1,1-Dimethylspiro<2.4>hepta-4,6-diene | 24321-67-3

• 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-Dimethylspiro<2.4>hepta-4,6-diene
• 英文别名: 1,1-dimethyl-spiro[2,4]hepta-4,6-diene；1,1-dimethylspiro[2.4]hepta-4,6-diene；1,1-Dimethyl-spiro<2.4>heptadien-(4,6)；1,1-Dimethylspiro-<2.4>-4,6-heptadien；1,1-Dimethylspiro<2.4>-4,6-heptadien；1,1-Dimethylspiro<2.4>4,6-heptadien；2,2-Dimethylspiro[2.4]hepta-4,6-diene
• CAS: 24321-67-3
• 化学式: C₉H₁₂
• 分子量: 120.194
• InChiKey: XOKZMFDMDVGPLN-UHFFFAOYSA-N

物化性质

• 沸点：
  40 °C(Press: 12 Torr)
• 密度：
  0.94±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 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-Dimethylspiro<2.4>hepta-4,6-diene 在 potassium diazodicarboxylate 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 以32%的产率得到2,2-Dimethylspiro[2.4]hept-6-ene
  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
• 作为产物：
  描述：

  2-Methylen-6,6-dimethylbicyclo<3.1.0>-3-hexen 以 正戊烷 为溶剂， 生成 1,1-Dimethylspiro<2.4>hepta-4,6-diene
  参考文献：
  名称：

  Slither motion of divalent carbon on .pi. systems in photochemical rearrangements. Exploratory and mechanistic organic photochemistry. LXIV

  摘要：

  DOI：

  10.1021/ja00744a019

文献信息

• Synthesis, Characterization and Stability of Spirodiene Complexes of Molybdenum(II): New Route to <i>ansa</i> ‐Molybdenocene and Ring‐Functionalized Molybdenocene Compounds
  作者：Jan Honzíček、Filipe A. Almeida Paz、Carlos C. Romão

  DOI：10.1002/ejic.200700121

  日期：2007.6

  The reactions of [Mo(CO)2(Cp)(NCCH 3 [ 2 ][BF4] (1) with spiro[2.4]hepta-4,6-diene and spiro[4.4]nona-1,3-diene give the complexes [Moη 4 -C5H4(CH2)2} (CO)2(Cp)][BF4] (3) and [Moη 4 -C 5 H 4 (CH 2 ) 4 }(CO) 2 (Cp)][BF 4 ] (4), respectively. [Moη 4 -C 5 H 4 (CH 2 ) 2 }(CO)2(Cp)][BF4] (3) is stable towards ring opening at room temperature, but its formation is accompanied by small amounts of ring-opening

  [Mo(CO)2(Cp)(NCCH 3 [ 2 ][BF4] (1) 与螺[2.4]庚-4,6-二烯和螺[4.4]壬-1,3-二烯的反应得到络合物 [Moη 4 -C5H4(CH2)2} (CO)2(Cp)][BF4] (3) 和 [Moη 4 -C 5 H 4 (CH 2 ) 4 }(CO) 2 (Cp) )][BF 4 ] (4) [Moη 4 -C 5 H 4 (CH 2 ) 2 }(CO)2(Cp)][BF4] (3) 在室温下对开环稳定，但它的形成伴随着少量的开环产物 [Mo(η 5 -C 5 H 4 CH 2 -η 1 -CH2)(CO)(Cp)][BF4] (5) 和 [Moη 5- C5H4(CH2)2-η 1 -CO}(CO)(Cp)][BF 4 ] (6). 与 1,1-二甲基螺[2.4]庚-4,6-二烯，两种异构体，下式形成[Moη 4 -C 5 H 4 CH
• Accessibility of triplet indenylidene in solution
  作者：Robert A. Moss、Claire M. Young

  DOI：10.1021/ja00356a024

  日期：1983.9

  Par photolyse du diazoindene, generation de l'indenylidene dont la reaction avec l'isobutene, les cis- et trans-butenes conduit a des produits d'addition et d'insertion comportant des cycles cyclopropane

  Par photolyse du diazoindene, generation de l'indenylidene dont la reaction avec l'isobutene, les cis- et trans-butenes pipe a des produits d'addition et d'insertioncomportant des cycle cyclopropane
• Scope and Limitations of Fulvene Syntheses. Preparation of 6-Vinyl-Substituted and -Functionalized Fulvenes. First Examples of Nucleophilic Substitution on a 6-(Chloromethyl)fulvene
  作者：Ihsan Erden、Fu-Pei Xu、Aladin Sadoun、Wyatt Smith、Greg Sheff、Madeleine Ossun

  DOI：10.1021/jo00109a010

  日期：1995.2

  Very few 6-vinylfulvenes have previously been reported in the Literature. In a few cases where Little's procedure (using pyrrolidine as base) has been employed, most enones undergo conjugate attack by the cyclopentadienyl anion followed by either a retroaldol reaction or dihydropentalene formation. In several cases, Diels-Alder reaction of the enone with cyclopentadiene occurs rather than condensation. We have found that in cases where the Little procedure fails to give the desired 6-vinylfulvenes, the Thiele method using NaOH (or NaOMe in some cases) as base gives satisfactory results. In the latter instances, Michael attack is completely suppressed in all but one example. By appropriate choice of base, a variety of fulvenes carrying functional groups on the 6-alkyl position can be prepared. Some of these fulvenes have been shown to undergo further functional group transformations (e.g., nucleophilic substitutions); giving rise to derivatives bearing SR, S(O)R, N-3 or SCN groups.
• Schroeer,W.-D.; Friedrichsen,W., Justus Liebigs Annalen der Chemie, 1978, p. 1648 - 1654
  作者：Schroeer,W.-D.、Friedrichsen,W.

  DOI：——

  日期：——
• Eilbracht, Peter; Totzauer, Walter, Chemische Berichte, 1982, vol. 115, # 5, p. 1669 - 1681
  作者：Eilbracht, Peter、Totzauer, Walter

  DOI：——

  日期：——