5,5-dimethyl-3-phenyl-1,4,2-dioxazole | 13715-50-9

• 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: 5,5-dimethyl-3-phenyl-1,4,2-dioxazole
• 英文别名: 2,2-Dimethyl-5-phenyl-1,3,4-dioxazol；5,5-Dimethyl-3-phenyl-5H-1,4,2-dioxazole
• CAS: 13715-50-9
• 化学式: C₁₀H₁₁NO₂
• 分子量: 177.203
• InChiKey: UQRHFUNHNDHFRQ-UHFFFAOYSA-N

物化性质

• 熔点：
  90 °C
• 沸点：
  210.5±23.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  30.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5,5-dimethyl-3-phenyl-1,4,2-dioxazole 在 Nafion-H 作用下， 以 异丙醇 为溶剂， 反应 30.0h， 以98%的产率得到苯甲羟肟酸
  参考文献：
  名称：

  5,5-Dimethyl-1,4,2-dioxazoles as Versatile Aprotic Hydroxamic Acid Protecting Groups

  摘要：

  5,5-Dimethyl-1,4,2-dioxazoles are readily installed by transketalization of 2,2-diethoxypropane, where both the NH and OH moieties are protected in a nonprotic form. The dioxazoles are stable to a wide variety of reaction conditions and readily revert back to the hydroxamic acid by treatment with Nafion-H in 2-propanol. The method is applicable to primary, secondary, tertiary, and aromatic hydroxamic acids, and the acidity of the protons adjacent to the dioxazole allows alpha-functionalization.

  DOI：

  10.1021/jo0256890
• 作为产物：
  描述：

  N-(1-Methoxy-1-methylethoxy)benzamid 以 环己烷 为溶剂， 反应 0.75h， 以78%的产率得到5,5-dimethyl-3-phenyl-1,4,2-dioxazole
  参考文献：
  名称：

  Cyclisierung von N-(1-Methoxy-1-methylethoxy)carboxamiden zu 5,5-Dimethyl-1,4,2-dioxazolen

  摘要：

  DOI：

  10.1002/prac.19943360616

文献信息

• The photochemistry of acyl azides — IX. Direct and sensitized photolytic generation of acylnitrenes for cycloaddition reactions
  作者：Kai-Uwe Clauss、Karin Buck、Werner Abraham

  DOI：10.1016/0040-4020(95)00366-g

  日期：1995.6

  types with respect to benzoylnitrene, which was generated by three different routes: direct photolysis of benzoyl azide, sensitization of azide decomposition via energy transfer, and photoinduced electron transfer. In all cases the same cycloadducts 23, 24, and 30 were obtained. Carbonyl activity determines the reactivity of unsaturated ketones and aldehydes with respect to benzoylnitrene.

  与乙氧基羰基丁烯相反，选择性反应-包括缩载反应-可以用苯甲酰基基丁烯进行。这项研究分析了通过三种不同的途径产生的各种键类型与苯甲酰氮的反应性顺序：苯甲酰叠氮化物的直接光解，通过能量转移引起的叠氮化物分解的敏化以及光诱导的电子转移。在所有情况下相同的cycloadducts 23，24，和30获得的。羰基活性决定了不饱和酮和醛相对于苯甲酰基氮丁烯的反应性。
• Alkynyl Thioethers in Gold-Catalyzed Annulations To Form Oxazoles
  作者：Raju Jannapu Reddy、Matthew P. Ball-Jones、Paul W. Davies

  DOI：10.1002/anie.201706850

  日期：2017.10.16

  regioselective, and convergent access to densely functionalized oxazoles is realized in a functional-group tolerant manner using alkynyl thioethers. Sulfur-terminated alkynes provide access to reactivity previously requiring strong donor-substituted alkynes such as ynamides. Sulfur does not act in an analogous donor fashion in this gold-catalyzed reaction, thus leading to complementary regioselective outcomes

  使用炔基硫醚以官能团耐受的方式实现非氧化、区域选择性和聚合获得密集官能化的恶唑。硫封端的炔烃提供了获得以前需要强供体取代的炔烃（例如炔酰胺）的反应性。在这种金催化反应中，硫不以类似的供体方式起作用，从而导致互补的区域选择性结果并解决使用炔酰胺的局限性。
• Mechanistic Studies on the Rh(III)-Mediated Amido Transfer Process Leading to Robust C–H Amination with a New Type of Amidating Reagent
  作者：Yoonsu Park、Kyung Tae Park、Jeung Gon Kim、Sukbok Chang

  DOI：10.1021/jacs.5b01324

  日期：2015.4.8

  bearing an amidating reagent was achieved, its facile conversion to an amido-inserted rhodacycle allowed for a clear picture on the C-H amidation process. The newly developed amidating reagent of 1,4,2-dioxazol-5-ones was applicable to a broad range of substrates with high functional group tolerance, releasing carbon dioxide as a single byproduct. Additional attractive features of this amino source, such

  对 Cp*Rh(III) 催化的直接 CH 胺化反应的机理研究使我们揭示了 1,4,2-dioxazol-5-one 及其衍生物作为高效氨基来源的新用途。CN 键形成过程的逐步分析表明，铑金属中心与酰胺化试剂或底物的竞争性结合与反应效率密切相关。在该系列中，观察到 1,4,2-二恶唑-5-酮对阳离子 Rh(III) 具有很强的亲和力，与叠氮化物相比，酰胺化效率显着提高。动力学和计算研究表明，1,4,2-dioxazol-5-one 的高酰胺化反应性除了高配位能力外，还可归因于亚氨基插入过程的低活化能。虽然实现了带有酰胺化试剂的阳离子 Cp*Rh(III) 复合物的表征，但它可以轻松转化为插入酰胺基的红丹环，从而可以清楚地了解 CH 酰胺化过程。新开发的 1,4,2-二恶唑-5-酮酰胺化试剂适用于具有高官能团耐受性的广泛底物，释放二氧化碳作为单一副产物。这种氨基源的其他吸引人的特点，例如与相
• Synthesis of five-membered cyclic nitrones based on the Lewis acid-catalysed [3+2]-annulation reaction of donor–acceptor cyclopropanes with 1,4,2-dioxazoles
  作者：Zhe-Hao Wang、Huan-Huan Zhang、Peng-Fei Xu、Yong-Chun Luo

  DOI：10.1039/c8cc04656e

  日期：——

  A novel synthesis of five-membered cyclic nitrones has been developed based on the Lewis acid-catalysed [3+2]-annulation reaction of D–A cyclopropanes with 1,4,2-dioxazoles. Broad substrate scope and generally good yield make this reaction useful in the preparation of nitrones. When a suitable 1,4,2-dioxazole was used, nitrone and tetrahydrofuran could be prepared in one pot with high atom economy

  基于路易斯酸催化D–A环丙烷与1,4,2-二恶唑的[3 + 2]环化反应，开发了五元环硝酮的新型合成方法。广泛的底物范围和通常良好的产率使该反应可用于制备硝酮。当使用合适的1,4,2-二恶唑时，可以在一个具有高原子经济性的锅中制备硝酮和四氢呋喃。
• Dioxazoles, a new mild nitrene transfer reagent in gold catalysis: highly efficient synthesis of functionalized oxazoles
  作者：Ming Chen、Ning Sun、Haoyi Chen、Yuanhong Liu

  DOI：10.1039/c6cc02776h

  日期：——

  A gold-catalyzed regioselective [3+2] cycloaddition of ynamides with 1,4,2-dioxazoles has been developed, which offers a novel approach to highly functionalized oxazoles under mild reaction conditions. 1,4,2-Dioxazole was found to act...

  已经开发了金催化的酰胺与1,4,2-二恶唑的区域选择性[3 + 2]环加成反应，这为在温和的反应条件下高官能化的恶唑提供了一种新颖的方法。发现1,4,2-二恶唑起作用...