(2007)
15
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ýÔ!î" PCB $zšú"›ēè²ŀ
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#)ĴÔ/$^„Ē/*‹ķú!|ĝ
(Table 1, entry 1)˜#ĀĽ",/¬Ļ2ĝ'/'
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Ñ!â²ê¹»ħÿī¢#â²2ØĠ˜2
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kåv!°xïĖg](entry 4)(
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10% Ru/C /$ 10% Pt/C $žç 24 Çı$
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PCB $zšú"Ð*›/*ì~#ķ"
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1100d\#ŀç¯.ç¨g]/B47
5–7)#xÍ$ě*-0!(N;H>5P
9>V2$*/É×í
uó/(zšú
2æĪ/"0°xïg] (entries 1, 9, and
mñÞ+‘†0/0+ŀçWŀŒWª’
10)1.0 «Ī$Á֙­˜"$ 10%
²Ëe]#°îq!ęďWÃ2¯/­
Pd/C 2iô
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Table 1
5PêćłPd/CŃ2˜ĕĿĒćz…í2½Ú
HO 2C
ćz/¥ç¥Œxïú"Ĕ’ćzĥĘ/
2n 1PCB2 €% DDT3 #ë×zÞüă
ÊÞ$B479>V"{À/ײ2É/=LRFX
PCB #o"+Ħô„Ē.žçņÇıœk"o
ë×zœĊ/­îq!Ã2¯›
k²ŀ
-"QAIXT` Pd/C ˜™]N;H>5Pī
¢2åv/ĕĿÄESKRXE-ESKT7UQ
AV@TMGT79>ŸÆ"Ĕĸ/2n
4#¶Þ2ĕĿĒćz…í#Ĕ’ćz"Ħô/
Úć8@2iô! PCB #oë×zÞ
1 (0.2 mmol)
Cl
catalyst (10 wt %)
metal
HO 2C
MeOH (2 mL), N2 (balloon)
rt, 24 h
2
entry
catalyst
metal (equiv)
1
:
2
1
2
3
4
5
6
7
8
9
10
10% Pd/C
10% Ru/C
10% Pt/C
–
10% Pd/C
10% Pd/C
10% Pd/C
10% Pd/C
10% Pd/C
10% Pd/C
Mg (1.5)
Mg (1.5)
Mg (1.5)
Mg (1.5)
Fe (1.5)
Cu (1.5)
Ni (1.5)
–
Mg (0.5)
Mg (1.0)
0
30
47
86
92
88
94
95
26
7
:
:
:
:
:
:
:
:
:
:
100
70
53
14
8
12
6
5
74
93
Ratios of 1:2 were determined by GC.
£ijėþ•šėˆzšûÞł502-8585 £ij¤[õáÌʼnZŊńņŃ
Laboratory of Organic Chemistry, Gifu Pharmaceutical University
(5-6-1, Mitahora-higashi, Gifu 502-8585, JAPAN)
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16
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1>HREDU
30%݆ÖpÅ
&ŒÜ…ê£Í݆Öpº«´z Í
*«É,
(entries 2 and 3)¹,±žÀˆ,I7
µPCB ݆Öp"éÉ/°ãPCB †
:S'tèá,‹×Þ*(entries
Ör‰¦(Ú¥aÚ)+ 209 Ñù˞cŠƒ
4 and 5)THF (AQ4S[t¶èá
½zÃdÉ-
¬ÊåÎÒԁO
(entries 6 and 7)Àˆ/N?DUQ€
S:SA)+“æ-Vj‰™+–„†Ö¦
…
Á—ts$šø/°ã0.2–0.4
-- 3.093.91 s
4.94 , PCB ½zÃAroclor
M N?DUQÀ¼[toÅbYä&*-
1242Aroclor 1248 s
Aroclor 1254 /…
PCB
(entries 8 and 9)0.1 M _Yt‹×(entries 1
·ž/۟,݆Öpώ‹×,œ
and 10)0.05 M %”à,t 24 ªò
,†Ö¦‘,L8C;2Mï/ 1.5 ™ï*
‹×(entry 11)üÁ—tèá¡k
2.0 , 2.2 ™ï‡ï×®# PCB
-N?DUQïZç)+L8C;2M
â}݆Öp mÄ Aroclor 1242 ݆Öp
qjÀ,¹Ö,N?D
¿Y 2 ªò_i‹×¬º«Éž˜Ð-
UQ*qjï¹Ör‰eØ-
*ŽõdÉ-APS<*¢
u
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Table 2
HO 2C
10% Pd/C (10 wt %)
Mg (1.5 equiv)
Cl
Table 3
HO 2C
10% Pd/C (10 wt %)
Mg (2.0 or 2.2 equiv vs. Cl#)
solvent, N2 (balloon)
rt, 24 h
1 (0.2 mmol)
2
Clm
entry
solvent
volume
(mL)
substrate
concentration (M)
1
:
2
1
2
3
4
5
6
7
8
9
10
11
MeOH
EtOH
iPrOH
H2O
hexane
THF
toluene
MeOH
MeOH
MeOH
MeOH
2.0
2.0
2.0
2.0
2.0
2.0
2.0
0.5
1.0
3.0
4.0
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.4
0.2
0.07
0.05
0
48
73
61
76
97
92
82
78
0
4
:
:
:
:
:
:
:
:
:
:
:
100
52
27
39
24
3
8
18
22
100
96
Ratios of 1:2 were determined by GC.
MeOH, N 2 (balloon)
rt
Cn
entry
PCBs (m + n)
time (h)
conversion (%)
1
2
3
4
Aroclor 1242 (3.09)
Aroclor 1248 (3.91)
Aroclor 1254 (4.94)
PCB from capacitor (3.29)
2
24
24
24
100
100
100
100
_X•¿T•‚Y,¹Ö/dÉßû
§†ÖpzÃ݆Öpº/ñ̬º²ßû
§†ÖpzÃ݆Öp«o+PCB ݆Öp
…·p'Éƃ’' 400 Wy
s! PCB |«APS<¨¬ifÓ,dÉ
-,]›<9UQ0@H{°ã)+
ÙN?DUQ[…
‘ 10 îï% 10%
Pd/C s
†Ör‰ 1.5 ™ï™,L8C;2MŠ
ƒY²ßû§†ÖpzÃ݆Öpt/°ã
ŽÉp/¤
(Scheme 1)×®JS=SÇÚ¥…Ñù(aÚ
1) a) H. Sajiki, A. Kume, K. Hattori, K. Hirota, Tetrahedron Lett.
ó.*oÅ)݆Öpèá¹Ö÷¸Y
2002, 43, 7247–7250; b) Y. Monguchi, A. Kume, K. Hattori, T.
Maegawa, H. Sajiki, Tetrahedron 2006, 62, 7926–7933.
2) a) H. Sajiki, A. Kume, K. Hattori, H. Nagase, K. Hattori,
Tetrahedron Lett. 2002, 47, 7251–7254; b) A. Kume A., Y.
Monguchi, K. Hattori, H. Nagase, H. Sajiki, Appl. Catal. B
Environ. 2008, 81, 274–282.
3) Y. Monguchi, A. Kume, H. Sajiki, Tetrahedron 2006, 62,
8384–8392.
4) a) H. Sajiki, A. Mori, T. Mizusaki, T. Ikawa, T. Maegawa, K.
HIrota, Org. Lett. 2006, 8, 987–990; b) A. Mori, T. Mizusaki, T.
Ikawa, T. Maegawa, Y. Monguchi, H. Sajiki, Chem. Eur. J. 2007,
13, 1432–1441.
tßû§5QKBQ…©ëg/vìÖ
Ýö¬­`Y5QKBQ…hëg-
Scheme 1
Cl
R
R=
R=
R=
R=
CH 3
OH
NH 2
OCH3
R=
R=
R=
R=
R = CO 2H
R = NH 2
Cl
COC6 H5
COCH 3
CONH 2
C6 H5
R
Cl
R = CO 2H
R = NH 2
R = COCH 3
Cl
Cl
R
CO 2H
Cl
Cl
NH2
Cl

2014 NAKP Overview - North American Deutsch Kurzhaar Club