diethyl 2-(4'-chlorophenylamino)fumarate | 35975-67-8

• 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: diethyl 2-(4'-chlorophenylamino)fumarate
• 英文别名: diethyl (Z)-2-(4-chloroanilino)but-2-enedioate
• CAS: 35975-67-8
• 化学式: C₁₄H₁₆ClNO₄
• 分子量: 297.738
• InChiKey: XDZWAFLDTSIKCV-XFXZXTDPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl 2-(4'-chlorophenylamino)fumarate 、 α-chlorobenzyl isocyanate 以 甲苯 为溶剂， 反应 24.0h， 以44%的产率得到diethyl 2-oxo-6-phenyl-3-(4-chlorophenyl)-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylate
  参考文献：
  名称：

  Heterocyclization of functionalized heterocumulenes with C,N-, C,O-, and C,S-Binucleophiles: XI. Synthesis of dialkyl 2-oxo-3,6-diaryl-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylates by cyclocondensation of 1-chlorobenzyl isocyanates with dialkyl anilinofumarates

  摘要：

  1-Chlorobenzyl isocyanates react with N-arylfumarates with the formation of dialkyl 2-oxo-3,6-diaryl-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylates that on alkaline hydrolysis are converted into 6-alkoxycarbonyl-1,4-diaryl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylic acids. The condensation of 1-chloro-1-phenyl-2,2,2-trifluoroethyl isocyanate with N-arylfumarates results in dialkyl 6-oxo-2,3-diaryl-2-trifluoromethyl-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylates.

  DOI：

  10.1134/s1070428010050209
• 作为产物：
  描述：

  对氯苯胺 、 丁炔二酸二乙酯 以 乙醇 为溶剂， 反应 24.0h， 以74%的产率得到diethyl 2-(4'-chlorophenylamino)fumarate
  参考文献：
  名称：

  乙二羧酸的胺和硫醇盐之间差异的探讨。

  摘要：

  X射线晶体分析证实，室温下在氯仿中亲核性地将硫醇盐加成到乙二酸二乙基二乙酯中，仅得到内消旋二硫代加成产物，而在乙醇中加成胺仅得到相应的（Z）-烯胺。在较低温度下制备和分离的硫醇盐加成的单加成产物也表现出（Z）-立体化学。伴随的对简化模型系统的计算研究解释了观察到的立体化学和乙炔二羧酸酯容易与硫醇盐亲核体发生两次加成反应的原因，并且（Z）-烯胺对硫醇盐或胺亲核体的添加反应性低得多。

  DOI：

  10.1021/acs.joc.9b01392

文献信息

• Introduction of a clean and promising protocol for the synthesis of β-amino-acrylates and 1,4-benzoheterocycles: an emerging innovation
  作者：Garima Choudhary、Rama Krishna Peddinti

  DOI：10.1039/c1gc15701a

  日期：——

  A highly efficient, elegant and simple procedure with exceptionally mild conditions has been proposed for the synthesis of β-amino-acrylate derivatives and an array of biologically and pharmaceutically active benzoheterocycles. The protocol offers a valuable alternative to known methods and will find applications in the field of green synthesis. The regio- and stereo-chemistry of the products were established by IR, NMR and single crystal X-ray analysis.

  提出了一种高效、优雅且简单的过程，用于合成β-氨基丙烯酸酯衍生物和一系列具有生物学及药物活性的苯并杂环化合物，条件极为温和。该方案为已知方法提供了一种有价值的替代方案，并将应用于绿色合成领域。产品的区域和立体化学性质通过红外光谱、核磁共振和单晶X射线分析得以确定。
• Enaminones in Heterocyclic Syntheses: Part 4. A New One-Step Synthetic Route to Pyrrolo[3,4-<i>b</i>]pyridine and Convenient Syntheses of 1,4-Dihydropyridines and 1,1′-(1,4-Phenylene)bis(1,4-dihydropyridine)
  作者：M. M. Mashaly、S. R. El-Gogary、T. R. Kosbar

  DOI：10.1002/jhet.1609

  日期：2014.7

  Reactions of cyano olefins with (i) enamino imides afforded novel pyrrolo[3,4‐b]pyridines; (ii) enamino esters afforded new 1,4‐dihydropyridines; and (iii) bisenamino ester afforded new 1,1′‐(1,4‐phenylene)bis(1,4‐dihydropyridine). The new derivatives are planned as suggested drug candidates.

  氰基烯烃与（i）烯氨基酰亚胺的反应提供了新型的吡咯并[3,4- b ]吡啶；（ii）烯氨基酯提供了新的1,4-二氢吡啶; （iii）联氨基酯提供了新的1,1'-（1,4-亚苯基）双（1,4-二氢吡啶）。新的衍生物计划作为候选药物。
• Method of treatment of plants with aniline derivatives
  申请人：MAY & BAKER LIMITED

  公开号：EP0201203A2

  公开（公告）日：1986-12-17

  A method of regulating plant growth at a locus which comprises applying to the locus an effective amount of a compound of the general formula: wherein R' and R2, which are the same, each represent a straight-or branched-chain alkyl group containing from 1 to 6 carbon atoms and R3 represents a phenyl group bearing substituents R' and (RS)n; wherein R' represents a cyano group, a straight-or branched-chain alkyl group containing from 1 to 4 carbon atoms which is fully substituted by halogen atoms, which may be the same or different, in the meta or para position; a hydroxy group or a fluorine or iodine atom in the meta position; a chlorine or bromine- atom or a nitro group or straight-or branched-chain alkoxy or alkylthio group containing from 1 to 4 carbon atoms which is fully substituted by halogen atoms, which may be the same or different, in the para position and R5 represents a hydrogen atom and n is 1; or R4 represents a fluorine, chlorine, bromine or iodine atom, a cyano, hydroxy or nitro group, or a straight-or branched-chain alkoxy or alkylthio group containing from 1 to 4 carbon atoms which is fully substituted by halogen atoms, which may be the same or different, or a straight-or branched-chain alkyl group containing from 1 to 4 carbon atoms which is unsubstituted or fully substituted by halogen atoms, which may be the same or different, and R5 represents a fluorine, chlorine, bromine or iodine atom, a cyano, hydroxy or nitro group, or a straight-or branched-chain alkoxy or alkylthio group containing from 1 to 4 carbon, atoms which is fully substituted by halogen atoms, which may be the same or different, or a straight-or branched-chain alkyl group containing from 1 to 4 carbon atoms which is unsubstituted or fully substituted by halogen atoms, which may be the same or different, and n is 1 or 2; it being understood that: a) when n is 1, R4 and R5 do not both represent unsubstituted alkyl groups, hydroxy groups or nitro groups and are different when in the 2,3-or 2,5-positions, b) when n is 2, one of the substituents represented by R4 and R5 is different from the others and does not represent an unsubstituted alkyl group, the positions of the various substituents on the phenyl ring referred to above being with respect to the nitrogen atom to which the phenyl ring is attached, is disclosed. Those compounds of the general formula depicted in Figure I which are new and their processes of preparation are further features of the present invention.

  一种调节植物生长部位的方法，包括向该部位施用有效量的通式化合物： 其中 R' 和 R2 相同，各自代表含有 1 至 6 个碳原子的直链或支链烷基，R3 代表带有取代基 R' 和 (RS)n 的苯基； 其中 R'代表氰基、在元位或对位被卤素原子（可以相同或不同）完全取代的含 1 至 4 个碳原子的直链或支链烷基、在元位的羟基或氟原子或碘原子；在对位的氯原子或溴原子或硝基或含有 1 至 4 个碳原子的直链或支链烷氧基或烷基硫基，这些基团可被相同或不同的卤素原子完全取代，且 R5 代表氢原子，n 为 1； 或 R4 代表氟、氯、溴或碘原子，氰基、羟基或硝基，或含有 1 至 4 个碳原子且被卤素原子完全取代的直链或支链烷氧基或烷基硫基，它们可以相同或不同，或含有 1 至 4 个碳原子且未被取代或被卤素原子完全取代的直链或支链烷基，它们可以相同或不同、和 R5 代表氟、氯、溴或碘原子，氰基、羟基或硝基，或含有 1 至 4 个碳原子且被卤素原子完全取代的直链或支链烷氧基或烷硫基，它们可以相同或不同，或含有 1 至 4 个碳原子且未被取代或被卤素原子完全取代的直链或支链烷基，它们可以相同或不同，和 n 是 1 或 2； 不言而喻 a) 当 n 为 1 时，R4 和 R5 不能同时代表未取代的烷基、羟基或硝基，且在 2、3 或 2、5 位时不相同、 b) 当 n 为 2 时，R4 和 R5 所代表的取代基中有一个与其他取代基不同，并且不代表未取代的烷基，上述苯环上各种取代基的位置相对于苯环所连接的氮原子而言。 图 I 所示通式的新化合物及其制备工艺是本发明的进一步特征。
• Exploration of the Differences between Amine and Thiolate Addition to Acetylenedicarboxylates
  作者：Robyn L. Crumbie、Gareth Chalmers、Mohan Bhadbhade、Renate Griffith

  DOI：10.1021/acs.joc.9b01392

  日期：2019.11.15

  Nucleophilic addition of thiolates to diethyl acetylenedicarboxylate in chloroform at room temperature affords solely the meso dithioaddition product, whereas the addition of amines in ethanol gives only the corresponding (Z)-enamine, as confirmed by X-ray crystal analysis. The monoaddition product of thiolate addition, prepared and isolated at lower temperatures, also exhibited (Z)-stereochemistry

  X射线晶体分析证实，室温下在氯仿中亲核性地将硫醇盐加成到乙二酸二乙基二乙酯中，仅得到内消旋二硫代加成产物，而在乙醇中加成胺仅得到相应的（Z）-烯胺。在较低温度下制备和分离的硫醇盐加成的单加成产物也表现出（Z）-立体化学。伴随的对简化模型系统的计算研究解释了观察到的立体化学和乙炔二羧酸酯容易与硫醇盐亲核体发生两次加成反应的原因，并且（Z）-烯胺对硫醇盐或胺亲核体的添加反应性低得多。
• Heterocyclization of functionalized heterocumulenes with C,N-, C,O-, and C,S-Binucleophiles: XI. Synthesis of dialkyl 2-oxo-3,6-diaryl-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylates by cyclocondensation of 1-chlorobenzyl isocyanates with dialkyl anilinofumarates
  作者：M. V. Vovk、O. V. Kushnir、V. A. Sukach、I. F. Tsymbal

  DOI：10.1134/s1070428010050209

  日期：2010.5

  1-Chlorobenzyl isocyanates react with N-arylfumarates with the formation of dialkyl 2-oxo-3,6-diaryl-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylates that on alkaline hydrolysis are converted into 6-alkoxycarbonyl-1,4-diaryl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylic acids. The condensation of 1-chloro-1-phenyl-2,2,2-trifluoroethyl isocyanate with N-arylfumarates results in dialkyl 6-oxo-2,3-diaryl-2-trifluoromethyl-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylates.