O-phenyl phenylphosphonothiochloridate | 20148-06-5

• 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: O-phenyl phenylphosphonothiochloridate
• 英文别名: phenyl(phenoxy)thiophosphonic chloride；phenyl phenylthiophosphonochloridate；phenyl-thiophosphonic acid-chloride O-phenyl ester；Phenyl-thiophosphonsaeure-chlorid-O-phenylester；O-Phenyl phenylphosphonochloridothioate；chloro-phenoxy-phenyl-sulfanylidene-λ5-phosphane
• CAS: 20148-06-5
• 化学式: C₁₂H₁₀ClOPS
• 分子量: 268.704
• InChiKey: KJZSIEYIBRWWKS-UHFFFAOYSA-N

物化性质

• 沸点：
  131-135 °C(Press: 0.45 Torr)
• 密度：
  1.32±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  41.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  O-phenyl phenylphosphonothiochloridate 在 一水合肼 作用下， 以62%的产率得到phenyl(phenoxy)thiophosphonic acid hydrazide
  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：

  苯酚 、 苯基硫代膦酰二氯 在 吡啶 作用下， 生成 O-phenyl phenylphosphonothiochloridate
  参考文献：
  名称：

  Nitrogen Compounds of the Phosphoric and Phosphonic Acids. IV. Some Derivatives of Phenylphosphonamidic and Phenylphosphonamidothioic Acids

  摘要：

  DOI：

  10.1021/jo01106a017

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。
• Kinetics and Mechanism of the Anilinolysis of O-Ethyl Phenyl Phosphonochloridothioate in Acetonitrile
  作者：Md. Ehtesham Ul Hoque、Hai-Whang Lee

  DOI：10.5012/bkcs.2012.33.8.2707

  日期：2012.8.20

  investigated in acetonitrile at . The deuterium kinetic isotope effects (DKIEs) invariably increase from a secondary inverse DKIE ( = 0.93) to a primary normal DKIE ( = 1.28) as the substituent of nucleophile (X) changes from electron-donating to electron-withdrawing. These can be rationalized by the gradual transition state (TS) variation from a backside to frontside attack. A concerted mechanism is proposed

  在乙腈中动力学研究了 O-乙基苯基硫代膦酰氯与取代苯胺 () 和氘代苯胺 () 的亲核取代反应。随着亲核试剂 (X) 的取代基从给电子变为吸电子，氘动力学同位素效应 (DKIE) 总是从次级逆 DKIE (= 0.93) 增加到初级正态 DKIE (= 1.28)。这些可以通过从背面到正面攻击的逐渐过渡状态（TS）变化来合理化。提出了一种协调机制。三角双锥型 TS 被提议用于背面攻击，而氢键四中心型 TS 被提议用于正面攻击。
• Duddeck, Helmut; Lecht, Rainer, Phosphorus and Sulfur and the Related Elements, 1987, vol. 29, p. 169 - 178
  作者：Duddeck, Helmut、Lecht, Rainer

  DOI：——

  日期：——
• Nitrogen Compounds of the Phosphoric and Phosphonic Acids. IV. Some Derivatives of Phenylphosphonamidic and Phenylphosphonamidothioic Acids
  作者：M. F. HERSMAN、L. F. AUDRIETH

  DOI：10.1021/jo01106a017

  日期：1958.12
• Pyridinolyses of O-Propyl and O-Isopropyl Phenyl Phosphonochloridothioates in Acetonitrile
  作者：Hasi Rani Barai、Hai Whang Lee

  DOI：10.5012/bkcs.2013.34.9.2811

  日期：2013.9.20