9-deuteriomethylanthracene | 88920-57-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 9-deuteriomethylanthracene
• 英文别名: 9-(Deuteriomethyl)anthracene
• CAS: 88920-57-4
• 化学式: C₁₅H₁₂
• 分子量: 193.252
• InChiKey: CPGPAVAKSZHMBP-MICDWDOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• 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

• 作为产物：
  描述：

  9-[(甲硫基)甲基]蒽 在 四甲基乙二胺 、 重水 、 叔丁基锂 作用下， 生成 9-deuteriomethylanthracene
  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

• Deuterium- and Electron-Shuttling Catalysis for Deoxygenative Deuteration of Alcohols
  作者：Bin-Qing He、Xuesong Wu

  DOI：10.1021/acs.orglett.3c02432

  日期：2023.9.8

  A practical and precise method for visible-light-promoted deoxygenative deuteration of common aliphatic alcohols using D2O as the deuterium source is reported. Upon intermediacy of xanthate anions, a variety of primary, secondary, and tertiary alcohols can be facilely transformed into deuterioalkanes with excellent D-incorporation at predicted sites. The deoxygenation and deuteration sequence is catalyzed

  报道了一种使用 D 2 O 作为氘源的可见光促进的常见脂肪醇脱氧氘化的实用且精确的方法。在黄原酸阴离子的中介作用下，各种伯醇、仲醇和叔醇可以很容易地转化为氘代烷烃，并且在预测位点具有出色的 D-结合。脱氧和氘化序列由原位形成的氘代2-巯基吡啶催化，它发挥着氘原子转移催化剂和电子穿梭的双重作用。
• Generation and the ambident character of 9-anthrylmethyl carbanions
  作者：T.A. Engler、H. Shechter

  DOI：10.1016/s0040-4039(00)86216-4

  日期：1983.1
• Takagi, Masato; Hirabe, Tomoatsu; Nojima, Masatomo, Journal of the Chemical Society. Perkin transactions I, 1983, p. 1311 - 1314
  作者：Takagi, Masato、Hirabe, Tomoatsu、Nojima, Masatomo、Kusabayashi, Shigekazu

  DOI：——

  日期：——
• TAKAGI, MASATO;HIRABE, TOMOATSU;NOJIMA, MASATOMO;KUSABAYASHI, SHIGEKAZU, J. CHEM. SOC. PERKIN TRANS., 1983, N 6, 1311-1314
  作者：TAKAGI, MASATO、HIRABE, TOMOATSU、NOJIMA, MASATOMO、KUSABAYASHI, SHIGEKAZU

  DOI：——

  日期：——
• ENGLER, T. A.;SHECHTER, H., TETRAHEDRON LETT., 1983, 24, N 43, 4645-4648
  作者：ENGLER, T. A.、SHECHTER, H.

  DOI：——

  日期：——