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Aryl(dimethylaminomethyl)phosphinic Acid Esters: Syntheses, Structures, and Reactions with Halogen Hydrogen Acids, Tin Halides, and Trimethyl Halosilanes
Author(s) -
Lutter Michael,
Jurkschat Klaus
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201800343
Subject(s) - chemistry , aryl , medicinal chemistry , iodide , tin , toluene , alkyl , halogen , dichloromethane , organic chemistry , solvent
This paper reports the synthesis of the aryl(iodomethyl)phosphinic acid ethyl esters, Ar(ICH 2 )P(O)OEt (Ar = Ph, Ar = mesityl), which, via dimethyamination, are converted to the corresponding aryl(dimethylaminomethyl)phosphinic acid ethyl esters, Ar(Me 2 NCH 2 )P(O)OEt (Ar = Ph, Ar = mesityl). Upon reaction with hydrogen chloride, compound Me 2 NCH 2 (Ph)P(O)OEt forms its hydrochloride salt as a crystalline material. Depending on the reaction conditions, treatment of Me 2 NCH 2 (Ph)P(O)OEt with SnCl 2 gave either [Me 2 HNCH 2 (Ph)P(O)OEt][SnCl 3 ] or the mixed‐valent dinuclear tin salt [{Me 2 HNCH 2 (Ph)P(O)O} 4 SnCl 2 ][SnCl 3 ] 2 , as its dichloromethane solvate. The reaction of Me 2 NCH 2 (Mes)P(O)OEt with SiMe 3 I gives the diorgano bis(trimethylsiloxy)phosphinium iodide [Me 2 NCH 2 (Mes)P(OSiMe 3 ) 2 ]I, as its toluene solvate. In solution, it is involved in an equilibrium with Me 2 NCH 2 (Mes)P(O)OSiMe 3 and SiMe 3 I. From the hydrolysis of [Me 2 NCH 2 (Mes)P(OSiMe 3 ) 2 ]I, the hydrogen iodide derivative [Me 2 HNCH 2 (Mes)P(O)OH]I was obtained as three different solvates. [Me 2 NCH 2 (Mes)P(OSiMe 3 ) 2 ]I reacted with SnF 2 to give a product mixture from which the mixed‐valent tin compound [{Sn II 2 Me 2 NCH 2 (Mes)P(O) 2 } 4 Sn IV F 2 ]I 2 , was isolated. The compounds were characterized by NMR and IR spectroscopy, electrospray ionization mass spectrometry, and single‐crystal X‐ray diffraction analysis.