Lithium diethyl cuprate

CH3 CH2 Cl

CH3 CH2CH2CH3

Example 3

Prepare 2-methylbutane from chloroethane and 2-chloropropane using Corey-House

synthesis.
Solution :

I. Li CH3CH2Cl
CH3CHCl ((CH3)2CH)2CuLi CH3CHCH2CH3
2. Cul

CH3 CH3 CH3

2-Chloropropane Lithium disopropyl cuprate

Example 4

Predict the products in the following reactions :

Ni
(i) Cyclopropane + H2 
120


CH3 CH3
(ii) C=C + H2 ?
D D

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Solution :
(1) Propane

H3C CH3
(ii) H C C H
D D
(Meso)

Chemical Reactions of Alkanes

Ć Alkanes are generally inert at room temperature as they have not any functional group
Ć They undergo free radical substitution reaction

Radical substitution Mechanism

CH4 + Cl2  CH3Cl + HCI

The organic product is chloromthane.

One of the hydrogen atoms in the methane has been replaced by a chlorine atom, so this is
substitution reaction. However, the reaction doesnÊt stop there, and all the hydrogens in the
methane can in turn be replaced by chlorine atom.

The mechanism

The mechanism involves a chain reaction. During a chain reaction, for every reactive species you
start off with, a new one is generated at the end ă and this keeps the process going.
The overall process is known as free radical substitution, or as a free radical chain reaction.

Chain initiation

The chain is initiated (started) by UV light breaking a chlorine molecule into free radicals

Cl2  2Cl •

Chain propagation reactions

These are the reactions which keep the chain going.

CH4 + ClĆ  CH3 Ć HCl

CH3Ć + Cl2  CH3CI + Cl •

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Chain termination reactions

These are reactions which remove free radicals from the system without replacing then by new
ones.

2ClĆ  Cl2

CH3Ć + ClĆ  CH3Cl

CH3Ć + CHĆ
3
 CH3CH3

The potential energy curve for the halogenation (chlorination) of alkane is shown as

Eact

RăH + Cl
Potential energy

R + Cl2

R ă Cl + Cl
Progress of reaction

In more complex alkanes, the abstraction of each different kind of hydrogen atom gives a different
isomeric product. Three factors determine the relative yields of isomeric product.
1. Probability Factor : This factor is based on the number of each kind of hydrogen atoms
in the alkane molecule. For example, in CH3CH2CH2CH3 there are six equivalent 1Ĉ H and
four equivalent 2Ĉ H. The probability of abstracting a 1Ĉ H to 2Ĉ H is 6 to 4, or 3 to 2.
2. Reactivity of HĆ : The order of reactivity of hydrogen atoms is 3Ĉ > 2Ĉ > 1Ĉ.
3. Reactivity of XĆ : The more reactive ClĆ is less selective and more influenced by the
probability factor. The less reactive BrĆ is more selective and less influenced by the probability
factor, as summarized by the Rea ctivity-Selec tivity Principle. If the attacking species is
more reactive, it will be less selective and the yields will be determined by the probability
factor as well as reactivity of hydrogen atoms while if the species attacking is less reactive
and more selective, the yield of the product is governed exclusively by reactivity of hydrogen
atoms.

Cl2 / h
CH3CH2CH2CH3 CH3CH2CH2CH2(Cl) + CH3CH2CH(Cl)CH3
25C
n-butane (28%) (72%)

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Cl 2 / h
(CH3)2CHCH3 (CH3)2CHCH2Cl + (CH3)3CăCl
25C
isobutane (64%) (36%)

Br / h
CH3CH2CH2CH3 
2 
 CH3CH2CH2CH2Br + CH3CH2CH(Br)CH3
127C

n-butane (2%) (98%)

Br / h
(CH3)2CHCH3 
2
127C

 (CH3)2CHCH2Br + (CH3)3CăBr

isobutane traces (over 99%)

In the chlorination of isobutane abstraction of one of the nine primary hydrogens leads to the
formation of isobutyl chlorides, whereas abstraction of a single tertiary hydrogen leads to the
formation of tertăbutyl chloride. The probability favours formation of isobutyl chloride by the ratio
of 9 : 1. But the experimental results show the ratio roughly to be 2 : 1 or 9 : 4.5. Evidently, about
4.5 times as many collisions with the tertiary hydrogen are successful as collisions with the
primary hydrogens. The Eact is less for abstraction of a tertiary hydrogen than for the abstraction
of a primary hydrogen.
The rate of abstraction of hydrogen atoms is always found to follow the sequence 3Ĉ > 2Ĉ > 1Ĉ.
At room temperature (25ĈC), the relative rates in chlorination are 5.0 : 3.8 : 1.0 respectively for
3Ĉ, 2Ĉ and 1Ĉ hydrogen atoms. Using these values, we can predict quite well the ratio of isomeric
chlorination products from a given alkane. For example,

Cl
CH3CH2CH2CH3   CH CH CH CH Cl + CH CH CHClCH
2
light, 25C 3 2 2 2 3 2 3

n  butyl chloride number of 1 H reactivity of 1 H 6 1.0 3 28%

     equivalent to
sec  butyl chloride number of 2 H reactivity of 2 H 4 3.8 7.6 72%

Inspite of these difference in reactivity, chlorination rarely yields a great excess of any single
isomer. In most cases, both the products are formed in considerable amounts.
The same sequence of reactivity, 3Ĉ > 2Ĉ > 1Ĉ, is found in bromination, but with enormously larger
reactivity ratios. At 127ĈC the relative rates per hydrogen atom in bromination are 1600 : 82 :
1 respectively for 3Ĉ, 2Ĉ and 1Ĉ hydrogen atoms. Here, differences in reactivity are so marked that
it outweights probability factor. Hence bromination almost exclusively gives selective product.
In bromination of isobutane at 127ĈC,

isobutyl bromide number of 1 H reactivity of 1 H

 
tert-butyl bromide number of 3 H reactivity of 3 H

9 1 9 0.5%
=   equivalent to
1 1600 1600 99.5%

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Hence, tert-butyl bromide happens to be the exclusive product (over 99%) with traces of isobutyl
bromide.

The reason for the higher selectivity in bromination as compared to chlorination is due to the
following explanation.

According to the general principle, for comparable reactions, the more endothermic (or less
exothermic) reaction has a transition state (TS), which more closely resembles the intermediate
and may more closely resemble the ground state (reactants). Since attack by BrĆ on alkane is
more endothermic than attack by Cl•, its TS shows more CăH bond breaking and more HăBr
bond formation. Any stabilization in the intermediate radical also occurs in the corresponding TS.
Therefore, a TS leading to a 3Ĉ RĆ, has a lower enthalpy than one leading to a 2ĈRĆ, which in
turn has a lower enthalpy than one leading to 1ĈRĆ, the relative rates of Hăabstraction by BrĆ
are 3Ĉ > 2Ĉ > 1Ĉ. The TS for Hăabstraction by ClĆ has less CăH bond breaking and less HăCl bond
formation. The nature of the incipient radical has less effect on the enthalpy of the TS and on
the rate of its formation. Hence there is less difference in the rate of formation of the three kinds
of RĆs. In the attack by the comparatively unreactive bromine atom, the transition state is
reached late in the reaction process, after the alkyl group has developed considerable radical
character. In the attack by the highly reactive chlorine atom, the transition state is reached early,
when the alkyl group has gained very little radical character. Thus bromination is more selective
than chlorination.

 
R ă H + Br R H Br R + H ă Br
low reactivity Transition state
high selectivity reached late, much
radical character

 
R ă H + Cl R H Cl R + H ă Br
Transition state
reached early, much
radical character

Ć Bromination is selective for the R–H that gives the most stable radical

Ć Chlorination is less selective.

Ć The termination steps are low probability due to the low concentration of the radical species
meaning that the chances of them colliding is very low.

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R adical chain mechanism for reaction of methane with Br 2

Step 1 (Initiation) : Heat or uv light cause

the Weak halogen bond to undergo homolytic
Br Br Br Br
cleavage to generate two bromine radicals and
stariting the chain process.

Step 2
(a) A bromine radical abstracts a hydrogen
to form HBr and methyl radical, then
(b) The methyl radical abstracts a bromine
atom from another molecule of Br2 to form Br H ă CH3 H ă Br ă CH3
the methyl bromide product and a nother
bromine radical, which can then itself
Br ă Br CH3 Br Bră CH3
undergo reaction 2(a) creating a cycle that
can repeat.

Step 3 (Termination) : Various reactions CH3 CH3 CH3 ă CH3

between the possible pairs of radicals allow for
the formation of ethane, Br2 or the product, Br Br Br ă Br
methyl bromide. These reactions remove
radicals and do not perpetueate the cycle. Br CH3 Br ă CH3

Free Radical Substitution of Aromatic Hydrocarbons

CH2 ă CH3 Cl
Cl2, h

Mechanism
Step 1 - Initiation

hv
 Cl   Cl 
Cl2 

Propagation

CH2 ă CH3 CH ă CH3

Cl Radical stabilized by resonance from ring.

Therefore it will be more stable.

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Termination :

Cl
CH ă CH3 CH ă CH3

Cl2
+ Cl

Ć Free Radicals donÊt rearrange generally.

Ć Most stable free radical is formed which decides the formation of product.
Example :

CH3 CH2 Br

(1) NBS

Me Cl Me
CH ă CH C ă CH
Me Me
Cl2 , h
(2)

Example 5

How many monochlorinated product are obtained by the chlorination of isohexane and
what is the percentage of each assuming the reactivity ratio of 3ĈH : 2ĈH : 1ĈH = 5 : 3.8 : 1.
Solution :
Isopentane on chlorination in presence of sun light gives five different monochlorinated products.

h
CH3 ă CH ă CH2 ă CH2 ă CH3 + Cl2 CH2 Cl ă CH ă CH2 ă CH2 ă CH3

CH3 CH3 (A)

CH3 ă CCl ă CH2 ă CH2 ă CH3 + CH3 ă CH ă CHCl ă CH2 ă CH3

CH3 (B) CH3 (C)

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CH3 ă CH ă CH2 ă CHCl ă CH3 + CH3 ă CH ă CH3 ă CH2 ă CH3Cl

CH3 (D) CH3 (E)

Product Reactivity factor x Probability factor = number of parts Percentage

(A) 1 x 6 = 6 20.6%
(B) 5 x 1 = 5 17.1%
(C) 3.8 x 2 = 7.6 26.0%
(D) 3.8 x 2 = 7.6 26.0%
(E) 1 x 3 = 3 10.3%
Total number of parts = 29.2

1. Oxidation

All alkanes readily burn in excess of air or oxygen to form carbon dioxide and water.

 3n  1  2n+2 
CnH2n+2 + O2  nCO2 ( g)    H2 O (l)
2  2 

On the other hand, controlled oxidation under various condition, leads to different products.
Extensive oxidation gives a mixture of products in which no chain fission has occurred. Under
moderate conditions mixed ketones are the major products and oxidation in the presence of boric
acid produces a mixture of secondary alcohols. The oxidation of alkanes in the vapour state occurs
via free radicals, e.g. alkyl (RĆ), alkylperoxy (ROOĆ) and alkoxy (ROĆ). Oxidising reagents such
as potassium permaganate readily oxidise a tertiary hydrogen atom to a hydroxyl group. For
example, isobutane is oxidised to t-butanol.

KMnO4
(CH3)3 CH + [O]   (CH3)3 COH

2. Sulplhonation

It is the process of replacing hydrogen atom by a sulphonic acid group, SO3H. Sulphonation of
a normal alkane from hexane onwards may be carried out by treating the alkane with oleum
(fuming sulphuric acid). The order of case of replacement of H-atoms in tertiary. Compounds is
very much easier than secondary compounds replacement of H-atoms by sulphonic is very slow
indeed. Isobutane, which contains a tertiary hydrogen atom, is readily sulphonated to give t-butyl
sulphonic acid.

(CH3)3 CH + H2SO4/SO3  (CH3)3 CSO3H + H2SO4

HYDRO CARBON
 QUIZRR 21

3. Nitration

Under certain conditions alkanes react with nitric acid, when a hydrogen atom will be replaced
by a nitro-group, NO2. This process is known as nitration. Nitration of the alkanes may be carried
out in the vapour phase between 150Ĉ and 475ĈC, when a complex mixture of mononitroalkanes
is obtaines. The mixture consists of all the possible mononitroderivatives and the nitro-compounds
formed by every possibility of chain fission of the alkane. For example, propane gives a mixture
of 1-nitropropane, 2-nitropropane, nitroethane and nitromethane.

NO2
HNO3
|
CH3 CH2 CH3   CH3 CH2 CH2 NO2  CH3 C HCH3  C2 H5 NO2  CH3 NO2
400C

4. Isomerisation

It is a process by which n-alkane is converted into a branched alkane containing a methyl group
in group in the side chain by heating the n-alkane with AlCl3 ă HCl at 300ĈC.
For example,
AlCl HCl
CH3  CH3  CH2  CH3 
3
300C
 CH3  CH  CH3
n butane |
CH3
isobutane

5. Cracking : (Pyrolysis)

Cracking involves either breaking of C ă C or C ă H bonds or both.

400 ă 600Ĉ C
CH3CH2CH3 CH2 = CH2 + CH4 {C ă C fission}

400 ă 600Ĉ C
CH3 ă CH = CH2 + H2 {C ă H fission}

6. Aromatisation :

Aromatisation of n-alkanes containing six or more carbon atoms into benzene and its homologues
takes place at high temperature (600ĈC) in pressure of Cr2O3 ă Al2O3 as a catalyst.

Cr2 O3 ă Al2 O3 ă3H2

600Ĉ C
Benzene

Cr2 O3 ă Al2 O3 ă3H2

600Ĉ C

n ă octane ethyl cyclohexane

HYDRO CARBON
22 QUIZRR

ALKENES

Structure

Ć The alkene functional group consists of two sp2 hybridised C

atoms bonded to each via a  and a  bond.
R R´´
Ć The  bond is produced by the side-to-side overlap of the
C C
p-orbitals not utilised in the hybrids.
R´ R´´´
Ć The substituents are attached to the C=C unit via  bonds.
Ć The 2 C of the C=C and the 4 atoms attached directly to the
C=C are all in the same plane.

Reactivity

Ć A  bond is a region of high electron density so alkenes are typically nucleophiles.

Ć Alkenes typically undergo addition reactions in which the  bond is converted to two new
 bonds.

Stability

There are 3 factors that influence alkene stability :

1. Degree of substitution : more highly alkylated alkenes are more stable, so tetra > tri > di >
mono-substituted.
2. Stereochemistry : trans > cis due to reduced steric interactions when R groups are on
opposite sides of the double bond.
3. Conjugated alkenes are more stable than isolated alkenes.
4. Degree of Unsaturation

 2n1  2  n2 
DU =  
 2 

where n1 = no. of C-atom

n2 = no. of H atom
Note : (1) If a halogen is attached, then take halogen as H atom
(2) If an oxygen atom is present we do not count it.
(3) If nitrogen is present, for every N atom deduct 1 H atom.
(4) If degree of unsaturation = 2 then there can be :
(a) 2 double bonds
(b) 1 triple bond
(c) one double bond + one cyclic ring

HYDRO CARBON
 QUIZRR 23

Example 6

A molecule for C8H12 does not show stereoisomerism. Upon hydrogenation, it absorbs
1 mole of H2. Upon reductive or oxidative ozonysis it gives some symmetrical diketone.
Deduce the structure of A.
Solution :

 2n1  2  n2 
DU =  
 2 

n1 = 8
n2 = 12

16  2  12
 DU = 3
2

Now, since it absorbs 1 mole of H2, hence only one double bond is present. And since on reductive
or oxidative ozonlysis it gives same diketone, therefore the double bond is of the form of

R R
C

R R

Hence, there is one possibility i.e.

(A)

General points regarding stability of rings :

(1)   unstable due to angle strain

(2) Stability increases with increase in the size of ring upto cyclohexane.
(3) Chair form of cyclohexane is the most stable.

HYDRO CARBON
24 QUIZRR
PREPARATION OF ALKENES
From alkynes

(1) Hydrogenation of alkynes

Reduction of alkynes is a useful method for the stereoselective synthesis of disubstituted alkene
is desired, hydrogenation in the presence of LindlarÊs catalyst is commonly used, though
hydroboration followed by hydrolysis provides an alternative approach. Reduction of the alkyne
by sodium metal in liquid ammonia gives the trans-alkene.

Lindlar's catalyst R R´
C C
2

(Pd/Baso4, quinoline)
H

H H
+

(Cis)
R·C·
· C · R´
·
R H
Na C C
Liq. NH3 H R´
(trans)

B2H6 R R´
C C
CH3 COOH
H H

R R´
Wilkinson's Catalyst
C C
Rhcl [(Ph3 P)] H H

(2) Preparation by elimination reaction

I. Dehydrohalogenation
An elimination is the loss of two atoms or groups from a molecule, which will typically result in
the formation of a new  bond.
E.g.

ă
C2H5O
H
 alc. KOH ă
CH2 CH2 ă
CH2 = CH2 + Cl + C2 H5 OH
C2H5O

Cl

IUPAC name : 1-2 elimination

commonname : -elimination

HYDRO CARBON
 QUIZRR 25

T ypes of elimination Reaction

(1) E1 elimination
This is an unimolecular elimination. Which means that RDS (Rate Determining step) involves
only one molecule. Also it is the slow ionization to generate a carbocation.
The second step is the fast removal of a proton by the solvent.
In general for on E1 reaction :
Step 1 : Carbocation formation (slow, rate determining)

CH3 CH3
+ ă Slow + ă
H3C C Cl CH3 C + Cl

CH3 CH3

Step 2 : Abstraction of proton (fast)

CH3 CH3
fast
CH3 C+ C
ă
H3C CH2
C2H5 O
CH3 H

(2) Second order elimination (E2)

Generally this elimination occurs with a strong base, which elimates a proton more quickly than
the substrate can ionize.
E2 elimination is bimolecular and takes place in only one step.

C2 H5 O ă
H C2H5O ă H

CH2 CH2 CH2 CH2

ă
Cl  + Cl +
R ă OH + H
H
O
ă R·O
rate = Kr [R ă X][B ]
R
Here solvation will release solvation energy.
Solvation energy +  bond formation energy is enough to break the CăCl bond.

HYDRO CARBON
26 QUIZRR
Saytzeff’s Rule

In this type of elimination reaction the two leaving groups are lost from the adjacent carbon
atoms. One of the leaving groups is the halogen atom and the C-atom from which the halogen
and the C-atom from which the halogen is lost is usually designated as 1 or () carbon atom.
Hydrogen, the other leaving group is lost from the neighbouring carbon which is designated as
2 or () carbon atom. Now, if the alkyl halide has two or more -carbon atoms, two or more
alkenes are possible. According to saytzeffÊs rule, dehydro halogenation of alkyl halides leads to
the formation of that alkene leads the major product which has maximum number of alkyl groups

attached to C = C For example

CH3 CH3 CH3

 alc. KOH
CH3 CH CH CH3 CH3 CH = C CH3 + CH2 = CH CH CH3
 
(major) (minor)
Cl

Note : Ć Use Sayteff rule only in E2 reaction, not in E1 to predict the product.
Ć That product will be formed in major amount which has more stable alkene.

In an E1 reaction, the rate determining step is the loss of the leaving group to form the intermediate
carbocation. The more stable the carbocation is, the easier it is to form, and the faster the E1
reaction will be. Some student fall into the trap of thinking that the system with the less stable
carbocation will react fastest, but they are forgetting that it is the generation of the carbocation
that is rate determining.

Since carbocation intermediates are formed during an E1, there is always the possibility of
rearrangements (e.g. 1, 2-hydride or 1, 2-alkyl shift) to generate a more stable carbocation.

However, if the size of base is increased, it finds it relatively easier to abstract proton from a less
substituted -carbon atom than from more substituted -carbon atom of alkyl halide. Therefore,
less stable alkene becomes the major product . This is known as HoffmannÊs rule.
For example

Br CH2 CH3
CH3

Et3N
(a bulky base)

(major) (minor)

In place of haloalkanes, suphonyl derivatives of alkanes can also be used in the base catalysed
elimination reaction for the preparation of alkenes.

HYDRO CARBON
 QUIZRR 27

CH3 O CH3 O
alc. KOH + ă
CH3 CH CH2 O S CH3 CH3 C = CH2 + K O S Ph CH3
isobutene
O O

Hoffman elimination also takes place when the leaving group is poor (In general strong bases
are poor leaving groups).
H

CH2 CH2

Cl leaving group

HF < HCl < HBr < HI

Weak acid
Fă > Clă > Bră > Iă
Strong base

Example 7
Predict the alkene formed in each case.

CH3
(a) Br CH3 H3C
H
but-1-ene

H3C
Br H H CH3 CH3

CH3
+ +
(b) H H3C
CH3 H H
H3C H
but-1-ene trans-but-2-ene cis-but-2-ene
(minor)

H3C H H H

(c) H3 C CH3 +
Br CH3
H CH3 CH3

trans-pent-2-ene cis-pent-2-ene

HYDRO CARBON
28 QUIZRR

CH3
H3C H H CH3
(d) H3C
CH3
Br CH3
H3C H
2-methylpent-2-ene 2-methylpent-1-ene CH3
(major)

CH3
CH3 CH3
H3 C CH3
CH3
(e) H3 C H

Br CH3 CH3
H3 C
H CH3
2, 3-dimethylbut-2-ene 2, 3-dimethylbut-1-ene
(major)

CH3
(f) H3 C CH3 CH3
H3 C CH3
CH3
H

Br CH3 H3C
CH3
H CH3
2, 3-dimethylbut-2-ene 2, 3-dimethylbut-1-ene
(major)

H3C

H3 C
CH3

H CH3

Example 8

Which of the following reaction is correct ?

CH3 CH3
Br alc.
(1)
CH3 KOH

H CH3

HYDRO CARBON
 QUIZRR 29

Br
CH3
CH3 alc. KOH
(2)
CH3
CH3
H
Solution :
(1) Reaction is correct as Br and H are in anti planar planes. In (2) Br & H are in same plane.
Therefore elimination canÊt take place in this way.

Instead
Br CH3
CH3 alc. KOH
CH3 CH3

H H

Example 9

Explain which of the following reactions would provide a better synthesis of 2-pentene.

ă CH3 OH
(i) H3C CH3 + CH3 O
Br

Br

ă CH3 OH
(ii) H3C CH3 + CH3 O

Solution :

(i) H3C CH3 H3C CH3

Br Only product

Br

H3C CH3 H3C CH2 + H3C CH3

(ii)

Mixture

HYDRO CARBON
30 QUIZRR
(3) Preparation by Vicinal dehalogenation

Dehalogenation of vicinal dihalides can be effected either by NaI in acetone or by zinc in presence
of acetic acid or ethanol.

Zn dust
CH3 ă CH Br ă CH Br ă CH3 
CH3COOH or
 CH ă CH = CH ă CH
3 3
C2H5OH

NaI
CH3 ă CH Br ă CH2Br 
acetone
CH3 ă CH = CH2

The reaction mechanism involves loss of two halogen atoms in two steps. The two halogen atoms
align themselves at 180Ĉ in the same plane before they are lost.

(i) With NaI in acetone

I
+
Iă X X

ăX ă
C C C C C=C + IX

(ii) With zinc dust

Zn  Zn2+ + 2eă

X
ă
ăX ă ă
C C C C C=C +X

2e ă X X

(4) Acid Catalysed Dehydration of Alcohols

H+
H C C OH C=C +H OH

Alkenes can be prepared by dehydrogenation of alcohol in presence of protonating acid such as

H2SO4 etc.

HYDRO CARBON
 QUIZRR 31

Conc. H2SO4
R ă CH = CH2 + H2O
(180Ĉ C)

H3PO4 Or P2O5
R CH2 ă CH2 ă OH R ă CH = CH2 + H2O
(200Ĉ C)

Al2O3
R ă CH = CH2 + H2O
(350Ĉ C)

with 3Ĉ alcohol, reaction always occurs by E1 mechanism.

Example 10

CH3 CH3
| + |
H
CH3  C  OH   CH3  C  CH2  H2 O
| 
CH3

Mechanism :

Reaction occurs in 3 steps

(1) Pr ot onat ion : At t ack by H + ion on ă OH group

CH3 CH3

CH3 C OH CH3 C OH2

+

CH3 CH3
+
H

(2) Dehydration : Removal of water & formation of carbocation slow step

CH3 CH3

CH3 C OH2 CH3 C + + H2 O
+

CH3 CH3

Ć Carbocation can rearrange according to stability

HYDRO CARBON
32 QUIZRR
+
(3) Deprotonation  Removal of H ion

CH3 CH3
H
CH3 C+ CH3 C = CH2
O H
CH3 H

Example 11

CH3
| H+
CH 3  CH  CH 2 OH 

 ?

Solution : CH3 CH3

+
CH3 CH CH2 OH CH3 CH CH2 OH2

ăH2O
+
H
CH3 CH3
+
CH3 C CH3 CH3 CH CH2
+ rearrangement
depronation

CH3

CH3 C = CH2

Example 12
+
OH
H
+ OăH
protonation
H

 dehydration
+

+ H2O
+
rearrangement
More stable carbocation

Ring Expansion

rearrangement + deprotonation
+

More stable
carbocation

HYDRO CARBON
 QUIZRR 33

Example 13

+
OH OH2
+
H +

(a)

II
I Correct

(b) (c)
Incorrect

II path is incorrect as carbocation always rearranges to more stable carbocation as carbocation

(b) is equally stable as (a).

Note :
Ć Reaction with 1Ĉ alcohol proceeds by E2 mechanism if steric hindrance is not present.
Ć As shown in previous examples sterically hundred alcohols dehydrate by E1 mechanism.
Ć Reaction is first order as only one molecule is involved in rate determining step.

Some Important Points :

(i) Primary alcohols require the most stringent conditions to undergo dehydration i.e., use of
conc. H2SO4 and high temperature.

(ii) Tertiary alcohols can be easily dehydrated by using 25% H2SO4 at 85ĈC.

Example 14

+ +
CH2 OH CH2 (OH2 ) CH2
+
+ +
H Rearrangement ăH
 ăH2O

This evidence shows the extra stability of six membered ring.

HYDRO CARBON
34 QUIZRR
H ofmann elimination

Hofmann elimination is a process where an amine is reacted to create a tertiary amine and an
alkene by treatment with excess methyl iodide followed by treatment with silver oxide, water and
heat.

ă
H H H OH
R R Ag2O
N
MeI ă R R
R R + I R + R R
+ H2O + ăH2O R CH3
N N N
R R R R R R
CH3 CH3

After the first step, a quaternary ammonium iodide salt is created. After replacement of iodine
by an hydroxyl anion, an elimination reaction takes place to the alkene.
With unsymmetrical amines, the major product is the least substituted and generally the least
stable, an observation known as the Hofmann rule. This is in direct contrast to normal elimination
reactions where the more substituted, stable product is dominant (Saytzeff’s rule).

4. Witting Reaction

This method involves a convenient method of converting aldehydes and ketones into alkenes by
using a special class of compounds called phosphorous yields also called wittig reagent. Primary
or secondary alkyl halide is first treated with triphenyl phosphine the phosphonium halide produced
in the above reaction is converted into phosphorane by adding a strong base like C6H5 Li or
n ă C4H9 ă Li, Phosphorane is stablised by resonance.

R R

CH X + Ph3P R CH PPh3

R´ R´

The Triphenyl group of phosphorane has a strong tendency to pull oxygen atom of the aldehyde
or ketone forming alkene.

R R´´ R´´ R

C PPh3 + O = C C = C + PPh3 = O
0

R´ R´´´ R´´´ R´

(R, RÊ, RÊÊ and RÊÊ may be hydrogen or any alkyl group).

HYDRO CARBON
 QUIZRR 35

5. Cleavage of Ethers

Olefins can be formed by the treatment of ethers with very strong bases such as alkylsodium,
alkylithium or sodamide.

  R´Na
C C C= C + RONa + R´H

H OR

The reaction is aided by electron withdrawing groups in the -position.

For example C2H5OCH2CH (COOC2H5)2 forms alkene just by heating without any base at all.


C2H5OCH2CH(COOC2H5)2   CH2 = C(COOC2H5)2 + C2H5OH

The mechanism probably involves a cyclic intermediate

(ă)
(ă) Ph ă CH ă O
B
Ph ă CH2 ă O ă CH2 ă CH3 CH2 = CH2 + Ph ă CH2 ă O
ăBH
H CH2

CH2

6. Pyrolysis of Esters

Thermal cleavage of an ester usually acetate involves the formations of a six membered ring as
the transition state leading to the elimination of acid leaving behind alkene.

H H
H
O
R2C O R2C O R2C
500Ĉ C
+ C
H2C C
H2C C H2C O Me
O Me
O Me

As a direct consequence of cyclic transition state, both the leaving groups namely proton and
carboxylate ion are in the cis position. This is an example of cis elimination.

HYDRO CARBON
 36 QUIZRR
REACTION OF ALKENES
(1) Addition Reaction
Rules governing adding reaction.

I. (a) Markonikov addition

+
C C=C · + X Y C C C
Y X

Mechanism for the addition of hydrogen halide to an alkene involves the following two
steps :

Slow
Step 1 : C=C + H X C C
(RDS) +

fast
Step 2 : C C + Xă C C
+

H X H

The above addition follows MarkonikovÊs rule. It states that in the addition of HX to an
alkene, the hydrogen atom adds to the carbon atom of the double bond that has the greater
number of hydrogen atoms or the negative part of reagent adds to carbon having less
number of hydrogen.

For example

CH3 CH2 CH=CH2 + HI  CH3 CH2  CH  CH 3

|
I
The addition of HBr to some alkenes gives a mixture of the expected alkyl bromide and an
isomer formed by rearrangement.

HYDRO CARBON
 QUIZRR 37

CH3
H+
CH2 = CH CH CH3 CH3 CH CH CH3
+

CH3

Rearrangement

CH3 CH3

CH3CH2 C CH3 CH3 CHBr CH D

+

CH3
Br ă

CH3

CH3 CH2 C CH3

Br

(b) Anti-markonikovÊs rule :

C C=C · + HBr C C C

Br H

C C C

H Br
antimarkonikov

When addition of HBr takes place in presence of peroxides (RăOăOăR or benzoyl peroxide),
addition occurs in an anti-MarkonikovÊs manner i.e., Br is added to the carbon having large
number of Hăatom.

ROOR
CH2 = CH ă CH3 + HBr   CH3 CH2 CH2 Br

Mechanism

R·O·O·R  2R · O

R · O + H · Br ROH + Br

HYDRO CARBON
 38 QUIZRR

Step 1 : CH3 CH = CH2 + Br CH3 CH CH2

Br
(2 radical)

Step 2 : CH3 · CH · CH2 + HBr

CH3 ă CH2CH2Br + Br

Example 15

Why does only Bromine gives anti-MarkonikovÊs addition :

Solution :
Only for HBr, both the steps are exothermic while for HF the second step is highly endothermic,
reflecting the strength of H-F bond and the difficulty of breaking it. For HCl, it is again the
second step that is endothermic while for HI, it is the first step that is endothermic, reflecting the
fact that the energy gained in forming the weak I-C bond is not as much as that lost in breaking
the C=C  bond.

II. (a) SYN

(cis type same side)

C = C + XY C C
X Y

+ X Y H H SYS

X Y
results in cis
product

(b) ANTI
(trans type  opp side)
X
C = C + XY C C
Y

+ X Y H Y
X X
results in trans product.

HYDRO CARBON
 QUIZRR 39

I. ADDITION REACTIONS

1. Catalytic Hydrogenation :
Alkenes react with hydrogen in the presence of many reagents such as :
(1) Na in liquid NH3 and alcohol
(2) H2, Pt O2/CH3COOH
(3) H2/Ni at 573 K
(4) H2/Pd-carbon in ethanol
It is a Âsyn-additionÊ reaction.

H2/Pt,Ni or pd
H H

CH3 CH3 CH3 CH3

cis-1,2-dimethyl cyclobexane

D2
H H
(duterium)

H H D D

H H
D2
CH3 · CH = CH · CH3 CH3 · CH · CH · CH3

D D

CH3 H
CH3
C D2
(Meso) D H
C Ni,
CH3 H (SYN)
D H
(Cis)
CH3

CH3 H
CH3
C D2 D H
C (SYN)
H CH3
H D
(Trans)
CH3

HYDRO CARBON
 40 QUIZRR
Reducing Agents
ă H2, Ni or Pd or Pt 300Ĉ C
ă H2, PtO2/CH3COOH exclusive for alkenes cannot reduce
N
O 
 
 X 
Pd  C
ă H2 /
(methanol) or ethanol

Note :
ă PtO2/CH3COOH is used exclusively for alkenes (  also)
ă LiAlH4  reduces all except alkenes
NaBH4 / OHă

Specially for C=0

C=0 CHOH

2. Addition of halogen acid HX

3. Addition of H2O / H+
4. Addition of dil H2SO4
* governed by Markonikov

1 a HX
C·C=C· C·C·C·

X H

b HBr
C·C·C·
Peroxide
(anti markonikov) H X

2 H2O (H+ OHă )

+
C·C·C·
H (conc.)
OH H
boil
3 dil. H2SO4 (H2O)
+ ă
C·C·C·
H O SO3 H
OSO3H H

HYDRO CARBON
 QUIZRR 41

1 a HX

H X
CH3 CH3

b HBr
Br H Or H H *
Peroxide

H CH3 Br CH3

2 H2O (H+ OHă )

H+ (conc.)
H OH
H CH3 boil
(H2O)
3 dil. H2SO4
+ ă
H O SO3 H
H CH3
H OSO3H

*Anti Markonikov is free radical addition Nothing is clear about cis & trans

(Nothing can be said about sterco chemistry)

Br CH3

Example 16

(1)
HBr +
attack by + Hydride
+ H+ shift
H
ring
expansion

Br + Carbocation +
Attack of Br
rearrangement

HYDRO CARBON
 42 QUIZRR
+
(2) CH = CH · CH3 CH · CH2 · CH3 CHBr · CH2 · CH3

HBr

OH OH OH
Carbocation stabilized
by resonance from
benzene ring

(3) H3C CH3 H3C CH3

+
C C CH3 CH3

HBr +

ring expansion

Br
+

Bră

Note : Rearrangement may be avoid by treatment of alkene with mercuric acetate (in THF)
followed by reduction with NaBH4 / NaOH

5. Addition of halogen X2 (in CCl 4)

Note : * the reaction follow anti addition
* Reaction also follows markonikov addition

Br
anti
C · C = C · + Br2 C·C·C·

Br

Some examples :

(1) + Br2 CCl4 H Br

Br H
transă1, 2ă dibromocyclohexane

HYDRO CARBON
 QUIZRR 43

(2) + Br2 CCl4 Br

(anti) (trans)
CH3 Br CH3

(3) + Br2 CCl4 CH3 Br

(anti) (trans)
CH3 CH3 Br CH3

Br

(4) CH3 · CH2 · CH = CH2 + Br2/CCl4 CH3 · CH2 · CH · CH2

Br

CH3 Br
CH3
(5) C = CH2 + Br2/CCl4 C · CH2
CH3 CH3
Br

Br

(6) CH3 · CH = CHCH3 + Br2/CCl4 CH3 · CH · *CH CH3

*
Br

NOTE :
Now the compound formed in (4)
Br

CH3 · CH2 · CH · CH2

Br

is optically active which can exist in isomers.

HYDRO CARBON
44 QUIZRR
For a compound having chiral centres, the isomers are
= 2n where n is the no of chiral centres
2n = 4 (n = 2)
CH3 CH3

H Br Br H

Br H H Br

CH3 CH3

(I) enantiomers (II)

(Resmic misture)

CH3 CH3

Br H H Br

Br H H Br

CH3 CH3

(III) (IV)
(Meso structure)
CH3
CH3 H
H Br
C Br2
enantiomers
(anti add.)
C Br H
CH3 H (cis)
CH3

CH3
CH3 H
Br H
C Br2
Meso structures
anti
C Br H
H CH3 (trans)
CH3
Br2
Note : Test of unsaturation
CCl4
(reddish brown)
(bromine water)
HYDRO CARBON
 QUIZRR 45

Example 17

Predict the product. Me

H
+ Br2 ?
D
T

Solution :
ă
Br
b a
D Me
+
 + 
T H
+
Br

Here the + I effect of Me stabalizes the + charge on carbon, hence path (a) is more stable.

Example 18

Find the major product in the reaction.

Me

H
D NaCl
+ Br2 ?
T

Solution :
Me ă
Cl Me
H
D H
+ Br2


T D Br

Me Me

Br H H Br
+
T Cl Cl T

D D
Here major product will be of chlorine because Clă is a better nucleophile than Bră

HYDRO CARBON
46 QUIZRR
6. Addition of halogen X2 (in H2O) aqueous solution :

ă 
Br2 / H2 O  HO  Br 

Note : This reaction also follow anti addition and markonikovÊs addition
Br
să s+
1. HO Br
C·C=C· C·C·C·
Br2/H2O
Markonikov add OH
anti addition

2. Br2 H OH
H2O
(anti)
Br H

3. Br2 H OH
H2O
CH3 Br CH3

4. Br2 OH
CH3
H2O
CH3 CH3 Br CH3

7. O xymercuration – Demercuration (reduction)

The reagent used is :

(1) Hg(OAC)2 / THF
<
<

O
||
(CH3 · C· O)2 · Hg (polar solvent)

HYDRO CARBON
 QUIZRR 47

(2) NaBH4 / OHă

NOTE : The reaction follows only Markonikov rule

Hg(OAC)2/THF/H2O
C=C C·C O

H O Hg · O · C · CH3 + CH3 · C · OH

(oxy ă mercurate) O

NaBH4/OHă

O
C·C + Hg + CH3 · C · OH
H OH

Hg(OAc) 2 /THF/H2O
C=C C·C
NaBH4 /OHă
H OH

1. Hg(OAc)2/THF/H 2O
2. NaBH4/OHă
H CH3
CH3 H OH

8. Hydroboration / Oxidation of Alkenes

1. BH3
C=C H ă C ă C ă OH
2. H2 O2 /NaOH

Ć Overall transformation : C = C to H ă C ă C ă OH
Ć Reagents (two steps) 1. BH3 or B2H6 then (2) NaOH/H2O2
Ć Anti-Markovnikov, since the B is the electrophile.
Ć Stereoselectivity : Syn since the C-B and C-H bonds form simultaneously from the BH3.
Ć The alcohol is formed over a series of steps involving the B center, with retention of
configuration at the C.

HYDRO CARBON
48 QUIZRR
R eactivity of Borane
Ć Borane reacts with alkenes via a concerted mechanism.
Ć Simultaneous making of C-B and C-H bonds as C=C and B-H break.
H
BH2
Ć Electrophilic B atom adds at the least substituted end of the alkene.
Ć Although a carbocation is not involved, the reaction occurs as if the electrophilic B atom were
making the more stable carbocation.

Mechanism :
Step 1 : The  electrons act as the nucleophilic with the electrophilic B and the H is transferred
to the C with syn stereochemistry.

2R ă CH = CH2 + B2H6  2RCH2CH2BH2

Step 2 : First step repeats twice again.

RCH2CH2BH2 + R ă CH = CH2 (R CH2CH2)2 BH

(R CH2 CH2)2 BH + R ă CH = CH2  (RCH2CH2)3B

Step 3 : Peroxide ion reacts as the nucleophile with the electrophilic B atom.

HăOăOH + HOă  HOOă + H2O

CH2 CH2R CH2 CH2R

B B
RH2CH2C CH2 CH2R RCH2H2C CH2CH2R
ă O OH
OOH

ă
CH2 CH2R OCH2CH2R
ă
OH 2HOO
B ă B
2 OH OCH2 CH2R
RH2CH2C OCH2 CH2R RH2CH2C
OH2

OCH2 CH2R ă
OCH2CH2R
ă OH
B B
RH2CH2CO OCH2 CH2R RH2CH2CO OCH2 CH2R
OH

ăRCH2CH2OH

OCH2 CH2R
2H2O
2RCH2CH2OH + H3BO3
B
RH2CH2CO OH

HYDRO CARBON
 QUIZRR 49

For Example :

B2H6 H2O2 /OH H Me

Me OH H
(syn addition)

Note :
Ć If instead of H2O2/OHă we use
Ag then an ether will be formed.

CH3  CH  CH2 

3
 CH3CH2CH2 3 B 
BH Ag
 CH3 CH2 CH2  O  CH2  CH2  CH3

Ć If we use acetic acid, an alkane will be formed

CH3  CH  CH2 

3
 CH3CH2CH2 3 B 
BH 3 CH COOH
 CH3CH2CH3

Example 19

CH3 CH3
D
BD3
OH
(1) H2O2

Here D of BD3 will add to the carbon having least H atoms.

CH3 CH3
H
BD3
OD
(2) D2O2

CH3 CH3
D
Hg(OAC)2 OH
(3) NaBD4, H2O

HYDRO CARBON
50 QUIZRR
8. Hydroxylation (of 2 – OH)

NOTE : follows syn addition

Baeyers reagent
alc
C=C C·C (glycol)
KMnO4
OH OH
(Test of unsaturation)

here purple color of KMnO4 is discharged in the reaction

alc
H H
KMnO4

CH3 OH OH

(Osmium tetroxide)
1. OsO4 /Pyridine
C=C C·C
2. NaHSO3
OH OH

CH3 H
CH3
C (Meso)
(Racemic H OH
Br2 alc
mixture)
C
CCl4 KMnO4
CH3 H H OH
(cis)
CH3

CH3 H
C
Br2 alc (Racemic
(Meso)
CCl4 C mixture)
KMnO4
(anti) H CH3 (Syn)
(trans)

HYDRO CARBON
 QUIZRR 51

Example 20

MCPBA
CH3 · CH = CH2 CH3 · CH · CH2
Synaddition

MCPBA = Metachloro Per oxy Acid

+ +
H (if further we add H )

H2O
+
CH3 · CH · CH2OH CH3 · CH · CH2

OH
+

OH

CH3 · CH · CH2

OH

Ć Final product is anti addition product.

9. Oxidation of Alkenes

1. Oxidation by O3 (ozone)
2. Oxidation by hot acidic KMnO4

Ozonolysis :

Ozone reacts vigorously with alkene to form unstable compound called molozonide, which rearranges
spontaneously to form a compound known as ozonide. Ozonides, themselves are unstable and
reduced directly with Zn and water. The reduction produces carbonyl compounds (aldehydes and
ketones) that can be isolated.

Ć Overall transformation : C=C to 2 ï C=O

Ć Ozonolysis implies that ozone causes the alkene to break (-lysis)

• a reducing work-up, either Zn in acetic acid or dimethyl sulfide, (CH3)2S

Ć an oxidising work-up, usually H2O2 (under these conditions, carboxylic acids are obtained
instead of aldehydes)

HYDRO CARBON
52 QUIZRR
Ć It is convenient to view the process as cleaving the alkene into two carbonyls

Ć The substituents on the C=O depend on the substituents on the original C=C

Ć The work-up determines the oxidation state of the products

Reductive work-up

Oxidative work-up

R R R R
O3
O+O
then
R H H2O2 R OH

Example 21

(1)
O
O O
O3 C·H
H3
Zn, AcOH
+ CH3 · C · H
C=O
CH3
O
O O
C · OH
O3 + H2O2
O + CH3 · C · OH

HYDRO CARBON
 QUIZRR 53

(2) CH3 CH3 O

O3
CH3 · C = CH · CH3 CH3 · C = O + CH3 · C · H
Zn, AcOH

CH3 O
O3/H2O
CH3 · C = O + CH3 · C · OH

Ć In reductive ozonolysis, break double bond and each double bonded carbon will have one
oxygen atom.
Ć In oxidative ozolysis, aldehydes obtained from reductive ozonolysis will be oxidised to acids
because H2O2 formed is highly oxidising in nature.

2. Oxidation by hot acidic KMnO4

[O]
R ă CH = CH2 
 RCOOH + HCOOH
KMnO4

Here is a comparative list of oxidation by KMnO4 and ozone

(O) O3
RCOOH + HCOOH (R·CH=CH2) RCHO + HCHO
KMnO4 Zn/H2O

R
(O) O3
C = O + CO2 + H2O (R · C = CH2) R · C = O + HCHO
KMnO4 Zn/H2O
R R R

(O) O3
2 RCOOH R ·CH = CHR 2 RCHO
KMnO4 Zn/H2O
(O) O3
RCOOH + R´COOH R · CH = CHR´ RCHO + R´CHO
KMnO4 Zn/H2O

R R R
(O) O3
C = O + ROOH C = CHR C = O + RCHO
KMnO4 Zn/H2O
R R R

HYDRO CARBON
54 QUIZRR
* Terminal alkenes always give formaldehyde on ozonolysis

* dialkylated alkenes always give ketones

Note : HCOOH is easily oxidized into

HCOOH  CO2 + H2 O

* Basically products on left hand side [by KMnO4] can be achieved by further oxidising the
products achieved on right by ozonolysis.

O zonolysis of Cycloalkenes

3 O O
1

3 2
O

4 1 O O
O

O O O O

O O
O

(O)
alc . KMno4 OH
OH
O O

HYDRO CARBON
 QUIZRR 55

(O) OH
alc . KMno4
OH

(O)
OH
alc . KMno4
OH
O
O

alc . KMno4
O= =O
OH OH

C ycloalkadienes

3 3
2
2 CHO +
O CHO O O
1

3
3
2 4 O
2 O +
1 5 O
O
6

3
2 4
O O +
1 5 O
O
2
6

HYDRO CARBON
56 QUIZRR
COOH
+ O O
COOH OH OH

COOH
+ O O
COOH OH OH

COOH

2 CH2

COOH

A lkadions

isomeric to alkynes & cycloalkenes

C=C·C=C
CHO COOH

CHO COOH

COOH
KMnO 4 O3
+ 2CO2 + 2CO2 C C·C C 2HCHO + CHO
COOH
CHO

2CO2 + 2H2O C C·C C 2 HCHO + H3C · C · CHO

O C O
CH3 · C · COOH ( ketoaldehyde)
 (Pyruvic acid)
(A keto acid)

HYDRO CARBON
 QUIZRR 57

II. Reaction with Carbenes

For carbenes generation we need a source of carbene

We use CH2N2 (diazomethane) or CH2=C=O (Ketene)

CH 2 N2 
 CH2: + N2
(carbene)
Ć Carbene is electron deficient. It adds across the double bond.
CH2
CH3 · CH = CH2 CH3 · CH · CH2

CH2
CH2N2
light
C= C + or C C
CH2CO
CH2
Mechanism :

Step 1 : Attack on double bond

· CH
CH3 · CH · CH3 · CH · CH2 CH3 · CH · CH2
2
·

CH2 CH2 CH2

Addition in Syn

CH3 CH3

CH light CH
+ CH2N2 CH2
CH CH
CH3 H3 C
(cis)

H3 C H3 C
CH Cu2+ CH
+ CH2N2 CH2
CH CH
CH3 CH3
(Trans)

HYDRO CARBON
58 QUIZRR
Ć In presence of potassium tert-butoxide, there is addition of dichloromethylene
(dichlorocarbone), : CCl2, when CHCl3 reacts with alkene.

ă ă1
t ă BuO K
CH3 · CH = CH · CH3 + CHCl3 CH3 · CH · CH · CH3 + t · BuOH + KCl

Cl Cl

first : CCl2 is formed by -elimination (1, 1-elimination) from CHCl3 and tăBuOH

I II. Simmons Smith Reaction

Alkene reacts with CH2I2 in presence of Cu-Zn to form cycloalkane. This reaction does not
actually involve a carbene, but rather a carbenoid, a organometallic species, that reacts like a
carbene.
CH2I2 + : Zn (Cu)  IăCH2ăZnăI (carbenoid)

CuăZn
CH3 ă CH = CH2  CH2 I2  CH3 · CH · CH2

CH2

(methyl cyclopropane)

IV. Hydroxylation

There are a number of reagents that can add two OH groups to alkenes. The two OH groups can
be either added from the same side (syn hydroxylation) or from the opposite side (anti-hydroxylation)

(a) Syn Hydroxylation

Osmium tetroxide (OsO4) adds to alkene to form cyclic osmic ester (2) which can be made to
undergo ready hydrolytic of their Os-O bonds to yield the vic-dio(3).

O O
Os

Me O HO
O HO
H
Me OsO4 Me H H2O Me H
+ (HO)2OsO2
Me H Me H
H
(1) (2) (3)

cis 2ăbutene (1) thus yields the meso butan-2, 3ădiol (3), i.e. the overall hydroxylation is
stereoselectively syn, as would be expected from OsăO cleavage in a necessarily cis cyclic ester.

HYDRO CARBON
 QUIZRR 59

The disadvantage of this reaction as a preparative method is expense and toxicity of OsO4.
However, this can be overcome by using it in catalytic quantities in association with H2O2 which
re-oxidises the osmic acid, (HO)2OsO2, formed to OsO4.
Alkaline permanganate, Mn18O4ă (a reagent used classically to test for unsautration), will so
effect stereoselective syn addition and this by analogy with the above, is thought to proceed via
cyclic (cis) permanganic ester. It has not proved possible actually to isolate such species but use of
Mn18O4ă, was found to lead to a vic-diol in which both oxygen atoms were O18 labeled. Thus both
were derived from MnO4ă, and neither from the solvent H2O, which provides support for a
permanganic analogue of (2) as an intermediate, provided that Mn18O4ă undergoes no O18 exchange
with the solvent H2O under these conditions. The disadvantage of MnO4ă for hydroxylation is
that the resultant 1,2ădiol is very much susceptible to further oxidation by it.

(b) Anti-Hydroxylation

Peroxyacids, RCOOH will also oxidize alkenes, e.g. trans 2ăbutene (4), by adding and oxygen
atom across the double bond to form an epoxide (5).
O
O
C
C
ă
R O
R O H
+ H O O
HăO + + RCO2H
Me Me Me
Me H H
Me H Me H
(4) (5)

Epoxides (though uncharged) have a formal resemblance to cyclic bromonium ion intermediates,
but unlike them are stable and may readily be isolated. However, they undergo nucleophilic
attack under either acid or base catalysed conditions to yield the 1, 2ădiol. In either case attack
by the nucleophile on carbon atom will be from the opposite side of the oxygen bridge in (5). Such
attack on the epoxide will involve inversion of configuration.

O H Me H Me
Oă HO
H OH ă H2O
OH OH
Me H
Me Me H Me
H OH ă
(5) (7)

H+
H OH OH
O
+
Me H Me H
H H2O ăH
+
H Me H Me
Me +
Me OH2 OH
H
(6) (7)
OH2
HYDRO CARBON
60 QUIZRR
Attack has been shown on only one of the two possible carbon atoms in (5) and (6), though on
different ones in the two cases. In each case, attack on the other carbon will lead to the same
product, the meso vicădiol (7). By comparing the configuration of (7) with that of the original
alkene by suitable choice of reagent, the hydroxylation of alkenes can be made stereoselectively
anit at will.
For example,

3CH2 = CH2 + 2KMnO4 + 4H2O 3CH2 ă CH2 + 2MnO2 + 2KOH

(dil alkaline KMnO4)
OH OH
(ethylene glycol)

V. Reaction with hot alkaline KMnO 4

O
||
alk KMnO4
CH3 ă CH2 ă CH = CH ă CH3   CH3CH2  C  OH  CH3COOH


Ć While writing the product, where double bond is present in alkene, break it from there.
O
||
Ć If CH is bond to double bond, convert it to  C OH
and other conversions are :
Rectant Product

O
= CH-  ||
 C OH

R O
= |  ||
C  C R

= CH2  CO2

Example 22

CH = CH2 COOH

KMnO4
(1) + CO2


H3C CH2 H3C O

KMnO4 COOH
(2) O + CO2


CH3 CH3

HYDRO CARBON
 QUIZRR 61

O
O
O C OH
KMnO4 C OH
(3) ? +
 C OH

Stereochemistry of Addition Reactions

Alkene + X2  anti addition reaction

alkene 
dil. cold

 syn addition
alkaline KMnO4

Type of alkene Type of addition Type of product

cis syn meso
cis anti enantioners/racemic mixture
trans syn enantiomers
mixture of d & l isomers
Trans anti meso i.e., optically inactive

VI. Dimerisation :

Isobutene C4H8 in presence of conc. H2SO4 or H3PO4 is converted into a mixture of two alkenes
of molecular formula C8H16, a dimer of C4H8. This is called dimerisation.

CH3 CH3 CH3 CH3 CH3

H2SO4
CH3 · C = CH2 CH2 = C · CH2 · C · CH3 + CH3 · C = CH · C · CH3
80Ĉ C
(A) CH3 (B) CH3

(A) and (B) are position isomers and hydrogenation will form the same alkane, 2, 2, 4-trimethyl
pentane.

(1) H2SO4 , 
CH = CH2 CH = CH · CH · Ph

CH3
hv
(2) 2CH = CH2 


HYDRO CARBON
62 QUIZRR
VII. Addition of Alkanes – Alkylation

2, 2, 4-trimethyl pentane is used as aviation fuel. It can be obtained by dimersion of isobutene.

Isobutene on reaction with isobutane (alkylation) in presence of H+ gives iso-octane.

CH3 CH3
Conc. H2SO4 or HF
CH3 · C = CH2 + H · C · CH3
0 ă 10Ĉ C

CH3
CH3 CH3

CH3 · CH · CH2 · C · CH3

CH3

Mechanism

CH3 CH3
H+
Step 1 : CH3 · C = CH2 CH3 · C · CH3
+

CH3 CH3 CH3 CH3

+
Step 2 : CH3 · C = CH2 + C · CH3 CH3 · C · CH2 · C · CH3
+

CH3 CH3

Step 3 :

CH3 CH3 CH3 CH3 CH3 CH3

+
CH3 · C · CH2 · C · CH3 + H · C · CH3 CH3 · C · CH2 · C · CH3 + CH3 · C
+

CH3 CH3 CH3 CH3 CH3

VIII. Polymerisation

One of the most important reactions of simple alkenes and conjugated dienes is polymerisation.
The joining together of many small molecules to make very large molecules.

HYDRO CARBON
 QUIZRR 63
O2, heat
(1) n CH2 = CH2 pressure · CH2CH2CH2CH2CH2CH2
Or
(· CH2 · CH2 ·)n
Polythelene

peroxide
(2) n CH2 = CH · CH2 · CH ·

Cl Cl n
vinyl chloride Poly vinyl chloride
(PVC)

CH3 CH3
(3)
CH2 = C · CH = CH2 · CH2 · C · CH = CH2 ·

isoprene natural rubber

Example 23

Limonene (A) is a naturally occurring C10H16 hydrocarbon that causes the odour of lemons.
When treated with excess of hydrogen in the presence of platinum catalyst, it takes up two
equivalents of hydrogen. When treated with ozone, followed by zinc in acetic acid, it forms
one mole of formaldehyde (C) and one mole of the tricarbonyl compound (B) shown below.

O O

1. O3 H3C CH3 + HCHO

Limonene
(A) 2. Zn, AcOH H (C)
(B)
O

Propose a suitable structure for limonene if it has one six membered ring.
Solution :

Limonene + 2H2  presence of two double bonds in (A)

1. O
Limonene   (B) (9 carbon) + (C) with 1 carbon
3
2. Zn.ACOH

This shows one (C = C) in an open chain, one (C = C) in a ring structure. We have following
randomness in which (A) has six membered ring. C of (C) is joined to C2 of (B) and C9, and C6
of (B) are joined by C = C bond.

 (C) is O = CH2.

HYDRO CARBON
64 QUIZRR
Hence
O CH2
1. O3
H3C H3C
O 2. Zn, AcOH
O CH3 CH3
H3C
CH3 H
(A) (B)

Thus (A) is

CH2

H3C
CH3

Example 24

Compound X consumes five moles of H2 to form

CH2CH2CH2CH3

It gives white precipitate with ethanoic AgNO3.

O
O O O
O3 CH
X Me S + H · C · C · H + H · C · C · O · H + H · C · O ·H
2 H
O
O O O
Solution :
5H2
Compound X Pt
CH2CH2CH2CH3

AgNO3
At OH

X must have five - bonds

X must have terminal alkyne

HYDRO CARBON
 QUIZRR 65

Ozonolysis products of X are :

O O O O O

H · C · CH2CH2 · C · C · H + H · C · C · H + H · C · C · OH + H · C · OH

O O O

6 carbonyls  3 alkenes, 2 carboxylic acids  1 alkyne.

Hence X is

CH

HYDRO CARBON
66 QUIZRR

A LKYNES
Functional group suffix = ă yne (review)
Disubstituted alkynes, R-CC-R´, are described as „internal‰ alkynes
Monosubstituted alkynes, R-CC-H, are described as „terminal‰ alkynes.

1. Stability :

Ć As with alkenes, the more highly substituted internal alkynes are more stable.
Ć By comparing thermodynamic data of alkynes and alkenes, it can be seen that the „extra‰
 bond in an alkyne is weaker than the alkene  bond.
Ć The alkyne functional group consists of two sp hybridised C atoms bonded to each other via
one  and two  bonds.
Ć The 2  bonds are produced by the side-to-side overlap of the two pairs of p-orbital not
utilised in the hybrids.
Ć The substituents are attached to the CC via sigma bonds.
Ć The 2 C of the CC and the 2 atoms attached directly to the CC are linear.
Ć Since alkynes are linear, they cannot exist as cis-/ trans-isomers.

2. Physical Properties

Ć As with hydrocarbons in general, alkynes are non-polar and are insoluble in water but
soluble in non-polar organic solvents.
Ć Liquified acetylene or when compared, in explosive, burns with luminous smoky flame due
to high carbon content, hence used for lighting purpose.
Ć In general bond length increases in the order

CC < C = C < C ă C

3. Reactivity

Ć The  bonds are a region of high electron density so alkynes are typically nucleophiles.
Ć Alkynes typically undergo addition reactions in which one or both of the -bonds are
converted to new  bonds.
Ć Terminal alkynes, R ă C  C ă H, are quite acidic for hydrocarbons, pKa = 26
Ć Deprotonation of a terminal acetylene gives an acetylide ion.
Ć The acetylide ion is a good nucleophile and can be alkylated to give higher alkynes.

HYDRO CARBON
 QUIZRR 67

4. Acidity of Terminal Alkynes

B:ă
 RăC  C:ă  B ă H
R ă C  C ă H 

Terminal alkynes are unusual for simple hydrocarbons in that they can be deprotonated (pKa =
26) using an appropriate base (typically NaNH2, pKa = 36) to generate a carbanion which can
function as a C centered nucleophile and so allow for the formation of new C-C bonds by reacting
with C centered electrophiles (such as alkyl halides).

·C·CăH C=C ·C CăH

H
p Ka = 62 p Ka = 45 p Ka = 26

In order to appreciate what makes the terminal alkyne more acidic than most other hydrocarbons,
we should look at the stability of the conjugate base (i.e., the carboanion).

ă
· C · Că sp3 C = Că ·C C sp

For each type of carbanion shown, the nature of the hybrid orbital containing the electron pair
is important. Increased s character (sp = 50%, sp2 = 33% and sp3 = 25%) implies that the alkyne
sp orbital is closer to the nucleus and so there is greater electrostatic stabilisation of the electron
pair. Therefore the conjugate base of the alkyne is the most stable and the most readily formed.
However the terminal alkyne C-H bond is not strongly acidic and a strong base, such as the amide
ion, NH2ă, is required to form the carbanion.

Preparation of Alkynes

1. Dehydrohalogenation

X X
NaNH2
·CăC· ·C C · + 2H ă X + 2NH3
in NH3
H H or alcKOH

H X
NaNH2
·CăC· ·C C · + 2H ă X + 2NH3
in NH3
H X or alc. KOH

Reaction Type : Elimination (E2)

HYDRO CARBON
68 QUIZRR
Ć The two  bonds of an alkyne can be formed using two consecutive elimination reactions.
Ć The leaving groups are usually halides (esp. Br or Cl)
Ć Reagent : usually NaNH2 (a strong base)
Ć Either geminal (1, 1-) or vicinal (1, 2-) dihalides can be used.
Ć Since 1,2-dihalides can be prepared by addition of X2 to an alkene, an alkene can be
converted into an alkyne in two steps.
Ć These reactions are typically E2 reactions and occur via an alkenyl halide.
Ć The strong base is needed in order to cause elimination of the alkenyl halide.
Ć 1,2-dihalides vicinal when treated with alcoholic KOH give alkynes by loss of two molecules
of hydrogen halide, the intermediate being vinyl halide.

Br H
alc. KOH alc. KOH
R·C·C·H R·C=C·H R·C C·H
·HBr ·HBr

H Br H Br

Ć The use of alcoholic KOH gives rise to side reactions and causes the migration of the C=C
bond to the centre of the molecule.

M echanism

H H
R H
ă ă
H·N + R·C·C·R C=C + NH3 + Br
Br R
H Br Br

R H
ă ă
C=C + N·H R·C C R + NH3 + Br
Br R
H

In this reaction elemination of the first molecule of HX results in the formation of vinyl halide
ă an alkene with halogen bonded to one of the carbons of the double bond. We take strong base
like NH2 to make the step II easier for elimination.

HYDRO CARBON
 QUIZRR 69

2. Industrial source {Hydrolysis of carbides}

CaC2 + 2H2O  Ca(OH)2 + HC  CH

calcium carbide ethyne
ă ă
Calcium carbide has doubly negative carbide ion (: C  C :) which is strongly basic and reacts with
water to form acetylene.

Ć Mg2 C3 + H2O  Mg (OH2) + CH3ăCCH

propyne

Mg2 C3 contain C34  (ăC  CăC3ă)

1500C
Ć 6CH4 + 2O2 
cracking
 2CH  CH + 2CO + 1 H
2 2

3. Kolbe’s Method

Electrolysis of concentrated solution of sodium or potassium salt of maleic or tumaric acid gives
acetylene at anode.

CHCO2 Na + 2H O CH
||  2  ||| + 2CO2 + 2NaOH + H2
CHCO2Na Current
CH

4. Dehalogenation of tetrahalide or Trihalide

X H
alcohol
R · C · C · H + 2Zn R·C C · H + 2ZnX2

H X


CHX3 + 6Ag + X3CH   HC  CH + 6AgX

5. Alkylation of acetylene and Terminal Alkynes

Ć This method is used to prepare higher alkynes

Ć Terminal alkyne is one that has one ă C  CH at the end of the chain.

HC  CH + Na 
Liquid NH3  RX
 HC  C Na   HC  CR

RC  CH + Na 
Liquid NH3  R´X
 RC  C Na  RC  CR ´
terminal alkyne

HYDRO CARBON
70 QUIZRR

(i) Na Liquid NH
CH3C  CH 
3  CH C  CCH CH
3 2 3
(ii) CH3CH2I
2 pentyne

Ć Above reaction shows that acetylinic and terminal H are reactive hence salt formation is
easier.
Ć RX and R´X should be 1Ĉ alkyl halides, since higher 2Ĉ and 3Ĉ halides give mainly alkenes
when they react with sodium salt of alkynes.

CH3 C  C  Na   CH3  CH  CH2  CH3  CH3  C  CH  CH3  CH  CH  CH3  NaCl

|
Cl

Alkylation can also be done using grignard reagent

HC  CH + CH3ăMgăBr  CH  CăMgăBr + CH4

HC  CăMgăBr + CH3Br  HC  CăCH3 + MgBr2

Example 25

Outline a synthesis of propyne from isopropyl or propyl bromide. The needed vic-dihalide
is formed from propene, which is prepared from the alkyl halides.
Solution :

CH3 CH 2CH2 Br 
n-Propylbromide 
 alc. Br2 alc. NaNH2
or  CH3  CH2  CH2   CH3CHBrCH2 Br CH3 CH  CHBr   CH3C  CH
KOH KOH
CH3CHBrCH3 
Isopropylbromide 


Example 26

Synthesize the following compounds from HC  CH and any other organic and inorganic
reagents (do not repeat steps) :
(a) 1-pentyne, (b) 2-hexyne
Solution :
 +
(a) NaNH CH CH CH I
H  C  C  H 
2
 H  C  C:Na 
3 2 2  H  C  C  CH CH CH
2 2 3

+  +
(b) CH I NaNH
Na :C  C  H 
3  CH  C  C  H 
3
2
 CH3  C  C : Na
CH CH CH I

3 2 2  CH  C  C ă CH CH CH
3 2 2 3

HYDRO CARBON
 QUIZRR 71

6. Alkylation of Alkynes

1.NaNH
RăC  CăH 
2  RăC  ăR'
2.R '  X

Ć Terminal alkynes are usual for simply hydrocarbons in that they can be deprotonated
(pKa = 26) using an appropriate base (typically NaNH2, pKa = 36) to generate a carbanion.
Ć 3Ĉ alkyl halides are more likely to undergo elimination.
Ć One or both of the terminal H atoms in ethylene (acetylene) H-CC-H can be substituted
providing access to monosubstituted (R-CC-H) and symmetrical (R = R´) or unsymmetrical
R  R´) disubstituted alkynes R-CC-R´.

Mechanism

Step 1 : An acid/base reaction : The amide ion acts ă

CH3 · C C·H NH2
as a base removing the acidic terminal H
to generate the acetylide ion, a carbon
nucleophile.
ă
CH3 · C C NH3
Step 2 : A nucleophilic substitution reaction. The
carbanion reacts with the electrophilic CH3CH2 · Br
+ ă
carbon in the alkyl halide with loss of the
leaving group, forming a new C-C bond. ă
CH3 · C C · CH2CH3 Br

7. Ozonolysis of alkynes

Ozonolysis of alkynes generally gives an acid anhydride or diketone product, not complete
fragmentation as for alkenes. A reducing agent is not needed for these reactions. The exact
mechanism is not completely known. If the reaction is performed in the presence of water, the
anhydride hydrolyzes to give two carboxylic acids.
O O
O3
R·C C · R´

O3 R R´

O O H2O O O

O
R R´ R OH HO R´

However, ethyne behaves differently. Ozonolysis followed by oxidative hydrolysis of ethyne gives
a mixture of glyoxal and formic acid.
1. O
HC  CH 
3 
2. H2O CHOăCHO + HCOOH

HYDRO CARBON
72 QUIZRR
8. Halogenation of Alkynes

·C C · + X2 C=C

Reaction type : Electrophilic Addition

Ć Overall transformation : CC to X-C=C-X (and potentially to X2C-CX2)

Ć Reagent : normally the halogen (e.g. Br2) in an inert solvent like methylene chloride,
CH2Cl2.
Ć Addition of X2 is not relevant since all the new bonds are the same, C-X.
Ć Reaction proceed via cyclic halonium ion.
Ć Stereoselectivity : anti since the two C-X bonds form in separate steps one from X2 the other
X ă.
Ć For HBr, care must be taken to avoid the formation of radicals as the alternate radical
addition occurs with opposite regiochemistry.

Br
HBr
|
CH3  C  CH   CH3 C  CH2  CH3 CH  CH2  Br
peroxides
major

9. Reaction of Alkynes with Hydrogen Halides

H X

·C C · + H ·X C=C

H X

·C C · + H ·X ·C·C·
excess
H X

Reaction type : Electrophilic Addition

Ć When treated with HX alkynes form vinyl halides.

Ć Hydrogen halide reactivity order : HI > HBr > HCI > HF (paralleling acidity order).
Ć Addition is predicted by MarkovnikovÊs rule with the H adding to the C with the most
H already present.

HYDRO CARBON
 QUIZRR 73

Br
HBr
|
CH3  C  CH  CH3 C  CH2  CH3CH  CH2  Br
major

Ć Reaction proceeds via protonation to give the more stable carbocation intermediate.
Ć Not stereoselective since reaction proceeds via planar carbocation.
Ć In the presence of excess HX, a second addition can occur to the product alkene giving a
geminal dihalide.

Br Br
| |
HBr
CH3 C  CH2  CH3 CCH3
|
Br

Example 27
OH

dil. H2SO4
(1)
+2
Hg

OH O

dil. H2SO4
(2) +2
Hg

D2O, HgSO4 + H2SO4

(3) C CH C · CHD2

10. Hydration of Alkynes

dil H2SO4
(1) CH CH 2+
H·C=C·H
Hg
H OH
vinyl alcohol

tautomerism

CH3 · C · H

HYDRO CARBON
74 QUIZRR
dil H2SO4
(2) CH3 · C CH 2+
CH3 · C = CH2
Hg
OH enolic

tautomerism

CH3 · C · CH3

O
Ć Intermediate is enolic compound that tantomerises to an aldehyde or keto compound.

Mechanism :
..
H2O OH H
2+
Hg
R·C C·H R·C=C·H C=C

Hg
2+ R Hg+

H3O+

R OH H

C · CH3 C=C
O R H

REACTIONS

1. Hydrogenation of Alkynes

Lindlar's
·C C· HăH C=C
catalyst
H H

Reaction Type : Electrophilic Addition

Ć Alkynes can be partially reduced to cis-alkenes with H2 in the presence of poisoned catalysts.
(eg. Pd/CaCO3 / quinoline which is also known as LindlarÊs catalyst).
Ć Alkynes when reduced with lindlars catalyst gives nearly 100% cis isomer while Na in liquid
ammonia gives nearly 100% trans isomer.
Ć Alkynes can be reduced to alkanes with H2 in the presence of catalyst (Pt, Pd, Ni etc.)
Ć The new C-H  bonds are formed simultaneously from H atoms absorbed onto the metal
surface.
HYDRO CARBON
 QUIZRR 75

Ć The reaction is stereospecific giving only the syn addition product.

Ć The “poisoned” catalyst prevents over-reduction, which would give the alkane by reducing
the alkene.

H H
Lindlar's catalyst
C=C
H3C CH3
(cis)
CH3 · C C · CH3 + H2
H CH3
Na in
C=C
Liq. NH3
H3C H
(trans)

2. Addition of Boron Hydrides

Diborane, the simplest hydride of boron reacts with alkyne to form trialkenylborane. Diborane
splits into two BH3 units and the addition of BH3 takes place following MarkownikoffÊs rule. The
addition continues as long as hydrogen is attached to boron atom.

2RăCCH + B2H6  2RăCH=CHăBH2

RăCCH + RăCH=CHăBH2  (RăCH=CH)2BH

R-C CH + (RăCH=CH)2BH  (RăCH=CH)3B

Trialkenylborane on hydrolysis gives alkene.

CH COOH
(RăCH=CH)3B 
3
hydrolysis
 3RăCH=CH + B(OH)
2 3

Internal alkynes give rise to alkenes where geometrical isomerism is possible. Hydroboration
followed by hydrolysis of alkynes gives cis alkene as the major product.

R R
CH3CO2H
R·C C · R + B2H6 (RCH = CR)3B C=C (Cis)

H H

HYDRO CARBON
76 QUIZRR
Oxidation of trialkenylborane with alkaline H2O2 results in the formation of carbonyl compounds.
Terminal alkynes give rise to aldehydes whereas internal alkynes give rise to ketones.

OH
|
 R  CH  CH 3 B 
H2O2 /NaOH tautomerizes

 R  CH  CH  
 R  CH2  CHO

OH O
| ||
 R  CH  CR 3 B 
H2O2 /NaOH tautomerizes

 R  CH= C  R  
 R  CH2  C  R

3. Dimerisation
Acetylene dimerises when treated with a mixture of Cu2Cl2 and NH4Cl to give vinyl acetylene.
Cu Cl  NH Cl
2CH  CH 
2 2 4  CH  CH  C  CH
2

The dimer undergoes addition reactions just like any other unsaturated hydrocarbon. The addition
reaction preferably takes place at the triple bond and not at the double bond inspite of the fact
that alkynes are less reactive than alkenes towards electrophilic addition reactions. For example,
addition of HCl to vinyl acetylene gives chloroprene.

Cl
|
CH2  CH  C  CH  HCl  CH 2  CH  C  CH2
Chloroprene 

4. Oxidation
Alkynes are oxidised by hot alkaline KMnO4, which causes cleavage of ăCCă resulting in the
formation of salts of carboxylic acids. The salts on acidification are converted into acids. Internal
alkynes give mixture of carboxylic acids while terminal alkynes give a carboxylic acid and the
terminal C-atom is oxidised to CO2 and H2O.

(i) KMnO / OH / 

CH3  C  CH 
4

 CH3COOH  CO2  H2 O
(ii ) H

(i ) KMnO / OH / 
CH3  C  C  CH2CH3 
4


 CH3COOH  CH3CH2COOH
(ii) H

5. Polymerisation Reactions
(i) Hydrochloric acid adds to acetylene in the presence of Hg2+ ion as catalyst to form vinyl
chloride. Polymerisation of vinyl chloride results in the formation of polyvinyl chloride (PVC).
 
Hg 2+  
Polymerization
HC  CH  HCl 
 CH2  CHCl 
 CH2  C H  
 | 
 Cl  n
(PVC)

HYDRO CARBON
 QUIZRR 77

(ii) Addition of HCN to ethyne is catalysed by Cu2Cl2 in HCl. The product obtained is acrylonitrile,
which on polymerisation gives polyacrylonitrile (PAN).

 
CuCl2 
Polymerization 
HC  CH  HCN   CH 2  CH  CN 
  CH2  C H  
HCl
 | 
 CN  n

(PAN)
Acrylonitrile is also used in the manufacture of a synthetic rubber called BuNaăN (a copolymer
of butadiene and acrylonitrile) and a thermoplastic called ABS (a terpolymer of acrylonitrile,
butadiene and styrene).
(iii) Acetic acid adds to ethyne in the presence of Hg2+ ion to give vinyl acetate, which is used
as monomer in the preparation of polyvinyl acetate (PVA).
2+
Hg
HC CH + CH3COOH CH2 = CHOOCCH3
(vinyl acetate)

6. Reaction with hot iron tube

Ć Acetylene when passed over red hot iron tube forms benzene.

red hot
3CH CH
Fe

This reaction involves a cyclic transition state in which 8eă participate. Such compounds have
aromatic character as aromatic compounds are relatively more stable. So these transition states
are more stable.
CH
CH
CH

CH
CH
CH
CH3
e.g.
Red hot
3CH3 · C CH
Fe
CH3 CH3

HYDRO CARBON
78 QUIZRR
7. Addition of Hypohalous acid

Alkynes react with hypohalous acid in the molar ratio of 1 : 2 to give dihalo Ketones.
Acetylene forms dihaloaldehyde

HOX
R·C C · H + HOX R · C(OH) = CHX
O
ăH2O
R · C · CHX2 R · C(OH)2 · CHX2

Test of Terminal Alkynes

(1) Terminal alklynes give silver mirror in reaction with ammonium solution in silver nitrate,
i.e., ammonium silver nitrate.

CH3 · O CH + AgNO3 + NH4OH CH3 · C CAg + NH4NO3 + H2O

or silver mirror
Ag(NH3)2+ (white ppt)

Ć This test is terminal alkyne.

(2) Another test for terminal alkynes :

They give red ppt in reaction with Cummonium solution in cupurous chloride, i.e., ammonium
cupurous chloride :

CH3 · C CH + CuCl + NH4OH CH3 · C CCu + NH3Cl + H2O

red ppt

This is replaced by Cu.

Example 28

2-butyne undergoes following reactions in steps as indicated. Identify A to H.

H2 D2/Pt
CH3C CCH3 A B
Ni2B

Na/EtOH D2/Pt
C D
H2 Br2
E F
Ni2B
Br2 H2
G H
Ni

HYDRO CARBON
 QUIZRR 79

Solution :
A is obtained by syn addition

H3C CH3
C C
A :
H H
Cis

B is also obtained by syn addition

H H

B : H3C · C · C · CH3

D D
meso

C is obtained by anti addition

H CH3
C·
·C
C :
H3C H
trans

D is mixture of d ă and l ă (racemic mixture)

H D

D : H3C · C · C · CH3 d ă and l - (racemic)

D H

E is obtained by syn addition

E : as A

Allylic systems

The position adjacent to C=C often enhanced reactivity compared to simple alkanes due to the
proximity of the adjacent  system. Such positions are referred as „allylic”. Recall that the term
„vinylic” is used to described the atoms directly associated with the C=C unit.

1. Allylic carbocations

The  system of a double bond can stablise an adjacent carbocation by donating electron density
through resonance. Remember that delocalising charge is a stabilising effect. This stablilisation is
equivalent to that of two alkyl groups, so the alkyl cation has similar stability to the 2-propyl cation.

HYDRO CARBON
80 QUIZRR

+ +
1+ 1+
+ + 2 2
resonance hybrid

Note that in the two resonance forms of the allylic cation, the positive charge is located on the
terminal carbon atoms and never on the middle carbon. This is reflected in the resonance hybrid.
Note that either of the carbons with +ve charge could be attacked by a nucleophile.
Due to the stability of these allylic cations, they are readily formed as intermediates during
chemical reactions, for example SN1 reactions of allylic halides.

2. Allylic radicals

resonance hybrid

The  system of a double bond can also stabilise an adjacent radical through resonance. Remember
that delocalising the radical is a stabilising effect.
Due to the stability of these allylic radicals, they are readily formed as intermediates during
chemical reactions, for example allylic halogenation.

Reactivity

Ć Allylic bonds are often weaker and are easily broken, for example compare the bond
dissociation energies :

H
H 410 kJ/mol (98 kcal/mol)

H
H 368 kJ/mol (88 kcal/mol)

Ć The stability of the allylic radical can be utilised in the preparation of allylic halides
(esp. -Cl and -Br)
Ć Allylic halides readily undergo substitution reactions via either SN1 or SN2 pathways.

HYDRO CARBON
 QUIZRR 81

3. Radical Halogenation of Allylic systems

H X
light or heat
X·X+ C C +H·X
X = Br, Cl

Reaction type : Radical Substitution

Ć When treated with Br2 or Cl2, radical substitution of allylic C-H generates the allyl halide
and HX.
Ć The process is very similar to that of alkanes.
Ć Reaction proceeds via an radical chain mechanism which involves radical intermediates.
Ć The stability of the allylic radical (due to resonance) favours substitution at the allylic
position.
Ć N-bromosuccinimide (NBS) can be used as an alternative source of Br2.

N · Br

Radical Chain Mechanism For Allylic Bromination

Step 1 (Initiation) Heat or uv light causes the weak halogen bond to undergo homolytic cleavage
to generate two bromine radicals and starting the chain process.

Br · Br Br Br

Step 2 (Propagation) :
(a) A bromine radical abstracts a hydrogen to form HBr and an allyl radical, then
(b) The allyl radical abstracts a bromine atom from another molecule of Br2 to form the allyl
bromide product and another bromine radical, which can then itself undergo reaction 2(a)
creating a cycle that can repeat.

Br H · CH2CH CH 2 H · Br CH2CH = CH 2

Br · Br CH2CH= CH2 Br Br · CH2CH = CH 2

Step 3 (Termination) : Various reactions between the possible pairs of radicals allow for the
formation of Br2 or the product, allyl bromide.

HYDRO CARBON
82 QUIZRR

Br Br Br · Br

Br CH2CH CH2 Br · CH2CH = CH2

N-Bromo succinimide (NBS)

NBS is a reagent which provides a low concentration of bromine. Hence, the most reactive
hydrogen is replaced by Br.

Example :

NBS
CH3  CH  CH2  CH2 Br  CH  CH2

Here CH3  C  CH2 is not formed, since the intermediate allylic free radical formed is very stable.
|
Br

Ć
CH2ăCH=CH2  CH2=CHăCĆH2

Other examples

CH3 CH3
Br
NBS

NBS

Br
Important : At high temperature, substitution takes place, while at low temperature addition
takes place.

Cl2
Example : CH3  CH  CH2   Cl  CH 2  CH  CH2
 high temp. 

4. Substitution Reactions of Allyl Halides

LG Nu
Nuă C C + LGă

Ć Allyl chlorides, bromides and iodides are good substrates for substitution reactions.
HYDRO CARBON
 QUIZRR 83

Ć A variety of nucleophiles can used to generate a range of new functional groups.

Ć The process can be complicated by the allylic rearrangement where the nucleophile can
attack either of the deficient sites.

H2O OH H2O Cl

Cl Na2CO3 HO and Na2CO3

85% 15%

+ +

3Ĉ 1Ĉ
Ć The 3Ĉ alcohol is the major product.

Preparation of Conjugated Dienes

Ć Dienes can be prepared by elimination reactions of unsaturated alcohols and allkyl halides.
Ć The outcome of eliminations typically favours the more stable product,
Ć Since conjugated dienes are more stable than isolated dienes, the formation of the conjugated
diene is usually favoured over the isolated diene unless the structure prevents the formation
of the conjugated system.

OH Br
KHSO4 KOH
heat heat

Reaction of Dienes

In general terms, dienes undergo electrophilic addition reactions in a similar fashion to alkenes
(review)
E E
+ ă ă
+ Nu
Nu · E
Nu
However, in a little more detail :
Ć Conjugated dienes undergo addition but the proxmity of the conjugated C=C influences the
reactions.
Ć Isolated dienes react just like alkenes
Ć Cumulated dienes react more like alkynes (after all, both have sp hybridised C atoms)
Our attention here will focus on conjugated dienes.
Ć The  bonds are a region of high electron density so dienes are typically nucleophiles.
Ć Dienes react with electrophiles (e.g. H+, X+)

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Ć Dienes can undergo addition reactions in which one or both of the  bonds are converted to
new stronger  bonds.
Ć Overall reaction : Electrophilic addition

1. Addition of Hydrogen Halides to Dienes

Conjugated dienes undergo addition reactions in a similar manner to simple alkenes, but two
modes of addition are possible.
These differ based on the relative positions of H and X in the products :

1 1 3 X
2 +
H·X +
H H 2 4
X
Direct or 1,2-addition Conjugate or 1,4-addition

Direct H-X adds „directly‰ across the ends of a C=C

Conjugate H-X adds across the ends of the conjugated system

The numbers 1,2- and 1,4- denote the relative positions of H and X in the products.
The distribution of the products depends on the reaction conditions as shown by the example
below :

HBr
81% 19%
ă80ĈC
Br Br

HBr
44% 56%
20Ĉ C
Bră Bră

+
H
+ H + H

At low temperature, the reaction is under kinetic control (equilibrium reversible conditions) and
the major product is the more stable system (note the more highly substituted alkene). This is
supported by the fact that heating pure samples of either 3-bromo-1-butene (direct addition
product) or 1-bromo-2-butene (conjugate addition product) gives the same 15 : 85 ratio of
3-bromo-1-butene to 1-bromo-2-butene.

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At high temperature, the reaction is under thermodynamic control (equilibrium reversible

conditions) and the major product is the more stable system.

2. Addition of Halogens to Dienes

Like the addition of hydrogen halides to conjugate dienes, halogoens add to dienes via direct and
conjugate addition pathways :

1 1 3 X
2 +
X·X +
X X 2 4
X
Direct or 1,2-addition Conjugate or 1,4-addition

The major products are usually the more stable, conjugate addition products with the more stable
E configuration of C=C.

3. Diels-Alder Reaction

Ć The Diels-Alder reaction is a conjugate addition reaction of a conjugated diene to an

alkene (the dienophile) to produce a cyclohexene.
Ć The simplest example is the reaction of 1,3-butadiene with ethene to form cyclohexene :

+
heat

Ć The analogous reaction of 1,3-butadiene with ethyne to form 1,4-cyclohexadiene is also

known :

+
heat

Ć Since the reaction forms a cyclic product, via a cyclic transition state, it can also be described
as a “cyc loaddition”.
Ć The reaction is a concerted process :

Ć Due to the high degree of regio-and stereoselectivity (due to the concerted mechanism), the
Diels-Alder reaction is a very powerful reaction and is widely used in synthetic organic
chemistry.

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Ć The reaction usually thermodynamically favourable due to the conversion of 2 ăbonds into
2 new stronger ăbonds.
Ć The two reactions shown above require harsh reaction conditions, but the normal Diels-
Alder reaction is favoured by electron withdrawing groups on the electrophilic
dienophile and by electron donating groups on the nucleophilic diene.
Ć Some common examples of the components are shown below :

Dienes

O O
CO2Me
CN CO2Me CO2Me
Dienophiles
O
CO2Me
MeO2C
O CO2Me

Stereoselectivity :
Ć The Diels-Alder reaction is stereospecific with respect to both the diene and the dienophile.

Ć Addition is syn on both components (bonds form from same species at the same time)

Ć This is shown by the examples below :

cis-dienophile gives cis-substituents in the product.
trans-dienophile gives trans-substituents in the product.

CO2Me CO2Me

CO2Me CO2Me

If both substituents on the diene are Z, then both end up on the same face of the product.

CO2Me CO2Me

MeO2C CO2Me

If substituents on the diene are E and Z, then they end up on opposite faces of the product.

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Cyclic dienes can give stereoisomeric products depending on whether the dienophile lies under or
away from the diene in the transition state. The endo product is usually the major product (due
to kinetic control).

O
O
+ O O
O O
O endo O exo
O

O
O O O
O O O O
O
O O O

Diene and dienophile aligned directly Diene and dienophile staggered with
over each other gives the endo product respect to each other gives the exo
(dienophile under or in = endo) product (dienophile exposed or out = exo)

Example 29

1 1
2 6 2
(1) + O 6 O
3 5 3 5
4 4

Diene Dienophate

COOH
1 1 COOH
6C 6
2 2
(2) +
3 3 5
5 C
4 4 COOH

Example 30

Dehydrohalogenation of 3-bromohexane gives a mixture of cis-2-hexene and trans-2-hexene.

How can this mixture be converted to pure
(a) cis-2-hexene ? (b) trans-2-hexene ?

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Solution :
Relatively pure alkene geometric isomers are prepared by stereoselective reduction of alkynes.

(a) Hydrogenation of 2-hexene with LindlarÊs catalyst gives cis-2-hexene.

Br2 2NaNH2
CH3CH = CHCH2CH2CH3 CH3CH · CHCH2CH2CH3

Br Br

H3C CH2CH2CH3
H2
CH3 CCH2CH2CH3 C=C
Lindlar's catalyst
H H
cis - 2-Hexene

(b) Reduction with Na in liquid NH3 gives the trans product.

H3C H
Na
CH3C CCH2CH2CH3 C=C
NH, (1)
H CH2CH2CH3
cis - 2-Hexene

Example 31

Use HC  CH as the only organic reagent to prepare

(a) (E) ă 3ăhexene and

(b) (Z)ă3ă henene.

Solution :

 HC  C  Na 
Na
HC  CH  ...(1)

H HCl
HC  CH 
2  CH  CH  CH  CH Cl
2 2 3 2 ...(2)

Combine (1) and (2)

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CH  Că Na+  CH3 CH2 Cl  HC  CăCH2 ă CH3

(i) Na
(ii) CH3CH2Cl

H3CH2CC CCH2CH3

lindlar catalyst / H2 Na / liq NH3

H3C · CH2 CH2 · CH3 H CH2CH3

C C C C

H H H3CCH2 H

(Z) - 3-hexane (E) - 3-hexane

In the above reaction acetylene is the only organic reagent used.

Example 32

Deduce the structural formula of a compound, C10H10(A), that gives ÂBÊ as the only organic
compound,

HOOCCH 2 CHCH 2 COOH

| (B)
CH 2 COOH

on oxidative cleavage, C10H10 is the molecular formula of the organic compound.

Solution :
The degree of unsaturation in the compound is

Number of hydrogen
= (number of carbon) ă 1
2

10
= (10 + 1) ă
2

= 11 ă 5 = 6
This compound contains 6 bonds on oxidative cleavage it is producing only one compound, so all
the multiple bonds should be at the terminal atom.

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+
KMnO4 /H
HC CH · CH2 · CH · C CH HOOC · CH2 · CH · CH2COOH

(A) CH2 · C CH (B) CH2COOH

Example 33

Identify (a) the chiral compound C, C10H14, that is oxidized with alk. KMnO4 to Ph COOH,
and (b) the achiral compound D, C10H14, inert to oxidation under the same conditions.
Solution :
Given
COOH

alk. KMnO 4
C10H14
Chiral
(C)
C10H14 Inert to oxidation
(D)
achiral

Since benzoic acid is the product ÂCÊ should be monosubstituted benzene.

C4H9
CH3

H3C ă C ă CH3
H5C2 · *CH · CH3 Achiral and resistant to
oxidation

(C) (D)

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