1,1,1-Trifluoro-3-(indol-3-yl)propan-2-one 2-oxime | 137496-19-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 1,1,1-Trifluoro-3-(indol-3-yl)propan-2-one 2-oxime
• 英文别名: 1,1,1-trifluoro-3-(1H-indol-3-yl)propan-2-one oxime；N-[1,1,1-trifluoro-3-(1H-indol-3-yl)propan-2-ylidene]hydroxylamine
• CAS: 137496-19-6
• 化学式: C₁₁H₉F₃N₂O
• 分子量: 242.2
• InChiKey: SZTIEJJWSMODBE-UHFFFAOYSA-N

物化性质

• 沸点：
  368.8±42.0 °C(Predicted)
• 密度：
  1.39±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  48.4
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,1,1-Trifluoro-3-(indol-3-yl)propan-2-one 2-oxime 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以41%的产率得到2-Amino-1,1,1-trifluoro-3-(3'-indolyl)propane
  参考文献：
  名称：

  Efficient synthesis of trifluoromethyl-substituted 5,6-dihydro-4H-1,2-oxazines by the hetero-Diels-Alder reaction of 1,1,1-trifluoro-2-nitroso-2-propene and electron-rich olefins

  摘要：

  1,1,1-Trifluoro-2-nitroso-2-propene (1) was generated in situ by treatment of the alpha-bromo oxime 5 with base. Moderate to excellent yields of the 3-trifluoromethyl-substituted 1,2-oxazines 17-27 were obtained from the reaction of 1 and the silyl enol ethers 6-16, respectively. Other dienophiles, i.e., allyltrimethylsilane, cyclopentadiene, furan, and dihydropyran, upon reaction with 1 provided the cycloadducts 31-34, respectively, in good yield. The results demonstrated that 1 is probably the most reactive heterodiene that has so far been employed in this type of Diels-Alder reaction (i.e., Diels-Alder reaction with inverse electron demand). The mechanism of the reaction and diastereoselectivity of the cycloadditions are discussed. The reaction of 1 with indole and acetyl acetone afforded the oxime 38 and a mixture of the isomers 40-42, respectively. Also, ring openings and other transformations of the trifluoromethyl-substituted 1,2-oxazines were effected. Acid-induced desilylation of the silylated 1,2-oxazines provided oximes like 46 and 48 or 6-hydroxy-1,2-oxazines like 47. Treatment of the 1,2-oxazines with Mo(CO)6 in the presence of trifluoroacetic acid produced 2-trifluoromethyl-substituted pyrroles (e.g., 18 --> 50). The reduction of the 1,2-oxazines afforded either gamma-hydroxy oximes (e.g., 19 --> 51) or amino alcohols (e.g., 32 --> 52, 31 --> 55). The reduction of the indole derivative 38 by LiAlH4 provided the trifluoromethyl-substituted tryptamine 56. The results of these explorative studies demonstrated that readily available trifluoromethyl-substituted 1,2-oxazines could be efficiently converted into other compounds that bear a trifluoromethyl group.

  DOI：

  10.1021/jo00027a058
• 作为产物：
  描述：

  吲哚 、 3-bromo-1,1,1-trifluoropropan-2-one oxime 在 sodium carbonate 作用下， 以 various solvent(s) 为溶剂， 反应 24.0h， 以68%的产率得到1,1,1-Trifluoro-3-(indol-3-yl)propan-2-one 2-oxime
  参考文献：
  名称：

  Efficient synthesis of trifluoromethyl-substituted 5,6-dihydro-4H-1,2-oxazines by the hetero-Diels-Alder reaction of 1,1,1-trifluoro-2-nitroso-2-propene and electron-rich olefins

  摘要：

  1,1,1-Trifluoro-2-nitroso-2-propene (1) was generated in situ by treatment of the alpha-bromo oxime 5 with base. Moderate to excellent yields of the 3-trifluoromethyl-substituted 1,2-oxazines 17-27 were obtained from the reaction of 1 and the silyl enol ethers 6-16, respectively. Other dienophiles, i.e., allyltrimethylsilane, cyclopentadiene, furan, and dihydropyran, upon reaction with 1 provided the cycloadducts 31-34, respectively, in good yield. The results demonstrated that 1 is probably the most reactive heterodiene that has so far been employed in this type of Diels-Alder reaction (i.e., Diels-Alder reaction with inverse electron demand). The mechanism of the reaction and diastereoselectivity of the cycloadditions are discussed. The reaction of 1 with indole and acetyl acetone afforded the oxime 38 and a mixture of the isomers 40-42, respectively. Also, ring openings and other transformations of the trifluoromethyl-substituted 1,2-oxazines were effected. Acid-induced desilylation of the silylated 1,2-oxazines provided oximes like 46 and 48 or 6-hydroxy-1,2-oxazines like 47. Treatment of the 1,2-oxazines with Mo(CO)6 in the presence of trifluoroacetic acid produced 2-trifluoromethyl-substituted pyrroles (e.g., 18 --> 50). The reduction of the 1,2-oxazines afforded either gamma-hydroxy oximes (e.g., 19 --> 51) or amino alcohols (e.g., 32 --> 52, 31 --> 55). The reduction of the indole derivative 38 by LiAlH4 provided the trifluoromethyl-substituted tryptamine 56. The results of these explorative studies demonstrated that readily available trifluoromethyl-substituted 1,2-oxazines could be efficiently converted into other compounds that bear a trifluoromethyl group.

  DOI：

  10.1021/jo00027a058

文献信息

• Glucocorticoid mimetics, methods of making them, pharmaceutical compositions, and uses thereof
  申请人：Kuzmich Daniel

  公开号：US20060154925A1

  公开（公告）日：2006-07-13

  Compounds of Formula (I) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are as defined herein, or a tautomer, prodrug, solvate, or salt thereof; pharmaceutical compositions containing such compounds, and methods of modulating the glucocorticoid receptor function and methods of treating disease-states or conditions mediated by the glucocorticoid receptor function or characterized by inflammatory, allergic, or proliferative processes in a patient using these compounds.

  化学式为（I）的化合物，其中R1、R2、R3、R4、R5、R6和R7如此定义，或其互变异构体、前药、溶剂化物或盐；含有这些化合物的药物组合物，以及使用这些化合物调节糖皮质激素受体功能的方法和治疗由糖皮质激素受体功能介导或以炎症、过敏或增生过程为特征的疾病状态或情况的方法。
• Efficient synthesis of trifluoromethyl-substituted 5,6-dihydro-4H-1,2-oxazines by the hetero-Diels-Alder reaction of 1,1,1-trifluoro-2-nitroso-2-propene and electron-rich olefins
  作者：Reinhold Zimmer、Hans Ulrich Reissig

  DOI：10.1021/jo00027a058

  日期：1992.1

  1,1,1-Trifluoro-2-nitroso-2-propene (1) was generated in situ by treatment of the alpha-bromo oxime 5 with base. Moderate to excellent yields of the 3-trifluoromethyl-substituted 1,2-oxazines 17-27 were obtained from the reaction of 1 and the silyl enol ethers 6-16, respectively. Other dienophiles, i.e., allyltrimethylsilane, cyclopentadiene, furan, and dihydropyran, upon reaction with 1 provided the cycloadducts 31-34, respectively, in good yield. The results demonstrated that 1 is probably the most reactive heterodiene that has so far been employed in this type of Diels-Alder reaction (i.e., Diels-Alder reaction with inverse electron demand). The mechanism of the reaction and diastereoselectivity of the cycloadditions are discussed. The reaction of 1 with indole and acetyl acetone afforded the oxime 38 and a mixture of the isomers 40-42, respectively. Also, ring openings and other transformations of the trifluoromethyl-substituted 1,2-oxazines were effected. Acid-induced desilylation of the silylated 1,2-oxazines provided oximes like 46 and 48 or 6-hydroxy-1,2-oxazines like 47. Treatment of the 1,2-oxazines with Mo(CO)6 in the presence of trifluoroacetic acid produced 2-trifluoromethyl-substituted pyrroles (e.g., 18 --> 50). The reduction of the 1,2-oxazines afforded either gamma-hydroxy oximes (e.g., 19 --> 51) or amino alcohols (e.g., 32 --> 52, 31 --> 55). The reduction of the indole derivative 38 by LiAlH4 provided the trifluoromethyl-substituted tryptamine 56. The results of these explorative studies demonstrated that readily available trifluoromethyl-substituted 1,2-oxazines could be efficiently converted into other compounds that bear a trifluoromethyl group.