chloro-ethoxy-phenoxy-sulfanylidene-λ5-phosphane | 95103-06-3

• 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: chloro-ethoxy-phenoxy-sulfanylidene-λ5-phosphane
• CAS: 95103-06-3
• 化学式: C₈H₁₀ClO₂PS
• 分子量: 236.659
• InChiKey: NUESSQYZNOVTAQ-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.57
• 重原子数：
  13.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  chloro-ethoxy-phenoxy-sulfanylidene-λ5-phosphane 、 乙酰乙酸乙酯 以68%的产率得到
  参考文献：
  名称：

  TANG, CHU-CHI;WU, GUI-PING;HUANG, JIA-WEI;CHEN, RU-YU, ACTA CHIM. SIN., 1984, 42, N 11, 1188-1191

  摘要：

  DOI：

文献信息

• Kinetics and Mechanism of the Pyridinolysis of Aryl Ethyl Chlorothiophosphates in Acetonitrile
  作者：Keshab Kumar Adhikary、Hai-Whang Lee

  DOI：10.5012/bkcs.2011.32.11.3947

  日期：2011.11.20

  The nucleophilic substitution reactions of Y-aryl ethyl chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $55.0^\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Me. The substituents of X = 4-CN and 4-Ac show great positive deviations from both the Hammett and Bronsted plots. The Hammett plots for substituent Y variations in the substrates exhibit biphasic concave upwards with a minimum point at Y = H. The obtained values of the cross-interaction constants ($\rho}_XY}$) are all in spite of the biphasic free energy correlations for both substituent X and Y variations, since the $\rho}_X$values with both the strongly and weakly basic pyridines are almost constant. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed where the distance between X and Y does not vary from the intermediate to the second transition state. A frontside attack is proposed with the strongly basic pyridines based on the considerably great magnitudes of $\rho}_X$ and $\beta}_X$ values and a backside attack is proposed with the weakly basic pyridines based on the relatively small magnitudes of $\rho}_X$ and $\beta}_X$. The positive deviations of the two strong $\pi}$-acceptor parasubstituents, X = 4-Ac and 4-CN, from both the Hammett and Bronsted plots are rationalized by the great extents of bond formation and breaking.

  在乙腈中，在 $55.0^\circ}C$ 条件下，对 Y-芳基氯硫代磷酸乙酯与 X-吡啶的亲核取代反应进行了动力学研究。亲核物中取代基 X 变化的 Hammett 图和 Bronsted 图呈现出双相凹向上的趋势，在 X = 3-Me 处出现断点。X = 4-CN 和 4-Ac 的取代基与哈密特图和布龙斯特图都有很大的正偏差。底物中取代基 Y 变化的哈梅特图显示出双相向上凹，在 Y = H 处为最小点。尽管取代基 X 和 Y 变化的自由能都是双相相关的，但得到的交叉作用常数（$\rho}_XY}$）值与强碱性和弱碱性吡啶的$\rho}_X$值几乎是恒定的。我们提出了一种具有限速离去基团离开中间体的逐步机制，在这种机制中，从中间体到第二过渡态，X 和 Y 之间的距离没有变化。根据 $\rho}_X$ 和 $\beta}_X$ 值的相当大的幅度，提出了强碱性吡啶的前侧攻击机制；根据 $\rho}_X$ 和 $\beta}_X$ 值的相对较小的幅度，提出了弱碱性吡啶的后侧攻击机制。两个强$\pi}$受体副基团（X = 4-Ac和4-CN）与哈米特图和勃朗斯特图的正偏离，是由于键形成和断裂的程度很大而合理化的。