9,10-dihydro-10-methyl-9-methyleneanthracene | 87551-87-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 9,10-dihydro-10-methyl-9-methyleneanthracene
• 英文别名: 10-methyl-9-methylene-9,10-dihydroanthracene；9-Methyl-10-methylidene-9,10-dihydroanthracene；9-methyl-10-methylidene-9H-anthracene
• CAS: 87551-87-9
• 化学式: C₁₆H₁₄
• 分子量: 206.287
• InChiKey: VSOGDOHSXUZZQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 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-dihydro-10-methyl-9-methyleneanthracene 在 三氯乙酸 作用下， 以 氯仿 为溶剂， 以100%的产率得到9,10-二甲基蒽
  参考文献：
  名称：

  Generation and the ambident character of 9-anthrylmethyl carbanions

  摘要：

  DOI：

  10.1016/s0040-4039(00)86216-4
• 作为产物：
  描述：

  9,10-二甲基蒽 在 (η⁵-C₅Me₅)Ir^III(3-phenylisoquinolin-2'-ido)H 作用下， 以 甲苯 为溶剂， 以50 %的产率得到9,10-dihydro-10-methyl-9-methyleneanthracene
  参考文献：
  名称：

  可见光驱动、铱催化氢原子转移：机理研究、中间体鉴定和催化剂改进

  摘要：

  可见光的收集是合成涉及氢的弱化学键的有力策略，该化学键低于自发 H 2的热力学阈值进化。钢琴凳氢化铱配合物可有效用于有机底物的蓝光驱动氢化和逆热力学去芳构异构化。在这项工作中，结合光谱测量、同位素标记、结构-反应性关系和计算研究已被用于探索这些化学计量和催化反应的机制。对氢化铱催化剂的光物理测量表明产生了长寿命的激发态，主要具有金属到配体电荷转移 (MLCT) 的特性。具有代表性底物蒽的瞬态吸收光谱研究揭示了 MLCT 状态的扩散控制动态猝灭。在猝灭事件后立即检测到蒽的三重态，表明三重态 - 三重态能量转移引发了光催化过程。通过使用三重态光敏剂和 HAT 试剂对苯二酚进行光催化氢化，进一步证明了三重态蒽在后能量转移步骤中的关键作用。DFT 计算支持协调的氢原子转移机制，而不是逐步的电子/质子或质子/电子转移途径。失活通道的动力学监测建立了逆动力学同位素效应，支持可逆 C(sp DFT 计算

  DOI：

  10.1021/jacsau.1c00460

文献信息

• Visible light enables catalytic formation of weak chemical bonds with molecular hydrogen
  作者：Yoonsu Park、Sangmin Kim、Lei Tian、Hongyu Zhong、Gregory D. Scholes、Paul J. Chirik

  DOI：10.1038/s41557-021-00732-z

  日期：2021.10

  bonds of metal amido and metal imido complexes, as well as organic compounds with bond dissociation free energies as low as 31 kcal mol−1. Key to this approach is the bifunctional behaviour of the chromophoric iridium hydride photocatalyst. Activation of molecular hydrogen occurs in the ground state and the resulting iridium hydride harvests visible light to enable spontaneous formation of weak chemical

  合成处于或接近热力学势的弱化学键是化学中的一项基本挑战，其应用范围从催化到生物学再到能源科学。使用分子氢的质子耦合电子转移是合成弱元素-氢键的一种有吸引力的策略，但本征热力学对反应性提出了挑战。在这里，我们描述了金属氨基和金属亚氨基配合物的极弱元素-氢键的直接光催化合成，以及键离解自由能低至 31 kcal mol -1的有机化合物. 这种方法的关键是发色氢化铱光催化剂的双功能行为。分子氢的活化发生在基态，由此产生的氢化铱会收集可见光，从而能够在接近热力学势的情况下自发形成弱化学键，而不会产生副产物。光物理和机理研究证实了基于自由基的反应途径，并强调了这种光驱动方法在促进新催化化学方面的独特性。
• 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).
• 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：——