(Z)-1-(4-chlorophenyl)-N-methylmethanimine oxide | 16089-64-8

• 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: (Z)-1-(4-chlorophenyl)-N-methylmethanimine oxide
• 英文别名: N-(4-chlorobenzylidene)methanamine oxide；1-(4-chlorophenyl)-N-methylmethanimine oxide
• CAS: 16089-64-8
• 化学式: C₈H₈ClNO
• 分子量: 169.611
• InChiKey: UXCJETAKFJCNJQ-POHAHGRESA-N

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：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  28.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-1-(4-chlorophenyl)-N-methylmethanimine oxide 在 碘甲烷 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 (Z)-ethyl 4-(4'-chlorophenyl)-2-oxo-3-butenoate
  参考文献：
  名称：

  Ring-Opening of 4-Isoxazolines: Competitive Formation of Enamino Derivatives and a,b-Enones

  摘要：

  Ring-opening of 3-substituted 4-isoxazolines, proceeding through the intermediate isoxazolinium salts, follows two competing reaction pathways leading to alpha,beta-enones and enamines respectively. The rearrangement courses can be controlled as a function of substitution pattern and experimental conditions.

  DOI：

  10.3987/com-92-6223
• 作为产物：
  描述：

  N-甲基羟胺 、 4-氯苯甲醛 在 sodium acetate 作用下， 反应 0.1h， 以92%的产率得到(Z)-1-(4-chlorophenyl)-N-methylmethanimine oxide
  参考文献：
  名称：

  Exploiting microwave-assisted neat procedures: synthesis of N-aryl and N-alkylnitrones and their cycloaddition en route for isoxazolidines

  摘要：

  Microwave irradiation allows increasing the speed of several reactions and also offers the possibility of eliminating poisoning organic solvents. In this work we report the microwave-assisted neat synthesis of alpha-phenyl-tert-butylnitrone (PBN) and other alkyl and aryl nitrones and also the rapid synthesis of isoxazolidines resulting from 1,3-dipolar cycloaddition of nitrones to ethyl trans-crotonate. (c) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.08.101

文献信息

• Regio‐ and Enantioselective (3+3) Cycloaddition of Nitrones with 2‐Indolylmethanols Enabled by Cooperative Organocatalysis
  作者：Tian‐Zhen Li、Si‐Jia Liu、Yu‐Wen Sun、Shuang Deng、Wei Tan、Yinchun Jiao、Yu‐Chen Zhang、Feng Shi

  DOI：10.1002/anie.202011267

  日期：2021.2

  regiospecificity. This approach enabled not only the first organocatalytic asymmetric (3+3) cycloaddition of nitrones but also the first C3‐nucleophilic asymmetric (3+3) cycloaddition of 2‐indolylmethanols. More importantly, theoretical calculations elucidated the role of the cocatalyst HFIP in helping CPA control the reactivity and enantioselectivity of the reaction, demonstrating a new mode of cooperative catalysis

  硝酮与2-吲哚基甲醇的区域和对映选择性（3 + 3）环加成反应是通过六氟异丙醇（HFIP）和手性磷酸（CPA）的协同催化完成的。使用这种方法，以高收率（高达98％），优异的对映选择性（高达96％ee）和排他的区域特异性合成了一系列吲哚稠合的六元杂环。这种方法不仅可以实现硝酮的首次有机催化不对称（3 + 3）环加成反应，而且还可以实现2-吲哚基甲醇的首次C3-亲核不对称（3 + 3）环加成反应。更重要的是，理论计算阐明了助催化剂HFIP在帮助CPA控制反应的反应性和对映选择性方面的作用，证明了一种新型的协同催化方式。
• Electronic effects in 1,3-dipolar cycloaddition reactions of N-alkyl and N-benzyl nitrones with dipolarophiles
  作者：Andrei Bădoiu、E. Peter Kündig

  DOI：10.1039/c1ob06144e

  日期：——

  1,3-Dipolar cycloadditions afforded fast access to isoxazolidines bearing N-alkyl or N-benzyl substituents. The electronic properties of the substituents in the nitrones define the activity of the dipoles and modulate diastereoselectivity in the non-catalyzed reactions. Using a chiral one-point binding ruthenium Lewis acid catalyst, products were obtained in good yields and with excellent regio-, diastereo-

  1，3-偶极环加成可快速接近带有N-烷基或N-苄基取代基的异恶唑烷。硝酮中取代基的电子性质定义了偶极子的活性，并调节了非催化反应中的非对映选择性。使用手性单点结合钌路易斯酸催化剂，可以以良好的收率和优异的区域，非对映和对映选择性获得产物。
• [3+2] Cycloadditions: Part XXXIV: Further Investigations of Cycloadditions of C,N-Diaryl- and C-Aryl-N-methyl Nitrones to α,β-Unsaturated Esters
  作者：Sumana Sengupta、Avijit Banerji

  DOI：10.14233/ajchem.2019.22232

  日期：2019.11.30

  as three atom components (TAC) to substituted methyl E-cinnamates and diethyl arylidene malonates have been further investigated. [3+2] Cycloadditions of cinnamates yielded mixtures of cycloadducts, the major products being the 3,4-trans-4,5-trans-2,3,5-triaryl-4-carbomethoxy products originating from the endo-carbonyl-exo-aryl meta channel approach of the cinnamate component. [3+2] Cycloadditions to

  进一步研究了 C,N-二芳基和 C-芳基-N-甲基硝酮作为三原子组分 (TAC) 与取代的 E-肉桂酸甲酯和亚芳基丙二酸二乙酯的 [3+2] 环加成反应。肉桂酸酯的[3+2]环加成反应产生环加合物的混合物，主要产物是源自内-羰基-外的3,4-反式-4,5-反式-2,3,5-三芳基-4-甲甲氧基产物肉桂酸酯成分的芳基元通道方法。[3+2]与亚芳基丙二酸二乙酯的环加成通过2π-组分的内芳基间通道方法提供单一环加合物-3,5-反式-2-甲基-3,5-二芳基-4,4-二乙氧基异恶唑烷。
• Synthesis and biological evaluation of diastereoisomerically pure N,O-nucleosides
  作者：Olga Bortolini、Antonio De Nino、Tommaso Eliseo、Riccardo Gavioli、Loredana Maiuolo、Beatrice Russo、Fabio Sforza

  DOI：10.1016/j.bmc.2010.08.024

  日期：2010.10

  Several N,O-nucleosides have been synthesized in good yields by direct 1,3-dipolar cyclization methodology, in the absence of solvent. A remarkable cis stereoselectivity (de 98%) was observed by tuning the substituents on the nitrone moiety. A good number of these N,O-nucleosides have been evaluated for cytotoxic activity against selected cellular lines. Some of the tested compounds have proven to

  在不存在溶剂的情况下，通过直接的1，3-偶极环化方法已经以高收率合成了几种N，O-核苷。通过调节硝酮部分上的取代基，观察到了显着的顺式立体选择性（98％）。已经评估了许多这些N，O-核苷对所选细胞系的细胞毒活性。已证明某些测试化合物是潜在的抗增殖药。
• New Strategies for Organic Catalysis:  The First Enantioselective Organocatalytic 1,3-Dipolar Cycloaddition
  作者：Wendy S. Jen、John J. M. Wiener、David W. C. MacMillan

  DOI：10.1021/ja005517p

  日期：2000.10.1

  catalytic strategy is also amenable to [3 + 2] cycloadditions between nitrones and α,β-unsaturated aldehydes to provide isoxazolidines (eq 3), useful synthons for the construction of biologically important amino acids, β-lactams, amino carbohydrates, and alkaloids. To our knowledge, this is the first example of an organocatalytic 1,3-dipolar cycloaddition. Moreover, this study further documents that

  我们的实验室一直致力于为使用有机化学品作为反应催化剂的对映选择性催化设计广泛有用的新策略。在我们最近的研究中，我们报道了使用手性咪唑烷酮 1 (eq 1) 可逆形成亚胺离子对 α,β-不饱和醛的 LUMO 降低活化是开发对映选择性有机催化 Diels-Alder 反应的宝贵平台。等式 2)。在这项工作中，我们揭示了这种催化策略也适用于硝酮和 α,β-不饱和醛之间的 [3 + 2] 环加成反应，以提供异恶唑烷（方程式 3），这是一种有用的合成子，可用于构建具有生物学意义的氨基酸，β-内酰胺、氨基碳水化合物和生物碱。据我们所知，这是有机催化 1,3-偶极环加成的第一个例子。而且，