spiro[2.4]heptane | 185-49-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 英文名称: spiro[2.4]heptane
• 英文别名: spiro<2.4>heptane；Spiro<2.4>heptan；Spiro[2.4]heptan；spiro[2,4]heptane；Spiro<2,4>heptan；Spiro<4.2>heptan
• CAS: 185-49-9
• 化学式: C₇H₁₂
• 分子量: 96.1723
• InChiKey: HEMCGZPSGYRIOL-UHFFFAOYSA-N

物化性质

• 沸点：
  102-107 °C
• 密度：
  0.8378 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  spiro[2.4]heptane 在 tert-butoxyl radical 作用下， 生成 cyclopentenylethyl radical
  参考文献：
  名称：

  Walton, John C., Journal of the Chemical Society. Perkin transactions II, 1987, p. 1809 - 1814

  摘要：

  DOI：
• 作为产物：
  描述：

  1,1-二甲酸乙酯环戊烷 在 吡啶 、 sodium bis(2-methoxyethoxy)aluminum hydride 、 ethylene diamine tetraacetic acid tetrasodium salt 、 lithium bromide 、 锌 作用下， 以 四氢呋喃 、 乙二醇乙醚 、 乙醇 为溶剂， 生成 spiro[2.4]heptane
  参考文献：
  名称：

  Laser-powered decomposition of spiro[2.n]alkanes (n = 2-5)

  摘要：

  The laser heating of spiro[2.n]alkanes (n = 2-5) and of their 1,1,2,2-tetradeuterated isotopomers reveals dissimilar modes of their thermal decomposition. Spiropentane decomposes into ethene and propadiene via two competing routes: the direct cleavage and the more important cleavage via intermediary methylenecyclobutane. Spirohexane decomposes through two important concurrent pathways which are the expulsions of ethene from the three-membered ring and a more feasible expulsion of ethene from the four-membered ring. Spiroheptane and spirooctane decompose by a radical-chain mechanism and afford complex mixtures of products; upon addition of propene both compounds rearrange into two cycloalkanes wherein the larger ring of the spiroalkane is preserved and substituted with ethylidene and a vinyl group.

  DOI：

  10.1021/jo00079a015

文献信息

• Stahl, Karl-Johannes; Hertzsch, Winfried; Musso, Hans, Liebigs Annalen der Chemie, 1985, # 7, p. 1474 - 1484
  作者：Stahl, Karl-Johannes、Hertzsch, Winfried、Musso, Hans

  DOI：——

  日期：——
• Alder,K. et al., Chemische Berichte, 1960, vol. 93, p. 1888 - 1895
  作者：Alder,K. et al.

  DOI：——

  日期：——
• Lee Hanlan; Ugolick; Fulcher, Inorganic Chemistry, 1980, vol. 19, # 6, p. 1543 - 1551
  作者：Lee Hanlan、Ugolick、Fulcher、Togashi、Bocarsly、Gladysz

  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.
• Slobodin, Ya.M., Journal of Organic Chemistry USSR (English Translation), 1981, vol. 17, p. 459 - 461
  作者：Slobodin, Ya.M.

  DOI：——

  日期：——