Oxy-and Thio Phosphorus Acid Derivatives of Tin. IX. Di- and Triorganotin (IV) Diphenylphosphate Esters.
OKLAHOMA UNIV NORMAN DEPT OF CHEMISTRY
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Six triorgano- and five diorganotinIV diphenylphosphates, R3SnO2POC6H52 where R CH3, C2H5, n-C3H7, n-C4H9, C6H5 and cyclo-C6H11, and R2SnO2PC6H522 where R CH3, C2H5, n-C4H9, C6H5 and n-C8H17, are synthesized by five routes elimination of water by condensation of diphenylphosphoric acid with triorganotinIV hydroxides R CH3, C6H5 and cyclo-C6H11, bis-triorganotinIV oxide R n-C3H7, n-C4H9, or diorganotinIV oxides R CH3, n-C4H9, n-C8H17, C6H5 where the released water is removed azeotropically to drive the reactions forward, or by precipitation of sodium chloride from the reaction of sodium diphenylphosphate with tri- R C6H5 or diorganotinIV R C2H5 chlorides. The products are crystalline solids, soluble in polar and non-polar solvents, except for the triorganotinIV derivatives below R CH3 which are oils. An NMR 2J119Sn-C-1H coupling constant of 73.0Hz is consistent with a five-coordinated structure for the trimethyltinIV derivative in solution. In none of the mass spectra are there parent molecular ions, ions of mass higher than the parent, or any di- or polytin-bearing species, thus ruling out association in the gas phase. The highest mass fragments derive from the loss of one organic group from tin from the tri- and from the loss of one ligand moiety from the diorganotin derivatives. Successive loss of phenyl groups can be seen in the phenyltin spectra.
- Organic Chemistry