(E)-2-(benzylideneamino)-4-methylphenol | 878193-80-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: (E)-2-(benzylideneamino)-4-methylphenol
• CAS: 878193-80-7
• 化学式: C₁₄H₁₃NO
• 分子量: 211.263
• InChiKey: CLQPFEYCMPYBLK-XNTDXEJSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  32.59
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (E)-2-(benzylideneamino)-4-methylphenol 在 2-甲基-2-丁烯 、 碘苯二乙酸 、 potassium carbonate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 5.0h， 生成 (1SR,2SR)-2-methyl-1-phenylbut-3-en-1-amine
  参考文献：
  名称：

  The First Allylation of Imines with Allyltrichlorosilanes Using Neutral Coordinate-Organocatalysts

  摘要：

  来自醛和2-氨基苯酚的亚胺与烯丙基三氯硅烷在DMF、HMPA或吡啶N-氧化物作为中性配位有机催化剂的存在下反应，得到相应的同烯丙胺，产率高且立体选择性强；这是亚胺与烯丙基三氯硅烷发生烯丙基化的首次例子。

  DOI：

  10.1055/s-2003-41437
• 作为产物：
  描述：

  邻氨基对甲苯酚 在 苯甲醛 作用下， 以 甲醇 为溶剂， 生成 (E)-2-(benzylideneamino)-4-methylphenol
  参考文献：
  名称：

  Carboxylic acid derivatives as IP antagonists

  摘要：

  这项发明涉及一类通常为IP受体拮抗剂的化合物，其由以下式I表示： 其中： R1、R2和R3在每次出现时各自独立地为芳基或杂环芳基； R4为—COOH或四唑基； A、B、m、n和r如规范中定义； 或其各个异构体、外消旋或非外消旋异构体混合物，或其药用可接受盐或溶剂合物。该发明还涉及含有这种化合物的药物组合物，以及将其用作治疗剂的方法和其制备方法。

  公开号：

  US20010056100A1

文献信息

• Synthesis of 2-substituted pyrimidines and benzoxazoles via a visible-light-driven organocatalytic aerobic oxidation: enhancement of the reaction rate and selectivity by a base
  作者：Lin Wang、Zhi-Gang Ma、Xiao-Jing Wei、Qing-Yuan Meng、Deng-Tao Yang、Shao-Fu Du、Zi-Fei Chen、Li-Zhu Wu、Qiang Liu

  DOI：10.1039/c4gc00337c

  日期：——

  An efficient visible-light-driven photocatalytic oxidation of various 2-substituted dihydropyrimidines and phenolic imines has been achieved using an organic photocatalyst eosin Y bis(tetrabutyl ammonium salt) (TBA-eosin Y) and inexpensive oxidant molecular oxygen. With the aid of a base, significantly enhanced photoinduced electron transfer from substrates dihydropyrimidines or phenolic imines to the excited state of TBA-eosin Y has enabled the aerobic oxidation to yield 2-(methylthio)pyrimidines or 2-arylbenzoxazoles selectively.

  利用有机光催化剂藻红Y双(四丁基铵盐)(TBA-藻红Y)和廉价氧化剂分子氧，已经实现了各种2-取代二氢嘧啶和酚亚胺的高效可见光驱动光催化氧化反应。在碱的辅助下，从底物二氢嘧啶或酚亚胺到TBA-藻红Y激发态的显著增强的光诱导电子转移，使得空气氧化能够选择性地生成2-(甲硫基)嘧啶或2-芳基苯并噁唑。
• Synthesis of Benzoxazoles Using Electrochemically Generated Hypervalent Iodine
  作者：Olesja Koleda、Timo Broese、Jan Noetzel、Michael Roemelt、Edgars Suna、Robert Francke

  DOI：10.1021/acs.joc.7b01686

  日期：2017.11.17

  The indirect (“ex-cell”) electrochemical synthesis of benzoxazoles from imines using a redox mediator based on the iodine(I)/iodine(III) redox couple is reported. Tethering the redox-active iodophenyl subunit to a tetra-alkylammonium moiety allowed for anodic oxidation to be performed without supporting electrolyte. The mediator salt can be easily recovered and reused. Our “ex-cell” approach toward

  据报道，使用基于碘（I）/碘（III）氧化还原对的氧化还原介体从亚胺间接（“细胞外”）电化学合成苯并恶唑。将氧化还原活性的碘代苯基亚基束缚到四烷基铵部分上，从而可以在不支持电解质的情况下进行阳极氧化。介体盐可以很容易地回收和再利用。我们对苯并恶唑进行电合成的“细胞外”方法与一系列对氧化还原敏感的官能团兼容。在控制实验和DFT计算的基础上，提出了前所未有的协同消除苯并恶唑形成的机理。
• Enantioselective Mannich-Type Reaction Catalyzed by a Chiral Brønsted Acid Derived from TADDOL
  作者：Takahiko Akiyama、Youichi Saitoh、Hisashi Morita、Kohei Fuchibe

  DOI：10.1002/adsc.200505167

  日期：2005.10

  dialkyl phosphate was synthesized starting from (+)-diethyl tartrate. Its catalytic activity as a chiral Brønsted acid has been examined in the Mannich-type reaction of a ketene silyl acetal with aldimines as a model reaction. The corresponding β-amino acid esters were obtained with high enantioselectivity.

  从（+）-酒石酸二乙酯开始合成新型的环状磷酸二烷基酯。在乙烯酮甲硅烷基乙缩醛与醛亚胺的曼尼希型反应中，已验证了其作为手性布朗斯台德酸的催化活性。以高对映选择性获得了相应的β-氨基酸酯。
• Oxidation of N-benzylidene-2-hydroxyaniline by dioxygen catalysed by a dicobalt complex †
  作者：Shian Yuh Chang、Yee Hsing Cheng、Bing-Jium Uang、Cheu Pyeng Cheng

  DOI：10.1039/a903699g

  日期：——

  The oxidation of N-benzylidene-2-hydroxyaniline and its related derivatives by O2 catalysed by [Co2L(µ-OH)] H3L = 2,6-bis[(2-hydroxyphenyl)iminomethyl]-4-methylphenol} in DMF at 363 K was investigated. The oxidation products were the corresponding 2-substituted benzoxazoles. However, a side reaction leading to 2-aminophenoxazine-3-one via hydrolysis of the starting compound with water produced in the oxidation, followed by the oxidation of aminophenol, was established. If a dehydrating agent such as anhydrous Na2SO4 or 4 Å molecular sieves was present in the reaction mixture the isolated product yields were above 87%. The fact that the reaction rate of the oxidation process in the presence of a radical scavenger was similar to that without suggests that it was a non-radical process. The initial oxidation rates depended linearly on the concentration of catalyst. The rates also depended linearly on the concentration of the organic substrate N-benzylidene-2-hydroxyaniline and O2 pressure when these variables were small ([substrate] < 0.2 M, O2 pressure < 70 kPa). At high concentration of substrate and O2 pressure the rate showed saturation behavior. These kinetic data could be satisfactorily accounted for by a mechanism with initial co-ordination of substrate to [Co2L(µ-OH)], followed by the co-ordination of O2 to the catalyst, then the rate limiting step of oxidation of substrate. The formation of the adduct between N-benzylidene-2-hydroxyaniline and catalyst at 298 K was characterized by UV-Vis spectroscopy. The variation of the initial rates among the organic substrates could be explained by stereoelectronic effects. Moreover, the influence of acetic acid which slowed the initial rate of oxidation and weak base (2,6-di-tert-butylpyridine) which had little effect on the rate could also be satisfactorily accounted for based on the acid–base properties of the proposed reaction intermediates.

  研究了 N-亚苄基-2-羟基苯胺及其相关衍生物在 [Co2L(µ-OH)] H3L = 2,6-双[(2-羟基苯基)亚氨基甲基]-4-甲基苯酚}催化下于 DMF 中于 363 K 发生的 O2 氧化反应。氧化产物是相应的 2-取代苯并恶唑。不过，通过起始化合物与氧化过程中产生的水发生水解，然后氨基苯酚发生氧化，最终生成 2-氨基苯并恶嗪-3-酮的副反应已经确定。如果在反应混合物中加入脱水剂（如无水 Na2SO4 或 4 à 分子筛），分离产物的产率可达 87%以上。在有自由基清除剂存在的情况下，氧化过程的反应速率与没有自由基清除剂的情况相似，这表明这是一个非自由基过程。初始氧化速率与催化剂浓度成线性关系。当有机底物 N-亚苄基-2-羟基苯胺的浓度和氧气压力较小时（[底物] < 0.2 M，氧气压力 < 70 kPa），速率也与这些变量成线性关系。当底物浓度和氧气压力较高时，速率呈现饱和状态。这些动力学数据可以用以下机制圆满地解释：底物与[Co2L(µ-OH)]最初配位，然后 O2 与催化剂配位，接着是底物氧化的限速步骤。在 298 K 下，N-亚苄基-2-羟基苯胺与催化剂之间形成的加合物用紫外可见光谱进行了表征。有机底物之间初始速率的变化可以用立体电子效应来解释。此外，醋酸会减慢初始氧化速率，弱碱（2,6-二叔丁基吡啶）对速率的影响很小，根据所提出的反应中间体的酸碱性质，这些影响也可以得到满意的解释。
• Manganese triacetate oxidation of phenolic schiffs bases: Synthesis of 2-arylbenzoxazoles
  作者：Rajender S. Varma、Dalip Kumar

  DOI：10.1002/jhet.5570350656

  日期：1998.11

  A concise synthesis of 2-arylbenzoxazoles, 5a-f, is described that occurs via the oxidative cyclization of Schiff's bases, 1a-f, using relatively benign reagent, manganese triacetate.

  描述了2-芳基苯并恶唑5a-f的简明合成，该合成通过使用相对温和的试剂三乙酸锰通过席夫碱1a-f的氧化环化而发生。