# 1.
General Methods of preparation of Haloalkanes
1. From alcohols
3R - OH + PX3 --------------> 3R - X + H3PO3
R - OH + PX5 --------------> R - X + POX3 + HX
R - OH + SOCl2 -------(pyridine)---------> R - Cl + SO2 + HCl
Eg-
2.
3.
a. Markownikoff addition
b. Anti Markonikoff addition
4.
5.
6.
HALO-ALKANES # 1.2
Chemical Reactions of Haloalkanes
1. Nucleophilic Substitution Reactions
Nucleophilic substitution reactions are of two types
(a) SN1 type (Unimolecular nucleophilic reactions) proceed in two steps:
• Rate, r = k [RX]. It is a first order reaction.
• Reactivity order of alkyl halide towards SN1 mechanism
3° > 2° > 1°
• Polar solvents, low concentration of nucleophiles and weak nucleophiles
favour SN1mechanism.
• In SN1 reactions, partial racemisation occurs due to the possibility of
frontal as well as backside attack on planar carbocation.
(b) SN2 type (Bimolecular nucleophilic substitution)
• These reactions proceed in one step and is a second order reaction with
r = k[RX] [Nu]
• During SN2 reaction, inversion of configuration occurs.
i.e., starting with dextrorotatory halide a laevo product is obtained and
vice- versa, e.g.,
• Reactivity of halides towards SN2 mechanism is
1° > 2° > 3°
• Rate of reaction in SN2 mechanism depends on the strength of the attacking
nucleophile. Strength of some common nucleophiles is
:CN- > : I- > : OR- > : OH- > CH3COO: > H2O > F-
• Non-polar solvents, strong nucleophiles and high concentration of
nucleophiles favour SN2 mechanism.
Relative rates of some alkyl halides in SN1 and SN2 reactions are in the order
Relative reactivity of alkyl halides for same alkyl group is
RI > RBr > RCI > RF
Q.1 Write all the steps involved in Hoffmann ammonolysis reaction.
Q.2 Why do haloalkanes give RCN when treated with KCN but give
RNC(isocyanide) with AgCN.
Q.3 Why do haloalkanes give R-ONO when treated with KNO2 but give
RNO2 with AgNO2.
Q.4 Which is the most reactive towards SN1 reaction? Give reason.
CH3CH2Br , (CH3)2CHBr , (CH3)3C-Br
Q.5 Why do tertiary alkyl halides undergo substitution by SN1 mechanism,
whereas primary alkyl halides by SN2 mechanism.
2. Elimination reaction
3. Reduction
Other reducing agents Commonly used –
• + H2 Ni /525k
• + [H] Zn-Cu couple /C2H5OH
• + [H] LiAlH4
4. Reaction with Metals
(i) Wurtz reaction
(ii) Wurtz – Fittigs reaction
(iii) Reaction with magnesium( formation of Grignards reagent)
R – X + Mg R – Mg – X
Grignard’s Reagent
• Grignard reagent is never isolated in the solid state as it explodes in dry
state. So it is used as ethereal solution.
CHLOROFORM (CHCl3) #1.3
➢ Preparation
6. Reduction
➢ CHCl3 + 2H CH2Cl2 + HCl
➢ CHCl3 + 6H CH4 + 3HCl
7. Chlorination
CHCl3 + Cl2 CCl4 + HCl
8. Carbylamine reaction
9. Reimer –Tiemann Reaction
10. Condensation with acetone
IODOFORM(CHI3)
➢ Preparation (Iodoform reaction)
CH3COCH3 +3I2 +4NaOH → CHI3 + 3NaI + CH3COONa + 3H2O
➢ Chemical properties of Iodoform
1. Reduction
CHI3 + 2H CH2I2 + HI
2. Hydrolysis
3. Carbylamine reaction
4. Dehalogenation
Structure of Freon
Structure of DDT
Dichlorodiphenyltrichloroethane
HALOARENES # 1.4
General Methods of preparation of Haloarenes
1. By halogenation by benzene
(electrophylic substitution reaction)
2. Sandmeyer's reaction
This reaction consists of treating freshly prepared diazonium salt solution with
cuprous chloride or cuprous bromide dissolved in corresponding halogen acids.
Chloro and bromoarenes are formed. Diazonium salts required for this purpose are
prepared by treating ice-cold solution of aniline in excess of dilute HCl with an
aqueous solution of sodium nitrite at low temperature (0-5oC). This reaction is
known as diazotization reaction.
The benzene diazonium salt is used for preparing aryl halides as:
3. Gattermann reaction
Physical properties of haloarenes or aryl halides
• Haloarenes are colorless liquids or crystalline solids.
• Aryl halides are heavier than water.
• Being heavier than water, they are insoluble in water but soluble in organic
solvents.
• The melting and boiling points of aryl halides are nearly the same as those of
alkyl halides containing the same number of carbon atoms. Boiling points of
monohalogen derivatives of benzene are in the order: iodo > bromo > chloro >
fluoro
For the same halogen atom, the melting and boiling points increase as the size of the
aryl group increases.
The boiling points of isomeric dihaloarenes are nearly the same, but their
melting points are quite different because in symmetrical structure, molecules
are closely packed in the crystal lattice. As a result, intermolecular forces of
attraction are stronger and therefore, greater energy is required to break lattice.
So it melts at higher temperatures.
Chemical Reactions of Haloarenes
2. Electrophilic reactions
Halogenation are deactivating but o, p directing. Thus chlorination, nitration,
sulphonation and friedel craft’s reaction give a mixture of o- and p- chloro substituted
derivatives.
3. Reaction with metals
(iii) Formation of Grignard’s reagent
4. Reduction
