3H-cyclobutapyrene | 83469-46-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: 3H-cyclobutapyrene
• 英文别名: 3H-cyclobuta[cd]pyrene；pentacyclo[11.3.1.03,16.06,15.09,14]heptadeca-1(17),3(16),4,6(15),7,9(14),10,12-octaene
• CAS: 83469-46-9
• 化学式: C₁₇H₁₀
• 分子量: 214.266
• InChiKey: WXKWVYDCLLYOPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.06
• 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 、 3H-cyclobutapyrene 以 苯 为溶剂， 以57%的产率得到3H-cyclobutapyrene: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：

  1-(甲氧基甲基)芘 在 四甲基乙二胺 、 叔丁基锂 作用下， -70.0~525.0 ℃ 、9.33 Pa 条件下， 生成 3H-cyclobutapyrene
  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

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：——
• 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%).