6,6-Dicyclopropylfulven | 4479-62-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 6,6-Dicyclopropylfulven
• 英文别名: 1,3-Cyclopentadiene, 5-(dicyclopropylmethylene)-；5-(dicyclopropylmethylidene)cyclopenta-1,3-diene
• CAS: 4479-62-3
• 化学式: C₁₂H₁₄
• 分子量: 158.243
• InChiKey: BFBOKQAQZQPBHT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  6,6-Dicyclopropylfulven 在 palladium on activated charcoal 氢氧化钾 、 氨 、 氢气 、 氧气 、 copper dichloride 作用下， 以 环己烷 为溶剂， 反应 1.75h， 生成 4,4-dicyclopropyl-2,3-dioxabicyclo<3.3.0>oct-5-ene
  参考文献：
  名称：

  Influence of the Geminal Biscyclopropyl Group in the Reactions of Trimethylenemethane:  Reversible Intersystem Crossing

  摘要：

  The azo compound precursor to Berson's trimethylenemethane (TMM) biradical system, 8-methylene-1,3-cyclopentanediyl, was substituted with two cyclopropyl groups on the exomethylene. Generation of the TMM species by pyrolysis, direct photolysis, and benzophenone-sensitized photolysis resulted in formation of both cyclopropane ring-opened monomer and cyclopropane ring-unopened dimers whose ratio depended directly on temperature and extent of dilution. The ground state appears to be triplet on the basis of ESR spectrometry. The results contrast with previous work (Waldemar Adam) showing that monocyclopropyl substitution on Person's TMM species gives both ring-opened monomer and ring-unopened dimers upon pyrolysis and gives mostly ring-unopened dimer upon direct photolysis at 0-20 degrees C in what appear to be concentration-independent reactions. The observations with the biscyclopropyl-substituted species are consistent with steric effects retarding dimerization of the triplet allowing reversible intersystem crossing back to singlet and perhaps with reduction in the singlet-triplet gap as well.

  DOI：

  10.1021/jo9513727
• 作为产物：
  描述：

  环戊二烯 、 双环丙基酮 在 sodium 作用下， 以 乙醇 为溶剂， 生成 6,6-Dicyclopropylfulven
  参考文献：
  名称：

  Influence of the Geminal Biscyclopropyl Group in the Reactions of Trimethylenemethane:  Reversible Intersystem Crossing

  摘要：

  The azo compound precursor to Berson's trimethylenemethane (TMM) biradical system, 8-methylene-1,3-cyclopentanediyl, was substituted with two cyclopropyl groups on the exomethylene. Generation of the TMM species by pyrolysis, direct photolysis, and benzophenone-sensitized photolysis resulted in formation of both cyclopropane ring-opened monomer and cyclopropane ring-unopened dimers whose ratio depended directly on temperature and extent of dilution. The ground state appears to be triplet on the basis of ESR spectrometry. The results contrast with previous work (Waldemar Adam) showing that monocyclopropyl substitution on Person's TMM species gives both ring-opened monomer and ring-unopened dimers upon pyrolysis and gives mostly ring-unopened dimer upon direct photolysis at 0-20 degrees C in what appear to be concentration-independent reactions. The observations with the biscyclopropyl-substituted species are consistent with steric effects retarding dimerization of the triplet allowing reversible intersystem crossing back to singlet and perhaps with reduction in the singlet-triplet gap as well.

  DOI：

  10.1021/jo9513727

文献信息

• Unexpected Coupling Reaction of 9-Lithiobromomethylene-9H-fluorene with 6,6-Dicyclopropylfulvene
  作者：Gitendra C. Paul、Joseph J. Gajewski

  DOI：10.1055/s-1997-4505

  日期：1997.5

  Metallation of 9-bis(bromomethylene)-9H-fluorene with one equivalent of BuLi at -78°C followed by qhenching with 6,6-dicyclopropylfulvene and subsequent warming (room temperature, 18 h) gave an adduct identified as compound 5 (∼70% yield). Under identical conditions dimethylfulvene and cyclopropylmethylfulvene failed to give a similar adduct. Simple and efficient synthesis of 9-bromomethylene- and 9-bis(bromomethylene)-9H-fluorene are also described.

  在-78°C 下，用 1 个等量的 BuLi 将 9-双（溴亚甲基）-9H-芴金属化，然后用 6,6-二环丙基富烯淬火，随后升温（室温，18 小时），得到一种加合物，确定为化合物 5（产率为 70%）。在相同条件下，二甲基富烯和环丙基甲基富烯未能产生类似的加合物。此外，还介绍了 9-溴亚甲基和 9-双（溴亚甲基）-9H-芴的简单高效合成。
• Possible reversible intersystem crossing in a geminal biscyclopropyl substituted m-xylylene
  作者：Gitendra C. Paul、Joseph J. Gajewski

  DOI：10.1016/0040-4039(95)01871-e

  日期：1995.11

  Reaction of 6,6-dicyclopropylfulvene with isobutylidene gives rise to products derived from a m-xylylene. Both cyclopropane ring opened monomers with o- and p-isocumene-like structures and dimers with intact cyclopropane rings are formed. Since m-xylylene would appear to be a relatively stable triplet and would not be expected to give cyclopropane ring opened monomeric products, it is suggested that

  6,6- dicyclopropylfulvene与异丁基的反应产生了由衍生产品米-xylylene。既形成具有邻-和对-异异丙烯样结构的环丙烷开环单体，又形成具有完整环丙烷环的二聚体。由于米-xylylene似乎是一个相对稳定的三重态，并且不会被预期以得到环丙烷环开的单体的产品，因此建议的位阻效应阻碍二聚体的形成从三重态，从而允许发生了开环单峰的状态。
• Substituted Cyclopentadienides of Magnesium from the Reaction of Dialkylmagnesium with Fulvenes
  作者：Matthias Westerhausen、Nikolaos Makropoulos、Birgit Wieneke、Konstantin Karaghiosoff、Heinrich Nöth、Holger Schwenk-Kircher、Jörg Knizek、Thomas Seifert

  DOI：10.1002/(sici)1099-0682(199807)1998:7<965::aid-ejic965>3.0.co;2-a

  日期：1998.7

  6-dicyclopropylfulvene with MgMe2 in thf solution yields [bis(tetrahydrofuran-O)][irocyclopropane-1,2′(1′-η5-cyclopentadienyl-1′,3′,3′-tricyclopropyl-1′,2′,3′,3a′-tetrahydropentalene)}-3a′-6′-η2-enyl]magnesium. In the absence of β-hydrogen atoms at the organometallic reagent as well as at the fulvene the addition reaction is the only possible reaction pathway. Thus, one Mg–C bond of MgMe2 adds to tetramethylfulvene

  正/仲二丁基镁与 6-甲基-6-苯基-和 6,6-二环丙基富烯反应得到 β-氢化物转移产物 1,1'-双（1-苯乙基）-和 1,1'-双-(二环丙基甲基)氧化镁，分别。后者以重叠构象结晶，而第一个在固态下显示反构象。二甲基镁使 6-甲基-6-苯基富烯去质子化，形成 1,1'-双（1-苯基乙烯-1-基）茂金属，分离后分解。6,6-二环丙基富烯与 MgMe2 在 thf 溶液中的去质子化产生 [双(四氢呋喃-O)][iro环丙烷-1,2'(1'-η5-环戊二烯基-1',3',3'-三环丙基- 1',2',3',3a'-四氢戊烯)}-3a'-6'-η2-烯基]镁。在有机金属试剂和富烯中不存在 β-氢原子的情况下，加成反应是唯一可能的反应途径。因此，MgMe2 的一个 Mg-C 键加到四甲基富烯上，得到定量的二聚甲基镁乙基四甲基环戊二烯化物。桥接甲基在空间上被屏蔽以防止富烯的进一步攻击。
• Hanack,M. et al., Chemische Berichte, 1963, vol. 96, p. 2532 - 2536
  作者：Hanack,M. et al.

  DOI：——

  日期：——
• Lubke, Bernhard; Edelmann, Frank; Behrens, Ulrich, Chemische Berichte, 1983, vol. 116, # 1, p. 11 - 26
  作者：Lubke, Bernhard、Edelmann, Frank、Behrens, Ulrich

  DOI：——

  日期：——