ISSN:
1042-7163
Keywords:
Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Lithium and sodium o-lithio-4,6-di-t-butyl-phenolates 1 and 2 react, successively, with ClP(NMe2)2 and ClSiMe3 to give 2-(Me2N)2P-4,6-t-Bu2C6H2OSiMe3 3. 1 and ClP(NMe2)Ph furnish a small amount of the analogous compound 4 but mainly diastereoisomers of a C, O-diphosphinylation product 5A/B, which exhibit large through-space coupling constants (4JPP = 152 and 237.5 Hz). Under certain conditions, the P-N bond is attacked, and triphosphines 6 and 7 are formed. Alcoholysis of 3-5 and subsequent reduction with LiAlH4 yields the respective bulky primary and secondary phosphinophenols 8 and 9. Both decompose partially on distillation, affording tBu2C6H3OH and the cyclic diphosphines 10 and 11. 10, a further dihydro-benzoxadiphosphol 13 and a phosphinidene-phosphorane 14 are formed by reaction of 8 with P(NMe2)3. The molecular structure of bicyclic 10, folded at the P-P bond, is reported. The uncommon features - unselective disubstitution of 1, P…P interactions in 5 and 6, facile P-C cleavage of 8 and 9, and diphosphine formation - reveal a dramatic influence of the bulky substituents in the 6-position on the chemistry of 2-phosphinophenols. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:183-193, 1998
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
