3-Phenyl-2-trimethylsilylcyclobutene-1,2-dione | 154473-76-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3-Phenyl-2-trimethylsilylcyclobutene-1,2-dione
• 英文别名: 3-phenyl-4-trimethylsilyl-3-cyclobutene-1,2-dione；3-Phenyl-4-trimethylsilylcyclobut-3-ene-1,2-dione
• CAS: 154473-76-4
• 化学式: C₁₃H₁₄O₂Si
• 分子量: 230.338
• InChiKey: PMSAOQPFUUUDCN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.49
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-Phenyl-2-trimethylsilylcyclobutene-1,2-dione 以 氘代氯仿 、 氯仿 为溶剂， 反应 28.0h， 生成 (Z)-4-(Ethoxycarbonylmethylene)-3-phenyl-2-trimethylsilylcyclobuten-1-one
  参考文献：
  名称：

  烯基烯酮：亲核、亲电和环加成反应中的多功能底物

  摘要：

  4-美基-2-三甲基硅基-3-苯基环丁烯酮 3 由相应的环丁烯二酮 7 经过特贝反应和彼得森反应获得，并在光解后生成 3-苯基取代的烯丙基酮烯 R1CH=C=C(Ph)C(SiMe3)=C=O 4。这些烯丙基酮烯在环闭合回到 3 时比 3-三甲基硅基类似物 1 更具反应性，这一预测基于分子轨道计算。烯丙基酮烯 1 和 4 的反应包括与 H2O 的加成后环化形成丁烯内酯 13，与苯胺的加成生成烯丙基氨基酸 14 和内酰胺 15，与 CF3CO2H 的加成形成烯丙基羧酸 17，以 1,4 方式与 Br2 的加成生成五烯酸衍生物 18，以及与间氯过苯甲酸反应生成独特的烯丙基酰基硅烷 23。[4 + 1] 环加成反应中 1 和 4 与 Me3SiCHN2 生成亚甲基环戊烯酮 24 和 25，而乙醛在 BF3·OEt2 催化下发生 [2 + 2] 环加成形成 β-内酯。[4 + 2] 环加成与苯甲醛反应形成高度拥挤的外亚甲基戊烯内酯 29，与 TCNE 反应生成亚甲基环己烯酮 31。

  DOI：

  10.1055/s-2000-6345
• 作为产物：
  描述：

  4,4-Dichloro-3-phenyl-2-trimethylsilylcyclobut-2-en-1-one 在 硫酸 作用下， 生成 3-Phenyl-2-trimethylsilylcyclobutene-1,2-dione
  参考文献：
  名称：

  Formation and Reactivity of Unsymmetrical Bis(ketenes): 2-Phenyl- and 2-Methyl-3-(trimethylsilyl)-1,3-butadiene-1,4-diones

  摘要：

  DOI：

  10.1021/ja00085a055

文献信息

• Generation of 1,2-Bisketenes from Cyclobutene-1,2-diones by Flash Photolysis and Ring Closure Kinetics¹^a
  作者：Annette D. Allen、Jim D. Colomvakos、François Diederich、Ian Egle、Xiaokuai Hao、Ronghua Liu、Janusz Lusztyk、Jihai Ma、Michael A. McAllister、Yves Rubin、Kuangsen Sung、Thomas T. Tidwell、Brian D. Wagner

  DOI：10.1021/ja9722685

  日期：1997.12.17

  The bisketenes 2 have been generated by flash photolysis, and the kinetics of their conversion to 1 have been studied by time-resolved infrared and ultraviolet spectroscopy. The rate constants of the ring closure of 2 are correlated by the ketene stabilization parameters (SE) and with calculated barriers. The rate constant of ring closure of the di-tert-butyl bisketene 2g to cyclobutenedione 1g is

  环丁烯-1,2-二酮 (1) 和 1,2-双烯酮 (RCCO)2 (2) 的相互转化已针对不同的取代基组合 R = H、Me、t-Bu、Ph、Me3Si、CN、 Cl、Br、R1O、炔基和PhS。双烯酮 2 是通过闪光光解产生的，并且通过时间分辨红外和紫外光谱研究了它们转化为 1 的动力学。2 的闭环速率常数与乙烯酮稳定参数 (SE) 和计算的势垒相关。二叔丁基双烯酮 2g 至环丁烯二酮 1g 的闭环速率常数仅比二甲基类似物小 40 倍，显示出相当适中的空间位阻。quinoketene 2s 的闭环速度很快，但没有根据计算的几何和热力学因素预期的那么快。
• Reactive Iron Carbonyl Reagents via Reaction of Metal Alkoxides with Fe(CO)₅ or Fe₂(CO)₉: Synthesis of Cyclobutenediones via Double Carbonylation of Alkynes
  作者：Mallesh Beesu、Mariappan Periasamy

  DOI：10.1021/jo102104a

  日期：2011.1.21

  Alkoxy bases such as t-BuOK react with Fe(CO)5 to give reactive iron carbonyl intermediates that in turn react with alkynes at 70 °C in THF to give 1,2-cyclobutenediones in 70−93% yields after CuCl2·2H2O oxidation. A novel 1,2-diacyloxyferrole derivative was isolated in the reaction of diphenylacetylene with Fe(CO)5/t-BuOK in the presence of acetyl chloride in contrast to the formation of a 1,4-diacyloxyferrole

  烷氧基碱（例如t -BuOK）与Fe（CO）5反应，生成反应性羰基铁中间体，然后在THF中与炔烃在70°C下反应，在CuCl 2 ·2H后以70-93％的产率生成1,2-环丁烯二酮2 O氧化。在二苯基乙炔与Fe（CO）5 / t- BuOK在乙酰氯存在下的反应中，分离了一种新型的1,2-二酰氧基铁络合物，与使用Fe的反应中形成的1,4-二酰氧基铁络合物形成了对比（CO）5 / Me 3 NO。铁2（CO）9 /吨-BuOK试剂系统还可以在类似的反应条件下，以63-90％的产率将炔烃转化为相应的环丁二烯。
• Aryl substituent effects on the thermal interconversion of cyclobutenediones and 1,2-bisketenes
  作者：Ronghua Liu、Thomas T. Tidwell

  DOI：10.1039/p29960002757

  日期：——

  The rates and activation parameters are reported for ring closure of 1,2 bisketenes OCC(C6H4X)C(SiMe3)CO (7), generated by photolysis of the corresponding cyclobutenediones 6. The rates at 70 °C are correlated with the σp+ constants of the aryl substituents by the relationship log k=–1.10 σp+–3.60 (r= 1.000). The greater reactivity in ring closure to 6 for electron-donating aryl substituents is consistent

  报告了速率和活化参数，用于通过相应环丁烯二酮6的光解反应生成的1,2双烯酮O C C（C 6 H 4 X）C（SiMe 3）C O（7）的闭环。C被与σ相关p +由关系日志常数芳基取代基的ķ = -1.10σ p + -3.60（ř= 1.000）。对于给电子的芳基取代基，闭环反应具有更大的反应性，达到6，这与通过电子供体基团稳定缺电子的环丁烯二酮环，通过π-受体基团进行乙烯酮稳定和通过电子-π-供体基团进行乙烯酮去稳定相一致。以前是根据理论计算得出的。还测量了7d（X = CH 3 CO）的平衡浓度，其平衡浓度从69.2°C时的1.6％变化到143.1°C时的9.7％，超出了7a的5.4–7.5倍（X = H）。CH 3 CO对双烯酮的支持与对反应速率的影响密切相关。
• [2 + 2], [4 + 1], and [4 + 2] Cycloaddition Reactions of Silylated Bisketenes
  作者：Jim D. Colomvakos、Ian Egle、Jihai Ma、David L. Pole、Thomas T. Tidwell、John Warkentin

  DOI：10.1021/jo961169r

  日期：1996.1.1

  Cycloaddition reactions of the bisketenes O=C=C(SiMe(3))CR=C=O (15, R = SiMe(3); 16, R = Ph) include BF3-catalyzed [2+2] cycloaddition of 15 with CH3CHO to form an isolable p-lactone Is adduct which undergoes thermal decarboxylation to the vinylketene 19. Reactions of 15 and 16 with CH2N2 proceed by [4+1] cycloaddition to give mixtures of cyclopentene-1,3-diones 20 and methylenefuranones 21, while Me(3)SiCHN(2) and PhCHN(2) give only 20. The reactions are interpreted in terms of a steric preference for nucleophilic attack by the substituted diazomethanes from the side of the ketene bearing the Me(3)SiC=C=O substituent, leading to formation of 20. With the less bulky CH2N2, attack occurs from both sides and approach from the side of the R group leads to formation of lactones 21. Reaction of tetramethoxyethylene with 15 yields both a cyclopentene-1,3-dione 24 from net addition of dimethoxycarbene and a spirocyclopropylbutenolide 25. Free dimethoxycarbene generated by heating an oxadiazoline precursor also reacted with 15 to give dione 24. Various electrophilic dienophiles do not react with 15, but nucleophilic alkynes react with 16 in thermal reactions to give spirocyclopropenylfuranones 33-36, and Me(3)SiC=COEt and 16 react by net [4 + 2] cycloaddition to give the quinone 37 as the major product.
• Spiro-Aziridine and Bislactam Formation from Bisketene−Imine Cycloadditions
  作者：Annette D. Allen、Jazmin Godoy、Nanyan Fu、Michelle Nagy、Sandra Spadaro、Thomas T. Tidwell、Sinisa Vukovic

  DOI：10.1021/ja077623y

  日期：2008.2.1

  1,2-Bisketenes 6 react with imines PhCH=NAr, (E)-2, forming spiro-aziridines 7. DFT computations indicate that this occurs by nucleophilic attack of the imine on the carbonyl carbon of the more reactive arylketene moiety, followed by cyclization, and not by prior cyclization of the 1,2-bisketene forming a carbene lactone intermediate. Computations also indicate that the previously studied bisketene 10 from benzocyclobutadiene 9 is 4.0 kcal/mol less stable than carbene lactone 12 that would result from cyclization but that the failure to observe 12 results from a lower barrier for 10 to instead revert to 9. 1,2-, 1,3-, and 1,4-Bisketenylbenzenes 16, 19, and 22 react with imines forming bis(beta- lactams), with a preference for formation of mixtures of trans, trans chiral (+/-) and achiral diastereomeric products.