phenyl(p-tolyloxy)thiophosphonic chloride | 20148-09-8

• 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: phenyl(p-tolyloxy)thiophosphonic chloride
• 英文别名: chloro-(4-methylphenoxy)-phenyl-sulfanylidene-λ5-phosphane
• CAS: 20148-09-8
• 化学式: C₁₃H₁₂ClOPS
• 分子量: 282.73
• InChiKey: WTYGPADBDJFJFB-UHFFFAOYSA-N

物化性质

• 沸点：
  375.0±35.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.25
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  phenyl(p-tolyloxy)thiophosphonic chloride 在 一水合肼 作用下， 以 氯仿 为溶剂， 生成 4-[hepta-O-acetyl-β-D-lactosyl]-1-[phenyl(p-tolyloxy)thiophosphoryl]thiosemicarbazide
  参考文献：
  名称：

  Synthesis of O-Aryl N⁴-Glycosyl(thiosemicarbazido)phosphonothioates

  摘要：

  A reaction of aryl(aryloxy)thiophosphonic acids hydrazides with glycosyl isothiocyanates was studied. Amides of N-(glycosylthioureylene)aryl(aryloxy)thiophosphonic acids were synthesized. The structure and composition of the new compounds were confirmed by the data of IR, H-1 and P-31 NMR and mass spectra, and by results of elemental analyses.

  DOI：

  10.1023/b:rujo.0000013135.25430.40
• 作为产物：
  描述：

  对甲酚 、 苯基硫代膦酰二氯 以 吡啶 、 乙醚 为溶剂， 反应 2.0h， 以30%的产率得到phenyl(p-tolyloxy)thiophosphonic chloride
  参考文献：
  名称：

  Synthesis of O-Aryl N⁴-Glycosyl(thiosemicarbazido)phosphonothioates

  摘要：

  A reaction of aryl(aryloxy)thiophosphonic acids hydrazides with glycosyl isothiocyanates was studied. Amides of N-(glycosylthioureylene)aryl(aryloxy)thiophosphonic acids were synthesized. The structure and composition of the new compounds were confirmed by the data of IR, H-1 and P-31 NMR and mass spectra, and by results of elemental analyses.

  DOI：

  10.1023/b:rujo.0000013135.25430.40

文献信息

• Transition State Variation in the Anilinolysis of O-Aryl Phenyl Phosphonochloridothioates in Acetonitrile
  作者：Keshab Kumar Adhikary、Bilkis Jahan Lumbiny、Shuchismita Dey、Hai-Whang Lee

  DOI：10.5012/bkcs.2011.32.8.2628

  日期：2011.8.20

  The nucleophilic substitution reactions of Y-O-aryl phenyl phosphonochloridothioates with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from an extremely large secondary inverse ($k_H/k_D$ = 0.439; min) to a primary normal ($k_H/k_D$ = 1.34; max) as both substituents of nucleophile (X) and substrate (Y) change from electron-donating to electron-withdrawing. These results are opposite to the DKIEs on Y-O-aryl methyl phosphonochloridothioates, and can be rationalized by the gradual transition state (TS) variation from backside to frontside attack. The trigonal bipyramidal pentacoordinate TS is proposed for a backside attack, while the hydrogen-bonded, four-center-type TS is proposed for a frontside attack. The negative values of the cross-interaction constants ($\rho}_XY(H)}$ = -0.38 for $XC_6H_4NH_2$ and $\rho}_XY(D)}$ = -0.29 for $XC_6H_4ND_2$) indicate that the reactions proceed by a concerted $S_N2$ mechanism.

  对Y-O-芳基苯基膦氯硫酸酯与取代苯胺（$XC_6H_4NH_2$）和氘代苯胺（$XC_6H_4ND_2$）在乙腈中的亲核取代反应进行了动力学研究，温度为$55.0^\circ}C$。随着亲核试剂（X）和底物（Y）的取代基从供电子变为吸电子，氘同位素效应（DKIEs）始终从极大幅度的次级逆效应（$k_H/k_D$ = 0.439；最小值）变为初级正效应（$k_H/k_D$ = 1.34；最大值）。这些结果与Y-O-芳基甲基膦氯硫酸酯的DKIEs相反，可以用从背面攻击到正面攻击的过渡态（TS）逐渐变化来合理化解释。对于背面攻击，提出了三角双锥五配位TS，而对于正面攻击，提出了氢键四中心型TS。交叉相互作用常数的负值（$\rho}_XY(H)}$ = -0.38表示$XC_6H_4NH_2$，$\rho}_XY(D)}$ = -0.29表示$XC_6H_4ND_2$）表明反应是通过协同的$S_N2$机制进行的。
• CHEN RUYU; JIN GUIYU; SHA YUEWU, CHEM. J. CHIN. UNIV., 7,(1986) N 9, 811-814
  作者：CHEN RUYU、 JIN GUIYU、 SHA YUEWU

  DOI：——

  日期：——
• LI, YU-GUI;BAO, RONG;ZHANG, ZONG-BING;YANG, JIAN-MEI;CAO, JIN-HONG;JIANG,+, ACTA CHIM. SIN., 45,(1987) N 7, 696-703
  作者：LI, YU-GUI、BAO, RONG、ZHANG, ZONG-BING、YANG, JIAN-MEI、CAO, JIN-HONG、JIANG,+

  DOI：——

  日期：——