trans-12b,12c-dimethyl-12b,12c-dihydrobenzopyrene | 66093-76-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: trans-12b,12c-dimethyl-12b,12c-dihydrobenzopyrene
• 英文别名: (12bR,12cR)-12b,12c-dimethylbenzo[a]pyrene
• CAS: 66093-76-3
• 化学式: C₂₂H₁₈
• 分子量: 282.385
• InChiKey: KJVCHJCISWBOIL-FGZHOGPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

SDS

反应信息

• 作为反应物：
  描述：

  trans-12b,12c-dimethyl-12b,12c-dihydrobenzopyrene 在 N-fluoro-2,4-dinitroimidazole 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 72.0h， 以4%的产率得到(12bR,12cR)-2-Fluoro-12b,12c-dimethyl-12b,12c-dihydro-benzo[def]chrysene
  参考文献：
  名称：

  Facile one-pot fluorination of polycyclic aromatic hydrocarbons (PAHs) with N-fluoro-2,4-dinitroimidazole; scope and limitation

  摘要：

  The synthetic utility of N-fluoro-2,4-dinitro-imidazole 'NF-2,4-DNI', a recently introduced NF fluorinating agent, has been tested for direct one-pot fluorination of several classes of polycyclic aromatic hydrocarbons, PAHs, namely pyrene, crowded alkyl(cycloalkyl)-pyrenes; hexahydro- and tetrahydro-pyrene; benzo[a] anthracene; benzo[a]- and benzo[e]pyrene; perylene; 2,7-di-tert-butylphenanthrene; chrysene; 9-methylanthracene and anthracene, as well as trans-15, 16-dimethyl-dihydropyrene; azuleno[1,2-a] acenaphthylene and azulene. Although the isolated yields are modest, the ease of handling of the reagent, simple operation (reflux in dichloroethane for 3 days) and the use of 1.1 equivalent of the reagent makes the procedure quite attractive for polynuclear aromatics, avoiding multi-step operations (NO2-PAH-->NH2-PAH-->N-2(+)-PAH-->F-PAH) or the use of toxic or costly reagents (CF3OF, XeF2, etc.); it provides direct one-pot access to a variety of F-PAHs that are not readily made using other fluorinating agents. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-1139(98)00224-3
• 作为产物：
  描述：

  2-Bromomethyl-3-methylnaphthalene 在 盐酸 、 氢氧化钾 、 sodium tetrahydroborate 、 正丁基锂 、 potassium tert-butylate 、 氢溴酸 、 溴 、 二异丁基氢化铝 、 dimethoxymethylium tetrafluoroborate 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 氯仿 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 104.55h， 生成 trans-12b,12c-dimethyl-12b,12c-dihydrobenzopyrene
  参考文献：
  名称：

  苄基化的环烯。6. 对苯苄基环烯的理解：[a]-环单苄基二氢芘的合成与性质

  摘要：

  由 1,3-双（溴甲基）萘（16）和 1,3-双（溴甲基）-2-甲基萘（22）（后者以 18% 的收率从 2 ,3-二甲基萘) 的总产率分别为 7.4% 和 4.8%，使用 Stevens 或 Wittig 重排-霍夫曼消除序列对二硫杂环芳烃 13 和 14，然后对所得环芳二烯 11 和 12 进行价互变异构化。二氢苯并芘酯 3 快速脱除苯并[a]芘(21)，而二甲基衍生物4相对稳定。3 和 4 的内部质子分别仅显示出母体烃 8 和 1 中相应质子屏蔽的约 50%，这种影响归因于苯甲环化环引起的键定位。3 或 4 的残余互向性大于相关的刚性较低的 40 或 41。与母体 1 不同，没有发现 4 到 12 的可逆价异构化的证据。4 的外部质子的耦合常数用于将键序与计算的键序进行比较，结果表明，根据 Giinther 的计算，4 的两个环都显着扰乱了另一个的离域。对 4 和苯并 [a] 芘 (21)

  DOI：

  10.1021/ja00373a036

文献信息

• An Experimental Estimation of Aromaticity Relative to That of Benzene. The Synthesis and NMR Properties of a Series of Highly Annelated Dimethyldihydropyrenes: Bridged Benzannulenes
  作者：Reginald H. Mitchell、Vivekanantan S. Iyer、Nasr Khalifa、Ramanathan Mahadevan、Santhanagopalan Venugopalan、Sirimevan Ananda Weerawarna、Pengzu Zhou

  DOI：10.1021/ja00110a008

  日期：1995.2

  The synthesis of 13 trans-dimethyldihydropyrenes (bridged [14]annulenes) fused to one or more benzene, naphthalene, phenanthrene, phenalene, or quinoxaline rings and 6 cis-dihydropyrene derivatives from benzenoid precursors using either a thiacyclophane route or an electrocyclic addition of a furan to an annulyne followed by deoxygenation is reported. Their H-1 NMR spectra are studied in detail to obtain correlations between (3)J(H,H) coupling constants and the internal methyl proton chemical shifts and also between the latter and the more distant external annulene ring proton shifts. These linear correlations are then used to obtain a relationship between the relative aromaticity of benzene and the fused ring in question, such that the aromaticity of the fused ring can be estimated relative to that of a benzene ring simply from a measurement of chemical shift in the fused annulene.
• The synthesis and trapping of the first [14]annulyne with benzyne like reactivity. A fast route to several annelated bridged annulenes.
  作者：Reginald H. Mitchell、Pengzu Zhou

  DOI：10.1016/s0040-4039(00)98049-3

  日期：1990.1
• Annelated Dimethyldihydropyrenes. Electrophilic Substitution and Valence Isomerization to Metacyclophanedienes
  作者：Reginald H. Mitchell、Vivekanantan S. Iyer、Ramanathan Mahadevan、Santhanagopalan Venugopalan、Pengzu Zhou

  DOI：10.1021/jo9601573

  日期：1996.1.1

  The reversible valence isomerization of cyclophanedienes to dihydropyrenes is discussed for a number of [a]- and [e]-annelated examples, 5 --> 6 and 7 --> 8, and is related to AM1 and MM2+Pi calculations. Only in [e]-fused systems is the isomerization easily seen to be reversible, Electrophilic substitution of dihydropyrenes is discussed. Nitration of the highly annelated 20 gives a mixture of 8- and 7-nitro derivatives, while NBS/DMF bromination of the benzo[a]dihydropyrene 3 gives mostly la-bromo derivative.