Patent GB-689977-A (GB)
Title: Manufacture of condensation products
IPC: C07C309/48
Filed: 1950-05-01
Abstract: Acyl-acetoacetyl compounds of amines which contain at least one water-solubilizing acid group are prepared by reacting an acetoacetyl compound of a primary amine which contains at least one water-solubilizing group, with an acylating agent which is derived from an acid with at least 3 carbon atoms.  If desired, the product may be reacted with a hydrolysing agent to split off one or more acetyl groups to give the corresponding acyl acetyl compounp.  The products may be of the general formul : <FORM:0689977/IV (b)/1> where -NH-R2-Y is the residue of a primary amine, <FORM:0689977/IV (b)/2> where -NH-R2-Y is the residue of a diazo-tizable amine, and -CO-R1-CO- is the residue of a dicarboxylic acid containing at least 3 carbon atoms, or <FORM:0689977/IV (b)/3> where <FORM:0689977/IV (b)/4> is the residue of a tetrasotizable amine, and in each formula R1-CO- is the residue of a carboxylic acid containing at least 3 carbon atoms, X is hydrogen or the acetyl group and Y is a water-solubilizing acid group, e.g. the sulphonic acid, sulphonic acid amide, or carboxyl group.  Aliphatic, aromatic or heterocyclic amines may be used.  Examples of the latter are dehydrothiotoluidine, 2 - aminothiazole, 2 - aminobenzothiazole, 2 - amino - 6-methoxy benzothiazole containing also a solubilizing group.  Other amines specified are the various monosulphonic acids of aniline, toluidines, o-anisidine, chloranilines and m and p-nitroanilines, aniline 2 : 4- and 2 : 5-disulphonic acids, 2 : 5-dichloroaniline-4-sulphonic acid, 4- and 5-sulphoanthranilic acid, 1-naphthylamine-2-sulphonic acid, 1-naphthylamine 4-, 5-, 6-, 7- or 8-sulphonamide or 4 : 8-or 3 : 6-disulphonic acid, 2-naphthylamine 6-6 : 8-, 4 : 8-, 3 : 6- or 5 : 7-disulphonic acid, 4 : 41 - diaminostilbene - 2 : 21 - disulphonic acid or 4 : 41-diaminodiphenyl-2 : 21-, 3 : 31-, di-, or 2-sulphonic acid.  Where the amine contains also -OH groups, the latter are protected, e.g. the O-esters with p-toluene sulphonic acid of 2-amino-5-oxynaphthalene-7-sulphonic acid, 2-amino-8-oxynaphthalene-6-sulphonic acid, 1 - amino - 8 - oxynaphthalene, 2 : 4- or 3 : 6-disulphonic acid, 2-(p-aminobenzoyl) - amino - 5 - oxynaphthalene - 7-sulphonic acid, 2 - (m - amino - benzoyl)-amino - 8 - oxynaphthalene - 6 - sulphonic acid, 2 - (p - aminophenyl) - amino - 5 or 8-oxynaphthalene-7 or 6-sulphonic acid may be used.  Azo compounds, e.g. 41-amino-4-oxy-1 : 11 - azobenzene - 3 - carboxylic acid are mentioned.  Acetoacetyl compounds are made by reacting such amines with diketene in aqueous medium. Acylating agents, e.g. acid chlorides of stearic acid, benzoic acid, 2-, 3, or 4-chloro-, ethoxy-, or methoxybenzene 1-carboxylic acid, 3- or 4-nitrobenzene-1-carboxylic acid, naphthalene 1- or 2-carboxylic acid, cinnamic acid, diphenyl-4 : 41-dicarboxylic acid or iso- or terephthalic acid are mentioned.  Compounds of the above formula where X is hydrogen can be coupled at X in the formation of azo dyestuffs.  In examples: (1) 1-acetoacetylaminobenzene - 4 - sulphonic acid is reacted with benzoyl chloride to give 1-benzoylacetoacetylamino benzene 4-sulphonic acid of formula <FORM:0689977/IV (b)/5> from which the acetyl group is removed by hydrolysis to give 1-benzoylacetylamino benzene-4-sulphonic acid-o-, m-, or p-Chlorobenzoyl chloride and the 2-chloro- or 2-methoxy derivatives of the sulphonic acid are specified as alternative starting materials; (2) by replacing the benzoyl chloride of (1) by terephthalic acid dichloride, 1 : 11 - terephthalolyl - acetoacetylaminobenzene 4 : 41-disulphonic acid and 1 : 11 - terephthaloyl - acetylaminobenzene-4 : 4-sulphonic acids are obtained.  The 2 : 21-and 3 : 31-disulphonic acids are similarly prepared; (3) 4 : 41 - di - (m - nitrobenzoylacetoacetyl) - aminostilbene - 2 : 21 - disulphonic acid is obtained in analogous manner and hydrolysed to 4 : 41-di-(m-nitrobenzoylacetyl)-amino - stilbene - 2 : 21 - disulphonic acid.  Similarly obtained are (4) 2-m-nitrobenzoylacetoacetyl - amino - 5 - (p - toluenesulpho)-oxynaphthalene-7 sulphonic acid and the corresponding de-acetylated product; (5) 4-benzoylacetoacetylamino - 41 - oxy - 1 : 11-azobenzene-31-carboxylic acid and 4-benzoylacetylamino - 41 - oxy - 1 : 11 - azobenzene-31-carboxylic acid; (6) 4-benzoylacetoacetylamino - 1 : 11 - azobenzene - 41 - sulphonic acid and 4 - benzoylacetylamino - 1 : 11 - azobenzene - 41 - sulphonic acid; (7) 4 - o - chlorobenzoylacetoacetylamino - 41 - oxy - 1 : 11-azobenzene-31 carboxylic acid, which is hydrolysed to 4-o-chlorobenzoylacetylamino-41-oxy-1 : 11 - azobenzene; (8) a  - furoyacetoacetyldehydrothio - p - toluidine sulphonic acid, which on hydrolysis yields a -furoylacetyldehydrothio-p-toluidine sulphonic acid; (9) benzoyl - acetoacetyl - amino - acetic acid, and an hydrolysis benzoyl-acetylamino acetic acid.  The acetoacetyl derivatives of the amines containing solubilizing groups which are employed as starting materials are obtained by reacting the appropriate amine with diketene.  In the examples, to obtain the acetoacetylamino compounds diketene is reacted with (1) sodium sulphanilate; (3) 4 : 41-diaminostilbene - 2 : 21 - disulphonic acid; (5) 4 - amino-41 - oxy - 1 : 11 - azobenzene - 31 - carboxylic acid; (9) glycocoll. Specification 632,341 is referred to.ALSO:Acyl-acetoacetyl compounds of amines which contain at least one water-solubilizing acid group (which includes sulphonic acid amide groups but not carboxylic acid amide groups) are prepared by reacting the acetoacetyl amino derivative of the amine with an acylating agent derived from an acid containing at least 3 carbon atoms.  If desired, the product may be reacted with a hydrolysing agent (e.g. ammonia) to split off one or more acetyl groups.  The starting materials may contain azo or stilbene groups.  Acylating agents mentioned are anhydrides or acid halides of aliphatic aromatic or heterocyclic mono or dicarboxylic acids, e.g. chlorides of higher fatty acids, benzoic acid, chlorobenzoic acids, methoxy- or ethoxy-benzoic acids, nitro-benzoic acids, naphthalene carboxylic acid, diphenyl 4 : 41-dicarboxylic acid, or iso- or terephthalic acid.  In examples: (3) 4 : 41-diphthalic acid.  In examples: (3) 4 : 41-di-(acetylamino) - stilbene - 2 : 21 - disulphonic acid is reacted with m- or p-nitrobenzoyl chloride to give 4 : 41-di-(m- or p-nitrobenzoyl-acetoacetyl) - aminostilbene - 2 : 21 - disulphonic acid, which on hydrolysis with ammonia yields 4 : 41 - di - (m- or p - nitrobenzoyl acetyl) - aminostilbene - 2 : 21 - disulphonic acid; (5) 4-acetoacetylamino-41-oxy-1 : 11-azobenzene - 31 - carboxylic acid is reacted with benzoyl chloride to give 4-benzoyl-acetoacetylamino - 41 - oxy - 1 : 11 - azobenzene-31-carboxylic acid which is hydrolysed to 4-benzoyl - acetylamino - 41 - oxy - 1 : 11 - azobenzene - 31 - carboxylic acid; (6) from 4-acetoacetylamino - 1 : 11 - azobenzene - 41-sulphonic acid are obtained similarly 4-benzoyl-acetoacetylamino - 41 - oxy - 1 : 11 - azobenzene-31 - carboxylic acid and 4 - benzoylacetylamino - 1 : 11 - azobenzene - 41 - sulphonic acid; (7) the corresponding o-chlorobenzoyl derivatives are obtained using o-chlorobenzoyl chloride in place of benzoyl chloride in the process of (5). Starting materials are obtained by reacting 4 : 41-diaminostilbene-2 : 21-disulphonic acid, 4-amino-41-oxy-1 : 11-azobenzene-31-carboxylic acid, and 4-amino-1 : 11-azobenzene-41-sulphonic acid, respectively with diketene.  The application of the process to other amines is illustrated (see Group IV (b)).  Specification 632,341, [Group IV (b)], is referred to.