Organophosphorus‐Selenium Heteroatom Derivatives from Selenation of Primary/Secondary Amines and Haloalkanes/Dihaloalkanes

Abstract

Reaction of 2,4‐bis(phenyl)‐1,3‐diselenadiphosphetane‐2,4‐diselenide (Woollins' reagent) with four equivalents of primary/secondary amines led to a series of ammonium phenylphosphonamido‐diselenoates or phenylphosphonamido‐diselenoic diamides 1a–n, the latter further reacted in situ with either two equivalents of haloalkanes or an equimolar amount of dihaloalkane, resulting in formation of the corresponding Se‐alkylphenyl‐Se‐alkylphenyl‐phosphonamidodiselenoates 2a–n and alkane bis(N‐alkyl‐P‐phenylphosphonamido‐diselenoate) derivatives 3a–n in good to excellent yields. All new compounds have been characterized spectroscopically including multinuclear NMR (1H, 13C, 31P and 77Se), IR and mass spectroscopy. Two representative X‐ray structures are also described.

Reaction of Vinyl Selenides with Secondary Phosphines and Elemental Selenium: One‐Pot Selective Synthesis of a New Family of Diselenophosphinic Se‐Esters

“…As for the synthesis of diselenophosphinic Se ‐esters and their ‐phosphate or ‐phosphonate congeners , the most conventional method is the reaction between organic halides and the salts of [R 2 PSe 2 ]Cat type (R = organic groups, RO or R 2 N; Cat = metal or ammonium). Alternatively, such Se ‐esters can be assembled by condensation of selenophosphinic chlorides, R 2 P(Se)Cl, with metal alkyl‐ or arylselenolates .…”