Reaction of secondary phosphine chalcogenides with diallylamine

Abstract

Diphenyl-or bis(2-phenylethyl)phosphine sulfides and -phosphine selenides react with diallylamine under radical initiation (UV or AIBN) to afford the corresponding diadducts and tetrahydropyrrolylmethyl phosphine chalcogenides. The yield and the ratio of the products depend on the structure of the starting secondary phosphine chalcogenides.Addition of secondary phosphines and phosphine chalcogenides to polyalkenes is a convenient atomeconomic approach to the synthesis of polyphosphines and polyphosphine chalcogenides including their functional derivatives. Reactions of this type have been successfully realized under radical conditions by the example of divinyl [1], diallyl [2, 3], trivinyl [4], tetravinyl [5] ethers, divinyl chalcogenides [6-9], as well as tris(4-vinylbenzyl)phosphine oxide [10]. As a result, promising polydentate ligands for metal complexes, including metallacrown ethers [1, 11-13] have been synthesized.At the same time, there are no data in the literature on the reaction of diallylamine with secondary phosphine chalcogenides, although substituted diallylamines react with diphenylphosphine oxide (AIBNinitiation) [2] and diphenylphosphine sulfide (microwave activation) [3] to give cyclic adducts, phosphoruscontaining pyrrolidines (Scheme 1).In the present work we have studied for the first time the radical addition of secondary phosphine sulfides and phosphine selenides to diallylamine in order to develop a general convenient atom-economic method of the synthesis of functional tertiary phosphine chalcogenides containing an amino group.Diphenylphosphine sulfide (I) turned out to react with diallylamine (in the ratio 2 : 1) in benzene or dioxane at UV irradiation (200W Hg arc Lamp) or in the presence of AIBN (5 wt %, 60-65 о С) in 2-2.5 h to give diadduct II as the main product (the isolated yield 52%). For the equimolar ratio of the reagents, compound II is also the main product (Scheme 2).