3-phenylhexahydro-1H-oxazolo[3,4-a]pyridine | 2563-84-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 3-phenylhexahydro-1H-oxazolo[3,4-a]pyridine
• 英文别名: 3-phenylhexahydrooxazolo[3,4-a]pyridine；3-phenyl-hexahydro-oxazolo[3,4-a]pyridine；d,l-3-Phenyl-hexahydro-3H-oxazolo<3,4-a>pyridin；3-phenyl-3,5,6,7,8,8a-hexahydro-1H-[1,3]oxazolo[3,4-a]pyridine
• CAS: 2563-84-0
• 化学式: C₁₃H₁₇NO
• 分子量: 203.284
• InChiKey: ROJRUMMOALVSBM-UHFFFAOYSA-N

物化性质

• 沸点：
  134-136 °C(Press: 8 Torr)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  3-phenylhexahydro-1H-oxazolo[3,4-a]pyridine 在 萘 、 lithium 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以95%的产率得到(1-benzylpiperidin-2-yl)methanol
  参考文献：
  名称：

  Diastereoselective electrophilic substitution of α-amino-substituted benzylic organometallics

  摘要：

  衍生自 2-羟甲基哌啶的非对映异构双环 2-苯基恶唑烷的还原金属化发生在苄基碳原子处外消旋化。中间体有机金属与烷基卤的反应以高度顺式选择性的方式提供取代的氨基醇。观察到的非对映选择性根据快速平衡差向异构中间体有机金属化合物合理化，其中一种在适当的反应条件下优先反应。相同中间体的氘化通常会产生具有低非对映选择性的氘化氨基醇，除非使用锂作为还原剂并且使所得混合物在氘化之前达到平衡。

  DOI：

  10.1039/b109633h
• 作为产物：
  描述：

  (1-benzylpiperidin-2-yl)methanol 在 sodium methylate 、 potassium iodide 作用下， 以 甲醇 为溶剂， 以60%的产率得到3-phenylhexahydro-1H-oxazolo[3,4-a]pyridine
  参考文献：
  名称：

  具有苄基的羟氨基化合物的电氧化环化

  摘要：

  摘要 通过在甲醇中使用电氧化法，分别从N-苄基-2-哌啶甲醇和N-苄基-2-哌啶甲醇合成了几种新颖的2-芳基-1,3-恶嗪烷和2-芳基-1,3-恶唑烷衍生物。对于这些反应，通过使用催化量的碘离子显着提高了相应环化化合物的产率。相反，3-二烷基氨基-1-苯基丙醇仅使用少量过量的碱即可得到预期的环状6-苯基-1,3-恶嗪烷衍生物。 通过在甲醇中使用电氧化法，分别从N-苄基-2-哌啶甲醇和N-苄基-2-哌啶甲醇合成了几种新颖的2-芳基-1,3-恶嗪烷和2-芳基-1,3-恶唑烷衍生物。对于这些反应，通过使用催化量的碘离子显着提高了相应环化化合物的产率。相反，3-二烷基氨基-1-苯基丙醇仅使用少量过量的碱即可得到预期的环状6-苯基-1,3-恶嗪烷衍生物。

  DOI：

  10.1055/s-0031-1290755

文献信息

• Pyrolysis of perhydro[1,2-c][1,3]oxazines: a green method of synthesizing 2,3-dehydropiperidine enamines
  作者：A. Gilbert Cook、Christine A. Schering、Pauline A. Campbell、Samantha S. Hayes

  DOI：10.1016/j.tetlet.2005.06.067

  日期：2005.8

  pyrolysis of the oxazines formed from 2-piperidineethanol produced 2,3-dehydropiperidine enamines. The same results were observed when these oxazines were irradiated with microwaves. Various 2-substituted perhydrooxazines were synthesized by allowing 2-piperidineethanol or 2-piperidinemethanol to react with aldehydes or ketones.

  由2-哌啶乙醇形成的恶嗪的热解产生了2，3-脱氢哌啶烯胺。当这些恶嗪用微波照射时，观察到相同的结果。通过使2-哌啶乙醇或2-哌啶甲醇与醛或酮反应，合成了各种2-取代的全氢恶嗪。
• Heteroalicyclic Aminoalkanol. II. Reactions of DL-2-Piperidinemethanol involving the Formation of DL-1-Azabicyclo[4, 1, 0]heptane
  作者：Tanezo Taguchi、Seiki Kasuga

  DOI：10.1248/cpb.13.241

  日期：——

  DL-2-Piperidinemethanol (I) was converted to O-acyl, 2-isothioureido and oxazolidine derivatives to be subjected to reactions such as acyl migration, transguanylation and oxidation with bromine respectively. The xanthate (XIII) derived from the N-methyl derivative of I (XII) was thermally rearranged to the corresponding dithiolcarbonate (XIV). In particular, I was converted to DL-1-azabicyclo[4, 1, 0]heptane (XXIV) via DL-2-piperidinemethanol hydrogen sulfate (XXIII). XXIV was easily polymerizable and therefore, stabilized in the form of picrate for identification. Structural proof for XXIV was provided from results of reactions to which it was subjected. In conclusion, the reaction sequences of I and XII were similar to those of acyclic analogues as be theoretically expected.

  DL-2-Piperidinemethanol (I) 被转化为 O-酰基、2-异硫脲基和噁唑烷衍生物，分别进行酰基迁移、反鸟苷酸化和溴氧化等反应。由 I 的 N-甲基衍生物（XII）衍生出的黄原酸酯（XIII）经热重排生成相应的二硫醇碳酸酯（XIV）。其中，I 通过 DL-2- 哌啶甲醇硫酸氢盐 (XXIII) 转化为 DL-1- 氮杂双环[4, 1, 0]庚烷 (XXIV)。XXIV 易于聚合，因此以吡啶甲酸盐的形式稳定下来以供鉴定。XXIV 的结构证明来自其所经历的反应结果。总之，I 和 XII 的反应顺序与理论上预期的无环类似物的反应顺序相似。
• Novel Application of Electrooxidative Method for the Cyclization of N-Benzyl-2-(hydroxymethyl)- and N-Benzyl-2-(2-hydroxyethyl)piperidines
  作者：Mitsuhiro Okimoto、Takashi Yoshida、Masayuki Hoshi、Kousuke Ohashi

  DOI：10.3987/com-10-12064

  日期：——

  Several novel 1,3-oxazinane and oxazolidine derivatives were obtained from the corresponding N-benzyl-2-(2-hydroxyethyl)- and N-benzyl-2-(hydroxymethyl)piperidines via electrochemical oxidation. The reactions were carried out in methanol under basic conditions. The yields of the cyclic products were significantly improved using catalytic amounts of iodide ions, which presumably act as effective electron carriers in the two-electron oxidation process.
• Diastereoselective electrophilic substitution of α-amino-substituted benzylic organometallics
  作者：Ugo Azzena

  DOI：10.1039/b109633h

  日期：2002.1.23

  Reductive metallation of a diastereoisomeric bicyclic 2-phenyloxazolidine derived from 2-hydroxymethylpiperidine occurs with racemization at the benzylic carbon atom. Reaction of intermediate organometallics with alkyl halides affords substituted amino alcohols in a highly syn-selective fashion. Observed diastereoselectivities are rationalized in terms of rapidly equilibrating epimeric intermediate organometallics, one of which reacts preferentially under appropriate reaction conditions. Deuteration of the same intermediates usually leads to deuterated amino alcohols with low diasteroselectivities, unless lithium is employed as the reducing agent and the resulting mixture is allowed to equilibrate before deuteration.

  衍生自 2-羟甲基哌啶的非对映异构双环 2-苯基恶唑烷的还原金属化发生在苄基碳原子处外消旋化。中间体有机金属与烷基卤的反应以高度顺式选择性的方式提供取代的氨基醇。观察到的非对映选择性根据快速平衡差向异构中间体有机金属化合物合理化，其中一种在适当的反应条件下优先反应。相同中间体的氘化通常会产生具有低非对映选择性的氘化氨基醇，除非使用锂作为还原剂并且使所得混合物在氘化之前达到平衡。
• Electrooxidative Cyclization of Hydroxyamino Compounds Possessing a Benzyl Group
  作者：Mitsuhiro Okimoto、Kousuke Ohashi、Haruki Yamamori、Shinnosuke Nishikawa、Masayuki Hoshi、Takashi Yoshida

  DOI：10.1055/s-0031-1290755

  日期：2012.5

  3-oxazinane derivatives using only a small excess of base. Several novel 2-aryl-1,3-oxazinane and 2-aryl-1,3-oxazolidine derivatives were synthesized from N-benzyl-2-piperidineethanols and N-benzyl-2-piperidinemethanols, respectively, by using electrooxidative methods in methanol. For these reactions, the yields of the corresponding cyclized compounds were significantly increased by using catalytic amounts

  摘要 通过在甲醇中使用电氧化法，分别从N-苄基-2-哌啶甲醇和N-苄基-2-哌啶甲醇合成了几种新颖的2-芳基-1,3-恶嗪烷和2-芳基-1,3-恶唑烷衍生物。对于这些反应，通过使用催化量的碘离子显着提高了相应环化化合物的产率。相反，3-二烷基氨基-1-苯基丙醇仅使用少量过量的碱即可得到预期的环状6-苯基-1,3-恶嗪烷衍生物。 通过在甲醇中使用电氧化法，分别从N-苄基-2-哌啶甲醇和N-苄基-2-哌啶甲醇合成了几种新颖的2-芳基-1,3-恶嗪烷和2-芳基-1,3-恶唑烷衍生物。对于这些反应，通过使用催化量的碘离子显着提高了相应环化化合物的产率。相反，3-二烷基氨基-1-苯基丙醇仅使用少量过量的碱即可得到预期的环状6-苯基-1,3-恶嗪烷衍生物。