Patented Sept. 10, 1946 ' 2,407,346 UNITED‘ vs'm'rII-ZYs OFFICE MANUFACTURE OF NEW-"COLORING - - MATTERS ' - I Maurice Arthur-TThorold Rogers, Blackley, Man chester,‘-England, ,assignor to Imperial Chemical Industries Limited, a corporation’ 1of' ‘Great Britain‘ .No Drawing’. Application July 9, 12943, 'S‘eriaLNo. 494,120. ‘In, Great BritainJuly 13,1942 3 Claims. (Cl. 260-13139 - 1 2 The present‘ invention-‘relates to the manufac ture of new coloring matters. In British application No. 16,2'76/41, and in copendin'g" application Serial No. 457,2'2‘8,*?led , 2 :2 ' :4 1 4 ’ - tetraphenyl-meso -phenyl-dipyrromon . omethine, The metal complexes may be formed by ‘using the metals themselves, for example in a ?nely September 3, '1;942,,.:now' ‘U. 1S‘. ‘Patent 2,382,914, 5 divided form, or by "using salts, for example the there' are ‘described vtetraaryleaza-dipyrrometh acetates, sulphates, chlorides, phosphates or dou inesofxformula: ble salts such as dichromates. . ' , ' _R1v N tate. and in copending application No. 494,126, ?led Ju1yf9, 1943, there are described tetraaryldipyr romonomethines of ‘formula I Rm__.((;_._'-g_._Rn,Rv-Q=G_Rvi RI-g '(IL-—-CR=’CIZ ‘(ll-RIV Good results have been obtained with, for example, copper acetate, copper sulphate, zinc acetate, chromimn ?uoride, 10 cobalt sulphate, cobaltacetate, and nickel ace V - ‘ ' I r " The reaction may be carried out by heating the reagents by' themselves or ‘in'the' presence of a solventfor one or both. Alternatively, when metal complexes ‘are to be 15 made ‘from water-soluble derivatives of tetra aryl-azaedipyrromethines Tor tetraaryldipy-rro monomethines, for example, their ‘sulphonic acid derivatives'which are‘ described in 'copen'ding ap-; wherev RI, R11, It,w and'R.V stand ‘for ,aryl radicals, 20 plication Serial No. 482,479, ?led April '9', 1943, ‘ N ‘ ~N now U. S. Patent~2;382,l91~7, or the‘ salts of their for example of-the benzenelorinaphthalene series, substituted or not, the same ordifferent, where Rm and R“ each. stand for hydrogen or for a amino-derivatives, they may be‘ made by treat ing dyeings of these Water-soluble compounds, R.‘ stands for hydrogen or an alkyl-, aralkyl or The invention is illustrated'but not limited by the following examples, inv which the parts are for example on wool, with aqueous‘ solutions of non-reactive substituent, the‘ same or di?’erent,“ for example, an'aryl-,,,alkyl-, alkylamino-, ben 25 the metal salts. In this way, the metal com plexes are formed on the ?bre. zylideneamino- or acylamino- radical, and where aryl-radical, or forra heterocyclic residue. The present invention is directed to the pro duction of’, ; metal “complexes, from. “these com pounds that is to say,,_from_:compounds of the formula ' ' ' expressed by Weight. Example I, 1 part of 2:2’,:4:4"-tetraphenyl-aza-dipyrro ' methine, 0.5 part‘ of copper acetate and 50 parts of butanol:are'rboiledtogether for 1 hourrand the coppery brown crystalline material which forms N If 35 is collected by ?ltration. The product analyses for C64H44N6Cu, and has the probable formula: : where RI, Rn, Rm, RI", RV and RVI have the sig ni?cance given above, and where A stands for nitrogen or for the group CR, R being, as before, hydrogen or an alkyl-, aralkyl- or aryl-radical, or a heterocyclic residue. According to the invention the metal com plexes are manufactured by a process which com prises bringing into reaction with each other a compound of the general formula given above and ametal of the group consisting of copper, zinc, nickel, cobalt, chromium and cadmium. Suitable compounds of the formula given above include 2:2’ : 4 :4’ -tetraphenyl-aza-dipyrrometh- 50 inc, 2:2’:4:4'-tetraphenyl - aza - dipyrromethine disulphonic acid, 2 :2’ -diphenyl-4 :4'-di- (p-meth oxyphenyl) -aza-dipyrromethine, 2:2’ :4 : 4’-tetra phenyldipyrromonomethine, 2: 2' :4-triphenyl-4' (p - methoxyphenyl) - dipyrromonomethine and OH=C—Ph rh-cli—-~<lin It is sparingly soluble in nitrobenzene, dioxan, pyridine and dimethylformamide forming solu tions which are blue in color. I _ In a similar manner, cobalt, nickel and zinc 55 acetates yield the corresponding complexes. 9,407,346 3 4 where R1, R11, R1", and Rv stand for aryl radi» Example II cals, RI11 and R" each are a member of the group consisting of hydrogen, aryl-_ alkyl-, alkylamino-, benzylideneamino-, and acylamino- radicals, A is a member of the group consisting of nitrogen and In place of the aza methine in Example I there is used 1 part of 2:2":4:4’-tetraphenyldipyrro monomethine. The copper complex forms cop-. pery brown platelets, which are crystallised from a mixture of pyridine and methyl alcohol in the the group . ‘ ,:,.= . ». . l I‘ .. ’ I form of platelets. The product analyses forv R CcsHnsNeCu and is believed to have a structure . similar to that assigned to the product of EXam-' 10 wherein R is a member of the group consisting of ple I. Example III p , hydrogen, alkyl-, aralkyl-, aryl-, and hetero cyclic radicals; and B is a metal of the group consisting of 'copper_ zinc, nickel, cobalt, chromi The disulphonic acid derivative of 2122414’ tetraphenyl-aza-dipyrromethine is dyed on to um, and cadmium. 2. Process for the manufacture of metal com wool from an acid dyebath. The dyed Wool so obtained is heated in a %% aqueous solution of copper sulphate for 1 hour at 80-90° C. The color of the dyeing changes from a reddish-blue to a greener color as the copper complex is formed. plexes, which comprises bringing into reaction with each other a, compound of the general for mula: 20 Example IV A compound of the formula T ~ M03931 _ where RI, RH, RW, and RV stand for aryl radi N(CHa)aI 25 cals, RIII and R“ each are a member. of the group consisting of hydrogen, ary1-, alkyl-, alkylamino-, benzylideneamino-, and acylaminoé radicals, Ais a. member of the group consisting of nitrogen and the group 1 ' _.G= l R made’ by interacting -2:2’-diphenyl-4:4’-(p-di wherein'R is a member of the group consisting of methyl-aminophenyl)-aza-dipyrromethine with hydrogen, alkyl-, aralkyl-, aryl-, and heterocyclic methyl iodide is dyed on to wool from a neutral dyebathp The greenish blue dyeing so obtained radicals, with a member taken from the group consisting of copper, zinc, nickel, cobalt, chromi is heated in a 1% aqueous solution of copper ace tate; I The color of the dyeing changes to a -red—, um, and cadmium and their salts. 3. The compound of the formula: dish blue as the copper complex is formed. I claim: 1 _ > > 1.‘ Metal complexes of the formula: (‘info-P11 Ph-C=GH Ph--C 0-——N=o \N/ 45 v C-Ph / 7 \‘Cu / , 50 55 ROGERS.