SN1 or SN2

1
SN1 or SN2?
SN1
????? ?????
??? SN2
SN1
????? ???? ????????
???? SN1
?????? ??????
2
????? ???
SN2
E?E
???????? ???? ???? ???? ?????? ?? ?????? SN2.
E
E
E
??? ?-??????
??? ??????
Reaction coordinate
3
????? ???
SN1
EgtE
E
??? ?????? ???? SN1.
E
E
??? ?-??????
??? ??????
Reaction coordinate
4
???? ???????? ???
?????? ???????? ????????? ?? 1 ?? 2 ?????? ?????.
1
2
1 ?-2 ?????? ????? SN1 ?????.
5
??? ??? ?????? ?? ??????? ????? ?????????,
??????? ?? ???? ??????? (k) ?-25 C.
??????? ?? ??????? 1, ????? ?????? ??? Y ?? ??
???. Y ?? 80 ?????/20 ??? ????? ?-1.
??? ????? ???? ?????? ("????"?????) ?? Y ??? ????
????
6
????? ??? ???? m.
?????? ???
log(k)mY
?????? SN1, ??????? ????????? ?? ???, ???? ???? m
?????? ?-1 (0.7-1.0).
?????? SN2, ????? ?????? ????????? ?? ???, ????
???? m ????? (0.0-0.3).
7
???????
?. ????? ?????? ?? ???? ?? ?????.
?. ????? ?????? ???? ??????.
8
???? ??????
SN1
Log(k)
SN2
Y
9
???? ????? ??? ?? ?????? ??????? ??????
..
d
ROH
??? ?????? ?????
10
N,N-dimethylformamide
dimethylsulfoxide
dimethylketone
acetone
DMF
DMSO
???????? ??????
11
E
EltE
E
??? ???????? ??????
E
??? ??????
??? ???????? ?????? ???? ????? SN2.
Reaction coordinate
12
E
E?E
E
??? ???????? ??????
E
??? ??????
??? ???????? ?????? ???? ???? ???? ?????? ?????
SN1.
Reaction coordinate
13
???? ????? ?????
??? ??????? ?????? ???? ???? ?? ?????? ????? ????.
?????? ?????? ???? ???? ??? ???? ????? ???? ????
????.
?? ?????? ?????? ??? ?????, ??? ???? ???? ???
??????? ?????? ???? ????.
??? ??????? ?????? ???? ???? ?? ??? ?????????
???? ????.
14
?????
CH3CH2Br OH ? CH3CH2OH Br
CH3CH2Br OH ? CH3CH2OH Br
H
CH3CH2OH Br ? CH3CH2Br H2O
15
????? ??????? ?????? ?????
Para-toluenesulfonate
trifluorometahnesulfonate
triflate
tosylate
???? ?????? ??????
AgX?
R-X LGAg ? R-LG
16
????? ????? ?????
EgtE
????? ????? ???? ????? SN1 ???? ???? SN2.
E
E
E
????? ????? ?????
????? ????? ????
Reaction coordinate