SN1 (Racemisation) SN2 (Inversion of Configuration)

Nucleophilic Substitution
–
Nu R1
HALOALKANES AND a
R1
b b a R1 R1

Reactions
d+ d– Slow d– d–
R1 R1 R1 X X –
d+ d– Slow +
R2 Nu Nu R2+ X
X C R2 Nu + Nu Nu– H H R2
HALOARENES
R2 –X– R2 H
R3 R3 R2 R3 R3 Substrate Transition State Product (Inverted)
Substrate Planar intermediate Racemic mixture
carbocation

Vinylic halide Aryl Alkyl halides undergo b-elimination reaction in the presence of potassium hydroxide in ethanol (high temperature) to yield alkenes.
e.g
n

halide
CH o ge

D CH
., X

E1 mechanism E2 mechanism
ih

Elimination Reactions
2X

X X
., R al

—
al 2C

X
e.g noh

og H 2

H R H R H H H H
Chemical
en —
o

On the basis 4
M

Single-step Process
alc. KOH alc. KOH

Two-steps Process
of number R C C R R C C R + X – R C C H R C C H
Compounds Properties Slow +
X

halgoen containing
H X H H X H X
H
atoms sp2 C—X
H R R Transition state

R C C R
Fast
R C C R + H2O R C C H
bond + OH –
Trihalogen H H H + H2O + KX
e.g., CHX3 Rate = k [Alkyl halide] Rate = k [Alkyl halide] [base]
5
Nature Optical Chirality :
Haloalkanes Stereochemistry
R—X 2 of Activity The objects Chiral Solution Chiral Solution
C—X Bond Plane polarised light which are non-
superimposable on
Compounds 1 Classification produced by passing ordinary
light through nicol prism is rotated their mirror images
containing are said to be
when it is passed through the
sp3 C—X chiral.
solutions of certain compounds.
bond +60° –60°
d+ d– Such compounds are
Allylic Benzylic C X called optically active The
halide halide compounds. direction and
C — F , C — Cl , C — Br , C — I magnitude of rotation
3 must be determined
Methods Size of halogen atoms increases experimentally. There is
X Ar
of ha
y l C — X bond length increases no correlation between (R) Clockwise Counterclockwise
l

X
ky

li Bond enthalpy decreases and (S) configuration

Preparation de rotation rotation
Al

de

CH2 and the direction of = dextrorotatory = laevorotatory

li
ha

X rotation. (d) or (+) (l) or (–)

 From Alkanes :  Direct halogenation of aromatic hydrocarbons :

Br2, AlBr3 Enantiomers : Diastereomers : Meso compounds : Racemic mixture :
R — Br + HBr Cl
Compounds having Compounds which are not These are optically inactive A mixture of equal
By halogenation
RH non-superimposable mirror images (I and III, II and compounds as there exists amounts of two
Cl2, Anhyd. FeCl3
Cl2, Sunlight mirror images with same IV) of each other with different a plane of symmetry which enantiomers is called
R — Cl + HCl 310-320 K
physical and chemical physical properties but same divides the molecule into two racemic mixture or
properties. chemical properties. identical halves. racemic modification.
 From Alcohols :  From diazonium salts :
PCl5
R — Cl + POCl3 + HCl Sandmeyer’s reaction (CuCl/HCl) and CH3 CH3 A racemic mixture is always
Red P/Br2 COOH
R — OH R — Br + H3PO3 Gattermann reaction (Cu/HCl) Cl H OH HO H optically inactive because
H OH COOH
SOCl2 H OH HO H the rotation caused by the
R — Cl + SO2 ↑ + HCl ↑ CuCl/HCl
C2H5 C2H5 HO H molecules of one enantiomer is
Pyridine N NCl– + N2 + Cl– COOH COOH
exactly cancelled by equal and
or, Cu/HCl (I) (II)
Dry acetone HO H opposite rotation caused by
 Finkelstein Reaction : R — X + NaI R — I + NaX H C R R C H CH3 CH3 H OH
Br COOH the same number of molecules
 Swarts Reaction : RBr + AgF R — F + AgBr H OH HO OH of the other enantiomer. It is
NH2 NH2 COOH
HO H H H represented by prefixing dl
 Hunsdiecker Reaction : CuBr/HBr
+ N2 + Cl– C2H5 C2H5 Plane of (Superimposable) or (±) before the name. For
CCl4/Reflux or, Cu/HBr
RCOOAg + Br2 R — Br + CO2 + AgBr (III) (IV) symmetry Meso-tartaric acid example, (±) butan-2-ol.