1,1,1-trifluoro-2-amino-5-hexene | 137515-61-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氟化物
• 英文名称: 1,1,1-trifluoro-2-amino-5-hexene
• 英文别名: 1,1,1-trifluorohex-5-en-2-amine
• CAS: 137515-61-8
• 化学式: C₆H₁₀F₃N
• 分子量: 153.147
• InChiKey: HZJYMSXOMJSKEG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  5,6-Dihydro-6-<(trimethylsilyl)methyl>-3-(trifluoromethyl)-4H-1,2-oxazine 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以30%的产率得到3,4,5,6-Tetrahydro-6-<(trimethylsilyl)methyl>-3-(trifluoromethyl)-2H-1,2-oxazine
  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

• Preparation of fluorinated methylaminoalkanoic acids, process intermediates and their preparation
  申请人：MERRELL TORAUDE ET COMPAGNIE

  公开号：EP0025370A2

  公开（公告）日：1981-03-18

  Fluorinated alkenylamines of the Formula V Formula V wherein n represents 0, 1, or 3; R1 represents hydrogen or C1-C10 alkyl and Y represents (a), when n represents 0, CH2F, (b), when n represents 1, CH2F or CHF2, or (c) when n represents 2 or 3, CH2F, CHF2 or CF3 are novel process intermediates. They are obtained by hydrolysis and subsequent reduction of the corresponding alkenyl fluorinated methyl ketimine magnesium halides, which are novel compounds resulting from reaction of the corresponding alkenyl magnesium halides with the corresponding fluorinated acetonitriles. The fluorinated alkenylamines of Formula V are oxidized whilst the amino group is protected to provide, after removal of the amine protecting group, the corresponding fluorinated methyl aminoalkanoic acids which are useful pharmacological or antibacterial agents.

  式 V 的氟化烯胺 式 V 其中 n 代表 0、1 或 3；R1 代表氢或 C1-C10 烷基，Y 代表(a)（当 n 代表 0 时）CH2F，(b)（当 n 代表 1 时）CH2F 或 CHF2，或(c)（当 n 代表 2 或 3 时）CH2F、CHF2 或 CF3 是新型工艺中间体。它们是通过水解和还原相应的烯基氟化甲基酮亚胺卤化镁而得到的，后者是相应的烯基卤化镁与相应的氟化乙腈反应生成的新型化合物。式 V 的氟化烯基胺在氨基被保护的同时被氧化，在去除胺保护基后，可得到相应的氟化甲基氨基烷酸，这种酸是有用的药剂或抗菌剂。
• US4326071A
  申请人：——

  公开号：US4326071A

  公开（公告）日：1982-04-20
• US4353828A
  申请人：——

  公开号：US4353828A

  公开（公告）日：1982-10-12
• 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.