Patent GB-691358-A (GB)
Title: Improvements in or relating to the production of unsaturated aliphatic phosphonamides
IPC: C07F9/24
Filed: 1949-11-25
Abstract: Unsaturated aliphatic phosphonamides of the general formula <FORM:0691358/IV (b)/1> where Ru is an unsaturated C3-5 aliphatic radical; R1 is hydrogen, a C1-3 alkyl radical, a methylol radical or an unsaturated C3-5 aliphatic radical and R2 is hydrogen, an unsaturated C3-5 aliphatic radical or the radical <FORM:0691358/IV (b)/2> wherein m is a whole integer from 1 to 5 and R1 and Ru are as above defined, are prepared by condensing a di-substituted phosphonyl chloride of the general formula <FORM:0691358/IV (b)/3> where R is an unsaturated C3-5 radical with ammonia, an appropriate unsaturated primary or secondary amine having 3-5 carbon atoms in the unsaturated radical, a saturated C1-3 primary amine or an appropriate saturated C2-5 diamine and where the methylene or methylol compounds are desired, reacting the amides containing free amido hydrogen atoms with formaldehyde. In a modification, the phosphoryl chloride is formed in situ by reacting the corresponding phosphate (RO)2POH and at least one molecular proportion of carbon tetrachloride with the ammonia or amine.  The compounds may be used as flame-proofing agents, water-proofing agents, coatings, plasticizers, lubricating oil modifiers, hydraulic fluid modifiers, corrosion inhibitors, insecticides and fungicides and as monomers or comonomers in polymerizations.  In examples: (1) diallyl phosphonamide is prepared by reacting phosphorus oxychloride with allyl alcohol, dissolving the resulting diallyl phosphoryl chloride in toluene and bubbling ammonia therethrough, or (2) by reacting phosphorus trichloride with allyl alcohol (3 mols.) in toluene, blowing with air and then anhydrous ammonia to remove HCl, preparing a solution of the resulting phosphite in carbon tetrachloride with or without the addition of benzene or toluene and then introducing ammonia at -15 DEG  to -20 DEG  C. until alkaline; (4) N-methylol diallyl phosphonamide is prepared by reacting the product of (1) or (2) with aqueous formaldehyde at room temperature; (5) N : N1-methylene bis diallyl amido phosphate is produced by reacting diallyl phosphonamide with the product of (4) or by reacting formaldehyde with 2 mols. of diallyl phosphonamide; (6) N-allyl diallyl phosphonamide is prepared by reacting diallyl phosphite in carbon tetrachloride with excess of allyl amine; (7) N-diallyl phosphonamide is prepared from diallyl amine by the method of (6); (8) N : N1-ethylene bis-diallyl amido phosphate is prepared by reacting excess ethylene diamine with diallyl phosphite in carbon tetrachloride; (9) dipropargyl phosphonamide is prepared by reacting propargyl alcohol with phosphorus trichloride in carbon tetrachloride, removing HCl by air blowing and then passing in ammonia to form the desired amide.  The Specification as open to inspection under Sect. 91 includes the production of phosphonamides of the above general formula wherein R1 may be a hydroxyalkyl radical of 1-3 carbon atoms and m is a small integer.  This subject-matter does not appear in the Specification as accepted.