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1
CHEMISTRY
GRIGNARDREAGENT, REDUCTION&ALKANE
1. GRIGNARD REAGENT
1.1 Organometallic compounds
Organometallic compounds are the organic compounds in which a metal atomis directly attached to carbon
of organic moetiy through covalent bond or ionic bond. For example
C M or
(Where C is a carbon atom of an organic molecule and M is a metal atom)
If the metal atom is attached to oxygen, nitrogen. sulphur, etc., then such an organic compound is not
regarded as an organometallic compound. The following structural formula do not belong to the family of
organometallic compounds.
RONa (Sodium alkoxide). CH
3
COONa (Sodium acetate), CH
3
COOAg(Silveracetate),RSK (Potassium
mercaptide) RNHK
(N-Alkylpotassamide), (CH
3
COO)
4
Pb (Lead tetraacetate), etc.
Note : It should be noted that (CH
3
)
4
Si (Tetramethylsilane, TMS) is also not an organometallic compound because
silicon is a nonmetal.
Most important examples of organometallic compounds are Grignard reagents. In Grignard reagent, the
carbon and magnesiumatoms arebonded witheach other through polar covalent bond and magnesiumatom
is attached to halogen by ionic bond.
(Functional part of a Grignard reagent molecule)
In organometallic compounds, the metal atom can be bonded to carbon atom of a hydrocarbon parts
(Saturated, unsaturated, aliphatic,
alicyclic or aromatic) or carbon atom of a heterocyclic part. Some examples are given below.
Saturated Aliphatic Grignard reagent :- CH
3
MgI
(Methylmagnesiumiodide)
Unsaturated Aliphatic Grignard reagent : -
(i) Alkenyl Grignard reagent : - CH
2
= CH CH
2
MgX (Allylmagnesium halide)
(ii) Alkynyl Grignard reagent : - CH C CH
2
MgX (Propargylmagnesium halide)
Alicyclic Grignard reagent : - (Cyclohexylmagnesium halide)
Aromatic Grignard reagent : (Phenylmagnesium halide)
Heterocyclic Aromatic Grignard reagent :- (Pyridine-4-magnesium halide)
Heterocyclic Nonaromatic Grignard reagent :- (Piperidene-4-magnesium halide)
1.2 Preparation of Grignard Reagent
RX + Mg
Ether
pure and Dry

RMgX
Ether is used as a solvent because it is a Lewis base that donates its lone pair of electrons to electron-
deficient magnesium atom, therefore providing stability to the Grignard reagent by completing the octet on
magnesiumatom.

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CHEMISTRY
1.3 Reactions of Grignard reagents
It has been found out by estimation that there is 35%ionic character in carbon-magnesium bond of Grignard
reagent. Therefore, there is a tendency of forming carbanion by heterolysis of this polar coordinate bond as
follows.
+
The carbanion (a nucleophile) formed as shown above, attacks the positively, charged electrophilic centre of
other compound. Therefore. It can be said that if a Grignard reagent is regarded as the substrate, then
electrophile displaces MgX, i.e. electrophilic substitution (S
E
) reaction takes place.
R MgX R E (S
E
Product)
Grignard reagents form adducts by addition on the following types of pi bonds.
, , and C N , N = O,
eg. R MgX +
Adduct
|
OMgX C R
|

On having same hydrocarbon radical, the order of reactivity of Grignard reagents will be as follows :
RMgI > RMgBr > RMgCl
1.4 Synthetic importance of Grignard reagents
1.4.1 Synthesis of Alkanes
(i) With compounds having reactive hydrogen atom
General reaction :
R MgX + H Z R H + ZMgX
CH
3
MgX + H OH CH
3
H + Mg(OH)X
C
2
H
5
MgX + H OR C
2
H
5
H + Mg(OR)X
C
3
H
7
MgX + H OC
6
H
5
C
3
H
7
H + Mg(OC
6
H
5
)X
C
2
H
5
MgX + H NH
2
C
2
H
5
H+ Mg(NH
2
)X
CH
3
MgX + H NHR CH
3
H + Mg(NHR)X
C
2
H
5
MgX + H NR
2
C
2
H
5
H+ Mg(NR
2
)X
CH
3
MgX + H NHC
6
H
5
CH
3
H + Mg(NHC
6
H
5
)X
C
2
H
5
MgX + H SR C
2
H
5
H + Mg(SR)X
CH
3
MgX + H C N CH
3
H + Mg(CN)X
C
2
H
5
MgX + H C CH C
2
H
5
H + HC C MgX (Ethynylmagnesium halide)
CH
3
MgX + H C CR CH
3
H + R C C MgX (Alkynylmagnesium halide)
Methane gas is released on reacting methylmagnesium iodide with a compound containing reactive
hydrogen atom. The reaction is used for estimation of reactive hydrogen atoms present in a molecule. This
method is called Zerewitinoff method of estimation of reactive hydrogen atoms.
(ii) With alkyl halide (coupling) :
R MgX + X' R' R R' + MgXX'
1.4.2 Synthesis of alkenes
R MgX + X'
halide Allyl
2 2
CH CH CH = R CH
2
CH = CH
2
+ MgXX'
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CHEMISTRY
1.4.3 Synthesis of higher alkynes
Non-terminal alkynes
R' C C H
RH
RMgx

R' C CMgX
2
MgX
X
R

''

R' C C R''
1.4.4 Synthesis of other organometallics
4R MgCl + 2PbCl
2
R
4
Pb + Pb + 4MgCl
2
Twoimportant antiknockingcompounds, tetraethyllead(T.E.L.) andtetramethyllead(T.M.L.) aremanufactured
by the above reaction.
2R MgCl + HgCl
2

rcury Diallkylme
MgCl 2 R Hg R
2
+
2R MgCl + CdCl
2

dmium Diallkylca
MgCl 2 R Cd R
2
+
4R MgCl + SnCl
4

tin Tetraalkyl
MgCl 4 Sn R
2 4
+
1.4.5 Synthesis of Alcohols
There are following methods to obtain alcohols from Grignard reagent.
(i) Fromcarbonyl compounds
R MgX +
|
OMgX C R
|


HOH
alcohol
|
OH C R
|

This is nucleophilic addition reaction
(a) Primary or 1 Alcohols
Primary alcohols are formed on taking formaldehyde
R MgX +
H
|
OMgX C R
|
H

HOH
Alcohol 1
H
|
OH C R
|
H

(b) Secondary or 2 alcohols
(1) FromRCHOSecondary alcohols are formed by the reaction of any aldehyde other
than formaldehyde.
R MgX +

Alcohol 2
H
|
OH C R
|
R

'
(2) From Formic Ester :
Secondary alcohols are obtained on hydrolysis of the product obtained by taking
excess of Grignard reagent and adding formic ester to it.
O MgX
|| |
OEt C R
|
H
+
O
||
C R
|
H

O H
RMgX
2

OH
|
R C R
|
H

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CHEMISTRY
(c) Tertiary or 3 alcohols
(1) Tertiary alcohols are formed by taking any ketone
R MgX +

''

'
R
|
OMgX C R
|
R
Alcohol 3
R
|
OH C R
|
R

''

'
(2) Tertiary alcohols are also obtained on hydrolysis of the product obtained by taking
excess of Grignard reagent and an ester of a higher homologue of formic acid.
O MgX
|| |
OEt C R
|
R
+
O
||
C R
|
R

O H
RMgX
2

OH
|
R C R
|
R

Various alcohols can be prepared by changing R in the above synthesis.
(iii) FromEpoxides

OMgX
|
CH CH R
2 2

C more two having
Alcohol 1
OH
|
CH CH R
2 2

(iv) From Oxygen
(a) Synthesis of alcohol
R MgX + O = O R O O MgX
R O O MgX + R MgX 2R O MgX
R O MgX + HOH R O H + Mg(OH)X
Primary, secondary and tertiary alcohols can be obtained by above reaction
(b) Synthesis of phenols
Phenol is obtained on hydrolysis of the product obtained by reaction of arylmagnesium
bromide with oxygen.
C
6
H
5
MgBr + O = O C
6
H
5
O OMgBr
C
6
H
5
O OMgBr + C
6
H
5
MgBr 2C
6
H
5
OMgBr
C
6
H
5
OMgBr + H
2
O C
6
H
5
OH + Mg(OH)Br
1.4.6 Synthesis of Aldehydes
Corresponding aldehyde is obtained on hydrolysis of the product obtained by reacting of formic ester and
Grignard reagent in equimolar ratio.
O MgX
|| |
OEt C R
|
H
+


EtO
O
||
C R
|
H

Tetrahedral intermediate
In this reaction tetrahedral intermediate is fromed so this mechanism is called S
N
2 Th mechanism
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CHEMISTRY
1.4.7 Synthesis of Ketones
(i) From Acid derivative


MgOG
O
||
C R
|
R

'
Where G = -OEt, Cl
The above reaction sequence can be simplified as follows for convenience.
R MgX +
O
||
R C G '

O
||
R C R ' + G MgX
eg. R MgX +
O
||
R C EtO '

O
||
R C R ' + EtO MgX
eg. R MgCl + Cl CO R'

R CO R' + MgCl
2
(ii) From Alkyl Cyanides
Aketimine is formed on hydrolysis of the adduct obtained by the reaction of Grignard reagent and an
alkyl cyanide, which gives ketone on further hydrolysis.
RMgX + RCN

R
2
C = NMgX

HOH
e min Keti
NH C R
2
=
HOH
Ketone
O C R
2
=
1.4.8 Synthesis of Carboxylic acids
A carboxylic acid is formed on hydrolysis of the adduct formed by passing carbon dioxide in the ethereal
solution of a Grignard reagent.
O
||
O C MgX R = +

O
||
OMgX C R
X ) OH ( Mg
HOH

O
||
OH C R
1.4.9 Synthesis of Carboxylic acid esters
Esters are formed on reacting the ethylchloroformate with Grignard reagent.
RMgCl + ClCOOEt RCOOEt + MgCl
2
1.4.10 Synthesisof Ethers
Higher ethers can be synthesised by reacting a lower chlorinated ether with Grignard reagent.
R MgCl + Cl CH
2
O R R CH
2
O R + MgCl
2
CH
3
MgCl +
ether ethyl yl Chlorometh
5 2 2
H C O CH Cl
ether Diethyl
5 2 2 3
H C O CH CH
1.4.11 Synthesis of Mercaptans
Alkanethiols, i.e. mercaptan is formed on hydrolysis of the product obtained by adding sulphur to the ethereal
solution of Grignard reagent.
R MgCl + S R S MgCl

HOH
R S H + Mg(OH)Cl
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CHEMISTRY
2. REDUCTION
Introduction
Reduction covers both the addition of hydrogen (or deuterium) to a double bond and the replacement of an
atomor group by hydrogen (or deuterium). In other words, reduction means hydrogenation or
hydrogenolysis.
Methods of Reduction :
2.1 Catalytic hydrogenation : The catalysts used can be divided into two broad classes, both of which
mainly consist of transition metals and their compounds :
2.1.1 Heterogeneous catalysts : (catalysts insoluble in the reaction medium)
In heterogeneous catalytic hydrogenation catalysts are used in powdered form (raney nickel (Ni), Palladium
on charcol (Pd/C), Platinum metal or its oxide). Substrate molecules are assumed to undergo homolysis
into atoms which are chemisorbed at the surface of the catalyst. The substrate is also chemisorbed on the
surface of the catalyst.
General Reaction C = C + H
2

Catalyst
) addition syn (
H H
| |
C C
| |

Hydrogenation of an alkene is an exothermic reaction (
~ A H
120 kJ mol
1
):
R CH = CH R + H
2

Ni
R CH
2
CH
2
R + heat
The process is exothermic, there is usually a high free energy of activation for uncatalyzed alkene
hydrogenation, therefore, the uncatalyzed reaction does not take place at room temperature. Hydrogenation
will take place readily at room temperature in the presence of a catalyst because the catalyst provides a new
pathway for the reaction that involves lower free energy of activation .
Heterogeneous hydrogenation catalysts typically involve finely divided platinum, palladium, nickel, or rhodium
deposition on the surface of powdered carbon ( charcoal). Hydrogenation actually takes place at the surface
of the metal, where the liquid solution of the alkene comes in contact with hydrogen and the catalyst.
Hydrogen gas is adsorbed into the surface of these metal catalysts and the catalyst weakens the H H
bond. In fact, if H
2
and D
2
are mixed in the presence of a Pt catalyst, the two isotopes quickly scramble to
produce a random mixture of HD, H
2
and D
2
. (No scrambling occurs in the absence of the catalyst.)
Hydrogenation is an example of heterogeneous catalysis, because the (solid) catalyst is in a different phase
from the reactant solution. In contrast, homogeneous catalysis involves reactants and catalyst in the same
phase, as in the acid-catalyzed dehydration of an alcohol.
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Both hydrogen atoms usually add from the same side of the molecule. This mode of addition is called a syn
addition.
The ease of reduction of various functional groups toward catalytic hydrogenation (Ni/Pd/Pt)
Lindlars catalyst : is a poisoned palladium catalyst, composed of powdered barium sulphate coated
with palladium, poisoned with quinoline. Nickel boride Ni
2
B (P-2 catalyst) (made from sodium acetate and
sodiumborohidride) is an excellent alternative catalyst for the conversion of alkyne into alkene. (syn addition)
The partial reduction of alkyne to alkene is heterogeneous hydrogenation with Lindlar's catalyst.
eg. CH
3
CH
2
C C CH
3
B Ni or
catalyst s ' Lindlar H
2
2

(syn addition)
Acid chloride reduced to aldehyde by using Pd /BaSO
4
catalyst


4 2
BaSO Pd / H
CH
3
CHO
This reaction is called Rosenmund Reduction
e.g. CH
3
CCCH
3
e.g. O
2
N CH = CH CH
2
CH
3

Pd / H
2 H
2
N CH
2
CH
2
CH
2
CH
3
e.g.

Pt or Pd / H
2
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CHEMISTRY
2.2 Reduction by Dissolving Metals
The general mechanism of reduction by dissolving metals is based on the fact that the metal acts as a
source of electrons first an electron adds to the substrate causing fission of a single bond into a free
radical and an anion or it can adds to a double bond forming a resonance - stablized radical ion.
A B

e -
A +
:

B or
:

A +
-
B
A = B

e -
O
B A
:
or
:
O
-
B A
2.2.1 Reduction by Na or Li /NH
3
(Birch reduction)
Mechanism:
Reagents Na(or Li,K) + liq NH
3
Na
+
+ e (solvated electron)
NaNH
2
+ (anti addition)
Typical example of reduction for aromatic system :-

3
NH / Na

3
NH / Na
R C C R

3
NH / Na
(anti addition)
e.g.

3
NH / Na
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CHEMISTRY
2.2.2 Reduction by Na/C
2
H
5
OH [Bouvealt - Blanc reduction]
Reduction of aldehydes ketones or esters by means of excess of Na/C
2
H
5
OHor n-butanol is called Bouvealt-
Blanc reduction reduction.
Mechanism:

Na

OH H C
5 2

Na
RCH
2
OH

OH H C
5 2 RCH
2
O

Na
RCH
2
O

OH H C
5 2

Na
R CH = O+ C
2
H
5
O

e.g. CH
3
CHO CH
3
CH
2
OH
Acetaldehyde Ethanol
CH
3
COCH
3
Acetone propane-2-ol
CH
3
CH
2
OH
Ethyl acetate Ethanol
2.3 Reduction by metal hydrides and alkoxides :
Certain complex metal hydrides, borane and aluminium isopropoxide, are reagents of choice for reduction
of carbonyl group.
2.3.1 LiAlH
4
(LAH) Lithium aluminium hydride : LAH is most common and versatile of this class of reagent. It
is sensitive to protic solvent and therefore used in carefully prepared nonhydroxylic solvent generally ether is
used as solvent, It may be regarded as derived from metal hydride.
LiH + AlH
3

4

H Al Li
+
Mechanism:

=O C R
2
4 R
2
CHOH

O H
3
Al

(OCHR
2
)
4

=O R C
2
O
l HA (OCHR
2
)
3
2.3.2 NaBH
4
(Sodiumborohydride) : It is more specific than LAHas a reducing agent. It is reduces only ketones
and aldehydes to the corresponding alcohols without affecting other functional groups. It is effective even in
protic solvent like alcohol. reduces acid chlorides but not and any other derivative of acid.
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CHEMISTRY
Mechanism:

=O C R
2
4 R
2
CHOH

O H
3
B

(OCHR
2
)
4

=O R C
2
O
B H
(OCHR
2
)
3
eg.

4
LiAlH
eg.

4
NaBH
eg.
2.3.3 DIBAL-H(Diisobutyl AluminiumHydride) (ALANE) :
Most important alane is diisobutyl aluminium hydride. It runs parallel to LAH(Lithiom aluminium hydride) as
a reducing agent but it is more selective.
eg. PhCH=CHCOOC
2
H
5
O H
THF LiAlH
2
4


PhCH
2
CH
2
CH
2
OH+C
2
H
5
OH
PhCH=CHCH
2
OH
ByDIBALat ordinarytemperatureesters arereducedtoalcohols but it lowtemperatureexters arereduced
to aldehyde.
eg. C
6
H
5
C
||
O
OCH
3
C 25 toluene
DIBAL

C
6
H
5
CH
2
OH
C
6
H
5
CHO
LAH reduce RCN to amine but DIBAL is found to be reduce it to aldehyde.
eg. CH
3
CN
O H
THF LiAlH
2
4


CH
3
CH
2
NH
2
CH
3
CHO
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CHEMISTRY
2.3.4 Reduction by isopropyl alcohol and aluminium isopropoxide. This is called the Meerwein-Pondorf-
Verley reduction
Mechanism:

CHOH ) CH (
2 3
eg. + +
2.4 Miscellaneous Reductions
2.4.1 Stephens Reductions
Whenreduction of compounds is carriedout withacidifiedstannous chloride(SnCl
2
/HCl) at roomtemperature,
imine hydrochloride is obtained which on subsequent hydrolysis with boiling water gives aldehyde. This
specific type of reduction of nitrile is called stephens reduction.
eg. CH
3
CN
O H ) ii (
HCl / SnCl ) i (
2
2

CH
3
CHO
Acetaldehyde
eg.
O H ) ii (
HCl / SnCl ) i (
2
2

Benzaldehyde
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CHEMISTRY
2.4.2 Clemmensens Reducation :
Used to get alkane from carbonyl compounds.
R CHO
A

HCl . conc / Hg Zn
RCH
3
+ H
2
O
' R C R
||
O
A

HCl . conc / Hg Zn
RCH
2
R' + H
2
O
eg. CH
3
CHO
A

HCl . conc / Hg Zn
CH
3
CH
3
+ H
2
O
eg.
5 2 3
H C C CH
||
O
+ 4[H]
A

HCl . conc / Hg Zn
CH
3
CH
2
C
2
H
5
+ H
2
O
Clemmensen reduction is not used for compounds which have acid sensitive group.
2.4.3 Wolff-kishner reduction with NH
2
NH
2
/ KOH
Used to get alkane from carbonyl compounds
Mechanism:
RCHO
A

KOH / NH NH
2 2
RCH
3
RCO R'
A

KOH / NH NH
2 2
RCH
2
R'
Wolff-kishner reduction is not used for compounds which have base sensitive groups.
2.4.4 By Red P & HI
A

+ HI P d Re
R CH
3 ;
A

+ HI P d Re
R CH
3
A

+ HI P d Re
R CH
3 ;
A

+ HI P d Re
R CH
2
R
eg.
A

+ HI P d Re
CH
3
CH
3
eg.
A

+ HI P d Re
CH
3
CH
2
CH
3
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CHEMISTRY
(*) double bond can be reduced by LiAlH
4
/ THF only in cinnamic system.
For eg. PhCH=CHCHO
O H
THF LiAlH
2
4


PhCH
2
CH
2
CH
2
OH
3. ALKANE
3.1 General method of preparation
3.1.1. By catalytic reduction of alkenes and alkynes
R C C R'
Pd or Pt , Ni
C 25 , H
2


R CH
2
CH
2
R'
R CH = CH R'
Pd or Pt , Ni
C 25 , H
2


R CH
2
CH
2
R'
Hydrogenation Addition of H
2
to unsaturated bond.
Hydrogenation is of two kinds
(a) Heterogeneous (b) Homogeneous
(a) Heterogeneous : It is two phase hydrogenation the catalyst is finely devided metal like Ni, Pt or Pd and
a solution of alkene.
(b) Homogeneous : It is one phase hydrogenation both catalyst and alkenes are in solution. In this
hydrogenation catalyst are organic complex of transition metal like Rh or Ir.
Hydrogenation is exothermic, quantitative and during the hydrogenation, total heat evolved to hydrogenate
onemole of unsaturatedcompoundis calledheat of hydrogenation. Heat of hydrogenationis themeasurment
of stability of isomeric alkenes.
stability of alkene
ion hydrogenat of Heat
1
Note : Hydrogenation of alkene or alkyne in presence of metal catalyst is syn addition
eg. + H
2
COOH CH
Pd
3

(Meso)
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CHEMISTRY
eg. + H
2
COOH CH
Pd
3

(Racemic mixture)
3.1.2. From alkyl halide
(i) By wurtz reaction
2R X + 2Na
ether dry
R R + 2NaX
R X + R' X
) dry ( ether
Na
R R, R R', R' R'
Mechanism Two mechanisms are suggested
(a) Ionic mechanism
2Na

Na 2 +
) 2 , 1 (
X R

+ 2e

2
N
S
R R
NaX
(b) Free radical mechanism
Na
R X +
-
R +
-
R +
-
R
R R
Note : The alkyl halide should be 1 or 2, with 3 R X S
N
2 and free radical coupling is not possible due to
steric hinderence so in that case elimination or disproportionation is possible.
In the ionic mechanism alkyl sodium gives strong base as well as nucleophile which gives S
N
2
with R X, ether should be dry otherwise if moisture is present than forms R Hinstead of R Rwith H
2
O.
e.g. CH
3
CH
2
Br

Na
CH
3
CH
2
CH
2
CH
3
e.g. CH
3
Cl + CH
3
CH
2
Cl

Na
CH
3
CH
3
+ CH
3
CH
2
CH
3
+ CH
3
CH
2
CH
2
CH
3
(ii) By reduction of alkyl halides
(A) with metal-acid

1
X R R H + HX
Reducing agent
Zn / HCl , Zn Cu / H
2
O or Zn Cu + CH
3
COOH
Zn Cu / C
2
H
5
OH, Na Hg / HCl, Al Hg / H
2
O etc.
Mechanism
Metal
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CHEMISTRY
(B) With metal hydrides
(a) TPH (Ph
3
SnH) Triphenyltin hydride : It reduces 1, 2 & 3 R X
3 / 2 / 1
X R
SnH Ph
3
R H
(b) NaBH
4
:


3 & 2
X R
4
NaBH
R H
(c) LiAlH
4
:


2 & 1
X R
4
LiAlH
R H

3
X R
4
LiAlH
Alkene
3.1.3 From organometallic compound
(i) By Grignard Reagent.

3 2 , 1
X R
ether
g
M

RMgX
RMgX +
compound
containg H
active all
R H
H O
2
ROH
NH
3
R C CH '
RSH
R COOH
R H + Mg (OH) X
+ Mg (OR) X
+ Mg (NH ) X
2
+ Mg (C CR ) '
+ Mg (SR) X
+ Mg (OCOR) X
RMgX
R H
R H
R H
R H
R H
X
(ii) By corey house alkane synthesis
) 3 , 2 , 1 (
X R


Li 2

CuX
) reagent s ' Gilman ( cuprate
dialkyl Lithium
CuLi R
2

>

'
) 2 1 (
X R
R R'
Mechanism
R
2
CuLi is the source of
O
R
R R'
R
2
CuLi does not reacts with NO
2
, CN, etc.
(iii) By Franklands reagent
R X + Zn + R X
Ether
R R + Zn X
2
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CHEMISTRY
Mechanism
3.1.4 From carboxylic acids: -
(i) By soda lime : Fatty acids are good source of hydrocarbon, continuous heating of sodium salt of carboxylic
acid (R COONa) with soda lime (NaOH CaO) gives hydrocarbon, this process is known as decarboxyla-
tion (e.g. replacement of COOH group by H) decarboxylation also takes place on heating only, when
compound is gem dicarboxylic acid or there is keto group or double bond on | carbon.
O
||
OH C R

NaOH
A

CaO
R H + Na
2
CO
3
(ii) By Kolbes electrolysis
2RCOOK + 2HOH
is Electrolys
R R + 2CO
2
+ H
2
+ 2KOH
Mechanism
RCO
2
K R CO
2

+ K
+
At Anode: - R CO
2

R
-
2
CO + e

(oxidation)
(I)
R
-
2
CO

-
R + CO
2
(II)
-
R +
-
R
R R
If n is the number of carbon atoms in the salt of carboxylic acid, the alkane formed has 2(n1) carbon atoms.
e.g. 2CH
3
COOK + 2H
2
O
is Electrolys
CH
3
CH
3
+ 2CO
2
+ H
2
+ 2KOH.
3.1.5 By Reduction
(i) By Clemmensens reduction : with Zn Hg / conc. HCl
R CHO
A

HCl . conc / Hg Zn
RCH
3
+ H
2
O
' R C R
||
O
A

HCl . conc / Hg Zn
RCH
2
R' + H
2
O
e.g. CH
3
CHO
A

HCl . conc / Hg Zn
CH
3
CH
3
+ H
2
O
5 2 3
H C C CH
||
O
+ 4[H]
A

HCl . conc / Hg Zn
CH
3
CH
2
C
2
H
5
+ H
2
O
Clemmensen reduction is not used for compounds which have acid sensitive group.
(ii) By Wolff-kishner reduction with NH
2
NH
2
/ KOH
RCHO
A

KOH / NH NH
2 2
RCH
3
RCO R'
A

KOH / NH NH
2 2
RCH
2
R'
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17
CHEMISTRY
Wolff-kishner reduction is not used for compounds which have base sensitive groups.
eg.
A

HCl . conc / Hg Zn
Clemmemsens reduction can be can be used to reduce the given compounds.
(iii) By red P & HI
Red P & HI is strong reducing agent
R COOH
+ I H
P
d Re
R CH
3
O
||
Cl C R
+ I H
P
d Re
R CH
3
O
||
OEt C R
+ I H
P
d Re
R CH
3
R X
+ I H
P
d Re
R H
R OH
+ I H
P d Re
R H
3.2 Physical Properties of Alkanes :
3.2.1 Physical state :
The first four members (C
1
to C
4
) are gases ; the next thirteen members, (C
5
to C
17
) are liquids while the
higher members are waxy solids.
3.2.2. Boiling points :
The boiling points of n-alkanes increase regularly with the increase in the number of carbon atoms.
Among the isomeric alkanes, the branched chain isomers have
relatively low boiling points as compared to their corresponding
straight chain isomers. Greater the branching of the chain, lower
is the boiling point. This is due to the fact that branching of the
chain makes the molecule more compact and brings it close to a
sphere, so the magnitude of vander wall forces decreases.
3.2.3. Melting Points
It is evident that the increase in melting point is relatively more in
moving from an alkane having odd number of carbon atoms to the
higher alkane with even no. of C while it is relatively less in mov-
ingfroman alkanewitheven number of carbonatoms to the higher
alkane.
Explanation : The alkanes with even no. of C atoms are more closely packed.
"manishkumarphysics.in"
18
CHEMISTRY
3.2.4. Solubility
In keeping with the popular rule like dissolves like hydrocarbons are insoluble in polar solvent like water
because they are predominantly non-polar in nature.
3.2.5. Density
The densities of alkanes increase with increasing molecular weight but become constant at about
0.8 g cm
3
. This means that all alkanes are lighter than water.
3.3 Chemical Reactions of Alkanes :
Characteristic reaction of alkanes are free radical substitution reaction, these reactions are generally
chain reactions which are completed in three steps.
(i) chain initiation (ii) chain propagation. (iii) chain termination
3.3.1. Halogenation :
R H + X
2
C 400 250
temp or Light UV


R X + HX
Mechanism of halogenation of alkane
(i) Chain initiation it is an endothermic step.
X
2
C 400 250
. temp or UV



X 2
(ii) Chain propagation

X + R H

R
+ HX

R
+ X X R X +

X
(iii) Chain termination it is always exothermic

X +

X
X
2

R
+

R
R R

R
+

X
R X
Steps of halogenation, Value of AH for each step. (Kcal/mole)
F Cl Br I
(i) X
2
2

X + 38 + 58 +46 +36
(ii)

X + CH
4

3

H C + HX 32 + 1 + 16 + 33
(iii)
3

H C + X
2

CH
3
X +

X 70 26 24 20
Reactivity of X
2
: F
2
> Cl
2
> Br
2
> I
2
Reactivity of H : 3H > 2H > 1 H
With F
2
alkanes react so vigorously that even in the dark and at roomtemperature, reactant is diluted with an
Inert gas. Iodination is reversible reaction, since HI formed as a by product and It is a strong reducing agent
and reduces alkyl iodide back to alkane. Hence iodination can be done only in presence of strong oxidising
agent like HIO
3
, HNO
3
or HgO.
R H + I
2
R I + HI
5HI + HIO
3
3H
2
O + 3I
2
2HI + HgO I
2
+ H
2
O + Hg
2HI + 2HNO
3
I
2
+ 2H
2
O + NO
2
Formation of alkyl free radical is rate determining step.
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CHEMISTRY
order of stability of Free radical

3
C Ph
>
H C Ph

2
>
2

H C Ph
>
2

2
H C CH CH =
> (CH
3
)
3
-
C > (CH
3
)
2
-
CH> CH
3
-
2
CH >
3

H C
eg. CH
4
u

h
Cl
2
HCl
Cl CH
3
+
u

h
Cl
2
HCl
Cl CH
2 2
+
u

h
Cl
2
HCl
CHCl
3
+
u

h
Cl
2
HCl
CCl
4
+
When equimolar amount of methane and Cl
2
is taken, a mixture of four possible products are formed, but
when we take excess of CH
4
then yield of CH
3
Cl will be high.
Each photon of light cleaves one chlorine molecule to form two chlorine radicals, each chlorine atom starts
a chain and on an average each chain contains 5000 repeatitions of the chain propagating cycle so about
10,000 molecules of CH
3
Cl are formed by one photon of light.
In a chain reaction following reagents are involved -
(i) Initiators they initiate the chain reaction, Initiators are peroxide (R
2
O
2
), Perester's etc.
R O O R
A

u
or
h

O R
O O
|| ||
R C O O C R
A

u
or
h
O
||
O C R


(ii) Inhibitors A substance that slows down or stops the reaction is known as inhibitors
For example O
2
is a good inhibitor

R
+ O
2


O O R +

R
R O O R
all reactive alkyl free radicals are consumed so reaction stops for a period of time.
Relative reactivity of halogen towards methane
Order of reactivity is F
2
> Cl
2
> Br
2
> I
2
which can be explained by the value of AH (enthalpy change)
Halogenation of higher alkane :
(i) CH
3
CH
2
CH
3
C 25 , light
Cl
2

% 55
Cl
|
CH CH CH
3 3
+
% 45
Cl CH CH CH
2 2 3

(ii) CH
3
CH
2
CH
2
CH
3
C 25 , light
Cl
2

% 72
Cl
|
CH CH CH CH
3 2 3

+
% 28
Cl CH CH CH CH
2 2 2 3

(iii)
3
3 3
CH
|
CH CH CH
C 25 , light
Cl
2

% 64
CH
|
Cl CH CH CH
3
2 3

+
% 36
Cl
|
CH C CH
|
CH
3 3
3

(iv) CH
3
CH
2
CH
3
C 127 , heat
Br
2

% 3
Br CH CH CH
2 2 3
+
% 97
Br
|
CH CH CH
3 3

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20
CHEMISTRY
(v)
3
3 3
CH
|
CH CH CH
C 127 , heat
Br
2

trace
CH
|
Br CH CH CH
3
2 3

+
% 99 over
CH
|
Br C CH
|
CH
3
3
3

Relative amounts of the various isomers differ remarkablydepending upon the halogen used. Fromtheabove
reaction, it is observed that chlorination gives mixture in which no isomer greatly dominates while, in bromi-
nation gives a mixture in which one isomer dominates greatly (97% 99%),
Factors affecting the relative yields :-
Factors determining the relative yields of the isomeric products.
(i) Probability factor : This factor is based on the number of each kind of H atom in the molecule.
(ii) Reactivity of hydrogen : The order of reactivity is 3 > 2 > 1 the relative rate per hydrogen atom is
found to be
(iii) Reactivity v/s selectivity principle The more reactive is halogen less selective it will be, so the
more reactive chlorine free radical is less selective and more influenced by the probability factor and the less
reactive
r B

is more selective and less influenced by the probability factors.

Based on relative reactivity of different types of H, percentage of each in the product mixture can be calcu-
lated.
e.g.
% yield A =
2 . 21
6
100 = 28.3 % ; % yield B =
2 . 21
2 . 15
100 = 71.%
3.3.2. Sulphonation : Lower alkanes are not easily sulphonated but hexane & higher members are sulphonated
on heating with oleum (conc. H
2
SO
4
+ SO
3
) at 400C
C
6
H
14
+ H
2
SO
4

C 400
C
6
H
13
SO
3
H+ H
2
O
3.3.3. Isomerisation :
CH
3
CH
2
CH
2
CH
3
C 300
HCl / AlCl . Anhyd
3

e tan Isobu
3
3 3
CH
|
CH CH CH
CH
3
(CH
2
)
3
CH
3 C 300
HCl / AlCl
3

e tan Neopen
3
3 3
3
CH
|
CH C CH
|
CH

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21
CHEMISTRY
3.3.4. Alkylation : Isoalkanes add to isoalkenes in presence of conc. H
2
SO
4
or HF to give higher branched alkane
e tan Isobu
3
3
3
CH
|
H C CH
|
CH

+
Isobutene
3
3 2
CH
|
CH C C H =
4 2
SO H . conc
e tan Isooc
CH CH
| |
CH CH CH C CH
|
CH
3 3
3 2 3
3

3.3.5. Aromatisation :
Alkanes containing 6 or more number of C atoms are oxidised (dehydrogenate & cyclised) in presence of
oxidising agent at higher temparature and formbenzene or its derivatives.
CH
3
(CH
2
)
4
CH
3
P High
C 600
3 2 3
2
O Al O Cr

+
+ 4H
2
CH
3
(CH
2
)
5
CH
3
P High
C 600
3 2 3
2
O Al O Cr

+
CH
3
(CH
2
)
6
CH
3
P High
C 600
3 2 3
2
O Al O Cr

+
+
3 4 2 3
3
CH CH ) CH ( CH
|
CH

P High
C 600
3 2 3
2
O Al O Cr

+
3 2 3 2 3
3
CH CH CH ) CH ( CH
|
CH

P High
C 600
3 2 3
2
O Al O Cr

+
3.3.6 Pyrolysis / Cracking
CH
3
CH
2
CH
3
CH
3
CH
3
+ CH
3
CH = CH
2
+ CH
2
= CH
2
+ CH
4
+ H
2
Higher alkanes are heated in absence of air so these compounds break down into smaller alkanes which are
better fuel. Mixture of products contains all lower alkanes, alkenes & hydrogens.
3.3.7. Combustion :
C
n
H
2n+2
+
|
.
|

\
| +
2
1 n 3
O
2
A

combustion
nCO
2
+ (n + 1) H
2
O (AH
combustion
= -ve)
exothermic reaction
C
x
H
y
+
|
.
|

\
|
+
4
y
x
O
2
A

combustion
xCO
2
+
2
y
H
2
O
C
5
H
12
+ 8O
2
A

combustion
5CO
2
+ 6H
2
O
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CHEMISTRY
Heat of combustion : Amount of heat liberated when 1 mole of hydrocarbon is completely burnt into CO
2
&
H
2
O.
A H of combustion is a measurement of stability of alkane :
Combustion is used as a measurment of stability.
More branched alkanes are more stable and have lower heat of combustion.
e.g. CH
3

I
2
CH
CH
2
CH
3
II
H
|
CH C CH
|
CH
3 3
3

AH
comb.
: I > II
Stability : II > I
Points to remember for A H of combustion
Homologes : Higher homologes have higher heat of combustion.
CH
4
< C
2
H
6
< C
3
H
8
Isomers : Branched isomer has lower heat of combustion.More branched alkane has more no. of primary
C Hbonds. (therefore it has more bond energy).
> >
Cyclo-alkanes : More strained ring has higher heat of combustion per CH
2
unit.
> > > (AH
comb.
per CH
2
unit)
3.3.8 Octane Number : It is a scale of fuel efficiency when the fuel burns during combustion, more branched
alkanes have lower knocking (cracking sound). so are better fuels. On commercial scale iso-octane has
been alotted a rating i.e. octane no. of Isooctane is 100 & n-heptane is - 0
If the octane no. of a fuel is 80, it means that the efficiency of the fuel is equivalent to the efficiency of mixture
of 80%isoctane and 20%n-heptane.
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CHEMISTRY
MISCELLANEOUS SOLVED PROBLEMS
1. Which of the following formula represents Grignard reagent ?
(A) H
2
NMgX (B) HC CMgX (C) R
2
Mg (D) Mg(OH)Br
Ans. B
Sol. Grignard reagent is represented by RMgX.
2. Which of the following is not a Grignard reagent ?
(A) (CH
3
)
2
CHMgCl (B) CH
3
COOMgI (C) C
6
H
11
MgBr (D) C
2
H
5
MgCl
Ans. B
Grignard reagent is represented by RMgX. Where R= Carbon.
3. What is the motive of adding iodine in small amount during preparation of methylmagnesium iodide ?
(A) It acts as a catalyst (B) It converts ether into alkyl iodide
(C) It decreases the violence of the reaction (D) It acts as an electrophilic
Ans. A
Sol. It acts as a catalyst
4. The reaction of an alkyl halide and magnesium is initially very slow, but later becomes very fast, because
(A) The reaction is autocatalytic (B) The Grignard reagent formed is ether-soluble
(C) The reaction is endothermic (D) The reaction is exothermic
Ans. D
RX +Mg RMgX AH = ve
5. AGrignard reagent is formed on reacting magnesium with
(A) Alkyl halide in the presence of dry ether
(B) Alkyl halide in the presence of phenol
(C) Alkyl halide in the presence of alcohol
(D) Alkyl halide in the presence of alcoholic ether
Ans. A
Sol. RX +Mg RMgX(Grignard Reagent)
6. Zerewitinoff's method is used for
(A) the estimation of reactive hydrogen atom (B) the estimation of alkoxy group
(C) the preparation of a higher ether (D) the preparation of a Grignard reagent
Ans. A
Sol. ZH + RMgX RH + MgXZ
This is estimation of reactive hydrogen atom.
7. Primary alcohol cannot be obtained by the reaction of a Grignard reagent with
(A) The simplest alkanal (B) Dimethylene oxide
(C) Ethylene glycol (D) Oxygen
Ans. C
Sol. RMgX+HCHO RCH
2
OH
RMgX+(CH
2
)
2
O RCH
2
CH
2
OH
RMgX+(CH
2
OH)
2
RH+MgXOCH
2
CH
2
OH
RMgX + O
2
ROH
8. Primary, secondary and tertiary alcohols can be obtained by hydrolysis of the products formed on reaction of
a Grignard reagent with
(A) Isobutyraldehyde (B) Butanone (C) Oxygen (D) Oxirane
Ans. C
Sol. RMgX + O
2
ROMgX

+
O H
3 ROH
(1, 2, 3) (1, 2, 3)
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CHEMISTRY
9. Whichof thefollowingis formedonthereactionof onemoleof acetyl chloridewithonemoleof methylmagnesium
chloride ?
(A) 2-Butanol (B) Acetone (C) Isobutyl alcohol (D) t-Butyl alcohol
Ans. B
Sol.
10. Identify the product - X
H
5
C
6
C C C
6
H
5

Catalyst s ' Lindlar
X
Sol.
11. IdentifyX

Pd / H
2
X
Sol. X =
12. Identify the product x and y
+ D
2

RhCl ) P Ph (
3 3 X
+ D
2

RhCl ) P Ph (
3 3 Y
Sol. X = ; Y =
(Meso) (dl) Recemic mixture
13. Identify product ?

4
LiAlH
P
Sol. P =
14.
Where x and y ?
Sol. x = Cis 2 butene , y = trans 2 butene
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CHEMISTRY
15.
Write the products.
Sol. (a) (b)
16.
Sol. In all cases product is
17. Arrange the following alkenes in decreasing order of their stability
R
2
C = CR
2
, CH
2
= CH
2
, R
2
C = CH
2
, R CH = CH R (cis, trans), R
2
C = CHR, RCH = CH
2
Sol. R
2
C=CR
2
> R
2
C = CHR >R
2
C = CH
2
>
trans
R CH CH R = >
cis
CHR RCH = > R CH = CH
2
> CH
2
= CH
2
18. What is the order of stability of following alkene
I
3
2 3
CH
|
CH CH CH CH =
,
II
3 2 2
3
CH CH C CH
|
CH
=
,
III
3
3 3
CH
|
CH CH C CH =
Ans. III > II > I
Sol. Stability of alkene Hyperconjugative Structure.
19. C
2
H
5
Cl
Ether
Na

products
Write all possible product
Sol. CH
3
CH
2
Cl
major
CH CH CH CH
3 2 2 3

CH
3
CH
2
Cl
2 3
H C CH
-

coupling
CH
3
CH
2
CH
2
CH
3

ion disproport
CH
3
CH
3
+ CH
2
= CH
2
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CHEMISTRY
20. Wurtz reaction will not be observed in
(A) (B) (C)
3
3
CH
|
Br CH CH (D) none of these
Ans. B
Sol.

Na
+ H
2
gas
21. CH
3
Br
Li
A
I Cu
B
Y
C
if C is CH
3
CH
2
(CH
2
)
5
CH
3
, than what is Y.
Ans. CH
3
(CH
2
)
6
Br
Sol. CH
3
Br
Li
CH
3
Li
I Cu
(CH
3
)
2
CuLi

X CH ) CH ( CH
2 5 2 3 CH
3
CH
2
(CH
2
)
5
CH
3
22.
A
A
A

/ CaO
NaOH
B
What are Aand B
Sol. A is , B is
23. Explain why the chain initiating step in thermal chlorination of CH
4
is
Cl
2

A
l C

and not CH
4

A
3

H C +

H
Sol. Because E
act
of Cl
2
is less than E
act
of CH
4
24. Chlorination of CH
4
involves following steps :
(i) Cl
2
l C 2

(ii) CH
4
+
l C

H C + HCl
(iii)
3

H C +
l C

CH
3
Cl
Which of the following is rate determining ?
(A) Step (i) (B) Step (ii) (C) Step (iii) (D) Step (ii) and (iii) both
Ans. B
Sol. Formation of alkyl free radical is Rds step.