Patent GB-716338-A (GB)
Title: Manufacture of compounds containing two 1:2:3-triazole rings
IPC: C07D249/22
Filed: 1952-01-07
Abstract: The invention comprises bis-naphthotriazoles of the formula <FORM:0716338/IV (b)/1> where R and R2 are the residues of the same or different naphthalene sulphonic acids attached in the 1 : 2-positions and R1 is a p-phenylene group; all the nuclei may contain further substituents.  These are made by (1) coupling a diazotized amine X-R1-NH2 (X being a substituent convertible to amino) with an o-coupling naphthylamine-sulphonic acid, oxidising the resulting NH2-R-N=N-R1-X to the triazole <FORM:0716338/IV (b)/2> converting X to amino, diazotizing, coupling with another mol. of the same or different o-coupling naphthylamine-sulphonic acid and oxidizing the azo product; (2) preparing the aminoazo compound NH2-R-N=N-R1-X as in (1), converting X to amino, diazotizing, coupling with a naphthylamine-sulphonic acid to give a disazo compound NH2-R-N= N-R1-N=N-R2-NH2 and oxidizing the latter; (3) tetrazotizing p-phenylene diamine (or nuclear substitution derivative thereof) coupling with two mols. of the same or different o-coupling naphthylamine-sulphonic acids to produce the disazo compound of (2), and oxidizing.  The naphthalene nuclei are preferably free from hydroxyl groups but may contain halogen, alkyl, alkoxy, keto, cyano, tertiary amino or acylamino substituents.  The benzene nucleus R1 may carry halogen, alkyl, alkoxy, keto, cyano, polyglycol ether, carboxylic or sulphonic acid substituents.  The group X is preferably nitro or acylamino, and is converted to amino by reduction (e.g. iron/acetic acid, sodium sulphide or catalytic hydrogenation) or hydrolysis (e.g. with caustic alkali).  Oxidation of the o-aminoazo compounds may be effected with chromic acid, hypochlorites or ammoniacal cupric salts.  The products form alkali metal, ammonium and amine salts, e.g. with methylamine, diethylamine or triethanolamine.  They are fluorescent brightening agents.  Examples show the preparation of 1-(31 : 61-disulphonaphtho-11 : 21-triazolyl)-4-(61-sulphonaphtho - 11 : 21 - triazolyl) - benzene from N-monoacetyl-p-phenylene diamine by method (2), 1 : 4 - bis - (31 : 61 - disulphonaphtho - 11 : 21 - triazolyl)-benzene from p-nitraniline by method (1), 1 : 4 - bis - (51 : 71 - disulphonaphtho - 11 : 21 - triazolyl)-benzene from N-monoacetyl-p-phenylene diamine by method (1) (the acetyl group is split off before the first oxidation), 1-(51 : 71-disulphonaphtho - 11 : 21 - triazolyl) - 4 - (61 - sulphonaphtho - 11 : 21 - triazolyl) - benzene from p-nitraniline by method (1), and 1-(51 : 71-disulphonaphtho - 11 : 21 - triazolyl) - 4 - (31 : 61 - disulphonaphtho - 11 : 21 - triazolyl) - benzene from p-nitraniline or N-monoacetyl-p-phenylene diamine by method (1).  Specification 683,895 is referred to.ALSO:Bis-naphthotriazoles of the formula: <FORM:0716338/IV(c)/1> where R and R2 are the same or different sulphonated naphthalene residues attached in the 1 : 2-positions and R1 is a p-phenylene group (which may be substituted), and their alkali metal, ammonium and amine salts, are applied to dyed or undyed materials for the purpose of brightening them.  The materials may be impregnated with aqueous solutions of the compounds and then dried.  They may be used in cojunction with washing agents such as soaps, salts of sulphonated 2-(higher alkyl)-benzimidazoles, monoesters of 4-sulphophthalic acid with higher fatty alcohols, fatty alcohol sulphates and condensation products of higher fatty acids with hydroxy- or amino-sulphonic acids.  The materials treated may be fibres or films of polyamides and other synthetic polymers, wool, silk, cotton, linen or regenerated cellulose.  Examples are given of the washing of cotton goods with soap and the sodium salt of 1-(3\sv : 6\sv-disulphonaphtho-1\sv : 2\sv-triazolyl)-4-(6\sv-sulphonaphtho-1\sv : 2\sv-triazolyl)-benzene. The treatment of printed cellulose materials is also mentioned. Specification 683,895 is referred to.  The preparation of the following aminoazo compounds is described, R and R2 being sulphonated naphthalene residues, R1 a p-phenylene group (which may be substituted and X a group convertible to amino, such as nitro or acylamino:-(1) NH2-R1-X --> R-NH2, and X subsequently converted to amino; (2) NH2-R-N- = N-R1-NH2 --> R2-NH2; (3) the triazole <FORM:0716338/IV(c)/2> (X converted to amino) --> R2-NH2; (4) R1(NH2)2 \sQ R-NH2 and R2-NH2. In each case coupling takes place ortho to the amino group. Examples of (1) are 4-aminoacetanilide --> 2-naphthylamine-3 : 6- or 5 : 7-disulphonic acid (hydrolysed) and 4-nitroaniline --> same components; (2) 2-naphthylamine-3 : 6-disulphonic acid \sM 4-amino-acetanilide (hydrolysed) --> 2-naphthylamine-6-sulphonic acid; and (3) 4-(3\sv : 6\sv-disulphonaphtha-1\sv : 2\sv-triazolyl)-aniline --> 2-naphthylamine-3 : 6-disulphonic acid, 4-(5\sv : 7\sv-disulphonaphtho-1\sv : 2\sv-triazolyl)-aniline --> 2-naphthylamine-6-sulphonic acid or -3 : 6- or -5 : 7-disulphonic acid.  Other naphthalene derivatives are mentioned and possible substituents in the nuclei are listed.ALSO:Bis-naphthotriazoles of the formula <FORM:0716338/III/1> where R and R2 are the same or different sulphonated naphthalene residues attached in the 1 : 2-positions and R1 is a p-phenylene group (which may be substituted), and their alkali metal, ammonium and amine salts, are incorporated in washing agents for the purpose of brightening fibrous materials. The washing agents may be soaps, salts of sulphonated 2-(higher alkyl)-benzimidazoles, monoesters of 4-sulphophthalic acid with higher fatty alcohols, fatty alcohol sulphates or condensation products of higher fatty acids with hydroxy- or aminosulphonic acids. An example shows soap mixed with the sodium salt of 1-(31 : 61-disulphonaphtho-11 : 21-triazolyl)-4-(61-sulphonaphtho-11 : 21-triazolyl)-benzene.  Other suitable naphthotriazoles are mentioned.  Specification 683,895 is referred to.