O,O,O-三(对氯苯基)硫代磷酸酯 | 3071-56-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机硫代磷酸及其衍生物
• 中文名称: O,O,O-三(对氯苯基)硫代磷酸酯
• 英文名称: O,O,O-tris(p-chlorophenyl) phosphorothioate
• 英文别名: O,O,O-tri(p-chlorophenyl) phosphorothioate；tris(O-4-chlorophenyl)phosphorothionate；thiophosphoric acid O,O',O''-tris-(4-chloro-phenyl ester)；Thiophosphorsaeure-O,O',O''-tris-(4-chlor-phenylester)；O.O.O-Tris-(4-chlor-phenyl)-thiophosphat；Tri-<4-chlorphenyl)-thiophosphat；Tris(4-chlorophenoxy)-sulfanylidene-lambda5-phosphane；tris(4-chlorophenoxy)-sulfanylidene-λ5-phosphane
• CAS: 3071-56-5
• 化学式: C₁₈H₁₂Cl₃O₃PS
• 分子量: 445.69
• InChiKey: UMFOZZGXJLITQR-UHFFFAOYSA-N

物化性质

• 熔点：
  85-86 °C(Solv: ethanol (64-17-5))
• 沸点：
  262-263 °C(Press: 4 Torr)
• 密度：
  1.477±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  59.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  O,O,O-三(对氯苯基)硫代磷酸酯 、 二乙胺 以 乙醚 为溶剂， 生成 diethyl-amidothiophosphoric acid O,O'-bis-(4-chloro-phenyl ester)
  参考文献：
  名称：

  Mel'nikov,N.N. et al., Journal of general chemistry of the USSR, 1961, vol. 31, # 11, p. 3361 - 3365

  摘要：

  DOI：
• 作为产物：
  描述：

  对氯苯酚 在 PEG-400 sodium hydroxide 、 三氯氧磷 作用下， 以 氯仿 、 水 为溶剂， 反应 3.0h， 以85%的产率得到O,O,O-三(对氯苯基)硫代磷酸酯
  参考文献：
  名称：

  Jadhav; Wadgaonkar; Salunkhe, Polish Journal of Chemistry, 1999, vol. 73, # 9, p. 1473 - 1475

  摘要：

  DOI：

文献信息

• Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride)
  作者：Jiří Hanusek、Mark A. Russell、Andrew P. Laws、Petr Jansa、John H. Atherton、Kevin Fettes、Michael I. Page

  DOI：10.1039/b616298c

  日期：——

  report, the sulfurisation of phosphorus(III) derivatives by 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride) does not yield carbon disulfide and cyanamide as the additional reaction products. The reaction of xanthane hydride with triphenyl phosphine or trimethyl phosphite yields triphenyl phosphine sulfide or trimethyl thiophosphate, respectively, and thiocarbamoyl isothiocyanate which has been trapped

  与先前的报告相反，3-氨基-1,2,4-二噻唑-5-硫酮（黄原氢化物）对磷（III）衍生物的硫化不会产生作为额外反应产物的二硫化碳和氰胺。黄原酸氢化物与三苯基膦或亚磷酸三甲酯的反应分别产生三苯基膦硫化物或三甲基硫代磷酸酯，以及已被亲核试剂捕获的硫代氨基甲酰基异硫氰酸酯。该反应途径涉及磷在黄原氢化物的硫代羰基旁边的硫处最初的亲核进攻，然后分解形成产物的intermediate中间体。乙腈中取代的三苯膦和亚磷酸三苯酯硫化的哈米特rho值约为-1.0。活化的熵非常负（-114 +/- 15 J mol-1 K-1），对溶剂的依赖性很小，这与导致过渡态的双分子缔合步骤相一致。ΔS（不等于）和rho值的负值表明，硫化反应的限速步骤是形成具有早期过渡态且几乎没有共价键形成的the离子中间体。亲核攻击的位点也已经通过计算得到证实。ΔS（不等于）和rho值的负值表明，硫化反应的限速步骤是形成具有早期过渡态
• 1,2,4-Dithiazole-5-ones and 5-thiones as efficient sulfurizing agents of phosphorus(iii) compounds – a kinetic comparative study
  作者：Oleksandr Ponomarov、Andrew P. Laws、Jiří Hanusek

  DOI：10.1039/c2ob26460a

  日期：——

  The existence of the phosphonium intermediate during sulfurization of triphenyl phosphine with 3-phenyl-1,2,4-dithiazole-5-thione (7a) was proven using kinetic studies. From the Hammett and Brønsted correlations and from other kinetic measurements it was concluded that the transition-state structure is almost apolar for the most reactive 1,2,4-dithiazoles whereas a polar structure resembling a zwitter-ionic

  25种3-取代的1,2,4-丁二唑-5-酮和5-硫酮对二甲苯的硫化效率 亚磷酸三苯酯 在 乙腈，DCM，THF和 甲苯评价在25℃下的温度。所有的1,2,4-二噻唑都是比市​​售试剂（PADS，TETD，Beaucage试剂）更好的硫化试剂。在所有溶剂中最有效的硫化剂是3-苯氧基（4），3-苯硫基（5）和3-乙氧基-1,2,4-二噻唑-5-一（1）其反应性比其他1,2,4-二噻唑高至少两个数量级。与以前的报告相反，用1进行硫化不会产生羰基硫 和 氰酸乙酯 作为其他反应产物，但不稳定 乙氧基硫代羰基异氰酸酯 被困住了 4-甲氧基苯胺。相似的捕集实验已证明，化合物4和5的攻击位点位于与C O基团相邻的硫上。反应途径包括限制磷对硫的初始亲核进攻，然后将intermediate中间体分解为相应的硫代磷酸酯和异氰酸酯/异硫氰酸酯。硫化过程中the中间体的存在三苯基膦使用动力学研究证明了使用3-苯基-1
• Strecker; Grossmann, Chemische Berichte, 1916, vol. 49, p. 75
  作者：Strecker、Grossmann

  DOI：——

  日期：——
• Mel'nikow; Chochlow, Zhurnal Obshchei Khimii, 1953, vol. 23, p. 1357,1358; engl. Ausg. S. 1419, 1420
  作者：Mel'nikow、Chochlow

  DOI：——

  日期：——
• Substituent effects on the 31P NMR chemical shifts of arylphosphorothionates
  作者：Javier Hernández、Francisco M. Goycoolea、Denisse Zepeda-Rivera、Josué Juárez-Onofre、Karla Martínez、Jaime Lizardi、Magali Salas-Reyes、Bárbara Gordillo、Carlos Velázquez-Contreras、Oscar García-Barradas、Samuel Cruz-Sánchez、Zaira Domínguez

  DOI：10.1016/j.tet.2005.12.053

  日期：2006.3

  Six tris(aryloxy)phosphorothionates substituted in the para position of the aromatic rings were synthesized and studied by P-31 NMR, X-ray diffraction techniques and ab initio calculations at a RHF/6-31G** level of theory, in order to find the main structural factors associated with the delta P-31 in these compounds. As the electron-withdrawing (EW) ability of the substituents was increased, an 'abnormal' shielding effect on delta P-31 of the arylphosphorothionates was observed. The analyses of the geometrical properties obtained through both experimental and theoretical methods showed that a propeller-type conformation is preferred for the arylphosphorothionates, except in the case of the tris(O-4-methylphenyl)phosphorothionate, since one of the aromatic rings is not rotated in the same direction as the other two in the solid state. The main features associated with the delta P-31 NMR of compounds 1-6 were a decrease of the averaged O-P-O angle and mainly the shortening of the P=S bond length, which is consistent with an increase of the thiophosphoryl bond order as delta P-31 values go upfield. On the other hand, comparison of the experimental and calculated bond lengths and bond angles involving a bonded atoms to phosphorus of the six compounds suggested that stereoelectronic interactions of the type n(pi)O-sigma*(P=S), n(pi)O-sigma*(P-OAr) and n(pi)S-sigma*(P-OAr) could be present in the arylphosphorothionates 1-6. (c) 2005 Elsevier Ltd. All rights reserved.