14? ??????p???

1
14? ??????p???
11
2
????????? ????????? ????????? ?????????
???????????????
3
14-1 ??????? p ?????? 2-??????(????)?
??????????
???????? ????
4
allyl radical ???????
allyl anion ???????
?????
allyl cation ???????
5
2-?????p??????????????
6
2-????????????????
p2 ?????????????? ?????,?????????, ?????,?????????
(???????????)
7
14-2 ???????????????
????????????????
radical allylic substitution
8
(No Transcript)
9
14-3 ????????????????? SN1???SN2??
??????????????? SN1??
10
????14-6
11
14-4 ??????????? ?????????
????
TMEDA?????
????? ????? ???(5 ??)
??????????????????????????????
12
14-5 ????????????????
??? Diene
Alkane Alkadiene
4
2
1
1
1
3
1,3-?????
???
2
1
2
1
4
3
3
1
13
1,3-butadiene????????
14
1,3-?????????p?????????????
119.5
1.47Å
1.34Å
122.9
1.09Å
15
1,3-??????p????
LUMO
HOMO
16
(No Transcript)
17
14-6 ?????????????????????????
1,3-???????????????? ?????????????????
18
d
????????? ???
19
?????? (??)
????? (??)
????0 ??? ???,40 ??? ??
20
(No Transcript)
21
14-7 ?????p??????????????????????
???????????????? ????p?????? (extended p system)
(1) ?????? (2) ????????????? (3) ??????????
22
???????????p???
???????????????????
23
14-8 ??????????? Diels-Alder ????
??????(cycloaddition reaction) ???? 4 2????
24
????????????????
?????(dienophile)
???????????????
25
Diels-Alder ??????
26
Diels-Alder ???????????
Diels-Alder ??????

150160? 20 h


68
cis-isomer
Dimethyl cis-4-cyclohexene-1,2-dicarboxylate (cis-
4-???????-1,2-??????????)

200205? 3.5 h


95
trans-isomer
Dimethyl trans-4-cyclohexene-1,2-dicarboxylate (tr
ans-4-???????-1,2-??????????)
27
Diels-Alder ???????????
tetracyanoethene (?????????)



cis-3,6-dimethyl-4,5-(tetracyano)- cyclohexene (c
is-3,6-????-4,5-(??????)- ???????)
trans,trans-2,4-hexadiene (trans,trans-2,4-??????
)
(E,E)-isomer
28
Diels-Alder ????????????
????????? ????????? ???
29
????
????????????????????????????????????
?????????
30
(No Transcript)
31
???,1,3-?????,1,3,5-??? ?????p????
p ? p??
????
hn
????
32
p???s?????
33
14-9 ??????
?????? (photochemical condition)
34

35
(No Transcript)
36
(No Transcript)
37
(No Transcript)
38
(No Transcript)
39
??????14-3
??????????????????
1,4-?????????
??????(calicheamicin)
40
Woodward-Hoffmann ?
?????? ??
?????? ???
s (??)??
C2 ??
???? ???
41
14-10 ??????????
1,3-?????? ???????? ??
42
??ca. 100 trans ??
??????100 cis ??
TiCl4, AlR3
polyisoprene (???????)
????copolymer
?????? ABABABABABABABABAB ????????
AAAAABBBBBAAAAABBBBBAAA ????????
AABABABBABAABBABABBAAAB ????????
AAAAAAAAAAAAAAAAAAAAAA
B B B B B B
B B B B B B
B B B B B B
43
??ca. 100 trans ??
??????100 cis ??
TiCl4, AlR3
polyisoprene (???????)
????copolymer
?????? ABABABABABABABABAB ????????
AAAAABBBBBAAAAABBBBBAAA ????????
AABABABBABAABBABABBAAAB ????????
AAAAAAAAAAAAAAAAAAAAAA
B B B B B B
B B B B B B
B B B B B B
44
Kevler
(1) ????????????? (2) ?????? (3) ???????????????
???? (4) ?? ???????,???? ????,???????,???
????,?????????????,??????????,?????,???,?????
45
?????????????????
46
(No Transcript)
47
(No Transcript)
48
(No Transcript)