Patent GB-785988-A (GB)
Title: Basic monoazo dyes of the benzene-azo-benzene series
IPC: C09B29/08
Filed: 1955-05-02
Abstract: The invention comprises water-soluble dyestuffs of formula: <FORM:0785988/IV (b)/1> where R1 is lower alkyl, R2 is lower alkyl or hydroxyalkyl, R3 is lower alkyl, hydroxyalkyl and monocyclic aralkyl and R1, R2 and R3 with N may be a monocyclic heterocyclic group, R4 is H, lower alkyl, hydroxyalkyl, acetylalkyl, cyanoalkyl, chloroalkyl and monocyclic aryl, R5 is H, lower alkyl, hydroxyalkyl or cyanoalkyl, X and Y are H, lower alkyl, halogen or alkoxyl, X1 is H, lower alkyl and halogen, Y1 is H and lower alkyl but when R1, R2, R3, R4 and R5 are all Me at least one of X, X1, Y or Y1 is lower alkyl, alkoxyl or halogen, 2 is an alkylene radicle of 1-3 carbon atoms, A is an inorganic or organic anion and the group containing 2 is in m or preferably p-position to the azo link.  They may be made by coupling appropriate diazotized amino-phenacyl ammonium salts and arylamines or by quaternizing the corresponding azo dyestuffs, e.g. by treatment with alkyl chlorides, bromides or sulphates or alkyl esters of organic sulphonic acids, e.g. methyl, ethyl, propyl and butyl p-tosylates.  Anions in the dyestuffs may be exchanged by normal metathetical reactions and as well as the salts instanced above phosphates are described.  The products dye polyacrylic fibres, which may be admixed with other fibres such as wool and cellulosic fibres, in red to red-orange or brown shades. In examples, and a Table, dyestuffs are prepared from the following diazo components p-aminophenacyl-, (3-amino-4-methyl- and -methoxy, 4-amino-2-chloro-, -3-bromo-, -2,5-dimethyl- and -3,5-dibromo-phenacyl)-, [2-(p-aminobenzoyl) ethyl and propyl]-and (p - amino - a  - methyl - phenacyl) - trimethyl - ammonium chlorides, p - aminophenacyl - pyridinium chloride, p - aminophenacyl - benzyldimethyl -, - methyl - di - (b -hydroxyethyl)- and -dimethyl-b -hydroxyethylammonium chlorides and [3-(p-aminobenzoyl) propyl] triethyl ammonium bromide, the coupling components being m-chloro- and methyl-N,N-diethylanilines, 2,5-, 3,5- and 2,6-dimethylanilines, N,N - di - (b  - cyano - hydroxy and ethyl)-anilines and -m-toluidines, m-toluidine, 2-methoxy-5-methyl-aniline, 5-chloro- and N - ethyl - o - toluidines, N - b  - cyanoethylaniline and o- and m-toluidines, N-methyl diphenylamine, N - b  - cyanoethyl - N - methyl-, -ethyl- and -b -hydroxyethyl-anilines, N-b -cyanoethyl - N - b  - hydroxyethyl - m - toluidine, N - b  - chloroethyl - N - ethyl - aniline, m-chloro-N,N-dimethyl- and o-chloro-N-b -cyanoethyl - anilines and 4 - (N - methylanilino)-butanone-2.ALSO:p - Acetaminophenacyl chloride [2 - (p-acetaminobenzoyl) ethyl chloride and p-acet-amino-b -methyl phenacyl chloride are made by treating acetanilide in the presence of aluminium chloride in sym.-tetrachlorethane with chloracetyl, a -chlorpropionyl and a -chlorpropionyl chlorides respectively and the products may be converted to the corresponding trimethyl ammonium chlorides by treatment with trimethylamine and hydrolysis of the acetamino group with hydrochloric acid.  (3-Amino-4-methyl) -, (4 - amino - 2 - chloro -), (4 - amino-2,5 - dimethyl) - and (3 - amino - 4 - methoxy)-phenacyl trimethyl ammonium chlorides may similarly be obtained from the appropriately substituted acetanilide. p-Acetaminophenacyl pyridinium and dimethyl (a -hydroxyethyl) ammonium and benzyldimethyl ammonium chlorides are made by treating p-acetaminophenacyl chloride in acetone with pyridine, a -dimethylaminoethanol and benzyldimethylamine respectively. 4-Amino-3-bromphenacyl trimethyl ammonium chloride is made by brominating p-acetaminophenacyl chloride in acetic acid to yield the 3-bromo-derivative thereof, treating with trimethylamine in acetone and hydrolysing with hydrochloric acid.  4-Amino - 3,5 - dibromophenacyl trimethyl ammonium chloride is made by hydrolysing p-acetamino - phenacyl - trimethyl ammonium chloride to the free p-amino derivative and brominating the product in acetic acid solution.  Free bases corresponding to some of the above anilides are obtained by hydrolysis of the acetamino group and quaternary ammonium sulphates and phosphates may be obtained on hydrolysis with sulphuric and phosphoric acids.  Bromides and alkyl salts of p-toluenesulphonic acid are also described. 4-(N-methylanilino)-butanone-2 is made by treating methyl vinyl ketone as an 85 per cent aqueous solution with N-methylaniline at 60-65 DEG  C.  The products are dyestuff intermediates, cf. Group IV (c).