4-ethoxycarbonyl-5-phenyl-N-methyldioxopyrroline | 55404-27-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: 4-ethoxycarbonyl-5-phenyl-N-methyldioxopyrroline
• 英文别名: N-methyl-3-etoxycarbonyl-2-phenyl-Δ²-pyrroline-4,5-dione；1-methyl-4,5-dioxo-2-phenyl-4,5-dihydro-pyrrole-3-carboxylic acid ethyl ester；Ethyl 1-methyl-4,5-dioxo-2-phenylpyrrole-3-carboxylate
• CAS: 55404-27-8
• 化学式: C₁₄H₁₃NO₄
• 分子量: 259.262
• InChiKey: LTEAGIYOKJUCPO-UHFFFAOYSA-N

物化性质

• 熔点：
  170-172 °C(Solv: benzene (71-43-2))
• 沸点：
  399.0±52.0 °C(Predicted)
• 密度：
  1.294±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  63.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-ethoxycarbonyl-5-phenyl-N-methyldioxopyrroline 在 氢氧化钾 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 1.0h， 以365 mg的产率得到Potassium; (E)-3-ethoxycarbonyl-4-methylamino-2-oxo-4-phenyl-but-3-enoate
  参考文献：
  名称：

  Sano, Takehiro; Horiguchi, Yoshie; Tsuda, Yoshisuke, Chemical and pharmaceutical bulletin, 1985, vol. 33, # 1, p. 110 - 120

  摘要：

  DOI：
• 作为产物：
  描述：

  4-Hydroxy-2-methoxy-1-methyl-5-oxo-2-phenyl-2,5-dihydro-1H-pyrrole-3-carboxylic acid ethyl ester 以 甲苯 为溶剂， 反应 2.0h， 以10 mg的产率得到4-ethoxycarbonyl-5-phenyl-N-methyldioxopyrroline
  参考文献：
  名称：

  Sano, Takehiro; Horiguchi, Yoshie; Tsuda, Yoshisuke, Chemical and pharmaceutical bulletin, 1985, vol. 33, # 1, p. 110 - 120

  摘要：

  DOI：

文献信息

• Dioxopyrroline. L. Skeletal Rearrangements of 7-Vinyl-7-trimethylsilyloxy-5-ethoxycarbonyl-1-phenyl-2-azabicyclo(3.2.0)heptane-3,4-diones under Thermal, Basic, and Acidic Conditions.
  作者：Takehiro SANO、Jun TODA、Yoshisuke TSUDA

  DOI：10.1248/cpb.40.36

  日期：——

  The oxyvinylcyclobutanes (2), photoadducts of the dioxopyrrolines (1) to trimethylsilyloxybutadienes, undergo two different types of skeletal rearrangements depending on the reaction conditions. Thermolysis of 2 caused expansion of the cyclobutane ring by a 1, 3-shift of the C1-C7 bond toward the vinyl group, giving rise to the hydroindoles (3) in moderate yields. This 1, 3-shift was enormously accelerated when an alkoxide was generated by the action of tetrabutylammonium fluoride (TBAF) on trimethylsilyloxyvinylcyclobutanes. Thus, 2a-d, on treatment with TBAF at -30°C, provided hydroindole derivatives in good yields, though in some cases (2a, b) accompanied with by-products (10). This demonstrates that the [2+2] photoannulation of dioxopyrroline, when coupled with the anionic 1, 3-shift, provides an efficient synthetic route to functionalized hydroindoles. Under acidic conditions, the oxyvinylcyclobutanes(2) rearranged to give exclusively the 2-azatricyclo[4.3.0.04, 9]nonanes (10), whose formation was rationalized in terms of the intramolecular Prins-type cyclization with concomitant expansion of the cyclobutane ring by 1, 2-shift of the C1-C7 bond toward the vinyl group.

  氧乙烯基环丁烷（2），二氧吡咯烷（1）与三甲基硅氧基丁二烯的加成物，根据反应条件的不同，会发生两种不同的骨架重排。热解2使得环丁烷环通过C1-C7键向乙烯基的1,3-迁移而扩张，中等产率地生成氢茚（3）。当通过四丁基氟化铵（TBAF）的作用在三甲基硅氧基乙烯基环丁烷中产生醇盐时，这种1,3-迁移极大加速。因此，2a-d在-30°C下与TBAF处理，以良好产率提供氢茚衍生物，尽管在某些情况下（2a, b）伴有副产物（10）。这表明，[2+2]光环加成反应与阴离子的1,3-迁移相结合，为功能化氢茚提供了有效的合成途径。在酸性条件下，氧乙烯基环丁烷（2）重排，唯一地生成2-氮杂三环[4.3.0.04,9]壬烷（10），其形成可以解释为通过C1-C7键向乙烯基的1,2-迁移伴随着环丁烷环的扩张，发生的分子内Prins型环化反应。
• Dioxopyrrolines. XLIX. Synthesis of azatropolones via photocycloaddition of 5-aryl-4-ethoxycarbonyl-1H-pyrrole-2,3-diones to acetylenes and ethylenes.
  作者：Takehiro SANO、Yoshie HORIGUCHI、Yoshisuke TSUDA

  DOI：10.1248/cpb.38.3283

  日期：——

  The first synthesis of derivatives of azatropolone, a new nitrogen heterocycle, and some of their chemical properties are described. Two routes to the azatropolone skeletone were developed; one is the photocycloaddition of dioxopyrrolines 1 to acetylenes followed by thermolysis or photolysis of the resulting cyclobutenes 2 to give the azatropolones 7 or 8, and the other is the ring expansion reaction of the cyclobutanes 5 obtained by the photocycloaddition of 1 to olefins followed by 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone dehydrogenation of the resulting dihydroazepines 16 to give the azatropolones 7.The azatropolone rapidly consumed diazomethane; thus 7 gave the 3-O-methylazatropolones 18, while 8 gave mixtures of 3-O-methyl-19 and 2-O-methylazatropolones 20. The position of methylation was proved by the unambiguous synthesis of 18 and of 2-O-ethyl derivatives 24 from 16. The azatropolones 7 and 8, when treated with a protonic solvent, readily underwent a ring contraction reaction giving rise to the pyridine-2-carboxylates 29 and 30, respectively, thus demonstrating that the azatropolone nucleus has a strongly electrophilic character.

  首次合成了氮杂环丙烷酮衍生物，并描述了它们的一些化学性质。开发了两条合成氮杂环丙烷酮骨架的途径；一种是将1，4-二氧杂环戊烯与乙炔进行光环加成，然后通过热解或光解得到的环丁烯2生成氮杂环丙烷酮7或8，另一种是通过环扩张反应将1，4-二氧杂环戊烯与烯烃光环加成得到的环丁烷5，然后通过2，3-二氯-5，6-二氰基-1，4-苯醌对得到的二氢氮杂卓16进行脱氢得到氮杂环丙烷酮7。氮杂环丙烷酮迅速消耗重氮甲烷；因此7得到了3-O-甲基氮杂环丙烷酮18，而8得到了3-O-甲基19和2-O-甲基氮杂环丙烷酮20的混合物。甲基化位置通过明确合成18和从16得到的2-O-乙基衍生物24得到了证明。当用质子溶剂处理时，氮杂环丙烷酮7和8容易发生环缩合反应，分别生成吡啶-2-羧酸酯29和30，这表明氮杂环丙烷酮核具有强亲电性。
• Dioxopyrrolines. XLV. (2+2)Photocycloaddition of 4-ethoxycarbonyl-5-aryl-1H-pyrrole-2,3-dione to cyclopentene derivatives: Formation of dihydropyridones.
  作者：Takehiro SANO、Yoshie HORIGUCHI、Kazue IMAFUKU、Yoshisuke TSUDA

  DOI：10.1248/cpb.38.366

  日期：——

  Photocycloaddition reactions of 4-ethoxycarbonyl-5-aryl-1H-pyrrole-2, 3-dione (1) with cyclopentadiene, indene, and cyclopentene gave the dihydropyridones 8, 11, and 12 as major products, respectively. Formation of them can be rationalized by assuming the formation of a 2s + 2a adduct predicted by the stereoselection rule and subsequent skeletal rearrangement. The stereochemical results seem to support the hypothesis that the donor-acceptor interaction as theoretically deduced by Epiotis plays an important role in determining the stereochemical pathway of photocycloaddition.

  4-乙氧羰基-5-芳基-1H-吡咯-2,3-二酮（1）与环戊二烯、茚和环戊烯的光环加成反应分别主要生成二氢吡啶酮8、11和12。它们的形成可以通过假设形成由立体选择规则预测的2s + 2a加合物并随后发生骨架重排来合理化。立体化学结果似乎支持了Epistis从理论上推导的供体-受体相互作用在决定光环加成的立体化学途径中起重要作用这一假设。
• Synthesis of Erythrina and related alkaloids. XVI Diels-Alder approach : Total synthesis of dl-erysotrine, dl-erythraline, dl-erysotramidine, dl-8-oxoerythraline and their 3-epimers.
  作者：TAKEHIRO SANO、JUN TODA、NORIAKI KASHIWABA、TAKESHI OHSHIMA、YOSHISUKE TSUDA

  DOI：10.1248/cpb.35.479

  日期：——

  Total synthesis of erythrinan alkaloids was achieved by a strategy based on the Diels-Alder reaction of activated butadienes to a dioxopyrroline. The reaction of isoquinolinopyrrolinedione (15) with 1, 3-bis-O-substituted butadienes proceeded in a regiospecific and stereoselective manner to give erythrinan derivatives (20) and (21). Lithium borohydride reduction of the adduct (20) or (21), followed by acid hydrolysis afforded the enone (33). Mesylation of 33 and subsequent demethoxycarbonylation of 42 under neutral conditions gave the dienone (43). Meerwein-Ponndorf reduction of 43 and subsequent methylation afforded erysotramidine (2a) and 8-oxoerythraline (2b). Aluminum hydride reduction of the 8-oxo derivatives (2) furnished dl-erysotrine (1a) and dl-erythraline (1b).

  基于激活的丁二烯与二氧吡咯啉进行Diels-Alder反应的策略，实现了erythrinan类生物碱的全合成。异喹啉吡咯二酮（15）与1,3-双氧取代的丁二烯反应，以区域特异性和立体选择性的方式生成erythrinan衍生物（20）和（21）。通过锂硼氢化物还原加合物（20）或（21），随后进行酸水解得到烯酮（33）。对33进行甲磺酰化，随后在中性条件下进行脱甲氧羰基化得到二烯酮（43）。对43进行Meerwein-Ponndorf还原，随后进行甲基化得到erysotramidine（2a）和8-氧代erythraline（2b）。对8-氧代衍生物（2）进行铝氢化还原得到dl-erysotrine（1a）和dl-erythraline（1b）。
• Dioxopyrrolines. Part LVIII. Rearrangement of 2,3-Dioxo-1,4-oxazines to 4,5-Dioxooxazoles in the Reaction with Dimethylsulfoxonium Methylide.
  作者：Jun TODA、Masaharu SEKI、Kazuko AMANO、Taichi OYAMA、Takehiro SANO、Fumiyuki KIUCHI、Yoshisuke TSUDA

  DOI：10.1248/cpb.42.739

  日期：——

  Reaction of 2, 3-dioxo-2, 3-dihydro-4H-1, 4-oxazines 2a-e with dimethylsulfoxonium methylide introduced an exo-methylene group with concomitant ring contraction to give 4, 5-dioxo-2, 3, 4, 5-tetrahydrooxazoles 3a-e in moderate yields. Mechanism of this unusual reaction was discussed.

  2, 3-二酮-2, 3-二氢-4H-1, 4-噁唑啉 2a-e 与二甲基亚磺酸钠甲基负离子的反应引入了一个外部亚甲基组，同时伴随环收缩，生成了4, 5-二酮-2, 3, 4, 5-四氢噁唑 3a-e，产率适中。讨论了这一非寻常反应的机制。