6-Isopropenyl-5,6-dihydro-3-(trifluoromethyl)-6-(trimethylsiloxy)-4H-1,2-oxazine | 137496-08-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 6-Isopropenyl-5,6-dihydro-3-(trifluoromethyl)-6-(trimethylsiloxy)-4H-1,2-oxazine
• 英文别名: Trimethyl-[[6-prop-1-en-2-yl-3-(trifluoromethyl)-4,5-dihydrooxazin-6-yl]oxy]silane；trimethyl-[[6-prop-1-en-2-yl-3-(trifluoromethyl)-4,5-dihydrooxazin-6-yl]oxy]silane
• CAS: 137496-08-3
• 化学式: C₁₁H₁₈F₃NO₂Si
• 分子量: 281.35
• InChiKey: ZALFYSOGHUJGNJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  30.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  6-Isopropenyl-5,6-dihydro-3-(trifluoromethyl)-6-(trimethylsiloxy)-4H-1,2-oxazine 在 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 溶剂黄146 为溶剂， 反应 24.0h， 生成 (Z)-1,1,1-trifluoro-5-hydroxy-6-methylpent-6-en-2-one oxime
  参考文献：
  名称：

  An Efficient and Simple Synthesis of 3,4,5,6-Tetrahydro-2H-1,2-oxazines by Sodium Cyanoborohydride Reduction of 5,6-Dihydro-4H-1,2-oxazines

  摘要：

  以氰基硼氢化钠为还原剂，在醋酸中还原相应的 5,6-二氢-4H-1,2-噁嗪，制备出 3,4,5,6-四氢-2H-1,2-噁嗪。该反应可得到 3,5-二取代的化合物 2a-c、2f-g 和 5a,b，顺式选择性良好，甚至极佳，而 3,6-二取代的 1,2-噁嗪会导致反式构型产物成为主要异构体。在相同的反应条件下，双环杂环 14 产生两种产物，即预期的化合物 15 和副产物环戊烯醇衍生物 16。此外，还介绍了由前体 17 和 19 生成三氟甲基酮肟 18 和 21 的过程。

  DOI：

  10.1055/s-1994-25636
• 作为产物：
  描述：

  2-trimethylsilyloxy-3-methyl-1,3-butadiene 、 3-bromo-1,1,1-trifluoropropan-2-one oxime 在 sodium carbonate 作用下， 以 various solvent(s) 为溶剂， 反应 120.0h， 以38%的产率得到6-Isopropenyl-5,6-dihydro-3-(trifluoromethyl)-6-(trimethylsiloxy)-4H-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

• 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.
• An Efficient and Simple Synthesis of 3,4,5,6-Tetrahydro-2<i>H</i>-1,2-oxazines by Sodium Cyanoborohydride Reduction of 5,6-Dihydro-4<i>H</i>-1,2-oxazines
  作者：Reinhold Zimmer、Thomas Arnold、Kai Homann、Hans-Ulrich Reissig

  DOI：10.1055/s-1994-25636

  日期：——

  3,4,5,6-Tetrahydro-2H-1,2-oxazines are prepared by reduction of the corresponding 5,6-dihydro-4H-1,2-oxazines with sodium cyanoborohydride as the reducing agent in acetic acid. This reaction gives the 3,5-disubstituted compounds 2a-c, 2f-g, and 5a,b with good to excellent cis selectivities, while a 3,6-disubstituted 1,2-oxazine leads to a trans configurated product as the major isomer. Under the same reaction conditions the bicyclic heterocycle 14 affords two products, the expected compound 15 and the cyclopentenol derivative 16 as a byproduct. Also, the formation of trifluoromethylated ketoximes 18 and 21 starting from the precursors 17 and 19 is described.

  以氰基硼氢化钠为还原剂，在醋酸中还原相应的 5,6-二氢-4H-1,2-噁嗪，制备出 3,4,5,6-四氢-2H-1,2-噁嗪。该反应可得到 3,5-二取代的化合物 2a-c、2f-g 和 5a,b，顺式选择性良好，甚至极佳，而 3,6-二取代的 1,2-噁嗪会导致反式构型产物成为主要异构体。在相同的反应条件下，双环杂环 14 产生两种产物，即预期的化合物 15 和副产物环戊烯醇衍生物 16。此外，还介绍了由前体 17 和 19 生成三氟甲基酮肟 18 和 21 的过程。