benzene | 53780-87-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: benzene
• 英文别名: [methoxy(trimethylsilyl)methyl]benzene；[Methoxy(phenyl)methyl]-trimethylsilane
• CAS: 53780-87-3
• 化学式: C₁₁H₁₈OSi
• 分子量: 194.349
• InChiKey: VUWIPHLLGOZYSY-UHFFFAOYSA-N

物化性质

• 沸点：
  204.6±20.0 °C(Predicted)
• 密度：
  0.905±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  benzene 在 tetrabutylammonium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  基于 C-C 键解离的“阳离子池”方法。Monocations 和 Dications 的有效生成

  摘要：

  烷氧基芳基碳正离子的“阳离子池”是通过低温电解氧化 CC 键离解有效产生的。本方法对于与碳亲核试剂反应的指示剂的产生和积累特别有效。

  DOI：

  10.1021/ja050414y
• 作为产物：
  描述：

  (甲氧基甲基)三甲基硅烷 在 溴 作用下， 以 四氢呋喃 、 四氯化碳 为溶剂， 反应 1.0h， 生成 benzene
  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

• A General Organocatalytic System for Enantioselective Radical Conjugate Additions to Enals
  作者：Emilien Le Saux、Dengke Ma、Pablo Bonilla、Catherine M. Holden、Danilo Lustosa、Paolo Melchiorre

  DOI：10.1002/anie.202014876

  日期：2021.3

  enantioselective conjugate addition of carbon‐centered radicals to aliphatic and aromatic enals. The process uses an organic photoredox catalyst, which absorbs blue light to generate radicals from stable precursors, in combination with a chiral amine catalyst, which secures a consistently high level of stereoselectivity. The generality of this catalytic platform is demonstrated by the stereoselective interception

  在此，我们报告了一种通用的基于亚胺离子的催化方法，用于碳中心自由基与脂肪族和芳香族烯醛的对映选择性共轭加成。该工艺使用有机光氧化还原催化剂，该催化剂吸收蓝光以从稳定的前体产生自由基，并结合手性胺催化剂，确保始终如一的高水平立体选择性。该催化平台的通用性通过对多种自由基的立体选择性拦截得到证明，包括通常难以参与不对称过程的不稳定的初级自由基。该系统还用于开发有机催化级联反应，将基于亚胺离子的自由基陷阱与烯胺介导的步骤相结合，一步提供立体化学致密的手性产物。
• Visible-light excitation of iminium ions enables the enantioselective catalytic β-alkylation of enals
  作者：Mattia Silvi、Charlie Verrier、Yannick P. Rey、Luca Buzzetti、Paolo Melchiorre

  DOI：10.1038/nchem.2748

  日期：2017.9

  organisms. Herein we demonstrate that the direct excitation of chiral iminium ions can unlock unconventional reaction pathways, enabling enantioselective catalytic photochemical β-alkylations of enals that cannot be realized via thermal activation. The chemistry uses readily available alkyl silanes, which are recalcitrant to classical conjugate additions, and occurs under illumination by visible-light-emitting

  化学家广泛使用由α，β-不饱和醛与胺催化剂缩合生成的手性亚胺离子，以使手性分子富化。相比之下，它们吸收光并促进立体控制的光化学过程的潜力仍未开发。尽管事实是亚硝酸根离子吸收可见光是自然发生的事件，触发高等生物的视觉机制。本文中，我们证明了手性亚胺离子的直接激发可以解锁非常规的反应途径，从而实现无法通过热活化实现的对映体的对映体选择性催化光化学β-烷基化。化学过程中使用了容易获得的烷基硅烷，这些烷基硅烷对传统的共轭添加物具有顽固性，并在可见光二极管的照明下发生。成功的关键是设计一种具有良好定制电子特性的手性胺催化剂，该催化剂可以产生光敏亚胺离子，同时提供立体化学诱导的来源。该策略有望为对映选择性催化光化学领域的反应设计提供新的机会。
• ANION RADICAL-INDUCED DESILYLATION OF ORGANOSILANE. REACTIONS OF BENZYLSILANES WITH ALDEHYDES AND RELATED COMPOUNDS IN THE PRESENCE OF BUTYLLITHIUM OR LITHIUM METAL
  作者：Shuji Kanemasa、Junji Tanaka、Hideki Nagahama、Otohiko Tsuge

  DOI：10.1246/cl.1985.1223

  日期：1985.8.5

  By the action of butyllithium or lithium metal in such polar aprotic solvent as DMF or HMPA in the presence of aldehydes or related compounds, some benzylsilanes suffer from anion radical-induced desilylation forming benzyl carbanions which add to the aldehydes and related compounds.

  在醛或相关化合物的存在下，通过丁基锂或锂金属在诸如 DMF 或 HMPA 等极性非质子溶剂中的作用，一些苄基硅烷发生阴离子自由基诱导的脱甲硅烷基化作用，形成苄基碳负离子，其添加到醛和相关化合物中。
• A NEW METHOD FOR NUCLEOPHILIC OXYMETHYLATION USING α-ALKOXYSlLANES. SYNTHESIS OF UNSYMMETRICAL 1,2-DIOLS
  作者：Otohiko Tsuge、Shuji Kanemasa、Hideki Nagahama、Junji Tanaka

  DOI：10.1246/cl.1984.1803

  日期：1984.10.5

  Desilylation of α-alkoxysilanes offers the convenient generation of carbinyl carbanions which react with a variety of carbonyl compounds giving mono-protected 1,2-diols of unsymmetrical type. Dehydration of these unsymmetrical diols leads to the regioselective formation of methyl ketones.

  α-烷氧基硅烷的脱烷基化提供了方便的羰基羰基负离子的生成，这些负离子与多种羰基化合物反应，产生不对称类型的单保护1,2-二醇。这些不对称二醇的脱水反应导致区域选择性形成甲基酮。
• Peterson Olefination of (α-Methoxybenzyl)silane with Aldehydes and Ketones Leading to Vinyl Ethers
  作者：Shuji Kanemasa、Junji Tanaka、Hideki Nagahama、Otohiko Tsuge

  DOI：10.1246/bcsj.58.3385

  日期：1985.11

  (α-Methoxybenzyl)trimethylsilane is deprotonated with butyllithium and then allowed to react with a variety of carbonyl compounds giving vinyl ethers which are convertible into methyl ketones under mild conditions.

  (α-甲氧基苄基)三甲基硅烷用丁基锂去质子化，然后与各种羰基化合物反应，得到乙烯基醚，在温和条件下可转化为甲基酮。