Silicon - Carbon unsaturated compounds. 74. Thermal behavior of 1-silacyclobut-3-enes generated from the reaction of acylpolysilanes with tert-butylacetylene

Akinobu Naka, Shingo Motoike, Norihito Senba, Joji Ohshita, Atsutaka Kunai, Kazunari Yoshizawa, Mitsuo Ishikawa

研究成果: ジャーナルへの寄稿記事

13 引用 (Scopus)

抄録

The thermolysis of 2-adamantyl-3-tert-butyl-2-(trimethylsiloxy)-1,1 -bis(trimethylsilyl)-1 -silacyclobut-3-ene (2a), obtained by the reaction of adamantoyltris(trimethylsilyl)silane with tert-butylacetylene, at 250 °C for 5 h gave two regioisomers, trans-4-adamantyl-2-tert-butyl- and trans-adamantyl-4-tert-butyl-1-(trimethylsiloxy)-1,2-bis(trimethylsilyl) -1-silacyclobut-3-ene (3a and 4a) in a ratio of 1.5:1, in 93% combined yield. The structure of 4a was confirmed by X-ray crystallographic analysis. Similar thermolysis of 2,3-di-tert-butyl-2-(trimethylsiloxy)-1,1 -bis(trimethylsilyl)-1 -silacyclobut-3-ene (2b), formed by the reaction of pivaloyltris(trimethylsilyl) silane with tert-butylacetylene, however, afforded a single isomer, trans-2,4-di-tert-buty1-1 -(trimethylsiloxy)-1,2-bis(trimethylsilyl)-1 -silacyclobut-3-ene (3b), in 93% yield. When 2a was heated in a sealed tube at 190 °C for 5 h, 1-adamantyl-2-(tert-butyl)-3-[(trimethylsiloxy) bis(trimethylsilyl)silyl]cycloprop-1-ene (5a), which cleanly isomerized at 250 °C to give a mixture of 3a and 4a, was obtained in quantitative yield. Similarly, the thermolysis of 2b at 190 °C for 5 h afforded 1,2-di-tert-butyl-3-[(trimethylsiloxy)bis(trimethylsilyl)silyl]cycloprop-1-ene (5b) in 90% yield, as the sole product. Treatment of 2a with methanol in a sealed glass tube at 160 °C gave an alkene derivative (7a) with an E configuration, arising from addition of methanol to a silicon-carbon double bond in the 1-sila-1,3-butadiene generated from the ring opening of 2a, in 84% yield. Similar treatment of 2b with methanol afforded (E)-1,2-di-tert-butyl-2- [(methoxybis(trimethylsilyl)silyl)methyl]-1-(trimethylsiloxy)ethene (7b) in 83% yield. The co-thermolysis of 2a,b with 2,3-dimethylbutadiene at 180 °C produced the respective silacyclohexene derivatives (8a,b), arising from [2 + 4] cycloaddition of the 1-sila-1,3-butadienes with the butadiene.

元の言語英語
ページ(範囲)2750-2755
ページ数6
ジャーナルOrganometallics
27
発行部数12
DOI
出版物ステータス出版済み - 6 23 2008

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Unsaturated compounds
carbon compounds
Thermolysis
Silicon
Carbon
Methanol
Silanes
silicon
butadiene
methyl alcohol
Derivatives
silanes
Cycloaddition
Alkenes
Isomers
tubes
cycloaddition
X rays
Glass
alkenes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

これを引用

Silicon - Carbon unsaturated compounds. 74. Thermal behavior of 1-silacyclobut-3-enes generated from the reaction of acylpolysilanes with tert-butylacetylene. / Naka, Akinobu; Motoike, Shingo; Senba, Norihito; Ohshita, Joji; Kunai, Atsutaka; Yoshizawa, Kazunari; Ishikawa, Mitsuo.

:: Organometallics, 巻 27, 番号 12, 23.06.2008, p. 2750-2755.

研究成果: ジャーナルへの寄稿記事

Naka, Akinobu ; Motoike, Shingo ; Senba, Norihito ; Ohshita, Joji ; Kunai, Atsutaka ; Yoshizawa, Kazunari ; Ishikawa, Mitsuo. / Silicon - Carbon unsaturated compounds. 74. Thermal behavior of 1-silacyclobut-3-enes generated from the reaction of acylpolysilanes with tert-butylacetylene. :: Organometallics. 2008 ; 巻 27, 番号 12. pp. 2750-2755.
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title = "Silicon - Carbon unsaturated compounds. 74. Thermal behavior of 1-silacyclobut-3-enes generated from the reaction of acylpolysilanes with tert-butylacetylene",
abstract = "The thermolysis of 2-adamantyl-3-tert-butyl-2-(trimethylsiloxy)-1,1 -bis(trimethylsilyl)-1 -silacyclobut-3-ene (2a), obtained by the reaction of adamantoyltris(trimethylsilyl)silane with tert-butylacetylene, at 250 °C for 5 h gave two regioisomers, trans-4-adamantyl-2-tert-butyl- and trans-adamantyl-4-tert-butyl-1-(trimethylsiloxy)-1,2-bis(trimethylsilyl) -1-silacyclobut-3-ene (3a and 4a) in a ratio of 1.5:1, in 93{\%} combined yield. The structure of 4a was confirmed by X-ray crystallographic analysis. Similar thermolysis of 2,3-di-tert-butyl-2-(trimethylsiloxy)-1,1 -bis(trimethylsilyl)-1 -silacyclobut-3-ene (2b), formed by the reaction of pivaloyltris(trimethylsilyl) silane with tert-butylacetylene, however, afforded a single isomer, trans-2,4-di-tert-buty1-1 -(trimethylsiloxy)-1,2-bis(trimethylsilyl)-1 -silacyclobut-3-ene (3b), in 93{\%} yield. When 2a was heated in a sealed tube at 190 °C for 5 h, 1-adamantyl-2-(tert-butyl)-3-[(trimethylsiloxy) bis(trimethylsilyl)silyl]cycloprop-1-ene (5a), which cleanly isomerized at 250 °C to give a mixture of 3a and 4a, was obtained in quantitative yield. Similarly, the thermolysis of 2b at 190 °C for 5 h afforded 1,2-di-tert-butyl-3-[(trimethylsiloxy)bis(trimethylsilyl)silyl]cycloprop-1-ene (5b) in 90{\%} yield, as the sole product. Treatment of 2a with methanol in a sealed glass tube at 160 °C gave an alkene derivative (7a) with an E configuration, arising from addition of methanol to a silicon-carbon double bond in the 1-sila-1,3-butadiene generated from the ring opening of 2a, in 84{\%} yield. Similar treatment of 2b with methanol afforded (E)-1,2-di-tert-butyl-2- [(methoxybis(trimethylsilyl)silyl)methyl]-1-(trimethylsiloxy)ethene (7b) in 83{\%} yield. The co-thermolysis of 2a,b with 2,3-dimethylbutadiene at 180 °C produced the respective silacyclohexene derivatives (8a,b), arising from [2 + 4] cycloaddition of the 1-sila-1,3-butadienes with the butadiene.",
author = "Akinobu Naka and Shingo Motoike and Norihito Senba and Joji Ohshita and Atsutaka Kunai and Kazunari Yoshizawa and Mitsuo Ishikawa",
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TY - JOUR

T1 - Silicon - Carbon unsaturated compounds. 74. Thermal behavior of 1-silacyclobut-3-enes generated from the reaction of acylpolysilanes with tert-butylacetylene

AU - Naka, Akinobu

AU - Motoike, Shingo

AU - Senba, Norihito

AU - Ohshita, Joji

AU - Kunai, Atsutaka

AU - Yoshizawa, Kazunari

AU - Ishikawa, Mitsuo

PY - 2008/6/23

Y1 - 2008/6/23

N2 - The thermolysis of 2-adamantyl-3-tert-butyl-2-(trimethylsiloxy)-1,1 -bis(trimethylsilyl)-1 -silacyclobut-3-ene (2a), obtained by the reaction of adamantoyltris(trimethylsilyl)silane with tert-butylacetylene, at 250 °C for 5 h gave two regioisomers, trans-4-adamantyl-2-tert-butyl- and trans-adamantyl-4-tert-butyl-1-(trimethylsiloxy)-1,2-bis(trimethylsilyl) -1-silacyclobut-3-ene (3a and 4a) in a ratio of 1.5:1, in 93% combined yield. The structure of 4a was confirmed by X-ray crystallographic analysis. Similar thermolysis of 2,3-di-tert-butyl-2-(trimethylsiloxy)-1,1 -bis(trimethylsilyl)-1 -silacyclobut-3-ene (2b), formed by the reaction of pivaloyltris(trimethylsilyl) silane with tert-butylacetylene, however, afforded a single isomer, trans-2,4-di-tert-buty1-1 -(trimethylsiloxy)-1,2-bis(trimethylsilyl)-1 -silacyclobut-3-ene (3b), in 93% yield. When 2a was heated in a sealed tube at 190 °C for 5 h, 1-adamantyl-2-(tert-butyl)-3-[(trimethylsiloxy) bis(trimethylsilyl)silyl]cycloprop-1-ene (5a), which cleanly isomerized at 250 °C to give a mixture of 3a and 4a, was obtained in quantitative yield. Similarly, the thermolysis of 2b at 190 °C for 5 h afforded 1,2-di-tert-butyl-3-[(trimethylsiloxy)bis(trimethylsilyl)silyl]cycloprop-1-ene (5b) in 90% yield, as the sole product. Treatment of 2a with methanol in a sealed glass tube at 160 °C gave an alkene derivative (7a) with an E configuration, arising from addition of methanol to a silicon-carbon double bond in the 1-sila-1,3-butadiene generated from the ring opening of 2a, in 84% yield. Similar treatment of 2b with methanol afforded (E)-1,2-di-tert-butyl-2- [(methoxybis(trimethylsilyl)silyl)methyl]-1-(trimethylsiloxy)ethene (7b) in 83% yield. The co-thermolysis of 2a,b with 2,3-dimethylbutadiene at 180 °C produced the respective silacyclohexene derivatives (8a,b), arising from [2 + 4] cycloaddition of the 1-sila-1,3-butadienes with the butadiene.

AB - The thermolysis of 2-adamantyl-3-tert-butyl-2-(trimethylsiloxy)-1,1 -bis(trimethylsilyl)-1 -silacyclobut-3-ene (2a), obtained by the reaction of adamantoyltris(trimethylsilyl)silane with tert-butylacetylene, at 250 °C for 5 h gave two regioisomers, trans-4-adamantyl-2-tert-butyl- and trans-adamantyl-4-tert-butyl-1-(trimethylsiloxy)-1,2-bis(trimethylsilyl) -1-silacyclobut-3-ene (3a and 4a) in a ratio of 1.5:1, in 93% combined yield. The structure of 4a was confirmed by X-ray crystallographic analysis. Similar thermolysis of 2,3-di-tert-butyl-2-(trimethylsiloxy)-1,1 -bis(trimethylsilyl)-1 -silacyclobut-3-ene (2b), formed by the reaction of pivaloyltris(trimethylsilyl) silane with tert-butylacetylene, however, afforded a single isomer, trans-2,4-di-tert-buty1-1 -(trimethylsiloxy)-1,2-bis(trimethylsilyl)-1 -silacyclobut-3-ene (3b), in 93% yield. When 2a was heated in a sealed tube at 190 °C for 5 h, 1-adamantyl-2-(tert-butyl)-3-[(trimethylsiloxy) bis(trimethylsilyl)silyl]cycloprop-1-ene (5a), which cleanly isomerized at 250 °C to give a mixture of 3a and 4a, was obtained in quantitative yield. Similarly, the thermolysis of 2b at 190 °C for 5 h afforded 1,2-di-tert-butyl-3-[(trimethylsiloxy)bis(trimethylsilyl)silyl]cycloprop-1-ene (5b) in 90% yield, as the sole product. Treatment of 2a with methanol in a sealed glass tube at 160 °C gave an alkene derivative (7a) with an E configuration, arising from addition of methanol to a silicon-carbon double bond in the 1-sila-1,3-butadiene generated from the ring opening of 2a, in 84% yield. Similar treatment of 2b with methanol afforded (E)-1,2-di-tert-butyl-2- [(methoxybis(trimethylsilyl)silyl)methyl]-1-(trimethylsiloxy)ethene (7b) in 83% yield. The co-thermolysis of 2a,b with 2,3-dimethylbutadiene at 180 °C produced the respective silacyclohexene derivatives (8a,b), arising from [2 + 4] cycloaddition of the 1-sila-1,3-butadienes with the butadiene.

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