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Ethyl octyl phosphite (EOP), a dialkyl phosphite with mixed alkyl groups was prepared, and utilized in the Kabachnik–Fields reaction. The condensation of EOP, paraformaldehyde and primary or secondary amines used in equimolar quantities afforded new α-aminophosphonates under microwave conditions. Methylation of the -α(alkylamino)phosphonates was also investigated. The double phospha-Mannich reaction of primary amines and two equivalents of EOP and paraformaldehyde furnished new bis(phosphonomethyl)amines.