Process for the production of 2-aryl-2H-benzotriazoles

Claim 2

A process for the production of 2-aryl-2H-benzotriazoles of the formula I. ##STR8## wherein R 1 is hydrogen or chlorine, R 2 is hydrogen, chlorine, lower alkyl of 1 to 4 carbon atoms, lower alkoxy of 1 to 4 carbon atoms or carboalkoxy of 2 to 9 carbon atoms, carboxy or -SO 3 H, R 3 is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl, phenyl substituted with alkyl groups, said alkyl groups having 1 to 8 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, carboalkoxy of 2 to 9 carbon atoms, chlorine, carboxyethyl or phenylalkyl of 7 to 9 carbon atoms, R 4 is hydrogen, lower alkyl of 1 to 4 carbon atoms, lower alkoxy of 1 to 4 carbon atoms, chlorine or hydroxyl, and R 5 is hydrogen, alkyl of 1 to 12 carbon atoms, chlorine, cycloalkyl of 5 to 6 carbon atoms or phenylalkyl of 7 to 9 carbon atoms, which comprises reducing and cyclizing the corresponding o-nitroazobenzene intermediate (II) ##STR9## with carbon monoxide at a temperature in the range of from about 20° C to about 150° C and at a pressure in the range of from about 15 psia (1.05 kg/cm 2 ,1 atmosphere) to about 1000 psia (70 kg/cm 2 ,66 atmospheres) when mixed in an alkaline medium having a pH greater that 10 in the presence of at least 0.05 mol, per mol of said o-nitroazobenzene intermediate, of a copper compound-amine complex catalyst consisting essentially of (a) a copper compound selected from the group consisting of copper oxide, copper hydroxide, copper carbonate and a copper salt of a weak organic acid, and (b) an amine of the formula R.sup.6 --NH--R.sup.7 wherein R 6 is hydrogen; or when R 7 is alkyl of 1 to 6 carbon atoms, R 6 is hydrogen or alkyl of 1 to 6 carbon atoms; R 7 is hydrogen, alkyl of 1 to 6 carbon atoms, β-hydroxyethyl, --(CH 2 ) n NH 2 where n is 4 to 6, or --(C x H 2x NH) y (C x H 2x )NH 2 where x is 2 or 3 and y is 0 to 3; or R 6 and R 7 together are alkylene of 4 to 5 carbon atoms, said complex containing at least two mols of said amine per mol of said copper compound, and recovering the desired 2-aryl-2H-benzotriazole.

Claim 3

A process according to claim 1 wherein the copper compound is copper acetate or copper carbonate.

Claim 4

A process according to claim 2 wherein the copper compound is copper acetate.

Claim 5

A process according to claim 1 wherein the amine is 1,3-diaminopropane or piperidine.

Claim 6

A process according to claim 1 for the production of a compound of formula I wherein R 1 is hydrogen, R 2 is hydrogen, chlorine, lower alkyl of 1 to 2 carbon atoms, methoxy or carboxy, R 3 is alkyl of 1 to 12 carbon atoms, cyclohexyl, phenyl, chlorine, α-methylbenzyl or carboxyethyl, R 4 is hydrogen, hydroxyl or methyl, and R 5 is hydrogen, alkyl of 1 to 12 carbon atoms, chlorine, cyclohexyl, benzyl or α-methylbenzyl.

Claim 7

A process according to claim 1 for the production of a compound of formula I wherein R 1 is hydrogen, R 2 is hydrogen or chlorine, R 3 is methyl, sec-butyl, tert-butyl, tert-amyl, tert-octyl, methoxy, cyclohexyl, chlorine or carboxyethyl, R 4 is hydrogen, and R 5 is hydrogen, chlorine, methyl, tert-butyl, sec-butyl, tert-amyl, tert-octyl or α-methylbenzyl.

Claim 8

A process according to claim 1 for the production of 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole.

Claim 9

A process according to claim 1 for the production of 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole.

Claim 10

A process according to claim 1 for the production of 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole.

Claim 11

A process according to claim 1 for the production of 2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

Claim 12

A process according to claim 1 for the production of 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

Claim 13

A process according to claim 1 for the production of 5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole.

Claim 14

A process according to claim 1 wherein the alkaline medium is an aqueous alkaline organic medium.

Claim 15

A process for the production of 2-aryl-2H-benzotriazole N-oxides of the formula Ia ##STR10## wherein R 1 is hydrogen or chlorine, R 2 is hydrogen, chlorine, lower alkyl of 1 to 4 carbon atoms, lower alkoxy of 1 to 4 carbon atoms or carboalkoxy of 2 to 9 carbon atoms, carboxy or --SO 3 H, R 3 is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl, phenyl substituted with alkyl groups, said alkyl groups having 1 to 8 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, carboalkoxy of 2 to 9 carbon atoms, chlorine, carboxyethyl or phenylalkyl of 7 to 9 carbon atoms, R 4 is hydrogen, lower alkyl of 1 to 4 carbon atoms, lower alkoxy of 1 to 4 carbon atoms, chlorine or hydroxyl, and R 5 is hydrogen, alkyl of 1 to 12 carbon atoms, chlorine, cycloalkyl of 5 to 6 carbon atoms or phenylalkyl of 7 to 9 carbon atoms, which comprises reducing and cyclizing the corresponding o-nitroazobenzene intermediate (II) ##STR11## with carbon monoxide at a temperature in the range of from about 20° C to about 150° C and at a pressure in the range of from about 15 psia (1.05 kg/cm 2 , 1 atmosphere) to about 1000 psia (70 kg/cm 2 , 22 atmospheres) when mixed in an alkaline medium having a pH greater than 10 in the presence of at least 0.05 mol, per mol of said o-nitroazobenzene intermediate, of a copper compound-amine complex catalyst consisting essentially of (a) a copper compound selected from the group consisting of copper oxide, copper hydroxide, copper carbonate and a copper salt of a weak organic acid, and (c) an amine of the formula R.sup.6 --NH--R.sup.7 wherein R 6 is hydrogen, or when R 7 is alkyl of 1 to 6 carbon atoms, R 6 is hydrogen or alkyl of 1 to 6 carbon atoms; R 7 is hydrogen, alkyl of 1 to 6 carbon atoms, β-hydroxyethyl, --(CH 2 ) n NH 2 where n is 4 to 6, --(C x H 2x NH) y (C x H 2x )NH 2 where x is 2 or 3 and y is 0 to 3; or R 6 and R 7 together are alkylene of 4 to 5 carbon atoms, said complex containing at least two mols of said amine per mol of said copper compound, and recovering the desired 2-aryl-2H-benzotriazole N-oxide.

Claim 16

A process for the production of 2-aryl-2H-benzotriazole N-oxides of the formula Ia ##STR10## wherein R 1 is hydrogen or chlorine, R 2 is hydrogen, chlorine, lower alkyl of 1 to 4 carbon atoms, lower alkoxy of 1 to 4 carbon atoms or carboalkoxy of 2 to 9 carbon atoms, carboxy or --SO 3 H, R 3 is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl, phenyl substituted with alkyl groups, said alkyl groups having 1 to 8 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, carboalkoxy of 2 to 9 carbon atoms, chlorine, carboxyethyl or phenylalkyl of 7 to 9 carbon atoms, R 4 is hydrogen, lower alkyl of 1 to 4 carbon atoms, lower alkoxy of 1 to 4 carbon atoms, chlorine or hydroxyl, and R 5 is hydrogen, alkyl of 1 to 12 carbon atoms, chlorine, cycloalkyl of 5 to 6 carbon atoms or phenylalkyl of 7 to 9 carbon atoms, which comprises reducing and cyclizing the corresponding o-nitroazobenzene intermediate (II) ##STR11## with carbon monoxide at a temperature in the range of from about 20° C to about 150° C and at a pressure in the range of from about 15 psia (1.05 kg/cm 2 , 1 atmosphere) to about 1000 psia (70 kg/cm 2 , 22 atmospheres) when mixed in an alkaline medium having a pH greater than 10 in the presence of at least 0.05 mol, per mol of said o-nitroazobenzene intermediate, of a copper compound-amine complex catalyst consisting essentially of (a) a copper compound selected from the group consisting of copper oxide, copper hydroxide, copper carbonate and a copper salt of a weak organic acid, and (c) an amine of the formula R.sup.6 --NH--R.sup.7 wherein R 6 is hydrogen, or when R 7 is alkyl of 1 to 6 carbon atoms, R 6 is hydrogen or alkyl of 1 to 6 carbon atoms; R 7 is hydrogen, alkyl of 1 to 6 carbon atoms, β-hydroxyethyl, --(CH 2 ) n NH 2 where n is 4 to 6, --(C x H 2x NH) y (C x H 2x )NH 2 where x is 2 or 3 and y is 0 to 3; or R 6 and R 7 together are alkylene of 4 to 5 carbon atoms, said complex containing at least two mols of said amine per mol of said copper compound, and recovering the desired 2-aryl-2H-benzotriazole N-oxide.

Claim 17

A process according to claim 14 wherein the copper compound is copper acetate or copper carbonate.

Claim 18

A process according to claim 15 wherein the copper compound is copper acetate.

Claim 19

A process according to claim 14, wherein the amine is 1,3-diaminopropane or piperidine.

Claim 20

A process for the production of 2-aryl-2H-benzotriazoles of the formula I ##STR12## wherein R 1 is hydrogen or chlorine, R 2 is hydrogen, chlorine, lower alkyl of 1 to 4 carbon atoms, lower alkoxy of 1 to 4 carbon atoms or carboalkoxy of 2 to 9 carbon atoms, carboxy or --SO 3 H, R 3 is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl, phenyl substituted with alkyl groups, said alkyl groups having 1 to 8 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, carboalkoxy of 2 to 9 carbon atoms, chlorine, carboxyethyl or phenylalkyl of 7 to 9 carbon atoms, R 4 is hydrogen, lower alkyl of 1 to 4 carbon atoms, lower alkoxy of 1 to 4 carbon atoms, chlorine or hydroxyl, and R 5 is hydrogen, alkyl of 1 to 12 carbon atoms, chlorine, cycloalkyl of 5 to 6 carbon atoms or phenylalkyl of 7 to 9 carbon atoms, which comprises reducing the 2-aryl-2H-benzotriazole N-oxide intermediate (Ia) ##STR13## which carbon monoxide at a temperature in the range of from about 20° C to about 150° C and at a pressure in the range of from about 15 psia (1.05 kg/cm 2 , 1 atmosphere) to about 1000 psia (70 kg/cm 2 , 66 atmospheres) when mixed in an alkaline medium having a pH greater than 10 in the presence of at least 0.05 mol, per mol of said 2-aryl-2H-benzotriazole N-oxide intermediate, of a copper compound-amine complex catalyst consisting essentially of (a) a copper compound selected from the group consisting of copper oxide, copper hydroxide, copper carbonate and a copper salt of a weak organic acid, and (b) an amine of the formula R.sup.6 --NH--R.sup.7 wherein R 6 is hydrogen; or when R 7 is alkyl of 1 to 6 carbon atoms, R 6 is hydrogen or alkyl of 1 to 6 carbon atoms; R 7 is hydrogen, alkyl of 1 to 6 carbon atoms, β-hydroxyethyl, --(CH 2 ) n NH 2 where n is 4 to 6, or --(C x H 2x NH) y (C x H 2x )NH 2 where x is 2 or 3 and y is 0 to 3; or R 6 and R 7 together are alkylene of 4 to 5 carbon atoms, said complex containing at least two mols of said amine per mol of said copper compound, and recovering the desired 2-aryl-2H-benzotriazole.

Claim 21

A process for the production of 2-aryl-2H-benzotriazoles of the formula I ##STR12## wherein R 1 is hydrogen or chlorine, R 2 is hydrogen, chlorine, lower alkyl of 1 to 4 carbon atoms, lower alkoxy of 1 to 4 carbon atoms or carboalkoxy of 2 to 9 carbon atoms, carboxy or --SO 3 H, R 3 is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl, phenyl substituted with alkyl groups, said alkyl groups having 1 to 8 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, carboalkoxy of 2 to 9 carbon atoms, chlorine, carboxyethyl or phenylalkyl of 7 to 9 carbon atoms, R 4 is hydrogen, lower alkyl of 1 to 4 carbon atoms, lower alkoxy of 1 to 4 carbon atoms, chlorine or hydroxyl, and R 5 is hydrogen, alkyl of 1 to 12 carbon atoms, chlorine, cycloalkyl of 5 to 6 carbon atoms or phenylalkyl of 7 to 9 carbon atoms, which comprises reducing the 2-aryl-2H-benzotriazole N-oxide intermediate (Ia) ##STR13## which carbon monoxide at a temperature in the range of from about 20° C to about 150° C and at a pressure in the range of from about 15 psia (1.05 kg/cm 2 , 1 atmosphere) to about 1000 psia (70 kg/cm 2 , 66 atmospheres) when mixed in an alkaline medium having a pH greater than 10 in the presence of at least 0.05 mol, per mol of said 2-aryl-2H-benzotriazole N-oxide intermediate, of a copper compound-amine complex catalyst consisting essentially of (a) a copper compound selected from the group consisting of copper oxide, copper hydroxide, copper carbonate and a copper salt of a weak organic acid, and (b) an amine of the formula R.sup.6 --NH--R.sup.7 wherein R 6 is hydrogen; or when R 7 is alkyl of 1 to 6 carbon atoms, R 6 is hydrogen or alkyl of 1 to 6 carbon atoms; R 7 is hydrogen, alkyl of 1 to 6 carbon atoms, β-hydroxyethyl, --(CH 2 ) n NH 2 where n is 4 to 6, or --(C x H 2x NH) y (C x H 2x )NH 2 where x is 2 or 3 and y is 0 to 3; or R 6 and R 7 together are alkylene of 4 to 5 carbon atoms, said complex containing at least two mols of said amine per mol of said copper compound, and recovering the desired 2-aryl-2H-benzotriazole.

Claim 22

A process according to claim 18 wherein the copper compound is copper acetate or copper carbonate.

Claim 23

A process according to claim 19 wherein the copper compound is copper acetate.

Claim 24

A process according to claim 18 wherein the amine is 1,3-diaminopropane or piperidine.