ethyl N,N-di(propan-2-yl)-N'-(trifluoromethylsulfonyl)carbamimidate

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: ethyl N,N-di(propan-2-yl)-N'-(trifluoromethylsulfonyl)carbamimidate
• 化学式: C₁₀H₁₉F₃N₂O₃S
• 分子量: 304.334
• InChiKey: MSDQFYOZKKTPEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  67.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  二异丙基氨腈 、 三氟甲磺酸酐 以 乙醚 为溶剂， 以90 mg的产率得到ethyl N,N-di(propan-2-yl)-N'-(trifluoromethylsulfonyl)carbamimidate
  参考文献：
  名称：

  Formation of Urea, Isourea, and Triazine Derivatives from Diisopropylcyanamide with Trifluoroacetic Anhydride and Trifluoromethanesulfonic Anhydride:  Thermal Instability of Urea and Isourea Derivatives

  摘要：

  Diisopropylcyanamide reacts exothermically with trifluoroacetic anhydride to give 2, an equilibrium mixture, in C6D6 solution, of 1:1 adducts, N,N-diisopropyl-N',O-bis(trifluoroacetyl), 2a (10%), and N,N-diisopropyl-N',N'-bis(trifluoroacetyl)urea, 2c (90%), at 27 degrees C. Compound 2c is a colorless solid, mp 49-51 degrees C. Thermolysis of 2, at 117 degrees C, shows first-order kinetics with the intital products being trifluoroacetonitrile, 4, and diisopropylcarbamic trifluoroacetic mixed anhydride, 3. Trifluoroacetonitrile trimerizes to 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, and 3 is thermally labile giving diisopropyltrifluoroacetamide and CO2. In the thermolysis reaction 4 reacts with 2a to give a small amount of 4-(diisopropylamino)-4-(trifluoroacetoxy)-2,6-bis(trifluoromethyl)-4H-1,3,5-oxadiazine 7. A related compound, 4,4-bis(diisopropylamino)-2,6-bis(trifluoromethyl)-4H-1,3-5-oxadiazine, 8, is formed from 7 and 2c going through a concentration maximum at 4000 s in the kinetic run. Compound 8 thermolytically dissociates to generate 4 and tetraisopropylurea. Compound 2 is a tirfluoroacetylating agent with methanol giving methyl trifluoroacetate in 97% yield. Accompanying this reaction is a methanol displacement of diisopropylamine giving a 1.7% yield of methyl-N-(trifluoroacetyl)urethane. Diisopropylcyanamide also reacts exothermically with trifluoromethanesulfonic anhydride to give 2,4,6-tris(diisopropylamino)-1-(trifluoromethanesulfonyl)triazinium trifluoromethanesulfonate, 15, in 96% yield. X-ray crystallographic structure drawing of 15 shows N1 (attached to CF3SO2) is pyramidal while N2, N4, and N6 (all diisopropylamino nitrogens) are sp(2)-planar. A small amount of O-ethyl-N,N-diisopropyl-N'-(trifluoromethanesulfonyl)isourea was also recovered, produced by the reaction of the initially formed intermediate, N,N-diisopropyl-N',O-bis(trifluoromethanesulfonyl)isourea, with ethanol contaminant in absolute ethyl ether solvent. Treatment of 15 with methanol, in the presence of K2CO3, gave a 90% yield of 2,4,6-tris(diisopropylamine)-1-(trifluoromethanesulfonyl)-4-methoxy-1,4-dihydrotriazine.

  DOI：

  10.1021/jo9710184

文献信息

• Formation of Urea, Isourea, and Triazine Derivatives from Diisopropylcyanamide with Trifluoroacetic Anhydride and Trifluoromethanesulfonic Anhydride:  Thermal Instability of Urea and Isourea Derivatives
  作者：William P. Norris、Lawrence H. Merwin、Gregory S. Ostrom、Richard D. Gilardi

  DOI：10.1021/jo9710184

  日期：1997.12.1

  Diisopropylcyanamide reacts exothermically with trifluoroacetic anhydride to give 2, an equilibrium mixture, in C6D6 solution, of 1:1 adducts, N,N-diisopropyl-N',O-bis(trifluoroacetyl), 2a (10%), and N,N-diisopropyl-N',N'-bis(trifluoroacetyl)urea, 2c (90%), at 27 degrees C. Compound 2c is a colorless solid, mp 49-51 degrees C. Thermolysis of 2, at 117 degrees C, shows first-order kinetics with the intital products being trifluoroacetonitrile, 4, and diisopropylcarbamic trifluoroacetic mixed anhydride, 3. Trifluoroacetonitrile trimerizes to 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, and 3 is thermally labile giving diisopropyltrifluoroacetamide and CO2. In the thermolysis reaction 4 reacts with 2a to give a small amount of 4-(diisopropylamino)-4-(trifluoroacetoxy)-2,6-bis(trifluoromethyl)-4H-1,3,5-oxadiazine 7. A related compound, 4,4-bis(diisopropylamino)-2,6-bis(trifluoromethyl)-4H-1,3-5-oxadiazine, 8, is formed from 7 and 2c going through a concentration maximum at 4000 s in the kinetic run. Compound 8 thermolytically dissociates to generate 4 and tetraisopropylurea. Compound 2 is a tirfluoroacetylating agent with methanol giving methyl trifluoroacetate in 97% yield. Accompanying this reaction is a methanol displacement of diisopropylamine giving a 1.7% yield of methyl-N-(trifluoroacetyl)urethane. Diisopropylcyanamide also reacts exothermically with trifluoromethanesulfonic anhydride to give 2,4,6-tris(diisopropylamino)-1-(trifluoromethanesulfonyl)triazinium trifluoromethanesulfonate, 15, in 96% yield. X-ray crystallographic structure drawing of 15 shows N1 (attached to CF3SO2) is pyramidal while N2, N4, and N6 (all diisopropylamino nitrogens) are sp(2)-planar. A small amount of O-ethyl-N,N-diisopropyl-N'-(trifluoromethanesulfonyl)isourea was also recovered, produced by the reaction of the initially formed intermediate, N,N-diisopropyl-N',O-bis(trifluoromethanesulfonyl)isourea, with ethanol contaminant in absolute ethyl ether solvent. Treatment of 15 with methanol, in the presence of K2CO3, gave a 90% yield of 2,4,6-tris(diisopropylamine)-1-(trifluoromethanesulfonyl)-4-methoxy-1,4-dihydrotriazine.