1,1-Dicyclopropylspiro<2.4>hepta-4,6-diene | 133744-74-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 英文名称: 1,1-Dicyclopropylspiro<2.4>hepta-4,6-diene
• 英文别名: 2,2-Dicyclopropylspiro[2.4]hepta-4,6-diene
• CAS: 133744-74-8
• 化学式: C₁₃H₁₆
• 分子量: 172.27
• InChiKey: ZTEZHBZFVVJZIO-UHFFFAOYSA-N

物化性质

• 沸点：
  249.9±7.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,1-Dicyclopropylspiro<2.4>hepta-4,6-diene 、 四氰基乙烯 生成 anti-1,1-Dicyclopropyl-4,7-vinylenespiro<2.4>heptane-5,5,6,6-tetracarbonitrile
  参考文献：
  名称：

  Nishida, Shinya; Asanuma, Naoki; Tsuji, Takashi, Chemistry Letters, 1991, # 3, p. 495 - 498

  摘要：

  DOI：
• 作为产物：
  描述：

  5-(2,2-dicyclopropylethylidene)cyclopenta-1,3-diene 在 iron(III) chloride 作用下， 以 甲醇 为溶剂， 以48%的产率得到1,1-Dicyclopropylspiro<2.4>hepta-4,6-diene
  参考文献：
  名称：

  甲酰基到苯基的转化：意外的光化学富烯重排

  摘要：

  通过计算设计并研究了涉及富烯和杜瓦苯衍生物作为中间体的将醛转化为芳烃的反应序列。不同富烯的辐照会导致不寻常的光致异构化并产生螺[2.4]庚二烯。

  DOI：

  10.1002/anie.202303119

文献信息

• Reactions of spiro[2.4]hept-4-ene derivatives with tetracyanoethylene. Extensive rearrangements involving aza-Cope process
  作者：Shinya Nishida、Naoki Asanuma、Masashi Murakami、Takashi Tsuji、Toshiro Imai

  DOI：10.1021/jo00043a024

  日期：1992.8

  In CH2Cl2 or CH3CN, 1,1-dicyclopropylspiro[2.4]hept-4-ene (4a) reacted readily with TCNE in a unique to give 4-[N-(dicyclopropylmethylene)amino]-6-methylenebicyclo[3.3.0]oct-3-ene-2,2,3-tricarbonitrile (8a), an imine after extensive rearrangements, and 3,3-dicyclopropylspiro[4.4]non-6-ene-1,1,2,2-tetracarbonitrile (9a), a [sigma-2 + pi-2] cycloadduct. In the reaction of 1-cyclopropyl-1-methyl derivative 4b, 3-(1,1,2,2-tetracyanoethyl)-1-(2-cyclopropylallyl)cyclopentene (10a), formally a vinylogous homoene type adduct, was also produced in addition to 8b and 9b. The reaction of 1,1-dimethyl derivative 4c produced 10b, exclusively. The reaction of 1,1-dicyclopropylbenzo[f]spiro[2.4]hept-4-ene (5a) gave exclusively imine 11, a benzoanalog of 8a, whereas the reaction of saturated benzo derivatives 7 produced 15, corresponding to 9. The production of 8 (as well as 11) and 10 might be depicted in a stepwise dipolar fashion, in which the first formed intermediate 17 will open its spiro-linked three-membered ring to give the second zwitterion 18, which then either cyclizes to a nine-membered adduct 19 or undergoes a proton transfer to give 20. 19 then undergoes aza-Cope rearrangement to afford 8, and 20 ultimately tautomerizes to 10. The parent spiroheptene 4d gave merely a mixture of [pi-2 + pi-2] cycloadduct 14 and [sigma-2 + pi-2] cycloadduct 9c. The formation of 8 and/or 10 is thus limited to occur in such vinylcyclopropanes that hold suitable pendant substituents which can provide greater stabilization to the zwitterionic intermediates. Even in the reaction of spiro[2.4]hepta-4,6-dienes with TCNE, 1,1-dicyclopropyl derivative 2a produced a sizable amount of 3a, corresponding to 8, as well as 16a-16a' in addition to the expected [pi-4 + pi-2] cycloadduct 1a, whereas 2b-2c produced simply the corresponding Diels-Alder adduct.
• NISHIDA, SHINYA;ASANUMA, NAOKI;TSUJI, TAKASHI;IMAI, TOSHIRO, CHEM. LETT.,(1991) N, C. 495-498
  作者：NISHIDA, SHINYA、ASANUMA, NAOKI、TSUJI, TAKASHI、IMAI, TOSHIRO

  DOI：——

  日期：——
• Nishida, Shinya; Asanuma, Naoki; Tsuji, Takashi, Chemistry Letters, 1991, # 3, p. 495 - 498
  作者：Nishida, Shinya、Asanuma, Naoki、Tsuji, Takashi、Imai, Toshiro

  DOI：——

  日期：——
• Toward a Formyl‐to‐Phenyl Conversion: An Unexpected Photochemical Fulvene Rearrangement
  作者：Monika M. Lindner、M. Wasim Alachraf、Benjamin Mitschke、Philipp Schulze、Markus Leutzsch、Benjamin List

  DOI：10.1002/anie.202303119

  日期：2023.8.28

  A reaction sequence toward a conversion of aldehydes into arenes involving a fulvene and a Dewar benzene derivative as intermediates was designed and studied computationally. Irradiation of different fulvenes results in an unusual photoisomerization and leads to spiro[2.4]heptadienes.

  通过计算设计并研究了涉及富烯和杜瓦苯衍生物作为中间体的将醛转化为芳烃的反应序列。不同富烯的辐照会导致不寻常的光致异构化并产生螺[2.4]庚二烯。