Patent GB-766609-A (GB)
Title: Improvements in and relating to diazoamino derivatives
Inventor: PETITCOLAS PIERRE
Filed: 1954-11-24
Abstract: The invention comprises compounds of formula <FORM:0766609/IV(b)/1> where R is an aryl residue and X is an alkyl or cycloalkyl group which may be substituted, and their water-soluble salts.  They are made by condensing an appropriate diazo-compound in a non-acid medium with the required substituted aniline-2,4-dicarboxylic acid or a water-soluble salt thereof.  Diazo compounds indicated for use may be derived from aniline, toluidines, xylidines, cresidines, anisidines optionally having halogen substituents, nitroanilines, nitrotoluidines, nitroanisidines, nitrocresidines, monoacrylated p-diamines which may have halogen, alkyl or alkoxy substituents, benzidine, tolidines, dianisidines, aromatic bases containing sulphonamido, sulphone or trifluoromethyl groups, aminobenzthiazoles, aminoindazoles, amino azo dyestuffs and "Solid Bases."  Preferred diazo compounds are those which do not contain solubilizing groups such as COOH or SO3H. Specified substituents which may be present in the ethyl or cycloalkyl groups are -OH, -OCH3, -OC2H5, -C6H5, -COOH, -SO3H, -OSO3H, -OPO3H2, -OPO2H2, -COOAlk and -CON< dicarboxylic acids specified being 1-methyl-, -ethyl-, isopropyl-, -propyl-, -isobutyl-, isoamyl-, -butyl-, benzyl-, - cyclohexyl -, - hydroxyethyl -, - dihydroxypropyl -, - (21 - hydroxy - 31 - sulpho - propyl) -, - glyco -, - (21 - methoxy - and - ethoxy - ethyl) and 1 - methyl - o  - sulphonic - aminobenzene - 2,4 - dicarboxylic acids, 1 - phenylglycineben-zene - 2,4 - dicarboxylic acid, N - (21,41 - dicarboxyphenyl) - b  - aminopropionic acid, - glycinamide and glycine methyl and ethyl esters.  The products mixed with coupling components are used in the preparation of insoluble azo dyestuffs on the fibre (c.f. Group IV (c)).  Examples are provided illustrating the preparation of diazoamino compounds from certain of the above specified dicarboxylic acids and diazo compounds of the following amines 4-chloro- and 5-nitro - 2 - aminotoluene, 5 - nitro - and 4 - diethylsulphonamidoanisol and 1 - amino - 5 - dimethylsulphonamido - 2 - methylbenzene.  The starting dicarboxylic acids may be made by condensing 1-halogeno-benzene-2,4-dicarboxylic acids with appropriate amines or with ammonia to yield a 1-aminobenzene-2,4-dicarboxylic acid which is condensed with compounds containing reactive halogen atoms such as glycol chlorhydrins, glycerol chlorhydrin, monochloracetic acid and its derivatives substituted at the COOH group, chloropropionic acids, 3-chloro-2-hydroxy-propane-sulphonic acid or with addition products of an aldehyde with sodium bisulphite. Examples illustrate the preparation of 1 - n - butyl -, - cyclohexyl-and-methylaminobenzene - 2,4 - dicarboxylic acids and N - (2,4-dicarboxyphenyl)-glycine by treating 1-chlorobenzene - 2,4 - dicarboxylic acid with the appropriate amine in the presence of caustic soda, copper powder and copper sulphate.ALSO:A printing paste for development on cellulosic fibres by means of steam contains a compound of the formula <FORM:0766609/IV(b)/1> where R is an aryl residue and X is an alkyl or cycloalkyl group which may be substituted, or a water-soluble salt thereof. Compounds in which R is derived from amines of accentuated basic character, e.g. chloroanilines, toluidines, cresidines, anisidines, which may be halogenated, monoacylated b -diamines, which may be halogenated, alkylated or alkoxylated, benzidine or o-dianisidine or in which X is a group containing at least 3 carbon atoms and R is derived from amines of less basic character than those listed above, e.g. nitro-analines, -toluidines, -anisidines and -cresidines and dichloranilines, may be used in neutral steaming processes. Acidsteaming increases the rate of colour development and the steaming process may be completed in from 30 seconds to 1 minute by the use of an acid vapour. Acidsteaming, or passage through an acid bath, may also be an advantage when using compounds in which X contains less than 3 carbon atoms or when using compounds obtained from amines of less basic character.  The paste may be made by dissolving the diazoamino-compound in a dilute alkali, with or without the addition of alcohol or dyeing assistants, and admixing with a thickener such as starch-tragacanth.  The preparation of the diazoamino-compounds is described (see Group IV(b)).  In example (10) cotton or other natural or regenerated fibres are printed with a paste prepared from a diazoamino compound made from 4-chloro-2-aminotoluene and 1-n-butylamino - benzene - 2, 4 - dicarboxylic acid, caustic soda, ethanol, the sodium salt of the o-phenetidide of b -hydroxynaphthoic acid and starch-tragacanth, a red colour being developed by neutral steaming.