LECTURE NOTES

Session - 2012-13

ORGANIC CHEMISTRY
TOPIC :
GRIGNARD REAGENT, REDUCTION & ALKANE

CONTENT :
1. Grignard Reagent
- Preparation
- Reactivity
- Reaction
- Di Grignard
2. Reduction
3. Alkane
- Physical properties
- Chemical reaction
- Preparation

Refer sheet : Grignard Reagent, Reduction & Alkane

JEE Syllabus [2009]
Alkane: Preparation, properties and reactions of alkanes: Homologous series, physical properties of alkanes
(melting points, boiling points and density); Combustion and halogenation of alkanes; Preparation of alkanes by
Wurtz reaction and decarboxylation reactions.
Grignard reactions: nucleophilic substitution reactions, nucleophilic addition reactions
Reduction : Reduction of alkenes, alkynes, aldehydes and ketones

Page # 1
LECTURE NOTES
Session - 2009-10
 GRIGNARD REAGENT
1. Introduction of Organometallic compounds
Organometallic compounds are the organic compounds in which a metal atom is directly attached to carbon
atom through covalent bond or ionic bond. For example
C–M or e.g. R-MgX, R2CuLi, R2Zn, RNa, RLi

(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). CH3COONa (Sodium acetate), CH3COOAg (Silver acetate), RSK (Potassium
mercaptide) RNHK (N-Alkylpotassamide), (CH3COO)4Pb (Lead tetraacetate), etc.

Note : It should be noted that (CH3)4Si (Tetramethylsilane, TMS) is also not an organometallic compound
because silicon is a nonmetal.
Most important examples of organometallic compounds are Grignard's reagents. In Grignard's reagent, the
carbon and magnesium atoms are bonded with each other through polar covalent bond and magnesium atom is
attached to halogen by ionic bond.

(Functional part of a Grignard's reagent molecule)

In organometallic compounds, the metal atom can be bonded to carbon atom of a hydrocarbon radical (Satu-
rated, unsaturated, aliphatic, alicyclic or aromatic) or carbon atom of a heterocyclic radical. Some examples are
given below.
1. Saturated Aliphatic Grignard's reagent
R – MgX (Alkylmagnesium halide)
CH3 – MgI (Methylmagnesium iodide)

2. Unsaturated Aliphatic Grignard's reagent

(i) Alkenyl Grignard's reagent
CH2 = CH – CH2 – MgX (Allylmagnesium halide)
(ii) Alkynyl Grignard's reagent
CH  C – CH2 – MgX (Propargylmagnesium halide)

3. Alicyclic Grignard's reagent

(Cyclohexylmagnesium halide)

4. Aromatic Grignard's reagent

(Phenylmagnesium halide)
C6H5CH2MgCl (Benzylmagnesium halide)

2. Preparation
Dry and pure
RX + Mg  Ether
  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's reagent by completing the octet on magnesium
atom.



Page # 3
 Process : To an etherial solution of alkyl halide Mg metal is added at very low temp. (0 – 5°C). A vigorous
reaction takes place , and a solution of G.R. is obtained. It cannot be evaporated to get it in solid state. The
reaction will be explosive. It is stable only in solution state.
Reactivity order with respect to X (For preparation of RMgX)
R–X:

Iodides forms organometallic compounds at the fastest rate.

Structural stability of G.R.
If the alkyl part has more stable negative charge, then RMgX is more stable. It will be less reactive
e.g. CH3 – CH2 – MgX ; CH2 = CH – MgX ; CH3C  C – MgX
Reactivity order : 1>2>3
Stability order : 1<2<3

3. Reactivity of Grignard Reagent :

It has been found out by estimation that there is 35% ionic character in carbon-magnesium bond of Grignard's
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 (SE) reaction takes place.

R – MgX  R – E (SE Product)

If Grignard reagent is regarded as the attacking reagent, then the nucleophilic carbanion of Grignard's reagent
will attack on the other compound taken as substrate.

+ 

3.1 Reactivity order of Grignard's reagent

On having same hydrocarbon radical, the order of reactivity of Grignard's reagents will be as follows :
* RMgI > RMgBr > RMgCl
* RMgX : 3º > 2º > 1º > CH3– > C=C > CC

3.2. Reactivity order with respect to different reactants

Acidic H > – CHO > > > >R–X

Except X (halogen) all other functional groups must be absent in the alkyl group otherwise. G.R. will be de-
stroyed by internal reactions.
[– NO2, – CN must also be absent]

4. Chemical Reactions
4.1 Reaction with acidic Hydrogen (H)
Compounds having reactive hydrogen or halogen atom give substitution products on reacting with Grignard's
reagent.
Z – H + R – MgX  R – H + Z – MgX

(where Z is an atom or group having high electron attracting capacity)

Z – X + R – MgX  Z – R + MgXX

(Where X and X are halogen atoms)

Both the above are examples of nucleophilic substitution reaction of Z – H and Z – X (not of the Grignard's
reagents).

Page # 4
 Examples :
R – MgX + H – Z  R – H + ZMgX
CH3 – MgX + H – OH  CH3 – H + Mg(OH)X
C2H5 – MgX + H – OR  C2H5 – H + Mg(OR)X
C3H7 – MgX + H – OC6H5  C3H7 – H + Mg(OC6H5)X
C2H5 – MgX + H – NH2  C2H5 – H + Mg(NH2)X
CH3 – MgX + H – NHR  CH3 – H + Mg(NHR)X
C2H5 – MgX + H – NR2  C2H5 – H + Mg(NR2)X
CH3 – MgX + H – NHC6H5  CH3 – H + Mg(NHC6H5)X
C2H5 – MgX + H – SR  C2H5 – H + Mg(SR)X
CH3 – MgX + H – C  N  CH3 – H + Mg(CN)X
C2H5 – MgX + H – C  CH  C2H5 – H + HC  C – MgX (Ethynylmagnesium halide)
CH3 – MgX + H – C  CR  CH3 – H + R – C  C – MgX (Alkynylmagnesium halide)
CH3 – MgX + RCONH2  CH4 + RCONHMgX
CH3 – MgX + HCl  CH4 + MgXCl

CH3 – MgX +  CH4 +

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.

4.2 Reaction with alkyl halide : Coupling between a Grignard reagent and alkyl halide containing a reactive
halogen atom can be effected directly ; this reaction is probably SN2.

The yield is very good if R” is allyl, t-butyl, or benzyl this reaction also works well for -halogenoethers.

(ii) With alkyl halide (coupling)

R – MgX + X – R  R – R + MgXX

Ex. R – MgX + X CH2  CH  CH2  R – CH2 – CH = CH2 + MgXX

Allyl halide

Ex. + C – C – C – Br

Me Me Me

H Cl ether
Ex. +   Ph H

D Et D
MgBr CH2 – CH3
| |
Ex. + CH3 – CH2 – Br 

Page # 5
Ex. Ph – MgX + X 

Resonance stabilized G.R : -

Mg O +

:
H2C = CH – CH2 – X  [H2C – CH = CH2]MgX
ether

4.3 Reactions involving addition on polar Bond (Nucleophilic Addition Reaction)

Grignard's reagents form adducts by addition on the following types of  bonds.
, , and C  N , – N = O,

Nucleophilic Addition Reaction With >C = O

|
R – MgX +  R  C  OMgX
|
Adduct
Reactivity order : HCHO > RCHO > RCOR
RCHO > ArCHO
RCOR > RCOAr > ArCOAr
(i). E.R.G at >C=O decreases rate
(ii) Crowding of R Group at >C=O decreasing rate

Example :

ether
 

(1)

H H
| |
HOH
(a) R – MgX +  R  C  OMgX  R  C  OH
| |
H H
1 Alcohol
R
|
(b) R – MgX +  R  C  OH
|
H
2 Alcohol

R R
| |
(c) R – MgX +  R  C  OMgX R  C  OH
| |
R R
3 Alcohol
Page # 6
Ex. CH3MgBr + CH3CHO  CH3CH(OH) CH3

Ex. CH3CH2MgBr 

4.4 SN2 Th (Substitution nucleophilic bimolecular with tetrahedral intermediate)

Acid derivatives gives SN2Th reaction with grignard reagent
(i) Reaction with (Acid halide)

R 'MgX R 'MgX H3 O 
 
   
  

(ii) Reaction with (anhydride)

R 'MgX
Ex.  
 

(iii) Reaction with (Ester)

Ex R ''MgX R ''MgX H3 O 
+ R'OMgX
     

H H
H H
| | | |
RMgX + C  O R   R  C  OR  R – C – H R CR R CR
|| | || | |
O OMgX O OMgX OH

Various alcohols can be prepared by changing R in the above synthesis.

(iv) Reaction with Epoxides

 R  CH2  CH2 R  CH2  CH2
| |
OMgX OH
1 Alcohol
having two more C

CH3
|
SN2
Ex.  R  CH2  CH  OH
( 2 )

CH3
|
SN2
 R  CH2  C  OH
|
CH3
( 3 )
Page # 7
 (v) Reaction with Oxygen
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.

Phenol is obtained on hydrolysis of the product obtained by reaction of arylmagnesium bromide with oxygen.
C6H5MgBr + O = O  C6H5O – OMgBr
C6H5O – OMgBr + C6H5MgBr  2C6H5 – OMgBr
C6H5 – OMgBr + H2O  C6H5 – OH + Mg(OH)Br

Other phenols can be prepared by taking any aryl (Ar) group in place of phenyl group.
OO Ar MgBr
Ar – MgBr   Ar – O – OMgBr     2Ar – O – MgBr

HOH
Ar – OMgBr 
 ArOH
For example, on taking p-toluenemagnesium bromide p-cresol is formed.
( i) O  O
(p)CH3 – C6H4 – MgBr (   (p)  CH3  C 6H4  OH
ii) HOH p  Cresol
p-Toluenemagnesium bromide
(vi) Reaction with CO2 (Synthesis of carboxylic acids)
A carboxylic acid is formed on hydrolysis of the adduct formed by passing carbon dioxide in the etherial solution
of a Grignard's reagent.
HOH
R–MgX + O=C=O  R  C  OMgX    R  C  OH
Mg(OH)X
|| ||
O O
(vii) Reaction with R – C  N

(1) rds HO
  2

NH3 +

Applications :
G.R. is used to prepare alcohols from those alkyl halides / aryl halides which do not give normal SN reactions

Ex. (i) (ii)

R R R R
| | | |
Ex. R  C  OEt  R  C  OEt R C R R CR
| || | | |
MgX O OMgX OMgX OH

Page # 8
Di Grignard Reagent :
Mg / ether
(i) CH3–CHCl2   CH2=CH2
Mg / ether
CH3–CHCl2  

(ii) C  C  C  C  C C–C–C–C=C
| |
X X
(1, 2)

(iii) C  C  C  C  C
| |
X X
(1, 3)

(iv) C  C  C  C  C
| |
X X
(1, 4 )

(v) C  C  C  C  C + C|  C  C  C  C
|
| | MgX MgX
X X
(1, 5)

Ex. Mg
C  C  C  C  C 
| |
Cl Cl

HO
2

Ex. CCCCC + + CH3OH

| | 
MgX MgX

Page # 9
 Reduction
Introduction
Reduction covers both the addition of hydrogen (or deuterium) to a double bond and the replacement of an
atom or group by hydrogen (or deuterium). In other words, reduction means hydrogenation or
hydrogenolysis.

Methods of Reduction :
2.1 Catalytic hydrogenation : The catalysts 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.

Catalyst
| |
General Reaction C=C + H2    C  C 
| |
H H
(syn addition)

Hydrogenation of an alkene is an exothermic reaction ( Hº  –120 kJ mol–1):

Ni
R –CH = CH – R + H2  R – CH2 – CH2 – 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
H2 and D2 are mixed in the presence of a Pt catalyst, the two isotopes quickly scramble to produce a random
mixture of HD, H2 and D2. (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.both hydrogen atoms usually add from the same
side of the molecule. This mode of addition is called a syn addition.

Page # 10
 Alkane released
Chemisorption ( desorbed )
   (     
2) fast step
(1) rds

Raney Ni (finely divided) provides large surface area

The reactants (alkene + H2) are adsorbed at the surface of catalyst (finely divided Ni) in the slow step.
Rate of adsorption is rate of hydrogenation.
During chemical adsorption the H – H  bond and C–C -bond undergoes homolysis.
In the state of adsorption two H are added on the same faces of alkene.

Rate of hydrogenation  Rate of adsorption

1
 Crowding at   bond

As crowding increases, rate of adsorption decreases

Reactivity order :

R2C = CR2 < R2C = CHR < R2C = CH2 < < < R –CH = CH2 < CH2 = CH2

1
Heat of hydrogenation (Hhyd) 
Stability of  bond

The ease of reduction of various functional groups toward catalytic hydrogenation (Ni/Pd/Pt)

Q. Why alkyne is more reactive than alkenes ?

Ans. becuse alkynes have more faster rate of adsorption due to less crowding (linear structure)

r
21 
Ex. r1
– C  C –  

H2
H1

r1 > r2
H1 > H2 [ a stronger vinylic C–H bond is formed]

Page # 11
Bond Dissociation energy order :

C–H>

Ex. H2 / Pd
O2N – CH = CH – CH2 – CH3    O2N – CH2 – CH2 – CH2 – CH3

Ex. H 2 / Pd or Pt
  

Ex. 

Ex.  CH –CH –CH –CH –CH –OH + CH OH

3 2 2 2 2 3

H / Pd / CaCO
Ex. R – C  C – R 2
3
 

Ex. D / Ni ......... Syn addition

2

Ex. H / Ni
2

D / Ni
Ex. 2
(Syn addition)

one stereoisomer of reactant one diastereomer

For Cis isomers

C=C or H / Ni
2 


Page # 12
 C=C or H / Ni
2 


D / Ni
Ex. CH=CH Br 2 
 (d + )

(trans)

D / Ni
(cis) 2 
 (d + )

The partial reduction of alkyne to alkene is heterogeneous hydrogenation with Lindlar's catalyst. Lindlar's
catalyst is a specially prepared Pd catalyst

H2 Lindlar 's catalyst

CH3 – CH2 – C  C – CH3       (syn addition)
or Ni2B

Lindlar’s catalyst is a poisoned palladium catalyst, composed of powdered barium sulphate coated with palla-
dium, poisoned with quinoline. Nickel boride Ni2B (P-2 catalyst) (made from sodium acetate and sodium
borohidride) is an excellent alternative catalyst for the conversion of alkyne into alkene. (syn addition)
Acid chloride reduced to aldehyde by using Pd /BaSO4 catalyst

H2 / Pd BaSO 4
     CH3 – CHO
This reaction is called Rosenmund Reduction

Deactivated Catalyst (Poisoned Catalyst) (quinoline)

Page # 13
Ex. CH3–CC–CH3

2.1.2 Homogeneous catalysts : (Catalysts soluble in reaction medium.)

eg. Tris (Triphenylphosphine) chloro rhodium (i) RhCl (Ph3P)3 Wilkinson’s catalyst.
In homogeneous catalysis hydrogen is activated not by chemisorption on the surface of a metal catalyst, but by
incorporation into the co-ordination sphere around a metal atom in solution phase.
It is highly selective for C = C / C  C and does not interfere with other groups like NO2 , C = O, C  N
Mechanism

(Ph3P)3RhCl

+ Rh Cl (PPh3)3  PPh
3 
 

where S = Solvent
2 3 3H /(Ph P ) RhCl
Ex. CH3 – CH = CH – CH3  CH 
 CH – CH – CH – CH
3 2 2 3
6 6

Ex. H2 /( Ph3P )3 RhCl

  

2.2 Reduction by metal hydrides and alkoxides :

Certain complex metal hydrides, borane and aluminium isopropoxide, are reagents of choice for reduction of
carbonyl group.
2.2.1 LiAlH4 (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 + AlH3  Li Al H4
Mechanism :

R CO
 2 

 
H3 O R CO
4 R2CHOH  Al– (OCHR2)4 2 HA l (OCHR2)3

Page # 14
 LiAlH
4
Ex.  
( 2 ) H

4 LiAlH
Ex. Ph–CH=CH–COOH  
 Ph–CH2–CH2–CH2–OH
( 2) H
Cinnamic acid
4 LiAlH
Ex. Ph–CH=CH–COOEt  
 Ph–CH2–CH2–CH2OH + EtOH
( 2) H

Ex. LiAlH
4
 

Ex. 4LiAlH
 

Note : LiAlH4 reduces C=C, CC in cinnamyl systems otherwise it does not reduce C=C, CC
2.2.2 NaBH4 (Sodium borohydride) : It is more specific than LAH as a reducing agent. It reduces only ketones and
aldehydes to the corresponding alcohols without affecting other functional groups, It also reduces acid halides
and alkyl halides but not any other fuctional groups . It is effective even in protic solvent like alcohol.
Mechanism

R 2C  O
  

 
H3 O R CO
4 R2CHOH  B– (OCHR2)4 2 H B (OCHR2)3

eg. LiAlH 4
 

NaBH 4
eg.  

Ex.

Page # 15
2.2.3 Reduction by isopropyl alcohol and aluminium isopropoxide. This is called the Meerwein-Pondorf-
Verley reduction

Mechanism

( CH ) CHOH
3 2
  

eg. + +

2.3 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.
–
e –
A + B : or A : + B
–
A – B 
–  
e : A – B  or A – B :
A = B 
2.3.1 Reduction by Na or Li /NH3 (Birch reduction)
Mechanism :
Reagents Na(or Li,K) + liq NH3  Na+ + e¯ (solvated electron)

NaNH2 + (anti addition)

Page # 16
  It is stereospecific anti-add. of two H–atoms.
 This reaction is given only by non-terminal alkynes and terminal alkenes.

1
+ H .
2 2

terminal alkyne  no reaction.

Terminal alkene also give Birch reduction.
3 Na / NH
R — CH = CH — H   R — CH2 — CH3 ;

Typical example of reduction for aromatic system :-

Na / NH
3
 

(In presence of electron releasing group –R , –OR, –NH2)

Na / NH
3
  

(In presence of electron withdrawing group –NO2 , –COOH, –CHO, –CN)

Na / NH
3
  

Na / NH3
R – C  C – R    (anti addition)

Ex. Na / NH
3
  

2.3.2 Reduction by Na/C2H5OH [Bouvealt - Blanc reduction]

Reduction of aldehydes ketones or esters by means of excess of Na/C2H5OH or n-butanol is called Bouvealt-
Blanc reduction reduction.
Mechanism :

Na C 2H5 OH Na

   


C 2H5 OH
RCH2OH  Na C 2H5 OH Na
  RCH2 – O   RCH2 – O·   R CH = O + C2H5 O–
–
   


Ex. CH3CHO CH3CH2OH

CH3–COCH3

CH3CH2OH

Page # 17
2.3.3 Clemmensen’s Reduction :
Used to get alkane from carbonyl compounds.

Zn  Hg / conc . HCl
R – CHO     
 RCH + H O
3 2

O
|| Zn  Hg / conc . HCl
R  C  R       RCH2R + H2O

Zn  Hg / conc . HCl
Ex. CH3 – CHO      
 CH3CH3 + H2O


O
||
Zn  Hg / conc . HCl
Ex. CH3  C  C 2H5 + 4[H]       CH3CH2C2H5 + H2O

Clemmensen reduction is not used for compounds which have acid sensitive group.
2.3.4 Wolff-kishner reduction with NH2NH2 / KOH

Used to get alkane from carbonyl compounds

Mechanism :

NH2NH2 / KOH
RCHO      RCH
3

NH2NH2 / KOH
RCO – R      RCH R
2

Wolff-kishner reduction is not used for compounds which have base sensitive groups.

Q. ?


(A) H2/Ni (B) NaBH4 (C*) NH2NH2/KOH (D) Zn(Hg)/HCl

Page # 18
Sol.

2.3.5 By Red P & HI

Re d P  HI
     R – CH
 3

Re d P  HI
     R – CH
 3

Re d P  HI
     R – CH
 3

Re d P  HI
     R – CH – R
 2

Re d P  HI
Ex.      CH – CH
 3 3

Re d P  HI
Ex.      CH – CH – CH
 3 2 3

2.4 DIBAL-H (Diisobutyl Aluminium Hydride) (ALANE) :

Most important alane is diisobutyl aluminium hydride. It runs parallel to LAH (Lithium aluminium hydride) as a
reducing agent but it is more selective.
LiAlH  THF
4   Ph–CH –CH –CH OH + C H OH
Ex. Ph–CH=CH—COOC2H5    2 2 2 2 5
H2O

Ph–CH=CH—CH2OH
By DIBAL at ordinary temperature esters are reduced to alcohols but at low temperature esters are reduced to
aldehyde.
O
|| DIBAL
Ex. C6H5– C –OCH3     C H CH OH
6 5 2
toluene  25 º C

C6H5CHO

LAH reduce RCN to amine but DIBAL is found to reduce it to aldehyde.

LiAlH  THF
4   CH –CH –NH
Ex. CH3–CN    3 2 2
H2O

CH3–CHO

Page # 19
 ALKANES
STRUCTURE, STABILITY AND PHYSICAL PROPERTIES OF ALKANES
(A) 1. Alkanes : are the saturated non polar hydrocarbon having general formula CnH2n+2.
2. Hydrocarbon : Those organic compounds which contain only carbon and hydrogen are known as hydrocar-
bons.
3. Structure & hybridisation :
In the alkanes all carbons are in sp3 hybridisation and have two types of bonds,
e.g. C – C and C – H
4. Bonding parameters :

Bond length Bond energy

C–C 1.54 Å 83 kcal/mol
C–H 1.09 Å 100-104 kcal/mol

Methane has six bond angles of 109°28

(B) Combustion & stability of alkanes :

 3n  1  combustion
1. Reaction : CnH2n+2 +   O     nCO2 + (n + 1) H2O (Hcombustion = -ve)
 2  2 
exothermic reaction
 y combustion y
CxHy +  x   O2     xCO2 + HO
 4   2 2
combustion
C5H12 + 8O2     5CO2 + 6H2O

2. Heat of combustion : Amount of heat i.e. liberated when 1 mole of hydrocarbon is completely burnt into
CO2 & H2O.
3. Heat of combustion as a measure of stability of alkane :
Combustion is used as a measurment of stability.
(a) In Homolouges : Higher homologes have higher heat of combustion.
(b) In Isomers : More branched alkanes are more stable and have lower heat of combustion.
More branched alkane has more no. of primary C – H bonds. (therefore it has more bond energy).

(c) In Cyclo-alkanes : More strained ring has higher heat of combustion per – CH2 – unit.
(d) In Alkenes & cyclo-alkanes : Alkenes have higher heat of combustion.
(C) Physical Properties of Alkanes :
1. Boiling points :
(a) In Homologs : The boiling points of n-alkanes increase regularly with the increase in the number of carbon
atoms.

Page # 20
 (b) In Isomers : 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.

2. Melting Points
(a) In Homologs : 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 moving
from an alkane with even number of carbon atoms to the higher alkane.
Explanation : The alkanes with even no. of ‘C’ atoms are more closely packed.

(b) In Isomers : In isomers due to branching melting point decreases but the most symmetric isomers has
highest melting point.
3. Density
(a) In Homologs : 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.
(b) In Isomers : In isomers due to branching density increases.
4. Physical state :
The first four members (C1 to C4) are gases ; the next thirteen members, (C5 to C17) are liquids while the higher
members are waxy solids.

5. 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.

Ex. Alkanes are less reactive or unreactive because

(A) They have non polar bonds (B) They have gaseous state
(C) They have lower bond energy. (D) Their m.p. & b.p. are very high
Ans. (A)

Ex. Heat of combustion

1. CH4 < C2H6 < C3H8

CH3
|
2. CH3 – CH2 – CH2 – CH3 > CH3  C  CH3
|
I H
II

CH3
CH3
| |
CH3  C  CH3
3. CH3 – CH2 – CH2 – CH2 – CH3 > CH3  CH  CH2  CH3 > |
CH3

4. > > > (Hcomb. per ‘CH2’ unit)

Page # 21
Ex. Isomers of C6H14 B.P.
n-Hexane 68.7 ºC
3-Methylpentane 63.3ºC
2-Methylpentane 60.3ºC
2,3-Dimethylbutane 58 ºC
2,2-Dimethylbutane 49.7 ºC

Ex. Melting point

propane < ethane < methane
(–188ºC ) (–138ºC) (– 130ºC)

Chemical Reactions of Alkanes :

Alkanes are nonreactive towards polar or ionic reagents like H2SO4 , NaOH, LiAlH4 or KMnO4 .
Characteristic reaction of alkanes are free radical substitution reactions, these reactions are generally chain
reactions which are completed in three steps mainly.
(i) chain initiation (ii) chain propagation. (iii) chain termination

(A) Free radical substitution (halogenation) :

UV or
R – H + X2      R – X + HX
250  400C

(i) Mechanism of halogenation :

Chain initiation : it is a endothermic step.
UV or temp. 
X2        2 X
250  400C

Chain propagation 
 
X + R – H  R + HX

 
R + X – X  R – X + X

Chain termination  it is always exothermic

 
X + X  X2

 
R + R  R – R

 
R + X  R – X
Each photon of light cleaves one chlorine molecule to form two chlorine atoms, each chlorine atom starts a
chain and on an average each chain contains 5000 repetitions of the chain propagating cycle so about 10,000
molecules of CH3Cl are formed by one photon of light.

(ii) Relative reactivity of halogen towards halogenation

Order of reactivity is F2 > Cl2 > Br2 > I2 which can be explained by the value of H (energy change)

Steps of halogenation, Value of H for each step. (Kcal/mole)

F Cl Br I

(i) X2  2 X + 38 + 58 +46 +36

 
(ii) X + CH4  C H + HX – 32 +1 + 16 + 33
3

 
(iii) C H + X2  CH3X + X – 70 – 26 – 24 – 20
3

Page # 22
(iii) Reactivity of alkanes :
R – H : 3º > 2º > 1º > CH4
The alkane which will form more stable radical will be more reactive towards halogenation

(iv) Kinetics of reaction

Step 1 :
 
Chain initiation step X2  X + X

Step : 2
Chain propagation step
(Xº + R – H  Rº + HX).

Step 3 :
Chain propagation
(Rº + X – X  R – X + Xº)

Step 4 :
Chain termination step
(e.g. Xº + Xº  X2 )

Page # 23
(v) Reactivity and selectivity
Reactivity : Cl2 > Br2
Selectivity : Br2 > Cl2
A faster reaction is less selective and a slower reaction is more selective.

Relative yield = Relative Reactivity X probability factor.

Re lative yield
% yield =  100
Total yield

Ex.1 : CH3 – CH3 – CH3 + Cl2 

% yield of I = 45%. and % yield of II = 55

Ex. 2 :CH3 – CH2 – CH3 + Br2  CH3 – CH2 – CH2Br + CH3CH(Br)CH3
% yield of  = 3.48 %
% yield of  = 96.72%

(vi) Initiators  which can initiate the chain reaction, Initiators are R2O2, Perester etc.

h
R – O – O – R  R O
or
temp


h
R CO O C R  R  C  O
or ||
|| || temp O
O O

(vii) Inhibitors  A substance that slow down or stop the reaction are known as inhibitors
For example O2 is a good inhibitor
 
R
+ O2  R  O  O + R  R – O – O – R
all reactive alkyl free radicals are consumed so reaction become stop for a period of time.

(viii) Halogenating agents :

Chlorination : Cl2 / h or SO2Cl2 / R2O2
Bromination : Br2 / h or SO2Br2 / R2O2
Iodination : I2 / h + HIO3 or HNO3
Halogenation with SO2Cl2
RO
R – H + SO2Cl2 2 
2
 R – Cl + SO2 + HCl

Page # 24
 Mech :
Chain initiation step
h
RO – OR  2RO°

O
||
RO° + Cl  S  Cl  R – OCl +
||
O

Chain propagation step

 SO2 +

R–H+ 



Examples & Questions

Ex. Explain why the chain initiating step in thermal chlorination of CH4 is
 *  * *
Cl2  C l and not CH4  C H 3 + H
Ans. Because Eact of Cl2 is less than Eact of CH4

Ex. Chlorination of CH4 involves following steps :

(i) Cl2  2 C *
l
* *
(ii) CH4 + C l  C H3 + HCl
* * 
(iii) C H3 + C l CH3Cl

Which of the following is rate determining ?

(A) Step (i) (B) Step (ii) (C) Step (iii) (D) Step (ii) and (iii) both
Ans. B
Ex. Which of the following reaction has zero activation energy
* * *
(A) CH4 + C l  C H3 + HCl (B) Cl2  2 C l
* * * *
(C) C H3 + C H3  CH3 – CH3 (D) C H3 + Cl – Cl  CH3 – Cl + C l

Ex. If the Eact for a forward reaction is given

 
CH3 – H + C l  C H3 + HCl H = + 1 kcal
Eact = 4 kcal
the Eact for backward reaction will be

(A) 1 kcal (B) 4kcal (C) – 4 kcal (D*) 3 kcal

Page # 25
Ex. Halogenations of higher alkane :
Cl2
(i) CH3 – CH2 – CH3    CH3  CH  CH3 + CH3  CH2  CH2  Cl
light, 25C
|
Cl 45%
55%

Cl
(ii) CH3 – CH2 – CH2 – CH3   CH3  CH2  CH  CH3 + CH3  CH2  CH2  CH2  Cl
2

light, 25C |
Cl 28%
72%

CH3
Cl2 |
(iii) CH3  CH  CH3   CH3  CH  CH2  Cl + CH3  C  CH3
light, 25C
| | |
CH3 CH3 Cl
64% 36%

Br
2
(iv) CH3 – CH2 – CH3     CH3  CH 2  CH2  Br + CH3  CH  CH3
light, 127C |
3% Br
97%

CH3
|
Br2
(v) CH  CH  CH     CH3  CH  CH2Br + CH3  C  Br
3 3 light, 127C
| |
|
CH3 CH 3
CH3
trace over 99%

General method of preparation

1. By catalytic reduction of alkenes and alkynes
(i) Hydrogenation : Addition of H2 to unsaturated bond.
H , 25 C
R – C  C – R  2  
 R – CH2 – CH2 – R
Ni, Pt or Pd

2 H , 25C
R – CH = CH – R    
 R – CH2 – CH2 – R
Ni, Pt or Pd

Hydrogenation is of two kinds

(a) Heterogenous and (b) Homogenous
(a) Heterogenous : It is two phase hydrogenation the catalyst is finally devided metal like Ni, Pt or Pd and a
solution of alkene.
(b) Homogenous : It is one phase hydrogenation both catalyst and alkenes are solution in this
hydrogenation catalyst are organic complex of transition metal like Rh or Ir.

(ii) Heat of hydrogenation : Hydrogenation is exothermic, quantitative and during the hydrogenation, total heat
evolved to hydrogenate one mole of unsaturated compound is called heat of hydrogenation.

(iii) Stability of alkene : Heat of hydrogenation is the measurment of stability of isomeric alkenes.
1
stability of alkene 
Heat of hydrogenat ion

1
(iv) Rate of hydrogenation : Rate of hydrogenation 
Steric crowding
Page # 26
2. From alkyl halide

(A) From organometallic compound : compound having bond. (M  metal)

(i) By Wurtz reaction
dry ether
2R – X + 2Na    R – R + 2NaX
Na
R – X + R – X     R – R, R – R, R – R
ether ( dry )

Mechanism : Two mechanisms are suggested

(a) Ionic mechanism
2Na  2Na  +

R  X + 2e¯ 
(1 , 2 )

SN 2
  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 SN2 and free radical coupling is not possible due to
steric hindrance so in that case elimination or disproportionation is possible.
In the ionic mechanism alkyl sodium gives strong base as well as nucleophile which gives SN2 with
R – X, ether should be dry otherwise if moisture is present then forms R – H instead of R – R with H2O.
Na
Ex. C2H5Cl   products
Ether
Write all possible product

Ans. CH3 – CH2 – Cl  CH3  CH2  CH2  CH3

major
•
CH3 – CH2 – Cl CH3  C H2
coupling
   CH3 – CH2 – CH2 – CH3

disproportionation
        CH3 – CH3 + CH2 = CH2

Ex. Wurtz reaction will not be observed in

(A) (B) (C) CH3  CH  Br (D) none of these

|
CH3

1
Ans.(B) Na + H 
 2 2

Page # 27
 CH3
|
Na
Ex. CH3  C  Br     products
dry ether
|
CH3
Products will be
CH 3
|
Ans. CH 3  C  H and
|
CH 3
in this reaction free radical coupling is not possible
CH3 CH3
| |
Na
CH3  C  Br  CH3  C  H +
| |
CH3 CH3

CH3
|
Na
CH3  C  Br 
|
CH3

CH3
|
CH3  C  H
| +
CH3
(ii) By Corey house alkane synthesis
R  X
2Li CuX (1  2)
RX 
   R 2 CuLi    R – R
(1, 2, 3 ) Lithium dialkyl
cuprate

Mechanism
R2CuLi is the source of

R – R

R2CuLi do not react with – NO2, – CN, etc.

Li CuI Y
Ex. CH3 – Br  A  B  C
if C is CH3 – CH2 – (CH2)5 – CH3, than what is Y.
Ans. CH3 – (CH2)6 – X

CH3
| Li CuI RX
Ex. CH3  C  Cl  A  B  R is ?
|
CH3

Ans. R=

Page # 28
 Li
Ex. CH3–CH2–Cl CH3CH2Li (CH3CH2)2CuLi CH3–(CH2)7–CH3

CH3
tC4H 9
| |
CH3– C – CH3 Li CuX
Ex.   tC4H 9 – CuLi CH3(CH2)3– CH2–Br
|
Cl

(iii) By Frankland's reagent

Ether
R – X + Zn + R – X  
 R – R + Zn X2

Mechanism

(iv) By grignard reagent

Ex.7 +  P + MgCl2

Compound 'P' is

(A) (B) (C) (D)

Ans. B
(B) By reduction of alkyl halides
(i) with metal-acid

RX R – H + HX
1

Reducing agent
Zn / acid, Zn – Cu / H2O or Zn – Cu + acid
Zn – Cu / C2H5OH, Na – Hg / acid, Al – Hg / H2O etc.
Mechanism

Metal 

Page # 29
 (iv) With metal hydrides
(a) TPH (Ph3SnH) : It reduces 1°, 2° & 3° R – X
3 Ph SnH
R – X    R – H

4 NaBH
(b) R  X    R – H
2 & 3

4 LiAlH
(c) R  X   R – H
1  & 2

4 LiAlH
R  X    Alkene
3

3. By reduction with red P & HI

Red P & HI is strong reducing agent

Re d P  H I
R – COOH     R – CH3
Re d P  H I
R  C  Cl      R – CH
3
||
O
Re d  H I
R  C  OEt  P  R – CH
3
||
O
Re d  H I
R – X  P  R – H
Re d  H I
R – OH  P  R – H
4. From fatty acids
(A) By soda lime Decarboxylation : Fatty acids are good source of hydrocarbon, on heating of sodium salt of
carboxylic acid (R – COONa) with soda lime (NaOH – CaO) gives hydrocarbon, which is known as decarboxy-
lation (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.
NaOH CaO
R  C  OH     R – H + Na CO
2 3

||
O

CaO
Ex.14 CH3COONa + NaOH   CH4 + Na2CO3.


CaO
Ex.15 C2H5COONa + NaOH   C2H6 + Na2CO3 .


CaO
Ex.16 + NaOH   + Na2CO3


(B) By Kolbe’s electrolysis

Electrolysis
2RCOOK + 2HOH    
 R–R + 2CO2 + H2 + 2KOH
Electrolysis
e.g. 2CH3 – COOK + 2H2O      CH3CH3 + 2CO2 + H2 + 2KOH.
If n is the number of carbon atoms in the salt of carboxylic acid, the alkane formed has 2(n–1) carbon atoms.
(C) By Decarboxylation of -keto acids
O O
|| ||
Zn / Hg

CH3  C  CH2  COOH  CH3  C  CH3     CH3 – CH2 – CH3
HCl

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  NaOH
Ex.  A   B
CaO / 

What are A and B

Ans. A is , B is


Ex.  A Write the structure of A and mention its stereochemistry

Ans.

5. Reduction of aldehydes, ketones :

(A) By Clemmensen’s reduction : with Zn – Hg / conc. HCl
Zn  Hg / conc . HCl
R – CHO     
 RCH + H O
3 2

O
|| Zn  Hg / conc . HCl
R  C  R       RCH2R + H2O

Zn  Hg / conc . HCl
e.g. CH3 – CHO      
 CH3CH3 + H2O


O
||
Zn  Hg / conc . HCl
CH3  C  C 2H5 + 4[H]       CH3CH2C2H5 + H2O
Clemmensen reduction is not used for compounds which have acid sensitive groups.

(B) By Wolff-kishner reduction with NH2NH2 / KOH

2 2 NH NH / KOH
RCHO     RCH3



2 2 NH NH / KOH
RCO – R     RCH2R


Wolff-kishner reduction is not used for compounds which have base sensitive groups.

O O O O
 Zn – Hg / HCl
Ex. HO

OH – 2CO
    
2

COOH
O O
 Zn – Hg / HCl
Ex. HOOC – C – C – H  CH3 – C – H      CH3 – CH3
–

– 3CO 2
COOH

O O O
HOOC– COOH
NaOH / CaO,  ZnHg
–
–

Ex. HOOC COOH         

– HCl
–

HOOC COOH COOH

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 Faculty Remark

Your suggessions / deficiencies are invite regarding this lecture note in detail.
please submit to the R & D coordinator (Organic chemistry)

S.No.

1.

2.

3.

4.

5.

NOTE : Please submit your valuable suggestions on previous lecture notes

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