4,5-dimethylene-3-phenyl-1,3-oxazolidin-2-one | 153897-88-2

• 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: 4,5-dimethylene-3-phenyl-1,3-oxazolidin-2-one
• 英文别名: 4,5-Dimethylidene-3-phenyl-1,3-oxazolidin-2-one
• CAS: 153897-88-2
• 化学式: C₁₁H₉NO₂
• 分子量: 187.198
• InChiKey: YQLAOWAKYJIJLH-UHFFFAOYSA-N

物化性质

• 沸点：
  275.9±23.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  4,5-dimethylene-3-phenyl-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 171.0h， 生成 8-methyl-3-phenyl-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：

  异氰酸苯酯 、 2,3-丁二酮 在 lithium carbonate 、 三乙胺 作用下， 生成 4,5-dimethylene-3-phenyl-1,3-oxazolidin-2-one
  参考文献：
  名称：

  One-Step Synthesis and Highly Regio- and Stereoselective Diels−Alder Cycloadditions of Novel exo-2-Oxazolidinone Dienes

  摘要：

  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.

  DOI：

  10.1021/jo962403g

文献信息

• 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。
• Total Synthesis of the Natural Carbazoles Murrayanine and Murrayafoline A, Based on the Regioselective Diels-Alder Addition of<i>exo</i>-2-Oxazolidinone Dienes
  作者：Joaquín Tamariz、Adriana Benavides、Javier Peralta、Francisco Delgado

  DOI：10.1055/s-2004-831213

  日期：——

  synthesis of the natural carbazoles Murrayanine (1) and Murrayafoline A (3) is described. The key step in the synthetic route involved the regioselective cycloaddition of the diene 4,5-dimethylene-3-phenyl-1,3-oxazolidin-2-one (4) to acrolein (6) catalyzed by Lewis acids at low temperature. Direct aromatization of the substituted cyclohexene moiety of adduct 7, and further hydrolysis of the 2-oxazolidinone

  描述了天然咔唑 Murrayanine (1) 和 Murrayafoline A (3) 的新合成方法。合成路线中的关键步骤涉及在路易斯酸的低温催化下，二烯 4,5-二甲基-3-苯基-1,3-恶唑烷-2-酮 (4) 与丙烯醛 (6) 的区域选择性环加成反应。加合物 7 的取代环己烯部分的直接芳构化，以及 2-恶唑烷酮环的进一步水解，被证明是一种比制备相应芳基苯胺 14 和 18 的相反合成序列更有效的策略。钯促进的环化后者以高总产率提供了所需的咔唑1和3。
• Total Synthesis of the Natural Carbazoles O-Demethylmurrayanine and Murrastanine A, and of a C4,C4′ Symmetric Murrastanine A Dimer from N-Phenyl-4,5-dimethylene-1,3-oxazolidin-2-one
  作者：Adriana Benavides、Hugo A. Jiménez-Vázquez、José Luis Avila-Melo、Alfredo Fuentes-Gutiérrez、Joaquín Tamariz

  DOI：10.1055/a-1385-9052

  日期：2021.7

  The synthesis of natural carbazoles O-demethylmurrayanine and murrastanine A starting from the title exo-heterocyclic diene­ is described. In the synthesis of murrastanine A, its symmetric C4,C4′ dimer can be obtained as the sole product under rather mild conditions. In all cases, the key intermediate is the same diarylamine. The carbazole nucleus is obtained through a Pd-promoted cyclization of the

  描述了以标题外-杂环二烯为原料的天然咔唑O-去甲基Murrayanine和Murrastanine A的合成。在合成莫拉斯坦宁A时，可以在相当温和的条件下将其对称的C4，C4'二聚体作为唯一产物获得。在所有情况下，关键中间体是相同的二芳基胺。通过适当的二芳基胺的钯促进环化获得咔唑核。为了合成O-去甲基尿嘧啶，环化反应发生在甲硅烷基化衍生物上。还介绍了墨累烷宁，两种二芳基胺和两种非天然咔唑中间体的晶体结构。
• Highly regio- and Stereoselective Diels–Alder Cycloadditions of α-Alkoxyvinyl(ethoxy)carbene complexes with exo-heterocyclic dienes
  作者：Alberto Feliciano、M. Inés Flores-Conde、Rosa Padilla、Carlos Espinoza-Hicks、Alejandro Camacho-Dávila、Marvin Rentería、Miguel Angel Vázquez、Joaquín Tamariz、Francisco Delgado

  DOI：10.1016/j.jorganchem.2018.08.024

  日期：2018.11

  A comparative study of reactivity and selectivity was carried out between the α-alkoxyvinyl(ethoxy)carbene complexes of group 6 metals (CO)5M = C[C(=CH2)(OR)]OEt [1a–c: M = Cr; 6a–c: M = Mo; 7a–c: M = W; a, R = Et; b, R = n–Pr; c, R = n–Bu] and exo-heterocyclic dienes 5a–e in Diels–Alder reactions. The cycloadditions of complexes 1, 6 and 7 with the unsubstituted diene 5a (R1 = H) were performed at

  在第6类金属（CO）5 M = C [C（= CH 2）（OR）] OEt [ 1a – c：M = 1 ]的α-烷氧基乙烯基（乙氧基）卡宾配合物之间进行了反应性和选择性的比较研究。铬 6a – c：M = Mo；7a – c：M = W；a，R = Et; b，R ＝  n- Pr；c，R =  n –Bu ]和Diels–Alder反应中的外杂环二烯5a – e。复合物的环加成1，6和7与未取代的二烯5A（R 1  = H）在25℃下进行，证明是有利于的高度选择性第五羰基cycloadducts 8，10和12。在另一方面，复合物的环加成1A - Ç和6A - ç与取代的二烯5B - ë（R 1  = Me或Et）发生在较高的温度（50℃），得到新的对位-内切Ç ，O-螯合的四羰基环加合物15a - f和17a – d分别具有高区域选择性和立体选择性。过渡态的DFT计算合理化了它们的选
• Hernandez, Raul; Sanchez, Jose M.; Gomez, Adriana, Heterocycles, 1993, vol. 36, # 9, p. 1951 - 1956
  作者：Hernandez, Raul、Sanchez, Jose M.、Gomez, Adriana、Trujillo, Gonzalo、Aboytes, Rossana、et al.

  DOI：——

  日期：——