Phenolysis of 2, 2′-Biphenoxy Thiophosphinic Chloride: Crystal Structures and DFT Calculations of 2, 2′-Biphenyl 4-Tert-Butylphenyl Thiophosphinate and 2, 2′-Biphenyl 3,4-di-Methylphenyl Thiophosphinate

In this work, firstly, thiophosphoryl chloride, PSCl3 (1), with 2,2’-dihydroxybiphenyl, 2,2′-HOC6H4C6H4OH (2) were reacted. 2, 2′-biphenoxy thiophosphinic chloride (3) was obtained from this reaction. Second, the reactions of compound (3) with sterically hindered phenol derivatives (4a–4h) were investigated. Novel alkyl-substituted phenyl 2, 2′-biphenyl-thiophosphinate esters (C6H4O)2P(S)OAr (5–12) were obtained from these reactions. Structures of (5–12) were defined by IR, 1H, 13C, 31P NMR spectroscopy, and elemental analysis. The molecular structures of 2, 2′-biphenyl 4-tert-butylphenyl thiophosphinate (11) and 2, 2′-biphenyl 3,4-di-methylphenyl thiophosphinate (6) were determined by single-crystal X-ray diffraction. Density functional theory (DFT) calculations of compounds 6 and 11 were made. The theoretical analysis of IR and NMR spectra was performed by DFT based on B3LYP level of theory.本研究首先将硫代磷酰氯（thiophosphoryl chloride, PSCl3，化合物1）与2,2'-二羟基联苯（2,2′-HOC6H4C6H4OH，化合物2）进行反应，成功得到2,2'-联苯氧基硫代次膦酰氯（化合物3）。其次，考察了化合物3与位阻酚衍生物（4a–4h）的反应，合成了一系列新型烷基取代苯基2,2'-联苯硫代次膦酸酯类化合物（C6H4O)2P(S)OAr（5–12）。采用红外光谱、1H核磁共振谱、13C核磁共振谱、31P核磁共振谱及元素分析对化合物5–12的结构进行了表征。通过单晶X射线衍射测定了2,2'-联苯-4-叔丁基苯基硫代次膦酸酯（化合物11）与2,2'-联苯-3,4-二甲基苯基硫代次膦酸酯（化合物6）的分子结构。对化合物6和11开展了密度泛函理论（Density Functional Theory, DFT）计算，并基于B3LYP泛函水平完成了红外光谱与核磁共振谱的理论分析。