1,12,13,14,15,15-hexachloropentacyclo<10.2.1.1^5,8.0^2,11.0^4,9>hexadeca-2(11),6,13-triene | 139259-29-3

• 分子结构分类: 有机化合物 - 有机卤素化合物
• 英文名称: 1,12,13,14,15,15-hexachloropentacyclo<10.2.1.1^5,8.0^2,11.0^4,9>hexadeca-2(11),6,13-triene
• 英文别名: 1,12,13,14,15,15-hexachloropentacyclo[10.2.1.1^5,8.0^2,11.0^4,9]hexadeca-2(11),6,13-triene
• CAS: 139259-29-3；150447-21-5
• 化学式: C₁₆H₁₂Cl₆
• 分子量: 416.989
• InChiKey: CJOSKEWFYVVNHS-HZWKNIRUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.36
• 重原子数：
  22.0
• 可旋转键数：
  0.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1,12,13,14,15,15-hexachloropentacyclo<10.2.1.1^5,8.0^2,11.0^4,9>hexadeca-2(11),6,13-triene 、 四苯基环戊二烯酮 以 二氯甲烷 为溶剂， 反应 336.0h， 以47%的产率得到1,16,17,18,19,19-hexachloro-7,8,9,10-tetraphenylheptacyclo<14.2.1.1^5,12.1^7,10.0^2,15.0^4,13.0^6,11>heneicosa-4(13),8,17-triene-20-one
  参考文献：
  名称：

  Sequential cycloaddition-cycloreversion-cycloaddition-cope rearrangement with an annelated norbornadiene and electrophilic dienes. unusual [π2s + π2a + σ2a] transformation of a pentacyclo-[11.4.0.17,10.04,13.06,11]octadeca-3,8,14,17-tetraene.1

  摘要：

  Hexachloronorbornadiene efficiently forms a 1:1 adduct 3 with 5,6-bismethylenenorbornene. Adduct 3 on reaction with 1,2,3,4-tetrachlorothiophene dioxide (TCTD) under mild conditions gives an SO2 bridged adduct, which loses SO2, the product cycloreverting to give 1,2,3,4-tetrachlorobenzene and an annelated cyclopentadiene 8; 8 reacts further with TCTD to give, in 1:1 ratio, two compounds (14 and 15) shown by mass, C-13 and H-1 NMR spectroscopy and single crystal X-ray structure determination to be the stereoisomeric products of a rare type of specific diene capture by TCTD. Evidence is presented that this result (and analogous examples) is best understood in terms of ''normal'' [4+2]pi cycloadditions to 8 as dienophile towards electron-deficient TCTD, followed by rapid Cope rearrangement of the SO2-bridged intermediate adducts to give the observed products. At low temperatures adduct 3 behaves as expected towards electron-deficient diene tetracyclone ; the [4+2]pi cycloadduct decarbonylates on mild thermolysis, concomitant cycloreversion also giving diene 8. At much higher temperatures in the presence of excess tetracyclone, diene 8 likewise behaves as dienophile; the carbonyl-bridged major cycloadduct decarbonylates to give an intermediate which undergoes an unusual thermally-allowed [pi2s + pi2a + sigma2a] 1,3-shift/cycloaddition, delivering a symmetrical cage-like structure 24, as indicated by mass and C-13 and H-1 NMR spectroscopy.

  DOI：

  10.1016/s0040-4020(01)81298-9
• 作为产物：
  描述：

  1,2,3,4,7,7-六氯双环[2.2.1]庚-2,5-二烯 、 5,6-dimethylenebicyclo[2.2.1]hept-2-ene 以 苯 为溶剂， 反应 24.0h， 以90%的产率得到1,12,13,14,15,15-hexachloropentacyclo<10.2.1.1^5,8.0^2,11.0^4,9>hexadeca-2(11),6,13-triene
  参考文献：
  名称：

  The unusual reaction of tetrachlorothiophene dioxide with an adduct of 5,6-bismethylenenorbornene and hexachloronorbornadiene

  摘要：

  六氯诺尔布尔烯与5,6-双亚甲基诺尔布尔烯形成1:1加合物3。当其与1,2,3,4-四氯噻吩二氧化物反应时，通过脱硫氧（SO2）、环逆转和进一步的环加成，生成两种化合物。这些化合物通过质谱、13C NMR和1H NMR光谱以及单晶X射线结构解析被鉴定为一种稀有特定二烯被过氯噻吩二氧化物捕获的异构体产物；对此及其他例子的合理解释被提出，同时还披露了诺尔布烯sp²C金字塔化的进一步实例。

  DOI：

  10.1039/c39910001763