3,4-bis<(tert-butyldimethylsilyl)ethynyl>-3-cyclobutene-1,2-dione bis(ethylene ketal) | 123002-92-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4-bis<(tert-butyldimethylsilyl)ethynyl>-3-cyclobutene-1,2-dione bis(ethylene ketal)
• 英文别名: Tert-butyl-[2-[11-[2-[tert-butyl(dimethyl)silyl]ethynyl]-1,4,7,10-tetraoxadispiro[4.0.46.25]dodec-11-en-12-yl]ethynyl]-dimethylsilane
• CAS: 123002-92-6
• 化学式: C₂₄H₃₈O₄Si₂
• 分子量: 446.734
• InChiKey: YZYVFPOEVDHSQW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.89
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,4-bis<(tert-butyldimethylsilyl)ethynyl>-3-cyclobutene-1,2-dione bis(ethylene ketal) 在 氢氧化钾 、 盐酸羟胺 、 copper(l) chloride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 33.0h， 生成 11-<(E)-2-(n-butylamino)ethenyl>-12-<4-(triisopropylsilyl)-1,3-butadiynyl>-1,4,7,10-tetraoxadispiro<4.0.4.2>dodec-11-ene
  参考文献：
  名称：

  Solution-spray flash vacuum pyrolysis: a new method for the synthesis of linear poliynes with odd numbers of C.tplbond.C bonds from substituted 3,4-dialkynyl-3-cyclobutene-1,2-diones

  摘要：

  We report a new method for the preparation of a wide range of linear poliynes, 1a-1i, with an odd number of C = C bonds. This method is based on solution-spray flash vacuum pyrolysis (SS-FVP) of the readily available 3,4-dialkynyl-3-cyclobutene-1,2-diones 3a-3i. It allows the synthesis of multigram quantities of a series of hexatriynes and decapentaynes from poorly volatile and thermally unstable precursors that cannot be subjected to conventional flash vacuum pyrolysis. Yields of the linear poliynes range from 42 to 99%. Similarly, the dodecahexayne 1j was obtained in 31% yield by SS-FVP of the bis(3-cyclobutene-1,2-dione) 3j. The synthesis of the new 3,4-dialkynyl-3-cyclobutene-1,2-diones 3h-3j via the ketals 7, 10, and 13 is reported. The X-ray crystal structure of 1,10-diphenyl-1,3,5,7,9-decapentayne (1c) was solved, and the crystal packing structure provides valuable information to explain the thermal polymerization behavior observed for this compound in the crystalline state.

  DOI：

  10.1021/ja00018a035
• 作为产物：
  描述：

  Copper(I) tert-butyldimethylsilylacetylide 在 三氟甲磺酸三甲基硅酯 作用下， 以 四氢呋喃 为溶剂， 反应 6.25h， 生成 3,4-bis<(tert-butyldimethylsilyl)ethynyl>-3-cyclobutene-1,2-dione bis(ethylene ketal)
  参考文献：
  名称：

  Precursors to the cyclo[n]carbons: [4n + 2]- and [4n]annulenes with unusual stabilities

  摘要：

  DOI：

  10.1021/ja00199a073

文献信息

• Precursors to the cyclo[n]carbons: from 3,4-dialkynyl-3-cyclobutene-1,2-diones and 3,4-dialkynyl-3-cyclobutene-1,2-diols to cyclobutenodehydroannulenes and higher oxides of carbon
  作者：Yves Rubin、Carolyn B. Knobler、Francois Diederich

  DOI：10.1021/ja00160a047

  日期：1990.2

  downfield resonances of the terminal acetylenic carbon atoms in the sup 13}C NMR spectra of the 3,4-dialkynyl-3-cyclobutene-1,2-diones are discussed. The oxidative Hay coupling of the acetonide of 3,4-diethynyl-3-cyclobutene-1,2-diol or of the bis(ethylene ketal) of 3,4-diethynyl-3-cyclobutene-1,2-dione gave two series of cyclobutenodehydroannulenes with 18pi}-, 24pi}-, and 30pi}-electron perimeters

  一系列新型环丁烯脱氢 (n) 环烯 (n = 18, 24, 30) 已被制备为环碳 Csub 18}、Csub 24} 和 Csub 30} 的有机方法的前体。在通往这些大环的道路上，已经开发了三类新烯二炔的合成条目。双（1-丙炔基）环丙烯酮是在 1-（三甲基甲硅烷基）-1-丙炔与三氯环丙烯鎓四氯铝酸盐的反应中制备的。3,4-dialkynyl-3-cyclobutene-1,2-dionines 是通过 3,4-dichloro-3-cyclobutene-1,2-dione 与 (tri-n-butylstannyl) 炔烃在存在下反应制备的催化量的 Pd(PPhsub 3})sub 4} 或与（三烷基甲硅烷基）乙炔的可溶性铜 (I) 乙炔化物。3,4-二炔基-3-环丁烯-1的sup 13}C NMR谱中末端炔碳原子的特殊低场共振，讨论了 2-diones。3,4-二乙炔-3-环丁烯-1
• Precursors to the cyclo[n]carbons: [4n + 2]- and [4n]annulenes with unusual stabilities
  作者：Yves Rubin、Francois Diederich

  DOI：10.1021/ja00199a073

  日期：1989.8
• Solution-spray flash vacuum pyrolysis: a new method for the synthesis of linear poliynes with odd numbers of C.tplbond.C bonds from substituted 3,4-dialkynyl-3-cyclobutene-1,2-diones
  作者：Yves Rubin、Sophia S. Lin、Carolyn B. Knobler、John Anthony、Armen M. Boldi、Francois Diederich

  DOI：10.1021/ja00018a035

  日期：1991.8

  We report a new method for the preparation of a wide range of linear poliynes, 1a-1i, with an odd number of C = C bonds. This method is based on solution-spray flash vacuum pyrolysis (SS-FVP) of the readily available 3,4-dialkynyl-3-cyclobutene-1,2-diones 3a-3i. It allows the synthesis of multigram quantities of a series of hexatriynes and decapentaynes from poorly volatile and thermally unstable precursors that cannot be subjected to conventional flash vacuum pyrolysis. Yields of the linear poliynes range from 42 to 99%. Similarly, the dodecahexayne 1j was obtained in 31% yield by SS-FVP of the bis(3-cyclobutene-1,2-dione) 3j. The synthesis of the new 3,4-dialkynyl-3-cyclobutene-1,2-diones 3h-3j via the ketals 7, 10, and 13 is reported. The X-ray crystal structure of 1,10-diphenyl-1,3,5,7,9-decapentayne (1c) was solved, and the crystal packing structure provides valuable information to explain the thermal polymerization behavior observed for this compound in the crystalline state.