ADDITION OF PHOSPHAZENOCUPRATES TO ALDEHYDES AND KETONES - A NEW ROUTE TO GEM-ORGANO-SUBSTITUTED CYCLOTRIPHOSPHAZENES

Novel gem-alkyl(hydroxyalkyl)tetrachlorocyclotriphosphazenes (2), (NPCl2)2NPR1C(OH)R2R3 (R1 = CH3, i-C3H7,t-C4H9; R2 = H, CH3; R3 = CH3, C2H5, C6H5, C6H4-o-NO2, C6H4-o-OCH3, cyclic C4H3O, COOC2H5, CH2Cl, CH=CHCH3, C6H4-p-CH=CH2, η5-C5H4-Fe-η5-C5H5; R2-R3 = -(CH2)5-), have been synthesized in moderate to high yields via the nucleophilic addition of phosphazenocuprates, [(NPCl2)2NPRl]2CuMgX·(n-C4H9)3P, to aldehydes and ketones followed by acid hydrolysis. The proton-decoupled 31P NMR spectra of compounds with R2 ≠ R3 show patterns typical of AXY spin systems, allowing determination of coupling constants between PC12 groupings. A proof for the assignment of the spin system was obtained from proton-decoupled homonuclear 31P shift-correlated 2-D NMR spectroscopy. A new structure for the phosphazenocuprate is proposed. In this structure copper is coordinated onto a phosphorus center, whereas magnesium is linked to a ring nitrogen. © 1990, American Chemical Society. All rights reserved.