132
M. Sawaguchi et al. / Journal of Fluorine Chemistry 97 (1999) 127±133
the ArN2BF4 or their related compounds (5±10 mmol)
in an organic base±nHF solution (5±11 ml) to the pre-
scribed temperatures (0±1608C). Photo-induced decompo-
sition was carried out by irradiating the reaction mixture
with a 500 W high pressure Hg-lamp (Eikohsha) in a
cooling water bath at lower than 208C. The mixture of
exhausted gases, N2 and BF3, was washed in a 5% NaOH
solution to reap BF3, and N2 was collected in a gas burette
holder. The decomposition rate and coef®cient of the dual
substituent parameter relationships were calculated based
on the amount of generated N2 gas recorded at a constant
period.
3093 (W), 1605 (m), 1504 (s), 1436 (s), 1258 (s), 1221 (m),
1076 (m), 1008 (m), 812 (m),745 (m) cm 1. EI-LR MS (m/
z): 171 (100, M ), 141 (30), 110 (32), 95 (39), 82 (30). EI-
HR MS, Calc. for (M ) C7H6O3NF: m/z 171.0332. Found:
m/z 171.0332.
Acknowledgements
This work was ®nancially supported by the Grant in Aid
from the Ministry of Education, Science, Sports and Culture
of Japan.
3.7. Spectra data
References
4-Hydoroxybenzenediazonium ¯uoroborate: 1H-NMR
(90 MHz, DSMO-d6) ꢃ: 7.14 (d, 2H, J9.2); 8.42 (d, 2H,
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J9.2). IR (nujol): 2270 (s), 1580(s), 1475 (s), 1380 (s),
1
1080 (s), 845(m) cm
Complex of o-benzoquinonediazide and 2-hydroxybenze-
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1
nediazonium¯uoroborate (1): H-NMR (90 MHz, DSMO-
d6) ꢃ: 4.70±5.75 (br. s 1H), 6.61±6.83 (m, 2H), 7.48±7.87
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(m, 2H). IR (nujol): 2250 (m), 2175 (m), 1585 (s), 1460 (s),
1
[4] I.L. Knunyants, G.G. Yakobson, Synthesis of Fluoroorganic
Compounds, Springer, Tokyo, 1985, p. 109.
1375 (s), 1055 (s), 845 (m), 752 (m) cm
.
Complex of p-benzoquinonediazide and 4-Hydroxyben-
zenedeazonium ¯uoroborate (2): 1H-NMR (90 MHz,
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IR (nujol): 2195 (s), 1580 (s), 1460 (s), 1375 (s), 1070 (s),
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850 (m) cm
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p-Benzoquinonediazide (3): 1H-NMR (90 MHz, DSMO-
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Tomita, J. Am. Chem. Soc. 112 (1990) 8563.
d6) ꢃ: 6.18 (d, 2H, J9.8), 7.78 (d, 2H, J9.8). IR (nujol):
2093 (s), 1575 (s), 1528(s), 1392 (s), 1130 (s), 848
1
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Arnold, London, 1985, p. 744.
(m) cm
.
Complex of 1-(4-hydroxyphenyl)-3,3-(1,5-pentanediyl)
1
triazene and piperidine (4): H-NMR (400 MHz, CDCl3)
ꢃ: 1.58 (s, 3H), 1.68 (br. s, 6H), 2.87 (s, 2H), 3.69 (br. s, 4H),
5.40 (s, 1.5H), 6.78 (d, 1H, J8.3 Hz) 7.33 (d, 1H,
J8.3 Hz). IR (KBr): 3431 (w), 2926(w), 1600 (m), 1503
(s), 1438 (s), 1360 (s), 1098 (s), 840 (s) cm 1. Analysis:
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C 65.25, H 8.27, N 19.35.
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1-(2-Methoxy-5-nitrophenyl)-3,3-(1,5-pentanediyl) tria-
1
zene (5): H-NMR (400 MHz, CDCl3) ꢃ: 1.74 (br. s, 6H),
3.88 (br. s, 4H), 4.00 (s, 3H), 6.97 (d, 1H, J9.0Hz), 8.04 (d,
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63 (1990) 2058.
1H, J9.0 Hz), 8.27 (s, 1H). IR (KBr): 2940 (w), 1579 (m),
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1011.
1
1579 (m), 1507 (s), 1337 (s), 1267 (s), 1105 (m) cm
.
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Analysis: Calc. For C12H16N4O3 C 54.54, H 6.10, N 21.20.
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4-Hydoroxybenzenediazonium chloride (6): 1H-NMR
(90 MHz, DSMO-d6) ꢃ: 7.37(d, 2H, J9.5); 8.56 (d, 2H,
J9.5). IR (nujol): 2240 (s), 1570 (s), 1315(s), 1090 (s), 850
1
(m) cm
.
2-Methoxy-5-nitro¯uorobenzene: 1H-NMR (400 MHz,
CDCl3) ꢃ: 4.00 (s, 3H), 7.04 (t, 1H, J8.5 Hz), 8.00 (dd,
1H, J10.7 Hz, J2.7 Hz), 8.06±8.09 (m, 1H). 19F-NMR
(376 MHz, CDCl3) ꢃ: 30.83 (t, 1F, J10.0 Hz). IR(KBr):
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