Patent GB-980886-A (GB)
IPC: C07D403/10
Filed: 1965-01-20
Abstract: The invention comprises substituted 2-(21-hydroxyphenyl)-benztriazole compounds of the general formula <FORM:0980886/C2/1> wherein one of X1 and X2 is the group <FORM:0980886/C2/2> wherein R1 represents hydrogen or an alkyl, alkenyl, cycloalkyl or aralkyl radical which may be substituted by carboxyl or carboxylic acid ester groups or R1 and "Acyl," together with the amino-nitrogen atom, can form a ring when R1 is a carbonyl or unsubstituted or alkyl-substituted methylene group and the other X represents, if attached to the 5-position, hydrogen, alkyl, alkoxy, carboxyl, carboxylic acid ester or amide, sulphonic acid amide or alkylsulphone groups or halogen and if attached to the 41-position, hydrogen, alkyl, cycloalkyl, aralkyl, aryl or alkoxy groups or halogen, and wherein the nucleus may be substituted in the 4- or 5-positions by alkyl or alkoxy groups or halogen and, if X2 is not acylamino of the formula <FORM:0980886/C2/3> also by carboxyl, carboxylic acid ester or amide, sulphonic acid amide or alkylsulphonyl groups and in the 31- or 51-positions by alkyl, cycloalkyl, aralkyl or aryl groups, alkoxy groups or halogens.  The "Acyl" group is a radical of the formula <FORM:0980886/C2/4> wherein X is a carbon atom or the radical <FORM:0980886/C2/5> and Y is oxygen, an imino group which with X and R2 forms a s-triazine or pyrimidine ring or, if X is carbon and provided R2 is an amino group, a sulphur atom, and R2 is an alkenyl cycloalkyl, aralkyl or substituted or unsubstituted alkyl or aryl group or if X is carbon R2 is hydrogen or an alkenyloxy, cycloalkyloxy, aralkyloxy or a substituted or unsubstituted alkoxy or aryloxy group, or a substituted or unsubstituted amino group, an imino group of a saturated monocyclic heterocycle or if R1 and R2 are linked together, together with X and R1, it represents the remainder of a lactam or dioxopyrrolidine ring. These compounds may be prepared by heating a 2 - (21 - hydroxyphenyl) - benztriazole compound having an acylatable amino group in the 41- or 5-position, said amino compounds being prepared, for example, by (a) reducing a 2-nitro - 21 - hydroxy - 41 - amino - 1,11 - azobenzene compound (see Division C4), (b) reducing a 2 - nitro - 5 - acylamino - 21 - hydroxy-1,11-azobenzene compound and saponifying the 2 - (21 - hydroxyphenyl) - 5 - acylaminobenztriazole compound so formed (c) oxidizing a 2,5-diamino - 21 - hydroxy - 1,11 - azobenzene compound, (d) oxidizing a 2,5-diamino-21-alkoxy-1,11-azobenzene compound and dealkylating the 2 - (21 - alkoxyphenyl) - 5 - aminobenztriazole formed, or (e) reducing the corresponding nitro compound.  Other methods of producing the compounds of the invention are: (1) oxidation of a 2-amino-21-hydroxy, or ester, particularly of sulphonic acids, -4,5- or 41-acylamino - 1,11 - azobenzene, (2) reduction of a 2 - nitro - 21 - hydroxy - 4,5- or 41 - acylamino -1,11-azobenzene, (3) dealkylation, or hydrolysis, of a 2-(21-alkoxy, or acyloxy, -phenyl)-benztriazole, and (4) modification of reactive groups in an existing compound of Formula I.  An intermediate of the formula <FORM:0980886/C2/6> may be isolated by the reduction of the corresponding 2 - nitro - 21 - hydroxy - 1,11 - azobenzene with hydrosulphite and may be converted into the desired triazole by catalytic or zinc dust reduction.  Several examples of the preparation and use of compounds of the invention are given (see Divisions B2, C3, C4 and G2).ALSO:Synthetic and natural polymers are stabilized against light by the incorporation, usually as 0.001 to 5% by weight, therein of a compound of the general formula <FORM:0980886/C3/1> wherein one of X1 and X2 is the group <FORM:0980886/C3/2> wherein R1 represents hydrogen or an alkyl, alkenyl, cycloalkyl or aralkyl radical which may be substituted by carboxyl or carboxylic acid ester groups or R1 and "Acyl," together with the amino-nitrogen atom, can form a ring when R1 is a carbonyl or unsubstituted or alkyl-substituted methylene group and the other X represents, if attached to the 5-position, hydrogen, alkyl, alkoxy, carboxyl, carboxylic acid ester or amide, sulphonic acid amide or alkylsulphone groups or halogen and if attached to the 41 position, hydrogen, alkyl, cycloalkyl, aralkyl, aryl or alkoxy groups or halogen, and wherein the nucleus may be substituted in the 4 or 5 positions by alkyl or alkoxy groups or halogen and, if X2 is not acylamino of the formula <FORM:0980886/C3/3> also by carboxyl, carboxylic acid ester or amide, sulphonic acid amide or alkylsulphonyl groups and in the 31 or 51 positions by alkyl, cycloalkyl, aralkyl or aryl groups, alkoxy groups or halogens.  The "Acyl" group is a radical of the formula <FORM:0980886/C3/4> wherein X is a carbon atom or the radical <FORM:0980886/C3/5> and Y is oxygen, an imino group which with X and R2 forms a S-triazine or pyrimidine ring, or if X is carbon and provided R2 is an amino group, a sulphur atom, and R2 is an alkenyl, cycloalkyl, aralkyl or substituted or unsubstituted alkyl or aryl group or if X is carbon R2 is hydrogen or an alkenyloxy, cycloalkyloxy, aralkyloxy or a substituted or unsubstituted alkoxy or aryloxy group or a substituted or unsubstituted amino group, an imino group of a saturated monocyclic heterocycle or if R1 and R2 are linked together, together with X and R1, it represents the remainder of a lactam or dioxopyrrolidine ring.  Specified polymers are the polymers and copolymers of ethylenically unsaturated monomers, polyacrylic compounds, polyesters, polyamides, polyester resins, cellulose, cellulose esters and ethers, and proteins.ALSO:Lacquers used to protect light-sensitive materials from light contain at least one compound of the general formula <FORM:0980886/C4-C5/1> wherein one of X1 and X2 is the group <FORM:0980886/C4-C5/2> Acyl, wherein R1 represents hydrogen or an alkyl, alkenyl, cycloalkyl or aralkyl radical which may be substituted by carboxyl or carboxylic acid ester groups or R1 and "Acyl," together with the amino-nitrogen atom, can form a ring when R1 is a carbonyl or unsubstituted or alkyl-substituted methylene group and the other X represents, if attached to the 5-position, hydrogen, alkyl, alkoxy, carboxyl, carboxylic acid ester or amide, sulphonic acid amide or alkylsulphone groups or halogen and if attached to the 41 position, hydrogen, alkyl, cycloalkyl, aralkyl, aryl or alkoxy groups or halogen, and wherein the nucleus may be substituted in the 4 or 5 positions by alkyl or alkoxy groups or halogen and, if X2 is not acylamino of the formula <FORM:0980886/C4-C5/3> Acyl also by carboxyl, carboxylic acid ester or amide, sulphonic acid amide or alkylsulphonyl groups and in the 31 or 51 positions by alkyl, cycloalkyl, aralkyl or aryl groups, alkoxy groups or halogens.  The "Acyl" group is a radical of the formula <FORM:0980886/C4-C5/4> R2 wherein X is a carbon atom or the radical <FORM:0980886/C4-C5/5> O and Y is oxygen, an imino group which with X and R2 forms a s-triazine or pyrimidine ring, or if X is carbon and provided R2 is an amino group, a sulphur atom, and R2 is an alkenyl, cycloalkyl, aralkyl or substituted or unsubstituted alkyl or aryl group or if X is carbon R2 is hydrogen or an alkenyloxy, cycloalkyloxy, aralkyloxy or a substituted or unsubstituted alkoxy or aryloxy group or a substituted or unsubstituted amino group, an imino group of a saturated monocyclic heterocycle or if R1 and R2 are linked together, together with X and R1, it represents the remainder of a lactam or dioxopyrrolidine ring.  In Example 43 a lacquer comprising a urea resin, hydrochloric acid, ethanol, butanol and 2 - (21 - hydroxyphenyl) - 5 - (dibutyl-aminoacetylamino - benztriazole is employed to treat bleached oak veneer.  Intermediates in the preparation of some of the compounds of formula I are amino-azo-dyes, e.g. those produced by diazo-coupling of o-nitro-anilines with m-amino-phenols, or o-nitro-anilines with phenols and reducing the nitro groups or by coupling diazotized o - hydroxy - or - alkoxy anilines with aromatic diamines.  A number of dyes are specified in the examples.ALSO:Light-sensitive materials are protected against the injurious effects of light by coating them with compositions containing at least one compound of the general formula: <FORM:0980886/B1-B2/1> wherein one of X1 and X2 is the group <FORM:0980886/B1-B2/2> wherein R1 represents hydrogen or an alkyl, alkenyl, cycloalkyl or aralkyl radical which may be substituted by carboxyl or carboxylic acid ester groups or R1 and "Acyl", together with the amino-nitrogen atom, can form a ring when R1 is a carbonyl or unsubstituted or alkylsubstituted methylene group and the other X represents, if attached to the 5-position, hydrogen, alkyl, alkoxy, carboxyl, carboxylic acid ester or amide, sulphonic acid amide or alkylsulphone groups or halogen and if attached to the 41 position, hydrogen, alkyl, cycloalkyl, aralkyl, aryl or alkoxy groups or halogen, and wherein the nucleus may be substituted in the 4 or 5 positions by alkyl or alkoxy groups or halogen and, if X2 is not acylamino of the formula:  <FORM:0980886/B1-B2/3> also by carboxyl, carboxylic acid ester or amide, sulphonic acid amide or alkylsulphonyl groups and in the 31 or 51 positions by alkyl, cycloalkyl, aralkyl or aryl groups, alkoxy groups or halogens.  The "Acyl" group is a radical of the formula:  <FORM:0980886/B1-B2/4> wherein X is a carbon atom or the radical <FORM:0980886/B1-B2/5> and Y is oxygen, an imino group which with X and R2 forms a s-triazine or pyrimidine ring, or if X is carbon and provided R2 is an amino group, a sulphur atom, and R2 is an alkenyl, cycloalkyl, aralkyl or substituted or unsubstituted alkyl or aryl group or if X is carbon R2 is hydrogen or an alkenyloxy, cycloalkyloxy, aralkyloxy or a substituted or unsubstituted alkoxy or aryloxy group or a substituted or unsubstituted amino group, an imino group of a