diisopropoxyphosphinylformylhydroxamic acid

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diisopropoxyphosphinylformylhydroxamic acid
• 英文别名: Diisopropoxyphosphorylformhydroxamic acid；1-di(propan-2-yloxy)phosphoryl-N-hydroxyformamide
• 化学式: C₇H₁₆NO₅P
• 分子量: 225.181
• InChiKey: KGSOZGLLVHBFBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  84.9
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  diisopropyl ethyl phosphonothiolformate 在 盐酸羟胺 作用下， 以 吡啶 为溶剂， 反应 72.0h， 以54%的产率得到二异丙基亚磷酰胺
  参考文献：
  名称：

  Spontaneous Lossen Rearrangement of (Phosphonoformyl)hydroxamates. The Migratory Aptitude of the Phosphonyl Group

  摘要：

  (i-PrO)(2)P(=O)COSEt (1) reacted with NH2OH in pyridine at room temperature to give mainly (i-PrO)(2)P(=O)NH2 (4). The formation of 4 was interpreted in terms of a spontaneous Lessen rearrangement of (i-PrO)(2)P(=O)CONHOH (2a) formed in the reaction. A transient (PNMR)-P-31 signal appearing in the reaction mixture at delta -1.8 was assigned to 2a. Trapping of (i-PrO)(2)P(=O)N=C=O (5), formed in the reaction of 1 and NH2OH, by cyclohexylamine gave (i-PrO)(2)P(=O)NHCONHC6H11 (6). Attempted isolation of 6 gave the hydrolyzed product N-cyclohexylurea (7). The reaction of 1 with NH2OMe proceeded slower than that with NH2OH and gave the expected (i-PrO)(2)P(=O)CONHOMe (2b), which was isolated and identified. 2b converts slowly to 4 in pyridine at room temperature. In contrast, MeNHOH reacted rapidly with 1 and gave the stable crystalline (i-PrO)(2)P(=O)CON(Me)OH (2c). The structure of hydroxamates 2 were assigned on the basis of H-1, C-13, and P-31 NMR spectral data. This facile Lossen rearrangement is discussed in terms of the unusually high migratory aptitude of the phosphonyl group.

  DOI：

  10.1021/jo962075k

文献信息

• Spontaneous Lossen Rearrangement of (Phosphonoformyl)hydroxamates. The Migratory Aptitude of the Phosphonyl Group
  作者：Claudio J. Salomon、Eli Breuer

  DOI：10.1021/jo962075k

  日期：1997.6.13

  (i-PrO)(2)P(=O)COSEt (1) reacted with NH2OH in pyridine at room temperature to give mainly (i-PrO)(2)P(=O)NH2 (4). The formation of 4 was interpreted in terms of a spontaneous Lessen rearrangement of (i-PrO)(2)P(=O)CONHOH (2a) formed in the reaction. A transient (PNMR)-P-31 signal appearing in the reaction mixture at delta -1.8 was assigned to 2a. Trapping of (i-PrO)(2)P(=O)N=C=O (5), formed in the reaction of 1 and NH2OH, by cyclohexylamine gave (i-PrO)(2)P(=O)NHCONHC6H11 (6). Attempted isolation of 6 gave the hydrolyzed product N-cyclohexylurea (7). The reaction of 1 with NH2OMe proceeded slower than that with NH2OH and gave the expected (i-PrO)(2)P(=O)CONHOMe (2b), which was isolated and identified. 2b converts slowly to 4 in pyridine at room temperature. In contrast, MeNHOH reacted rapidly with 1 and gave the stable crystalline (i-PrO)(2)P(=O)CON(Me)OH (2c). The structure of hydroxamates 2 were assigned on the basis of H-1, C-13, and P-31 NMR spectral data. This facile Lossen rearrangement is discussed in terms of the unusually high migratory aptitude of the phosphonyl group.