1-(diethoxyphosphoryl)oxy-1,3-cyclohexadiene | 1046759-26-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: 1-(diethoxyphosphoryl)oxy-1,3-cyclohexadiene
• 英文别名: 1-(diethoxyphosphoryloxy)-1,3-cyclohexadiene；cyclohexa-1,3-dien-1-yl diethyl phosphate；Di-ethyl cyclohexadienyl phosphate
• CAS: 1046759-26-5
• 化学式: C₁₀H₁₇O₄P
• 分子量: 232.216
• InChiKey: ZYWBBBAZEFNKHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(diethoxyphosphoryl)oxy-1,3-cyclohexadiene 、 (2-methyl-4-phenyl-1-oxabuta-1,3-diene)tricarbonyliron(0) 以 甲苯 为溶剂， 反应 16.0h， 以84%的产率得到
  参考文献：
  名称：

  磷酸二烯基磷酸三羰基铁络合物作为水溶性酶引发的释放CO的分子（ET-CORMs）

  摘要：

  一系列外消旋磷酰基取代的（η的4 -cyclohexadiene）的Fe（CO）3配合物被利用（二烯醇）的Fe（CO）的O-磷酸合成3个从对应的triisopropylsiloxy保护的复合物在原位产生的中间体。通过光谱方法对磷酸化产物进行了充分表征，包括在四种情况下的单晶X射线衍射。用三甲胺对两种磷酸二甲酯衍生物进行单脱保护，生成了（环己二烯基磷酸甲酯）Fe（CO）3的四甲基铵盐复合体。这些化合物是最早的水溶性酶触发的CO释放分子（ET-CORM）。通过GC监测磷酸酶诱导的CO释放。在不同的细胞测定中评估了生物学活性。该化合物仅显示出轻微毒性，并且在基于可诱导性NO合酶（iNOS）诱导的NO产生抑制作用的测定中确定了中等的抗炎潜力。

  DOI：

  10.1021/om300359a
• 作为产物：
  描述：

  环己-3-烯-1-酮 、 氯磷酸二乙酯 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 生成 1-(diethoxyphosphoryl)oxy-1,3-cyclohexadiene
  参考文献：
  名称：

  Synthesis of cyclohexadienylstannanes – Novel example of vinylic SRN1 mechanism: A theoretical and experimental study

  摘要：

  The reaction of trimethyltinsodium (1) with 1-(diethoxyphosphoryl) oxy-1,3-cyclohexadienes in liquid ammonia under irradiation affords the corresponding 1-trimethylstannylcyclohexadienes. We suggest that these reactions occur by an S(RN)1 mechanism. On the other hand, 2-(diethoxyphosphoryl)oxy-1,3-cyclohexadiene reacts very slowly towards 1 and the substitution product decomposes under the reaction conditions employed. Thus, structurally similar compounds do not behave in the same way under ET conditions. We suggest that this behavior is mainly due to differences in spin density of their radical anions, which affect their fragmentation rates. Our results are supported by computational calculations. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.04.018

文献信息

• Iron Dienylphosphate Tricarbonyl Complexes as Water-Soluble Enzyme-Triggered CO-Releasing Molecules (ET-CORMs)
  作者：Steffen Romanski、Hannelore Rücker、Eleni Stamellou、Miguel Guttentag、Jörg-Martin Neudörfl、Roger Alberto、Sabine Amslinger、Benito Yard、Hans-Günther Schmalz

  DOI：10.1021/om300359a

  日期：2012.8.27

  Monodeprotection of two dimethyl phosphate derivatives with trimethylamine led to the tetramethylammonium salts of the (cyclohexadienyl methyl phosphate)Fe(CO)3 complexes. These compounds are the first water-soluble enzyme-trigged CO-releasing molecules (ET-CORMs). The phosphatase-induced CO release was monitored by means of GC. The biological activity was assessed in different cellular assays. The compounds were

  一系列外消旋磷酰基取代的（η的4 -cyclohexadiene）的Fe（CO）3配合物被利用（二烯醇）的Fe（CO）的O-磷酸合成3个从对应的triisopropylsiloxy保护的复合物在原位产生的中间体。通过光谱方法对磷酸化产物进行了充分表征，包括在四种情况下的单晶X射线衍射。用三甲胺对两种磷酸二甲酯衍生物进行单脱保护，生成了（环己二烯基磷酸甲酯）Fe（CO）3的四甲基铵盐复合体。这些化合物是最早的水溶性酶触发的CO释放分子（ET-CORM）。通过GC监测磷酸酶诱导的CO释放。在不同的细胞测定中评估了生物学活性。该化合物仅显示出轻微毒性，并且在基于可诱导性NO合酶（iNOS）诱导的NO产生抑制作用的测定中确定了中等的抗炎潜力。
• Synthesis of cyclohexadienylstannanes – Novel example of vinylic SRN1 mechanism: A theoretical and experimental study
  作者：Viviana B. Dorn、Mercedes A. Badajoz、María T. Lockhart、Alicia B. Chopa、Adriana B. Pierini

  DOI：10.1016/j.jorganchem.2008.04.018

  日期：2008.7

  The reaction of trimethyltinsodium (1) with 1-(diethoxyphosphoryl) oxy-1,3-cyclohexadienes in liquid ammonia under irradiation affords the corresponding 1-trimethylstannylcyclohexadienes. We suggest that these reactions occur by an S(RN)1 mechanism. On the other hand, 2-(diethoxyphosphoryl)oxy-1,3-cyclohexadiene reacts very slowly towards 1 and the substitution product decomposes under the reaction conditions employed. Thus, structurally similar compounds do not behave in the same way under ET conditions. We suggest that this behavior is mainly due to differences in spin density of their radical anions, which affect their fragmentation rates. Our results are supported by computational calculations. (C) 2008 Elsevier B.V. All rights reserved.