(E)-3-(4-dimethylaminophenyl)-2-methyl acrylic acid methyl ester | 50704-04-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-3-(4-dimethylaminophenyl)-2-methyl acrylic acid methyl ester
• 英文别名: (E)-methyl 3-(4-dimethylaminophenyl)-2-methylacrylate；(E)-3-(4-dimethylaminophenyl)-2-methylacrylic acid methyl ester；methyl (E)-3-[4-(dimethylamino)phenyl]-2-methylprop-2-enoate
• CAS: 50704-04-6
• 化学式: C₁₃H₁₇NO₂
• 分子量: 219.283
• InChiKey: XHWZYDHVSCSHKG-MDZDMXLPSA-N

物化性质

• 沸点：
  340.8±25.0 °C(Predicted)
• 密度：
  1.071±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  4-溴-N,N-二甲基苯胺 、 甲基丙烯酸甲酯 在 tris(dibenzylideneacetone)dipalladium (0) 、 三叔丁基膦 、 Cy₂NMe₂ 作用下， 以 1,4-二氧六环 为溶剂， 反应 24.0h， 以100%的产率得到(E)-3-(4-dimethylaminophenyl)-2-methyl acrylic acid methyl ester
  参考文献：
  名称：

  在温和条件下用于芳基氯化物和芳基溴化物的 Heck 反应的多功能催化剂

  摘要：

  在 Cy2NMe 存在下，Pd/P(t-Bu)3 可作为一种非常温和且用途广泛的催化剂，用于芳基氯化物和溴化物的 Heck 反应。空间和电子上不同的芳基溴化物阵列以及活化的芳基氯化物，在室温下与一系列单取代和双取代的烯烃偶联，为芳基化产物提供高 E/Z 立体选择。广泛的电子中性和富电子芳基氯化物的相应反应在升高的温度下进行，并且具有高选择性。在范围和温和性方面，Pd/P(t-Bu)3/Cy2NMe 代表了先前报道的这些 Heck 偶联过程的催化剂的进步。

  DOI：

  10.1021/ja010988c

文献信息

• Process for producing phosponium borate compound, novel phosphonium borate compound, and method of using the same
  申请人：Masaoka Shin

  公开号：US20070098616A1

  公开（公告）日：2007-05-03

  The invention relates to a phosphonium borate compound represented by Formula (I) (hereinafter, the compound (I)). The invention has objects of providing (A) a novel process whereby the compound is produced safely on an industrial scale, by simple reaction operations and in a high yield; (B) a novel compound that is easily handled; and (C) novel use as catalyst. Formula (I): (R 1 )(R 2 )(R 3 )PH.BAr 4 (I) wherein R 1 , R 2 , R 3 and Ar are as defined in the specification. The process (A) includes reacting a phosphine with a) HCl or b) H 2 SO 4 to produce a) a hydrochloride or b) a sulfate; and reacting the salt with a tetraarylborate compound. The compound (B) has for example a secondary or tertiary alkyl group as R 1 and is easily handled in air without special attention. The use (C) is characterized in that the compound (I) is used instead of an unstable phosphine compound of a transition metal complex catalyst for catalyzing C—C bond, C—N bond and C—O bond forming reactions and the compound produces an effect that is equal to that achieved by the transition metal complex catalyst.

  本发明涉及一种磷酸盐硼化合物，其由式(I)表示（以下简称化合物(I)）。本发明的目的是提供（A）一种新的工艺，通过简单的反应操作和高产率安全地在工业规模下生产化合物；（B）一种易于处理的新化合物；以及（C）新的用途作为催化剂。式(I)：（R1）（R2）（R3）PH.BAr4（I），其中R1，R2，R3和Ar如规范中所定义。工艺（A）包括将磷化物与a）HCl或b）H2SO4反应，以产生a）盐酸盐或b）硫酸盐；然后将盐与四芳基硼酸盐化合物反应。化合物（B）例如具有二级或三级烷基作为R1，在空气中易于处理而不需要特殊注意。用途（C）的特点是，化合物（I）代替过渡金属复合催化剂的不稳定磷化物化合物，用于催化C-C键，C-N键和C-O键形成反应，并且该化合物产生与过渡金属复合催化剂相同的效果。
• Process for producing phosphonium borate compound, novel phosphonium borate compound, and method of using the same
  申请人：Masaoka Shin

  公开号：US20090305877A1

  公开（公告）日：2009-12-10

  The invention relates to a phosphonium borate compound represented by Formula (I) (hereinafter, the compound (I)). The invention has objects of providing (A) a novel process whereby the compound is produced safely on an industrial scale, by simple reaction operations and in a high yield; (B) a novel compound that is easily handled; and (C) novel use as catalyst. Formula (I): (R 1 )(R 2 )(R 3 )PH.BAr 4 (I) wherein R 1 , R 2 , R 3 and Ar are as defined in the specification. The process (A) includes reacting a phosphine with a) HCl or b) H 2 SO 4 to produce a) a hydrochloride or b) a sulfate; and reacting the salt with a tetraarylborate compound. The compound (B) has for example a secondary or tertiary alkyl group as R 1 and is easily handled in air without special attention. The use (C) is characterized in that the compound (I) is used instead of an unstable phosphine compound of a transition metal complex catalyst for catalyzing C—C bond, C—N bond and C—O bond forming reactions and the compound produces an effect that is equal to that achieved by the transition metal complex catalyst.

  本发明涉及一种磷酸铵硼酸盐化合物，其化学式表示为（I）（以下简称化合物（I））。本发明的目的是提供（A）一种新的工艺，能够通过简单的反应操作和高产率安全地在工业规模上生产化合物；（B）一种易于处理的新化合物；以及（C）作为催化剂的新用途。 化学式（I）：（R1）（R2）（R3）PH·BAr4（I） 其中，R1、R2、R3和Ar的定义如规范中所述。 工艺（A）包括将磷化物与a）HCl或b）H2SO4反应，以产生a）盐酸盐或b）硫酸盐；然后将盐与四芳基硼酸盐化合物反应。 化合物（B）例如具有R1为次级或三级烷基，可以在空气中轻松处理，无需特别注意。 用途（C）的特点是，化合物（I）用于催化C-C键、C-N键和C-O键形成反应，而不是不稳定的过渡金属配合物催化剂中的磷化物化合物，其产生的效果与过渡金属配合物催化剂相当。
• Process for Producing Phosphonium Borate Compound, Novel Phosphonium Borate Compound, and Method of Using the Same
  申请人：MASAOKA Shin

  公开号：US20110166389A1

  公开（公告）日：2011-07-07

  The invention relates to novel phosphonium borate compounds represented by the Formula: (R 1 )(R 2 )(R 3 )PH.BAr 4 , wherein R 1 , R 2 , R 3 and Ar 4 are as defined herein, and compositions including such phosphonium borate compounds in combination with a transition metal, transition metal salt, transition metal oxide or transition metal complex for use in carbon-carbon bond forming reactions, carbon-nitrogen bond forming reactions and carbon-oxygen bond forming reactions.

  本发明涉及一种新型的磷酸盐硼酸盐化合物，其化学式表示为：（R1）（R2）（R3）PH.BAr4，其中R1、R2、R3和Ar4如本文所定义，并包括这种磷酸盐硼酸盐化合物与过渡金属、过渡金属盐、过渡金属氧化物或过渡金属配合物的组合物，用于碳-碳键形成反应、碳-氮键形成反应和碳-氧键形成反应。
• PROCESS FOR PRODUCING PHOSPHONIUM BORATE COMPOUND, NOVEL PHOSPHONIUM BORATE COMPOUND, AND METHOD OF USING THE SAME
  申请人：HOKKO CHEMICAL INDUSTRY CO. LTD.

  公开号：EP1688424A1

  公开（公告）日：2006-08-09

  The invention relates to a phosphonium borate compound represented by Formula (I) (hereinafter, the compound (I)). The invention has objects of providing (A) a novel process whereby the compound is produced safely on an industrial scale, by simple reaction operations and in a high yield; (B) a novel compound that is easily handled; and (C) novel use as catalyst.         Formula (I) : (R1)(R2)(R3)PH·BAr4     (I) wherein R1, R2, R3 and Ar are as defined in the specification. The process (A) includes reacting a phosphine with a) HCl or b) H2SO4 to produce a) a hydrochloride or b) a sulfate; and reacting the salt with a tetraarylborate compound. The compound (B) has for example a secondary or tertiary alkyl group as R1 and is easily handled in air without special attention. The use (C) is characterized in that the compound (I) is used instead of an unstable phosphine compound of a transition metal complex catalyst for catalyzing C-C bond, C-N bond and C-O bond forming reactions and the compound produces an effect that is equal to that achieved by the transition metal complex catalyst.

  本发明涉及一种由式（I）表示的硼酸鏻化合物（以下简称化合物（I））。本发明的目的是：(A)提供一种新的工艺，通过简单的反应操作和高产率，在工业规模上安全地生产该化合物；(B)提供一种易于处理的新化合物；(C)提供作为催化剂的新用途。 式 (I) : (R1)(R2)(R3)PH-BAr4 (I) 其中 R1、R2、R3 和 Ar 如说明书中所定义。 工艺 (A) 包括将膦与 a) HCl 或 b) H2SO4 反应生成 a) 盐酸盐或 b) 硫酸盐；并将该盐与四芳基硼酸盐化合物反应。 化合物(B)的 R1 例如是仲烷基或叔烷基，在空气中容易处理，无需特别注意。 用途(C)的特点是用化合物(I)代替过渡金属络合催化剂中不稳定的膦化合物来催化C-C键、C-N键和C-O键形成反应，并且该化合物产生的效果与过渡金属络合催化剂产生的效果相同。
• Ligandless, Anionic, Arylpalladium Halide Intermediates in the Heck Reaction
  作者：Brad P. Carrow、John. F. Hartwig

  DOI：10.1021/ja909306f

  日期：2010.1.13

  We report the isolation and reactivity of a series of "ligandless," anionic arylpalladium complexes of the general structure [Pd(Ar)Br-2](2)(2-) by the reaction of ('Bu3P)Pd(Ar)(Br) and bromide. These anionic complexes insert olefins at room temperature, and these fast insertions indicate that the anionic complexes are kinetically competent to be intermediates in Heck-Mizoroki reactions conducted under "ligandless" conditions (lacking added dative ligand). Kinetic studies showed that the anionic complexes insert olefins much faster than the corresponding neutral, P(t-Bu)(3)-ligated complexes. Addition of halide to the reaction of the neutral complex ('Bu3P)Pd(Ar)(Br) and styrene led to a significant rate acceleration, suggesting that the anionic complex Forms rapidly and reversibly in situ from the neutral species prior to migratory insertion. These data, along with studies on the regioselectivity for reaction of aryl halides with butyl vinyl ether in the presence of the different starting catalysts, are consistent with the intermediacy of the same anionic, arylpalladium intermediates in Heck reactions catalyzed by palladium complexes containing bulky trialkylphosphine ligands as in reactions conducted under ligandless conditions.