| Project/Area Number |
02640404
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Gakushuin University, Faculty of Science |
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Principal Investigator |
SUEHIRO Tadashi Gakushuin University Faculty of Science Professor, 理学部, 教授 (60080462)
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| Co-Investigator(Kenkyū-buntansha) |
TAKAYASHIKI Yukiko Gakushuin University Faculty of Science Assistant, 理学部, 助手 (00226929)
YAMAUCHI Atushi The University of Kyoto College of Liberal Arts and Sciences Assistant Professor, 教養部, 助教授 (10027071)
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| Project Period (FY) |
1990 – 1991
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| Project Status |
Completed (Fiscal Year 1991)
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| Budget Amount *help |
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1991: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1990: ¥1,100,000 (Direct Cost: ¥1,100,000)
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| Keywords | (Aryl) (arylthio) diazenes / ^2H, ^<13>C, ^<15>N-Labled diazenes / ESR / Nitrosobenzene-1- ^<13>C / CIDNP / Diaryl sulfides / (Aryl) (cyclohexadienyl) diazenes / Spin Trapping / (アリリ-ル)(オキソシクロヘキサジェニル)ジアゼン / MNDO RHFーCI / 4ーメトキシフェニルジアゼニルー1ー^<13>C |
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| Research Abstract |
1. (4-t-Butylphenylthio)(4-methoxyphenyl-1- ^<13>C)diazene, (4-t-butylphenylthio)(4-chlorophenyl-1- ^<13>C)diazene, (4-t-butylphenylthio)(1-naphthyl)diazene, its 1- ^<13>C, 1- ^<13>C-1- ^<15>N, 2, 4-d_2-labled compounds, and(4-t-butylphenylthio)(2-naphthyl)diazene were studied by the ESR method to determined hfs constants of H, ^<13>C, and N nuclei. In the ESR experiments by using nitrosobenzene-1- ^<13>C under electrode oxidation we observed a nitroxide of unknown free radical. Using more dilute solutions the experiment will be continued.
2. TRIPPLE resonance ESR technique was unsuccessful to 4-methoxyphenyldiazenyl because of low concentration of the transients.
3. Identification of E lines(delta-135)and A lines(delta-133 ppm)in CIDNP spectra from(aryl)(arylthio)diazenes was completed by reference to chemical shifts of authentic 9 chloroarenes(A)and 18 diaryl sulfides(E).
Signes of his constants of 1-C and 2-C of 4-methoxyphenyldiazenyl in CIDNP is probably reversal to each other with relative intensity ratio-30 : 1 for 1-C to 2-C.
4. Trapping of 4-methoxyphenyldiazenyl by deuterio-tetramethylnitrosobenzene was attempted. The diazenyl-trapped nitroxide was not confirmed, but a nitroxide of unknown radical of higher g-value was detected together with arylphenylnitroxide in a ratio ca. 4 : 1.
5. Spin densities on 1-C and 1-N of aryldiazenyl may explain a rate of H-abstraction by aryl radical relative to diazenyl from substituted toluenes.
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