PREPARED BY: SIR MOHAMMAD SHAHARYAR (B.

E MECHANICAL)
 INTRODUCTION:
𝑶𝒓𝒈𝒂𝒏𝒊𝒄 𝑪𝒐𝒎𝒑𝒐𝒖𝒏𝒅𝒔 𝒕𝒉𝒂𝒕 𝒄𝒐𝒏𝒕𝒂𝒊𝒏𝒔 𝒂𝒕 𝒍𝒆𝒂𝒔𝒕 𝒐𝒏𝒆 𝒉𝒂𝒍𝒐𝒈𝒆𝒏𝒔 𝒂𝒕𝒐𝒎 𝒃𝒐𝒏𝒅𝒆𝒅 𝒘𝒊𝒕𝒉 𝒂𝒏 𝒂𝒍𝒌𝒚𝒍 𝒈𝒓𝒐𝒖𝒑
𝒂𝒓𝒆 𝒄𝒂𝒍𝒍𝒆𝒅 𝒉𝒂𝒍𝒐𝒂𝒍𝒌𝒂𝒏𝒆𝒔

OR

𝑯𝒂𝒍𝒐𝒈𝒆𝒏 𝒅𝒆𝒓𝒊𝒗𝒂𝒕𝒊𝒗𝒆 𝒐𝒇 𝒂𝒍𝒌𝒂𝒏𝒆𝒔 𝒂𝒓𝒆 𝒄𝒂𝒍𝒍𝒆𝒅 𝒂𝒍𝒌𝒚𝒍 𝒉𝒂𝒍𝒊𝒅𝒆𝒔

(𝑹 − 𝑿) 𝒉𝒂𝒗𝒊𝒏𝒈 𝒈𝒆𝒏𝒆𝒓𝒂𝒍 𝒇𝒐𝒓𝒎𝒖𝒍 𝑪𝒏 𝑯𝟐𝒏+𝟏 𝑿
REPRESENTATION

𝑹−𝑿

GENERAL FORMULA
𝑪𝒏 𝑯𝟐𝒏+𝟏 𝑿

FOR EXAMPLE

𝑪𝑯𝟒 + 𝑪𝒍𝟐 − − − −−→ 𝑪𝑯𝟑 𝑪𝒍 + 𝑯𝑪𝒍

Methane Methyl Chloride

CLASSIFICATION OF ALKYL HALIDE:

Alkyl Halide are classified on the basis of the number of 𝛼 − 𝐶 − 𝐴𝑡𝑜𝑚𝑠. Accordingly

1) PRIMARY ALKYL HALIDE

Those alkyl halide in which halogen atom is attached with primary c-atom are called primary alkyl
halide. When primary carbon atom is that 𝛼 − 𝐶 − 𝑎𝑡𝑜𝑚 which bonded with one 𝐶 − 𝑎𝑡𝑜𝑚
FOR EXAMPLE

H
H3C C Cl
H
Primary ethyl Chloride
10-ethyl Chloride

2) SECONDARY ALKYL HALIDE

Those alkyl halide in which halogen atom is attached with secondary c-atom are called secondary
alkyl halide. When secondary carbon atom is that 𝛼 − 𝐶 − 𝑎𝑡𝑜𝑚 which bonded with two other 𝐶 −
𝑎𝑡𝑜𝑚

PREPARED BY: SIR MOHAMMAD SHAHARYAR (B.E MECHANICAL)

FOR EXAMPLE
CH3
a
H3C C Cl
H
Secondary propyl Chloride
20-propyl Chloride
iso-propyl-chloride
2-chloro-propane

3) TERTIARY ALKYL HALIDE

Those alkyl halide in which halogen atom is attached with tertiary c-atom are called tertiary alkyl
halide. When tertiary carbon atom is that 𝛼 − 𝐶 − 𝑎𝑡𝑜𝑚 which bonded with three other 𝐶 − 𝑎𝑡𝑜𝑚
FOR EXAMPLE

CH3
a
H3C C Cl
CH3
Tertiary Butyl Chloride
30-butyl Chloride
2-chloro-butane

STRUCTURE OF ALKYL HALIDE

Let us consider methyl chloride 𝐶𝐻3 − 𝐶𝑙 as an alkyl halide. The geometry of molecule is
explained by hybrid orbital theory. Carbon of methyl halide is bonded with four atoms which
means carbon is utilizing its all four valence electrons to produce four 𝑠𝑝3 hybrid orbitals, which
are oriented at an angle of 109° to give a tetrahedral geometry. These four 𝑠𝑝3 hybrid orbitals are
shared with three s-orbitals of hydrogen atoms and one p-orbital of chlorine by head to head
overlapping to make four sigma bonds.

PREPARED BY: SIR MOHAMMAD SHAHARYAR (B.E MECHANICAL)

 PHYSICAL PROPERTIES OF ALKYL HALIDE
1) PHYSICAL STATE:
Alkyl Halide with lower number of carbon atom and different halogens atoms exist at gas or
liquid at room temperature. While, alkyl halides with higher carbon atoms. I,e beyond 18-carbon
atoms are colorless solid
2) SOLUBILITY
Alkyl halide are soluble in organic solvents but are slightly soluble in non polar solvent (I,e
water)
3) MELTING POINT AND BOILING POINTS:
Alkyl halide possess higher melting points than alkanes of comparable molecular weight,
this is due to the increasing strength of intermolecular forces of attraction.

PREPARATION OF ALKYL HALIDE

1) REACTION OF ALCOHOL WITH HYDROGEN HALIDE (HX)
a) REACTION OF ALCOHOL WITH HYDROGEN CHLORIDE (HCl)
H H H H
ZnCl 2
H C C OH + H Cl H C C Cl + H OH

H H H H
ethyl alcohol ethyl chloride

2) REACTION OF ALCOHOL WITH PX3 , SOX2

a) REACTION OF ALCOHOL WITH PCl3:

+1 -1 +3 -3
3 H3C CH2 OH + PCl3 3 H3C CH2 Cl + P(OH) 3
ethyl alcohol ethyl chloride

b) REACTION OF ALCOHOL WITH SOCl2:

C2H5N
H3C O H + Cl S Cl HCl + SO2 + H3C Cl
methyl chloride
methanol thionyl Chloride

3) HALOGENATION OF ALKANE:
𝑪𝑯𝟒 + 𝑪𝒍𝟐 − − − −−→ 𝑪𝑯𝟑 𝑪𝒍 + 𝑯𝑪𝒍
Methane Mthyl Chloride

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 REACTIVITY OF ALKYL HALIDE
The high reactivity of alkyl halide is attributed to the polarity of carbon halogen bond.

Reactivity of alkyl halide is depend upon:

a) Bond polarity
b) Bond energy

a) BOND POLARITY OF C-X BOND:

E.N difference between the two bonded atom is called bond polarity
𝑩𝒐𝒏𝒅 𝑷𝒐𝒍𝒂𝒓𝒊𝒕𝒚 ∝ 𝒓𝒆𝒄𝒕𝒊𝒗𝒊𝒕𝒚
REACTIVITY ORDER:
𝑪 − 𝑭 > 𝑪 − 𝑪𝒍 > 𝑪 − 𝑩𝒓 > 𝑪 − 𝑰
b) BOND ENERGY OF C-X BOND:
Amount of energy required to break a bond called bond energy
𝟏
𝑩𝒐𝒏𝒅 𝑬𝒏𝒆𝒓𝒈𝒚 ∝
𝑹𝒆𝒂𝒄𝒕𝒊𝒗𝒊𝒕𝒚
REACTIVITY ORDER:
𝑪 − 𝑰 > 𝑪 − 𝑩𝒓 > 𝑪 − 𝑪𝒍 > 𝑪 − 𝑭

NUCLEOPHILPIC SUBSTITUTION REACTION:

A type of chemical reaction in which a strong nucleophile replaces the weak nucleophile of the
substrate is termed as nucleophilic substitution reaction

MECHANISM OF NUCLEOPHILIC SUBTITUTION REACTIONS:

The mechanism of nucleophilic substitution reaction is divided into:
(i) 𝐒𝐍𝟏 − 𝐑𝐄𝐀𝐂𝐓𝐈𝐎𝐍𝐒
(ii) 𝐒𝐍𝟐 − 𝐑𝐄𝐀𝐂𝐓𝐈𝐎𝐍𝐒

(i) 𝑺𝑵𝟏 −REACTIONS:

𝑆𝑁1 stands for unimolecular substitution reaction in couple of steps. Important features of this
reaction are given below.
The 𝑆𝑁 1 −reaction mechanism proceeds in two distinct steps:
STEP NO 01: DEPARTURE OF HALOGEN FROM SUBSTRATE TO FORM CARBOCATION
In the first step involving the departure of the leaving group (the halogen atom) from the substrate
molecule, leading to the formation of the carbocation intermediate, followed by the nucleophilic
attack in the second step:

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STEP NO 02: ATTACK OF STRONG NUCLEOPHILE ON CARBOCATION TO FORM PRODUCT:
In the 2nd step of 𝑆𝑁1 − 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 , the attacking nucleophile approaches the t-butyl carbonium ion
from the either sides and given retention product

Tertiary butyl halides under goes 𝑆𝑁1 reactions more readily than primary or secondary alkyl halides
The rate of reaction only depend on the concentration of substrate i.e it is 1st order reaction but not
on the nucleophile involved in the reaction
𝑹𝒂𝒕𝒆 = 𝑲[𝑺𝒖𝒃𝒔𝒕𝒓𝒂𝒕𝒆]
𝟐
(iI) 𝑺𝑵 −REACTIONS:
𝑆𝑁 2 stands for bi molecular nucleophilic substitution reaction in single step. Important features of
this reaction are given below:
1) In the 𝑆𝑁 2 Mechanism, bond formation and bond breaking occurs simultaneously in a single step
2) 𝑆𝑁 2 reaction is carried out in primary alkyl halide in the presence of non-polar solvent like dry
acetone
3) Rate of 𝑆𝑁 2 reaction depends upon both the concentration of substrate and the attacking
nucleophile i.e. it is 2nd order reaction
𝑹𝒂𝒕𝒆 = 𝑲[𝑺𝒖𝒃𝒔𝒕𝒓𝒂𝒕𝒆 ][𝑵𝒖− ]
1) In 𝑆𝑁 2 −Mechanism the nucleophile is directly attacks the electrophile carbon atom of the
substrate, leading to the departure of the halogen atom attached to the electrophile carbon.
2) The nucleophile attacks from the back side because the front side is sterically hindered by the
nucleophile of the substrate

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 STABILITY OF CARBOCATION:
Carbocation are organic ions that have a positively carbon atom. They are formed when a carbon
atom loses a pair of electrons.

CLASSIFICATION CARBOCATION
Carbocations are classified into primary, secondary and tertiary depending upon the number of
carbon atoms bonded to positively charged carbon atom.
Carbocations are highly reactive species, they can be formed as intermediates during a chemical
reaction.

STABILITY OF CARBOCATION:
Tertiary carbocations are more stable than secondary and primary carbocation because of
electron donating tendency of alkyl group.
H H CH3 CH3

H C
+
< H3C C
+
< H3C C
+
< H3C C
+

H H H CH3
methyl radical ethyle radical iso propyl radical t-butyl radical
10-Carbocation 20-Carbocation 30-Carbocation

increase in stability of carbocation

ELIMINATION REACTION:

When an alkyl halide reacts with alcoholic potassium hydroxide, the removal of hydrogen and
halogen atoms from two adjacent carbon atoms of substrate take place and formation of multiple
bond products.

Elimination reaction are also called 1,2 elimination reaction of 𝛽 − 𝐸𝑙𝑖𝑚𝑖𝑛𝑎𝑡𝑖𝑜𝑛 Reaction.

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 TYPES OF ELIMINATION REACTIONS:
Elimination reaction are of two types:

1) E2−REACTION:
It stands from bi molecular elimination Reaction. Important features of this reaction are given below:
(i) The mechanism completes in a single step In which both substrate and attacking base are involved
(ii) The substrate for the E2 reaction is feasible in primary alkyl halide
(iii) In E2 reaction base first attack on ethyl bromide and abstract proton from 𝛽 −
𝐶𝑎𝑟𝑏𝑜𝑛. Simultaneously halide ion eliminates from 𝛼 − 𝐶𝑎𝑟𝑏𝑜𝑛 and the lone pair of electron shifted
towards 𝛼 𝑎𝑛𝑑 𝛽 carbon to give an ethene
(iv) The rate of E2 reaction is depend upon both concentration of substrate and attacking base (i.e it is 2nd
order reaction). The rate law may be written as
𝑹𝒂𝒕𝒆 = 𝑲[𝑺𝒖𝒃𝒔𝒕𝒓𝒂𝒕𝒆][𝑹𝒆𝒂𝒈𝒆𝒏𝒕]

H H
H H
+&
H C
+ C
-& K
– H C Br H2O + KBr +
HO
C
ethyl bromide
H
substrate
10-RX H H
olefene
ethene

2) E1−REACTIONS
It stands for unimolecular elimination reaction occur in two steps:
STEP NO 1: FORMATION OF CARBOCATION:
In the first step the halogen atoms depart from the substrate forming a carbocation, which is the slow and
rate determining step,

PREPARED BY: SIR MOHAMMAD SHAHARYAR (B.E MECHANICAL)

 H3C CH3
+
H3C C Cl
K +

slow
KCl + C

H3C t-butyl chloride

Substrate H3C CH3
(30-RX)
planer & stable
t-butyl carbocation
STEP NO 2: ATTACK OF BASE ON 𝜷-HYDROGEN AND FORMATION OF MULTIPLE BOND
In the second step a base abstract a proton from the 𝛽 Carbon, leading to the formation of a double bond
between two adjacent carbon atom
H
H
H
H

H - C
C + HO

C
+
H2O +
C
H3C CH3

H3C CH3
olefene
2-methly-propene
iso-butene

SOME IMPORTANT FEATURES OF E1-REACTION ARE:

In the rate determining step E1-Reaction involves the unimolecular ionization of the substrate
molecule. Therefore, the rate of reaction depends only on the concentration of reactant, and not
on the concentration of base.

PREPARED BY: SIR MOHAMMAD SHAHARYAR (B.E MECHANICAL)

 ORGANO METALLIC COMPOUNDS
Organic compound that possess at least one bond between a carbon atom and a metal atom the
compound is called organo metallic compound.

EXAMPLE OF ORGANO METALLIC COMPOUNDS

(i) Grignard reagent: it is highly reactive organic compound and used in organic synthesis
(ii) Methylcobalamine: It is a derivative of Vitamin B-12
(iii) Dimethyl Zinc: It is used as insecticide
(iv) Tetraethyl Lead: It is used as knock inhibitor in petroleum industry

GRIGNARD REAGENT:

Grignard Reagent is an oraganometallic compound that contains a carbon−magnessium bond

(C−Mg) bond

Grignard reagent was discovered by Victor Grignard in 1902 and got Noble Prize in 1912.

PREPARATION OF GRIGNARD REAENT:

Grignard reagent is prepared by the action of magnesium metal on alkyl halide in the presence
of dry ether
𝑹 − 𝑿 + 𝑴𝒈 − − − −−→ 𝑹 − 𝑴𝒈𝑿
Where R= alkyl group or aryl group (Such As: CH3 , C2H5 etc) and X = Halogens (Such As: Cl , Br ,I)
FOR EAXMPLE:
𝑪𝑯𝟑 − 𝑰 + 𝑴𝒈 − − − −−→ 𝑪𝑯𝟑 − 𝑴𝒈𝑰
(METHYL IODIDE) (METHYL MAGNESSIUM IODIDE)
. (Grignard Reagent)
FACTORS WHICH ARE EASE TO THE PRODUCTION OF GRIGNARD REAGENT:

(i) SIZE OF ALKYL GROUP:

The larger the size of alkyl group , the more difficult in the formation of Grignard Reagent

(ii) NATURE OF HALOGENS ATOM:

It is ease of formation of Grignard Reagent is also depends upon nature of Halogens
atom attached to an alkyl group. The order is 𝐼 > 𝐵𝑟 > 𝐶𝑙 because the bond between
iodine and carbon bond is weaker than corresponding bond with other halogens.

REACTIVITY OF GRIGNARD REAGENT:

In Grignard reagent the carbon-magnesium bond is covalent and highly polar due to high
electronegativity of carbon atom than magnesium metal, which creates more electron density on
carbon of alkyl group. As a result the carbon atom bears a partial negative charge and acts as
nucleophile. Due to this nucleophilic nature of alkyl parts, Grignard reagent reacts with polarized
molecules either by nucleophilic substitution or nucleophilic addition.
-& +&
R Mg X

PREPARED BY: SIR MOHAMMAD SHAHARYAR (B.E MECHANICAL)

 REACTIONS OF GRIGNARD REAGENT:
(1) REACTION OF GRIGNARD REAGENT WITH WATER/FORMATION OF ALKANE:

(2) REACTION OF GRIGNARD REAGENT WITH PRIMARY AMINE/FORMATION OF

ALKANE:
Br
-& +& -& +&
H3C N H + H3C MgBr CH4 + Mg
Methane
H
Primary methyl amine
NH(CH3)
(3) REACTION OF GRIGNARD REAGENT WITH ESTER/FORMATION OF ACETONE:
-& +&
O MgBr O
-& O Br
-& +& +&
H3C MgBr + H3C C O CH3 H3C C O CH3 H3C C CH3+ Mg
Methyl Acetate
Acetone
(OCH3)
CH3
REACTION OF GRIGNARD REAGENT WITH FORMALDEHYDE (METHANAL) /
FORMATION OF PRIMARY ETHYL ALCOHOL(ETHANOL):
H H
CH3 H OH
H
HO H
+ C H3C C H Mg + H3C C H
Mg I
I
O O Mg I OH
methyl magnessium Methanal unstable
iodide primary alcohol
10-ethyl alcohol
(4) REACTION OF GRIGNARD REAGENT WITH ACETALDEHYDE (ETHANAL) /
FORMATION OF SECONDARY PROPYL ALCOHOL(2-PROPANOL):

PREPARED BY: SIR MOHAMMAD SHAHARYAR (B.E MECHANICAL)

 CH3 CH3
CH3 H3C H OH
HO H
+ C H3C C H Mg + H3C C H
Mg I
I
O O Mg I OH
methyl magnessium ethanal unstable
iodide secondary alcohol
20-propanol
isopropyl alcohol

(5) REACTION OF GRIGNARD REAGENT WITH ACETONE(2-PROPANONE) /

FORMATION OF TERTIARY BUTYL ALCOHOL (2-PROPANONE):
H3C
CH3
CH3 CH3
CH3 OH
HO H
+ C H3C C CH3 Mg + H3C C CH3
Mg I
I
O O Mg I OH
methyl magnessium propanone unstable
iodide tertiary alcohol
30-butanol
ter butyl alcohol

(6) REACTION OF GRIGNARD REAGENT WITH ACETONE(2-PROPANONE) /

FORMATION OF TERTIARY BUTYL ALCOHOL (2-PROPANONE):
O O O
CH3 OH
HO H
+ C H3C C Mg + H3C C
Mg I
I
O O Mg I OH
methyl magnessium Carbondioxide unstable
iodide ethanoic acid/vinegar

X
Engr.MOHAMMAD SHAHARYAR
XII CHEMISTRY NOTES

PREPARED BY: SIR MOHAMMAD SHAHARYAR (B.E MECHANICAL)

 AMINES:
Organic compounds that contain a nitrogen atom bonded to one or more alkyl or aryl group
are known as amines. Amines are the derivative of ammonia

CLASSIFICATION OF AMINES

PHYSICAL PROPERTIES OF AMINE:

(1) PHYSICAL STATE: Lower members exist in gaseous state at room temperature where as higher
member are liquids
(2) ODOUR AND COLOUR: Mostly they are colourless with an unpleasant smell.
(3) SOLUBILITY: Amines are soluble in water , their solubility decreases with the increases in non-
polar hydrocarbon chain.
(4) MELTING AND BOILING POINT: Amines are polar in nature and formed hydrogen bonding with
each other that’s why their melting and boiling points are relatively higher than those hydrocarbons
of comparable molecular mass

STRUCTURE OF AMINE:
In amine nitrogen atom is sp3−Hybridized and contains four sp3−Hybrid orbital, out of which three
sp3− hybrid orbitals involved in formation of sigma bond whereas , fourth sp 3−Hybrid orbital contains
lone pair of electrons. These four sp3−hybrid orbital are oriented in space in tetrahedral pyramidal
geometry

BASICITY OF AMINE:
The basicity of amine is explained by the presence of non bonding lone pair of electrons on nitrogen
atom due to which it is capable of accepting Proton [H+]
+ –
R NH2 + HCl R NH3 Cl
Amine alkylammoniachloride salt

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 FACTOR AFFECTING THE BASICITY OF AMINE
The basicity of amine can be affected by the number of alkyl or aryl group attached to the nitrogen
atom. Greater the no of alkyl group greater will be the basicity. The order of basicity of amine is:

H H CH3 CH3

H N
< H3C N
< H3C N
< H3C N

H H H CH3
Ammonia Primary Amine Secondary Amine Tert Amine

Basicity of amine increases

X
Engr.MOHAMMAD SHAHARYAR
XII CHEMISTRY NOTES

PREPARATION OF AMINE
1) BY THE ALKYLATION OF AMMONIA BY ALKYL HALIDE:

2) BY THE REDUCTION OF NITRILES:

H H
LiAlH 4
H3C C N + 4 [H] H3C C N H
methyl cyanide
H
Primary Ethyl Amine

PREPARED BY: SIR MOHAMMAD SHAHARYAR (B.E MECHANICAL)

3) BY THE REDUCTION OF AMIDE
O
H

LiAlH 4
H3C C NH2 + 4 [H]
H3C C NH2 + H2O

Acet Amide H
Primary Ethyl Amine

REACTIVITY OF AMINE
Amines are reactive due to the presence of lone pair of electrons on nitrogen atom and behave as
nucleophile or a base. However, the reactivity of amines can be influenced by the nature and
number of alkyl groups attached to nitrogen atom.

REACTIONS OF AMINE

1) REACTION OF ETHYL AMINE WITH METHYL IODIDE/FORMATION OF

SECONDARY AMINE:

2) REACTION OF SECONDARY AMINE WITH METHYL IODIDE/FORMATION OF

TERTIARY AMINE:

3) REACTION OF ETHYL AMINE WITH ALDEYHDE AND KETONE

Primary amine can react with aldehyde and ketone to produce imines which is also referred as
Schiff Base
(a) REACTION OF PRIMARY AMINE WITH ACETALDETHYDE/FORMATION OF IMMINE:
H CH3 CH3

H3C N + O C H3C N C
+ H2O

H H H
immine (Schiff Base)
Primary Amine Acetaldyhde

(b) REACTION OF PRIMARY AMINE WITH ACETONE / FORMATION OF IMMINE:

H CH3 CH3

H3C N + O C H3C N C
+ H2O

H CH3 CH3
immine (Schiff Base)
Primary Amine Acetone

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4) REACTION OF PRIMARY AMINE WITH ACYL HALIDE / FORMATION OF
AMIDES
O
O

H3C N H + Cl C CH3 H3C N C CH3 + HCl

H Ethanoyl chloride/
Acetyl Chloride H
Primary Amine
N-methylacetamide

5) REACTION OF PRIMARTY AMINE WITH NITROUS ACID IN THE PRESSENCE

OF HCL / FORMATION OF DIAZONIUM SALT

H3C N + OH NO H3C N
+
N + HO– + H2O
Primary Amine H

+ – –
H3C N N + HO + HCl H3C N
+
N Cl + H2O

H
–
H3C N + OH NO + HCl o
below 10 C
H3C N
+
N Cl + 2 H2O
Primary Amine methyl diazonium salt
H

X X
Engr.MOHAMMAD SHAHARYAR Engr.MOHAMMAD SHAHARYAR
XII CHEMISTRY NOTES XII CHEMISTRY NOTES

PREPARED BY: SIR MOHAMMAD SHAHARYAR (B.E MECHANICAL)