Patent GB-887335-A (GB)
Title: Aminoaryl esters and amides of phosphoric and thio-phosphoric acids
IPC: C07F9/12
Filed: 1959-01-29
Abstract: Amino aryl phosphorus compounds having the formula: <FORM:0887335/IV (a)/1> wherein X is an oxygen or sulphur atom, n is 0, 1 or 2, A is a radical obtained by removing two active hydrogen atoms from a di-hydroxy terminated polyester, polyether, or alcohol, R is an O-aryl, O-aralkyl, O-alkaryl, O-cycloalkaryl, NH-aryl, N-(aryl)2, N-aryl-N-lkyl, N-(aralkyl)2, NH-alkaryl, NH-aralkyl, N-(alkaryl)2, NH-cycloalkaryl, or N-(cycloalkaryl)2 radical, R1 and R11 are the same or different and represent the same groups as R or represent an O-alkyl, O-cycloalkyl, NH-alkyl, NH-cycloalkyl, N-(alkyl)2, N-(cycloalkyl)2, O-vinyl or an O-cyclopentadienyl radical, at least one of the said aryl radicals containing at least one unsubstituted amino group bonded to a carbon atom of the said aromatic ring as the sole nitrogen-containing substituents (see Group IV(b)) can be transformed into polyamides with polyfunctional carboxylic acid chlorides or reacted with diisocyanates to form polyureas.  They can also be used as cross linking agents for epoxy resins.  The radical A can be derived from a polyester such as the reaction product of succinic acid with trimethylol propane or 1,4-butylene glycol or from a polyether derived from an alkylene oxide and diethylene glycol.ALSO:The invention comprises organophosphorus compounds having the general formula <FORM:0887335/IV (b)/1> wherein X is an oxygen or sulphur atom, n is 0, 1 or 2, A is a radical obtained by removing two active hydrogen atoms from a di-hydroxy-terminated polyester, polyether or alcohol, R is an O-aryl, O-aralkyl, O-alkaryl, O-cycloalkaryl, NH-aryl, N-(aryl)2, N-aryl-N-alkyl, N-(aralkyl)2, NH-alkaryl, NH-aralkyl, N-(alkaryl)2, NH-cycloalkaryl or N-(cycloalkaryl)2 radical, R1 and R11 are the same or different and represent the same groups as R or represent an O-alkyl, O-cycloalkyl, NH-alkyl, NH-cycloalkyl, N-(alkyl)2, N-(cycloalkyl)2, O-vinyl or an O-cyclopentadienyl radical, at least one of the said aryl radicals present containing at least one unsubstituted amino group bonded to a carbon atom of the aromatic ring as the sole nitrogen-containing substituent of the said aromatic ring.  The groups R, R1 and/or R11 may also contain as further substituents halogen, e.g. Cl, Br or I, alkoxy, and/or carboxylic acid ester groups.  The radical A may suitably be derived from ethylene glycol, 1,3-propylene glycol or 1,4-butylene glycol, the reaction product of succinic acid with trimethylol propane or ethylene glycol, or from the compound obtained by condensing alkylene oxides with diethylene glycol.  The products may be obtained by catalytic reduction of the corresponding nitro aryl phosphoric or thiophosphoric acid derivatives with hydrogen. The starting materials containing a nitro group can be made by nitration of the appropriate phosphoric or thiophosphoric acid esters and amides or by reacting the corresponding phosphoric or thiophosphoric acid chlorides with nitroaromatic alcohols or phenols. The catalytic reduction with hydrogen is preferably carried out in an inert solvent, e.g. ethanol, propanol, an ether, e.g. dibutyl ether, tetrahydrofuran, or dioxane, or an ester, e.g. methyl acetate. Suitable catalysts are Raney-nickel, -iron, or -cobalt, or precious metals.  Preferred hydrogenation temperatures are between 30 DEG C. and 90 DEG C. and atmospheric or higher or lower pressures may be employed.  Examples are given for the production of tri-(p-aminophenyl) phosphate and thiophosphate, diethyl p-aminophenyl thiophosphate, bis-(p-aminophenyl) phosphor - N,N - dimethyl (and -N,N-methyl phenyl)-amidate, the compound <FORM:0887335/IV (b)/2> and the compound <FORM:0887335/IV (b)/3> Several other products are also mentioned including ethyl vinyl 4-aminonaphthyl thiophosphate, tri-(4-aminobenzyl) phosphate and thiophosphate, cyclopentadienyl 4-aminophenyl phosphordimethyl amidate, ethyl phosphor-bis-(N-methyl-N-4-amino-phenyl amidate), 4-amino-6-chlorophenyl diethyl phosphate and thiophosphate and O,O-diphenyl phosphor-N-(4-aminobenzyl) amidate.  The products are useful in the manufacture of dyestuffs and plastics (see Groups IV(a) and IV(c)).ALSO:Amino-aryl phosphorus compounds having the general formula <FORM:0887335/IV (c)/1> wherein X is an oxygen or sulphur atom, n is 0, 1 or 2, A is a radical obtained by removing two active hydrogen atoms from a di-hydroxy terminated polyester, polyether or alcohol, R is an O-aryl, O-aralkyl, O-alkaryl, O-cycloalkaryl, NH-aryl, N-(aryl)2, N-aryl-N-alkyl, N-(aralkyl)2, NH-alkaryl, NH-aralkyl, N-(alkaryl)2, NH-cycloalkaryl or N-(cycloalkaryl)2 radical, R1 and R11 may be the same or different and represent the same groups as R or represent an O-alkyl, O-cycloalkyl, NH-alkyl, NH-cycloalkyl, N-(alkyl)2, N-(cycloalkyl)2, O-vinyl or an O-cyclopentadienyl radical, at least one of the said aryl radicals containing at least one unsubstituted amino group bonded to a carbon atom of the aromatic ring as the sole nitrogen-containing substituent of said ring (see Group IV (b)) may be diazotised and then coupled to give azo dyes.