3-(4-chlorophenyl)-4,5-dimethylene-1,3-oxazolidin-2-one | 153897-92-8

• 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: 3-(4-chlorophenyl)-4,5-dimethylene-1,3-oxazolidin-2-one
• 英文别名: (4-chlorophenyl)-4,5-dimethylene-2-oxazolidinone；3-(4-Chlorophenyl)-4,5-dimethylidene-1,3-oxazolidin-2-one
• CAS: 153897-92-8
• 化学式: C₁₁H₈ClNO₂
• 分子量: 221.643
• InChiKey: BXRZJTTVRNOBGX-UHFFFAOYSA-N

物化性质

• 沸点：
  324.2±44.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  3-(4-chlorophenyl)-4,5-dimethylene-1,3-oxazolidin-2-one 在 对苯二酚 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 219.0h， 生成 3-(p-chlorophenyl)-8-methyl-1-oxa-3-azaspiro[4.5]dec-7-ene-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：

  对氯苯异氰酸酯 、 2,3-丁二酮 在 lithium carbonate 、 三乙胺 作用下， 以 1,4-二氧六环 为溶剂， 反应 30.0h， 以41%的产率得到3-(4-chlorophenyl)-4,5-dimethylene-1,3-oxazolidin-2-one
  参考文献：
  名称：

  Hernandez, Raul; Sanchez, Jose M.; Gomez, Adriana, Heterocycles, 1993, vol. 36, # 9, p. 1951 - 1956

  摘要：

  DOI：

文献信息

• Activation of aldehydes by exocyclic iridium(<scp>i</scp>)-η⁴:π²-diene complexes derived from 1,3-oxazolidin-2-ones
  作者：Rosa Padilla、Verónica Salazar-Pereda、Daniel Mendoza-Espinosa、José M. Vásquez-Pérez、Noemí Andrade-López、Joaquín Tamariz、José G. Alvarado-Rodríguez、Julián Cruz-Borbolla

  DOI：10.1039/c6dt02866g

  日期：——

  The Ir(I) complexes [TpMe2Ir(η4-1,4-diene)] 2b and 2c react thermally with a variety of aromatic aldehydes, 3a–e, to generate the metallabicyclic compounds 4e–k and the Fischer-type carbenes 5a–b in moderate yields. These reactions are proposed to take place with the initial formation of η1-aldehyde adducts as key intermediates. The formation of the metallabicyclic compounds 4e–k involves a formal

  红外（我）络合物[TP ME2的Ir（η 4 -1,4-二烯）]图2b和2c中与各种芳香醛，进行热反应3A-E ，以生成metallabicyclic化合物4E-K和费-型卡宾5a–b的产量中等。这些反应提议发生与初始形成的η 1 -醛加合物作为关键中间体。所述metallabicyclic化合物的形成4E-K包括在正式脱羧过程外型-2-恶唑烷酮二烯和一个邻芳环的金属化。费歇尔型卡宾5a–b的产生是一系列基于金属的重排中间体而未观察到脱羧的结果。的η的治疗4 -二烯配合物2b的从与多种路易斯碱诱导的二烯配位体的结合模式的改变的η 4：π 2至η 2：σ 2形成的Ir（III）衍生物的6B-d的组合物TP ME2 IR-（η 4：π 2 -1,4-二烯）（L）（L = CO，乙腈，和C 5 ħ 5 N）。络合物2b反应的研究用单或多氘代醛进行了分析，以了解此类过程的机理。这些研究的结果用于确
• 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。
• Synthesis of η⁴:π²-Exocyclic-Diene Iridium(I) Complexes Derived from 1,3-Oxazolidin-2-ones and Their Transformation into Iridium(III) Derivatives by Reaction with a Phosphine and with Aldehydes
  作者：Verónica Salazar、Oscar R. Suárez-Castillo、Rosa Padilla、J. Carlos Macías P.、Miguel Ángel Méndez-Rojas,、Joaquín Tamariz、Adriana Benavides

  DOI：10.1021/om050582z

  日期：2006.1.1

  dienes like N-substituted 4,5-dimethylene-2-oxazolidinones a and b, and KTpMe2 yields derivatives of the composition TpMe2Ir(a or b) (1a,b). Derivative 1a reacts with Ph2PC⋮CPPh2, with the formal oxidative addition of the diene moiety to the metal center and coordination of the phosphine in the κ1 mode. Derivatives 1a,b react with aromatic aldehydes to form the new compounds 3 (with benzaldehyde) and

  二聚体[Ir（μ-Cl）（coe）2 ] 2与两个环外二烯如N-取代的4,5-二亚甲基-2-恶唑烷二酮a和b的反应，以及KTp Me2产生组成为Tp Me2 Ir的衍生物（a或b）（1a，b）。衍生物1A的Ph发生反应2 PC⋮CPPh 2，与正式氧化加成二烯部分的磷化氢的金属中心，并协调在κ 1模式。导数1a，b与芳族醛反应形成新化合物3（与苯甲醛）和4（茴香醛），其中包含由两个有机片段（二烯和醛）偶联形成的精心设计的二齿配体。化合物3a，b的结构已经通过X射线衍射分析确定。
• 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.