Patent GB-729586-A (GB)
Title: Improvements relating to substituted amides of phosphorus thioacids
IPC: C07F9/564
Filed: 1952-11-27
Abstract: New compounds consisting of substituted amides of phosphorus thioacids having the formula <FORM:0729586/IV (a)/1> in which R is hydrogen or an aliphatic hydrocarbon radical and A is an aliphatic, aromatic, heterocyclic, ethyleneimino, or alkyl-substituted ethyleneimino radical or the group <FORM:0729586/IV (a)/2> in which R1 and R11 are hydrogen or aliphatic radicals (see Group IV (b)) may be polymerized to form new plastics.ALSO:The invention comprises as new compounds substituted amides of phosphorus thioacids having the formula <FORM:0729586/IV (b)/1> in which R is hydrogen or an aliphatic hydrocarbon radical and A is an aliphatic, aromatic, heterocyclic, ethyleneimino, or alkyl substituted ethyleneimino radical or the group <FORM:0729586/IV (b)/2> in which R1 and R11 are hydrogen or aliphatic radicals.  The compounds may be prepared by reacting a halide of a phosphorus thioacid having the formula <FORM:0729586/IV (b)/3> in which B is an aliphatic, aromatic, heterocyclic, ethyleneimino or alkyl-substituted ethyleneimino radical or a halogen atom or the group <FORM:0729586/IV (b)/4> in which R1 and R11 are as defined above and X is a halogen atom, with an ethyleneimino compound having the formula <FORM:0729586/IV (b)/5> in which R is as defined above, the reaction being carried out in the presence of an acid acceptor.  The reaction is generally carried out at 0-80 DEG  C. and preferably in an organic solvent which may be benzene, ether, or dioxane and the acid acceptor may be a tertiary amine such as triethylamine, N-ethylmorpholine or pyridine.  The reaction can also be carried out in water or in a substantially aqueous solution in which case the acid acceptor may be an alkaline substance such as an alkali metal carbonate or bicarbonate. Specified starting materials are thiophosphonyl dichlorides or dibromides, e.g. ethane-, beta-chloroethane-, butane-, cyclohexane-, benzene-, 4-methylbenzene-, 2-chlorobenzene-, 1-naphthalene-, and 2-thiophenethiophosphonyl dichlorides.  The ethyleneimine compound may be ethyleneimine itself or a C-substituted ethyleneimine such as 2-methyl-; 2-ethyl-; 2,2-dimethyl-; 2-propyl-; 2,2-diethyl-; or 2-hexyl-ethylenimine.  When the product contains three identical amide groups it may be obtained by reacting a thiophosphoryl halide with the desired ethyleneimine but when the amide groups are different the product may be obtained by first reacting the thiophosphoryl halide with an aliphatic or heterocyclic secondary amine which replaces one of the halogen atoms to form an intermediate compound which is then reacted with two molecular equivalents of an ethyleneimine to form the ethyleneimide.  In examples (1) N,N1-diethylenebenzenethiophosphondiamide is obtained by reacting benzenethiophosphonyl dichloride with ethyleneimine in benzene in the presence of triethylamine; (2) N,N1,N11-triethylenethiophosphoramide is obtained by reacting thiophosphoryl chloride with ethyleneimine by a procedure as in (1); (3) N,N-diethyl-N1,N11-diethylenethiophosphoramide is obtained by reacting ethyleneimine with N,N-diethylamidothiophosphoryl chloride in benzene in the presence of triethylamine; (4) N,N1,N11-tris-(methylethylene)-thiophosphoramide is obtained from methylethyleneimine and thiophosphoryl chloride by reaction as in (1).  The products are stated to be effective in causing inhibition or remission of tumors (see Group VI).  They may also be polymerized to form new plastics.ALSO:New compounds consisting of substituted amides of phosphorus thio acids having the formula:- <FORM:0729586/VI/1> in which R is hydrogen or an aliphatic hydrocarbon radical and A is an aliphatic, aromatic, heterocyclic, ethyleneimino, or alkyl-substituted ethyleneimino radical or the group <FORM:0729586/VI/2> in which R1 and R11 are hydrogen or aliphatic radicals (see Group IV (b)) are stated to be effective in causing inhibition or remission of tumors.  Those that are water-soluble may be administered in saline solution and those having liquid-solubility may be administered in vegetable oils.