Patent GB-744633-A (GB)
Title: N-alkyl-(or-aralkyl-) substituted alkylene polyamine methylene phosphonic acid compounds
IPC: C07F9/38
Filed: 1953-06-05
Abstract: The invention comprises as new products compounds having the formula: <FORM:0744633/IV(a)/1> wherein R is an alkyl or aralkyl group containing up to 18 carbon atoms; A is an alkyl or aralkyl group containing up to 18 carbon atoms, or -CH2.PO(OM)2; alkylene is -CH2CH2-, -CH(CH3)CH2- or -CH2.CH2 CH2-; n is 0, 1, 2, 3 or 4; and M is hydrogen, alkali metal, ammonium or alkyl-ammonium.  The compounds may be obtained by dissolving a N-alkyl- (or -aralkyl-) substituted alkyleine polyamine in water containing sufficient caustic alkali to give a pH of from 10-11, heating the solution to a temperature of about 80-100 DEG  C. and adding chloromethyl phosphonic acid disodium salt in an amount sufficient to substitute all the amino hydrogens present on the amine.  The solution is then refluxed for about 10 hours or more.  If the substituted alkylene polyamine is insoluble in water the reaction is carried out in absolute alcohol by dissolving the substituted alkylene polyamine in 5-10 times its volume of absolute ethanol and adding solid sodium hydroxide in a molar amount equivalent to the number of replaceable hydrogen atoms on the nitrogen atoms of the amine.  An equal number of moles of chloromethyl phosphonic acid diethyl ester are then added while the solution is stirred and refluxed.  The sodium chloride formed is filtered off, the ethanol removed by distillation and the substituted polyamine methylene phosphonic acid isolated by acid hydrolysis of the reaction product.  The acids form metal chalate compounds with polyvalent metal ions such as those of Al, Ba, Ca, Pb.  Typical examples of such metallic compounds are the barium compound of N,N1-dibenzyl ethylene diamine-N,N1-dimethylene phosphonic acid and the lead compound of N-octadecyl-ethylene diamine trimethylene phosphonic acid.  Such metallic compounds may be prepared by dissolving the metal oxide, hydroxide, or carbonate in a solution of the organic alkyl- (or -aralkyl-) substituted alkylene polyamine methylene phosphonic acid.  The residual charges on these metal derivatives may be neutralized by such salt forming groups as alkali metal and alkyl ammonium ions. N,N1-dibutyl ethylenediamine - N,N1 - dimethylenephosphonate ion is stated to be an effective deactivator of alkaline earth metal ions such as the magnesium ion.  Examples are given for the production of: (1) N-butyl-ethylene diamine trimethylenephosphonic acid and its sodium salt; (2) dibenzyl ethylene diamine dimethylenephosphonic acid; (3) N-octadecyl diethylene triamine tri-(methylenephosphonic acid) and its sodium salt; (4) N,N1-dioctadecyl ethylene diamine di-(methylene phosphonic acid); (5) N,N1-dimethyl propylene diamine di-(methylene phosphonic acid); (6) the sodium salt of N,N1111-dibutyl tetraethylene pentamine penta-(methylene phosphonic acid), this salt is stated to be a sequestering agent with high capacity for combination with alkaline earth and heavy metal ions; (7) the sodium salt of N-monobutyl tetraethylene pentamine hexa-(methylene phosphonic acid) which is stated to have a greater affinity for alkaline earth metal ions than the compound (6); (8) N-monobenzyl trimethylene diamine tri-(methylene phosphonic acid); and (9) N,N1-dibutyl trimethylene diamine di-(methylene phosphonic acid).  The products are stated to be valuable as detergents, metal carriers and as additives for lubricating oils. Specification 703,181 is referred to.