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

Abstract

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.

Graphical Abstract

Keywords:

• Sterically hindered phenols
• thiophosphoryl chloride
• phosphorothionates
• 2,2′-dihydroxybiphenyl
• X-ray crystal structure
• DFT calculations

Acknowledgments

Dr. Yu. Chumakov is grateful to project financed by the National Agency of Research and Development of R. Moldova – ANCD 20.80009.5007.15 of the Institute of Applied Physics.

Disclosure statement

No potential conflict of interest was reported by the author(s).

Additional information

Funding

This work was financially supported by İnönü University Research Fund [İ.Ü.B.A.P: 2008/49] and the National Agency of Research and Development of R. Moldova [ANCD 20.80009.5007.15] of the Institute of Applied Physics.