2,2'-(azinodimethylidyne)bis-benzoic acid | 55294-88-7

• 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: 2,2'-(azinodimethylidyne)bis-benzoic acid
• 英文别名: bis-(2-carboxy-benzylidene)-hydrazine；Bis-(2-carboxy-benzyliden)-hydrazin；2-[(E)-[(E)-(2-carboxyphenyl)methylidenehydrazinylidene]methyl]benzoic acid
• CAS: 55294-88-7
• 化学式: C₁₆H₁₂N₂O₄
• 分子量: 296.282
• InChiKey: VEKFVASUNHMHME-BEQMOXJMSA-N

物化性质

• 沸点：
  522.1±50.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  99.3
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,2'-(azinodimethylidyne)bis-benzoic acid 在 4-二甲氨基吡啶 、 benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate 、 三乙胺 、 N,N-二异丙基乙胺 、 对甲苯磺酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 39.0h， 生成
  参考文献：
  名称：

  Resolved Chiral 3,4-Diazaphospholanes and Their Application to Catalytic Asymmetric Allylic Alkylation

  摘要：

  One-pot condensation of PhPH2, phthaloyl chloride, and the azine of 2-carboxybenzaldehyde (1) results in the new phosphine, rac-N,N'-phthaloyl-2,3-(2-carboxyphenyl)-phenyl-3,4-diazaphospholane (rac-2), in 88% yield. Resolution via selective crystallization of the diastereomeric alpha-methylbenzylamine salts followed by coupling with amino acids and other amines provides rapid access to new collections of chiral phosphines (3). Pd-catalyzed alkylation of 1,3-dimethylallyl acetate and 1,3-diphenylallyl acetate at room temperature in the presence of 3 exhibits enantioselectivities as high as 92% ee and 97% ee, respectively, with strong sensitivity to the nature of the amino acid appendages. The presence of PF6- salts profoundly affects both the yield and the selectivity of catalytic allylic alkylation.

  DOI：

  10.1021/ja036359f
• 作为产物：
  描述：

  邻羧基苯甲醛 在 一水合肼 作用下， 以 乙醇 为溶剂， 反应 1.0h， 以91%的产率得到2,2'-(azinodimethylidyne)bis-benzoic acid
  参考文献：
  名称：

  Resolved Chiral 3,4-Diazaphospholanes and Their Application to Catalytic Asymmetric Allylic Alkylation

  摘要：

  One-pot condensation of PhPH2, phthaloyl chloride, and the azine of 2-carboxybenzaldehyde (1) results in the new phosphine, rac-N,N'-phthaloyl-2,3-(2-carboxyphenyl)-phenyl-3,4-diazaphospholane (rac-2), in 88% yield. Resolution via selective crystallization of the diastereomeric alpha-methylbenzylamine salts followed by coupling with amino acids and other amines provides rapid access to new collections of chiral phosphines (3). Pd-catalyzed alkylation of 1,3-dimethylallyl acetate and 1,3-diphenylallyl acetate at room temperature in the presence of 3 exhibits enantioselectivities as high as 92% ee and 97% ee, respectively, with strong sensitivity to the nature of the amino acid appendages. The presence of PF6- salts profoundly affects both the yield and the selectivity of catalytic allylic alkylation.

  DOI：

  10.1021/ja036359f

文献信息

• An Ullmann Coupling of Aryl Iodides and Amines Using an Air-Stable Diazaphospholane Ligand
  作者：Minghua Yang、Fei Liu

  DOI：10.1021/jo0712291

  日期：2007.11.1

  A copper-based catalytic system, using an air-stable diazaphospholane as the ligand, was developed for an efficient Ullmann reaction between aryl iodides and alkyl or heterocyclic amines.

  为了使芳基碘化物与烷基或杂环胺发生有效的乌尔曼反应，开发了一种使用空气稳定的二氮杂膦烷作为配体的铜基催化体系。
• Highly Active, Regioselective, and Enantioselective Hydroformylation with Rh Catalysts Ligated by Bis-3,4-diazaphospholanes
  作者：Thomas P. Clark、Clark R. Landis、Susan L. Freed、Jerzy Klosin、Khalil A. Abboud

  DOI：10.1021/ja050148o

  日期：2005.4.1

  styrene, allyl cyanide, and vinyl acetate under mild pressures (20-500 psig of CO/H2) and temperatures (40-120 degrees C) reveals high activities and selectivities for all three substrates. At 60 degrees C and 500 psig syn gas, the best ligand provides outstanding regio- and enantioselectivities (styrene, 89% ee, b:l = 30:1; allyl cyanide, 87% ee, b:l = 4.8:1; vinyl acetate, 95% ee, b:l = 40:1) while

  由肼与邻甲酰基苯甲酸反应制得的肼与 1,2-二膦基苯和琥珀酰氯或邻苯二甲酰氯在约 2 小时内反应。30% 的产率得到在 2 和 5 位带有苯甲酸基团的外消旋-双-3,4-二氮杂膦。苯甲酸官能团与对映体纯胺的缩合得到非对映苯甲酰胺，其可通过快速色谱分离。在温和压力（20-500 psig 的 CO/H2）和温度（40-120 摄氏度）下，解析的双 3,4-二氮杂膦烷在 Rh 催化的苯乙烯、丙烯腈和醋酸乙烯酯的对映选择性加氢甲酰化中的应用显示出高三种底物的活性和选择性。在 60 摄氏度和 500 psig 合成气下，最好的配体提供了出色的区域选择性和对映选择性（苯乙烯，89% ee，b：l = 30:1；烯丙基氰化物，87% ee，b:l = 4.8:1；醋酸乙烯酯，95% ee，b:l = 40:1)，同时实现约的周转频率。3000 小时-1。
• Liebermann; Bistrzycki, Chemische Berichte, 1893, vol. 26, p. 534
  作者：Liebermann、Bistrzycki

  DOI：——

  日期：——
• Griehl; Hecht, Chemische Berichte, 1958, vol. 91, p. 1816
  作者：Griehl、Hecht

  DOI：——

  日期：——
• US3886154A
  申请人：——

  公开号：US3886154A

  公开（公告）日：1975-05-27