5,6-dihydro-2-hydroxy-2,3-dimethyl-2H-1,4-oxazine | 106913-66-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: 5,6-dihydro-2-hydroxy-2,3-dimethyl-2H-1,4-oxazine
• 英文别名: 5,6-Dimethyl-2,3-dihydro-1,4-oxazin-6-ol
• CAS: 106913-66-0
• 化学式: C₆H₁₁NO₂
• 分子量: 129.159
• InChiKey: HSRRWDSHQQANQS-UHFFFAOYSA-N

物化性质

• 熔点：
  74-76 °C(Solv: benzene (71-43-2))
• 沸点：
  210.5±40.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  41.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5,6-dihydro-2-hydroxy-2,3-dimethyl-2H-1,4-oxazine 以 氘代氯仿 为溶剂， 生成 2-Butanone, 3-[(2-hydroxyethyl)imino]- (9CI)
  参考文献：
  名称：

  Reaction of .alpha.-diketones with 2-amino alcohols. Intramolecular competitive 6-exo-trig vs 5-endo-trig processes. A systematic and kinetic study

  摘要：

  2-Aminoethanol and C-substituted derivatives 1 react with diacetyl, benzil, and 1-phenyl-1,2-propanedione, models of alpha-diketones 2 to give with remarkable regio- and stereoselectivity 2-hydroxy-5,6-dihydro-2H-1,4-oxazines 3, cis-octahydro[1,4]oxazino[3,2-b]oxazines 4, alpha-imino ketones 6, 2-acetyl-1,3-oxazolidines 7, N,N'-bis(2-hydroxy-2-methylpropyl)-2,3-butanediimines 8, and 2,2'-dimethyl-2,2'-bioxazolidines 9 depending on the nature of the reagents and the reaction conditions. On the basis of isolated intermediates, a reasonable mechanism taking into account the stereoelectronic effects observed on the cyclization has been proposed for these processes. In addition, a kinetic study of the ring-chain-ring tautomeric equilibrium of oxazines 3a-c, 3i-k, and 3o-q has been studied by H-1 NMR and C-13 NMR. In solution, compounds 3a-c and 3i-k exhibit a three-component tautomeric equilibria consisting of the following: the beta-iminohemiacetal 3, the beta-hydroxyimino ketone 6, and the 2-acetyl- or 2-benzoyl-1,3-oxazolidine 7. The calculated rate constants for this process show that the equilibrium is shifted toward the formation of the five-membered ring by 0.4-4.8 kJ mol-1 over the six-membered ring depending on the substitution patterns. Compounds 3p-q exist in solution as equimolar mixtures of the ring and open-chain tautomers. Compound 3o exists predominantly in the open-chain form. In addition, 2-acylthiazolidines 13a-c do not evidence any dynamic processes in solution.

  DOI：

  10.1021/jo00034a046
• 作为产物：
  描述：

  2-Butanone, 3-[(2-hydroxyethyl)imino]- (9CI) 以 氘代氯仿 为溶剂， 生成 5,6-dihydro-2-hydroxy-2,3-dimethyl-2H-1,4-oxazine
  参考文献：
  名称：

  Reaction of .alpha.-diketones with 2-amino alcohols. Intramolecular competitive 6-exo-trig vs 5-endo-trig processes. A systematic and kinetic study

  摘要：

  2-Aminoethanol and C-substituted derivatives 1 react with diacetyl, benzil, and 1-phenyl-1,2-propanedione, models of alpha-diketones 2 to give with remarkable regio- and stereoselectivity 2-hydroxy-5,6-dihydro-2H-1,4-oxazines 3, cis-octahydro[1,4]oxazino[3,2-b]oxazines 4, alpha-imino ketones 6, 2-acetyl-1,3-oxazolidines 7, N,N'-bis(2-hydroxy-2-methylpropyl)-2,3-butanediimines 8, and 2,2'-dimethyl-2,2'-bioxazolidines 9 depending on the nature of the reagents and the reaction conditions. On the basis of isolated intermediates, a reasonable mechanism taking into account the stereoelectronic effects observed on the cyclization has been proposed for these processes. In addition, a kinetic study of the ring-chain-ring tautomeric equilibrium of oxazines 3a-c, 3i-k, and 3o-q has been studied by H-1 NMR and C-13 NMR. In solution, compounds 3a-c and 3i-k exhibit a three-component tautomeric equilibria consisting of the following: the beta-iminohemiacetal 3, the beta-hydroxyimino ketone 6, and the 2-acetyl- or 2-benzoyl-1,3-oxazolidine 7. The calculated rate constants for this process show that the equilibrium is shifted toward the formation of the five-membered ring by 0.4-4.8 kJ mol-1 over the six-membered ring depending on the substitution patterns. Compounds 3p-q exist in solution as equimolar mixtures of the ring and open-chain tautomers. Compound 3o exists predominantly in the open-chain form. In addition, 2-acylthiazolidines 13a-c do not evidence any dynamic processes in solution.

  DOI：

  10.1021/jo00034a046

文献信息

• Reaction of α-diketones with ethanolamine
  作者：Benito Alcaide、Rafael Pérez-Ossorio、Joaquín Plumet、Manuel Rico、Ignacio M. Rodriguez-Campos

  DOI：10.1016/s0040-4039(00)84264-1

  日期：1986.1

  Butanedione and ethanolamine react to yield 4-5-diaza-1,5-dioxadecalin , 2,3-epoxy-8-aza-1, 4,5-trioxadecalin , and 2-hydroxy-1,6-dihydro-oxazine according to the molar ratios of the reagents. With benzil and 1-phenyl-1,2-propanedione only the related oxazines . are obtained in equilibrium with their open-chain tautomers.

  丁二酮和乙醇胺反应4-5二氮杂-1,5- dioxadecalin得到，2,3-环氧基-8-氮杂- 1，4,5- trioxadecalin ，和2-羟基-1,6-二氢恶嗪根据试剂的摩尔比。与苄基和1-苯基-1,2-丙二酮仅相关的恶嗪。与它们的开链互变异构体平衡获得。
• Anatomy of a three species tautomeric process: The ring-chain tautomerism in 5,6-dihydro-2-hydroxy-2,3-dimethyl-2H-1,4-oxazine
  作者：Benito Alcaide、Ramon González Rubio、Joaquín Plumet、Ignacio M. Rodriguez-Campos

  DOI：10.1016/s0040-4039(00)97584-1

  日期：1990.1

  A ring-chain tautomerism involving two single processes hydroxyketone-hemiacetal and hydroxyimine-1,3-oxazolidine is kinetically studied.

  动力学研究了涉及两个单一过程的羟基酮-半缩醛和羟基亚胺-1,3-恶唑烷的环链互变异构现象。
• ALCAIDE, B.;PEREZ-OSSORIO, R.;PLUMET, J.;RICO, M.;RODRIGUEZ-CAMPOS, I. M., TETRAHEDRON LETT., 1986, 27, N 12, 1381-1384
  作者：ALCAIDE, B.、PEREZ-OSSORIO, R.、PLUMET, J.、RICO, M.、RODRIGUEZ-CAMPOS, I. M.

  DOI：——

  日期：——