-:

Nucleophilic Substitution

) (

Nucleophilic
Substitution

 -:

Nucleophilic Substitution

Nucleophilic Substitution

))SP3-C

-: ) (alkyl halide

-:
SN2 -1
] Rate = k2 [ RX ] [ Nu
SN1 -2
] Rate = k1 [ RX
-: ) (bromomethane

SN2
) (

OH
SP2
C-Br
C-OH SN2

Substitution Nucleophilic Bimolecular

2-bromo-2 -: )( t-butylbromide
methylpropane SN1
] [OH )

 -:

Nucleophilic Substitution

(
) ( OH

SN1
Substitution Nucleophilic Unimolecular


OH H2O

.Stereo-Electronic effects in T.S
-: SN2
/ ) (R
) (X ) (
OH
/ OH

) (crowding )
( ) (

SN2

 -:

Nucleophilic Substitution

-: SN1

-: -C

-: Stereo effect
) ( SP3
) ( SP2

 -:

Nucleophilic Substitution

) (H-CH3 Carbcation
SN1
/ SN1
Benzylchloride
,
Triphenylchloridemethane
)C6H5CH2-Cl(C6H5

> (C6H5)2CH-Cl

Diphenylmethylchloride
>

C-Cl

Triphenylchloridemethane

C6H5CH2Cl 100 CH3CH2Cl

SN2 SP2 PZ
OH Cl

-:

SN2

 -:

Nucleophilic Substitution

SN1 SN2
Benzyl cation

SN1

SN1
Benzylcation

 -:

Nucleophilic Substitution

)(allyl halides SN1

Carbcation

) (vinyl halides SN1

SN2

/ SN1 SP2
C-Cl
dipole
/ SN2
T . S

SN2 1--1
bromo-2,2-dimethylpropane

>

bromo-2-methylpropane

Eto H

 -:

Nucleophilic Substitution

Stereochemistry of SN Mechanisms
-1 SN2

-:

/ )(Optically active

OH chiral center
T . S
)
(Inversion of configuration

 -:

Nucleophilic Substitution

) (1 Tosyl
C-O ) (2
.
) (2 -MeCOO
ArSO2 -MeCOO C-O
). acetate (3
4 3 *O-C
) (+ . ((3
((4 ((1
(-) (4)(+) ((1
.
) (2 Br
) (5 -: ((2
) (SN2 ) (5
) (3 ((1
) (SN2 SN2
Inversion of configuration
-:
SN2
)( -:

polarmeter
) (Racemic

SN1

-:Racemization

 -:

Nucleophilic Substitution

-:
Carbcation .

-: OH
H2O 50 : 50


) (Racemisation

) ( -:
-1 /
-2 /

) ( Inversion of configuration
SN1

 -:

Nucleophilic Substitution
+

R
+R
R+





+
R
Br

+R

Solvolysis (+) C6H5CHMeCl

%98 (+) C6H13CHMeCl %34

Benzyl
carbcation

 -:

Nucleophilic Substitution

carbcation

Solvolysis phenylmethylchloride
)(+ %80 %20

+R

SNi
configuration

of

Retension

)( Substitution Nucleophilic
Internal SN2

 -:

Nucleophilic Substitution

SOCl2 ROH RCl

) (

HCl ((1 SOCl2

-C5H5NHCl Cl

 -:

Nucleophilic Substitution

) (1 SN2
SN2

SN1

-:

) (
Participitation
of
neigbouring group in SN

) (


-:

 -:

Nucleophilic Substitution

-: bromopropanoate anion -2
-OH ) (
]
[OH

104

) (S

) (
)(SN2

 -:

Nucleophilic Substitution

) -: (:N
Me2NCH2CH2Cl

) (

)
(

 -:

Nucleophilic Substitution

) H2O ( MeOH )

and
Entering groups

Leaving

Effect

1 -: Entering group )(Nu

SN1
Rate = K1
] [ RX
SN2
] Rate = K2 [RX
][Nu

-:

: Nu
-1

:B

-1

-2
-2
-3 -:
-a

3- -:

 -:
H2O: ,
NH3
-b
ph-NH2 Ph-
OCH3

-4
SN1 EtOH ,
CO3 , HCO3 , H2O SN2
OH- EtO

Nucleophilic Substitution
-a hard bases


:OH , OR - R3N
,
-b soft bases


- RS- I- SCN

-4

EtO > PhO > MeCO2 > NO3

-5
I > Br > Cl





-6

/ I

-F

 -:

Nucleophilic Substitution

2 -: Leaving group
SN2 -:

H2O Cl
-:

)Nucleophilic Catalysis

NH2 , OR , OH

 -:

Nucleophilic Substitution

-Another SN :
SN
OH H2O

Nucleophilic Substitution

-: