# US 5,703,017 A · 3-(Het) arylcarboxylic acid derivatives, their preparation and intermediates for their preparation

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- Number: US 5,703,017 A
- Document ID: US5703017A
- Status: Granted
- Kind: A
- Application number: 08/537,843
- Filed: 1995-10-19
- Granted: 1997-12-30
- Earliest claimed: 1993-04-23
- Assignees: BASF SE
- Inventors: Ernst Baumann; Joachim Rheinheimer; Uwe Josef Vogelbacher; Matthias Bratz; Hans Theobald; Matthias Gerber; Karl-Otto Westphalen; Helmut Walter; Wilhelm Rademacher
- Web page: https://patentgrep.com/patent/US5703017A

## CPC

- C07D 401/12: linked by a chain containing hetero atoms as chain links
- A01N 43/54: 1,3-Diazines; Hydrogenated 1,3-diazines
- C07C 69/708: Ethers
- C07C 69/734: Ethers
- C07D 239/60: Three or more oxygen or sulfur atoms
- C07D 403/12: linked by a chain containing hetero atoms as chain links
- C07D 405/12: linked by a chain containing hetero atoms as chain links
- C07D 409/12: linked by a chain containing hetero atoms as chain links
- C07D 413/12: linked by a chain containing hetero atoms as chain links
- C07D 477/12: with hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached in position 6
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

3-(Het)arylcarboxylic acid derivatives of the formula I ##STR1## where R is formyl, CO.sub.2 H or a radical hydrolyzable to COOH and the other substituents have the following meanings: R.sup.2 and R.sup.3 are each halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; X is nitrogen or CR.sup.14, where R.sup.14 is hydrogen or, together with R.sup.3, forms an alkylene or alkenylene chain, in each of which a methylene group is replaced by oxygen; R.sup.4 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; R.sup.5 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl or phenyl; R.sup.6 is C.sub.1 -C.sub.8 -alkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.6 -alkynyl or C.sub.3 -C.sub.4 -cyclo-alkyl, each of which may be mono- or polysubstituted; Y is sulfur, oxygen or a single bond; and Z is sulfur or oxygen; with the proviso that R.sup.6 is not unsubstituted C.sub.1 -C.sub.4 -alkyl when R.sup.4 is unsubstituted phenyl, Z is oxygen and simultaneously R.sup.5 is methyl or hydrogen.

## Claims

### Claim 1

A 3-(het)arylcarboxylic acid derivative of the formula I ##STR15## where R is formyl, CO.sub.2 H or a radical hydrolyzable to COOH and R.sub.2 is halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -alkylthio;
X is nitrogen or CR.sup.14, where R.sup.14 is hydrogen or, together with R.sup.3, forms a 3-membered or 4-membered alkylene or alkenylene chain, in each of which a methylene group is replaced by oxygen;
R.sup.3 is halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -alkylthio or R.sup.3 is linked to R.sup.14 as stated above to form a 5-membered or 6-membered ring;
R.sup.4 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, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylamino, di-C.sub.1 -C.sub.4 -alkylamino, C.sub.1 -C.sub.4 -alkylcarbonyl or C.sub.1 -C.sub.4 -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, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylamino, C.sub.1 -C.sub.4 -dialkylamino, C.sub.1 -C.sub.4 -alkylcarbonyl, C.sub.1 -C.sub.4 -alkoxycarbonyl or phenyl;
R.sup.5 is hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.6 -alkynyl, C.sub.3 -C.sub.8 -cycloalkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxyalkyl, C.sub.1 -C.sub.4 -alkylthioalkyl or phenyl;
R.sup.6 is C.sub.1 -C.sub.8 -alkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.6 -alkynyl or C.sub.3 -C.sub.8 -cycloalkyl, it being possible for these radicals to be mono- or polysubstituted in each case by: halogen, nitro, cyano, C.sub.1 -C.sub.4 -alkoxy, C.sub.3 -C.sub.6 -alkenyloxy, C.sub.3 -C.sub.6 -alkynyloxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -haloalkoxy, C.sub.1 -C.sub.4 -alkylcarbonyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.1 -C.sub.4 -alkylamino, di-C.sub.1 -C.sub.4 -alkylamino, phenyl or phenyl or phenoxy which is mono- or polysubstituted, for example mono- to trisubstituted, by halogen, nitro, cyano, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -alkylthio;
Y is sulfur or oxygen or a single bond; and
Z is sulfur or oxygen;
with the proviso that R.sup.6 is not unsubstituted C.sub.1 -C.sub.4 -alkyl when R.sup.4 is unsubstituted phenyl, Z is oxygen and simultaneously R.sup.5 is methyl or hydrogen.

### Claim 2 (depends on 1)

A 3-(het)arylcarboxylic acid derivative of the general formula I as claimed in claim 1, where R is ##STR16## where R.sup.1 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:
C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -alkylthio;
d) a radical ##STR17## where m is 0 or 1 and R.sup.7 and R.sup.8, which may be identical or different, have the following meanings:
hydrogen;
C.sub.1 -C.sub.8 -alkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.6 -alkynyl or C.sub.3 -C.sub.8 -cycloalkyl, where each of these radicals may carry one to five halogen atoms or one or two of the following groups: C.sub.1 -C.sub.4 -alkoxy, C.sub.3 -C.sub.6 -alkenyloxy, C.sub.3 -C.sub.6 -alkynyloxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.3 -C.sub.6 -alkenylthio, C.sub.3 -C.sub.6 -alkynylthio, C.sub.1 -C.sub.4 -haloalkoxy, C.sub.1 -C.sub.4 -alkylcarbonyl, C.sub.3 -C.sub.6 -alkenylcarbonyl, C.sub.3 -C.sub.6 -alkynylcarbonyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.3 -C.sub.6 -alkenyloxycarbonyl, C.sub.3 -C.sub.6 -alkynyloxycarbonyl, di-C.sub.1 -C.sub.4 -alkylamino, C.sub.3 -C.sub.8 -cycloalkyl, phenyl or phenyl which is monosubstituted or polysubstituted by halogen, nitro, cyano, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or c.sub.1 --C.sub.4 -alkylthio;
phenyl which may be substituted by one or more of the following radicals: halogen, nitro, cyano, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -alkylthio;
R.sup.7 and R.sup.8 together form a cyclic, optionally substituted C.sub.4 -C.sub.7 -alkylene chain or together form a cyclic, optionally substituted C.sub.3 -C.sub.6 -alkylene chain containing a heteroatom selected from the group consisting of oxygen, sulfur and nitrogen;
e) R.sup.1 is furthermore a group ##STR18## where R.sup.9 is C.sub.1 -C.sub.4 -alkyl, phenyl or phenyl which is monosubstituted or polysubstituted by halogen, nitro, cyano, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -alkylthio, or C.sub.1 -C.sub.4 -haloalkyl, C.sub.3 -C.sub.6 -alkenyl or C.sub.3 -C.sub.6 -alkynyl, p may be 1, 2, 3 or 4 and k may be 0, 1 or 2;
f) a radical OR.sup.10, where R.sup.10 is:
i) hydrogen, an alkali metal cation, one equivalent of an alkaline earth metal cation, the ammonium cation or an organic ammonium ion;
ii) C.sub.3 -C.sub.8 -cycloalkyl Which may carry one to three C.sub.1 -C.sub.4 -alkyl radicals;
iii)C.sub.1 -C.sub.8 -alkyl which may carry one to five halogen atoms or one of the following radicals:
C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, cyano, C.sub.1 -C.sub.4 -alkylcarbonyl, C.sub.3 -C.sub.8 -cycloalkyl, C.sub.1 -C.sub.4 -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, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -alkylthio;
iv) C.sub.1 -C.sub.8 -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, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -alkylthio;
v) C.sub.2 -C.sub.6 -alkyl which carries one of the following radicals in the 2 position: C.sub.1 -C.sub.4 -alkoxyimino, C.sub.3 -C.sub.6 -alkenyloxyimino, C.sub.3 -C.sub.6 -haloalkenyloxyimino or benzyloxyimino;
vi) C.sub.3 -C.sub.6 -alkenyl or C.sub.3 -C.sub.6 -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, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -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, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -alkylthio;
ix) R.sup.10 is furthermore a group ##STR19## where R.sup.11 and R.sup.12 , may be identical or different and are each:
C.sub.1 -C.sub.8 -alkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.6 -alkynyl or C.sub.3 -C.sub.8 -cycloalkyl, where these radicals may carry one C.sub.1 -C.sub.4 -alkoxy or C.sub.1 -C.sub.4 -alkylthio or one phenyl radical;
phenyl which may be substituted by one or more of the following radicals:
halogen, nitro, cyano, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -alkylthio;
or R.sup.11 and R.sup.12 together form a C.sub.3 -C.sub.12 -alkylene chain which may carry one to three C.sub.1 -C.sub.4 -alkyl groups;
g) or R.sup.1 forms a radical ##STR20## where R.sup.13 is: C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.6 -alkynyl or C.sub.3 -C.sub.8 -cycloalkyl, where these radicals may carry one C.sub.1 -C.sub.4 -alkoxy or C.sub.1 -C.sub.4 -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, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy or C.sub.1 -C.sub.4 -alkylthio.

### Claim 3 (depends on 1)

A 3-arylcarboxylic acid derivative of the formula I as claimed in claim 1, in which R.sup.4 is phenyl which may be substituted as stated in claim 1, and the remaining substituents have the meanings stated in claim 1.

### Claim 4 (depends on 1)

A 3-arylcarboxylic acid derivative of the formula I as claimed in claim 1, in which Z is oxygen, R.sup.4 is phenyl which may be substituted as stated in claim 1, R.sup.5 is methyl, X is CH, R.sup.2 and R.sup.3 are each methoxy and Y, R.sup.1 and R.sup.6 have the meanings stated in claim 1.

### Claim 5 (depends on 1)

A 3-hetarylcarboxylic acid derivative of the formula I as claimed in claim 1, in which R.sup.4 is a five- or six-membered heteroaromatic structure as claimed in claim 1 and the remaining substituents have the meanings stated in claim 1.

### Claim 6 (depends on 1)

A 3-hetarylcarboxylic acid derivative of the formula I as claimed in claim 1, in which Z is oxygen, R.sup.4 is a five- or six-membered heteroaromatic structure as claimed in claim 1, R.sup.5 is methyl, X is CH, R.sup.2 and R.sup.3 are methoxy and Y, R.sup.1 and R.sup.6 have the meanings stated in claim 1.

### Claim 7 (depends on 1)

A herbicide containing a compound of the formula I as claimed in claim 1 and conventional inert additives.

### Claim 8 (depends on 1)

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.

### Claim 9 (depends on 1)

An agent for influencing plant growth, containing a compound of the formula I as claimed in claim 1 and conventional inert additives.

### Claim 10 (depends on 1)

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.

### Claim 11 (depends on 1)

A 3-(het)arylcarboxylic acid derivative of the formula VI ##STR21## where R, R.sup.4, R.sup.5, R.sup.6 and Z have the meanings stated in claim 1, with the proviso that R.sup.6 is not unsubstituted alkyl when R.sup.4 is unsubstituted phenyl or 4-isobutylphenyl, Z is oxygen and R.sup.5 is simultaneously methyl or hydrogen.

### Claim 12 (depends on 1)

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, R.sup.4 and R.sup.5 have the meanings stated in claim 1, is reacted with a compound of the formula V
R.sup.6 --ZH
where R.sup.6 and Z have the meanings stated in claim 1, with the proviso that R.sup.6 is not unsubstituted alkyl when R.sup.4 is unsubstituted phenyl or 4-isobutylphenyl, Z is oxygen and R.sup.5 is simultaneously methyl or hydrogen, if required in an inert solvent or with the addition of a suitable catalyst.

### Claim 13 (depends on 1)

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 R.sup.15 is halogen or R.sup.16 SO.sub.2 -- and R.sup.16 is C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl or phenyl, in an inert solvent in the presence of a base.

### Claim 14 (depends on 1, 12)

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 R.sup.2, R.sup.3 and X have the meanings stated in claim 1, with the proviso that R.sup.6 is not unsubstituted alkyl when R.sup.4 is unsubstituted phenyl or 4-isobutylphenyl, Z is oxygen and R.sup.5 is simultaneously methyl or hydrogen.