1,4-dimethyl-[1,2,4]triazolidine-3,5-dione | 34771-26-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 1,4-dimethyl-[1,2,4]triazolidine-3,5-dione
• 英文别名: 1,4-Dimethyl-[1,2,4]triazolidin-3,5-dion；1,4-Dimethyl-1,2,4-triazolidine-3,5-dione
• CAS: 34771-26-1
• 化学式: C₄H₇N₃O₂
• 分子量: 129.118
• InChiKey: NWNNZPUYFSACQS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-dimethyl-[1,2,4]triazolidine-3,5-dione 、 9-溴芴 在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 反应 12.67h， 生成 1-(9H-fluoren-9-yl)-2,4-dimethyl-1,2,4-triazolidine-3,5-dione 、 1,3-Dimethylspiro[1,3,5-triazinane-6,9'-fluorene]-2,4-dione
  参考文献：
  名称：

  Fluorenyl Participated Ring Transformation of Urazoles to Triazinanediones

  摘要：

  Fluorenylation of 1,4-disubstituted urazole (1) with 9-bromofluorene affords corresponding fluorenylurazole (2) along with the rearrangement product triazinanedione (3). The ratio of two products is closely related to the acidity of starting urazole (1). Compound (2) can be transformed into 3 upon treated with potassium t-butoxide. A mechanism involving N-acylimine as ring opening intermediate is proposed. The dual roles of urazole anion (1-K) are discussed.

  DOI：

  10.3987/com-00-9087
• 作为产物：
  描述：

  1-carbethoxy-2,4-dimethylsemicarbazide 在 氢氧化钾 作用下， 反应 0.33h， 生成 1,4-dimethyl-[1,2,4]triazolidine-3,5-dione
  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

文献信息

• Conversion of Alcohols into Haloalkanes in Tertiary Phosphine/Methyl Halide/4-Methyl-1,2,4-triazolidine-3,5-dione (MTAD) System
  作者：Tatsuo Oshikawa、Mitsuji Yamashita

  DOI：10.1246/bcsj.57.2675

  日期：1984.9

  Alcohols were succesfully converted to the corresponding alkyl halides using the betaine provided by tertiary phosphine/4-methyl-1,2,4-triazolidine-3,5-dione (MTAD) system. Stereospecific reaction involving inversion of configuration on the carbon atom (SN2 reaction) was clarified.

  醇成功转化为相应的烷基卤化物，使用了由三羟甲基磷和4-甲基-1,2,4-三唑烷-3,5-二酮（MTAD）体系提供的甜菜碱。涉及碳原子构型反转的立体特异性反应（SN2反应）得到了阐明。
• Racemic α,α'-o-Xylylene-1,1'-bis[(3,5-dimethyl-5,6-dihydro-1,3,5-triazine-6-spiro-9'-fluorene)-2,4(1H,3H)-dione]
  作者：P. D. Robinson、Y. Gong、M. J. Bausch

  DOI：10.1107/s010827019600621x

  日期：1996.9.15

  The title compound, C42H36N6O4, was synthesized via a sequence of reactions in which the product of the reaction between the potassium salt of 1,4-dimethylurazole and 9-bromofluorene was allowed to react with (a) potassium tert-butoxide and (b) o-(ClCH2)(2)C6H4. The X-ray crystal structure of the title compound features a tilted T-shaped edge-to-face aromatic interaction between the two fluorene moieties and the resultant molecular distortion produces chirality which leads to the formation of a racemic structure. The distortion also causes marked differences in the conformations of the two half-chair triazinedione rings. Intermolecular C-H ... O interactions produce infinite cross-linked double chains of hydrogen-bonded molecules.
• 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.
• Fluorenyl Participated Ring Transformation of Urazoles to Triazinanediones
  作者：Yong Gong、Mark J. Bausch、Linhua Wang

  DOI：10.3987/com-00-9087

  日期：——

  Fluorenylation of 1,4-disubstituted urazole (1) with 9-bromofluorene affords corresponding fluorenylurazole (2) along with the rearrangement product triazinanedione (3). The ratio of two products is closely related to the acidity of starting urazole (1). Compound (2) can be transformed into 3 upon treated with potassium t-butoxide. A mechanism involving N-acylimine as ring opening intermediate is proposed. The dual roles of urazole anion (1-K) are discussed.