Ethyl α-(diethoxyphosphinyl)-α-(4-nitrophenyl)acetate | 152302-91-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Ethyl α-(diethoxyphosphinyl)-α-(4-nitrophenyl)acetate
• 英文别名: ethyl α-diethoxyphosphoryl-α-(4-nitrophenyl)acetate；Ethyl 2-diethoxyphosphoryl-2-(4-nitrophenyl)acetate
• CAS: 152302-91-5
• 化学式: C₁₄H₂₀NO₇P
• 分子量: 345.289
• InChiKey: UIWGCKMQNYTVBQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  108
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Ethyl α-(diethoxyphosphinyl)-α-(4-nitrophenyl)acetate 在 palladium on activated charcoal 四氯化碳 、 硼烷 、 氢气 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 51.0h， 生成 diethyl 1-(4-aminophenyl)-2-chloroethylphosphonate
  参考文献：
  名称：

  Novel Irreversible Butyrylcholinesterase Inhibitors: 2-Chloro-1-(substituted-phenyl)ethylphosphonic Acids

  摘要：

  2-Chloroethylphosphonic acid (ethephon) as the dianion phosphorylates butyrylcholinesterase (BChE) at its active site. In contrast, the classical organophosphorus esterase inhibitors include substituted-phenyl dialkylphosphates (e.g., paraoxon) with electron-withdrawing aryl substituents. The chloroethyl and substituted-phenyl moieties are combined in this study as 2-chloro-1-(substituted-phenyl)ethylphosphonic acids (1) to define the structure-activity relationships and mechanism of BChE inhibition by ethephon and its analogues. Phenyl substituents considered are 3- and 4-nitro, 3- and 4-dimethylamino. and 3- and 4-trimethyl-ammonium. Phosphonic acids 1 were synthesized via the corresponding O,O-diethyl phosphonate precursors followed by deprotection with trimethylsilyl bromide. They decompose under basic conditions about 100-fold faster than ethephon to yield the corresponding styrene derivatives. Electron-withdrawing substituents on the phenyl ring decrease the hydrolysis rate while electron-donating substituents increase the rate. The 4-trimethylammonium analogue has the highest affinity (K-i = 180 muM) and potency (IC50 = 19 muM) in first binding reversibly at the substrate site (possibly with stabilization in a dianion-monoanion environment) and then progressively and irreversibly inhibiting the enzyme activity. These observations suggest dissociation of chloride as the first and rate-limiting step both in the hydrolysis and by analogy in phosphorylation of BChE by 1 bound at the active site. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(01)00391-1
• 作为产物：
  描述：

  4-硝基碘苯 、 Sodium; (E)-2-(diethoxy-phosphoryl)-1-ethoxy-ethenolate 以87%的产率得到
  参考文献：
  名称：

  Minami Toru, Isonaka Takeshi, Okada Yoshiharu, Ichikawa Junji, J. Org. Chem, 58 (1993) N 25, S 7009-7015

  摘要：

  DOI：

文献信息

• Copper(I) salt-mediated arylation of phosphinyl-stabilized carbanions and synthetic application to heterocyclic compounds
  作者：Toru Minami、Takeshi Isonaka、Yoshiharu Okada、Junji Ichikawa

  DOI：10.1021/jo00077a018

  日期：1993.12

  The copper-mediated reaction of phosphinyl-stabilized carbanions 2a-c with aryl halides 1a-i in DMF or HMPA produced (arylmethyl)phosphonates 3-11 in good yields. Similar treatment of N-(2-iodophenyl)- and N-(2-iodophenyl)-N-methyl-alpha-(diethoxyphosphinyl)acetamides (12 and 14) led to 2-[(diethoxyphosphinyl)methyl]benzoxazole (13) and 1-methyl-3-(diethoxyphosphinyl)oxindole (15) in 71 and 85% yields, respectively. 4-(Ethoxycarbonyl)-3,4-dihydroisoquinoline N-oxide (33) was synthesized by the reaction of ethyl alpha-(o-formylphenyl)acrylate (31), derived from 6 and paraformaldehyde,with hydroxylamine. The cycloaddition of 33 to olefins such as dimethyl maleate, methyl acrylate, and styrene was studied.