Claims for Patent: 5,703,017

Summary for Patent: 5,703,017

Title:	3-(Het) arylcarboxylic acid derivatives, their preparation and intermediates for their preparation
Abstract:	3-(Het)arylcarboxylic acid derivatives of the formula I ##STR1## where R is formyl, CO2 H or a radical hydrolyzable to COOH and the other substituents have the following meanings:R2 and R3 are each halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio;X is nitrogen or CR14, where R14 is hydrogen or, together with R3, forms an alkylene or alkenylene chain, in each of which a methylene group is replaced by oxygen;R4 is phenyl or naphthyl, each of which is unsubstituted or substituted or an unsubstituted or substituted five-membered or six-membered heteroaromatic structure containing one to three nitrogen atoms or one sulfur or oxygen atom;R5 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl or phenyl;R6 is C1 -C8 -alkyl, C3 -C6 -alkenyl, C3 -C6 -alkynyl or C3 -C4 -cyclo-alkyl, each of which may be mono- or polysubstituted;Y is sulfur, oxygen or a single bond; andZ is sulfur or oxygen;with the proviso that R6 is not unsubstituted C1 -C4 -alkyl when R4 is unsubstituted phenyl, Z is oxygen and simultaneously R5 is methyl or hydrogen.
Inventor(s):	Ernst Baumann, Joachim Rheinheimer, Uwe Josef Vogelbacher, Matthias Bratz, Hans Theobald, Matthias Gerber, Karl-Otto Westphalen, Helmut Walter, Wilhelm Rademacher
Assignee:	Royalty Pharma Collection Trust
Application Number:	US08/537,843
Patent Claims:	1. A 3-(het)arylcarboxylic acid derivative of the formula I ##STR15## where R is formyl, CO2 H or a radical hydrolyzable to COOH and R2 is halogen, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio;X is nitrogen or CR14, where R14 is hydrogen or, together with R3, forms a 3-membered or 4-membered alkylene or alkenylene chain, in each of which a methylene group is replaced by oxygen; R3 is halogen, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio or R3 is linked to R14 as stated above to form a 5-membered or 6-membered ring; R4 is phenyl or naphthyl which may be substituted by one or more, in particular one to three, of the following radicals: halogen, nitro, cyano, hydroxyl, mercapto, amino, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy, C1 -C4 -alkylthio, C1 -C4 -alkylamino, di-C1 -C4 -alkylamino, C1 -C4 -alkylcarbonyl or C1 -C4 -alkoxycarbonyl; a five-membered or six-membered heteroaromatic structure which contains one to three nitrogen atoms and/or one sulfur or oxygen atom and may carry one or more of the following radicals: halogen, nitro, cyano, hydroxyl, mercapto, amino, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy, C1 -C4 -alkylthio, C1 -C4 -alkylamino, C1 -C4 -dialkylamino, C1 -C4 -alkylcarbonyl, C1 -C4 -alkoxycarbonyl or phenyl; R5 is hydrogen, C1 -C4 -alkyl, C3 -C6 -alkenyl, C3 -C6 -alkynyl, C3 -C8 -cycloalkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxyalkyl, C1 -C4 -alkylthioalkyl or phenyl; R6 is C1 -C8 -alkyl, C3 -C6 -alkenyl, C3 -C6 -alkynyl or C3 -C8 -cycloalkyl, it being possible for these radicals to be mono- or polysubstituted in each case by: halogen, nitro, cyano, C1 -C4 -alkoxy, C3 -C6 -alkenyloxy, C3 -C6 -alkynyloxy, C1 -C4 -alkylthio, C1 -C4 -haloalkoxy, C1 -C4 -alkylcarbonyl, C1 -C4 -alkoxycarbonyl, C1 -C4 -alkylamino, di-C1 -C4 -alkylamino, phenyl or phenyl or phenoxy which is mono- or polysubstituted, for example mono- to trisubstituted, by halogen, nitro, cyano, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio; Y is sulfur or oxygen or a single bond; and Z is sulfur or oxygen;with the proviso that R6 is not unsubstituted C1 -C4 -alkyl when R4 is unsubstituted phenyl, Z is oxygen and simultaneously R5 is methyl or hydrogen. 2. A 3-(het)arylcarboxylic acid derivative of the general formula I as claimed in claim 1, where R is ##STR16## where R1 has the following meanings: a) hydrogen;b) a succinylimidoxy group; c) a 5-membered heteroaromatic structure which is bonded via a nitrogen atom, contains two or three nitrogen atoms and may carry one or two halogen atoms or one or two of the following radicals:C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio; d) a radical ##STR17## where m is 0 or 1 and R7 and R8, which may be identical or different, have the following meanings:hydrogen; C1 -C8 -alkyl, C3 -C6 -alkenyl, C3 -C6 -alkynyl or C3 -C8 -cycloalkyl, where each of these radicals may carry one to five halogen atoms or one or two of the following groups: C1 -C4 -alkoxy, C3 -C6 -alkenyloxy, C3 -C6 -alkynyloxy, C1 -C4 -alkylthio, C3 -C6 -alkenylthio, C3 -C6 -alkynylthio, C1 -C4 -haloalkoxy, C1 -C4 -alkylcarbonyl, C3 -C6 -alkenylcarbonyl, C3 -C6 -alkynylcarbonyl, C1 -C4 -alkoxycarbonyl, C3 -C6 -alkenyloxycarbonyl, C3 -C6 -alkynyloxycarbonyl, di-C1 -C4 -alkylamino, C3 -C8 -cycloalkyl, phenyl or phenyl which is monosubstituted or polysubstituted by halogen, nitro, cyano, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or c1 --C4 -alkylthio; phenyl which may be substituted by one or more of the following radicals: halogen, nitro, cyano, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio; R7 and R8 together form a cyclic, optionally substituted C4 -C7 -alkylene chain or together form a cyclic, optionally substituted C3 -C6 -alkylene chain containing a heteroatom selected from the group consisting of oxygen, sulfur and nitrogen; e) R1 is furthermore a group ##STR18## where R9 is C1 -C4 -alkyl, phenyl or phenyl which is monosubstituted or polysubstituted by halogen, nitro, cyano, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio, or C1 -C4 -haloalkyl, C3 -C6 -alkenyl or C3 -C6 -alkynyl, p may be 1, 2, 3 or 4 and k may be 0, 1 or 2; f) a radical OR10, where R10 is:i) hydrogen, an alkali metal cation, one equivalent of an alkaline earth metal cation, the ammonium cation or an organic ammonium ion; ii) C3 -C8 -cycloalkyl Which may carry one to three C1 -C4 -alkyl radicals; iii)C1 -C8 -alkyl which may carry one to five halogen atoms or one of the following radicals:C1 -C4 -alkoxy, C1 -C4 -alkylthio, cyano, C1 -C4 -alkylcarbonyl, C3 -C8 -cycloalkyl, C1 -C4 -alkoxycarbonyl, phenyl, phenoxy or phenylcarbonyl, where the aromatic radicals in turn may each carry one to five halogen atoms or one to three of the following radicals: nitro, cyano, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio; iv) C1 -C8 -alkyl which may carry one to five halogen atoms and carries one of the following radicals: a 5-membered heteroaromatic structure containing one to three nitrogen atoms or a 5-membered heteroaromatic structure containing one nitrogen atom and one oxygen or sulfur atom, which may carry one to four halogen atoms or one or two of the following radicals: nitro, cyano, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio; v) C2 -C6 -alkyl which carries one of the following radicals in the 2 position: C1 -C4 -alkoxyimino, C3 -C6 -alkenyloxyimino, C3 -C6 -haloalkenyloxyimino or benzyloxyimino; vi) C3 -C6 -alkenyl or C3 -C6 -alkynyl, where these groups in turn may carry one to five halogen atoms; vii)phenyl which may carry one to five halogen atoms or one to three of the following radicals: nitro, cyano, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio; viii) a 5-membered heteroaromatic structure which has bonded via a nitrogen atom, contains one to three nitrogen atoms and may carry one or two halogen atoms or one or two of the following radicals: nitro, cyano, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio; ix) R10 is furthermore a group ##STR19## where R11 and R12 , may be identical or different and are each:C1 -C8 -alkyl, C3 -C6 -alkenyl, C3 -C6 -alkynyl or C3 -C8 -cycloalkyl, where these radicals may carry one C1 -C4 -alkoxy or C1 -C4 -alkylthio or one phenyl radical; phenyl which may be substituted by one or more of the following radicals: halogen, nitro, cyano, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio; or R11 and R12 together form a C3 -C12 -alkylene chain which may carry one to three C1 -C4 -alkyl groups; g) or R1 forms a radical ##STR20## where R13 is: C1 -C4 -alkyl, C3 -C6 -alkenyl, C3 -C6 -alkynyl or C3 -C8 -cycloalkyl, where these radicals may carry one C1 -C4 -alkoxy or C1 -C4 -alkylthio or one phenyl radical; phenyl which may be substituted by one to five halogen atoms or one to three of the following radicals: nitro, cyano, C1 -C4 -alkyl, C1 -C4 -haloalkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkoxy or C1 -C4 -alkylthio. 3. A 3-arylcarboxylic acid derivative of the formula I as claimed in claim 1, in which R4 is phenyl which may be substituted as stated in claim 1, and the remaining substituents have the meanings stated in claim 1. 4. A 3-arylcarboxylic acid derivative of the formula I as claimed in claim 1, in which Z is oxygen, R4 is phenyl which may be substituted as stated in claim 1, R5 is methyl, X is CH, R2 and R3 are each methoxy and Y, R1 and R6 have the meanings stated in claim 1. 5. A 3-hetarylcarboxylic acid derivative of the formula I as claimed in claim 1, in which R4 is a five- or six-membered heteroaromatic structure as claimed in claim 1 and the remaining substituents have the meanings stated in claim 1. 6. A 3-hetarylcarboxylic acid derivative of the formula I as claimed in claim 1, in which Z is oxygen, R4 is a five- or six-membered heteroaromatic structure as claimed in claim 1, R5 is methyl, X is CH, R2 and R3 are methoxy and Y, R1 and R6 have the meanings stated in claim 1. 7. A herbicide containing a compound of the formula I as claimed in claim 1 and conventional inert additives. 8. A method for controlling undesirable plant growth, wherein a herbicidal amount of a compound of the formula I as claimed in claim 1 is allowed to act on the plants or on their habitat. 9. An agent for influencing plant growth, containing a compound of the formula I as claimed in claim 1 and conventional inert additives. 10. A method for regulating plant growth, wherein a bioregulatory amount of a compound of the formula I as claimed in claim 1 is allowed to act on the plants or on their habitat. 11. A 3-(het)arylcarboxylic acid derivative of the formula VI ##STR21## where R, R4, R5, R6 and Z have the meanings stated in claim 1, with the proviso that R6 is not unsubstituted alkyl when R4 is unsubstituted phenyl or 4-isobutylphenyl, Z is oxygen and R5 is simultaneously methyl or hydrogen. 12. A process for the preparation of a 3-(het)arylcarboxylic acid derivative of the formula VI ##STR22## wherein an epoxide of the formula IV ##STR23## where R, R4 and R5 have the meanings stated in claim 1, is reacted with a compound of the formula V R.sup.6 --ZH where R6 and Z have the meanings stated in claim 1, with the proviso that R6 is not unsubstituted alkyl when R4 is unsubstituted phenyl or 4-isobutylphenyl, Z is oxygen and R5 is simultaneously methyl or hydrogen, if required in an inert solvent or with the addition of a suitable catalyst. 13. A process for the preparation of 3-(het)arylcarboxylic acid derivatives of the formula I as claimed in claim 1, where is oxygen wherein the 3-het(aryl)carboxylic acid derivative of the formula VI ##STR24## where the substituents have the meanings stated in claim 1, is reacted with a pyrimidyl or triazinyl derivative of the formula VII ##STR25## where R15 is halogen or R16 SO2 -- and R16 is C1 -C4 -alkyl, C1 -C4 -haloalkyl or phenyl, in an inert solvent in the presence of a base. 14. A process for the preparation of a 3-het(aryl)carboxylic acid derivative of the formula I as claimed in claim 1, where Y is sulfur, wherein a 3-het(aryl)carboxylic acid derivative of the formula VIII ##STR26## where the substituents have the meanings stated in claim 12, is reacted with a pyrimidyl--or triazinylthiol of the formula IX ##STR27## where R2, R3 and X have the meanings stated in claim 1, with the proviso that R6 is not unsubstituted alkyl when R4 is unsubstituted phenyl or 4-isobutylphenyl, Z is oxygen and R5 is simultaneously methyl or hydrogen.