3-(2,6-dichloro-phenyl)-isoxazole-5-carboxylic acid methyl ester | 359688-70-3

• 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: 3-(2,6-dichloro-phenyl)-isoxazole-5-carboxylic acid methyl ester
• 英文别名: 3-(2,6-dichlorophenyl)isoxazole-5-carboxylic acid methyl ester；methyl 3-(2,6-dichlorophenyl)isoxazole-5-carboxylate；5-Isoxazolecarboxylic acid, 3-(2,6-dichlorophenyl)-, methyl ester；methyl 3-(2,6-dichlorophenyl)-1,2-oxazole-5-carboxylate
• CAS: 359688-70-3
• 化学式: C₁₁H₇Cl₂NO₃
• 分子量: 272.087
• InChiKey: IPTDZMPDEBUJGB-UHFFFAOYSA-N

物化性质

• 熔点：
  116-118 °C
• 沸点：
  388.1±42.0 °C(Predicted)
• 密度：
  1.413±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  17
• 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：

  1,4-dihydro-4-(3-(3-methoxyphenyl)-1-phenyl-1H-pyrazol-4-yl)-2,6-dimethyl-pyridine-3,5-dicarbonitrile 在 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 18.0h， 生成 3-(2,6-dichloro-phenyl)-isoxazole-5-carboxylic acid methyl ester
  参考文献：
  名称：

  基于Wang树脂结合的1-苯基硒基丙烯酸酯固相有机合成5-甲基异恶唑-5-羧酸酯

  摘要：

  摘要 开发了一种新型 Wang 树脂结合的 1-苯基硒基丙烯酸酯试剂，并将其用作偶极试剂，用于与腈氧化物的 1,3-偶极环加成反应，以区域选择性合成 3-取代异恶唑-5-羧酸甲酯，收率和纯度良好。图形概要

  DOI：

  10.1080/00397911.2011.580641

文献信息

• Efficient Access to Isoxazoles from Alkenes
  作者：Ashton Hamme II、Jianping Xu

  DOI：10.1055/s-2008-1042906

  日期：2008.4

  The direct regioselective synthesis of 3,5-disubstituted isoxazoles was achieved in one reaction vessel through a sequence of reactions involving the net bromination of an electron-deficient alkene, in situ generation of a nitrile oxide, 1,3-dipolar cycloaddition, and loss of HBr from an intermediate 5,5-disubstituted bromoisoxazoline. This one-pot process enables the synthesis of 3,5-disubstituted

  3,5-二取代异恶唑的直接区域选择性合成是在一个反应​​容器中通过一系列反应实现的，包括缺电子烯烃的净溴化、腈氧化物的原位生成、1,3-偶极环加成和损失HBr 来自中间体 5,5-二取代溴异恶唑啉。这种一锅法可以直接从缺电子烯烃合成 3,5-二取代异恶唑，从而消除 1,1-二取代溴烯烃炔替代物的分离。
• Electrochemical and yeast-catalysed ring-opening of isoxazoles in the synthesis of analogues of the herbicide Grasp ®
  作者：Christopher J. Easton、Graham A. Heath、C. Merrîcc M. Hughes、Connie K. Y. Lee、G. Paul Savage、Gregory W. Simpson、Edward R. T. Tiekink、George J. Vuckovic、Richard D. Webster

  DOI：10.1039/b008081k

  日期：——

  Isoxazoles substituted with an electron-withdrawing group at the 4-position undergo electrochemical and yeast-catalysed N–O bond cleavage. The electrolysis is much more efficient and, with acyl- and alkoxycarbonyl-substituted isoxazoles, it affords the enolised dicarbonylimine functionality characteristic of the herbicide Grasp®. Regioisomeric 4- and 5-substituted isoxazoles are accessible through nitrile oxide cycloaddition chemistry, using halogen as a steric auxiliary to control the regiochemistry of reaction. Crystal data for compounds 11 and 19b are presented.

  4位带有吸电子基团的异恶唑在电化学和酵母催化下发生N–O键断裂。电解过程更为高效，并且对于酰基和烷氧羰基取代的异恶唑，它能生成草剂Grasp®所特有的烯醇化双羰基亚胺结构功能。通过使用卤素作为立体辅助控制反应区域化学的氰氧基团环加成反应，可以获得4位和5位取代的异恶唑的区域异构体。化合物11和19b的晶体数据已给出。
• Methyl 3-substituted-isoxazole-5- carboxylates syntheses on solid supports via wang resin-bound 2,3-dibromopropionate
  作者：Shou-Ri Sheng、Ai-Ying He、Mei-Hong Wei、Ai-Li Zhu、Ming-Zhong Cai

  DOI：10.1002/hc.21035

  日期：——

  A novel Wang resin-bound 2,3-dibromopropionate reagent has been developed and used as a potential dipolarophile for the facile preparation of methyl 3-substituted-isoxazole-5-carboxylates through triethylamine, promoting a sequence of reactions involving the in situ generation of 2-bromoacrylate resin and nitrile oxide, regioselective 1,3-dipolar cycloaddition, and loss of hydrogen bromide in one pot

  一种新型 Wang 树脂结合 2,3-二溴丙酸酯试剂已被开发并用作潜在的偶极试剂，用于通过三乙胺轻松制备 3-取代-异恶唑-5-羧酸甲酯，促进一系列反应，包括原位生成2-溴丙烯酸酯树脂和氧化腈，区域选择性1,3-偶极环加成，一锅失去溴化氢，然后用甲醇钠从树脂上裂解。该方法的优点是操作简单，条件温和，收率好，产品纯度高。© 2012 Wiley Periodicals, Inc. 杂原子化学 23:444–448, 2012; 在 wileyonlinelibrary.com 上在线查看这篇文章。DOI 10.1002/hc.21035
• Substituent effects in isoxazoles: identification of 4-substituted isoxazoles as Michael acceptors
  作者：Connie K. Y. Lee、Christopher J. Easton、Mariana Gebara-Coghlan、Leo Radom、Anthony P. Scott、Gregory W. Simpson、Anthony C. Willis

  DOI：10.1039/b207808b

  日期：2002.12.6

  Crystallographic and theoretical studies have been used to investigate substituent effects, which are manifest in electrochemical and yeast-catalysed reactions of 4- and 5-acyl-, alkoxycarbonyl-, cyano- and phenyl-substituted isoxazoles. The results show that isoxazoles substituted at the 4-position with π-electron-withdrawing substituents have enhanced C4–C5 bond polarity and are structurally similar to Michael acceptors. As a consequence there is elongation and weakening of their N–O bonds. By contrast, their 5-substituted regioisomers and isoxazoles substituted at C4 with conjugating, but not π-electron-withdrawing, substituents have diminished C4–C5 bond polarity. This results in the selective electrochemical and yeast-catalysed reduction of 4-substituted isoxazoles, as well as their hydrogenolytic ring cleavage and conjugate reduction with sodium borohydride.

  我们利用晶体学和理论研究来探讨取代基效应，这些效应体现在 4-和 5-酰基、烷氧羰基、氰基和苯基取代的异噁唑的电化学反应和酵母催化反应中。结果表明，在 4 位上被π-电子吸收取代基取代的异噁唑具有更强的 C4-C5 键极性，在结构上类似于迈克尔受体。因此，它们的 N-O 键会变长和变弱。相比之下，它们的 5-取代基异构体和在 C4 处被共轭取代（而不是被π-电子吸收取代）的异噁唑的 C4-C5 键极性则会减弱。这导致 4-取代的异噁唑在电化学和酵母催化下发生选择性还原，以及与硼氢化钠一起发生氢解环裂解和共轭还原。
• Isoxazoles from 1,1-disubstituted bromoalkenes
  作者：Sureshbabu Dadiboyena、Jianping Xu、Ashton T. Hamme

  DOI：10.1016/j.tetlet.2006.12.005

  日期：2007.2

  The regioselective synthesis of 3,5-disubstituted isoxazoles was achieved through the 1,3-dipolar cycloaddition of nitrile oxides with 1,1-disubstituted bromoalkenes. The substituted bromoalkenes function as alkyne synthons which were used to construct 5,5-disubstituted bromoisoxazoline intermediates that aromatize to the analogous isoxazoles through the loss of HBr.

  3,5-二取代异恶唑的区域选择性合成是通过腈氧化物与 1,1-二取代溴烯烃的 1,3-偶极环加成实现的。取代的溴烯烃用作炔合成子，用于构建 5,5-二取代的溴异恶唑啉中间体，通过失去 HBr 芳构化为类似的异恶唑。