Solvent-modulated reactivity of PCl₃ with amines

The reactivity of phosphorus trichloride towards amines in ionic liquids has been investigated and compared with that in conventional organic solvents. In addition to easing the synthetic procedures thus far required for the preparation of aminochlorophosphines in molecular solvents, for example the ability to operate at 20 °C, under non-anhydrous and high concentration conditions with short reaction times and rapid addition of reagents, bis((trifluoromethyl)sulfonyl)imide-based ionic liquids offer a tight control over the selectivity during the reaction and offer access to monoamination and bisamination products in high yields and chemoselectively. Furthermore, these ionic liquids offer a unique storage medium for these highly moisture sensitive aminochlorophosphines.