Patent GB-393271-A (GB)
Title: Manufacture of intermediate products and dyestuffs therefrom
IPC: C09B57/00
Filed: 1931-11-17
Abstract: Acidylamino compounds; pyrazolone dyes; azo dyes; azo dyes forming on the material; printing.--Intermediates capable of coupling with diazo compounds or condensing with aldehydes to form dyestuffs and of the general formula R<1>,CO,NH,R<3>,(NH,CO,R<2>)n in which R<1> is the residue of an aromatic carboxylic acid containing a -CO,CH2- group capable of coupling with diazo compounds or condensing, R<2> is the residue of any aromatic carboxylic acid capable of coupling with diazo compounds, R<3> is the residue of an aromatic diamine or polyamine and n is a whole number, are obtained by acylation of the amines with the acids. Specified amines are m- and p-phenylenediamines, the toluylenediamines, the halogenated phenylenediamines, the anisylenediamines and phenetylenediamines, the naphthylenediamines, e.g. 1 : 5-naphthylenediamine, benzidine, the tolidines, dianisidines and diphenetidines, the o-p-, o-p<1>, o-o<1>- and p-p<1>-diaminodiaryl ethers, the o-p-p<1>-triaminodiaryl ethers, such as 2 : 4 : 4<1>-triaminodiphenyl ether and generally diamines and polyamines in which substituted or unsubstituted aromatic residues are connected by a divalent connecting member such as <FORM:0393271/IV/1> or a heterocyclic residue such as <FORM:0393271/IV/2> (one of the three free valencies of the triazine and pyrimidine residues being linked to any suitable atom or group), and diamines and triamines derived from complexes containing condensed heterocyclic and aromatic nuclei, such as dehydrothiotoluidines or dehydrothioxylidines containing further amino groups, diamino- and polyamino-dibenzimidazoles, dibenzoxazoles, and dibenzotriazoles.  Specified aromatic carboxylic acids containing the group -CO,CH2- capable of coupling or condensing are the 1-aryl-5-pyrazolones carrying a -CO,OH group in the aryl nucleus (obtained by condensing with acetoacetic or oxalacetic esters the hydrazines derived from aminocarboxylic acids such as m- or p-aminobenzoic acids, chloroaminobenzoic acids, aminotoluic acids, methoxy- and ethoxy-aminobenzoic acids and nitroaminobenzoic acids), the acetoacetic arylides carrying a -CO,OH group in the aryl nucleus, such as those derived from o-, m- and p-aminobenzoic acids, the arylbarbituric acids carrying a -CO,OH group in the aryl nucleus, such as 3-carboxyphenylbarbituric acid and derivatives of benzoylacetone carrying nuclear CO,OH, such as benzoylacetone-o-carboxylic-acid.  Other specified aromatic carboxylic acids capable of coupling are the oxycarboxylic acids of the benzene series, especially those, such as p-cresotinic acid, coupling in o-position to the -OH group, the oxynaphthalenecarboxylic acids, e.g. 2 : 3-oxynaphthoic acid and its 7-methoxy- and 6-phenylaminoderivatives, the oxycarbazolecarboxylic acids, the oxyphenanthrenecarboxylic acids, the oxynaphthocarbazolecarboxylic acids and the oxydiphenylaminecarboxylic acids.  The products are soluble in alkalies and may be absorbed from the solutions by animal or vegetable fibres.  As examples of dyestuffs obtainable by their condensation with aldehydes are specified the condensation products from benzidine symmetrically di-acylated with 1-(3<1>-carboxy) phenyl-3-methyl-5-pyrazolone and (a) benzaldehyde, (b) dimethyl - 4 - aminobenzaldehyde, the product in the latter case being described as an orange pigment.  The azo dyes obtainable by coupling with diazo compounds from unsulphonated amines, such as aniline, toluidines, halogen-anilines, halogen-toluidines, halogen-xylidines and halogen-anisidines are fast yellow to yellow-orange and brown pigments and may also be produced upon the fibre; with diazotized nitranilines, diazoazo compounds and diazotized aminodiphenylamines such as 4-amino-4<1>-ethoxydiphenylamine yellow to orange-yellow, brown-orange and deep brown shades are obtainable; with o-oxyor o-carboxy-diazo compounds the products are convertible, in substance or on the fibre, into metal compounds.  The following examples are specified: (1) A mixture of 1-(3<1>-carboxy) phenyl-3-methyl-5-pyrazolone (2 mols.) and benzidine (1 mol.) is heated to about 100 DEG  C. in diethylaniline and phosphorus trichloride is slowly added while ensuring that the temperature does not rise above 110-115 DEG  C.; after about 4 hours at this temperature the mixture is introduced into dilute hydrochloric acid and filtered, the solid matter being then suspended in dilute sodium carbonate from which the diethylaniline is removed by distillation in steam; the arylide is then dissolved in dilute caustic soda and precipitated by dilute acid, the diethylaniline may be replaced by pyridine or toluene, the pyrazolone by the corresponding 4<1>-carboxy compound or by the 3-carboxy derivative of acetoacetanilide, and the benzidine by tolidine, dianisidine or 1 : 5-naphthylenediamine.  (2) A mixture of 1-(4<1>-carboxy)-phenyl-3-methyl-5-pyrazolone (2 mols.) and dianisidine (1 mol.) is heated to about 100 DEG  C. in pyridine with gradual addition of phosphorus trichloride and the temperature is maintained at 115-120 DEG  C. for about 6 hours; the mixture is introduced into dilute hydrochloric acid and filtered and the solid matter is washed with dilute acid and with water, dissolved in dilute caustic soda and precipitated from the solution by carbon dioxide, the pyrazolone may be replaced by the corresponding 2<1>-carboxy- or 4<1>-chloro-3<1>-carboxy-derivatives.  (3) A mixture of 1 - (3<1> - carboxy) phenyl - 3 - methyl - 5 - pyrazolone (1 mol.) and benzidine (1 mol.) is heated to about 80 DEG  C. in diethylaniline with gradual addition of phosphorus trichloride and maintained at about 80 DEG  C. for 2 hours; 2 : 3-oxynaphthoic acid (1 mol.) and more phosphorus trichloride are then added and the temperature is gradually raised to 120-125 DEG  C. and so maintained for 4 hours; the mixture is then introduced into dilute hydrochloric acid and filtered, the solid matter being washed, stirred with dilute sodium carbonate, freed from diethylaniline by steam distillation and dissolved in dilute caustic soda, and the arylide being precipitated from the solution by carbon dioxide. (4) The condensation product from dianisidine (1 mol.) and 1-(3<1>-carboxy)phenyl-3-methyl-5-pyrazolone (2 mols.) is coupled with diazotized sulphanilic acid; the product dyes cotton yellow. (5) Cotton yarn is grounded in a dilute caustic soda solution containing turkey red oil, common salt, and the condensation product of (1) above, and developed with diazotized - 2 - chloro - 2 - aminodiphenylether to obtain a fast pure p  yellow dyeing.  (6) Cotton material, impregnated with an alkaline solution of the condensation product from p-phenylenediamine (1 mol.) and 1-(3<1>-carboxy)phenyl - 3 - methyl - 5 - pyrazolone (2 mols.), is printed with a preparation containing diazotized 2 : 5-dichloraniline to obtain a fast yellow print.  (7) The condensation product of (1) above is coupled with diazotized 4-sulphoaniline-2-carboxylic acid; the product gives on cotton green-yellow dyeings which may be made fast to light and washing by treatment with agents yielding metal, e.g. copper salts; if the diazo component is replaced by 4-sulpho-2-aminophenol-6-carboxylic acid or other o-aminophenolsulphonic acid, the dyeings are orange to brown. Indigoid dyes.--The Provisional Specification refers also to the production of dyestuffs by the condensation of the intermediates with isatin chlorides or anilides.  2 : 4 : 4<1>-Triaminodiphenylether is obtained by reducing the nitro groups of the product of nitration of the condensation product from 2 : 4-dinitrochlorobenzene and sodium phenate.  3-Carboxyphenylbarbituric acid is obtained by condensing ethyl malonate with 3-carboxyphenylurea.  1-(4<1> - Chloro - 3<1> - carboxy)phenyl - 3 - methyl5-pyrazolone is obtained by condensing the hydrazine from 2-chloro-5-aminobenzoic acid with acetoacetic ester.