6,8-di-tert-butyl-3-(3,5-di-tert-butyl-2-hydroxybenzyl)-2H-3,4-dihydrobenz-1,3-oxazine | 120695-69-4

• 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: 6,8-di-tert-butyl-3-(3,5-di-tert-butyl-2-hydroxybenzyl)-2H-3,4-dihydrobenz-1,3-oxazine
• 英文别名: 6,8-di-tert-butyl-3-(3,5-di-tert-butyl-2-hydroxybenzyl)-2H-3,4-dihydrobenz(e)-1,3-oxazine；6,8-di-tert-butyl-3-(3,5-di-tert-butyl-2-hydroxybenzyl)-2H-3,4-dihydrobenz-1,3-oxazine；6,8-ditert-butyl-3-(3,5-di-tert-butyl-2-hydroxybenzyl)-2H-3,4-dihydrobenz-1,3-oxazine；2,4-di-tert-butyl-6-[(6,8-di-tert-butyl-2H-1,3-benzoxazin-3(4H)-yl)methyl]phenol；2,4-Ditert-butyl-6-[(6,8-ditert-butyl-2,4-dihydro-1,3-benzoxazin-3-yl)methyl]phenol
• CAS: 120695-69-4
• 化学式: C₃₁H₄₇NO₂
• 分子量: 465.72
• InChiKey: FNYOUULNRLBNMC-UHFFFAOYSA-N

物化性质

• 熔点：
  169-170 °C(Solv: hexane (110-54-3); methanol (67-56-1))
• 沸点：
  493.8±45.0 °C(Predicted)
• 密度：
  1.008±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  34
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  32.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6,8-di-tert-butyl-3-(3,5-di-tert-butyl-2-hydroxybenzyl)-2H-3,4-dihydrobenz-1,3-oxazine 在 lithium aluminium tetrahydride 作用下， 以85%的产率得到Methylimino-2,2'-dimethylene-bis-(4,6-di-tert-butyl-phenol)
  参考文献：
  名称：

  Anomalous Duff reaction with 2,4-di-tert-butylphenol

  摘要：

  DOI：

  10.1007/bf00962532
• 作为产物：
  描述：

  tris(4,6-di-tert-butyl-2-hydroxybenzyl)amine 在 水 、 sodium hydroxide 作用下， 反应 1.0h， 生成 6,8-di-tert-butyl-3-(3,5-di-tert-butyl-2-hydroxybenzyl)-2H-3,4-dihydrobenz-1,3-oxazine
  参考文献：
  名称：

  Multimetallic Synergic Sedation of a Labile Sodium Atrane: Synthesis and Characterization of a Tetranuclear Sodium Atrane Cation Complex

  摘要：

  A series of sodium and aluminum atrane complexes of Na3L(THF)(5) (1), [AlLMe][Na4L(THF)(6)] (2), AlL(THF) (3), AlNaLMe(THF)(2) (4), and AlNaLOBn(THF)(2) (5), wherein L = tris(2-oxy-4,6-di-tert-butyl-benzyl)amine, were synthesized and characterized by NMR, X-ray crystallography, and elemental analysis. The trinuclear sodium atrane complex of Na3L(THF)(5) (1) is labile at room temperature; however, the tetranuclear sodium atrane cation in complex 2 can be stabilized by a multimetallic synergetic effect due to a firm interaction ring of -[Na-O-benzene](3)-. Complex 2 is also the first example of a sodatrane and alumatrane ion-paired complex in which both the cationic and anionic moieties contain an atrane ligand.

  DOI：

  10.1021/ic2013123

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。
• Anomalous Duff reaction with 2,4-di-tert-butylphenol
  作者：N. L. Komissarova、I. S. Belostotskaya、O. V. Shubina、V. V. Ershov、V. N. Voznesenskii、I. I. Chervin

  DOI：10.1007/bf00962532

  日期：1988.9
• Steric effects on forming different by-products in the formylation reaction of 2,4-dialkylphenol (dialkyl=t-Bu/t-Bu, t-Bu/Me and Me/Me) proved by their structural and spectral characterizations
  作者：Wei Huang、Zhaolian Chu、Feng Xu

  DOI：10.1016/j.molstruc.2007.10.035

  日期：2008.8

  In the formylation reaction of 2,4-dialkylphenol (2,4-di-tert-butylphenol, 2-tert-butyl-4-methylphenol and 2,4-dimethylphenol) in the presence of hexamethylenetetramine, steric effects of alkyl groups play important roles in forming different types of by-products, namely 2,4-di-tert-butyl-6-[(6,8-di-tei-t-butyl-2H-1,3-benzoxazin-3(4H)-yl)methyl]phenol (1), 2-tert-butyl-4-methyl-6-[(6-tert-butyl-8-methyl-2H-1,3-benzoxazin-3(4H)-yl)methyl]phenol (2) and tris(2-hydroxy-3,5-dimethylbenzyl)amine hydrochlorate (3). These three compounds are fully characterized and single-crystal structures of 1 and 3 are further elucidated. (C) 2007 Elsevier B.V. All rights reserved.
• Urotropin synthesis of 3,5-di-tert-butylsalicylic acid derivatives
  作者：V. B. Vol’eva、I. S. Belostotskaya、N. L. Komissarova、L. N. Kurkovskaya、A. P. Pleshakova、T. I. Prokofeva

  DOI：10.1134/s1070428007100132

  日期：2007.10

  The stability of 3,5-di-tert-butylsalicylic aldehyde against oxidation is due to autoinhibiting of the chain process. However its oxidation into 3,5-di-tert-butylsalicylic acid was performed at the use of acetyl protection of the hydroxy group. In reaction of 6-bromo-2,4-di-tert-butylphenol with urotropin the formation was discovered of 3,5-di-tert-butylsalicylic acid, its nitrile and amide.
• SHUBINA, O. V.;GOLUBEVA, I. A.;VISHNYAKOVA, T. P.;ZARAKOVSKAYA, E. P., OSN. ORGAN. SINTEZ I NEFTEXIMIYA,(1989) N5, S. 87-90
  作者：SHUBINA, O. V.、GOLUBEVA, I. A.、VISHNYAKOVA, T. P.、ZARAKOVSKAYA, E. P.

  DOI：——

  日期：——