methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate | 119344-54-6

• 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: methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate
• 英文别名: MCPOC；Methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate
• CAS: 119344-54-6
• 化学式: C₁₁H₈ClNO₃
• 分子量: 237.642
• InChiKey: GSLOJICKWGLNHN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  52.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  methyl 2-azido-3-chloro-3-benzoylpropenoate 以 甲苯 为溶剂， 反应 7.0h， 以98%的产率得到methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate
  参考文献：
  名称：

  4-Halo-1,3-oxazoles: Unambiguous structural assignment of 2-halo-2-benzoyl-2H-azirine-3-carboxylates thermal ring expansion products

  摘要：

  IR spectroscopy in cryogenic argon matrix of methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate and methyl 4-chloro-5-phenylisoxazole-3-carboxylate was applied for the structural assignment of these isomeric heterocycles. It was demonstrated that methyl 2-benzoyl-2-halo-2H-azirine-3-carboxylates undergo thermal ring expansion to give 4-halo-5-phenyl-1,3-oxazole-2-carboxylates and not the isomeric isoxazoles. (c) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2008.08.014

文献信息

• Structure and photochemical behaviour of 3-azido-acrylophenones: a matrix isolation infrared spectroscopy study
  作者：Susy Lopes、Cláudio M. Nunes、Andrea Gómez-Zavaglia、Teresa M.V.D. Pinho e Melo、Rui Fausto

  DOI：10.1016/j.tet.2011.07.084

  日期：2011.10

  characterized both structurally and spectroscopically, and its photochemistry used to probe the mechanism of photo-induced conversion of 3-azido-acrylophenones into oxazoles. In situ UV irradiation (λ = 235 nm) of matrix-isolated MACBP yielded as primary photoproduct a 2H-azirine, which undergoes subsequent photoisomerization to methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate. In a competitive process, a ketenimine

  （Z）-3-叠氮基-3-甲氧基羰基-2-氯丙烯酮（MACBP）已合成，在低温氩气和氙气基质中分离并通过FTIR光谱研究，辅以DFT（B3LYP）/ 6-311 ++ G（d，p）计算。该分子在结构上和光谱上都得到了表征，其光化学用于探测光诱导的3-叠氮基丙烯酮转化为恶唑的机理。基质分离的MACBP的原位UV辐射（λ = 235 nm）作为初级光产物产生2H-偶氮胺，其随后进行光异构化为4-氯-5-苯基-1,3-恶唑-2-羧酸甲酯。在竞争过程中，在MACBP光解后还会形成一个烯酮亚胺。报道的结果表明，该酮亚胺必须通过Curtius型协同重排由起始的3-叠氮基-丙烯酮形成。
• Photochemistry and Vibrational Spectra of Matrix-Isolated Methyl 4-Chloro-5-phenylisoxazole-3-carboxylate
  作者：Susy Lopes、Cláudio M. Nunes、Andrea Gómez-Zavaglia、Teresa M. V. D. Pinho e Melo、Rui Fausto

  DOI：10.1021/jp110705c

  日期：2011.2.24

  converted into conformer II during deposition of the matrices, a result that is in agreement with the predicted low III → II energy barrier (<0.3 kJ mol−1) . In situ UV irradiation (λ > 235 nm) of matrix-isolated MCPIC yielded as final photoproduct the corresponding oxazole (methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate). Identification of the azirine and nitrile-ylide intermediates in the spectra

  合成了4-氯-5-苯基异恶唑-3-羧酸甲酯（MCPIC），在低温氩气和氙气基质中进行了分离，并通过FTIR光谱进行了研究。通过对分子的DFT（B3LYP）/ 6-311 ++ G（d，p）势能面进行系统研究，对MCPIC的低能构象体进行了表征。理论计算预测了三种低能构象体的存在。在低温基质中通过实验观察到了其中的两个（I和II）。发现第三个（III）在基质沉积过程中转化为构象异构体II，其结果与预测的低III → II相符能量垒（<0.3 kJ mol -1）。基质分离的MCPIC的原位UV辐射（λ> 235 nm）产生相应的恶唑（4-氯-5-苯基-1,3-恶唑-2-羧酸甲酯）作为最终的光产物。在辐照基体光谱中鉴定出叠氮基和腈基中间体，证实了它们在异恶唑→恶唑光异构化中的机理相关性。
• On the photophysical behaviour of 4-halo-5-phenyl-oxazoles and isoxazoles: A correction and observations on the photoinduced isomerisation and degradation of methyl 4-halo-5-phenyl-isoxazole-3-carboxylates
  作者：Sofia M. Fonseca、Hugh D. Burrows、Cláudio M. Nunes、Teresa M.V.D. Pinho e Melo

  DOI：10.1016/j.cplett.2009.04.028

  日期：2009.5

  Photophysical data in cyclohexane solutions, including measurements of energies of lowest excited singlet and triplet states, fluorescence quantum yields, lifetimes, phosphorescence and triplet-singlet difference absorption spectra, reported in a previous Letter as due to methyl 4-halo-5-phenylisoxazole-3-carboxylates [S. M. Fonseca, H.D. Burrows, C.M. Nunes, T.M.V.D. Pinho e Melo, A.M.d'A. Rocha Gonsalves, Chem. Phys. Lett. 414 (2005) 98] are reassigned to the isomeric oxazoles. These are compared with data on the isoxazoles synthesised by an unambiguous route. In addition, results are presented on the photoinduced isomerization of 4-halo-5-phenylisoxazoles to oxazoles in cyclohexane, which is shown to proceed via a nonconcerted pathway, possibly involving thermal reaction of an azirine intermediate. (C) 2009 Elsevier B. V. All rights reserved.
• 4-Halo-1,3-oxazoles: Unambiguous structural assignment of 2-halo-2-benzoyl-2H-azirine-3-carboxylates thermal ring expansion products
  作者：Susy Lopes、Cláudio M. Nunes、Rui Fausto、Teresa M.V.D. Pinho e Melo

  DOI：10.1016/j.molstruc.2008.08.014

  日期：2009.2

  IR spectroscopy in cryogenic argon matrix of methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate and methyl 4-chloro-5-phenylisoxazole-3-carboxylate was applied for the structural assignment of these isomeric heterocycles. It was demonstrated that methyl 2-benzoyl-2-halo-2H-azirine-3-carboxylates undergo thermal ring expansion to give 4-halo-5-phenyl-1,3-oxazole-2-carboxylates and not the isomeric isoxazoles. (c) 2008 Elsevier B.V. All rights reserved.