dimethyl cis-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate | 4916-25-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl cis-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate
• 英文别名: dimethyl (2S,3R)-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate
• CAS: 4916-25-0
• 化学式: C₁₃H₁₅NO₅
• 分子量: 265.266
• InChiKey: MDNCBWWWVBAQLX-BVUQATHDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  64.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,2,4,4-四甲基-1,3-环丁烷二硫酮 、 dimethyl cis-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate 以 xylene 为溶剂， 反应 3.0h， 以62%的产率得到dimethyl trans-7-(4-methoxyphenyl)-1,1,3,3-tetramethyl-2-thioxo-5-thia-7-azaspiro[3.4]octane-6,8-dicarboxylate
  参考文献：
  名称：

  摘要：

  The reaction of 2,2,4,4-tetramethyl-3-thioxocyclobutanone (1) with cis-1-alkyl-2,3-diphenylaziridines 5 in boiling toluene yielded the expected trans-configured spirocyclic 1,3-thiazolidines 6 (Scheme 1). Analogously, dimethyl trans-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (trans-7) reacted with 1 and the corresponding dithione 2, respectively, to give spirocyclic 1,3-thiazolidine-2,4-dicarboxylates 8 (Scheme 2). However, mixtures of cis- and trans-derivatives were obtained in these cases. Unexpectedly, the reaction of 1 with dimethyl 1.3-diphenylaziridine-2,2-dicarboxylate (11) led to a mixture of the cycloadduct 13 and 5-(isopropylidene)-4-phenyl- 1.3-thiazolidine-2,2-dicarboxylate (14). a formal cycloadduct of azomethine ylide 12 with dimethyl-thioketene (Scheme 3). The regioisomeric adduct 16 was obtained from the reaction between 2 and 11. The structures of 6b, cis-8a, cis-8b, 10, and 16 have been established by X-ray crystallography.

  DOI：

  10.1002/1522-2675(200209)85:9<2644::aid-hlca2644>3.0.co;2-v
• 作为产物：
  描述：

  甲醇 、 diethyl cis-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate 在 magnesium acetate 作用下， 反应 96.0h， 以96%的产率得到dimethyl cis-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate
  参考文献：
  名称：

  乙酸镁–二烷基氮丙啶二羧酸酯酯交换反应中羰基的有效亲电子活化剂

  摘要：

  开发了一种在乙酸镁存在下通过亲电活化羰基并保留氮丙啶的方法，通过羰基的亲电活化来酯化二烷基氮丙啶二羧酸酯中的酯基的方法，并将改性的氮丙啶二羧酸酯用于合成富勒烯C60的位阻衍生物证明了2'，5'-二取代的全吡咯烷。

  DOI：

  10.1007/s10593-020-02744-y

文献信息

• 1,3-Thiazolidine-dicarboxylates from Thioketones and Thermally Generated Azomethine Ylides
  作者：Grzegorz Mlostoń、Katarzyna Urbaniak、Heinz Heimgartner

  DOI：10.1002/1522-2675(200207)85:7<2056::aid-hlca2056>3.0.co;2-o

  日期：2002.7

  nonstereoselective course to provide a mixture of trans- and cis-substituted cycloadducts. This result can be explained by an isomerization of the intermediate azomethine ylide. Dimethyl 1,3-thiazolidine-2,2-dicarboxylates 14 and 15 were formed in the thermal reaction of dimethyl aziridine-2,2-dicarboxylate 11 with aromatic thioketones (Scheme3). On treatment of 14 and 15 with Raney-Ni in refluxing EtOH

  9H-芴-9-硫酮 (1) 与 1-(4-甲氧基苯基)-氮丙啶-2,3-二甲酸二甲酯的顺式和反式异构体（分别为顺式和反式 2）的反应110° 的二甲苯仅产生分别具有反式和顺式构型的螺环环加合物（反式和顺式 3，分别；方案 1）。类似地，反应性较低的硫酮，例如噻二苯甲酮(5)和顺式-2立体选择性反应，得到相应的反式-1,3-噻唑烷-2,4-二羧酸酯(例如，反式-8；方案2)。另一方面，5 和 trans-2 的反应以非立体选择性过程进行，得到反式和顺式取代的环加合物的混合物。该结果可以通过中间体甲亚胺叶立德的异构化来解释。二甲基 1,3-thiazolidine-2, 2-二羧酸盐 14 和 15 是在氮丙啶-2,2-二羧酸二甲酯 11 与芳族硫酮的热反应中形成的（方案 3）。在回流的 EtOH 中用 Raney-Ni 处理 14 和 15，脱硫和环收缩分别导致氮杂环丁烷-2,2-二羧酸盐 17
• [2+3] Cycloadditions of Azomethine Ylides with 1,3-Thiazole-5(4H)-thiones
  作者：Grzegorz Mlosto?、Anthony Linden、Heinz Heimgartner

  DOI：10.1002/hlca.19980810309

  日期：——

  reactions of 1,2,3-trisubstituted aziridines 1 with 1,3-thiazole-5(4H)-thiones 6 in toluene yielded, in general, a mixture of two diastereoisomeric spirocyclic [2+3] cycloadducts. The formation of these products can be explained by a stereoselective electrocyclic ring opening of 1 to give an azomethine ylide 2 as the reactive intermediate, which is trapped immediately by 6via a stereoselective 1,3-dipolar

  1,2,3-三取代的氮丙啶1与1,3-噻唑-5（4 H）-硫酮6在甲苯中的热反应通常产生两种非对映异构的螺环[2 + 3]环加合物的混合物。这些产物的形成可以通过将立体选择性的电环开环为1来给出，以得到作为反应性中间体的甲亚胺基内酯2，其通过立体选择性的1,3-偶极环加成立即被6捕获。仅在的情况下，反式-二甲基-1-（4-甲氧基苯基）氮丙啶-2,3-二羧酸酯（反式- 1A，四个非对映异构cycloadducts形成）（方案4）。该结果是通过所述中间偶氮甲碱内鎓盐的异构化合理化顺-图2a到反式-图2a。
• Magnesium acetate – an effective electrophilic activator of the carbonyl group in transesterification of dialkylaziridine dicarboxylates
  作者：Angelina V. Kazakova、Dmitriy V. Androsov、Alexander S. Konev、Alexander F. Khlebnikov

  DOI：10.1007/s10593-020-02744-y

  日期：2020.7

  magnesium acetate with the preservation of the aziridine ring was developed and the use of modified aziridine dicarboxylates in the synthesis of sterically hindered derivatives of fullerenes C60, 2',5'-disubstituted fulleropyrrolidines, was demonstrated.

  开发了一种在乙酸镁存在下通过亲电活化羰基并保留氮丙啶的方法，通过羰基的亲电活化来酯化二烷基氮丙啶二羧酸酯中的酯基的方法，并将改性的氮丙啶二羧酸酯用于合成富勒烯C60的位阻衍生物证明了2'，5'-二取代的全吡咯烷。
• ——
  作者：Grzegorz Mlostoń、Katarzyna Urbaniak、Anthony Linden、Heinz Heimgartner

  DOI：10.1002/1522-2675(200209)85:9<2644::aid-hlca2644>3.0.co;2-v

  日期：2002.9

  The reaction of 2,2,4,4-tetramethyl-3-thioxocyclobutanone (1) with cis-1-alkyl-2,3-diphenylaziridines 5 in boiling toluene yielded the expected trans-configured spirocyclic 1,3-thiazolidines 6 (Scheme 1). Analogously, dimethyl trans-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (trans-7) reacted with 1 and the corresponding dithione 2, respectively, to give spirocyclic 1,3-thiazolidine-2,4-dicarboxylates 8 (Scheme 2). However, mixtures of cis- and trans-derivatives were obtained in these cases. Unexpectedly, the reaction of 1 with dimethyl 1.3-diphenylaziridine-2,2-dicarboxylate (11) led to a mixture of the cycloadduct 13 and 5-(isopropylidene)-4-phenyl- 1.3-thiazolidine-2,2-dicarboxylate (14). a formal cycloadduct of azomethine ylide 12 with dimethyl-thioketene (Scheme 3). The regioisomeric adduct 16 was obtained from the reaction between 2 and 11. The structures of 6b, cis-8a, cis-8b, 10, and 16 have been established by X-ray crystallography.