4H-cyclobutaphenanthrene | 83469-43-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 4H-cyclobutaphenanthrene
• 英文别名: 4H-Cyclobuta[jk]phenanthrene；tetracyclo[7.5.1.02,7.011,15]pentadeca-1(14),2,4,6,8,11(15),12-heptaene
• CAS: 83469-43-6
• 化学式: C₁₅H₁₀
• 分子量: 190.244
• InChiKey: NHFHYJAEVKHXAU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  2,4,7-Trinitro-fluorenon 、 4H-cyclobutaphenanthrene 以 乙醇 、 苯 为溶剂， 以54%的产率得到4H-cyclobutaphenanthrene:2,4,7-trinitrofluoren-9-one complex
  参考文献：
  名称：

  Synthesis of peri-Cyclobutarenes by Thermolysis of [Methoxy(trimethylsilyl)methyl]arenes

  摘要：

  [Methoxy(trimethylsilyl)methyl]arenes are readily prepared by reactions of chlorotrimethylsilane with (alpha-methoxy)arenylmethyllithium reagents as obtained from (methoxymethyl)arenes and t-BuLi. The [methoxy(trimethylsilyl)methyl] arenes eliminate methoxytrimethylsilane at 525-675 degrees C/0.05-0.10 mm to yield peri-cyclobutarenes as derived from arenylcarbenes. Of importance is the fact that the initial arenylcarbenes generated insert into adjacent peri C-H bonds and/or isomerize to other arenylcarbenes that insert into their peri C-H bonds to give peri-cyclobutarenes. Thus, flash-vacuum pyrolysis of 1-[methoxy(trimethylsilyl)methyl]naphthalene (13) at 575-675 degrees C/0.05-0.10 mm yields 1H-cyclobuta[de]naphthalene (6, up to 39%) in practical quantities. 2-[Methoxy(trimethylsilyl)methyl]naphthalene (23) also affords 6 as a major thermolysis product. At 510 degrees C/ 0.05-0.10 mm 4-methoxy-1-[methoxy(trimethylsilyl)methyl]naphthalene (29) decomposes to 4-methoxy-1H-cyclobuta[de]naphthalene (31, 46%). Under similar conditions, 2-methoxy-1-[methoxy(trimethylsilyl)methyl]naphthalene (33) converts to 1,2-dihyrdronaphtho[2,1-b]furan (35, 64%) and naphtho[2,1-b]furan (36, 31%), presumably by insertion of 2-methoxy-1-naphthylcarbene (34) into a C-H bond of its o-methoxy group and then dehydrogenation of the resultant dihydrofuran. Further, 1-[methoxy(trimethylsilyl)methyl]-6-methylnaphthalene (39) pyrolyzes (510 degrees C/0.10-0.20 mm) to 6-methyl-1-naphthylcarbene (40), which isomerizes in part to 7-methyl-1-naphthylcarbene (49); carbenes 40 and 49 then undergo peri C-H insertion to give 3-methyl-1H-cyclobuta[de]naphthalene (41) and 2-methyl-1H-cyclobuta[de]naphthalene (42) in an 8:1 ratio and a combined yield of 44%. The pyrolytic method is particularly valuable for preparing higher peri single carbon atom bridged arenes such as 4H-cyclobuta[jk]phenanthrene (53, 65%) and 3H-cyclobuta[cd]pyrene (59, 86%).

  DOI：

  10.1021/jo981104j
• 作为产物：
  描述：

  9-腈菲 在 sodium azide 、 氯化铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 120.0~600.0 ℃ 、13.33 Pa 条件下， 反应 288.0h， 生成 4H-cyclobutaphenanthrene
  参考文献：
  名称：

  卡宾重排中环丙烯中间体的力场-SCF计算。与实验比较

  摘要：

  苯并环丙烯，环丙烷[ b ]萘，双环[4.1.0]庚-2,4,7-三烯和苯甲酰化衍生物的形成热和几何形状已通过组合力场-SCF程序进行了计算。双环庚烯相对于异构芳基卡宾通过苯甲酰化是稳定的，并且由于失去芳香性和/或增加的应变而不稳定。1-Naphthylcarbene，2- naphthylcarbene，分别用对应的芳烃醛甲苯磺酰腙的钠盐，重氮甲烷，或5- aryltetrazoles的气相热解产生的9- phenanthrylcarbene和9- anthrylcarbene，并重新安排以cyclobuta [ DE ]萘（21），环丁酮[ jk ]菲（33）和环丁酮[ de分别为]蒽（38）。10,11-二氢二苯并[ ad ]环庚基-5-亚烷基（15），类似地由5-重氮-10,11-二氢-5H-二苯并[ ad ]环庚烯（39）生成，重排为5a，9b-二氢-5 H-苯并[3,4]环丁[1

  DOI：

  10.1016/s0040-4020(01)96400-2

文献信息

• Peri-methanoarenes by thermolysis of [methoxy(arenyl)methyl]trimethylsilanes
  作者：T.A. Engler、H. Shechter

  DOI：10.1016/s0040-4039(00)87439-0

  日期：——

  Practical synthesis of varied peri-methanoarenes have been developed.

  已经开发了各种环甲基芳烃的实用合成方法。
• ENGLER, T. A.;SHECHTER, H., TETRAHEDRON LETT., 1982, 23, N 27, 2715-2718
  作者：ENGLER, T. A.、SHECHTER, H.

  DOI：——

  日期：——
• Force field-SCF calculations on cyclopropene intermediates in carbene rearrangements. Comparison with experiment
  作者：Curt Wentrup、Claude Mayor、Jürgen Becker、Hans Jörg Lindner

  DOI：10.1016/s0040-4020(01)96400-2

  日期：1985.1

  derivatives have been calculated with a combined force field-SCF program. The bicycloheptatrienes are stabilized relative to the isomeric arylcarbenes by benzannelation, and destabilized by loss of aromaticity and/or increased strain. 1-Naphthylcarbene, 2-naphthylcarbene, 9-phenanthrylcarbene and 9-anthrylcarbene were generated by gas-phase pyrolysis of the corresponding arene aldehyde tosylhydrazone sodium

  苯并环丙烯，环丙烷[ b ]萘，双环[4.1.0]庚-2,4,7-三烯和苯甲酰化衍生物的形成热和几何形状已通过组合力场-SCF程序进行了计算。双环庚烯相对于异构芳基卡宾通过苯甲酰化是稳定的，并且由于失去芳香性和/或增加的应变而不稳定。1-Naphthylcarbene，2- naphthylcarbene，分别用对应的芳烃醛甲苯磺酰腙的钠盐，重氮甲烷，或5- aryltetrazoles的气相热解产生的9- phenanthrylcarbene和9- anthrylcarbene，并重新安排以cyclobuta [ DE ]萘（21），环丁酮[ jk ]菲（33）和环丁酮[ de分别为]蒽（38）。10,11-二氢二苯并[ ad ]环庚基-5-亚烷基（15），类似地由5-重氮-10,11-二氢-5H-二苯并[ ad ]环庚烯（39）生成，重排为5a，9b-二氢-5 H-苯并[3,4]环丁[1
• Synthesis of <i>peri</i>-Cyclobutarenes by Thermolysis of [Methoxy(trimethylsilyl)methyl]arenes
  作者：Thomas A. Engler、Harold Shechter

  DOI：10.1021/jo981104j

  日期：1999.6.1

  [Methoxy(trimethylsilyl)methyl]arenes are readily prepared by reactions of chlorotrimethylsilane with (alpha-methoxy)arenylmethyllithium reagents as obtained from (methoxymethyl)arenes and t-BuLi. The [methoxy(trimethylsilyl)methyl] arenes eliminate methoxytrimethylsilane at 525-675 degrees C/0.05-0.10 mm to yield peri-cyclobutarenes as derived from arenylcarbenes. Of importance is the fact that the initial arenylcarbenes generated insert into adjacent peri C-H bonds and/or isomerize to other arenylcarbenes that insert into their peri C-H bonds to give peri-cyclobutarenes. Thus, flash-vacuum pyrolysis of 1-[methoxy(trimethylsilyl)methyl]naphthalene (13) at 575-675 degrees C/0.05-0.10 mm yields 1H-cyclobuta[de]naphthalene (6, up to 39%) in practical quantities. 2-[Methoxy(trimethylsilyl)methyl]naphthalene (23) also affords 6 as a major thermolysis product. At 510 degrees C/ 0.05-0.10 mm 4-methoxy-1-[methoxy(trimethylsilyl)methyl]naphthalene (29) decomposes to 4-methoxy-1H-cyclobuta[de]naphthalene (31, 46%). Under similar conditions, 2-methoxy-1-[methoxy(trimethylsilyl)methyl]naphthalene (33) converts to 1,2-dihyrdronaphtho[2,1-b]furan (35, 64%) and naphtho[2,1-b]furan (36, 31%), presumably by insertion of 2-methoxy-1-naphthylcarbene (34) into a C-H bond of its o-methoxy group and then dehydrogenation of the resultant dihydrofuran. Further, 1-[methoxy(trimethylsilyl)methyl]-6-methylnaphthalene (39) pyrolyzes (510 degrees C/0.10-0.20 mm) to 6-methyl-1-naphthylcarbene (40), which isomerizes in part to 7-methyl-1-naphthylcarbene (49); carbenes 40 and 49 then undergo peri C-H insertion to give 3-methyl-1H-cyclobuta[de]naphthalene (41) and 2-methyl-1H-cyclobuta[de]naphthalene (42) in an 8:1 ratio and a combined yield of 44%. The pyrolytic method is particularly valuable for preparing higher peri single carbon atom bridged arenes such as 4H-cyclobuta[jk]phenanthrene (53, 65%) and 3H-cyclobuta[cd]pyrene (59, 86%).