methyl trifluoroacetylurethane | 146463-86-7

• 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: methyl trifluoroacetylurethane
• 英文别名: methyl N-(2,2,2-trifluoroacetyl)carbamate
• CAS: 146463-86-7
• 化学式: C₄H₄F₃NO₃
• mdl: MFCD01793687
• 分子量: 171.076
• InChiKey: BXNMRYNUZALJPE-UHFFFAOYSA-N

物化性质

• 密度：
  1.421±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl trifluoroacetylurethane 在 1,2-亚苯基三氯磷酸 作用下， 以 乙醚 、 硝基苯 为溶剂， 以56%的产率得到N-(methoxycarbonyl)trifluoroacetimidoyl chloride
  参考文献：
  名称：

  Boiko; Sinitsa; Onys'ko, Russian Journal of General Chemistry, 1999, vol. 69, # 12, p. 1879 - 1882

  摘要：

  DOI：
• 作为产物：
  描述：

  氨基甲酸甲酯 、 三氟乙酸酐 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 以43%的产率得到methyl trifluoroacetylurethane
  参考文献：
  名称：

  氟化 2-氮杂环丁烷：合成、应用、生物测试和催化工艺的开发

  摘要：

  开发了一种高效且简单的膦促进的串联氮杂迈克尔加成/分子内维蒂希反应用于合成多官能化2-氮杂环丁烷。在证明这种转化可以通过用苯基硅烷原位还原氧化膦在膦中进行催化之后，已经证明了不同的转化后步骤，包括原始的[2 + 2]光二聚化。初步生物学测试强调，这些氟化 1,2-二氢氮杂-2,3-二羧酸盐对人类肿瘤细胞系表现出显着的细胞毒性。

  DOI：

  10.1021/acs.orglett.3c01888

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.
• N-Substituted 2,2,2-trifluoroethanimidic acid 1-methylethylidene hydrazides as synthetic blocks for trifluoromethylated nitrogen heterocycles: syntheses and oxidative cyclizations
  作者：Kenji Uneyama、Kouji Sugimoto

  DOI：10.1021/jo00048a042

  日期：1992.10

  N-Substituted 2,2,2-trifluoroethanimidic acid 1-methylethylidene hydrazides have been prepared and allowed to react with tert-butyl hypochlorite in CH2Cl2. N-Aryl-, N-alkyl-, and N-(methoxycarbonyl)amidrazones 2-4 undergo three types of cyclizations via the initially formed N-chloro intermediates leading to 3-(trifluoromethyl)-1,2,4-benzotriazines, 5, 3-(trifluoromethyl)-5-alkyltriazoles 8 and 9, and 3-chloro-3-(trifluoromethyl)-4-N-(methoxycarbonyl)-5,5-dimethyltriazoline (11), respectively. Reaction mechanisms for the cyclizations are discussed.
• UNEYAMA, KENJI;MORIMOTO, OSAMU;YAMASHITA, FUMIO, TETRAHEDRON LETT., 30,(1989) N6, C. 4821-4824
  作者：UNEYAMA, KENJI、MORIMOTO, OSAMU、YAMASHITA, FUMIO

  DOI：——

  日期：——
• Boiko; Sinitsa; Onys'ko, Russian Journal of General Chemistry, 1999, vol. 69, # 12, p. 1879 - 1882
  作者：Boiko、Sinitsa、Onys'ko

  DOI：——

  日期：——
• Fluorinated 2-Azetines: Synthesis, Applications, Biological Tests, and Development of a Catalytic Process
  作者：Romain Losa、Charlotte Lorton、Pascal Retailleau、Jérôme Bignon、Arnaud Voituriez

  DOI：10.1021/acs.orglett.3c01888

  日期：2023.7.14

  addition/intramolecular Wittig reaction was developed for the synthesis of polyfunctionalized 2-azetines. After demonstrating that this transformation could be made catalytic in phosphine through in situ reduction of phosphine oxide with phenylsilane, different post-transformation steps have been demonstrated, including an original [2 + 2] photodimerization. Preliminary biological tests highlighted that these fluorinated

  开发了一种高效且简单的膦促进的串联氮杂迈克尔加成/分子内维蒂希反应用于合成多官能化2-氮杂环丁烷。在证明这种转化可以通过用苯基硅烷原位还原氧化膦在膦中进行催化之后，已经证明了不同的转化后步骤，包括原始的[2 + 2]光二聚化。初步生物学测试强调，这些氟化 1,2-二氢氮杂-2,3-二羧酸盐对人类肿瘤细胞系表现出显着的细胞毒性。