Organic Chemistry-I

Substituent Effects & Linear Free Energy Relationship

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Organic Chemistry-I

Substituent Constants

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Organic Chemistry-I

Reaction Constants

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Organic Chemistry-I

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Organic Chemistry-I

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Organic Chemistry-I

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Organic Chemistry-I

TWO LOOK-ALIKE REACTIONS

1)

CH3 Br + NaOH

80% ethanol55oC
20% water

CH3 OH + Br
high conc. NaOH

rate = k2 [RBr] [NaOH]

CH3
H3C

2)

CH3

Br + NaOH

CH3

80% ethanol
20% water

55oC

H3C

C OH + Br

CH3
( + some alkene by E1,E2 )

rate = k1 [RBr]

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low conc. NaOH

Organic Chemistry-I

THE SN1 AND SN2 REACTIONS

The mechanisms are supported by four evidences:
(1) Kinetics
(2) Stereochemistry
(3) Reactivity of substrates
(4) Rearrangements

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Organic Chemistry-I

The Nature of the Leaving Group

The leaving group can be an anion or a neutral molecule

The best leaving groups are weak bases which are relatively
stable

The poor leaving group hydroxide can be changed into the good
leaving group water by protonation

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Organic Chemistry-I

S N1

Rate of Reaction in Solvents

Polar protic solvent > polar aprotic solvent > non-polar solvent

S N2
Polar aprotic solvent > non-polar solvent > polar protic solvent
SN1 reactions prefer polar-protic solvents that can solvate
the anion and cation formed in the rate-determining step.
SN2 reactions prefer non-polar solvents, or polaraprotic solvents that do not solvate the nucleophile.

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Organic Chemistry-I

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Organic Chemistry-I

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Organic Chemistry-I

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Organic Chemistry-I

Evidences for Ion Pair Mechanism

Solvolysis of unlabeled substrate in the presence of

labeled HOSO2Ar showed that there was some
intermolecular exchange (320%), but not nearly
enough to account for the amount of scrambling
found in the original experiments.
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Organic Chemistry-I

Evidences for Ion Pair Mechanism

Special Salt Effect. The addition of LiClO4 or LiBr in
the acetolysis of certain tosylates produced an initial
steep rate acceleration that then decreased to the
normal linear acceleration (caused by the ordinary
salt effect)

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Organic Chemistry-I

Evidences for Ion Pair Mechanism

1. Optically active p-chlorobenzhydryl chloride racemizes
30 times faster than it solvolyzes in acetic acid.

2. phenolysis of optically active -phenylethyl chloride,

proceed with partial retention. Partial retention was
obtained in this system only with chloride or other
neutral leaving groups; with leaving groups bearing a
positive charge no retention was found.
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Organic Chemistry-I

Hydrolysis of 2-octyl brosylate

C6H13
75% aq Dioxane
HO
C6H13
H
H3C

C6H13

H
CH3

H
H3C

OH

Inversion with 77% Optical Actrivity

C6H13

OBs
75% aq Dioxane
NaN3

HO

H
CH3

C6H13

C6H13
+

H
H3C

OH

H
N3
CH3
100% Inversion

Solvolysis of 2-octyl brosylate in pure methanol or of 2-octyl

methanesulfonate in pure water, in the absence of azide ions, gave methyl
2-octyl ether or 2-octanol, respectively, with 100% inversion of
configuration
In the absence of azide ions, the amount of inverted 2-octanol decreased
with an increasing percentage of dioxane in the solvent.
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Organic Chemistry-I

Borderline Mechanism
CH2OH
CH2Cl

Aq
%
70

tone
e
c
A

70%
OCH3

Aq
Ace
ton
NaN
e

OCH3
CH2OH

CH2N3
+

OCH3

OCH3

On addition of azide ions :

Rate of Ionization Increases
Rate of Hydrolysis Decreases
Overall Rate of Reaction is always greater than rate of
ionization
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Organic Chemistry-I

Evidences for Ion Pair Mechanism

1.

2.

Product Spread
CH3CH=CHCH2Cl

CH3CH=CHCH2OH
60%

CH3CH(Cl)CH=CH2

CH3CH=CHCH2OH +
38%

C
H
=
C
H
C
M
e
C
l
2
2

CH3CH(OH)CH=CH2
40%
CH3CH(OH)CH=CH2
62%

lC
H
C
H
=
C
M
e
c
O
C
H
C
H
=
C
M
e
C
H
=
C
H
C
M
e
O
A
c+A
2
2
2
2+C
2
2

Isomerization was faster than acetate formation

Rate of formation of rearranged chloride was
unaffected by addition of external chloride

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Organic Chemistry-I

Kinetic Vs Thermodynamic Control

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