3-(2-Bromo-phenyl)-4,5-dimethylene-oxazolidin-2-one | 189953-32-0

• 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-(2-Bromo-phenyl)-4,5-dimethylene-oxazolidin-2-one
• 英文别名: 3-(2-Bromophenyl)-4,5-dimethylidene-1,3-oxazolidin-2-one
• CAS: 189953-32-0
• 化学式: C₁₁H₈BrNO₂
• 分子量: 266.094
• InChiKey: HXVAVNGEEMBFNH-UHFFFAOYSA-N

物化性质

• 沸点：
  325.5±44.0 °C(Predicted)
• 密度：
  1.59±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 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-(2-Bromo-phenyl)-4,5-dimethylene-oxazolidin-2-one 在 四(三苯基膦)钯 氢氧化钾 、 三氟化硼乙醚 、 sodium carbonate 、 potassium carbonate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 lithium chloride 作用下， 以 乙醇 、 二氯甲烷 、 水 、 丙酮 、 乙腈 、 苯 为溶剂， 反应 102.42h， 生成 1-甲氧基-9H-咔唑-3-甲醛
  参考文献：
  名称：

  涉及4,5-二亚甲基恶唑烷丁二酮和钯（0）催化的二芳基插入的Murrayanine的全合成。

  摘要：

  以4,5-二亚甲基恶唑烷丁-2-酮12为起始原料，开发了一种新的天然咔唑Murrayanine（1）的全合成方法。后者与丙烯醛（= prop-2-enal; 13）进行了高度区域选择性的Diels-Alder环加成反应，得到加合物14（方案3）。这种加合物转化成二芳基胺衍生物9进行经由水解和甲基化（方案4）。与我们之前的合成方法不同，在这种合成方法中，二芳基胺衍生物被Pd II转化为1-化学计量环化，该新方法包括通过更有效的Pd 0催化的分子内二芳基偶合偶联（已应用于9）改善了环化作用，从而以较高的总收率获得了天然咔唑1。

  DOI：

  10.1002/hlca.200790148
• 作为产物：
  描述：

  异氰酸2-溴苯酯 、 2,3-丁二酮 在 lithium carbonate 、 三乙胺 作用下， 生成 3-(2-Bromo-phenyl)-4,5-dimethylene-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

• 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.
• Total Synthesis of Murrayanine Involving 4,5-Dimethyleneoxazolidin-2-ones and a Palladium(0)-Catalyzed Diaryl Insertion
  作者：Pablo Bernal、Joaquín Tamariz

  DOI：10.1002/hlca.200790148

  日期：2007.8

  A new total synthesis of the natural carbazole murrayanine (1) was developed by using the 4,5-dimethyleneoxazolidin-2-one 12 as starting material. The latter underwent a highly regioselective Diels–Alder cycloaddition with acrylaldehyde (=prop-2-enal; 13) to give adduct 14 (Scheme 3). Conversion of this adduct into diarylamine derivative 9 was carried out via hydrolysis and methylation (Scheme 4).

  以4,5-二亚甲基恶唑烷丁-2-酮12为起始原料，开发了一种新的天然咔唑Murrayanine（1）的全合成方法。后者与丙烯醛（= prop-2-enal; 13）进行了高度区域选择性的Diels-Alder环加成反应，得到加合物14（方案3）。这种加合物转化成二芳基胺衍生物9进行经由水解和甲基化（方案4）。与我们之前的合成方法不同，在这种合成方法中，二芳基胺衍生物被Pd II转化为1-化学计量环化，该新方法包括通过更有效的Pd 0催化的分子内二芳基偶合偶联（已应用于9）改善了环化作用，从而以较高的总收率获得了天然咔唑1。