Yunnan University

1
????
Yunnan University
??????? ?????????????
2
?????? (?)????????????? (?)?????????????????????
(?)???????????? (?)??????????? (?)??ß-?????????
???????????? (?)???????????????
3
10.1 ??????????
1.??
???????????H???-OH????????
R H
ROH
??? ?? O-H ??O ?????SP3 ?????H???1S ?????????
C-O ??O ?????SP3 ?????C???SP3 ????????? ??,O
?????????????????????SP3?????
4
10.1 ??????????
2.?????????
? ??-OH????? ??? CH3CH2OH
??? OHCH2CH2OH
??? ?
? ?-OH???C?????? ?? 1 -CH2OH
?? 2
CHOH
?? 3 ?COH
? ?????????????????????
5
10.1 ??????????
3. ??
? ?????????????????????
? ?????
6
10.1 ??????????
3. ??
????-OH?????,??????? ???-OH???????
? ?????
? ?????????????,???????-OH???
?  ?? ???? ????? ?
7
10.1 ??????????
3. ??

• ?????????????,????????
• ????????????????,?????
• ???????LUPAC???????????

???(???)???,??,?????(????????),?,?,?,?,?,??,?,?,??
,?????? -X,-NO2?????????????
8
10.2 ??????
C1C4R????????? C5C11?????????????? C12????????
???????
1.  ????
????????,????????? a ??????????????
??(32)64.9???(30)-88.6? b. ?C????????????,
???????(CH2)?????18-20??
c.C???????????????????
2. ??
3. ???
??????????C????????? ???????????????
4. ??
?????????,???1 ????????1?
5. ??????????????????????
????
??CO??????10001200cm-1,?? ????10601030cm-1???
???1100cm-1??????1140cm-1??? ??CO??????1230cm-1?
??OH??????,??????OH?36003610cm-1????????????O
H?36003210cm-1??????????
1. IR
2. NMR
NMR??OH??????????????,NMR????d?15.5??????
9
10.3 ????
10.3.1. ???????
???ltHOH ??RO-gtOH-
B.?????????? CH3O-H gt 1gt 2gt 3
C.????? ???????????????,???NaOH??
?????????????(RO-)??????
D.??????????? ?Mg,Al-Hg
10
10.3.2 ?????????
a-CH?????
A.??
?CrO3/?????????????????????????????????????,??????
??????????????????,????????????????????
B. ??
11
10.3.3 ????????
A.?HX??
?? HXHI gt HBr gt HCl
???? gt3gt 2gt1
Lucas?? HCl(?) ZnCl2??????
??Lucas????????????
B. ???
???????????????????????
???????????????(??)?
C.???????,?????????????????????
12
10.3.3 ????????
D.?????????????
SN1?? ??????????????SN1???
SN2?? ??????????SN2?????
13
10.3.4 ????
(C-O ???)
14
10.3.4 ????
1) ????????????????? HX???? HI gt HBr gt
HCl ????? ???? gt ?? gt ?? gt ?? gt CH3OH 2)
??HX?????????,???SN2??,
???????SN1??,
???? SN1??? 3) ß????????????HX????????????
??????SN1?????? ????????????-????(Wagner-
Meerwein)??,??????????
15
10.3.4 ????

• ????????

? ?????????????
16
SOCl2 ????????
10.3.4 ????

• SOCl2 ? ROH ??????? R-Cl
• ? ? R ??????,????????? !!
• ??p288
• ????????????(SNi??),?????????
• ? ?? ??????,??? warden??????
• ??p288-289
• ??? SN2 ????,?????--???,???? ?

17
10.3.5 ??????
??????????????????
???? 3OH gt 2OH gt 1OH
????????????? ??????????????????? ??????
?CH3CH2CH2OH ? CH3CCH
18
10.3.6 a-??????
A.????? ?????????
B.?HIO4??
C.????? ??????,??????,????????
19
10.3.7 ????
?????????????????????????,????p?????
????????
1,2 ????(ß-????)
1,1 ????(a-????)
1,3 ????(?-????)
20

• ?????

• ??????????? ?-??H?,????,?????
• ?-?? ?????

• ???????????????,??1?6??????

21

• ??1

• ??2

22
1. a-????
??????????????????????????,??a-??????????
???
? ?????
1)???????,??HCl??????
2)????????????????
23
? ?????
???????????????,?????????,????????????????
????????????????????,???????,??????????????
24
? ?????
1) ???????? ????????,???????????????
2) ????(insertion) ???????????????C-H???
25
10.4 ????
1.?????
2.??????
??????? ????EtOH NaLiAlH4NaBH4??????
?
26
3.?????-????
??????,????,????????????
???????????????????,?? ???????????????
4.?Grignars????
5. ?????
? ????? ????
27
?
??
28
??? ??1(p321-)

• 2
• 4(1,2,3,4,5,6,7)
• 5

29
??ß-??
??????
1.  ????
E2?????
??
??? ?????? ? kCH3CH2CH2BrCH3CH2OH
?SN2??
?????????????E2??? ß-H????SN2????a-C???
???? E2?SN2??????
30
??ß-??
??????
E1?????
??
??? ?????,? k(CH3)3C-L
31
2. ???????
??ß-??
??????
A. Saytzeff???????????????(??????)???
E2
???(?)????(?)?????????,??,???(?)???,??????????????
????????2-???
E1
32
??ß-??
B. ???????
E23gt 2 gt 1 E13gt 2gt 1
C.  ??????????

• ??????????E2???????,L(??
• ??) ??,?????Saytzeff?????

• ß-H?????????????,ß-H????
• ? ??,?????Saytzeff?????

• ????????,?????Saytzeff???
• ??

33
??ß-??
3. ??????????????
A.????
34
??ß-??
B.????

• ????????,????,???E2
• ????????????SN2???

• ??????????????E1
• ???????????SN1?

• ?????????,??????a-C??,
• ????ß-H????,????E2??????

C.????????????????,??????
D.?????????,????????
35
??ß-??
4. ????????? ????
?C6H5CHBrCHCH3C6H5???????,???????
36
??a-??
1. ?????
???????,???????????????????(Carbenes)
,?a-?????????(CH2)????????????????
CH2CCl2CF2
??????????????????? ??????
37
??a-??
2. ???????
A.?????

• ???????????????
• ????????????

B. ?????

• ????????????????
• ???????
• ??????????42KJ/mol?
• ??????,????????????
• ?????????????????

38
??a-??
3.  ?????
A.?????????
??????????

• ??????????,??????????
• ??????????,???????????
• ????????????,?????????
• ?????????

B.????
??
39
???????
10-3 ?
1.  ?? ??Ar-OH,??????????
2. ?? ??????,??????????????