Patent GB-991204-A (GB)
Title: Improvements relating to new substituted 2-(2-hydroxyphenyl)-benztriazole compounds
IPC: C08K5/3475
Filed: 1962-06-15
Abstract: The invention comprises substituted 2-(21-hydroxyphenyl)-benztriazoles of the general formula <FORM:0991204/C2/1> wherein one of X1 and X2 is the group <FORM:0991204/C2/2> in which R1 represents hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, R2 represents an alkyl, alkenyl, cycloalkyl, aralkyl, aralkenyl or aryl radical and wherein the aryl radical can be substituted by halogen, alkoxy, alkyl, free or modified carboxyl groups and the alkyl group can be further substituted by halogen, etherified mercapto, free or modified hydroxy groups, primary, secondary or tertiary amino groups and free or modified carboxyl groups, n is 1 or 2 and if n is 1, R1 and R2, together with the amino nitrogen atom, can form a ring when R1 is a carbonyl or unsubstituted or alkyl-substituted methylene group and R2 is an alkylene or alkylidene group, and wherein the nucleus A may be substituted at the 4, 5 or 6 positions by alkyl, alkoxy, carboxyl, carboxylic acid ester or amide, sulphonic acid amide, alkylsulphonyl groups or halogens and the nucleus B may be substituted at the 41 position by alkyl, cycloalkyl, aralkyl or aryl groups, alkoxy groups or halogens and the other X is hydrogen or a substituent mentioned for the 41 position. These compounds may be prepared by reacting a 2-(21-hydroxyphenyl)-benztriazole, which may be substituted at the 31 or 51 position, with the N-methylol derivative of a carboxylic acid amide or urethane or a functional derivative thereof in the presence of an acid condensing agent, preferably anhydrous sulphuric acid.  In certain preparations a mixture of formaldehyde and carbacylamine may be employed instead of the N-methylol compound.  Other methods of preparation are: (1) reduction of a 2-nitro-21 - hydroxy - 31 - X1 - 51 - X2 - 1,11 azobenzene; and (2) acylation, advantageously in an organic solvent, of a 2 - (21 - hydroxy - 31 or 51-aminophenyl) - benztriazole and subsequent partial saponification should the 21-hydroxyl group have been acylated.  2-(21-Hydroxy-31 or 51-carbacylaminomethyl phenyl) benztriazole compounds having the carboxylic acid radical substituted in the a  or b  position by an -OR, -SR or <FORM:0991204/C2/3> group, wherein R, R1 and R11 represent aliphatic, cycloaliphatic, araliphatic or aromatic radicals and R1 and R11 can also represent hydrogen or, together with the amino nitrogen atom, form a heterocyclic ring, may also be obtained by the reaction of a 2-(21-hydroxy-31 or 51- a - or b -halogen-alkanoylamino methyl phenyl) benztriazole compound with an organic hydroxyl compound, mercaptan or primary or secondary amine. Said carbacylaminomethyl compounds wherein the carboxylic acid is substituted in the b -position may also be prepared by adding an organic hydroxyl or thiol compound or ammonia or a primary or secondary amine to a 2(21-hydroxy-31- or 51-alkenoylaminomethylphenyl) benztriazole compound having an olefinic double bond in the a ,b  position to the carbonyl group. Several examples of the preparation and use of the compounds of the invention are given (see Divisions C3, C4, D1 and G2).  Reference has been directed by the Comptroller to Specification 878,362.ALSO:Synthetic and natural polymers are stabilized against light by the incorporation, usually as 0.001 to 5% by weight, therein of substituted 2 - (21 - hydroxyphenyl) - benztriazoles of the general formula <FORM:0991204/C3/1> wherein one of X1 and X2 is the group <FORM:0991204/C3/2> in which R1 represents hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, R2 represents an alkyl, alkenyl, cycloalkyl, aralkyl, aralkenyl or aryl radical and wherein the aryl radical can be substituted by halogen, alkoxy, alkyl, free or modified carboxyl groups and the alkyl group can be further substituted by halogen, etherified mercapto, free or modified hydroxy groups, primary, secondary or tertiary amino groups and free or modified carboxyl groups, n is 1 or 2 and if n is 1, R1 and R2, together with the amino nitrogen atom, can form a ring when R1 is a carbonyl or unsubstituted or alkylsubstituted methylene group and R2 is an alkylene or alkylidene group, and wherein the nucleus A may be substituted at the 4, 5 or 6 positions by alkyl, alkoxy, carboxyl, carboxylic acid ester or amide, sulphonic acid amide, alkylsulphonyl groups or halogens and the nucleus B may be substituted at the 41 position by alkyl, cycloalkyl, aralkyl or aryl groups, alkoxy groups or halogens and the other X is hydrogen or a substituent mentioned for the 41 position. Specified polymers are the polymers and copolymers of ethylenically unsaturated monomers, polyacrylic compounds, polyesters, polyamides, polyester resins, cellulose, cellulose esters and ethers, and proteins.  Reference has been directed by the Comptroller to Specification 878,362.ALSO:Lacquers used to protect light-sensitive materials from light contain at least one substituted 2 - (21 - hydroxyphenyl) - benztriazole of the general formula <FORM:0991204/C4-C5/1> wherein one of X1 and X2 is the group <FORM:0991204/C4-C5/2> in which R1 represents hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, R2 represents an alkyl, alkenyl, cycloalkyl, aralkyl, aralkenyl or aryl radical and wherein the aryl radical can be substituted by halogen, alkoxy, alkyl, free or modified carboxyl groups and the alkyl group can be further substituted by halogen, etherified mercapto, free or modified hydroxy groups, primary, secondary or tertiary amino groups and free or modified carboxyl groups, n is 1 or 2 and if n is 1, R1 and R2, together with the amino nitrogen atom, can form a ring when R1 is a carbonyl or unsubstituted or alkyl-substituted methylene group and R2 is an alkylene or alkylidene group, and wherein the nucleus A may be substituted at the 4, 5 or 6 positions by alkyl, alkoxy, carboxyl, carboxylic acid ester or amide, sulphonic acid amide, alkylsulphonyl groups or halogens and the nucleus B may be substituted at the 41-position by alkyl, cycloalkyl, aralkyl or aryl groups, alkoxy groups or halogens and the other X is hydrogen or a substituent mentioned for the 41-position. Intermediates in one of the methods of preparing compounds of Formula I are azo-dyes produced by diazo-coupling of o-nitro-anilines with 2-or 4-acyl-aminomethyl phenols.  Example 23 relates to the diazo-coupling of o-nitro-aniline and 2-heptane carboxylic acid amidomethylphenol.  Reference has been directed by the Comptroller to Specification 878,362.ALSO:Polyacrylonitrile fibres are proofed against u.v. light by treatment for 30 minutes at 80-100 DEG C. in a bath containing 1% by weight of 2-(21-hydroxy-31-N-methyl-N-cyclohexylamino -acetamidomethyl-51 methyl phenyl) benztriazole and 4% by weight formic acid, calculated on the weight of the fibres.  Reference has been directed by the Comptroller to Specification 878,362.