???????????????????????????????: R

1
??? ??? (Halides)
??????????????????????????????? RX?
????????????????????????????
???(?Cl)???????? ??????????????
??????????????????????????????
2
??? ?????
????
1.??????
n?2
n?2
3
????
CH3CH2Cl
2.?C-X?C???
????
CH3CHClCH3
????
(CH3)3C-Cl
4
????
1. ????? ?(?)????????
CHCl3
????
??
???
C2H5Cl
???
n-C4H9-Cl i-C4H9-Cl (CH3)3CBr
????
????
????
????
CH2CHCl
???
5
????
3-???
CH2CH-CH2
Br
6
2.????
????????,? X ?????????????????
?????????????????
???? ????????????
3 2 1
1 2 3 4
H
C
C
H
C
H
C
H
3
3
C
H
B
r
3
7
2-??-1-???
CH2CH-CH-CH2-Br CH3
3-??-4-?-1-??
CH3 I
5-??-1-????
8
?????????????
???????,??????,????????
9
??? ??????
?????,???????X.
??????
d
d-

C X
CgtX ??????CF gt CCl gt CBr gt
CI,?????????????????????????(????)
10
??????????? ???,????gt??? gt???,???
????,????????????????????
11
????????(Nucleophilic Substitution, SN)
???
????
???????????????C?a ???,???????,???????
?????????????,?????????(Nucleophilic
reagent, Nu or Nu-).
???Nu??,CX???, X-??????,??????(Leaving
group, L).
?????????????????????????????,???????,? SN
???
12
???????????,??????????,?????????????????
??????????,??????? ??????????????????
13
1. ??(?-OH??) ???? NaOH ? KOH
??????,-X?-OH??,????????????????????
???????-OH???????????,????????-OH?????-X?????
14
2. ??(?????) ????NaCN?KCN??????,X?-CN??,??
??
H/H2O
??????,????????????????CN-?????COOH??CH2NH2
?????
15
3. ??????????????,????
RX NH3(??) gt RNH2 HX
???????????????,???????????,???????????,?
??????????????
16
4. ?????? ??????(???)??, - X?
-OR??,??????????????,?Williamson?????
RX NaORgt ROR NaX
????????????,???????,????????,?????????????????
?????????,???????
17
(No Transcript)
18
7. ?????? ???????? ?AgNO3??????,??????A
gX ??
????RI gt RBr gt RCl
19
8. ????????
?????????????
NaBr?NaCl?????,?NaI?????,???????????
???? ???? gt ???? gt ????
(???SN2????)
20
??????(Elimination) ???????????(?HX?H2O?)???????
?????????,? E ???
21
???????????,????????????????
KOH/EtOH
CH3CH2CHCH3 gt CH3CHCHCH3 CH3CH2CHCH2
Br
2-?? (81) 1-?? (19)
???????????????(??????) ,???????? HX
?,?????H???b-C???,???????????,???Saytzeff???
22
Note???????????????????????p-p?????
23
(2)? -????????
?????????????,???????,????
?-H??????
??????????
2. ?X2
24
1,3?1,4?1,5?1,6????????????????????????????????
1.?Mg??
????(Grignard reagent)
25
Grignard????????????,???Lewis?,?Grignard??
??Lewis???????????????
26
??????????H????? H2O?R-OH?NH3 ? R-NH2 ? HX?
HOOCCH3????????????
RMgX H-OH gt RH Mg(OH)X
?????????????????????,??????????????
27
???????????????
?????????,???Grignard??,?????,?????
28
??????????,?????
????????????(?????????)
29
2. ????
?Hexane
Solvent Ether?
???????CO2????????!
?????
30
Corey-House???????
31

• 3. ?Na??
• Wurtz???-??????

RX???1????
32
????

(1)????H2,Ni?Pd?Pt (2)????LiAlH4?NaBH4?
Zn/HCl?Na-NH3
??????,?????????????????,??????????????????
33
??? ???????? ???????????(SN2)
???????????? ?????????????????,??OH-??????,?????
??????? ??????? kCH3-Br OH-
34
Inversion of configuration at carbon
Nucleophilic backside attack
Transition state
35

• SN2 ?????????
• ??????,
• ????(Walden????)?SN2??????????
• ??????????

36
Stereochemical Evidence for SN2 Mechanism
(1)
37
??????X???????? SN2????????????????????,
??????,???SN2??
SN2????????,?????? gt????gt ???? gt ????
gt????,??????
38
?????????????
?????????????????,???(OH-)?????,???????????? ?????
?? k(CH3)3C-Br
???????????(SN1)
39
(No Transcript)
40
HO-
CH3
H3C

C
Br
C
CH3
CH3
CH3
CH3
41

• SN1?????????
• ??????????
• ?????????????????
• ????????
• ???????????
• SN1???????????????

????????????????SN1?
SN1????????,?????? gt ???? gt ???? gt
???? gt ????,??????
42

• SN2?????????
• ??????,
• ????
• ??????????

• SN1?????????
• ????
• ?C??,??????
• ??????????
• ????????????

43
??? (S.Winstein)???????p.253(????)
????????????????,????????
44
???? (a) ???????????????,?????????? (b)
????????,?????????? (c) ???????????
???????????????,??????????
??????SN1?SN2?????????,?????SN??
45
??????????????
1. ??????????
R
R CH3X RCH2X R-CH-X
R -C-X R
SN2 and SN1 ?SN2??,?SN1??
??? SN2?
???????????SN1?
46
???????????
a. ???????????SN1?SN2????????
SN1C?? SN2?????(??? ??????)
b. ?????????????SN???
SN1 C-X????? SN2?????????
c. ????,???SN??(????????????)
SN1????????? SN2???Nu ?????
47

????????,???????SN1???
48
2. ??????????
C-X??,X-????C-X??,X-????
C-X????X-???????????????
?????????????? ????????????????
X-????I- gt Br- gt Cl- gt F-
????SN ?????RIgtRBrgtRClgtRF
?????????SN1??,??????????SN2??
49
3. ?????????????????
?SN1???????
??????????,????,?SN2???????
??????????????1)?????(?????)2)???????(?????
???)?
????????????????????????????????????????????????
?
50
1) ?????(???????????????)
a. ???????????????,??????????? ????,??????
RO- gt HO- gtArO-gt RCO2- gt ROH gt H2O
b. ???????????,???????????(?????????)?
c. ???????,??????????????
-OH gt H2O, RO- gt ROH,NH2- gt NH3
51
2)???????(???????????????) ???????????(????)?,??
???(?????)???????
??????,??????????,????????
CH3O- CH3CH2O- (CH3)2CHO- (CH3)3CO -
?????? ???????
?????????????
52
4.??????????????
????????? ?????????,???????????
?????
???? e??, ????????
?????CCl4,, CS2, ??
??????,?????
(µ 0)
????????? ???????
???-???H??? EtOH, H2O, CH3COOH
????
????THF, Et2O, CH3COCH3,DMF, DMSO, CH3CN,??,?????
?,?????????
(µ? 0)
53
??????????,??????????
?????????? I-gtBr-gtCl-gtF- (?????) ??????????? F-
gtCl- gtBr- gtI- (?????)
Note I-???????,????????,????????????I-?????
54
????(????????) (??)
??SN2?????SN1?????????????????????
???????,????????(??),???????????????????(??),????
????????????,???????
??????,???SN1??
55
??????, ????SN2??
????,?????
?????????,????????????????,???SN2??
56
?? ??????????????????????????,?????????????
???????? ?????????????????????????
57
?????SN2??
???????????????????,?????? ?SN2??( SNi2 )
??????,???????,???????????, ?????????
58
????????
1.???????
?
????
Ag2O
S-2-??? S-??
??
?????????SN2,????
59
????????(?????)??????????????????,????????

• 2. ????????
• ??????
• ???????????(????????????????????????????????)
• ?????????????????

60
3. ????????? (1)?????????(?COO-?OH? -O- ?
OR?NH2?SR?Cl?Br?I ....)
61
(2)??????
62
??? ??????
1. E1???????
E1?SN1???????,???????????SN1???????E1
,?????????? gt ???? gt ?????
???????????,???????
63
2. E2 ???????
64
??? E2 ???????????????? (H-C - C-X ???)
?????????????????
??????? ??????? (???)
Note??????
65
?????????,??????,??????????????
66
??????, ??????,???E2?
3. ??????? ??E1?E2,??????????????????????
???????????saytzeff??? ???????????,?(CH3)3CO-,?Ho
fmann??(??????????)
67
4. ????????
???????
5. ????????????
??????????????????????????????
68
???????????????
1. ????????????????????
??????????, ??????????.
2. ????? ????,????,??????? 3. ?????
??????????? 4. ????? ??????????
69
??? ??????????????
1. ?????????
???????????,??????,????????????,???
70
????????,????????????
71
????,???????-NO2, -OR,-NH2 ??????????????
??????,???CN?RO?PhO ?NH3?H2NNH2?)???????
????????????,????????
IgtBrgtClgtF
???????????,????????
FgtgtClgtBrgtI
72
???????
???
???

????????????,???????F,?????????,?
F Clgt Br gtI? ????????????????,??????????
73
??????????????????, ???????????
74
?????????????????HCl,??????????,??????????????????
??NH3,??????????????????????????,???????
75
??????????
?????????????????(???? ?????sp2????,?????
?,????p? ????)???????????????????
76
???,???????,????????(??????????sp2??????????p
????????p?????)?
77
????????????
??? ??????(??)