US2407346A

US2407346A - Manufacture of new coloring matters

Info

Publication number: US2407346A
Application number: US494120A
Authority: US
Inventors: Rogers Maurice Arthur Thorold
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1942-07-13
Filing date: 1943-07-09
Publication date: 1946-09-10
Anticipated expiration: 1963-09-10

Description

Patented Sept. 10, 1946 MANUFACTURE OF NEW-"COLORING MATTERS I Maurice Arthur- Thorold Rogers, Blackley, Manchester,-England, ,assignor to Imperial Chemical Industries Limited, Britain a corporation of' Great .No Drawing. Application July 9, 12943, 'S eriaLNo. 494,120. In, Great BritainJuly 13,1942

3 Claims.

The present invention-relates to the manufacture of new coloring matters.

In British application No. 16,2'76/41, and in copendin'g" application Serial No. 457,2'28,*filed September 3, '1 942,,.:now' U. 1S. Patent 2,382,914, there' are described tetraaryl aza-dipyrromethinesofxformula:

and in copending application No. 494,126, filed Ju1y 9, 1943, there are described tetraaryldipyrromonomethines of formula I m '-g n, v-Q=G vi R '(IL--CR=CIZ l-R where R R It, and'R. stand for aryl radicals, for example of-the benzene orinaphthalene series,

substituted or not, the same ordifferent, where R and R each. stand for hydrogen or for a non-reactive substituent, the same or difierent,

for example, an'aryl-,,,alkyl-, alkylamino-, benzylideneaminoor acylaminoradical, and where R. stands for hydrogen or an alkyl-, aralkyl or aryl-radical, or forra heterocyclic residue.

The present invention is directed to the production of metal complexes, from. these compounds that is to say, from :compounds of the formula N If include 2:2 4 :4 -tetraphenyl-aza-dipyrrometh- 50 2 2 :2 :4 1 4 tetraphenyl-meso -phenyl-dipyrromonomethine,

The metal complexes may be formed by using the metals themselves, for example in a finely 5 divided form, or by "using salts, for example the acetates, sulphates, chlorides, phosphates or double salts such as dichromates. Good results have been obtained with, for example, copper acetate, copper sulphate, zinc acetate, chromimn fluoride, cobalt sulphate, cobaltacetate, and nickel acetate. 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 made from water-soluble derivatives of tetraaryl-aza dipyrromethines or tetraaryldipy-rromonomethines, for example, their sulphonic acid derivatives'which are described in 'copen'ding application Serial No. 482,479, filed April '9', 1943, now U. S. Patent-2;382, 91-7, or the salts of their amino-derivatives, they may be made by treating dyeings of these Water-soluble compounds, for example on wool, with aqueous solutions of the metal salts. In this way, the metal complexes are formed on the fibre.-

The invention is illustrated'but not limited by the following examples, in which the parts are expressed by Weight.

Example I,

1 part of 2: :4:4"-tetraphenyl-aza-dipyrromethine, 0.5 part of copper acetate and 50 parts of butanol:are'rboiledtogether for 1 hourrand the coppery brown crystalline material which forms is collected by filtration. The product analyses for C64H44N6Cu, and has the probabl formula:

OH=CPh rh-c i-- in It is sparingly solubl in nitrobenzene, dioxan, pyridine and dimethylformamide forming solutions which are blue in color. I In a similar manner, cobalt, nickel and zinc acetates yield the corresponding complexes.

Example II In place of the aza methine in Example I there is used 1 part of 2:2":4:4-tetraphenyldipyrromonomethine. The copper complex forms cop-. pery brown platelets, which are crystallised from a mixture of pyridine and methyl alcohol in the form of platelets.

The product analyses for CcsHnsNeCu and is believed to have a structure similar to that assigned to the product of EXam-' ple I.

Example III p The disulphonic acid derivative of 2122414- tetraphenyl-aza-dipyrromethine is dyed on to 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.

Example IV A compound of the formula T M03931 N(CHa)aI 4 where R R R and R stand for aryl radi cals, R and R" each are a member of the group consisting of hydrogen, arylalkyl-, alkylamino-, benzylideneamino-, and acylaminoradicals, A is a member of the group consisting of nitrogen and the group l I wherein R is a member of the group consisting of hydrogen, alkyl-, aralkyl-, aryl-, and heterocyclic radicals; and B is a metal of the group consisting of 'copper zinc, nickel, cobalt, chromium, and cadmium.

2. Process for the manufacture of metal complexes which comprises bringing into reaction with each other a, compound of the general formula:

where R R RW, and R tand for aryl radicals, R and R each are a member. of the group consisting of hydrogen, ary1-, alkyl-, alkylamino-,

benzylideneamino-, and acylamino radicals, Aisa. member of the group consisting of nitrogen and the group 1 wherein'R is a member of the group consisting of hydrogen, alkyl-, aralkyl-, aryl-, and heterocyclic radicals, with a member taken from the group consisting of copper, zinc, nickel, cobalt, chromium, and cadmium and their salts.

3. The compound of the formula:

n o-P11 Ph-C=GH v Ph--C 0-N=o C-Ph 7 Cu ROGERS.