3-Benzoxepin-2-on | 87220-52-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噁庚英
• 英文名称: 3-Benzoxepin-2-on
• 英文别名: 4,5-dihydro-3-benzoxepin-2(1H)-one；8,9-dihydro-5H-7-oxa-benzocyclohepten-6-one；3-Benzoxepin-2(1H)-one, 4,5-dihydro-；2,5-dihydro-1H-3-benzoxepin-4-one
• CAS: 87220-52-8
• 化学式: C₁₀H₁₀O₂
• 分子量: 162.188
• InChiKey: PVNBMBVFRXCGKO-UHFFFAOYSA-N

物化性质

• 熔点：
  165-166 °C
• 沸点：
  342.5±31.0 °C(Predicted)
• 密度：
  1.145±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-Benzoxepin-2-on 在 氢氧化钾 作用下， 反应 0.5h， 以33%的产率得到2-[2-(2-羟乙基)苯基]乙酸
  参考文献：
  名称：

  Meise, Werner; Arth, Christoph, Liebigs Annalen der Chemie, 1992, # 2, p. 163 - 166

  摘要：

  DOI：
• 作为产物：
  描述：

  β-四氢萘酮 在 间氯过氧苯甲酸 作用下， 生成 3-Benzoxepin-2-on
  参考文献：
  名称：

  Crystal Structures of Cyclohexanone Monooxygenase Reveal Complex Domain Movements and a Sliding Cofactor

  摘要：

  Cyclohexanone monooxygenase (CHMO) is a flavoprotein that carries out the archetypical Baeyer-Villiger oxidation of a variety of cyclic ketones into lactones. Using NADPH and O-2 as cosubstrates, the enzyme inserts one atom of oxygen into the substrate in a complex catalytic mechanism that involves the formation of a flavin-peroxide and Criegee intermediate. We present here the atomic structures of CHMO from an environmental Rhodococcus strain bound with FAD and NADP(+) in two distinct states, to resolutions of 2.3 and 2.2 angstrom. The two conformations reveal domain shifts around multiple linkers and loop movements, involving conserved arginine 329 and tryptophan 492, which effect a translation of the nicotinamide resulting in a sliding cofactor. Consequently, the cofactor is ideally situated and subsequently repositioned during the catalytic cycle to first reduce the flavin and later stabilize formation of the Criegee intermediate. Concurrent movements of a loop adjacent to the active site demonstrate how this protein can effect large changes in the size and shape of the substrate binding pocket to accommodate a diverse range of substrates. Finally, the previously identified BVMO signature sequence is highlighted for its role in coordinating domain movements. Taken together, these structures provide mechanistic insights into CHMO-catalyzed Baeyer-Villiger oxidation.

  DOI：

  10.1021/ja9010578

文献信息

• Macrolactonization of Alkynyl Alcohol through Rh(I)/Yb(III) Catalysis
  作者：Wen-Wen Zhang、Tao-Tao Gao、Li-Jin Xu、Bi-Jie Li

  DOI：10.1021/acs.orglett.8b02858

  日期：2018.10.19

  A catalytic macrolactonization through oxidative cyclization of alkynyl alcohol by synergistic transition-metal and Lewis-acid catalysis was developed. Because the alkynyl alcohol substrates involved in this method are different from the seco acids that are used in conventional macrolactonization methods, the current method provides a strategically distinct entry to macrolactones. In addition to the

  通过协同过渡金属和路易斯酸催化的炔醇的氧化环化反应，开发了一种催化大内酯化反应。由于该方法涉及的炔醇底物不同于常规大内酯化方法中使用的癸二酸，因此当前方法为大内酯提供了战略上独特的入口。除了操作简单之外，这种大环内酯化方案以相对高的浓度进行，从而排除了需要高稀释或缓慢添加过程的需要。
• Fluoride-induced activation of molybdenum hexacarbonyl: formation of esters and lactones from alkyl iodides
  作者：Mich�le Imbeaux、H�l�ne Mestdagh、Khadija Moughamir、Christian Rolando

  DOI：10.1039/c39920001678

  日期：——

  In the presence of fluoride ion, alkyl iodides RI are carbonylated by molybdenum hexacarbonyl to esters RCO2R, and diiodides lead to good yields of the corresponding lactones.

  在氟离子存在下，烷基碘RI通过六羰基钼进行羰基化反应生成酯RCO2R，而二碘化物则能高效制备相应的内酯。
• A FACILE OXIDATIVE LACTONIZATION OF 1,ω-DIOLS WITH SODIUM BROMITE
  作者：Toshifumi Kageyama、Shuji Kawahara、Kohji Kitamura、Yoshio Ueno、Makoto Okawara

  DOI：10.1246/cl.1983.1097

  日期：1983.7.5

  A practically useful method for the oxidation of 1,ω-diols to lactones is described. The scope and limitations are also presented.

  本文描述了一种实用有效的方法，用于将1,ω-二醇氧化成内酯。同时还介绍了其适用范围和局限性。
• Lithium 2-(2-lithiomethylphenyl)ethanolate from isochroman: Easy preparation of substituted benzoxepines and functionalised arenes
  作者：Juan Almena、Francisco Foubelo、Miguel Yus

  DOI：10.1016/0040-4020(95)00065-g

  日期：1995.3

  The reaction of isochroman (1) with an excess of lithium powder and a catalytic amount of DTBB (2.5 mol %) in THF at 20°C yields the title intermediate, which by reaction with different electrophiles (H2O, D2O, CO2 and carbonyl compounds) at temperatures ranging between −78 and 20°C yields, after hydrolysis, the corresponding products 3. Diols 3h-m, derived from benzaldehyde or ketones, give upon treatment

  异色满（1）与过量的锂粉和催化量的DTBB（2.5 mol％）在THF中在20°C下反应生成标题中间体，该标题中间体通过与不同的亲电试剂（H 2 O，D 2 O， CO 2和羰基化合物）在-78至20°C的温度范围内水解后，会产生相应的产物3。衍生自苯甲醛或酮的三元醇3h-m在用85％磷酸处理后得到相应的苯并氧杂5h-m。在其他情况下，获得了由形成的第一个碳鎓离子的重排而产生的弗瑞德-克拉夫茨产品。
• Synthesis of multi-substituted cyclobutenes: Cyclic strategy for [2 + 2] cycloaddition of ketene silyl acetals with propiolates
  作者：Yousuke Yamaoka、Motoki Ueda、Tohru Yamashita、Kazuma Shimoda、Ken-ichi Yamada、Kiyosei Takasu

  DOI：10.1016/j.tetlet.2017.06.039

  日期：2017.7

  Cyclic ketene silyl acetals were utilized for [2 + 2] cycloaddition with propiolates to prevent an undesired electrocyclic ring opening reaction. Trimethylaluminum catalyzed this cycloaddition to afford the cyclobutene derivatives in high yields. The advantage of this reaction was highlighted by the successful application of β-substituted propiolates to afford the multi-substituted cyclobutenes. Furthermore

  环状乙烯酮甲硅烷基缩醛用于与丙酸酯的[2 + 2]环加成反应，以防止发生不希望的电环开环反应。三甲基铝催化该环加成反应以高收率提供环丁烯衍生物。通过成功地应用β-取代的丙酸酯提供多取代的环丁烯，突出了该反应的优点。此外，我们将此方法应用于天然产物青蒿素的后期功能化。