2-trimethylsilyl-3-phenyl-1,3-butadiene-1,4-dione | 154473-77-5

• 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: 2-trimethylsilyl-3-phenyl-1,3-butadiene-1,4-dione
• CAS: 154473-77-5
• 化学式: C₁₃H₁₄O₂Si
• 分子量: 230.338
• InChiKey: UEKWMJNSTXUMTJ-UHFFFAOYSA-N

物化性质

• 沸点：
  224.6±40.0 °C(Predicted)
• 密度：
  0.985±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.54
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• 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：

  2-trimethylsilyl-3-phenyl-1,3-butadiene-1,4-dione 以 正己烷 为溶剂， 生成 3-Phenyl-2-trimethylsilylcyclobutene-1,2-dione
  参考文献：
  名称：

  芳基取代基对环丁烯二酮和1,2-双烯酮的热转化的影响

  摘要：

  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。

  DOI：

  10.1039/p29960002757
• 作为产物：
  描述：

  3-Phenyl-2-trimethylsilylcyclobutene-1,2-dione 以87%的产率得到2-trimethylsilyl-3-phenyl-1,3-butadiene-1,4-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。
• Bisketene derivatives and process for production and use thereof
  申请人：Tidwell, Thomas T.

  公开号：EP0650970A1

  公开（公告）日：1995-05-03

  The novel 1,2-bisketene of Formula I: wherein:    R¹ is SiR³R⁴R⁵;    R² is selected from the group comprising SiR³R⁴R⁵, hydrogen, methyl, a substituted or unsubstituted C₂₋₂₀linear or branched alkyl group, a substituted or unsubstituted C₆₋₂₀ aryl group, a substituted or unsubstituted C₅₋₂₀ cycloalkyl group and a halogen; and    each of R³, R⁴ and R⁵ are the same or different and are selected from the group comprising hydrogen, methyl, a substituted or unsubstituted C₂₋₂₀ linear or branched alkyl group, a substituted or unsubstituted C₆₋₂₀ aryl group, a substituted or unsubstituted C₇₋₂₀ aralkyl group and substituted or unsubstituted a C₅₋₂₀ cycloalkyl group, is useful in e.g. preparing a succinate ester, or in reacting with a polyfunctional alcohol or ester to produce a polyester or polyamide.

  化合物1,2-双烯的化学式I：其中：R¹为SiR³R⁴R⁵; R²选自包括SiR³R⁴R⁵，氢，甲基，取代或未取代的C₂₋₂₀线性或支链烷基，取代或未取代的C₆₋₂₀芳基，取代或未取代的C₅₋₂₀环烷基和卤素的基团; R³，R⁴和R⁵中的每一个都相同或不同，选自包括氢，甲基，取代或未取代的C₂₋₂₀线性或支链烷基，取代或未取代的C₆₋₂₀芳基，取代或未取代的C₇₋₂₀芳基烷基和取代或未取代的C₅₋₂₀环烷基的基团。该化合物可用于制备琥珀酸酯，或与多官能团醇或酯反应以产生聚酯或聚酰胺。
• [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.
• A Novel Copper Chelate Catalyzed Ring Closure Reaction of 1,2-Bisketenes with Alcohols To Give 5-Alkoxy-2,3-dihydrofuran-2-ones
  作者：Michael M. Dejmek、Rüdiger Selke

  DOI：10.1002/(sici)1521-3773(19980619)37:11<1540::aid-anie1540>3.0.co;2-x

  日期：1998.6.19

  Copper complexes with distorted tetrahedral structure in solution catalyze regioselectively the cyclization of 1,2-bisketenes with alcohols to give 5-alkoxy-2,3-dihydrofuran-2-ones in very high yields (shown on the right). It seems remarkable that these new compounds could remain undiscovered despite having structural similarities with a great number of well-investigated and biologically active butenolides.
• Allen Annette D., Lai Wing-Yan, Ma Jihai, Tidwell Thomas T., J. Amer. Chem. Soc, 116 (1994) N 6, S 2625-2626
  作者：Allen Annette D., Lai Wing-Yan, Ma Jihai, Tidwell Thomas T.

  DOI：——

  日期：——