2H-cyclopentafluorene | 208-69-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 2H-cyclopentafluorene
• 英文别名: 2H-cyclopenta[jk]fluorene；2H-Cyclopentafluoren；2H-Cyclopenta(jk)fluoren；Tetracyclo[6.6.1.02,7.011,15]pentadeca-1(14),2,4,6,8,11(15),12-heptaene
• CAS: 208-69-5
• 化学式: C₁₅H₁₀
• 分子量: 190.244
• InChiKey: ITNDTVZEYBQPEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 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：

  2H-cyclopentafluorene 在 palladium on barium sulfate 氢气 作用下， 生成 Octahydro-1H-cyclopenta(jk)fluoren
  参考文献：
  名称：

  Luger,P. et al., Chemische Berichte, 1976, vol. 109, p. 2596 - 2614

  摘要：

  DOI：
• 作为产物：
  描述：

  1-(methoxymethyl)anthracene 在 四甲基乙二胺 、 叔丁基锂 作用下， 反应 0.25h， 生成 2H-cyclopentafluorene
  参考文献：
  名称：

  Preparative Methodology and Pyrolytic Behavior of Anthrylmonocarbenes:  Synthesis and Chemistry of 1H-Cyclobuta[de]anthracene

  摘要：

  This study involves (1) the behavior of organolithium reagents (1-6), (2) development of efficient methods for preparing 9(7)- and 1(8)-[methoxy(trimethylsilyl)methyl] anthracenes and their analogues, (3) the intramolecular chemistry of the 9(9)- and 1(l0)-anthrylcarbenes generated by pyrolyses of 7 and 8, respectively, and (4) investigation of thermal behavior and bromination of the 1H-cyclobuta[de]anthracene (11) obtained from 9 or 10. alpha-Methoxy-9-anthrylmethyllithium (1), prepared from 9-(methoxymethyl)anthracene (14) and t-BuLi in TMEDA/Et2O/pentane, reacts at C-10 with D2O, chlorotrimethylsilane, dimethyl sulfate, benzoyl chloride, acetaldehyde, benzaldehyde, and acetone to give, after neutralization, 9,10-dihydro-9-(methoxymethylene)-10-substituted- anthracenes 15 and 21a-f. However, lithiation of 9-(thiomethoxymethyl)anthracene (25) with t-BuLi/TMEDA/Et2O/pentane occurs by an apparent radical-anion displacement process to give 9-anthrylmethyllithium (3), which then reacts with chlorotrimethylsilane to yield 9-(trimethylsilylmethyl)anthracene (28). Similarly, 28 is formed from 25 and from 9-(trimethylsilyloxymethyl)-anthracene (29) with lithium and then chlorotrimethylsilane. The electrophiles D2O, dimethyl sulfate, and benzaldehyde react with 3 at its methyl and its C-10 positions. [Methoxy(trimethylsilyl)methyl]arenes 40-42 and 7 are obtained by reactions of their aryllithium and arylmagnesium bromide precursors with bromo(methoxy)methyltrimethylsilane (39). 1-(Methoxymethyl)anthracene (45) is converted conveniently by t-BuLi and chlorotrimethylsilane to 8. Flash-vacuum pyrolyses of 7 and 8 yield 11 preparatively; 11 then thermolyzes to 2H-cyclopenta[jk]fluorene (46). Decomposition of 9-deuterio-10-[methoxy(trimethylsilyl)methyl]anthracene (55) at 650 degrees C/10(-3) mm results in 10(56)- and 1(57)-deuteriocyclobutanthracenes, thus revealing that the 10-deuterio-9-anthrylcarbene inserts to give 56 and also isomerizes extensively before yielding 57. Of note is that 56 isomerizes thermally by C-10-D movement to form 2-deuteriocyclopentafluorene 58, 57 rearranges by Clo-H movement to yield deuteriocyclopentafluorene 59, and 58 and 59 equilibrate 1,5-sigmatropically. Possible mechanisms for the isomerizations of 56 and 57 are outlined. Further, bromine adds rapidly to 11 to form 9,10-dibromo-9,10-dihydro-1H-cyclobuta[de]anthracene (94), which eliminates HBr on warming to yield 10-bromo-1H-cyclobuta[de]anthracene (95).

  DOI：

  10.1021/jo981105b

文献信息

• C₁₅H₁₀ and C₁₅H₁₂ Thermal Chemistry: Phenanthrylcarbene Isomers and Phenylindenes by Falling Solid Flash Vacuum Pyrolysis of Tetrazoles
  作者：Curt Wentrup、Jürgen Becker、Manfred Diehl

  DOI：10.1021/acs.joc.5b01007

  日期：2015.7.17

  products. The products are explained in terms of the formation of N-phenyl-C-phenylethynylnitrile imine/(phenylazo)(phenylethynyl)carbene 45 and its cyclization to 3-(phenylethynyl)-3H-indazole 46b. Pyrolytic loss of N2 from 46b generates C15H10 intermediate 48. Cyclization of 48 to a dibenzocycloheptatetraene derivative and further rearrangements with analogies in the chemistry of phenylcarbene and

  2-苯基-5-（苯基乙炔基）四唑44为C 15 H 10能量表面提供了新的入口。使用降落固体闪蒸热解法（FS-FVP）的闪蒸真空热解法44提供了环戊五[ def ]菲31和环戊[ jk ]芴52作为主要产物。该产品在地层的来解释N-苯基Ç -phenylethynylnitrile亚胺/（苯偶氮基）（苯基乙炔基）卡宾45和它的环化3-（苯基乙炔基）-3- H-吲唑46B。N 2的热解损失从46b中产生C 15 H 10中间体48。将48环化成二苯并环庚二烯衍生物，并进一步类似于苯卡宾和萘基卡宾的化学反应进行重排，得到最终产物。2-苯基-5-苯乙烯基噻唑43的类似热解得到3-苯乙烯基吲唑58，其进一步热解消除了N 2以经由C 15 H 12中间体产生3-和2-苯基茚61和62。
• LUGER P.; TUCHSCHERER C.; GROSSE M.; REWICKI D., CHEM. BER. <CHBE-AM>, 1976, 109, NO 7, 2596-2614
  作者：LUGER P.、 TUCHSCHERER C.、 GROSSE M.、 REWICKI D.

  DOI：——

  日期：——
• Preparative Methodology and Pyrolytic Behavior of Anthrylmonocarbenes:  Synthesis and Chemistry of 1<i>H</i>-Cyclobuta[<i>de</i>]anthracene
  作者：J. Kirby Kendall、Thomas A. Engler、Harold Shechter

  DOI：10.1021/jo981105b

  日期：1999.6.1

  This study involves (1) the behavior of organolithium reagents (1-6), (2) development of efficient methods for preparing 9(7)- and 1(8)-[methoxy(trimethylsilyl)methyl] anthracenes and their analogues, (3) the intramolecular chemistry of the 9(9)- and 1(l0)-anthrylcarbenes generated by pyrolyses of 7 and 8, respectively, and (4) investigation of thermal behavior and bromination of the 1H-cyclobuta[de]anthracene (11) obtained from 9 or 10. alpha-Methoxy-9-anthrylmethyllithium (1), prepared from 9-(methoxymethyl)anthracene (14) and t-BuLi in TMEDA/Et2O/pentane, reacts at C-10 with D2O, chlorotrimethylsilane, dimethyl sulfate, benzoyl chloride, acetaldehyde, benzaldehyde, and acetone to give, after neutralization, 9,10-dihydro-9-(methoxymethylene)-10-substituted- anthracenes 15 and 21a-f. However, lithiation of 9-(thiomethoxymethyl)anthracene (25) with t-BuLi/TMEDA/Et2O/pentane occurs by an apparent radical-anion displacement process to give 9-anthrylmethyllithium (3), which then reacts with chlorotrimethylsilane to yield 9-(trimethylsilylmethyl)anthracene (28). Similarly, 28 is formed from 25 and from 9-(trimethylsilyloxymethyl)-anthracene (29) with lithium and then chlorotrimethylsilane. The electrophiles D2O, dimethyl sulfate, and benzaldehyde react with 3 at its methyl and its C-10 positions. [Methoxy(trimethylsilyl)methyl]arenes 40-42 and 7 are obtained by reactions of their aryllithium and arylmagnesium bromide precursors with bromo(methoxy)methyltrimethylsilane (39). 1-(Methoxymethyl)anthracene (45) is converted conveniently by t-BuLi and chlorotrimethylsilane to 8. Flash-vacuum pyrolyses of 7 and 8 yield 11 preparatively; 11 then thermolyzes to 2H-cyclopenta[jk]fluorene (46). Decomposition of 9-deuterio-10-[methoxy(trimethylsilyl)methyl]anthracene (55) at 650 degrees C/10(-3) mm results in 10(56)- and 1(57)-deuteriocyclobutanthracenes, thus revealing that the 10-deuterio-9-anthrylcarbene inserts to give 56 and also isomerizes extensively before yielding 57. Of note is that 56 isomerizes thermally by C-10-D movement to form 2-deuteriocyclopentafluorene 58, 57 rearranges by Clo-H movement to yield deuteriocyclopentafluorene 59, and 58 and 59 equilibrate 1,5-sigmatropically. Possible mechanisms for the isomerizations of 56 and 57 are outlined. Further, bromine adds rapidly to 11 to form 9,10-dibromo-9,10-dihydro-1H-cyclobuta[de]anthracene (94), which eliminates HBr on warming to yield 10-bromo-1H-cyclobuta[de]anthracene (95).
• Luger,P. et al., Chemische Berichte, 1976, vol. 109, p. 2596 - 2614
  作者：Luger,P. et al.

  DOI：——

  日期：——