(Z)-5-ethylidene-4-methylene-3-phenyl-1,3-oxazolidin-2-one | 189953-33-1

• 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: (Z)-5-ethylidene-4-methylene-3-phenyl-1,3-oxazolidin-2-one
• 英文别名: (5Z)-N-phenyl-4-methylene-5-ethylidene-2-oxazolidinone；(Z)-5-ethylidene-4-methylene-3-phenyloxazolidin-2-one；(5Z)-5-ethylidene-4-methylidene-3-phenyl-1,3-oxazolidin-2-one
• CAS: 189953-33-1
• 化学式: C₁₂H₁₁NO₂
• 分子量: 201.225
• InChiKey: JKHZLRRFRMFPNI-JYOAFUTRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 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：

  (Z)-5-ethylidene-4-methylene-3-phenyl-1,3-oxazolidin-2-one 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以58%的产率得到(5Z)-5-ethylidene-N-phenyl-1,3-oxazolidine-2,4-dione
  参考文献：
  名称：

  Synthesis and Cycloaddition Reactions of New Captodative Olefins, N-Substituted 5-Alkylidene-1,3-oxazolidine-2,4-diones

  摘要：

  DOI：

  10.3987/com-00-9094
• 作为产物：
  描述：

  2,3-戊二酮 、 异氰酸苯酯 在 lithium carbonate 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 20.5h， 以30%的产率得到(Z)-5-ethylidene-4-methylene-3-phenyl-1,3-oxazolidin-2-one
  参考文献：
  名称：

  通过的高度选择性狄尔斯-阿尔德环加成的4,5,6,7- tetrahydrobenzoxazol -2-酮的合成外-恶唑烷-2-酮与查耳酮二烯

  摘要：

  本文报道了新颖的4,5,6,7-四氢苯并恶唑-2-酮的合成。它们是通过N-取代的外-恶唑烷-2-酮二烯与查耳酮或双查耳酮作为亲二烯体的高度区域选择性和立体选择性Diels-Alder环加成反应而以中等至良好的产率获得的。

  DOI：

  10.1016/j.tetlet.2019.04.027

文献信息

• Stereoselective Synthesis of 4,5-Diethylidene-Oxazolidinones as New Dienes inDiels-Alder Reactions
  作者：Rafael Martínez、Hugo A. Jiménez-Vázquez、Alicia Reyes、Joaquín Tamariz

  DOI：10.1002/1522-2675(200202)85:2<464::aid-hlca464>3.0.co;2-u

  日期：2002.2

  The N-substituted isomeric (4Z,5Z)- and (4E,5Z)-4,5-diethylideneoxazolidin-2-ones 5 and 6 were synthesized, the latter being favored during the one-step process from the α-diketone 1c and different isocyanates. The steric interaction between the N-substituent and the Me group attached to the exocyclic diene moiety plays a decisive role in controlling the observed stereoselectivity, as suggested by

  合成了 N-取代的异构体 (4Z,5Z)-和 (4E,5Z)-4,5-二亚乙基恶唑烷-2-酮 5 和 6，后者在 α-二酮 1c 和不同的异氰酸酯。正如计算的两种异构体的自由能所示，N-取代基与连接到环外二烯部分的 Me 基团之间的空间相互作用在控制观察到的立体选择性方面起决定性作用。在热 Diels-Alder 反应中，两种二烯都经过有效添加到对称亲双烯体中，分别产生加合物 11 和 13。这些分子根据其 X 射线晶体结构显示出有趣的 C−H⋅⋅⋅π 和 C−H⋅⋅⋅X (X=O, Cl) 相互作用。异构体 6 与非对称亲双烯体（如甲基乙烯基酮或丙炔酸甲酯）发生高度立体选择性和区域选择性加成。由 6 中指向内的 Me 组促进的空间相互作用似乎可以解释这种选择性。根据 FMO 理论，这些结果也通过从头计算得到了合理化。
• Diels-Alder Reactions of 2-Oxazolidinone Dienes in Polar Solvents Using Catalysis or Non-conventional Energy Sources
  作者：Ayde� Fuentes、Rafael Mart�nez-Palou、Hugo A. Jim�nez-V�zquez、Francisco Delgado、Alicia Reyes、Joaqu�n Tamariz

  DOI：10.1007/s00706-004-0244-0

  日期：2005.2

  isocyanates. Diels - Alder cycloadditions of these dienes were carried out in the presence of the dienophiles methyl vinyl ketone, methyl propiolate, and a captodative olefin, under conditions such as solvents of high polarity, Lewis acid catalysis, and non-conventional energy sources. The reactions carried out either with mixtures of H2O/ Me OH or under BF3·Et2O catalysis yielded the highest regio-

  （ Z ） -N- 取代的4-亚甲基-5-亚丙基-2-恶唑烷酮二烯通过一步合成从2，3-己二酮和异氰酸酯开始制备。 狄尔斯 - 这些二烯的 Alder 环加成反应是在亲二烯体甲基乙烯基酮，丙酸甲酯和可俘获烯烃的存在下，在诸如高极性溶剂， 路易斯 酸催化和非常规能源等条件下进行的。反应可用H 2 O / Me OH的混合物或在BF 3 ·Et 2下进行O催化产生最高的区域选择性和立体选择性。离子液体，微波和超声波的使用并未显着提高选择性。
• Synthesis and Reactivity of η⁴-Diene-Fe(CO)₃ Complexes from <i>exo</i>-2-Oxazolidinone Dienes. A Facile Generation of Stable Conjugated Enol-Enamido Species
  作者：Fernando Ortega-Jiménez、Adriana Benavides、Francisco Delgado、Hugo A. Jiménez-Vázquez、Joaquín Tamariz

  DOI：10.1021/om900772z

  日期：2010.1.11

  A synthesis of new η4-diene-Fe(CO)3 complexes derived from the novel exo-2-oxazolidinone dienes is described. These complexes were prepared by thermal complexation of the substituted dienes with diiron nonacarbonyl to afford the corresponding complexes as crystal solids. The X-ray single-crystal structure analysis revealed characteristic structural properties for diene-iron complexes, showing that

  新η的合成4 -二烯的Fe（CO）3个配合物从小说衍生外描述了-2-恶唑烷酮二烯。这些配合物是通过将取代的二烯与二铁九碳二烯进行热络合制备的，以提供相应的配合物，为结晶固体。X射线单晶结构分析揭示了二烯-铁配合物的特征结构性质，表明在扭曲的三角锥锥体几何构象中，两个羰基从金属指向金属的顶点C4和C5原子。杂环。通过烯丙基位置的酰化或烷基化对二烯部分的不成功的官能化表明这些二烯的强稳定性。这种稳定性促进了稳定和空前的共轭烯胺-烯醇酯-和en烯-烯醇-Fe（CO）3的生成 通过动力学或热力学控制反应条件形成配合物。
• New Synthesis of Carbazoles from Novel<i>exo</i>-2-Oxazolidinone Dienes
  作者：Ashis B. Mandal、Francisco Delgado、Joaquín Tamariz

  DOI：10.1055/s-1998-1571

  日期：1998.1

  A new synthesis of carbazoles, via regioselective Diels-Alder reaction of novel exo-2-oxazolidinone dienes 1, is described. Cyclization with palladium acetate of the intermediate diaryl amines, obtained by a one-pot three-step procedure from the cycloadducts, yielded the desired substituted carbazoles.

  本文介绍了通过新型外-2-噁唑烷酮二烯 1 的区域选择性 Diels-Alder 反应合成咔唑的新方法。用乙酸钯对中间体二芳基胺进行环化反应，从环加成物中通过一步法三步反应得到了所需的取代咔唑。
• One-Step Synthesis and Highly Regio- and Stereoselective Diels−Alder Cycloadditions of Novel <i>exo</i>-2-Oxazolidinone Dienes
  作者：Ashis B. Mandal、Adriana Gómez、Gonzalo Trujillo、Francisco Méndez、Hugo A. Jiménez、María de Jesús Rosales、Rafael Martínez、Francisco Delgado、Joaquín Tamariz

  DOI：10.1021/jo962403g

  日期：1997.6.13

  An improved synthesis of exo-heterocyclic dienes like N-substituted 4,5-dimethylene 2-oxazolidinones 1, by a one-step method from diacetyl and isocyanates, was described. This highly convergent synthetic strategy has been successfully used for the preparation of novel (Z)-5-ethylidene-4-methylene analogs 4 in fair yields. Both dienes 1 and 4 undergo efficient addition of symmetric dienophiles in thermal Diels-Alder reactions, inasmuch as they react stereo- and regioselectively with the unsymmetric olefins methyl vinyl ketone (MVK) and methyl propiolate. This regioselectivity was greatly improved by using Lewis acid catalysts (TiCl4, AlCl3). The nitrogen atom of the 2-oxazolidinone ring seems to control the orientation of the dienophile approach. These results have been rationalized in terms of the frontier molecular orbital theory by ab initio calculations. For dienes 4, addition of MVK gave the endo isomer as the major product. Dimerization of dienes 4 was also highly regio-, chemo-, and stereoselective, giving only isomer 17. This reaction furnished a second product, which corresponded to dienes 18 obtained by the [1,5] sigmatropic rearrangement of 4. The structure of the dienes and main products was established by NMR experiments and X-ray diffraction analysis.