5-[(E)-2-(4-methoxyphenyl)-1-ethenyl]-3-methyl-4-nitroisoxazole | 51978-98-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5-[(E)-2-(4-methoxyphenyl)-1-ethenyl]-3-methyl-4-nitroisoxazole
• 英文别名: (E)-5-(4-methoxystyryl)-3-methyl-4-nitroisoxazole；5-(4-methoxystyryl)-3-methyl-4-nitroisoxazole；5-(4-methoxy-styryl)-3-methyl-4-nitro-isoxazole；5-(4-methoxy-trans-styryl)-3-methyl-4-nitro-isoxazole；5-(4-Methoxy-trans-styryl)-3-methyl-4-nitro-isoxazol；3-Methyl-4-nitro-5-(p-methoxystyryl)isoxazol；5-[(E)-2-(4-methoxyphenyl)ethenyl]-3-methyl-4-nitro-1,2-oxazole
• CAS: 51978-98-4；53557-95-2
• 化学式: C₁₃H₁₂N₂O₄
• 分子量: 260.249
• InChiKey: YTRXYZQOCQHIMO-VMPITWQZSA-N

物化性质

• 熔点：
  148 °C(Solv: ethanol (64-17-5))
• 沸点：
  443.1±33.0 °C(Predicted)
• 密度：
  1.296±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  81.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5-[(E)-2-(4-methoxyphenyl)-1-ethenyl]-3-methyl-4-nitroisoxazole 在 sodium hydroxide 作用下， 反应 6.0h， 以70%的产率得到反式-4-甲氧基肉桂酸
  参考文献：
  名称：

  Sarti-Fantoni, P.; Donati, D.; Fiorenza, M., Journal of Heterocyclic Chemistry, 1980, vol. 17, p. 621 - 622

  摘要：

  DOI：
• 作为产物：
  描述：

  3-[1-(4-Methoxy-phenyl)-2-(3-methyl-4-nitro-isoxazol-5-yl)-ethyl]-pentane-2,4-dione 、 乙二胺 生成 5-[(E)-2-(4-methoxyphenyl)-1-ethenyl]-3-methyl-4-nitroisoxazole
  参考文献：
  名称：

  REDDI, K. M.;RAO, C. J.;MURTHY, A. K., INDIAN J. CHEM., 1981, 20, N 7, 607-608

  摘要：

  DOI：

文献信息

• [EN] A METHOD FOR PREPARING SULFUR-CONTAINING COMPOUNDS<br/>[FR] PROCÉDÉ POUR LA PRÉPARATION DE COMPOSÉS CONTENANT DU SOUFRE
  申请人：ROYAL COLLEGE OF SURGEONS IE

  公开号：WO2010066450A1

  公开（公告）日：2010-06-17

  The invention provides a method for preparing sulfur-containing compounds, the method comprising reacting a donor compound comprising at least one sulfur having at least one lone pair of electrons, with an acceptor compound; wherein the reaction occurs in the presence of an amine, optionally an amine catalyst, capable of activating the sulfur having at least one lone pair of electrons; and wherein the reaction occurs via the formation of an transient intermediate species, optionally a transient intermediate species, between the amine, optionally the amine catalyst and the donor compound; and wherein the donor compound is selected from the group consisting of a sulfurous acid, a sulfenic acid and a sulfinic acid or a salt, ester or amide of a sulfurous acid, a sulfenic acid and a sulfinic acid. The invention also provides sulfur-containing compounds of the formula: wherein R is selected from: (a) 1 -(4-Nitro-phenyl)-3-oxo-3-phenyl-propane; (b) 2-(3-Methyl-4-nitro-isoxazol-5-yl)-1 -phenyl-ethane; (c) 1-(4-Methoxy-phenyl)-2-(3-methyl-4-nitro-isoxazol-5-yl)-ethane; (d) 2-(3-Methyl-4-nitro-isoxazol-5-yl)-1-(4-nitro-phenyl)-ethane; (e) 1-(4-Fluoro-phenyl)-2-(3-methyl-4-nitro-isoxazol-5-yl)-ethane; (f) 1 -(4-Chloro-phenyl)-2-(3-methyl-4-nitro-isoxazol-5-yl)-ethane; and (g) 3-Oxo-cyclohexane. Finally, the invention provides use of chiral sulfur-containing compounds obtainable by the above-mentioned method or chiral sulfur-containing compounds as mentioned above for the resolution of racemic mixtures of amines.

  该发明提供了一种制备含硫化合物的方法，该方法包括将包含至少一个硫原子且至少一个孤对电子的给体化合物与受体化合物反应；其中，在胺的存在下进行反应，可选地，在能够激活至少一个硫原子具有至少一个孤对电子的胺的存在下进行反应；反应通过形成瞬态中间体物种进行，可选地，通过胺、可选地胺催化剂和给体化合物之间的瞬态中间体物种进行反应；给体化合物选自包括亚硫酸、亚硫酸和亚砜酸或亚硫酸、亚硫酸和亚砜酸的盐、酯或酰胺的群；该发明还提供了符合以下公式的含硫化合物：其中R选自：(a) 1-(4-硝基苯基)-3-氧代-3-苯基-丙烷；(b) 2-(3-甲基-4-硝基异噁唑-5-基)-1-苯基-乙烷；(c) 1-(4-甲氧基苯基)-2-(3-甲基-4-硝基异噁唑-5-基)-乙烷；(d) 2-(3-甲基-4-硝基异噁唑-5-基)-1-(4-硝基苯基)-乙烷；(e) 1-(4-氟苯基)-2-(3-甲基-4-硝基异噁唑-5-基)-乙烷；(f) 1-(4-氯苯基)-2-(3-甲基-4-硝基异噁唑-5-基)-乙烷；和(g) 3-氧代环己烷。最后，该发明提供了通过上述方法获得的手性含硫化合物或上述提到的手性含硫化合物用于分离胺的外消旋混合物。
• Trifluoromethylation of Aromatic Isoxazoles: Regio- and Diastereoselective Route to 5-Trifluoromethyl-2-isoxazolines
  作者：Hiroyuki Kawai、Kentaro Tachi、Etsuko Tokunaga、Motoo Shiro、Norio Shibata

  DOI：10.1002/anie.201102442

  日期：2011.8.16

  It all adds up: The activation of aromatic isoxazoles with a nitro group at the 4‐position has enabled the first regio‐ and diastereoselective trifluoromethylation at the 5‐position of isoxazoles by nucleophilic addition using Me3SiCF3 (see scheme; DMF=N,N′‐dimethylformamide). The process was demonstrated with a broad range of 3,5‐aromatic, heteroaromatic and aliphatic substrates.

  所有这些加起来：在4位上带有硝基的芳香异恶唑的活化，使得能够通过Me 3 SiCF 3的亲核加成在异恶唑的5位上进行第一次区域和非对映选择性的三氟甲基化（参见方案； DMF = N ，N'-二甲基甲酰胺）。广泛的3,5-芳族，杂芳族和脂族底物都证明了该方法。
• Asymmetric Construction of Remote Vicinal Quaternary and Tertiary Stereocenters via Direct Doubly Vinylogous Michael Addition
  作者：Subhrajit Rout、Harshit Joshi、Vinod K. Singh

  DOI：10.1021/acs.orglett.8b00493

  日期：2018.4.20

  An asymmetric direct doubly vinylogous Michael addition has been developed for the generation of sterically congested vicinal quaternary and tertiary stereocenters. This doubly vinylogous Michael addition of β,γ-unsaturated butenolides to 3-methyl-4-nitro-5-alkenyl isoxazoles, powered by a bifunctional squaramide, affords a broad range of densely functionalized enantioenriched γ,γ-disubstituted butenolides

  已经开发出不对称的直接双乙烯基迈克尔加成物，用于产生空间拥挤的邻近四元和三元立体中心。在双官能的方酰胺的作用下，β，γ-不饱和丁烯内酯的双乙烯基迈克尔加成反应到3-甲基-4-硝基-5-链烯基异恶唑上，可以高收率得到各种致密的对映体富集的γ，γ-二取代丁烯内酯，在大多数情况下，出色的非对映选择性和对映选择性。此外，该策略突出了在不对称的1,6-共轭加成中首次应用β，γ-不饱和丁烯内酯。
• Phase transfer catalyzed enantioselective cyclopropanation of 4-nitro-5-styrylisoxazoles
  作者：Claudia Del Fiandra、Linda Piras、Francesco Fini、Paolo Disetti、Maria Moccia、Mauro F. A. Adamo

  DOI：10.1039/c2cc30401e

  日期：——

  substituted cyclopropane esters were prepared in high yields, complete diastereoselection and high (up to 96%) enantioselectivity. The reaction described herein entailed reacting 4-nitro-5-styrylisoxazoles, a class of cinnamate synthetic equivalent, with 2-bromomalonate esters under the catalysis of 5 mol% of a Cincona derived phase-transfer catalyst. The reaction allowed multi-gram preparation of desired

  以高收率，完全非对映选择性和高（高达96％）对映选择性制备重取代的环丙烷酯。本文所述的反应需要在5mol％的Cincona衍生的相转移催化剂的催化下使一类肉桂酸酯合成等同物4-硝基-5-苯乙烯基恶唑与2-溴丙二酸酯反应。该反应允许所需产物的多克制备。
• Enantioselective 1,6-Michael addition of anthrone to 3-methyl-4-nitro-5-alkenyl-isoxazoles catalyzed by bifunctional thiourea-tertiary amines
  作者：Hong-Wei Sun、Yu-Hua Liao、Zhi-Jun Wu、Hao-Yu Wang、Xiao-Mei Zhang、Wei-Cheng Yuan

  DOI：10.1016/j.tet.2011.04.032

  日期：2011.6

  efficient method for the enantioselective 1,6-Michael addition reaction of anthrone to a series of 3-methyl-4-nitro-5-alkenyl-isoxazoles with a bifunctional thiourea-tertiary amine as catalyst is described. This transformation proceeds smoothly with 10 mol % catalyst and provides a series of Michael adducts bearing 3-methyl-4-nitro-isoxazole and anthrone units with good to high enantioselectivities (up

  描述了一种简单有效的方法，该方法以双官能硫脲-叔胺为催化剂，使蒽与一系列3-甲基-4-硝基-5-烯基-异恶唑进行对映选择性的1,6-Michael加成反应。使用10 mol％的催化剂，该转化过程平稳进行，并提供一系列带有3-甲基-4-硝基-异恶唑和蒽酮单元的迈克尔加合物，具有良好的对映选择性（高达96％ee）和很高的产率（高达99％） ％）。