2'-methylspiro[bicyclo[2.2.1]hept-5-ene-7,1'-cyclopropane]-2,2,3,3-tetracarbonitrile | 133744-73-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2'-methylspiro[bicyclo[2.2.1]hept-5-ene-7,1'-cyclopropane]-2,2,3,3-tetracarbonitrile
• CAS: 133744-73-7
• 化学式: C₁₄H₁₀N₄
• 分子量: 234.26
• InChiKey: OBDJFAFPMIYFHQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  18.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  95.16
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  1-Methyl-spiro<2.4>heptadien-(4,6) 、 anti-1,1-Dicyclopropyl-4,7-vinylenespiro<2.4>heptane-5,5,6,6-tetracarbonitrile 以 氘代乙腈 为溶剂， 以78%的产率得到2'-methylspiro[bicyclo[2.2.1]hept-5-ene-7,1'-cyclopropane]-2,2,3,3-tetracarbonitrile
  参考文献：
  名称：

  Reactions of spiro[2.4]hept-4-ene derivatives with tetracyanoethylene. Extensive rearrangements involving aza-Cope process

  摘要：

  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.

  DOI：

  10.1021/jo00043a024

文献信息

• 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：——
• 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.