CAN t

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 Electronegativity and Inductive effect

What is it?
Electronegativity is the power of an atom to attract electron density in a covalent bond
I
The higher the value, the more electronegative element
Fluorine is the most electronegative element It has an electronegativity value of 4.0

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 Inductive effect
Permanent polarization along the carbon chain due to the presence of
electron donating or electron withdrawing group.

Types of inductive effect

I b
+ I effect - when the substituents are electron donating groups Live d
2 3 y
e.g., CH3 < C2H5 < CH(CH3)2 < C(CH3)3
T
ppg -δ -δ -δ +δ
e.g. C3 C1 CH3 acts is a
C2
The –ve charge at C1 ˃ C2 ˃ C3 because the + I effect of CH3 decreases with the distance
u
– I effect - when the substituents are electron withdrawing gps

(e.g., - NO2 > –CN ˃ C=O > F > Cl > Br > I > OCH3…etc.)

g'Te.g. +δ +δ +δ -δ
I C3 C2 C1 CN

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 Inductive Effects and Carbocation Stability

LEAST STABLE MOST STABLE

H CH3 CH3 CH3

C C C C
H H H H H3C H H3C CH3

Methyl Primary Secondary Tertiary

Carbocation Carbocation Carbocation
C Carbocation

Carbon atom is electron deficient (only has 6 electrons in CH3

its outer valence).
The methyl groups have +I inductive effects.
Thus, extra electron density is ‘pushed’ onto the
C
carbocation, which stabilises the carbocation. H3C CH3

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 - Hyperconjugation
It involves σ and π bond orbitals
CY 15,46
- Stabilization of cations 0kt 31 it
As the number of methyl groups attached to carbon carrying positive charge increase, as the
number of hyperconjugative structures increase, as the stability of ion or molecule

H H H H H H H
H
H C C H C C H C C H C C

H H H H H H H H

one methyl group give 3 hyperconjogation structures

3Conj H3C CH2 CH2

Inetty CH3 CH CH3 H3C CH2

nmethyl 2 CH3 grps one CH3 grps I CHz 2

one CH2 group
6 hyperconjugative strs 3 hyperconjugative strs 2 hyperconjugative strs

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 -Resonance Effect
Resonance is the process whereby p-electrons can be delocalised

by exchanging double bonds and single bonds.

Resonance can be used to delocalise both lone pairs of electrons and

cationic charges which are adjacent to double bonds.

Generally, resonance effect is more effective than inductive effect and does
not depend on the distance as in the case of inductive effect

CH2 CH CH 2 CH2 CH CH 2

CH2 CH2 CH2 CH2

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1) As befor in (ch 3) SN1 and E1
CH3 CH3 CH3
Cl Y
CH3 C Cl CH3 C CH3 C Y
slow fast
CH3 CH3 CH3
E1 or SN1
Y best
CH3
Y = OH, OCOCH 3, N3 CH2 C + YH

CH3
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 2- From alcohols:
H
fast slow
C C OH + H3O C C O H C C + H2O
H H H
Carbocation
Caltsolt
It -H+

C C + H3O

3-

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 Seo É I 7 84 A
Erbocation

5- (Friedel craft
acylation)

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10
12504

c
c

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12
 (Ring opening)

Mech.

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Mech.

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 Pinacol Rearrangements
Mechanism of symmetrical glycol

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Regioselectivity of the pinacol rearrangement
of an unsymmetrical glycol
O Me

Ph
Me Ph Me Ph
H2SO4
HO OH C
Me Ph X Me O
A Ph
Me Ph
E

Mechanism
Me Ph Me Ph O Me
H2SO4
++
HO OH HO C Ph
Ph
Me Ph Me Me Ph
stable by resonance
A B C
Me Ph Me O

+C+ OH Ph
Me Me Ph
Ph

D E

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 IV- Carbenes

Carbenes are highly reactive intermediates that

contain uncharged divalent carbon.
X
C Carbenes exist as singlet (with the two electrons
paired) or triplet (with the two electrons having
Y
parallel spins)
Multiplicity =2S+1 (S is spin quantum no.)

CH2 CH2

L Singlet Triplet
+1/2, -1/2 +1/2, +1/2
so S = 0 so S=1
multiplicity = 1 muliplicity = 3
singlet triplet
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A- Generation of carbenes:
a) From chloroform:
OH - Cl
CHCl3 CCl3 CCl2

dichlorocarbene

b) From diazo compounds:

R hν or R
R C N N C + N2
C N N Δ R
R R

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 B- Reactions of carbenes:
1) Addition to olefins:
Singlet carbenes add to olefins stereospecifically; i.e.
a cis olefin gives a cis 2,3-disubstituted cyclopropane and a
trans olefin gives a trans 2,3-disubstituted cyclopropane.
Br Br
C
H3 C H CBr 2 H3 C H
C C C C
H CH3 singlet
carbene H CH3
trans-2-butene trans 1,1-dibromo-2,3-dimethylcyclopropane

Br Br
C
H3 C CH3 CBr 2 H3 C CH3
CC C C
H H singlet
carbene H H
cis-2-butene cis-1,1-dibromo-2,3-dimethylcyclopropane

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 In singlet carbenes, the two electrons have opposite
spins. The two electrons can form two C-C bonds
simultaneously. Thus, there is no time between the
first and the second bond formations, and the
reaction therefore is stereospecific.
H3 C CH3
C C CH3 CH3
H H
One step H H
CH2

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 Triplet carbenes (methylenes) add to olefins non-
stereospecifically; i.e. a mixture of cis and trans-
disubstituted cyclopropanes is obtained from either
cis- or trans-2,3-disubstituted olefin.
H 3C H
C C
H CH 3
Br Br Br Br
trans-2-butene C C
H 3C H H 3C CH 3
or + CR 2 C C +
C C
Methylene H CH 3 H H
H 3C CH 3 (triplet carbene)
C C trans- cis-
H H
1,1-dibromo-2,3-dimethylcyclopropane
cis-2-butene

Explanation: Singlet carbenes add in one step

(concerted), whereas triplet carbenes (methylenes)
add in two steps (stepwise).
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 same spin so bond can't formed
stable bond formed btween opposite spin

H3C CH3 H3C CH3 H3C CH3

C C C C C C
H H H H Or H H
CH2 CH2
CH2
Spin Spin
at CH2
inversion inversion at Alkene

H3C CH3 H3C H

C C C C
H H + H CH3
CH2 CH2

CH3 CH3 CH3 H

+
H H H CH3

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By the same methode

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 2) Reimer Tiemann Reaction: Sub. Rx of carbene
OH OH O
CHO
+ CHCl3 + OH +

Me Me Me CHCl2
(A) (B)
Mechanism:
CHCl3 + OH CCl2 + H2 O + Cl

O H O H OH OH
CCl2 CHCl2 CHO
CCl2
H
OH
OH
Me Me Me Me
(A)
H
O H O O
Me CCl2

Me Me CCl2 Me CHCl2
(B)
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