2-methyl-3-phenyl-4,5-dicarbomethoxy-Δ4-isoxazoline | 109787-18-0

• 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: 2-methyl-3-phenyl-4,5-dicarbomethoxy-Δ4-isoxazoline
• 英文别名: 2-methyl-3-phenyl-4,5-dicarbomethoxyisoxazoline；4,5-dicarbomethoxy-3-phenyl-N-methylisoxazoline；dimethyl 2-methyl-3-phenyl-3H-1,2-oxazole-4,5-dicarboxylate
• CAS: 109787-18-0
• 化学式: C₁₄H₁₅NO₅
• 分子量: 277.277
• InChiKey: RFDIECWISGGBSW-UHFFFAOYSA-N

物化性质

• 熔点：
  64.9-65.6 °C
• 沸点：
  367.9±52.0 °C(Predicted)
• 密度：
  1.263±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-methyl-3-phenyl-4,5-dicarbomethoxy-Δ4-isoxazoline 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 以85%的产率得到methyl 4-phenyl-3-carbomethoxy-2-oxo-3-butenoate
  参考文献：
  名称：

  Peracid oxidation of 4-isoxazolines as a method for the preparation of .alpha.,.beta.-unsaturated carbonyl compounds

  摘要：

  DOI：

  10.1021/jo00245a021
• 作为产物：
  描述：

  苯甲醛肟 在 cesium fluoride 作用下， 以 乙二醇二甲醚 为溶剂， 反应 12.0h， 生成 2-methyl-3-phenyl-4,5-dicarbomethoxy-Δ4-isoxazoline
  参考文献：
  名称：

  Silyl group transfer in the cycloaddition reactions of silyl iminium salts derived from aryl-substituted oximes

  摘要：

  DOI：

  10.1021/jo00279a036

文献信息

• Site selectivity in the reactions of 1,3-dipoles with norbornadiene derivatives
  作者：D. Cristina、M. De Amici、C. De Micheli、R. Gandolfi

  DOI：10.1016/s0040-4020(01)92451-2

  日期：1981.1

  2-diazopropane and C-pnenyl-N-methyl-nitrone react with the sole tetrasubstituted double bond of 1a–c in stereo- and site-specific cycloadditions. The quantitative evaluation of the two possible reaction paths was performed by glc analysis. The compounds detected were those arising from Diels-Alder cycloreversions of the thermally labile intermediate adducts 2 and 3 (Scheme 1). The results were rationalized

  芳基叠氮化物，苄腈氧化物和二苯基腈亚胺与降冰片二烯衍生物1a–c的环加成反应显示出不同程度的位点和立体选择性。对于双极性亲和剂1a，芳基叠氮化物和苯甲腈氧化物优先攻击电子贫的四取代双键，而在1b和1c的情况下，则是进入环加成的取代双键。相比之下，2-重氮丙烷和C-亚苯基-N-甲基-硝基与立体和位点特定的环加成反应中与1a–c的唯一四取代双键反应。通过glc对两种可能的反应路径进行定量评估分析。检测到的化合物是由热不稳定的中间体加合物2和3的Diels-Alder环还原所产生的化合物（方案1）。在仅考虑边界轨道相互作用的定性摄动处理的基础上，对结果进行了合理化。
• Reaction of N-(phenyl and methyl)-C-arylnitrones with DMAD in ionic liquid: Efficient synthesis of Δ4-isoxazolines
  作者：Hassan Valizadeh、Esmail Vesally、Leila Dinparast

  DOI：10.1002/jhet.682

  日期：2012.1

  Facile synthesis of N‐(methyl and phenyl)‐Δ4‐isoxazolines via the reaction of (Z)‐N‐(methyl and phenyl)‐C‐arylnitrones with dimethyl acethylenedicarboxylate, DMAD, in ionic liquid is described. (Z)‐N‐methyl‐C‐arylnitrones afforded the high yield of N‐methyl‐Δ4‐isoxazolines 4a, 4b, 4c, 4d, 4e in ionic liquid, [bmim]BF4, at room temperature. However, the reaction of (Z)‐N‐phenyl‐C‐arylnitrones with DMAD

  的简便合成ñ - （甲基和苯基）-Δ 4 -通过（Z）反应-isoxazolines Ñ - （甲基和苯基） - c ^ -arylnitrones与二甲acethylenedicarboxylate，DMAD，在离子液体中描述。（Z） - ñ甲基Ç -arylnitrones得到的高收率Ñ甲基- Δ 4个-isoxazolines图4a，图4b，图4c，图4d，图4e中的离子液体，离子液体[bmim] BF 4，在室温下。但是，（Z）‐N‐苯基‐C的反应-arylnitrones与DMAD，得到顺式的相关的反式异构体混合物和Ñ苯基Δ 4个-isoxazolines（图5a，图5b，图5c，图5d，图5e，图5f，5克，5H，5I，5J，图6a，图6b，图6c，图6d（6e，6f，6g，6h，6i，6j）在这些条件下。J.杂环化​​学。（2012）。
• Rapid, Highly Efficient, and Room-Temperature TiCl₄-Catalyzed Synthesis of Δ⁴-Isoxazolines Under Solvent-Free Conditions
  作者：Hassan Valizadeh、Leila Dinparast

  DOI：10.1080/00397910903537349

  日期：2010.12.22

  4-Isoxazoline derivatives were synthesized in excellent yields via the titanium tetrachloride-catalyzed 1,3-dipolar cycloaddition reaction of nitrones with ,-unsaturated compounds under neat conditions at room temperatures in very short reaction time.
• Benzaldehyde oxime as a 1,3-dipole chameleon
  作者：Albert Padwa、William Dent、Philip E. Yeske

  DOI：10.1021/jo00226a050

  日期：1987.8
• Thiones as Superdipolarophiles. Rates and Equilibria of Nitrone Cycloadditions to Thioketones
  作者：Rolf Huisgen、Lubor Fisera、Henry Giera、Reiner Sustmann

  DOI：10.1021/ja00143a008

  日期：1995.9

  1,3-Dipolar cycloadditions of N-methyl-C,C-diphenylnitrone (15) and N-methyl-C-phenylnitrone (16) with aliphatic thioketones are equilibrium reactions. The 1,4,2-oxathiazolidines were characterized and their dissociation constants measured by H-1 NMR analysis and by visible spectrophotometry. K-diss Of the adduct 28 from 16 and 2,2,6,6-tetramethylcyclohexanethione (27) was determined from 20-76 degrees C, revealing Delta H-add = -10.8 kcal mol(-1) and Delta S-add = -28 eu. The inertness of diaryl thioketones vs nitrones has thermodynamic reasons. According to rate measurements with 16, the activity of the highly hindered thione 27 exceeds 5-fold that of dimethyl acetylenedicarboxylate (DMAD), the top dipolarophile with a CC multiple bond; the cycloaddition to adamantanethione-despite adverse steric effects-is 1500 times faster than that to DMAD. Rate constants for the cycloaddition of 16 to 2,2,4,4-tetramethyl-3-thioxocyclobutanone (10) were measured in 12 solvents. The small and slightly inverse relation to solvent polarity rules out a zwitterionic intermediate but is consistent with a concerted pathway.