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US4230867A Expired / Lapsed US ⏱️ 0.0 years remaining

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

Assignee: BASF Corp
•
Filing: 1977-11-25
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Granted: 1980-10-28
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Expires: 1997-11-25
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Abstract

Abstract A process for the production of 2-aryl-2H-benzotriazoles comprises reducing and cyclizing the corresponding o-nitroazobenzenes with hydrogen at a temperature in the range of about 20° C. to about 100° C. and at a pressure in the range of about 15 psia (1 atmosphere) to about 1000 psia (66 atmospheres) in an organic solvent mixture containing an organic amine at a pH over 10 in the presence of noble metal hydrogenation catalyst, preferably palladium. High yields of pure product are obtained with a concomitant reduction of undesired by-products and a reduction in effluent pollution problems.

Inventors

  • 👤 Siegfried Kintopf
  • 👤 Ulrich Kress

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-08 19:19
CPC Classifications
C; C07; C07D; C07D249/00; C07D249/16; C07D249/18; C07D249/20

Claims Analysis

Total Claims: 22
Claim 1
Independent Claim 312 words
A process for the production of 2-aryl-2H-benzotriazoles of the formula I ##STR7## 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, 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 ##STR8## with hydrogen at a temperature in the range of from about 20° C. to about 100° 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) while mixed in an alkaline organic solvent mixture comprising an organic amine in a concentration of at least 0.1 mole of amine per mole of o-nitroazobenzene in the presence of hydrogenation catalyst selected from the group consisting of the noble metals of Group VIII of the Periodic Table with the proviso that the hydrogenation catalyst cannot be palladium-on-asbestos, and with the proviso that, when R 1 , R 2 , R 3 , R 4 or R 5 is chlorine, the hydrogenation catalyst cannot be palladium, separating the catalyst which is suitable for recycle, and recovering the desired 2-aryl-2H-benzotriazole.
Claim 2
Dependent Claim 312 words
A process for the production of 2-aryl-2H-benzotriazoles of the formula I ##STR7## 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, 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 ##STR8## with hydrogen at a temperature in the range of from about 20° C. to about 100° 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) while mixed in an alkaline organic solvent mixture comprising an organic amine in a concentration of at least 0.1 mole of amine per mole of o-nitroazobenzene in the presence of hydrogenation catalyst selected from the group consisting of the noble metals of Group VIII of the Periodic Table with the proviso that the hydrogenation catalyst cannot be palladium-on-asbestos, and with the proviso that, when R 1 , R 2 , R 3 , R 4 or R 5 is chlorine, the hydrogenation catalyst cannot be palladium, separating the catalyst which is suitable for recycle, and recovering the desired 2-aryl-2H-benzotriazole.
Claim 3
Dependent Claim 37 words
A process according to claim 1 which further comprises removing the noble metal catalyst by filtration, distilling the organic solvent to recover the crude product, and purifying the crude product by removing amine impurities by acid extraction.
Claim 4
Dependent Claim 55 words
A process according to claim 1 wherein the hydrogenation catalyst is selected from the group consisting of palladium, platinum and rhodium, and the organic solvent mixture consists of a water-miscible organic alcohol or ether, optionally containing non-polar hydrocarbon solvent, with at least 0.1 mole of organic amine per mole of o-nitroazobenzene being reduced and cyclized.
Claim 5
Dependent Claim 21 words
A process according to claim 3 wherein the organic solvent mixture comprises toluene and methanol and the organic amine is diethylamine.
Claim 6
Dependent Claim 18 words
A process according to claim 3 wherein the organic solvent comprises isopropanol and the organic amine is diethylamine.
Claim 7
Dependent Claim 20 words
A process according to claim 3 wherein at least 0.9 mole of organic amine per mole of o-nitroazobenzene is used.
Claim 8
Dependent Claim 12 words
A process according to claim 1 wherein the hydrogenation catalyst is palladium.
Claim 9
Dependent Claim 17 words
A process according to claim 7 characterized in that said palladium is composited on charcoal or alumina.
Claim 10
Dependent Claim 73 words
A process according to claim 7 for the production of a compound of formula I wherein R 1 is hydrogen, R 2 is hydrogen, lower alkyl of 1 to 2 carbon atoms, methoxy or carboxy, R 3 is alkyl of 1 to 12 carbon atoms, cyclohexyl, phenyl, α-methylbenzyl or carboxyethyl, R 4 is hydrogen, hydroxyl or methyl, and R 5 is hydrogen, alkyl of 1 to 12 carbon atoms, cyclohexyl, benzyl or α-methylbenzyl.
Claim 11
Dependent Claim 51 words
A process according to claim 7 for the production of a compound of formula I wherein R 1 is hydrogen, R 2 is hydrogen, R 3 is methyl, sec-butyl, tert-butyl, tert-amyl, tert-octyl, cyclohexyl or carboxyethyl, R 4 is hydrogen, and R 5 is hydrogen, methyl, tert-butyl, sec-butyl, tert-amyl, tert-octyl or α-methylbenzyl.
Claim 12
Dependent Claim 11 words
A process according to claim 7 for the production of 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole.
Claim 13
Dependent Claim 11 words
A process according to claim 7 for the production of 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole.
Claim 14
Dependent Claim 11 words
A process according to claim 7 for the production of 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole.
Claim 15
Dependent Claim 12 words
A process according to claim 1 wherein the hydrogenation catalyst is rhodium.
Claim 16
Dependent Claim 15 words
A process according to claim 14 characterized in that said rhodium is composited on charcoal.
Claim 17
Dependent Claim 76 words
A process according to claim 14 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 18
Dependent Claim 56 words
A process according to claim 14 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 19
Dependent Claim 11 words
A process according to claim 14 for the production of 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.
Claim 20
Dependent Claim 11 words
A process according to claim 14 for the production of 5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole.
Claim 21
Dependent Claim 36 words
A process according to claim 1 wherein the hydrogenation catalyst is selected from the group consisting of palladium, platinum and rhodium, and the organic solvent consists essentially of an organic aliphatic or alicyclic amine or morpholine.
Claim 22
Dependent Claim 59 words
A process according to claim 1 wherein the organic amine is selected from the group consisting of primary aliphatic amines with alkyl groups of 1 to 6 carbon atoms, secondary aliphatic amines with alkyl groups of 1 to 6 carbon atoms, tertiary aliphatic amines with alkyl groups of 1 to 6 carbon atoms, piperidine, piperazine, morpholine, pyrrolidine and guanidine.

References Cited (Backward Citations)

US3978074A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1983-10-28 1984-04-28 1984-10-28 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1987-10-28 1988-04-28 1988-10-28 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1991-10-28 1992-04-28 1992-10-28 $7700.00 Window Closed / Lapsed

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