1-Ethoxycarbonyl-2-methyl-4-phenylsemicarbazid | 34771-21-6

• 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: 1-Ethoxycarbonyl-2-methyl-4-phenylsemicarbazid
• 英文别名: ethyl N-[methyl(phenylcarbamoyl)amino]carbamate
• CAS: 34771-21-6
• 化学式: C₁₁H₁₅N₃O₃
• 分子量: 237.258
• InChiKey: ACLNSLQSPVDNAF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  70.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-Ethoxycarbonyl-2-methyl-4-phenylsemicarbazid 在 氢氧化钾 作用下， 生成 1-Methyl-4-phenyl-1,2,4-triazolidin-3,5-dion
  参考文献：
  名称：

  Proton-transfer chemistry of urazoles and related imides, amides, and diacyl hydrazides

  摘要：

  Equilibrium acidity constants have been determined for 1,2,4-triazolidine-3,5-dione (urazole), several substituted urazoles, and other related acids, in both dimethyl sulfoxide (DMSO) and aqueous solution. In DMSO, urazole has a pK(a) of 13.1. In water, urazole has a pK(a) of 5.8. In general, N-methyl and N-phenyl substituents are found to acidify the urazole moiety, in both DMSO and water. The acidifying effects of these substituents are attenuated by a factor of 3.3 in water. The solvent effects are ascribed to the aqueous stabilization of urazole anions via hydrogen-bonding interactions and the aqueous-promoted relief of lone pair-lone pair electronic interactions that manifest themselves upon deprotonation of a hydrazyl proton in 1 and related species. That a hydrazyl proton in 1 is at least as acidic as the imide proton in 1 is comparison of C-13 NMR spectra for the urazoles and related nitrogen acids with C-13 spectra for the conjugate bases derived from these species. Upon loss of an imide proton, in both DMSO-d6 and D2O solutions, carbonyl carbon atoms present in succinimide as well as appropriately substituted urazoles and hydantoins experience substantial (13-17 ppm) downfield shifts. In contrast, deprotonation of 4-substituted and 1,4-substituted urazoles, 4,4-dimethylpyrazolidine-3,5-dione, and diacetylhydrazine (species that contain hydrazyl acidic protons) results in shifts in the positions of the carbonyl resonances that range from 5 ppm upfield to 3 ppm downfield. Deprotonation of species containing both imide and hydrazyl protons (i.e., urazole and 1-substituted urazoles) results in shifts in the carbonyl carbon resonances consistent with hydrazyl proton removal. Comparison of DMSO-phase pK(a)'s for acetamide (25.5), diacetylhydrazine (16.7), 4,4-dimethylpyrazolidine-3,5-dione (13.5), and urazole (13.5), and urazole (13.1) suggest that the remarkable acidity of the hydrazyl proton in urazole and substituted urazoles is due mainly to its cyclic diacyl hydrazide structure.

  DOI：

  10.1021/jo00019a034
• 作为产物：
  描述：

  N-(甲氨基)氨基甲酸乙酯 、 异氰酸苯酯 以 苯 为溶剂， 生成 1-Ethoxycarbonyl-2-methyl-4-phenylsemicarbazid
  参考文献：
  名称：

  甲基肼的酰化反应

  摘要：

  甲基肼在 1 和 2 位被二甲基和二乙基碳酸酯酰化；进一步用异氰酸酯处理产生酰基氨基脲，其环化为尿唑衍生物。另一方面，在与甲酸甲酯和甲酸乙酯的甲酰化反应中，只有 1-甲酰基-1-甲基肼被捕获并转化为带有羰基化合物的亚烷基衍生物。

  DOI：

  10.1002/ardp.19713040912

文献信息

• Acylierungsreaktionen an Methylhydrazin
  作者：G. Zinner、U. Gebhardt

  DOI：10.1002/ardp.19713040912

  日期：——

  Methylhydrazin wird mit Dimethyl‐ und Diäthylcarbonat in 1‐ und in 2‐Stellung acyliert, weitere Behandlung mit Isocyansäureestern führt zu Acylsemicarbaziden, die zu Derivaten des Urazols cyclisiert werden. Bei der Formylierung mit Methyl‐ und Äthylformiat wurde dagegen nur 1‐Formyl‐1‐methylhydrazin gefaßt und mit Carbonyl‐Verbindungen in Alkyliden‐Derivate überführt.

  甲基肼在 1 和 2 位被二甲基和二乙基碳酸酯酰化；进一步用异氰酸酯处理产生酰基氨基脲，其环化为尿唑衍生物。另一方面，在与甲酸甲酯和甲酸乙酯的甲酰化反应中，只有 1-甲酰基-1-甲基肼被捕获并转化为带有羰基化合物的亚烷基衍生物。
• Proton-transfer chemistry of urazoles and related imides, amides, and diacyl hydrazides
  作者：M. J. Bausch、B. David、P. Dobrowolski、C. Guadalupe-Fasano、R. Gostowski、D. Selmarten、V. Prasad、A. Vaughn、L. H. Wang

  DOI：10.1021/jo00019a034

  日期：1991.9

  Equilibrium acidity constants have been determined for 1,2,4-triazolidine-3,5-dione (urazole), several substituted urazoles, and other related acids, in both dimethyl sulfoxide (DMSO) and aqueous solution. In DMSO, urazole has a pK(a) of 13.1. In water, urazole has a pK(a) of 5.8. In general, N-methyl and N-phenyl substituents are found to acidify the urazole moiety, in both DMSO and water. The acidifying effects of these substituents are attenuated by a factor of 3.3 in water. The solvent effects are ascribed to the aqueous stabilization of urazole anions via hydrogen-bonding interactions and the aqueous-promoted relief of lone pair-lone pair electronic interactions that manifest themselves upon deprotonation of a hydrazyl proton in 1 and related species. That a hydrazyl proton in 1 is at least as acidic as the imide proton in 1 is comparison of C-13 NMR spectra for the urazoles and related nitrogen acids with C-13 spectra for the conjugate bases derived from these species. Upon loss of an imide proton, in both DMSO-d6 and D2O solutions, carbonyl carbon atoms present in succinimide as well as appropriately substituted urazoles and hydantoins experience substantial (13-17 ppm) downfield shifts. In contrast, deprotonation of 4-substituted and 1,4-substituted urazoles, 4,4-dimethylpyrazolidine-3,5-dione, and diacetylhydrazine (species that contain hydrazyl acidic protons) results in shifts in the positions of the carbonyl resonances that range from 5 ppm upfield to 3 ppm downfield. Deprotonation of species containing both imide and hydrazyl protons (i.e., urazole and 1-substituted urazoles) results in shifts in the carbonyl carbon resonances consistent with hydrazyl proton removal. Comparison of DMSO-phase pK(a)'s for acetamide (25.5), diacetylhydrazine (16.7), 4,4-dimethylpyrazolidine-3,5-dione (13.5), and urazole (13.5), and urazole (13.1) suggest that the remarkable acidity of the hydrazyl proton in urazole and substituted urazoles is due mainly to its cyclic diacyl hydrazide structure.