N-methyl-2,3-dihydro-1H-6,8-bis(1,1-dimethylethyl)benz[1,2-e][1,3]oxazine | 128203-42-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶嗪类
• 英文名称: N-methyl-2,3-dihydro-1H-6,8-bis(1,1-dimethylethyl)benz[1,2-e][1,3]oxazine
• 英文别名: 6,8-di-tert-butyl-3-methyl-2H-3,4-dihydro-1,3-benzoxazine；6,8-ditert-butyl-3-methyl-3,4-dihydro-2H-[1,3]benzoxazine；6,8-ditert-butyl-3-methyl-2,4-dihydro-1,3-benzoxazine
• CAS: 128203-42-9
• 化学式: C₁₇H₂₇NO
• 分子量: 261.407
• InChiKey: IUKSTIPRSHIEOI-UHFFFAOYSA-N

物化性质

• 沸点：
  303.9±41.0 °C(Predicted)
• 密度：
  0.961±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-methyl-2,3-dihydro-1H-6,8-bis(1,1-dimethylethyl)benz[1,2-e][1,3]oxazine 在 sodium tetrahydroborate 、 manganese(II) acetate 、 manganese triacetate 作用下， 以 溶剂黄146 、 异丙醇 为溶剂， 反应 8.0h， 生成 3,5-二叔丁基水杨醛
  参考文献：
  名称：

  Oxidation of 2-dialkylaminomethyl-4,6-di-tert-butylphenols

  摘要：

  Oxidative transformations of 2-dialkylaminomethyl-4,6-di-tert-butylphenols depend on the nature of the oxidant, the character of the substituents at the nitrogen atom, and the medium. A mechanism of the oxidation of these compounds is suggested. The molecular structure of the compound obtained as a result of oxidative trimerization of 2-dimethylaminomethyl-4,6-di-tert-butylphenol was established by X-ray structural analysis.

  DOI：

  10.1007/bf02495927
• 作为产物：
  描述：

  2,4-二叔丁基苯酚 在 sodium hydroxide 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 反应 48.5h， 生成 N-methyl-2,3-dihydro-1H-6,8-bis(1,1-dimethylethyl)benz[1,2-e][1,3]oxazine
  参考文献：
  名称：

  II-FeCl 2 / Fe 0 / O 2体系中的氧化'氨基甲基-2'酚

  摘要：

  在铁和氯化铁（II）的催化量存在下，氧被分子氧氧化的2-氨基甲基苯酚1（a：R = CH 3 ; b：R = H）主要提供醛2，甲酰胺4和恶嗪5。讨论了这些氧化的机理和反应性的性质。尤其是叔胺氧化物1c在叔胺1a的氧化脱烷基中的可能的中间作用。

  DOI：

  10.1016/s0040-4020(01)81363-6

文献信息

• New Opportunities for Duff Reaction
  作者：I. S. Belostotskaya、N. L. Komissarova、T. I. Prokof’eva、L. N. Kurkovskaya、V. B. Vol’eva

  DOI：10.1007/s11178-005-0229-4

  日期：2005.5

  Reaction of 2,4-di-tert-butylphenol with urotropin in conditions of Duff reaction takes an abnormal route and instead of the expected di-tert-butylsalicylaldehyde provides a mixture of N-substituted 3,5-di-tert-butyl-2-hydroxybenzylamines and redox conjugate benzoxazines containing mostly 6,8-di-tert-butyl-3-(3,5-di-tert-butyl-2-hydroxybenzyl)-2H-3,4-dihydrobenz[e][1,3]oxazine. A solvolysis of an individual benzoxazine in the system HO(CH2)2OH-H2O-HCl affords di(3,5-di-tert-butyl-2-hydroxybenzyl)amine, and in AcOH 3,5-di-tert-butylsalicilaldehyde. A mechanism of Duff reaction was suggested involving the formation of a benzoxazine intermediate.

  2,4-二叔丁基苯酚与尿素在达夫反应条件下的反应采取了异常路径，未能生成预期的二叔丁基水杨醛，而是提供了N取代的3,5-二叔丁基-2-羟基苯甲胺的混合物以及主要包含6,8-二叔丁基-3-(3,5-二叔丁基-2-羟基苯甲基)-2H-3,4-二氢苯【e】【1,3】氧杂环的氧化还原共轭物。在HO(CH2)2OH-H2O-HCl体系中，单一的氧杂环的溶解水解生成二(3,5-二叔丁基-2-羟基苯甲基)胺，而在醋酸中则生成3,5-二叔丁基水杨醛。提出了一种达夫反应的机理，涉及到苯氧杂环中间体的形成。
• Synthesis of dioxazaborocines from N-substituted-bis(2-hydroxyaryl)aminomethylamines
  作者：Paul D Woodgate、Gillian M Horner、N.Paul Maynard、Clifton E.F Rickard

  DOI：10.1016/s0022-328x(99)00510-0

  日期：1999.12

  The preparation of a number of tripodal amines from aminoalkylation of 1,3-benzoxazines by phenols is presented. A series of ligands prepared in this manner were successfully coordinated to boron, giving dioxazaborocines. X-ray crystal structures of two analogues are reported. These compounds are capable of releasing berate ions and are therefore potentially biologically active. (C) 1999 Elsevier Science S.A. All rights reserved.
• Semi-hindered phenols. 1. Synthesis of 3,5-di-tert-butylsalicylic aldehyde
  作者：M. A. Dokukina、V. B. Vol'eva、I. S. Belostotskaya、N. L. Komissarova、A Yu Karmilov、V. V. Ershov

  DOI：10.1007/bf00863824

  日期：1992.10

  Some differences were observed in the solid- and liquid-phase benzylic oxidation of 2-(hydroxy- or dialkylamino)-methyl-4,6-di-tert-butylphenols. Oxidation of these semi-hindered phenols with lead tetraacetate gave a new compound: 3,5-di-tert-butyl-ortho-benzoquinone diacylal.
• ——
  作者：V. B. Vol'eva

  DOI：10.1023/a:1023498730408

  日期：——

  The possibility was revealed for exhaustive protonation of 2,4-di-tert-butyl-6-dimethylamino-methylphenol with participation of one electron pairs on both nitrogen and oxygen atoms. The reaction of the title compound with alkyl halides includes concurrent and consecutive processes leading to formation of the corresponding hydrohalides and quaternization products. The latter undergo spontaneous oxidation with atmospheric oxygen to give quaternary 6,8-di-tert-butyl-3-methyl-2H-3,4-dihydro-1,3-benzoxazine derivatives which were detected by H-1 NMR spectroscopy.
• II - Oxydation catalytique d'aminomethyl-2 phenols par un systeme FeCl2/Fe 0/O2
  作者：Daniel Sparfel、Joële Baranne-Lafont、Nguyen Kim Cuong、Patrice Capdevielle、Michel Maumy

  DOI：10.1016/s0040-4020(01)81363-6

  日期：1990.1

  H) oxidized by molecular oxygen in presence of iron and iron(II) chloride in catalytic amount chiefly afford aldehyde 2, formamide 4 and oxazine 5. The mechanisms of these oxidations and the nature of the reactive species are discussed; in particular the possible intermediate role of tertiary amine oxide 1c in the oxidative dealkylation of tertiary amine 1a.

  在铁和氯化铁（II）的催化量存在下，氧被分子氧氧化的2-氨基甲基苯酚1（a：R = CH 3 ; b：R = H）主要提供醛2，甲酰胺4和恶嗪5。讨论了这些氧化的机理和反应性的性质。尤其是叔胺氧化物1c在叔胺1a的氧化脱烷基中的可能的中间作用。