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2) Eletrophilic substitution :
R H
3) Nucleophilic addition :
R1 X R2
R = aromatic
R1 X Y H R1 R2 XH Y
Y R2
X = O , NH
4) Eletrophilic addition :
+
5) Rearrangements :
R1 R
2
Y X X X
_X
R2 R3 X
R1
R1
Y
R2 R
3
R1 R2 Y R3
R3
Two types of discrete mechanism : SN1 Substitution Nucleophilic unimolecular SN2 Substitution Nucleophilic Bimolecular
SN1 :
R X
slow
SN2 mechanism :
R X
Y R
2nd order kinetics Q. Do all SN2 reactions follow 2nd order kinetics? Ans. If Y- is in large excess as compared to R-X, ( eg. If solvent is the nucleophile) then
K [Y ]
~K
Rate = K1[R_X]
Effect of structure and solvent : Which mechanism will be operative will depend on structure and solvent polarity.
_
C
Q.
C6H13 C Me H I
I*
C6H13 I* C
( )
Me H
(+)
For SN1 :
R1 R2 R3 C X R3 R1 R2 R1 R1 C R3 Nu
Nu
R2
+ Nu
C R3
R2
Racemization is expected Extent of inversion = extent of retention However, due to ion pair formation, more inversion then retention. Ion pair mechanism :
R2 R3 R1 C X R3 R1
R2 X
Br
Explain?
10-6
10-14
Me HC C C Me 1.0
Explain
Me Cl H2C C H C Me 10,000 Cl
Factors Affecting the Rates of SN1 and SN2 reactions : 1) The structure of the substrate 2) Concentration and Reactivity of Nucleophile (for bimolecular reactions only) 3) The effect of solvent. 4) The nature of leaving group (nucleofuge) Effect of substrate structure : For SN2 methyl > primary > secondary >> tertiary (unreactive)
R Substituent Methyl 1o 2
o
3o Neopentyl
N + CH3I
CH3 +
Me
N 1.00
N 2.27
Me
N 0.47
Me
N
0.042
Me
Solvent effect For SN1 : Greater the ionizing ability of the solvent, faster will be the reaction. Dielectric constant reflects the ionizing ability.
H3C H2C H3C C OH
water
H3C H3C C Br
MeOH
H3C H3C
H3C H3C
OMe
Br
Rate of increase of [ Br- ] increases with increase in proportion of water. Dielectric constant
H2O MeOH 80 33
(CH3)3N + CH3-S(CH3)2
(CH3)3N-CH3 + S(CH3)2
Effect of Nucleophile :
rapid
CH3O
+ +
H3C
CH3OCH 3
+ +
very
CH3OH H3C I
CH3OCH 3
HI
slow
CH3OH
Nucleophilicity of
CH3O
>
OH
>
>
>
F
Br
>
Cl
>
Br
>
Cl
>
>
Problem
Ph
Relative rates of SN2 reactions of alkyl chlorides with the iodide ion
Alkyl chloride Me Cl relative rate 200
0.02 Cl
Cl Cl
79
200
Me O Cl O Cl
920
1,00,000
I H H Br
Br
Nu