9,10-dibromo-9,10-dihydro-1H-cyclobutaanthracene | 235426-26-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 9,10-dibromo-9,10-dihydro-1H-cyclobutaanthracene
• 英文别名: 1,8-Dibromotetracyclo[7.5.1.02,7.013,15]pentadeca-2,4,6,9,11,13(15)-hexaene
• CAS: 235426-26-3
• 化学式: C₁₅H₁₀Br₂
• 分子量: 350.052
• InChiKey: OXLOBUZBFCAACC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 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：

  9,10-dibromo-9,10-dihydro-1H-cyclobutaanthracene 以 苯 为溶剂， 反应 0.33h， 以19%的产率得到10-bromo-1H-cyclobutaanthracene
  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
• 作为产物：
  描述：

  1H-cyclobutaanthracene 在 溴 作用下， 以 四氯化碳 为溶剂， 反应 0.08h， 以62%的产率得到9,10-dibromo-9,10-dihydro-1H-cyclobutaanthracene
  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

• 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).