?H

1
12? ???????
2
12-1 ???????????????????
????
?12?1
?H? 11 33 kcal/mol
????????????????????????????, ????????????????????
?
?H 33 kcal/mol
101
101
3
12-2 ???????????
???????
???????
CH3CH3
4
H?H
H2CCH2
- H?H
- H2CCH2
????
5
12-3 p??????????????????????
??????
?????
??????????
6
Markovnikov??????????????????????????
??????????????????????
?????????
7
Markovnikov?????????????????????????
?????C2???????
????1
?????????? (??????)
?????C1???????
????2
?????????? (?????)
8
?????C1?? C2???????????????????
TS-1
??????? (??????)
TS-1
E
?????
????
???????????HX???????,?????????????????, ??????????
???????????????????????????
9
??????????????????????????
???Markovnikov ????????
???????? ?????????
??????
????
????
10
12-4 ??????????????????????
Markovnikov ?
Electrophilic hydration
??
???????????
SN1
E1
11
????????????????????????????????
?????????????
H(-H2O)
- H
H
H
- H
H
?????
?????
??
????
? ??????????interconversion) ? ?????(
thermodynamic control)??????
12
12-5 ????????????????????
??????????
, CCl4
?????? ???????
1-hexene
90 1,2-dibromohexane
?????????????????????????????
Please remember ! ??????????????????????? ?,?????
???????,??????????????????
13
????????????????
(1R,2R)
(1S,2S)
83 yield
cyclohexene
racemic trans-1,2-dibromocyclohexane
2-?????????????
racemic
cis-2-butene
(2R,3R)
(2S,3S)
2,3-dibromobutane
meso
(2R,3S)
(2S,3R)
trans-2-butene
14
?????????????????????????
Bromonium ion (?????????)
??????????? ???????????
???
SN2

???
15
Observing Halonium Ions X-ray Crystallography
Bellucci, Lenoir, Herges, J. Am. Chem. Soc.
1995 Lenoir, Chiappe, Chem. Eur. J. 2003
-SbCl6
SbCl5, Cl2
Kochi, Chem. Commun. 1998
16
12-6 ???????????
????????????????????????????????
- H
- Br-
??? Williamson ether synthesis
17
??????????????????????
?????????????
SN2
?????????????????????????
1-bromo-2-methyl-2-propanol
????????????????????????? ?????????(390??????)
18
12-7 ??????-??????????????
19
Hg
20
12-8 ???????-???????? Markovnikov ????
???????
Hydroboration H. C. Brown 1979 Nobel Prize
??????????
d
d
d-
??p??
21

???-??????
???
??????????
??????????
22
?????????????
????? ?????
(RO)3B 3 NaOH
Na3BO3 3 ROH
23
(No Transcript)
24
12-9 ?????????????????????
????????????????,??????????????????????
25
????????????
SimmonsSmith???
???????
SimmonsSmith??? (??????)
26
(No Transcript)
27
(No Transcript)
28
12-10 ??????????(?????)???????????????
? ? (peracid)
29
cis-??????
????????????????? ???????????
?????????? ????????
30
???????????????
??????
????
?90??
90
n?p?????????
olefin plane
Sarzi-Amadè et al. J. Org. Chem. Dec. 2002
31
anti dihydroxylation (???????????)
?????
SN2
32
(No Transcript)
33
(No Transcript)
34
12-11 ???????????????????????
?????????????????????
?????????
??????????????Os(VI)?????? ???????????????
35
??
OsO4, THF25 ?, 48 h
H2S
OsO4 ??,???
RCOOH
????
??? ???? ????
????
????????????????
36
(No Transcript)
37
????????????????????????????
??????12-3
38
12-12 ????????????
??? (ozone)
39
(No Transcript)
40
12-13 ???????? ? Markovnikov ??????
??????????
???????????????,???????????! 1930?? M. S.
Kharasch????ROOR???????!
41
DH 39 kcal/mol
DH - 17 kcal/mol
104 kcal/mol
DH - 5 kcal/mol
98.5 kcal/mol
DH - 11.5 kcal/mol
HCl ? HI ??????? ???????????? ?,?????????? ???????
(???? ???)
?????????(kcal/mol) H?Cl 103 CC 65
C?Cl 84 H?Br 87 C?Br 71
H?I 71 C?I 56
42
S?H 81 kcal/mol
???? 1 DH -23 kcal/mol ???? 2 DH 3
kcal/mol DH -17.5 kcal/mol
S?C 62 kcal/mol
Bis(1,1-dimethylethyl) peroxide ??(1,1-???????)???
???
Dibenzoyl peroxide ????????????
43
12-14 ?????2??,????????????
? ?
????????p?????
H
H
H
2??
44
???????????????????
45
????????????
1856 Alexander Parke ????? ???????? ?????
? ?????????,? ??????(?????????????
???????????,? ???????????
1891 Louis Chardonnet ???? ???????? ?
????(Chardonnet Silk),? ???????????????
Hermann Staudinger 1953 ????? ?
??????????????????????????????(?? ?????????)
???????????????
46
12-15 ???????
?????????????????
47
????(??)??????
??????
48
??????? ??????
??????
??????
?????
49
??????????????Ziegler-Natta ?????(1963 Nobel
Prize)
??
??
p??
ß??
50
????????????
(1) ???????
(2) ?????????
???????????????,?????
?????????(????)
??????????????????
51
Ziegler-Natta ???????????????
???????
52
12-16 ??? ???????????
Wacker ?
53
12-17 ??????????? ???????
????????????????????????????? ??????????????
?
???????? ??????
????????????????