(Z)-2-(2-bromophenyl)-4-benzylidene-5(4H)-oxazolone

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (Z)-2-(2-bromophenyl)-4-benzylidene-5(4H)-oxazolone
• 英文别名: (Z)-4-Benzylidene-2-(2-bromophenyl)oxazol-5(4H)-one；(4Z)-4-benzylidene-2-(2-bromophenyl)-1,3-oxazol-5-one
• 化学式: C₁₆H₁₀BrNO₂
• 分子量: 328.165
• InChiKey: LJDTVODLOJLOOW-UVTDQMKNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (Z)-2-(2-bromophenyl)-4-benzylidene-5(4H)-oxazolone 在 sodium hydroxide 作用下， 以 1,4-二氧六环 为溶剂， 生成 Sodium; (Z)-2-(2-bromo-benzoylamino)-3-phenyl-acrylate
  参考文献：
  名称：

  Palcut, Marian; Benko, Jan; Mueller, Norbert, Journal of Chemical Research, 2004, # 10, p. 649 - 653

  摘要：

  DOI：
• 作为产物：
  描述：

  [(2-溴苯甲酰基)氨基]乙酸 、 苯甲醛 在 sodium acetate 、 乙酸酐 作用下， 生成 (Z)-2-(2-bromophenyl)-4-benzylidene-5(4H)-oxazolone
  参考文献：
  名称：

  Ortho-Palladation of (Z)-2-Aryl-4-Arylidene-5(4H)-Oxazolones. Structure and Functionalization

  摘要：

  Ortho-palladated complexes of (Z)-2-aryl-4-arylidene-5(4H)-oxazolones have been prepared through oxidative addition. The reaction of (Z)-2-phenyl-4-(2-bromobenzylidene)-5(4H)-oxazolone (4) with Pd-2(dba)(3)center dot CHCl3 gives the six-membered cyclopalladated dinuclear complex [Pd(mu-Br)(o-C6H4CH=CNC(O)OCPh)](2) (7). The reaction of 7 with PPh3 gives dinuclear 9, which incorporates one phosphine per Pd atom through cleavage of the Pd-N bond, and preserves the bromide bridging system. However, reaction with PPh2Me gives mononuclear 8, which incorporates two phosphines as a results of the cleavage of the mu-Br system and N displacement. In contrast, the reaction of 7 with pyridine gives complex 12 due to Simple cleavage of the Br bridge, leaving the N-bonding intact. Therefore, three different reaction pathways have been characterized. The reactivity of the Pd-C bond in 7 has also been examined, and functionalized oxazolones can be obtained. The reaction of 7 With PhI(OAc)(2) in acetic acid gives the starting oxazolone C6H4-2-Br-CH=CNC(O)OCPh (4), through the presumed oxidation of the Pd center and C-Br bond formation by reductive coupling. In contrast, the reaction of the acetate dimer 14 with PhI(OAc)(2) in acetic acid gives C6H4-2-OAc-CH=CNC(O)OCPh (20) through C-O coupling. When treatment of 7 with PhI(OAc)(2) is performed in MeOH or EtOH, the oxazolones C6H4-2-OR-CH=CNC(O)OCPh (R = Me (18), Et (19)) are obtained. The reaction of 7 with CO in alcohols ROH gives cleanly the oxazolones C6H4-2-CO2R-CH=CNC(O)OCPh (R = Me (21), Pr-i (22)) through CO migratory insertion into the Pd-C bond and further nucleophilic attack of the RO- fragment.

  DOI：

  10.1021/om901068f

文献信息

• Synthesis and anticholinesterase activity of 2-(dimethylamino)ethyl and choline esters of n-substituted α, β-dehydroamino acids
  作者：A. A. Grigoryan、A. A. Ambartsumyan、M. V. Mkrtchyan、V. O. Topuzyan、G. P. Alebyan、R. S. Asatryan

  DOI：10.1007/s11094-006-0077-8

  日期：2006.3

  A new method for the synthesis of tertiary and quaternary aminoesters of N-substituted α,β-dehydroamino acids is described. Aseries of 16 dehydroamino acids esterified to choline or to its tertiary analog have been synthesized by the proposed method with a yield of 84–93%, and their interactions with human erythrocyte acetylcholinesterase (ACE) and human plasma butyrylcholinesterase (BCE) has been studied. The half-inhibiting concentrations IC50 of the synthesized compounds (determined with respect to cholinesterase hydrolysis of a model substrate, 0.1 mM ATC) vary within a broad range (0.16–1840 µM). The values of traditional parameters of the wave functions of ligands estimated using the Hartree-Fock method do not explain the observed pattern of the anticholinesterase activity. The specific properties of the molecules, especially in their quaternary ammonium salt forms, are probably related to their structural features, in particular, to the ability of the inhibitors to form cyclic conformations (so-called crown structures). Such structures are probably stabilized as a result of the formation of intramolecuar hydrogen bonds between protons of the choline residue and oxygen of the terminal peptide group.

  本文介绍了一种合成 N-取代的 α、β-脱氢氨基酸的三级和四级氨基酯的新方法。通过所提出的方法合成了 16 种与胆碱或其三级类似物酯化的脱氢氨基酸系列，产率为 84-93%，并研究了它们与人红细胞乙酰胆碱酯酶（ACE）和人血浆丁酰胆碱酯酶（BCE）的相互作用。合成化合物的半抑制浓度 IC50（根据胆碱酯酶水解模型底物 0.1 mM ATC 测定）在很宽的范围内变化（0.16-1840 µM）。使用哈特里-福克方法估算的配体波函数的传统参数值并不能解释所观察到的抗胆碱酯酶活性模式。分子的特殊性质，尤其是季铵盐形式的分子，可能与它们的结构特征有关，特别是与抑制剂形成环状构象（所谓的冠状结构）的能力有关。这种结构的稳定可能是胆碱残基的质子与末端肽基的氧之间形成分子内氢键的结果。
• GRIMSHAW J.; TROCHA-GRIMSHAW J., TETRAHEDRON LETT. <TELE-AY>, 1975, NO 30, 2601-2602
  作者：GRIMSHAW J.、 TROCHA-GRIMSHAW J.

  DOI：——

  日期：——
• Ortho-Palladation of (<i>Z</i>)-2-Aryl-4-Arylidene-5(4<i>H</i>)-Oxazolones. Structure and Functionalization
  作者：Gheorghe-Doru Roiban、Elena Serrano、Tatiana Soler、Maria Contel、Ion Grosu、Carlos Cativiela、Esteban P. Urriolabeitia

  DOI：10.1021/om901068f

  日期：2010.3.22

  Ortho-palladated complexes of (Z)-2-aryl-4-arylidene-5(4H)-oxazolones have been prepared through oxidative addition. The reaction of (Z)-2-phenyl-4-(2-bromobenzylidene)-5(4H)-oxazolone (4) with Pd-2(dba)(3)center dot CHCl3 gives the six-membered cyclopalladated dinuclear complex [Pd(mu-Br)(o-C6H4CH=CNC(O)OCPh)](2) (7). The reaction of 7 with PPh3 gives dinuclear 9, which incorporates one phosphine per Pd atom through cleavage of the Pd-N bond, and preserves the bromide bridging system. However, reaction with PPh2Me gives mononuclear 8, which incorporates two phosphines as a results of the cleavage of the mu-Br system and N displacement. In contrast, the reaction of 7 with pyridine gives complex 12 due to Simple cleavage of the Br bridge, leaving the N-bonding intact. Therefore, three different reaction pathways have been characterized. The reactivity of the Pd-C bond in 7 has also been examined, and functionalized oxazolones can be obtained. The reaction of 7 With PhI(OAc)(2) in acetic acid gives the starting oxazolone C6H4-2-Br-CH=CNC(O)OCPh (4), through the presumed oxidation of the Pd center and C-Br bond formation by reductive coupling. In contrast, the reaction of the acetate dimer 14 with PhI(OAc)(2) in acetic acid gives C6H4-2-OAc-CH=CNC(O)OCPh (20) through C-O coupling. When treatment of 7 with PhI(OAc)(2) is performed in MeOH or EtOH, the oxazolones C6H4-2-OR-CH=CNC(O)OCPh (R = Me (18), Et (19)) are obtained. The reaction of 7 with CO in alcohols ROH gives cleanly the oxazolones C6H4-2-CO2R-CH=CNC(O)OCPh (R = Me (21), Pr-i (22)) through CO migratory insertion into the Pd-C bond and further nucleophilic attack of the RO- fragment.
• Palcut, Marian; Benko, Jan; Mueller, Norbert, Journal of Chemical Research, <hi>2004</hi>, # 10, p. 649 - 653
  作者：Palcut, Marian、Benko, Jan、Mueller, Norbert、Hritzova, Ol'ga、Vollarova, Ol'ga、Melikian, Gaugik S.

  DOI：——

  日期：——