5-甲氧基-1,2-苯并异噁唑 | 39835-06-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并异恶唑
• 中文名称: 5-甲氧基-1,2-苯并异噁唑
• 英文名称: 5-Methoxy-benzisoxazol
• 英文别名: 5-Methoxybenzo[d]isoxazole；5-methoxy-1,2-benzoxazole
• CAS: 39835-06-8
• 化学式: C₈H₇NO₂
• mdl: MFCD06659646
• 分子量: 149.149
• InChiKey: OPLJFHFYIHBFEJ-UHFFFAOYSA-N

物化性质

• 沸点：
  257.6±13.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.125
• 拓扑面积：
  35.3
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2934999090

反应信息

• 作为反应物：
  描述：

  5-甲氧基-1,2-苯并异噁唑 在 palladium on activated charcoal 甲酸铵 作用下， 以 甲醇 为溶剂， 反应 16.0h， 以52%的产率得到2-[[(2-Hydroxy-5-methoxyphenyl)methylamino]methyl]-4-methoxyphenol
  参考文献：
  名称：

  由肟和苯并异恶唑生产仲胺的温和方法

  摘要：

  在甲醇中甲酸铵/钯-碳的温和条件下，可以还原2-羟基苯甲酰肟，生成仲胺。苯并异恶唑在相同的温和条件下反应，得到相同的产物。提出了一种可能的机制，其中涉及苯并异恶唑在肟转化中的中介作用。

  DOI：

  10.1016/s0040-4039(03)01623-x
• 作为产物：
  描述：

  2-hydroxy-5-methoxybenzaldehyde oxime 在 三苯基膦 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 0.02h， 生成 5-甲氧基-1,2-苯并异噁唑
  参考文献：
  名称：

  [3 + 2]-氮杂烯丙基阳离子与1,2-苯并异恶唑的环加成反应：恶唑啉的快速进入

  摘要：

  已开发出新颖且有效的氮杂烯丙基阳离子与1,2-苯并恶唑的[3 + 2]环加成反应以生成恶唑啉衍生物。该转化可在温和且无过渡金属的条件下快速进入功能化的恶唑啉骨架，这将大大扩展杂环化学的反应类型，并为生物活性化合物的合成铺平道路。

  DOI：

  10.1021/acs.joc.9b01166

文献信息

• Ring opening [3 + 2] cyclization of azaoxyallyl cations with benzo[d]isoxazoles: Efficient access to 2-hydroxyaryl-oxazolines
  作者：Yicheng He、Chao Pi、Yangjie Wu、Xiuling Cui

  DOI：10.1016/j.cclet.2019.09.025

  日期：2020.2

  Abstract A selective ring-opening [3 + 2] cyclization reaction of benzo[d]isoxazoles with 2-bromo-propanamides has been developed. The azaoxyallyl cation intermediates are employed as C∼O 3-atom synthon to build oxa-heterocycles via the selectivity of suitable cyclization partners. This transformation provides rapid access to highly functionalized 2-hydroxyaryl-oxazolines under mild conditions and

  摘要研究了苯并[d]异恶唑与2-溴-丙酰胺的选择性开环[3 + 2]环化反应。氮杂烯丙基阳离子中间体可作为C〜O 3-原子合成子，通过合适的环化配偶体的选择性构建氧杂杂环。这种转化提供了在温和条件下快速获得高度官能化的2-羟基芳基-恶唑啉和出色的区域选择性的能力。
• Bioinspired Iron-Catalyzed Dehydration of Aldoximes to Nitriles: A General N–O Redox-Cleavage Method
  作者：Hongjie Gao、Jia-Yi Chen、Zhiqiang Peng、Lei Feng、Chen-Ho Tung、Wenguang Wang

  DOI：10.1021/acs.joc.2c01122

  日期：2022.8.19

  Inspired by OxdA that operates biocatalytic aldoxime dehydration, we have developed an efficient iron catalyst, Cp*Fe(1,2-Cy2PC6H4O) (1), which rapidly converts various aliphatic and aromatic aldoximes to nitriles with release of H2O at room temperature. The catalysis involves redox activation of the N–O bond by a 1e– transfer from the iron catalyst to the oxime. Such redox-mediated N–O cleavage was

  受操作生物催化醛肟脱水的 OxdA 的启发，我们开发了一种高效的铁催化剂 Cp*Fe(1,2-Cy 2 PC 6 H 4 O) ( 1 )，它可以将各种脂肪族和芳香族醛肟快速转化为腈，同时释放H 2 O 在室温下。催化涉及通过 1e 对 N-O 键的氧化还原活化-从铁催化剂转移到肟。这种氧化还原介导的 N-O 裂解通过从酮肟底物的反应中分离出亚氨基亚铁中间体来证明。这种铁催化的无受体脱水方法代表了制备腈的一般方法，它还通过催化 Kemp 消除反应提供水杨腈。
• Utility of Nitrogen Extrusion of Azido Complexes for the Synthesis of Nitriles, Benzoxazoles, and Benzisoxazoles
  作者：Phongprapan Nimnual、Jumreang Tummatorn、Charnsak Thongsornkleeb、Somsak Ruchirawat

  DOI：10.1021/acs.joc.5b01305

  日期：2015.9.4

  The utility of the nitrogen extrusion reaction of azido complexes, generated in situ from the corresponding aldehydes or ketones with TMSN3 in the presence of ZrCl4 or TfOH, has been described. These azido complexes could undergo three different pathways, depending on the substrates. First, azido methanolate complexes or imine diazonium ions could lead to benzisoxazole products via an intramolecular nucleophilic substitution. Second, imine diazonium ions could also undergo either the elimination of proton to provide nitrile products in good to excellent yields or an aryl migration, followed by an intramolecular nucleophilic addition, to give benzoxazole products in good yields.
• Isoxazole derivatives for use as cerebro-active drugs and central muscle relaxants
  申请人：Sankyo Company Limited

  公开号：EP0335723B1

  公开（公告）日：1991-12-04
• On the Magnitude and Specificity of Medium Effects in Enzyme-like Catalysts for Proton Transfer
  作者：Florian Hollfelder、Anthony J. Kirby、Dan S. Tawfik

  DOI：10.1021/jo015723v

  日期：2001.8.1

  Medium effects are normally studied by comparing the rates of reactions in different solvents. However, medium effects at the active site of enzymes differ dramatically from bulk solvents, both in their diversity (the presence of more than one type of "solvent") and in their spatial arrangement. We describe medium effects in a simple catalytic system, obtained by systematic alkylation of a polymeric scaffold bearing amine groups to give synzymes that catalyze the Kemp elimination of benzisoxazoles with remarkable efficiency. Our analysis indicates that catalysis by these synzymes is driven primarily by specific, localized enzyme-like medium effects, and these effects seem to differ dramatically from the nonspecific medium effects (i.e., desolvation activation) exhibited by solvents. Ligand-binding studies indicate that the synzyme active sites provide localized microenvironments affording a combination of hydrophobic and apolar regions on one hand and dipolar, protic, and positively charged on the other. Such localized microenivronments are not available in bulk solvents. A Bronsted (leaving group) analysis indicates that, in comparison to solvent catalysis, the efficiency of synzyme catalysis shows little sensitivity to leaving group pK(a). We show that enzyme-like medium effects alone, in the absence of efficient positioning of the catalytic amine base relative to the substrate, can give rise to rate accelerations as high as 10(5), for both activated and nonactivated substrates. Supported by the accidental identification of active sites on the surfaces of noncatalytic proteins and the promiscuous activities found in many enzymes, our findings suggest that the interfaces of protein surfaces and their hydrophobic cores provide a microenvironment that is intrinsically active and may serve as a basis for further evolutionary improvements to give proficient and selective enzymes.