Triphenylphosphonio-dicarbomethoxymethanol | 19491-23-7

• 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: Triphenylphosphonio-dicarbomethoxymethanol
• 英文别名: Triphenylphosphonio-dicarbomethoxymethanid；Malonic acid, (triphenylphosphoranylidene)-, dimethyl ester；dimethyl 2-(triphenyl-λ5-phosphanylidene)propanedioate
• CAS: 19491-23-7
• 化学式: C₂₃H₂₁O₄P
• 分子量: 392.391
• InChiKey: BXNHZDBICLFYJE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  Triphenylphosphonio-dicarbomethoxymethanol 在 potassium carbonate 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 Dimethyl (2-allyloxyphenyl)methylenemalonate
  参考文献：
  名称：

  Carboxylic esters radical leaving groups: a new and efficient gas-phase synthesis of benzofurans

  摘要：

  邻烯丙基肉桂酸酯的闪速真空热解（FVP）可通过苯氧自由基的环化和随后的羧基酯功能裂解，得到高产率的苯并呋喃；相应苯酚的 FVP 可得到香豆素。

  DOI：

  10.1039/c39930000959
• 作为产物：
  描述：

  氯甲酸甲酯 、 甲氧羰基亚甲基三苯基正膦 生成 Triphenylphosphonio-dicarbomethoxymethanol
  参考文献：
  名称：

  Comparison of Conformations of Diesters of Stabilized Phosphonium Ylides in Solution and in the Crystal

  摘要：

  Computed bond lengths and angles of methyl ethyl and dimethyl triphenyl phosphonium ylidic diesters, 1b, c, respectively, are similar to those in the crystal, as for the diethyl ester, 1a, where both acyl oxygens are anti to phosphorus. The 1H and 13C NMR spectra of the methyl ethyl diester, 1b, where one acyl oxygen is syn and the other anti to phosphorus, are as expected in terms of the conformation in the crystal, but the dimethyl ester, 1c, in the crystal is an equimolar mixture of conformers. For a given ylidic diester the different conformers have similar energies from B3LYP//6-31G(d) computations, interconversions of conformers should not be slow at ambient temperatures and 1H and 13C NMR signals in solution are sharp. Estimation of Natural Atomic Charges indicates significant cationoid character on phosphorus and the acyl carbons, and anionoid character on the ylidic carbon and the ester oxygens depending on orientations towards phosphorus.

  DOI：

  10.1080/10426500802077242

文献信息

• Design, Preparation, X-ray Crystal Structure, and Reactivity of <i>o</i>-Alkoxyphenyliodonium Bis(methoxycarbonyl)methanide, a Highly Soluble Carbene Precursor
  作者：Chenjie Zhu、Akira Yoshimura、Lei Ji、Yunyang Wei、Victor N. Nemykin、Viktor V. Zhdankin

  DOI：10.1021/ol301268j

  日期：2012.6.15

  The preparation, X-ray structure, and reactivity of new, highly soluble, and reactive iodonium ylides derived from malonate methyl ester and bearing an ortho substituent on the phenyl ring are reported. These new reagents show higher reactivity than common phenyliodonium ylides in the Rh-catalyzed cyclopropanation, C–H insertion, and transylidation reactions under homogeneous conditions.

  报道了衍生自丙二酸酯甲酯且在苯环上带有邻位取代基的新型，高度可溶性和反应性碘鎓的制备，X射线结构和反应性。这些新试剂在均相条件下，在Rh催化的环丙烷化，CH插入和酰化反应中显示出比普通苯基碘鎓碘化物更高的反应性。
• [EN] PHOSPHORANES AS COUPLING AGENTS AND THEIR PREPARATION<br/>[FR] PHOSPHORANES UTILISES EN TANT QU'AGENTS COUPLEURS ET LEUR PREPARATION
  申请人：CYTEC CANADA INC

  公开号：WO2004000778A1

  公开（公告）日：2003-12-31

  Provided is a use as a coupling agent for condensation reactions of a compound of formula (I): wherein each of R1, R2, and R3 is independently H, hydrocarbyl, or hydrocarbyloxy, provided that not more than one of R1, R2, and R3 is H ; and at least one of Y1 and Y2 is an electron-withdrawing group and the other, if not an electron-withdrawing group, is H or a group that has no electron-donating properties, with the proviso that when one of Y1 and Y2 is H, the other is not -CN. Some of the compounds of formula (I) are novel, and methods of their preparation are also provided.

  提供的是一种用作缩聚反应的偶联剂的用途，其中化合物的结构式为（I）：其中R1、R2和R3中的每一个独立地是H、烃基或烃氧基，前提是R1、R2和R3中不超过一个是H；而且Y1和Y2中至少一个是电子吸引基团，另一个，如果不是电子吸引基团，则是H或者具有无电子给予性质的基团，但是当Y1和Y2中的一个是H时，另一个不是-CN。其中一些具有结构式（I）的化合物是新颖的，同时还提供了它们的制备方法。
• Metal salt-catalysed carbenoids. Part IX. The catalysts in trialkyl phosphite–copper(<scp>I</scp>) complex catalysed decomposition of diazomalonic esters in cycloalkenes
  作者：David S. Wulfman、Nguyen van Thinh、Robert S. McDaniel、Billy W. Peace、Charles W. Heitsch、M. Tom Jones

  DOI：10.1039/dt9750000522

  日期：——

  Partial rate data, asymmetric induction studies, interrupted experiments, and additives studies indicate that copper(I) salt–phosphite complexes are destroyed during the course of reactions with dimethyl diazomalonate (1) and ethyl diazoacetate (2). All evidence is consistent with the copper(I) being oxidized to copper(II) and copper(0) being oxidized by impurities in the olefin which most probably

  部分速率数据，不对称诱导研究，间断实验和添加剂研究表明，在与重氮丙二酸二甲酯（1）和重氮乙酸乙酯（2）反应的过程中，亚铜盐（I）络合物被破坏。所有证据均与铜（I）被烯烃中的杂质（最可能是氢过氧化物）氧化为铜（II）和铜（0）一致。
• Neiland,O.Ya.; Kalnin',S.V., Journal of Organic Chemistry USSR (English Translation), 1968, vol. 4, p. 132 - 138
  作者：Neiland,O.Ya.、Kalnin',S.V.

  DOI：——

  日期：——
• Gompper,R.; Wolf,U., Liebigs Annalen der Chemie, 1979, p. 1388 - 1405
  作者：Gompper,R.、Wolf,U.

  DOI：——

  日期：——