exit

1
??? ???
exit
2
????
???? ? ???? ?
3
???? ????
??? ??????? ??? ???? ???
?????? ??? ??????????? ??? ???? ??? ????
4
??? ???????
???????????????? ??????????????????
? ??
?? ???
???? ??? ???
???
??? ???
?? ?
5
? ??
???(??)
? ? ?
??
???(??)
???(??)
??
? ? ?
???
???
???(??)
6
??? ????
? ??????(????????)
???????
? ?????(????????)
CH3
CH3CH2CHOH
????
???
7
? ?????(?????????)
????
3-??-1-?
5-????
5,5-???-2-??
3-???-1,7-???
3-??-4-?????
8
??? ??????

• 1 ????????sp3????????????????sp2?????????
• 2 ??????????????,???????sp3???
• ??????2D??????????u1.71D?
• 4 ????,?????????????????????,???????????????,????
  ??????????????

9
??? ???????????
? ????
??????????? ??,?????????,???????
?????????????????????,??????????
????????????,?????????????
????????????????,???????????????
? ????(?????)
10
? ???(???)
??????????????????????????,????????
MgCl2? 6CH3OH CaCl2 ? 4C2H5OH
?????????????????????,?????????????,???????????
?? ???????????????
???????????,??CaCl2????????????
11
??? ????
? ???????? ? ???????? ? ??????,???????? ?
???? ? ???? ? ???? ? ????????
12
? ????????
?????? ?
????
?
?
??(?????)
????
????
13
? ????????
???? ????
1 2C2H5OH 2Na 2C2H5ONa
H2
C2H5OH NaOH C2H5ONa H2O
??????74.1?18.5?7.4(64.9)
14
2 2(CH3)3COH 2K 2(CH3)3COK
H2
????? ????????
15
3 2C2H5OH Mg (C2H5O)2Mg
H2 (C2H5O)2Mg H2O
2C2H5OH MgO
???
???????????????,???????
??????????????
16
HgCl2 or AlCl3
4 6(CH3)2CHOH 2Al

2 (CH3)2CHO3Al
3H2
??????
17
?????????
????????
H2O gt CH3OH gt RCH2OH gt R2CHOH gt R3COH gt HC?CH gt
NH3 gt RH
????????
(CH3)3CCH2OH gt (CH3)3COH gt (CH3)2CHOH gt C2H5OH gt
CH3OH gt H2O
????,??????????????????
???????????,??RO-???
1oROH??????,???????
3oROH??????,???????
18
? ??????,????????
1 ????????
??? ROH HX
RX H2O
?????? ???, ??? gt 3oROH gt 2oROH gt 1oROH gt CH3OH
HX????? HI gt HBr gt HCl
19
????
???1oROH??SN2???????
86 14
80 20
100
3oROH ????2oROH????? 1oROH?SN1???????
20
????
???????,?????????????????
H
(CH3)3CCH2OH
-H2O
???????SN2

Cl-
(CH3)2CClCH2CH3
(CH3)2CCH2CH3
21
HBr

HBr
(dl)
H
22
2. ??????????????????
(1)??????
?
??????(TSCl)
?????(TSOH)
23
(2)??????
C6H5SO2Cl
????
NaI ??
1oROH?2oROH ??????????
NaBr ???? KCl DMF
????
24
3. ????????
(1)???????
PCl5 ?PCl3 ? PBr3 ? P I2 PI3
(2)?????
3ROH PBr3 3RBr H3PO4
5ROH PX5 RX
HX POX3
(3)????
?????1oROH, 2oROH ???????3oROH?????
25
(4)????
1oROH (SN2)
SN2
SN2
BrCH2CH3
26
2oROH , 3oROH (SN1)
SN2
SN1
(CH3)3C HOPBr2
Br -
(CH3)3CBr
27
4 ????????
(1) ?????
?????????????,?????,???,??????
(2) ???? (????????)
??????????
1oROH
SOCl2
PBr3 or NaBr H2SO4
P I2
2oROH
3oROH
?HCl (0oC)
HBr (0oC)
HI (0oC)
28
? ????
???????????????????
1 ???????????
????
?????
??????(????)
???????
29
2 ??????
3C4H9OH
3HCl
?????
Ca
?????
30
3 ??????????????
2 HOSO2OH (??) 2 ClSO2OH(???) 2 SO3(????)
2 CH3OSO2OH ?????
2 CH3OH
C2H5OH
????
CH3OSO2OCH3
-H2SO4
NaOH
?????
?????
C2H5OCH3 CH3OSO3Na H2O
2oROH , 3oROH?????????
(????????????????)
31
? ????
??? ????
ROH ??
???
???
RCH2OH RCHO
RCOOH
???
R2CHOH
H
???
R2CCH2
HCOOH
????????????????
32
??????????-1
??? ??? ???
??? ?????
KMnO4 ?,?,??, ??,??
? ?
????,?
K2Cr2O7
? ? ?
????,? ????
4050H2SO4
? HNO3 ?
? ?
? ? ????,?
????
?? ?? ?? ? ??
33
??????????-2
??? ???
??? ??? ?????
?????????

??MnO2
???
??
?
?
????????
??,??????,?????????
?????
?
?
CrO3???
????
?(????,???)
??,??????,?????????
?
CrO3?H2SO4
?? (H3PO4) , ?????????
?
?(????)
???-?????
????????????
?(??????????,???)
??,??,??????????
???????(??????)

?
34
???-????????????
Dicyclohexyl Carbodiimide
35
??????????
???????????????,??????(????,???)????,?????
????,??????????(Oppenauer,R.V)???,??????????-???(M
eerwein-Ponndorf)???
Al(OCMe3)3
???????
R2CHOH
R2CHO
????-?????
???????
??????? ??????? ????-?????????????????,????????
?????????????H?????,??????????
???????????????????
36
H2O2 ? Ag ?? ???? 1oROH 2oROH?
Ag , ??
300oC
H2O2
Fe3
???
?????
37
? ????
1oROH ????? 2oROH?????
3oROH????????
? ?
????CuCrO4 Pd Cu (orAg) ?????????????
???????????(300oC, ????????)
38
? ?
CuCrO4
CH3CH2CH2CH2OH
CH3CH2CH2CHO
300-345oC
CuCrO4
250-345oC
?????,???
Cu (orAg)
CH3OH 1/2 O2
CH2O H2O
450-600oC
Cu (orAg)
CH3OH CH2O H2
????,???
450-600oC
????30-50,???65,(??85-95)
39
? ????????
1 ???????(H5IO5)??????(KIO4)
??????(NaIO4)??
? ? ?
1 ?H2O???? 2 ???????????
40
? ? ? ?
-2H2O
I 7
-H2O
IO3-

I 5
41
????????????
?
?-???? ?-??? ?-????1-??-2-???????????????
42
2 ??????????
? ? ?
??????,?-???? ?-???? ?-?????-??? ??????????
43
? ? ? ?
C6H6
- 2HOAc
C6H5OCH2CHO CH2O Pb(OAc)2
44
? ?
Pb(OAc)4
OHC(CH2)3CHO
CH3COOH, 20-25oC
V?? gt 3000
Pb(OAc)4
OHC(CH2)3CHO
V?? 1
CH3COOH, 20-25oC
45
??????????
-AcO -
AcOPb(OAc)3
OHC(CH2)3CHO Pb(OAc)2 HOAc
-H
???
46
3 ?????
???????????????????????????
(1) ??
(2) ???
H2SO4
? HCl
???
???
Al2O3, 420-470oC (??)
47
(3) ????
-H2O
H
???????C?
? ?
-H
?????????????????????????????????
?????????????
V?? 500 16
12 1 0.7

????????,?3o gt 2o gt 1o
48
(4) ??
H
H
49
??? ????
? ????? ? ??????
50
? ?????
1 ????? ???-???? 2 ?????? 3 ??????? 4
???????? (???????)
51
1 ?????(??????)
(1) ?????-??????
Hg(OAc)2, H2O
NaBH4
NaOH 0oC
THF
-AcO-
Hg(OAc)2,
-H
???ROH??H2O,??????,????????-??????
OH2

???????(1)???,(2)????,(3)??????(4)???????
52
(2) ?????????
????
????
????
???-??
???-??
????
?????
????
????
????
??
??
??
??,???
??,???
????
???? ???? ???? ??,??
?? ???? ??? ??,??
1
1
??
??
??
2
2
53
2 ??????? (??????)
(1)????????????????????NaOH???
NaOH-H2O
H2CCHCH2Cl
H2CCHCH2OH
?
NaOH -H2O
?
NaOH -H2O
?
54
(2) SN2?E2?????????????AgOH(???)????????????????E
2? ?-??1oRX?2oRX?????
AgOH
H2O
CH3COO-
DMF 100oC SN2
-OH(?)
CH3COO-

H2O
(3) 3oRX??NaHCO3-H2O????????
55
3 ????????
????
????
56
??????????
??(1)
??
??(2)
???
???? ? ?????
??,????
?(????),???????,???
???
???
?,?(?????),??
1 ??(2)????????????,??-???-??????
??(2)?????????????,??-???-?????? 2
?????????(2),??????????(1)? 3 ?????????????(2)???
????????????????????(2)???
? ?
57
????
???
?? (CH3)2CHCH2 CH2 OH
?
?
?
??
(CH3)2CHCH2MgX CH2O
???
(CH3)2CHCH2CH2OMgX
(CH3)2CHCH2CH2OH
H2O
????????????
??
(CH3)2CHMgX
???
(CH3)2CHCH2CH2OMgX
(CH3)2CHCH2CH2OH
H2O
??????????????
58
???
?? (C2H5)2CHOH
OMgX
???
CH3CH2MgX HCOOC2H5
C2H5CHOC2H5
OMgX
H H2O
CH3CH2MgX
- C2H5OMgX
CH3CH2CHO
C2H5CHC2H5
???
OH
CH3CH2 CH CH2CH3
?
?
?
???????????2oROH
59
???
? ? ? ?
??
???
(CH3)2CHMgX
H H2O
????????????????????
60
???
??
AlCl3
CH3CH2MgX

???
H H2O
3oROH??????
61
???
??
CH3CH2MgX
-ClMgBr
???
H H2O
CH3CH2MgX
??????????3oROH???????????
????????????
62
?????????

???
???
???? (1)

?
?
?
?
?
?

??
?
(2)
?

?
????????????
?
63
? ?
?? 10ml ???? 30ml??
?????
?????
????(95.5) ????(99.5) ????(99.95) ????(?????
???)
??????? ??????? ???(gt12???????)
64
???? ????
??? ??????? ??? ??????????? ??? ???? ???
????
65
??? ???????
???????? ????????
??????????
CH3OCH2CH3 ?????ethylmethyl ether
?????? cyclopentyl phenyl ether
??????????
(CH3)2CCH2CH2OCH3
OH 2-??-4-???-2-?? 4-methoxy-2-methyl-2-butanol
????? cyclopentyloxybenzene
66
??????????????
1 ????????????
????
??
2 ????????????
??(?)oxa ??(?)Azo ??(?)thia
1,4-?????? (1,4-????) (???)
3 ??? ???? ?? ??
4-??-4,5-??-1-?? 4,5-epoxy-4-methyl-1-pentene
67
???????????
??? ???? ? ????
(??)???-18-?-6 ??? ????????????
2,3,11,12-???-1,4,7,10,13,16-???????
68
??? ???????????
? ? ? ?????????????1,4-?????????????,?????
???,???????
????(?????)
69
??? ????
? ?????? ? ?????? ? ???????-???
70
? ??????
1 ??????
RO-Na RX
ROR NaX
ROR NaOSO2OH
ROSO2OH
ROR
2 ??????
NaX
RX
NaOH
C6H5OR NaOSO2OH
C6H5OH ROSO2OH
H2O
ROSO2C6H5
NaOSO2C6H5
71
3 ????????
???SN2
RONa
HOCH2CH2CH2CH2Cl
-Cl-
NaOH
HOCl
???SN2
NaOH
E2
72
4 ?????
HO-CH2-CH2-OH 2
SOCl2
HOCH2CH2OCH2CH2OCH2CH2OH
?????(???)
ClCH2CH2OCH2CH2OCH2CH2Cl
1,2-?(2-????)??
HOCH2CH2OCH2CH2OCH2CH2OH
KOH THF-H2O

ClCH2CH2OCH2CH2OCH2CH2Cl
18-?-6
73
? ??????
-H2O SN2
-H
CH3CH2OCH2CH3
?????,???H2SO4????????????
74
???,1oROH?????, 2oROH??????,3oROH???????,????,????
??
H
(CH3)3COC (CH3)3
-H
-(CH3)3COH
H
-H2O
(CH3)3C
(CH3)3COH
-H
H2O
-H
(CH3)2CCH2
????
75
? ???????-???
(CH3)3CCHCH2 Hg(OOCCF3)2 C2H5OH
-CF3COOH
??
(CH3)3CCHCH2HgOOCCF3
(CH3)3CCHCH3 Hg -OOCCF3
NaBH4
OC2H5
OC2H5
??????????????????,?????????????
????????,???????????? ???????????,??,???????????
?
76
??? ????
? ???? ? ??? ? ? ????????? ? 1,2??????????
?
77
? ????
1 ??
?????????????????????,?????????,??????????
?
O2
(CH3)2CHOCH3
????
??-???H
????????3oH???-???H???C-H?????????
78
2 ????
??????????????????
??
R O2
ROO

ROO (CH3)2CHOCH3
ROOH (CH3)2COCH3
???????????
???

(CH3)2COCH3 O2
(CH3)2COCH3
OO
(CH3)2COCH3 (CH3)2CHOCH3
OO

(CH3)2COCH3 (CH3)2COCH3
OOH
?????
79
? HCl?
CH3CH2OCH2CH3
???HCl??
?????HCl??

RNH3Cl-? CH3CH2OCH2CH3
RNH2?????
???
80
???
RF
ROR BF3
???
CH3CH2I AgBF4 CH3CH2OCH2CH3
ROCH2CH3 CH3CH2OCH2CH3 HBF4
81
? ?????????
CH3OCH3 HI(1mol)
CH3I CH3OH
SN2
HI
CH3OH
CH3I H2O
SN2
82
(CH3)3C OCH3 HI(1mol)
(CH3)3CI CH3OH

SN1
I- (CH3)3C OCH3
I- (CH3)3C CH3OH
H
???????????????,?????CH3OH??SN2???????
????1oC??,??SN2, ??2oC? 3oC??,??SN1?
83
???????
HBr
BrCH2CH2CH2CH2OH
HBr
BrCH2CH2CH2CH2Br
ZnCl2
HCl
ClCH2CH2CH2CH2OH
HCl, ZnCl2
ClCH2CH2CH2CH2Cl
?
HBr
84
????
(1)????????HIgtHBrgtHCl (?) (2)??????,????????
3o??gt 2o??gt 1o??gt??gt???
85
? 1,2??????????
1. ????????????????
H
18
-H
?
?
18
86
???????????
B2H6
2
H2O
(CH3CH2CH2O)3B
CH3CH2CH2OH
87
2. 1,2????????????
88
?????????????
LiAlH4
3
H2O
(CH3)2CHO4Al Li
4 (CH3)2CHOH LiAlO2
89
3. ????????????
(1)??????
190-220oC, 2.2MPa
HOCH2CH2OH
H2O
O.5 H2SO4, 50-70oC
?????(?????)
90
(2)??????????
HOCH2CH2OH
HOCH2CH2OCH2CH2OH
??????(???)
HOCH2CH2OCH2CH2OCH2CH2OH
??????(???)
91
(3)?????
Cl2 500oC ??
ClCH2CHCH2
CH3CHCH2
HOCl
ClCH2CHOHCH2Cl ClCH2CHClCH2OH
Ca(OH)2
NaOH
HCl
H2O