dodecachloroheptafulvalene | 35228-70-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: dodecachloroheptafulvalene
• 英文别名: Dodecachlorheptafulvalen；1,2,3,4,5,6-Hexachloro-7-(2,3,4,5,6,7-hexachlorocyclohepta-2,4,6-trien-1-ylidene)cyclohepta-1,3,5-triene；1,2,3,4,5,6-hexachloro-7-(2,3,4,5,6,7-hexachlorocyclohepta-2,4,6-trien-1-ylidene)cyclohepta-1,3,5-triene
• CAS: 35228-70-7；97906-28-0；97906-29-1
• 化学式: C₁₄Cl₁₂
• 分子量: 593.59
• InChiKey: QGJTZBMDGFOBEA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.5
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  dodecachloroheptafulvalene 生成 十氯菲
  参考文献：
  名称：

  Perchloroheptafulvalene. Its synthesis, structure, and bonding

  摘要：

  DOI：

  10.1021/ja00754a077
• 作为产物：
  描述：

  八氯环庚三烯 在 acetylacetonatobis(ethylene)rhodium(I) 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以68%的产率得到dodecachloroheptafulvalene
  参考文献：
  名称：

  The metal-mediated conversion of octachlorocycloheptatriene into dodecachloroheptafulvalene: a synthetic, structural, and EHMO study

  摘要：

  八氯环庚三烯，C7Cl8，与多种有机金属前体反应，例如Fe2（CO）9，Co2（CO）8，[(C5H5)Fe（CO）2] -，产生十二氯七氟烯，C14C12，12，收率为54％至68％。没有证据支持C7Cl6 = MLn这种类型的卡宾配合物的中间体存在，因此建议反应通过C7Cl8的脱氯反应进行，从而产生六氯环戊烯，其二聚体形成观察到的产物。扩展的Hückel分子轨道计算用于表明氯化卡宾C7Cl6应比相应的母体系统C7Cl6更稳定。EHMO计算还显示，平面七氟烯在电子上不受欢迎，应该优先以S-anti构象存在，就像C14H12一样。X射线晶体学显示，分子C14Cl12，12仅以同构体形式形成，其在高温下异构化为反式结构。 12中的两个七元环的构象与八氯环庚三烯本身非常相似。C7Cl8，3以正交晶系空间群Pnma结晶，a = 7.140（1）Å，b = 13.329（3）Å，c = 12.595（3）Å，V = 1198.7（4）Å3，Z = 4.3采用严重弯曲的船型结构，其中平面C（1）-C（7）-C（6）和C（2）-C（3）-C（4）-C（5）分别与C（1）-C（2）-C（5）-C（6）平面成51.8°和32.4°的角度。关键词：八氯环庚三烯，七氟烯，金属介导的二聚化。

  DOI：

  10.1139/v96-254

文献信息

• Reactions of Dimethoxycarbene with Cyclic Perchlorinated Olefins and Ketones
  作者：James A. Dunn、John Paul Pezacki、Michael J. McGlinchey、John Warkentin

  DOI：10.1021/jo9823846

  日期：1999.6.1

  Reactions of dimnethoxycarbene (2), a carbonyl group equivalent, with perchlorinated olefins and ketones were investigated. Thermolysis of 2,2-dimethoxy-5,5-dimethyl-Delta(3)-1,3,4-oxadiazoline (1) at 110 degrees C generated 2, which reacted with hexachlorocyclopentadiene (4), octachlorocycloheptatriene (12), octachlolobicyclo[3.2.0]hepta-3,6-diene (24), hexachlorotropone (28), hexachlorobicyclo[3.2.0]-hepta-3,6-dien-2-one (32), and tetrachloro-1,4-benzoquinone (35). Reactions of 2 with perchlorinated olefins 4, 12, and 24 led to esters or, in the case of 12, to a ketene acetal. Their formation is rationalized in terms of Michael-like addition and displacement (S(N)2' or S(N)2", if concerted) of allylic chlorine atoms by 2, yielding ion pairs that either dechloromethylate to esters or dechlorinate to a ketene acetal, In contrast, the reactions of 2 with unsaturated perchloroketones 28, 32, and 35 led to ring contraction, ring expansion, and aromatization, respectively. The products from these reactions are consistent with nucleophilic addition of 2 at the carbonyl moiety rather than Michael-type addition. Dimethoxycarbene-d(3) was used to show that demethylation in the latter reaction was intermolecular. Mechanisms for the different reaction courses are proposed.
• Huegel, Helmut M.; Horn, Ernst; Snow, Michael R., Australian Journal of Chemistry, 1985, vol. 38, # 3, p. 383 - 389
  作者：Huegel, Helmut M.、Horn, Ernst、Snow, Michael R.

  DOI：——

  日期：——
• The metal-mediated conversion of octachlorocycloheptatriene into dodecachloroheptafulvalene: a synthetic, structural, and EHMO study
  作者：James A. Dunn、Hari K. Gupta、Alex D. Bain、Michael J. McGlinchey

  DOI：10.1139/v96-254

  日期：1996.11.1

  Octachlorocycloheptatriene, C₇Cl₈, 3, reacts with a variety of organometallic precursors, e.g., Fe₂(CO)₉, Co₂(CO)₈, [(C₅H₅)Fe(CO)₂]⁻, to give dodecachloroheptafulvalene, C₁₄C₁₂,12, in yields ranging from 54 to 68%. There is no evidence to support the intermediacy of carbene complexes of the type C₇Cl₆=ML_n, and it is suggested that the reaction proceeds by the dechlorination of C₇Cl₈ to give hexachlorotropylidene, which dimerizes to the observed product. Extended Hückel molecular orbital calculations are used to show that the chlorinated carbene, C₇Cl₆, should be more stable than the corresponding parent system, C₇Cl₆. The EHMO calculations also reveal that planar heptafulvalenes are electronically disfavored and should exist preferentially in the S-anti conformation, as is the case for C₁₄H₁₂. The molecule C₁₄Cl₁₂,12, is shown by X-ray crystallography to be formed only as the syn conformer, which isomerizes to the anti structure only at high temperature. The conformations of the two seven-membered rings in 12 closely resemble that found in octachlorocycloheptatriene itself. C₇Cl₈, 3, crystallizes in the orthorhombic space group Pnma with a = 7.140(1) Å, b = 13.329(3) Å, c = 12.595(3) Å, and V = 1198.7(4) ų for Z = 4.3 adopts a severely bent boat structure in which the planes C(1)-C(7)-C(6) and C(2)-C(3)-C(4)-C(5) make angles of 51.8° and 32.4°, respectively, with the C(1)-C(2)-C(5)-C(6) plane. Key words: octachlorocycloheptatriene, heptafulvalenes, metal-mediated dimerization.

  八氯环庚三烯，C7Cl8，与多种有机金属前体反应，例如Fe2（CO）9，Co2（CO）8，[(C5H5)Fe（CO）2] -，产生十二氯七氟烯，C14C12，12，收率为54％至68％。没有证据支持C7Cl6 = MLn这种类型的卡宾配合物的中间体存在，因此建议反应通过C7Cl8的脱氯反应进行，从而产生六氯环戊烯，其二聚体形成观察到的产物。扩展的Hückel分子轨道计算用于表明氯化卡宾C7Cl6应比相应的母体系统C7Cl6更稳定。EHMO计算还显示，平面七氟烯在电子上不受欢迎，应该优先以S-anti构象存在，就像C14H12一样。X射线晶体学显示，分子C14Cl12，12仅以同构体形式形成，其在高温下异构化为反式结构。 12中的两个七元环的构象与八氯环庚三烯本身非常相似。C7Cl8，3以正交晶系空间群Pnma结晶，a = 7.140（1）Å，b = 13.329（3）Å，c = 12.595（3）Å，V = 1198.7（4）Å3，Z = 4.3采用严重弯曲的船型结构，其中平面C（1）-C（7）-C（6）和C（2）-C（3）-C（4）-C（5）分别与C（1）-C（2）-C（5）-C（6）平面成51.8°和32.4°的角度。关键词：八氯环庚三烯，七氟烯，金属介导的二聚化。
• Perchloroheptafulvalene. Its synthesis, structure, and bonding
  作者：Michihiro Ishimori、Robert West、Boon Keng Teo、Lawrence F. Dahl

  DOI：10.1021/ja00754a077

  日期：1971.12