US 12,384,785 B2
Procedure for the formation of 2H-benzotriazole bodies and congeners
Reinhold Oehrlein, Rheinfelden-Herten (DE); and Gabriele Baisch, Binzen (DE)
Assigned to BASF SE, Ludwigshafen am Rhein (DE)
Appl. No. 17/311,196
Filed by BASF SE, Ludwigshafen am Rhein (DE)
PCT Filed Dec. 2, 2019, PCT No. PCT/EP2019/083232
§ 371(c)(1), (2) Date Jun. 4, 2021,
PCT Pub. No. WO2020/114936, PCT Pub. Date Jun. 11, 2020.
Claims priority of application No. 18210785 (EP), filed on Dec. 6, 2018.
Prior Publication US 2022/0017527 A1, Jan. 20, 2022
Int. Cl. C07D 487/04 (2006.01); C07D 249/20 (2006.01); C07D 471/04 (2006.01)
CPC C07D 487/04 (2013.01) [C07D 249/20 (2013.01); C07D 471/04 (2013.01)] 18 Claims
 
1. Process for the preparation of a benzotriazole compound according to the general formula (I):

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wherein R1 is hydrogen, linear or branched C1-C24alkyl, linear or branched C2-C18alkenyl, C5-C12cycloalkyl, unsubstituted C7-C15phenylalkyl, C7-C15phenylalkyl with the phenyl moiety substituted once, twice, three times or four times with C1-C4alkyl, unsubstituted phenyl, phenyl substituted once, twice, three times or four times with C1-C4alkyl;
R2 is, independently from R1, linear or branched C1-C24alkyl, linear or branched C2-C18alkenyl, C5-C12cycloalkyl, unsubstituted C7-C15phenylalkyl, C7-C15phenylalkyl with the phenyl moiety substituted once, twice, three times or four times with C1-C4alkyl, unsubstituted phenyl, phenyl substituted once, twice, or three times with C1-C4alkyl, wherein alkyl is optionally substituted by one or more —OH, —OCO—R3, —OR4, —NCO, —NH2 or combinations thereof, wherein R3 is hydrogen, linear or branched C1-C16alkyl, C5-C12cycloalkyl, linear or branched C3-C6alkenyl, phenyl, naphthyl or C7-C15phenylalkyl and R4 is hydrogen, linear or branched C1-C24 alkyl; —OR4, —C(O)OR4, —C(O)NHR4 or —C(O)NR4R4;
—SR5, —NHR5, or —N(R5)2, wherein R5 is C1-C20alkyl, C2-C20hydroxyalkyl; C3-C18alkenyl, C5-C12cycloalkyl, C7-C15phenylalkyl, unsubstituted phenyl, unsubstituted naphthyl, phenyl substituted once or twice with C1-C4alkyl, or naphthyl substituted once or twice with C1-C4alkyl;
—(CH2)m—CO—X1—(Z)p—Y—R6, wherein X1 is —O— or —NR7—, Y is —O— or NR8— or a direct bond, Z is C2-C12alkylene, C4-C12alkylene interrupted by one to three nitrogen atoms, oxygen atoms or combinations thereof, C3-C12alkylene, butenylene, butynylene, cyclohexylene or phenylene, wherein each of which may be additionally substituted by a hydroxyl group; or a group selected from the following list of structures:

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wherein * denotes a bond;
or when Y is a direct bond, Z can additionally also be a direct bond;
m is zero, 1 or 2;
p is 1, or p is also zero when X and Y are —N(R7)— and —N(R8)—, respectively,
R6 is hydrogen, C1-C12 alkyl, or —C(O)—C(R9)═C(H)R10, or when Y is —N(R8)—, forms together with R8 a group —C(O)—CH═CH—CO—, wherein
R9 is hydrogen or methyl, and R10 is hydrogen, methyl or —CO—X1—R11, wherein
R11 is hydrogen or C1-C12 alkyl,
R7 and R8 independently of each other are hydrogen, C1-C12alkyl, C3-C12 alkyl interrupted by 1 to 3 oxygen atoms, cyclohexyl, unsubstituted C7-C15phenylalkyl, or C7-C15phenylalkyl with the phenyl moiety substituted once, twice, three times or four times with C1-C4alkyl and R7 together with R8 in case where Z is ethylene, also forms ethylene;
A1, A2, A3 and A4 are defined to form a saturated or unsaturated, alicylic or heterocyclic, non-aromatic, aromatic or heteroaromatic ring in formula (I) by being, independently from each other, CH, CH2, CHR12, CR12, C(R12)2, COH, COR12, CCO2H, CCO2R12, CNH2, CNHR12, CN(R12)2, N, NR12, CO, C(SO2)R12 or C-Hal with Hal being F, Cl or Br, with R12 being defined independently for A1, A2, A3 and A4 by R1, R2 or R1 with one or more hydrogen atoms in R1 being optionally replaced by halogen;
or A1, A2, A3 and A4 are defined to form a compound according to formula (II) having an additional ring defined by substituents B1, B2, B3 and B4,

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wherein B1, B2, B3 and B4 form an additional five-membered or six-membered, saturated or unsaturated, alicylic or heterocyclic, non-aromatic, aromatic or heteroaromatic ring in formula (II) with B1, B2, B3 and B4 being, independently from each other, absent, CH, CH2, CHR12, CR12, C(R12)2, COH, COR12, CCO2H, CCO2R12, CNH2, CNHR12, CN(R12)2, N, NR12, or CO, with R12 being defined independently for B1, B2, B3 and B4 by R1, R2 or R1 with one or more hydrogen atoms in R1 being optionally replaced by halogen,
the process comprising the step of converting the ortho-hydroxydiarylazo compound according to formula (III) to the benzotriazole compound according to formula (I) by oxidative ring closure in the presence of a metal salt,

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characterized in that the oxidation with metal salt is carried out at a molar ratio of metal salt to diarylazo compound (III) from 0.001 to 4.5;
wherein the process comprises the additional step of preparing the ortho-hydroxydiarylazo compound according to formula (III) by reacting the 1,2-phenylenediamine compound (IV) with an ortho-nitrosophenol compound (V) in the presence of a Lewis acid to obtain the diarylazo compound according to formula (III)

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