4-benzoyl-2,3-dihydro-4H-1,4-oxazine | 79323-29-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-benzoyl-2,3-dihydro-4H-1,4-oxazine
• 英文别名: 2,3-Dihydro-1,4-oxazin-4-yl(phenyl)methanone
• CAS: 79323-29-8
• 化学式: C₁₁H₁₁NO₂
• 分子量: 189.214
• InChiKey: ZBBAYJNIKZEIOD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  乙烯 、 一氧化碳 、 4-benzoyl-2,3-dihydro-4H-1,4-oxazine 在 十二羰基三钌 作用下， 以 甲苯 为溶剂， 160.0 ℃ 、506.62 kPa 条件下， 反应 20.0h， 以47%的产率得到1-(4-Benzoyl-5,6-dihydro-4H-[1,4]oxazin-3-yl)-propan-1-one
  参考文献：
  名称：

  Ru₃(CO)₁₂- and Rh₄(CO)₁₂-Catalyzed Reactions of Pyridylolefins or N-(2-Pyridyl)enamines with CO and Olefins. Carbonylation at Olefinic C−H Bonds

  摘要：

  This paper describes a study of the Ru-3(CO)(12)-catalyzed carbonylation at an olefinic C-K bond. The reaction of pyridylolefins with CO and ethylene in the presence of a catalytic amount of Ru-3(CO)(12) in toluene results in propionylation at an olefinic C-H bond in pyridylolefins. The carbonylation occurs regioselectively ata position gamma to the pyridine nitrogen. Transition-metal complexes other than Ru3(CO)12 that have thus far been examined exhibit no catalytic activity, and ethylene serves as the only olefin. A similar tendency has been noted in the previously reported carbonylation at a C-H bond in the benzene ring of pyridylbenzenes. This reaction can be also applied to N-(2-pyridyl)enamines, in which an olefin unit is separated from the pyridine ring by an sp(3)-nitrogen atom. The reaction of N-(2-pyridyl)enamines with CO and ethylene gives the corresponding ethyl ketones as the coupling products. Interestingly, Rh-4(CO)(12) also shows high catalytic activity in the case of N-(2-pyridyl)enamines. In addition, olefins such as propene, 1-hexene, 3,3-dimethyl-1-butene, styrene, cyclopentene, acryl acid methyl ester, ethyl vinyl ether, and trimethylvinylsilane can also be used. This is in sharp contrast to the case of the carbonylation at a C-H bond in pyridylbenzenes reported previously and to the results of pyridylolefins as mentioned above, where Ru-3(CO)(12) is the only active catalyst and hexene-cannot substitute for ethylene.

  DOI：

  10.1021/jo980335n
• 作为产物：
  描述：

  2-acetoxy-4-benzoyl-1-oxa-4-azacyclohexane 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 2.0h， 以66%的产率得到4-benzoyl-2,3-dihydro-4H-1,4-oxazine
  参考文献：
  名称：

  Effects of substitution on nitrogen on barriers to rotation of amides. 2—Evaluation of the importance of resonance effects

  摘要：

  AbstractAnalogs of N‐acetyl‐ and N‐benzoyl‐azacyclohex‐2‐enes having an oxygen atom, a methylene‐d2 group or a carbonyl group in place of the C‐4 methylene group have been synthesized. The amide rotational barriers in these compounds have been measured by the total line‐shape analysis of variable‐temperature 1H NMR spectra. The free energies of activation for both the N‐acetyl and N‐benzoyl series decrease in the sequence O≃CD2 > CO. The barriers for the first two compounds in each series are similar to those of the corresponding saturated analogs, a result which confirms recent reports that the long accepted barrier‐decreasing effect of an α‐olefinic substituent on nitrogen is counteracted. Evidence is presented that resonance stabilization of the rotational transition state in the unsaturated compounds still obtains. It is suggested that the introduction of an α‐olefinic substituent on nitrogen has a negligible effect on the amide rotational barriers in the cases of the oxygen and methylene‐d2 analogs, since any increase in the stabilization of the transition state by resonance is offset by the accompanying decrease in the sp3 character of the nitrogen atom. In cases in which a substituent on the olefinic group can interact directly with the lone pair on nitrogen, for example in the carbonyl analogs, then the resonance stabilization of the transition state is dominant.

  DOI：

  10.1002/mrc.1270221103

文献信息

• Ruthenium‐Catalyzed Dehydrogenation Through an Intermolecular Hydrogen Atom Transfer Mechanism
  作者：Lin Huang、Alessandro Bismuto、Simon A. Rath、Nils Trapp、Bill Morandi

  DOI：10.1002/anie.202015837

  日期：2021.3.22

  The direct dehydrogenation of alkanes is among the most efficient ways to access valuable alkene products. Although several catalysts have been designed to promote this transformation, they have unfortunately found limited applications in fine chemical synthesis. Here, we report a conceptually novel strategy for the catalytic, intermolecular dehydrogenation of alkanes using a ruthenium catalyst. The combination

  烷烃直接脱氢是获得有价值的烯烃产品的最有效方法之一。尽管已经设计了几种催化剂来促进这种转变，但不幸的是它们在精细化学合成中的应用有限。在这里，我们报告了一种使用钌催化剂催化烷烃分子间脱氢的概念新颖的策略。氧化还原活性配体和空间位阻芳基自由基中间体的组合释放了这种新策略。重要的是，已经进行了机理研究，为进一步开发这种新型催化脱氢系统提供了概念框架。
• General, Mild, and Selective Method for Desaturation of Aliphatic Amines
  作者：Padon Chuentragool、Marvin Parasram、Yi Shi、Vladimir Gevorgyan

  DOI：10.1021/jacs.8b00488

  日期：2018.2.21

  desaturation of amines. These hybrid Pd-radical intermediates are efficiently generated under mild photoinduced conditions and are capable of a 1,n-HAT (n = 5-7) event at C(sp3)-H sites. The selectivity of HAT is tunable by varying different auxiliaries, which highlight the generality of this method. Remarkably, this desaturation method, which operates under mild conditions and does not require employment

  开发了一种将脂肪胺去饱和为烯胺以及烯丙胺和高烯丙胺的新方法。该通用方案通过假定的芳基杂化 Pd-自由基中间体进行操作，该中间体结合了自由基化学、氢原子转移 (HAT) 过程和过渡金属化学、选择性 β-氢化物消除步骤的标志性特征，以实现高效和选择性的去饱和胺类。这些杂化 Pd 自由基中间体在温和的光诱导条件下有效生成，并且能够在 C(sp3)-H 位点发生 1,n-HAT (n = 5-7) 事件。 HAT 的选择性可以通过不同的助剂来调节，这突出了该方法的通用性。值得注意的是，这种去饱和方法在温和的条件下进行，不需要使用外源光敏剂或氧化剂，可以通过简单的胺以实际可扩展的方式进行。
• Catalytic Desaturation of Aliphatic Amides and Imides Enabled by Excited-State Base-Metal Catalysis
  作者：Chenyang Wang、Luis Miguel Azofra、Phong Dam、Michael Sebek、Norbert Steinfeldt、Jabor Rabeah、Osama El-Sepelgy

  DOI：10.1021/acscatal.2c01723

  日期：2022.8.5

  Herein, we report a photoexcited base-metal-catalyzed selective desaturation of aliphatic amides and imides. The reaction is catalyzed by a base-metal cobalt complex under visible-light irradiation. This transformation can be efficiently processed at room temperature and enables the synthesis of valuable cyclic and acyclic enamides and enimides from abundant chemicals. Density functional theory (DFT)

  在此，我们报道了一种光激发贱金属催化的脂肪族酰胺和酰亚胺的选择性去饱和。该反应由贱金属钴络合物在可见光照射下催化。这种转化可以在室温下进行有效处理，并能够从丰富的化学物质中合成有价值的环状和非环状烯酰胺和烯酰亚胺。密度泛函理论 (DFT) 分析、电子顺磁共振 (EPR) 和 UV-vis 研究使已发现的钴催化剂对光化学 C(sp 3 )-H 活化反应的反应性合理化。最后，我们通过使用连续流动光反应器的放大实验证明了我们工艺的潜力。
• Selective desaturation of amides: a direct approach to enamides
  作者：Xinwei Li、Zengrui Cheng、Jianzhong Liu、Ziyao Zhang、Song Song、Ning Jiao

  DOI：10.1039/d2sc02210a

  日期：——

  A novel and regioselective N-α,β-desaturation and dehydrogenative N-β-halogenation of amides was developed. This chemistry with high selectivity and broad substrate scope provides an efficient approach to enamides from simple amides.

  一种新颖且区域选择性的酰胺的N-α，β-脱饱和和脱氢N-β-卤代化学反应被开发出来。这种具有高选择性和广泛基质范围的化学反应为从简单酰胺制备烯酰胺提供了一种有效的方法。
• Nicola, Massimo; Gaviraghi, Giovanni; Pinza, Mario, Journal of Heterocyclic Chemistry, 1981, vol. 18, p. 825 - 828
  作者：Nicola, Massimo、Gaviraghi, Giovanni、Pinza, Mario、Pifferi, Giorgio

  DOI：——

  日期：——