Silicon-carbon unsaturated compounds. 69. Reactions of silenes produced thermally from pivaloyl- and adamantoyltris (trimethylsilyl) silane with silyl-substituted butadiynes and enynes

Akinobu Naka, Hidenobu Ohnishi, Ikuko Miyahara, Ken Hirotsu, Yoshihito Shiota, Kazunari Yoshizawa, Mitsuo Ishikawa

研究成果: ジャーナルへの寄稿記事

21 引用 (Scopus)

抄録

The thermolysis of pivaloyl- and adamantoyltris(trimethylsilyl)silane (1a and 1b) with bis(trimethylsilyl)butadiyne and bis(dimethylphenylsilyl)butadiyne at 120°C gave regiospecifically 2-trimethylsiloxy-3-silylethynyl-1-silacyclobut-3-ene derivatives (2a, 2b and 3a, 3b), arising from the reaction of silenes generated thermally from 1a and 1b with the butadiynes. Similar treatment of 1a and 1b in the presence of bis(trimethylsilyl)butadiyne and bis-(dimethylphenylsilyl)butadiyne at 160 °C gave 2,5-dihydro-1,2-oxasilole derivatives (4a, 4b and 5a, 5b). When 2a and 2b were heated in the presence of methanol at 160 °C, methanol adducts 6a and 6b were obtained, respectively, as the sole product. The ring-opening processes of 2a and the regiochemistry of [2 + 2] cycloaddition of the silene with bis(silyl)-butadiyne and bis(silyl)but-1-en-3-yne are discussed on the basis of theoretical treatment, The thermolysis of 1a and 1b with bis(tert-butyldimethylsilyl)butadiyne at 160 °C produced [2 + 2] cycloadducts (7a and 7b). With bis(tert-butyldimethylsilyl)butadiyne at 220 °C, 1a and 1b gave 2,5-dihydro-1,2-oxasilole derivatives (8a and 8b). The reaction of 1a and 1b with (E)-1,4-bis(dimethylpnenylsilyl)but-1-en-3-yne and (E)-1,4-bis(pentamethyldisilanyl)-but-1-en-3-yne at 120 °C produced regiospecifically 2trimethylsiloxy-3-[trans-(silyl)ethenyl] -1-silacyclobut-3-ene derivatives (9a, 9b and 10a, 10b). At 200 °C, similar treatment of 1a and 1b with silyl-substituted but-1-en-3-ynes afforded 2,5-dihydro-1,2-oxasilole derivatives (11a, 11b and 12a, 12b, respectively). UV-vis absorption and fluorescence spectra have been reported.

元の言語英語
ページ(範囲)4277-4287
ページ数11
ジャーナルOrganometallics
23
発行部数18
DOI
出版物ステータス出版済み - 8 30 2004

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Unsaturated compounds
carbon compounds
Silanes
Silicon
silanes
Carbon
Derivatives
silicon
methyl alcohol
Thermolysis
cycloaddition
Methanol
adducts
Cycloaddition
absorption spectra
fluorescence
rings
products
Fluorescence

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

これを引用

Silicon-carbon unsaturated compounds. 69. Reactions of silenes produced thermally from pivaloyl- and adamantoyltris (trimethylsilyl) silane with silyl-substituted butadiynes and enynes. / Naka, Akinobu; Ohnishi, Hidenobu; Miyahara, Ikuko; Hirotsu, Ken; Shiota, Yoshihito; Yoshizawa, Kazunari; Ishikawa, Mitsuo.

:: Organometallics, 巻 23, 番号 18, 30.08.2004, p. 4277-4287.

研究成果: ジャーナルへの寄稿記事

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title = "Silicon-carbon unsaturated compounds. 69. Reactions of silenes produced thermally from pivaloyl- and adamantoyltris (trimethylsilyl) silane with silyl-substituted butadiynes and enynes",
abstract = "The thermolysis of pivaloyl- and adamantoyltris(trimethylsilyl)silane (1a and 1b) with bis(trimethylsilyl)butadiyne and bis(dimethylphenylsilyl)butadiyne at 120°C gave regiospecifically 2-trimethylsiloxy-3-silylethynyl-1-silacyclobut-3-ene derivatives (2a, 2b and 3a, 3b), arising from the reaction of silenes generated thermally from 1a and 1b with the butadiynes. Similar treatment of 1a and 1b in the presence of bis(trimethylsilyl)butadiyne and bis-(dimethylphenylsilyl)butadiyne at 160 °C gave 2,5-dihydro-1,2-oxasilole derivatives (4a, 4b and 5a, 5b). When 2a and 2b were heated in the presence of methanol at 160 °C, methanol adducts 6a and 6b were obtained, respectively, as the sole product. The ring-opening processes of 2a and the regiochemistry of [2 + 2] cycloaddition of the silene with bis(silyl)-butadiyne and bis(silyl)but-1-en-3-yne are discussed on the basis of theoretical treatment, The thermolysis of 1a and 1b with bis(tert-butyldimethylsilyl)butadiyne at 160 °C produced [2 + 2] cycloadducts (7a and 7b). With bis(tert-butyldimethylsilyl)butadiyne at 220 °C, 1a and 1b gave 2,5-dihydro-1,2-oxasilole derivatives (8a and 8b). The reaction of 1a and 1b with (E)-1,4-bis(dimethylpnenylsilyl)but-1-en-3-yne and (E)-1,4-bis(pentamethyldisilanyl)-but-1-en-3-yne at 120 °C produced regiospecifically 2trimethylsiloxy-3-[trans-(silyl)ethenyl] -1-silacyclobut-3-ene derivatives (9a, 9b and 10a, 10b). At 200 °C, similar treatment of 1a and 1b with silyl-substituted but-1-en-3-ynes afforded 2,5-dihydro-1,2-oxasilole derivatives (11a, 11b and 12a, 12b, respectively). UV-vis absorption and fluorescence spectra have been reported.",
author = "Akinobu Naka and Hidenobu Ohnishi and Ikuko Miyahara and Ken Hirotsu and Yoshihito Shiota and Kazunari Yoshizawa and Mitsuo Ishikawa",
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T1 - Silicon-carbon unsaturated compounds. 69. Reactions of silenes produced thermally from pivaloyl- and adamantoyltris (trimethylsilyl) silane with silyl-substituted butadiynes and enynes

AU - Naka, Akinobu

AU - Ohnishi, Hidenobu

AU - Miyahara, Ikuko

AU - Hirotsu, Ken

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Ishikawa, Mitsuo

PY - 2004/8/30

Y1 - 2004/8/30

N2 - The thermolysis of pivaloyl- and adamantoyltris(trimethylsilyl)silane (1a and 1b) with bis(trimethylsilyl)butadiyne and bis(dimethylphenylsilyl)butadiyne at 120°C gave regiospecifically 2-trimethylsiloxy-3-silylethynyl-1-silacyclobut-3-ene derivatives (2a, 2b and 3a, 3b), arising from the reaction of silenes generated thermally from 1a and 1b with the butadiynes. Similar treatment of 1a and 1b in the presence of bis(trimethylsilyl)butadiyne and bis-(dimethylphenylsilyl)butadiyne at 160 °C gave 2,5-dihydro-1,2-oxasilole derivatives (4a, 4b and 5a, 5b). When 2a and 2b were heated in the presence of methanol at 160 °C, methanol adducts 6a and 6b were obtained, respectively, as the sole product. The ring-opening processes of 2a and the regiochemistry of [2 + 2] cycloaddition of the silene with bis(silyl)-butadiyne and bis(silyl)but-1-en-3-yne are discussed on the basis of theoretical treatment, The thermolysis of 1a and 1b with bis(tert-butyldimethylsilyl)butadiyne at 160 °C produced [2 + 2] cycloadducts (7a and 7b). With bis(tert-butyldimethylsilyl)butadiyne at 220 °C, 1a and 1b gave 2,5-dihydro-1,2-oxasilole derivatives (8a and 8b). The reaction of 1a and 1b with (E)-1,4-bis(dimethylpnenylsilyl)but-1-en-3-yne and (E)-1,4-bis(pentamethyldisilanyl)-but-1-en-3-yne at 120 °C produced regiospecifically 2trimethylsiloxy-3-[trans-(silyl)ethenyl] -1-silacyclobut-3-ene derivatives (9a, 9b and 10a, 10b). At 200 °C, similar treatment of 1a and 1b with silyl-substituted but-1-en-3-ynes afforded 2,5-dihydro-1,2-oxasilole derivatives (11a, 11b and 12a, 12b, respectively). UV-vis absorption and fluorescence spectra have been reported.

AB - The thermolysis of pivaloyl- and adamantoyltris(trimethylsilyl)silane (1a and 1b) with bis(trimethylsilyl)butadiyne and bis(dimethylphenylsilyl)butadiyne at 120°C gave regiospecifically 2-trimethylsiloxy-3-silylethynyl-1-silacyclobut-3-ene derivatives (2a, 2b and 3a, 3b), arising from the reaction of silenes generated thermally from 1a and 1b with the butadiynes. Similar treatment of 1a and 1b in the presence of bis(trimethylsilyl)butadiyne and bis-(dimethylphenylsilyl)butadiyne at 160 °C gave 2,5-dihydro-1,2-oxasilole derivatives (4a, 4b and 5a, 5b). When 2a and 2b were heated in the presence of methanol at 160 °C, methanol adducts 6a and 6b were obtained, respectively, as the sole product. The ring-opening processes of 2a and the regiochemistry of [2 + 2] cycloaddition of the silene with bis(silyl)-butadiyne and bis(silyl)but-1-en-3-yne are discussed on the basis of theoretical treatment, The thermolysis of 1a and 1b with bis(tert-butyldimethylsilyl)butadiyne at 160 °C produced [2 + 2] cycloadducts (7a and 7b). With bis(tert-butyldimethylsilyl)butadiyne at 220 °C, 1a and 1b gave 2,5-dihydro-1,2-oxasilole derivatives (8a and 8b). The reaction of 1a and 1b with (E)-1,4-bis(dimethylpnenylsilyl)but-1-en-3-yne and (E)-1,4-bis(pentamethyldisilanyl)-but-1-en-3-yne at 120 °C produced regiospecifically 2trimethylsiloxy-3-[trans-(silyl)ethenyl] -1-silacyclobut-3-ene derivatives (9a, 9b and 10a, 10b). At 200 °C, similar treatment of 1a and 1b with silyl-substituted but-1-en-3-ynes afforded 2,5-dihydro-1,2-oxasilole derivatives (11a, 11b and 12a, 12b, respectively). UV-vis absorption and fluorescence spectra have been reported.

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