3-carbomethoxy-2,3-bis(trimethylsilyl)prop-1-en-1-one | 152530-72-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 3-carbomethoxy-2,3-bis(trimethylsilyl)prop-1-en-1-one
• CAS: 152530-72-8
• 化学式: C₁₁H₂₂O₃Si₂
• 分子量: 258.465
• InChiKey: JFQDPZOUGSVTGO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-carbomethoxy-2,3-bis(trimethylsilyl)prop-1-en-1-one 、 苄胺 以 二氯甲烷 为溶剂， 反应 0.25h， 生成 erythro-N-benzyl-2,3-bis(trimethylsilyl)-4-methoxy-4-oxobutanamide 、 erythro-N-benzyl-2,3-bis(trimethylsilyl)-4-methoxy-4-oxobutanamide
  参考文献：
  名称：

  Amination of Bis(trimethylsilyl)-1,2-bisketene to Ketenyl Amides, Succinamides, and Polyamides:  Preparative and Kinetic Studies

  摘要：

  The reaction of the bisketene (Me3SiC=C=O)(2) (1) with amines is facile and proceeds by two distinct steps forming first ketenylcarboxamides 3 and then succinamides 5. Successive reaction of 1 with two different amines gives mixed succinamides, while phenylhydrazine gives succinimide 7. The reactions of 1.8 equiv of 1 with 1,4-(H2NCH2)(2)C6H4 gives alpha,omega-bisketenyldiamide 13, while equivalent amounts of 1 and diamines gave polymeric amides. Mixed ester amides 8 are formed by sequential reaction of 1 with an alcohol, followed by an amine, or vice versa. Kinetic studies of the amination reaction of 1 with excess amines in CH3CN gave rate constants k(obs) for the formation of ketenylcarboxamides that were fit by the relationship k(obs) = k(a)[amine](2) + k(b)[amine](3). Further reaction of the n-butyl ketenylcarboxamide 3b with n-BuNH2 to give the succinamide 5b was first order in [n-BuNH2], while the further reaction of the CF3CH2 ketenylcarboxyamide 3c with CF3CH2NH2 to form 5c was fit by the equation k(obs) = k(c)[amine](2)/(k(d)[amine] + 1). The reaction of 3b with CH3OH to form the ester amide 8a is strongly accelerated compared to CH3OH addition to the corresponding ketenyl ester and gives significant stereoselectivity for formation of erythro product, and both these effects, as well as the absence of higher order kinetic terms in the reaction of 3b with n-BuNH2 may arise from coordination by the carboxamido group to the nucleophile.

  DOI：

  10.1021/jo9825052
• 作为产物：
  描述：

  甲醇 、 bis(trimethylsilyl)-1,2-bisketene 生成 3-carbomethoxy-2,3-bis(trimethylsilyl)prop-1-en-1-one
  参考文献：
  名称：

  持久稳定的甲硅烷基取代双烯酮的制备和反应性

  摘要：

  2,3-Bis(trimethylsilyl)-1,3-butadiene-1,4-dione (1) 是 3,4-bis-(trimethylsilyl)cyclobut-3-ene-1,2 热解的唯一产物-二酮(2)，2的开环速率与取代环丁烯和环丁烯酮的开环速率相当。2 的光解也形成 1，它以逐步方式与乙醇反应，更快地加入一个乙醇分子，得到可分离的单烯酮 18，其在更慢的步骤中反应得到琥珀酸二酯，并伴随脱甲硅烷基化。2,3-双(叔丁基二甲基甲硅烷基)-1,3-丁二烯-1,4-二酮 (3)，类似于 1 制备，同样加入一分子甲醇得到可分离的单烯酮 20，然后反应得到二甲基2,3-双(叔丁基二甲基甲硅烷基)琥珀酸酯(21)为主要产品

  DOI：

  10.1021/ja00075a027

文献信息

• Alkoxide-Induced Succinate Ester Formation from Alcohols and Bis(trimethylsilyl) 1,2-Bisketene
  作者：Ian Egle、Wing-Yan Lai、Patrick A. Moore、Paul Renton、Thomas T. Tidwell、Da-chuan Zhao

  DOI：10.1021/jo961333a

  日期：1997.1.1

  Reaction of the 1,2-bisketene (Me(3)SiC=C=O)(2) (1) with alcohols (ROH) catalyzed by LiOR gives rapid and efficient conversion to mixtures of the meso and dl succinates (Me(3)SiCHCO(2)R)(2) (4). There is a change in selectivity with the dl/meso ratio varying from 18/82 with MeOH to 92/8 for t-BuOH. This procedure occurs with minimal desilylation, which is the predominant path in the uncatalyzed reaction

  1,2-双烯酮（Me（3）SiC = C = O）（2）（1）与LiOR催化的醇（ROH）的反应可快速有效地转化为内消旋和dl琥珀酸酯的混合物（Me（3 ）SiCHCO（2）R）（2）（4）。选择性发生变化，dl /内消旋比从MeOH的18/82变为t-BuOH的92/8。该过程以最小的甲硅烷基化作用进行，这是未催化反应的主要途径。提出锂的醇盐对由烯丙基氧与烯基氧的配位作用诱导的烯酮的羰基碳的优先进攻，以解释低甲硅烷基化程度。内消旋和dl构型的立体化学分配是基于混合琥珀酸酯和（13）C，（1）H卫星光谱的邻位H，H偶合常数，并通过X射线结构测定得到证实。