4-methyl-3,4-dihydro-2H-[1,4]oxazine

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-methyl-3,4-dihydro-2H-[1,4]oxazine
• 英文别名: 2,3-dehydro-N-methylmorpholine；4-methyl-2,3-dihydro-1,4-oxazine
• 化学式: C₅H₉NO
• 分子量: 99.1326
• InChiKey: GEGDLANPARTRKE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  4-methyl-3,4-dihydro-2H-[1,4]oxazine 、 天然维生素E 在 silver(l) oxide 作用下， 以 正己烷 为溶剂， 反应 0.17h， 以55.7%的产率得到3,5,6,8-tetramethyl-3-(4,8,12-trimethyltridecyl)-2,3,7a,8,9,10,11a,12-octahydro-1H-4,7,11-trioxa-8-azabenzo[a]anthracene
  参考文献：
  名称：

  Confirmation by trapping, synthesis, and reactivity of 2,3-dehydro-N-methylmorpholine (DNMM)

  摘要：

  The elusive 4-methyl-3,4-dihydro-2H-[1,4] oxazine (2,3-dehydro-N-methylmorpholine, DNMM, 5) was confirmed to occur as degradation product of N-methylmorpholine-N-oxide (1) by trapping with the alpha-tocopherol-derived ortho-quinone methide in a hetero-Diels-Alder reaction with inverse electron demand. The regioselectivity of the addition was in good agreement with DFT computational data. An authentic sample of 5 was synthesized from formmorpholide (16) via 2-methoxy-formmorpholide in 38% overall yield. (c) 2007 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2007.09.055
• 作为产物：
  描述：

  2,3-dihydro-[1,4]oxazine-4-carbaldehyde 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 4.0h， 以79%的产率得到4-methyl-3,4-dihydro-2H-[1,4]oxazine
  参考文献：
  名称：

  Confirmation by trapping, synthesis, and reactivity of 2,3-dehydro-N-methylmorpholine (DNMM)

  摘要：

  The elusive 4-methyl-3,4-dihydro-2H-[1,4] oxazine (2,3-dehydro-N-methylmorpholine, DNMM, 5) was confirmed to occur as degradation product of N-methylmorpholine-N-oxide (1) by trapping with the alpha-tocopherol-derived ortho-quinone methide in a hetero-Diels-Alder reaction with inverse electron demand. The regioselectivity of the addition was in good agreement with DFT computational data. An authentic sample of 5 was synthesized from formmorpholide (16) via 2-methoxy-formmorpholide in 38% overall yield. (c) 2007 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2007.09.055

文献信息

• Selective Catalytic Transfer Dehydrogenation of Alkanes and Heterocycles by an Iridium Pincer Complex
  作者：Wubing Yao、Yuxuan Zhang、Xiangqing Jia、Zheng Huang

  DOI：10.1002/anie.201306559

  日期：2014.1.27

  Catalytic alkane dehydrogenation is a reaction with tremendous potential for application. We describe a highly active PSCOP‐pincer iridium catalyst for transfer dehydrogenation of cyclic and linear alkanes. The dehydrogenation of linear alkanes occurs under relatively mild conditions with high regioselectivity for α‐olefin formation. In addition, the catalyst system is very effective in the dehydrogenation

  催化烷烃脱氢是一种具有巨大应用潜力的反应。我们描述了一种用于环状和直链烷烃转移脱氢的高活性PSCOP-pincer铱催化剂。线性烷烃的脱氢反应在相对温和的条件下进行，对α-烯烃的形成具有很高的区域选择性。另外，该催化剂体系在杂环脱氢以形成杂芳烃和烯烃产物方面非常有效。
• Iridium Pincer-Catalyzed Dehydrogenation of Ethers Featuring Ethylene as the Hydrogen Acceptor
  作者：Thomas W. Lyons、David Bézier、Maurice Brookhart

  DOI：10.1021/acs.organomet.5b00501

  日期：2015.8.24

  We describe efficient methods to dehydrogenate ethers by using iridium pincer complexes ((ipr4)Anthraphos)-Ir(H)(Cl), 4, (PC)-P-ipr4(sp(3))P-Ir(H)(Cl) 5, and ((PCP)-P-ipr4)-Ir(H)(Cl), 6. At 120 degrees C, cyclic ethers were dehydrogenated with high turnover numbers (over 400 in many cases). Acyclic ethers such as diethyl ether can also be dehydrogenated catalytically with TONs up to 90. The efficient dehydrogenation of cyclic and acyclic ethers using ethylene as a more practical hydrogen acceptor has been demonstrated for the first time.
• Confirmation by trapping, synthesis, and reactivity of 2,3-dehydro-N-methylmorpholine (DNMM)
  作者：Falk Liebner、Peter Schmid、Christian Adelwöhrer、Thomas Rosenau

  DOI：10.1016/j.tet.2007.09.055

  日期：2007.11

  The elusive 4-methyl-3,4-dihydro-2H-[1,4] oxazine (2,3-dehydro-N-methylmorpholine, DNMM, 5) was confirmed to occur as degradation product of N-methylmorpholine-N-oxide (1) by trapping with the alpha-tocopherol-derived ortho-quinone methide in a hetero-Diels-Alder reaction with inverse electron demand. The regioselectivity of the addition was in good agreement with DFT computational data. An authentic sample of 5 was synthesized from formmorpholide (16) via 2-methoxy-formmorpholide in 38% overall yield. (c) 2007 Published by Elsevier Ltd.