9-bromo-10-deuterioanthracene | 108748-41-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 9-bromo-10-deuterioanthracene
• 英文别名: 9-Bromoanthracene-10-d；9-bromo-10-deuterio-anthracene；9-Brom-10-deuterio-anthracen；9-Brom-10-deuterioanthracen
• CAS: 108748-41-0
• 化学式: C₁₄H₉Br
• 分子量: 258.122
• InChiKey: ZIRVQSRSPDUEOJ-QOWOAITPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.76
• 重原子数：
  15.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  9-bromo-10-deuterioanthracene 在 正丁基锂 作用下， 反应 0.5h， 生成 1-deutero-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：

  9-溴蒽 在 正丁基锂 、 2,6-二叔丁基吡啶 、 三溴甲烷 、 重水 作用下， 以 乙腈 为溶剂， 生成 9-bromo-10-deuterioanthracene
  参考文献：
  名称：

  Aryl Proton Transfer Reactions of 9-Arylanthracene and 9-Substituted Anthracene Radical Cations with 2,6-Di-tert-butylpyridine

  摘要：

  Radical cations of anthracenes with substituents at the O-position (Br, CN, or NO2) or those of 9-arylanthracenes were observed to undergo proton transfer reactions with 2,6-di-tert-butylpyridine (TBP) to generate the corresponding anthracenyl radical. Under the same conditions 2,6-dimethylpyridine (LUT) undergoes combination reactions with the radical cations, and the proton transfer reactions could not be detected. The characteristic features of the reactions producing the anthracenyl radicals are as follows: (a) primary deuterium kinetic isotope effects are observed on substitution of the 10-H with 10-D, (b) the apparent Arrhenius activation energies vary from -2 to -11 kcal/mol, and (c) 10-Br-substituted anthracenes are formed during bromine atom abstraction from bromoform by the free radicals. The intermediate bromo derivatives are further oxidized under the reaction conditions. A two-step mechanism involving a reversible pi-complex formation followed by rate-determining proton transfer is proposed. The results of the reactions with TBP are compared to those obtained from the corresponding reactions of the radical cations with LUT.

  DOI：

  10.1021/jo00101a015

文献信息

• Anthracene Photodimers. I. Elimination and Substitution Reactions of the Photodimer of 9-Bromoanthracene¹
  作者：Douglas E. Applequist、Robert L. Litle、Edwin C. Friedrich、Robert E. Wall

  DOI：10.1021/ja01511a048

  日期：1959.1