CA2231493A1 - Heterocycle-substituted salicylic acid derivatives - Google Patents
Heterocycle-substituted salicylic acid derivatives Download PDFInfo
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- CA2231493A1 CA2231493A1 CA002231493A CA2231493A CA2231493A1 CA 2231493 A1 CA2231493 A1 CA 2231493A1 CA 002231493 A CA002231493 A CA 002231493A CA 2231493 A CA2231493 A CA 2231493A CA 2231493 A1 CA2231493 A1 CA 2231493A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/60—Three or more oxygen or sulfur atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/68—One oxygen atom attached in position 4
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
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- Environmental Sciences (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention relates to salicylic acid derivatives of formula I, in which the substituents have the following meaning: A is a five membered heteroaromatic with a oxygen atom, nitrogen atom or sulphur atom or with one to four nitrogen atoms or with one to two nitrogen atoms and additionally a sulphur atom or an oxygen atom in the ring which can carry at least one -B-R5 group and additionally one or a plurality of the following substituents: nitro, halogen, cyano, optionally substituted alkyl, alkyl thio, alkyl sulfonyl, alkyl sulfinyl, formyl or a R5 group; a six membered hereroaromatic with two to three nitrogen atoms in the ring which can carry at least one -B-R5 group and additionally one or a plurality of the following substituents: nitro, halogen, cyano, optionally substituted alkyl, alkyl thio, alkyl sulfonyl, alkyl sulfinyl, formyl or a R5 group; B is oxygen, sulphur, SO, SO2; X is oxygen or sulphur; Y is nitrogen or C-H; Z is nitrogen or a C-R4 grouping, the substituents R1, R2, and R3 having the meaning given in claim 1. The invention also relates to a process for the preparation of these derivatives, herbicidal agents and a method of controlling undesirable vegetation.
Description
Heterocycle-substituted salicylic acid derivatives The present invention relates to salicylic acid derivatives of 5 the formula I
~ N ~ Z
A ~ X Y R2 o~R3 where the substituents have the following meanings:
A is a 5-membered heteroaromatic ring having one oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one to two nitrogen atoms and additionally one sulfur or oxygen atom in the ring which has attached to it at least one radical -B-R5 and which can additionally have attached to it one or more of the following substituents: nitro, halogen, cyano, unsubstituted or substituted alkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, formyl or a radical Rs; a 6-membered heteroaromatic ring having two to three nitrogen atoms in the ring which has attached to it at least one radical -B-R5 and which can additionally have attached to it one or more of the following substituents:
nitro, halogen, cyano, unsubstituted or substituted alkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, formyl or a radical R5;
B is oxygen, sulfur, SO, S02;
35 X is oxygen or sulfur;
Y is nitrogen or C-H;
Z is nitrogen or a group C-R4;
Rl is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino and/or dialkylamino;
R2 is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino and/or dialkylamino;
R3 is hydrogen;
a succinyliminooxy group;
a S-membered heteroaromatic ring containing one to three nitrogen atoms which can have attached to it one to four halogen atoms and/or one to two of the following radicals: alkyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
a radical oR6;
a radical (~)m - N
~0 where R7 and R8 can be identical or different and where m can assume the values 0 or 1;
or a radical o Il O
R4 is hydrogen, alkyl, halogen;
35 R5 is unsubstituted or substituted alkyl, dialkylamino or unsubstituted or substituted phenyl;
R6 is hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
an alkyl group which can have attached to it one to five halogen atoms and/or one or two of the following radicals: alkoxy, alkylthio, cyano, alkylcarbonyl, alkoxycarbonyl, cycloalkyl, a radical -0-N=CR10Rll, phenyl, phenoxy, or phenylcarbonyl, it being possible for the aromatic radicals, in turn, to have attached to them one to five halogen atoms and/or one to three of the following radicals: al:kyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
an alkyl group which can have attached to it one to five halogen atoms, and a 5-membered heteroaromatic ring containing one to three nitrogen atoms, or a 5-membered heteroaromatic ring containing one to three nitrogen atoms and additionally one sulfur or oxygen atom in the ring, it being possible for these to have attached to them one to four halogen atoms and/or one to two of the following radicals: alkyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
an alkyl group which has attached to it in the 2-position one of the following radicals: alkoxyimino, alkenyloxyimino, haloalkenyloxyimino or benzyloxyimino;
an alkenyl or an alkynyl group, it being possible for these groups, in turn, to have attached to them one to five halogen atoms;
phenyl which is unsubstituted or mono- to trisubstituted by nitro, alkyl or alkoxy or mono- to pentasubstituted by halogen;
a radical -N=CRl0R1l where Rl~ and Rll can be identical or different;
a 5-membered aromatic heterocycle bonded via a nitrogen atom and having one to four nitrogen atoms in the ring or a benzo-fused 5-membered aromatic heterocycle bonded via a nitrogen atom and having one to three nitrogen atoms in the ring, it being possible for these to be substituted by halogen, alkyl, haloalkyl;
R7,R8 are hydrogen;
alkyl, alkenyl, alkynyl, it being possible for each of these radicals to have attached to it one to five halogen atoms and/or one to two of the following groups: alkoxy, alkylthio, cyano, alkylcarbonyl, alkoxycarbonyl, bis-dialkylamino, cycloalkyl;
phenyl or substituted phenyl;
together are a cycli2ed alkylene chain or together are a cyclized alkylene chain having a hetero atom, which can be oxygen, sulfur or ni.trogen, it being possible for each of these to haYe attached to it one to three alkyl substituents;
or a group CH ~
~--R13 15 R9 is alkyl or phenyl, which can have attached to them one to four of the following substituents: halogen, nitro, cyano, alkyl;
R10,Rll are alkyl which can have attached to it a phenyl radical, an alkoxy and/or an alkylthio group, or are cycloalkyl, phenyl, or together are an alkylene chain which can have attached to it one to five alkyl groups and which can be bridged by an alkylene chain;
25 R12 is hydrogen or alkyl which can be substituted by hydroxyl, amino, hydrogen sulfide, alkylthio, carboxyl, carbamoyl, guanidinyl, phenyl, hydroxyphenyl, imidazolyl or indolyl radicals, or together with R7 is linked via an alkylene chain to form a ring;
Rl3 is alkyl, alkenyl or a:Lkynyl;
where 35 sub~tituted alkyl, substituted alkoxy, substituted alkylthio, sub~tituted alkylsulfinyl, substituted alkylsulfonyl, substituted alkylamino and substituted dialkylamino are to be understood as meaning in each case that the alkyl groups can be substituted by one up to the maximum possible number of halogen atoms and/or can 40 have attached to them one to three of the following radicals:
nitro, cyano, haloalkoxy, alkyl.thio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three hal.oqen atoms or one to three methyl groups, or phenoxy or phenoxy which is substituted by one to 45 three halogen atoms or one to t.hree methyl groups, substituted phenyl, substituted phenoxy, substituted phenylthio and substituted phenylsulfonyl are to be understood as meaning in each case that the phenyl ring can have attached to it one to five halogen atoms, one to three alkyl or alkoxy groups and/or 5 one to three of the following radicals: nitro, cyano, haloalkyl, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three halogen atoms or one to three methyl groups, or phenoxy or phenoxy which i8 substituted by one to three halogen atoms or one 10 to three methyl groups.
Preferred salicylic acid derivatives of the formula I are those where the substituents have the following meanings:
15 A is a 5-membered heteroaromatic ring having one oxygen, nitrogen or sulfur atom or h~ving one to four nitrogen atoms or having one to two nitrogen atoms and additionally one sulfur or oxygen atom in the ring which has attached to it at ].east one radical -B-R5 and which can additionally have attached to it one or more of the following substituents: nitro, halogen, cyano, unsubstituted or substi.tuted Cl-C6-alkyl, C1-C4-alkylthio, C1-C4-alkylsulfonyl, C1-C4-alkylsulfinyl, formyl or a radical R5; a 6-membered heteroaromatic ring having two to three nitrogen atoms in the ring which has attached to it at least one radical -B-R5 and which can additionally have attached to it one or more of the following sub~tituents: nitro, halogen, cyano, unsubstituted or substituted Cl-C6-alkyl, Cl-C4-alkylthio, Cl-C4-alkylsulfonyl, C1-C4-alkylsulfinyl, formyl or a radical R5; preferably a 5 -mhered heteroaromatic ring having one oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one to two nitrogen atoms and additionally one sulfur or oxygen atom in the ring which has attached to it at least one radcial -o-R5 or a 6-membered heteroaromatic ring having two to three nitrogen atoms in the ring which has attached to it at least one radical -o-R5;
40 B is oxygen, sulfur, SO or SO2;
X is oxygen or sulfur;
Y is nitrogen or C-H, preferably nitrogen;
Z is nitrogen or a group C-R4, preferably a group C-H or nitrogen;
Rl is halogen, Cl-C6-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl-C4-alkylthio, Cl-C4-alkylamino and/or di-Cl-C4-alkylamino; preferably halogen, Cl-C4-alkyl, Cl-C4 -alkoxy, Cl-C 4- haloalkoxy;
R2 is halogen, Cl-C6-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl-C4--alkylthio, Cl-C4-alkylamino and/or di-Cl-C4-alkylamino, preferably halogen, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, especially preferably Cl-C2-alkoxy and C1-C2-haloalkoxy;
15 R3 is hydrogen;
a succinyliminooxy group;
a 5 s ~ered heteroaromatic ring containing one to three nitrogen atoms which can have attached to it one to four halogen atoms and/or one to two of the following radical~: Cl-C6-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy and/or Cl-C4-alkylthio;
a radical oR6;
a radical (~)m - N
where R7 and R8 can be identical or different and where m can assume the values () or l;
or a radical o preferably hydrogen, a radical oR6, a radical ~(o)m-NR7R8, especially preferably a radical oR6;
R4 is hydrogen, C1-C4-alkyl, halogen;
R5 is unsubstituted or substituted C1-C6-alkyl, di-C1-C4-alkylamino or unsubstituted or substituted phenyl; especially preferably unsubstituted or substituted C1-C4-alkyl;
R6 i8 hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
a Cl-C8-alkyl group which can have attached to it one to five halogen atoms and/or one or two of the following radicals: Cl-C4-alkoxy, Cl-C4-alkylthio, cyano, Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl, C3-c6-cYcloalkyl~ a radical -O-N=CR1OR11 where R10 and can be identical or diiferent, phenyl, phenoxy, or phenylcarbonyl, it being possible for the aromatic radicals, in turn, to have attached to them one to five halogen atoms and/or one to three of the following radicals: C1-C6-alkyl, Cl-C4-haloalkyl, C1-C4-alkoxy, Cl-C4-haloalkoxy and/or C1-C4-alkylthio;
a C1-C6-alkyl group which can have attached to it one to five halogen atoms, and a 5-membered heteroaromatic ring containing one to three nitrogen atoms, or a 5-membered heteroaromatic ring containing one to three nitrogen atoms and additionally one sulfur or oxygen atom in the ring, it being possible for these to have attached to them one to four halogen atoms and/or one to two of the following radicals: Cl-C4-alkyl, C1-C4-haloalkyl, Cl-C4-alkoxy, C1-C4-haloalkoxy and/or Cl-C4-alkylthio;
a Cl-C6-alkyl group which has attached to it in the 2-position one of the following radicals:
Cl-C4-alkoxyimino, Cl-C4-alkenyloxyimino, Cl-C4-haloalkenyloxyimino or benzyloxyimino;
a C3-C6-alkenyl or a C3--C6-alkynyl group, it being possible for these groups, in turn, to have attached to them one to five halogen atoms;
.
OOS0/~6245 phenyl which is unsubstituted or mono- to trisubstituted by nitro, Cl-Cg-alkyl or Cl-C4-alkoxy or mono- to pentasubstituted by halogen;
a radical -N=CRl~Rll where Rl~ and Rll can be identical or different;
a 5-membered aromatic heterocycle bonded via a nitrogen atom and having one to four nitrogen atoms in the ring or a benzo-fused 5 ;~ ~ered aromatic heterocycle bonded via a nitrogen atom and having one to three nitrogen atoms in the ring, it being possible for these to be substituted by halogen, Cl-C6-alkyl, Cl-C4-haloalkyl;
15 R7,R8 are hydrogen;
Cl-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, it being possible for each of these radicals to have attached to it one to five halogen atoms and/or one to two of the following groups: Cl-Cg-alkoxy, Cl-C4-alkylthio, cyano, Cl-C4-alkylcarbonyl, C~-C4-alkoxycarbonyl, bis-di-Cl-Cg-alkylamino, cyclo-C3-C6-alkyl;
phenyl or substituted phenyl;
together are a cyclized Cl-C6-alkylene chain or together are a cyclized Cl-C6-alkylene chain having a hetero atom, which can be oxygen, sulfur or nitrogen, it being possible for each of these to have attached to it one to three Cl-C4-alkyl subsl:ituents;
or a group - CH
\~--R13 40 R9 is Cl-C6-alkyl or phenyl, which can have attached to them one to four of the following substituents: halogen, nitro, cyano, Cl-C4-alkyl;
Rl~,Rll are Cl-C6-alkyl which can have attached to it a phenyl radical, a Cl-C4-alkoxy and/or a Cl-Cg-alkylthio group, or are C3-C6-cycloalkyl, phenyl, or together are a Cl-C6-alkylene chain which can have attached to it one to five Cl-C4-alkyl groups and which can be bridged by a Cl-C6-alkylene chain; especially preferably are Cl-C4-alkyl, and together a Cl-C5-alkylene chain;
5 R12 i9 hydrogen or Cl-C6-alkyl which can be substituted by hydroxyl, amino, hydrogen sulfide, alkylthio, carboxyl, carbamoyl, guanidinyl, phenyl, hydroxyphenyl, imidazolyl or indolyl radicals, or together with R7 is linked via a Cl-C4-alkylene chain to form a ring;
Rl3 is Cl-C6-alkyl, Cl-C4-a].kenyl or Cl-C4-alkynyl;
where 15 substituted alkyl, substituted alkoxy, substituted alkylthio, substituted alkylsulfinyl, substituted alkylsulfonyl, substituted alkylamino and substituted dialkylamino are to be understood as meaning in each case that the a:Lkyl groups can be substituted by one up to the ~ possible number of halogen atoms and/or can 20 have attached to them one to three of the following radicals:
nitro, cyano, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three halogen atoms or one to three methyl groups, or phenoxy or phenoxy which is substituted by one to 25 three halogen atoms or one to three methyl groups, and substituted phenyl, substituted phenoxy, substituted phenylthio and substituted phenylsulfonyl are to be understood as meaning in each case that the phenyl ring ~_an have attached to it one to 30 five halogen atoms, one to three alkyl or alkoxy groups and~or one to three of the following radicals: nitro, cyano, haloalkyl, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three halogen atoms or one to three methyl groups, or phenoxy or 35 phenoxy which is substituted by one to three halogen atoms or one to three methyl groups.
Preferred salicylic acid derivatives of the formula I are those where the substituent R6 has the following meanings:
R6 is hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
a Cl-C4-alkyl group which can have attached to it one to five halogen atoms and~or one or two of the following radicals: Cl-C4-alkoxy, Cl-C4-alkylthio, cyano, Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl, .
C3-C6-cycloalkyl, a radical -0-N=CR10Rll where Rl~ and R
can be identical or different, phenyl, phenoxy, or phenylcarbonyl, it being possible for the aromatic radicals, in turn, to have attached to them one to five halogen atoms and/or one to three of the following radicals: Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy and~or Cl-C4-alkylthio;
a C2-C4-alkenyl or a C2--C4-alkynyl group, it being possible for these groups, in turn, to have attached to them one to five halogen atoms;
phenyl which is unsubstituted or mono- to trisubstituted by nitro, alkyl or alkoxy or mono- to pentasubstituted by halogen;
a radical -N=CRl~Rll where R10 and Rll can be identical or different;
20 and the remaining substituents have the abovementioned meanings.
~urthermore preferred salicylic acid derivatives of the formula I
are those where the substituents R7 and R8 have the following meanings:
R7,R8 are hydrogen;
Cl-C4-alkyl, Cl-C4-alkenyl, Cl-C4-alkynyl;
phenyl or substituted phenyl;
together are a cyclized C1-C6-alkylene chain or together are a cyclized Cl-C6-alkylene chain having a hetero atom, which can be oxygen, sulfur or nitrogen, it being possible for each of these to have attached to it one to three alkyl substituent:s;
and the remaining substituents have the abovementioned meanings.
40 ~urthermore preferred salicylic acid derivatives of the formula I
are those where the substituent R6 has the following meanings:
R6 i5 hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
1~
a Cl-C2-alkyl group which can have attached to it one to five halogen atoms and~or one of the following radicals:
alkoxy, alkylthio, phenyl;
5 and the remaining substituents have the abovementioned -Anings Other preferred salicylic acid derivatives of the formula I are those where the substituents R6, R7 and R8 have the following ~AningS:
R6 is hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
a Cl-C4-alkyl group which can have attached to it one to lS five halogen atoms and/or one or two of the following radicals: C1-C4-alkoxy, Cl-C4-alkylthio, cyano, Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl, C~-C6-cycloalkyl, a radical -O-N=CR10R11 where R10 and R
can be identical or different, phenyl, phenoxy, or phenylcarbonyl, it being possible for the aromatic radicals, in turn, to have attached to them one to five halogen atoms and/or one to three of the following radicals: C1-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy and/or Cl-C4-alkylthio;
a C2-C4-alkenyl or a C2-C4-alkynyl group, it being possible for these groups, in turn, to have attached to them one to five halogen atoms;
phenyl which is unsubstituted or mono- to trisubstituted by nitro, alkyl or alkoxy or mono- to pentasubstituted by halogen;
a radical -N=CRl~Rll where Rl~ and Rll can be identical or ~5 different;
R7,R8 are hydrogen;
Cl-C4-alkyl, Cl-C4-alkenyll Cl-C4-alkynyl;
phenyl or substituted phenyl;
together are a cyclized C1-C6-alkylene chain or together are a cyclized C1-C6-alkylene chain having a hetero atom, which can be oxygen, slllfur or nitrogen, it being possible for each of these to have attached to it one to three alkyl substituents;
and the remaining substituents have the abovementioned meanings.
Also preferred salicylic acid derivatives of the formula I are those where the substituents R6, R7 and R8 have the following meanings:
10 R6 is hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
a C1-C2-alkyl group which can have attached to it one to five halogen atoms and/or one of the following radicals:
alkoxy, alkylthio, phenyl;
R7,R8 are hydrogen;
Cl-C4-alkyl, Cl-C4-alkenyl, Cl-C4-alkynyl;
phenyl or substituted phenyl;
together are a cyclized C1-C6-alkylene chain or together are a cyclized Cl-C6-al.kylene chain having a hetero atom, which can be oxygen, sulfur or nitrogen, it being possible for each of these to have attached to it one to three alkyl substituents;
and the remaining substituents have the abovementioned meanings.
Especially preferred salicylic acid derivatives of the formula I
are those where the substituents Rl, R2 and Y have the following meanings:
35 Rl,R2 are alkoxy and Y is nitrogen and the remaining substituents have the abovementioned -Anings.
Other especially preferred salicylic acid derivatives of the formula I are those where the substituents Rl, R2, Y and R3 have the following meanings:
45 Rl,R2 are alkoxy, Y is nitrogen, Z is C-H and 5 R3 is hydroxyl and the remaining substituents have the abovementioned meanings.
Very especially preferred salicylic acid derivatives of the 10 formula I are those where the substituents Rl, R2, Y, R3 and A
have the following meanings:
Rl,R~ are alkoxy, 15 Y is nitrogen, R3 is hydroxyl and A is a 5 ~ - 'ered heteroaromatic ring having one oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one to two nitrogen atoms and additionally one sulfur or oxygen atom in the ring which has attached to it at least one radical -~-R5 and which can additionally have attached to it one or more of the following substituents; nitro, halogen, cyano, unsubstituted or substituted alkyl, alkylthio, alkylsulfonyl, alkylswlfinyl, formyl or a radical R5, and the remaining substituents have the abovementioned meanings.
Patent Applications Wo 91/13065 and DE-A 39 19 435 disclose herbicidally active salicylaldehyde derivatives and salicylic acid derivatives, respectively, which have a heterocyclic substituent. The activity of the compounds known from the 35 literature is not always satisfactory with a view to herbicidal action, crop plant selectivity or bioregulatory action.
It is therefore an object of the present invention to provide heterocycle-substituted salicylaldehyde and salicylic acid 40 derivatives which have an improved biological activity.
Accordingly, we have found that this object is achieved by the heterocycle-substituted salicylic acid derivatives I defined at the outset. The novel compounds I have an outstanding herbicidal 45 action combined with an improved selectivity in crop plants.
We have furthermore found processes for the preparation of the compounds I and their use as herbicides and growth regulators.
The compounds of the formula I are accessible via a plurality of 5 routes. Particularly advantageous is the route via the benzo[l,3]-dioxinones IV which can be prepared by known processes from the heterocyclic tin compounds II and the benzodioxinones III with palladium catalysis (EP 657 441) and which are first opened with a nucleophile R3-H in a manner known per se in the 10 presence or absence of a base to give the salicylic acid derivatives V, which are then reacted with heterocycles of the type VI in a manner known per se in the presence or absence of a base:
base Pd~/pdII ~ R3 - H ~
SnR123 + Rl6 ~ X A ~ X A ~ XH
0 ~ o ~ 0 ~ o ~ ~ ~ R3 II III IV V
~
N ~ Z N ~ Z
A ~ X Y R2 Rl4 ~ Y ~ R2 o R3 I VI
The radicals have the abovement:ioned meanings, Rl2 is Cl-C6-alkyl and Cl-C6-cycloalkyl, Rl6 is a halogen atom, preferably bromine or 35 iodine, or a trifluoromethylsulfonyloxy group, Rl4 is a nucleofugic leaving group such as halogenf alkyl- or arylsulfonyl.
Furthermore, a derivative A-R16 can be reacted with a 40 tin-substituted benzoic acid of the formula VII where Rl5 is unsubstituted or substituted benzyl, Cl-C4-alkyl, dihydropyranyl, trialkylsilyl, alkoxyalkyl and dialkoxyalkyl with palladium catalysis and the resulting benzoic acid VIII can be converted in a manner known per se into the salicylic acids Va where 45 R3 = hydrogen:
A - R16 + R123Sn ~ , R15 ~ , R15 ~ OH
OH O OH O OH
VII VIII Va 10 A catalytically active palladium compound i9 employed in each of the two abovementioned processes. Any palladium salts or complexes which are at least partially soluble in the reaction mixture are suitable. The oxidation level of the palladium can be 0 or 2. Suitable counterions for the palladium salts are, inter 15 alia, the following: chloride, bromide, iodide, sulfate, acetate, trifluoroacetate, acetylacetonate or hexafluoro-2,4-pentadionate.
A large number of different palladium complexes can be used. The only prerequisite is that the ligands of the palladium can be displaced by the substrate under the reaction conditions.
20 Especially suitable ligands are phosphine ligands, eg.
aryl-alkylphosphines such as, inter alia, methyldiphenylphosphine, isopropyldiphenylphosphine, triarylphosphines such as, inter alia, triphenylphosphine, tritolylphosphine, trixylylphosphine, trihetarylphosphines, such 25 as trifurylphosphine, or dimer:ic phosphines. Substances which are also well suited are olefinic ligands, such as, inter alia, dibenzylideneacetone or its saLts, cycloocta-1,5-diene or amines such as trialkylamines (eg. triethylamine, tetramethylethylenediamine, N-methylmorpholine) or pyridine.
The complex used can be employed directly in the reaction. This procedure can be followed using, for example, tetrakistriphenylphosphinepalladium(0), bistriphenylphosphinepalladium dichloride, 35 bistriphenylphosphinepalladium diacetate, a dibenzylideneacetone/palladium(0) complex, tetrakismethyl-diphenylphosphinepalladium(0) or bis(1,2-diphenylphosphinoethane)palladium dichloride. It is also possible to use a palladium salt and additionally a suitable 40 ligand, and the catalytically active complex is formed in situ only then. This procedure is suitable, for example, for the abovementioned salts and phosphine ligands, eg. trifurylphosphine or tritolylphosphine. Palladium complexes, eg.
tris~dibenzylideneacetone)dipalladium, 45 bis(dibenzylideneacetone)palladium or 1,5-cyclooctadienepalladium dichloride can also be further activated by the addition of ligands, eg. trifurylphosphine or tritolylphosphine.
As a rule, 0.001 to 10 mol%, in particular 0.005 to 5 mol%, of 5 the palladium compound (salt or complex) is used, based on the compounds II or VII. Higher amounts are possible, but tend to be uneconomical. The amount of II or VII based on the reactants III
and A-R13, respectively, is generally from 0.8 to 3, preferably 0.95 to 1.5, mole equivalents. All solvents which do not react l0 themselves with the substrates used are suitable for the reaction. Polar solvents accelerate the reaction. Especially suitable are ethers such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, amides such as dimethylformamide, dimethylacet:amide, N-methylpyrrolidone, lS dimethylpropyleneurea, or amines such as triethylamine. The use of mixtures, eg. of ethers with amides, is frequently advantageous. Other suitable components for mixtures are alkyl alcohols and water, especially when the radical B contains a boron atom. The addition of te1:raalkylammonium halides or alkali 20 metal halides, eg. lithium chloride, is frequently useful and particularly recommended when X is a sulfonyloxy radical. It is frequently useful to add an organic or inorganic base, such as potassium carbonate, sodium carbonate, calcium carbonate, calcium hydroxide, sodium hydroxide, potassium hydroxide, potassium 25 phosphate, sodium phosphate, pyridine or an amine, such as triethylamine, especially when the radical B contains a boron atom.
The reaction temperature is from -20 to 200 C, preferably from 50 30 to 160 C. The reaction times are usually from a few minutes to 50 hours, in most cases 0.5 to l0 hours. When using low-boiling solvents, it is sometimes useful to carry out the reaction in the autoclave under inherent pressure.
35 The organotin compounds of the formula VII are prepared by metallating the benzoic acid on which they are based with a suitable base at low temperatures and subsequently reacting the product with a trialkyltin compound to give VII:
COOH COOH
R1s~ ~ 1) base R1s~ ~ SnR123 VII
Suitable bases are mainly cycloalkyl- or alkyllithium compounds, especially suitable being the commercially available butyl- and hexyllithium isomers. It is frequently expedient to add an auxiliary to aid metalation. Suitable substances are ethers, 5 alcoholates, eg. potassium tert-butylate, or amines such as tetramethylethylene~i ~ri ne The metalation can be effected at from (-130) C to 0 C, preferably from ~-100) to ~-50) C. All solvents which are normally used for metalation reactions are also suitable for this reaction, diethyl ether, methyl tert-butyl 10 ether, tetrahydrofuran and simple hydrocarbons being especially suitable; it may be advantageous to use mixtures of these. The reaction times for the metalation can be from a few minutes to a few hours. The trialkyltin compound is subsequently added, R13 being the customary leaving groups, preferably chlorine or 15 bromine. As regards the temperature during the addition and the subsequent reaction time, what has been described above also applies here. This may be followed by aqueous or non-aqueous work-up; it may be useful in the first case to keep constant the pH of the aqueous phase by means of a buffer. The yield may be 20 increased considerably when a substance which is suitable for destroying excess base is added at low temperatures prior to work-up. Suitable substances are, for example, carbon dioxide, water, alkyl halides or benzyl halides. If required, the organotin compounds of the formula I can be purified further, for 25 example by chromatography on silica gel. They prove to be stable during work-up and also to water at various pH values and can be stored at room temperature.
Another possibility of synthesizing active ingredients of the 30 formula I is to convert a heterocyclic formyl compound IX by known methods into the corresponding crotonaldehyde X, which is then reacted in a manner known per se ~EP 402 751) via the cyclohexenone XI and the salicylic acid derivative XII to give the active ingredient.
O O
5 o ~ A H ~ ~ ~ ~ oR6 ~B=CH3 or Ph3P=CH) IX X XI
R
N ~ Z
Rl R14Y ~ R2 OH O
A ~ ~ VI ~ oR6 o OR6 Ib XII
20 Benzoic acid derivatives, ie. compounds I where R3 is an OH group, can also be synthesized by con~erting a suitable precursor I
where R3 is oR6 into the free acid Ia by means of hydrolysis or hydrogenation.
Rl R
¦ hydrolysis or ~ N'~z hydrogenation ~ N ~ z A ~ X Y ~ R2 A ~ X Y ~ R2 30~ ~ R3 0 OH
I Ia Compounds of the formula I can also be synthesized by starting from the free acids Ia, ie. substances where R3 is OH, and 35 converting them into an activated form, such as a halide or an imidazolide, which are then reacted with a nucleophile R3-H in the presence or absence of a base. Alternatively, it is also possible first to activate the salicylic acids III and then to react the resulting derivatives V with heterocycles IV to give the active 40 ingredients I.
A ~ O~ ~ N 1 z OH O OH
III-OH Ia 1. activation 1. activation 102. R3-H ~2. R3-H
Rl A ~ OH ~ A ~ X Y R2 o R3 III I
20 In the description, the substituents mentioned preferably have the following meanings:
Cl-C4-alkyl: methyl, ethyl, l-p:ropyl, 2-propyl, l-butyl, 2-butyl, 2-methyl-propyl, l,l-dimethyl-ethyl;
Cl-C6-alkyl: C1-C4-alkyl and 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-butyl, 3-methyl-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 1,1-dimethylpropyl, 1,2-dimethyl-propyl, 2,2-dimethylpropyl, l-hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl, 30 3-methylpentyl, 4-methylpentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl.butyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 3,3-dimethyl.-2-butyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, in particular 35 methyl, ethyl, propyl, 2-propy]., butyl, 2-butyl, l,l-dimethylethyl, pentyl, 2,2-dimethylpropyl, hexyl;
Cl-C4-haloalkyl: chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, 40 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 1,1,2,2-tetrafluoroethyl, 2,2,~-trifluoroethyl, 2-chloro-1,1,2-trifluoroethyl and pentafluoroethyl, decafluorobutyl, l,1-bis-trifluoromethyl-2,2,2-trifluoroethyl, preferably difluoromethyl, trifluoromethyl, trichloromethyl and 45 chlorodifluoromethyl;
C3-C8-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, especially preferably cyclopropyl, cyclopentyl and cyclohexyl;
5 C3-Cl2-cycloalkyl: C3-C8-cycloalkyl and cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl, especially pre~erably cyclopropyl, cyclopentyl and cyclohexyl;
Cl-C4-alkylcarbonyl: acetyl, propionyl, l-propylcarbonyl, 10 2-propylcarbonyl, l-butylcarbonyl, 2-butylcarbonyl, 2-methyl-propylcarbonyl, l,1-dimethyl-ethylcarbonyl;
Cl-C4-alkoxycarbonyl: ethoxycarbonyl, propoxycarbonyl, l-propyloxycarbonyl, 2-propyloxycarbonyl, l-butyloxycarbonyl, 15 2-butyloxycarbonyl, 2-methyl-propyloxycarbonyl, l,l-dimethyl-ethoxycarbonyl;
C3-C6-alkenyl: propenyl, l-butenyl, 2-butenyl, 2-methylpropenyl, pentenyl, 2-pentenyl, 2-methy.lbutenyl, 3-methylbutenyl, 20 2-methyl-2-butenyl, hexenyl, 2-hexenyl, 3-hexenyl, 2-methylpentenyl, 3-methylpentenyl, 4-methylpentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 2,3-dimethylbutenyl, 2-ethylbutenyl, 3,3-dimethylbutenyl, 2,3-dimethyl-2-butenyl;
C3-C6-alkynyl: propynyl, butynyl, 2-butynyl, pentynyl, 2-pentynyl, 3-methylbutynyl, hexynyl, 2-hexynyl, 3-hexynyl, 3-methyl-pentynyl, 4-methyl-pentynyl, 4-methyl-2-pentynyl;
30 Cl-C4-alkoxy: methoxy, ethoxy, propoxy, l-methylethoxy, butoxy, 2-butoxy, l-methylpropoxy, 2-methylpropoxy, l,l-dimethylethoxy, in particular methoxy, ethoxy, l-methylethoxy;
Cl-C6-alkoxy: Cl-C4-alkoxy and pentoxy, 2-pentoxy, 3-pentoxy, 35 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methyl-2-butoxy, 3-methyl-2-butoxy, l,l-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 40 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, in particular methoxy, ethoxy, 1-methylethoxy;
45 Cl-C8-alkoxy: Cl-C6-alkoxy and heptoxy, octoxy, 2-ethylhexoxy;
0050~46245 Cl-C4-haloalkoxy: difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, l-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy and S pentafluoroethoxy, 1,1,2,3,3,3-hexafluoropropoxy, heptafluoro-propoxy, decafluorobutoxy, 1,1-bis-trifluoromethyl-2,2,2-trifluoroethoxy, preferably difluoromethoxy, trifluoromethoxy and chlorodifluoromethoxy;
0 Cl-C12-cyc loalkoxy: cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy, cyclodecyloxy, cycloundecyloxy and cyclododecyloxy, especially preferably cyclopropoxy, cyclopentoxy and cyclohexyloxy;
15 Cl-C4-alkylcarbonyloxy: acetoxy, propionyloxy, l-propylcarbonyloxy, 2-propylcarbonyloxy, l-butylcarbonyloxy, 2-butylcarbonyloxy, 2-methyl-propylcarbonyloxy, l,1-dimethyl-ethylcarbonyloxy;
20 Cl-C4-alkylthio: methylthio, ethylthio, propylthio, l-methylethylthio, butylthio, ~-butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, in particular methylthio, ethylthio, 1-methylethylthio;
25 C1-C4-alkylsulfinyl: methylsulfinyl, ethylsulfinyl, propylsulfinyl, l-methylethylsulfinyl, butylsulfinyl, 2-butylsulfinyl, l-methylpropylsulfinyl, 2-methylpropylsulfinyl, l,l-dimethylethylsulfinyl, in particular methylsulfinyl, ethylsulfinyl, l-methylethylsulfinyl;
Cl-C4-alkylsulfonyl: methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 2-butylsulfonyl, l-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, in particular methylsulfonyl, 35 ethylsulfonyl, 1-methylethylsulfonyl;
Cl-C4-alkylamino: methylamino, ethylamino, propylamino, l-methylethylamino, butylamino r 2-butylamino, 1-methylpropylamino, 2-methylpropylamino, l,l-dimethylethylamino, 40 in particular methylamino, ethylamino, 1-methylethylamino;
di-Cl-C4-alkylamino: dimethylamino, N-methyl-N-ethylamino, diethylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, dipropylamino, diisopropylamino, N-isopropyl-N-methylamino, 45 N-ethyl-N-isopropylamino, N-isopropyl-N-propylamino, dibutylamino, di-2-methylpropy:Lamino, di-l-methylpropylamino, N-butyl-N-methylamino and isomers, N-butyl-N-ethylamino and isomers, N-butyl-N-propylamino and isomers;
C3-C6-alkylene chain: propylene r butylene, pentylene, hexylene;
5-membered heteroaromatics which may be mentioned are mainly the following heterocycles: 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, l-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, l-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, l-imidazolyl, 2-imidazolyl, 10 4-imidazolyl, 5-imidazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 1,2,3-triazol-1-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, ~lH)1,2,4-triazol-1-yl, 15 (lH)1,2,4-triazol-3-yl, (lH)1,2,4-triazol-5-yl, (4H)1,2,4-triazol-2(5)-yl, (4H~1,2,4-triazol-4-yl, l-tetrazolyl, 5-tetrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 20 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 3(4)-furazanyl, 1,3,4-oxadiazol-2(5)-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,2,5-thiadiazol-3-yl, 1,3,4-thiadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl.
~ N ~ Z
A ~ X Y R2 o~R3 where the substituents have the following meanings:
A is a 5-membered heteroaromatic ring having one oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one to two nitrogen atoms and additionally one sulfur or oxygen atom in the ring which has attached to it at least one radical -B-R5 and which can additionally have attached to it one or more of the following substituents: nitro, halogen, cyano, unsubstituted or substituted alkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, formyl or a radical Rs; a 6-membered heteroaromatic ring having two to three nitrogen atoms in the ring which has attached to it at least one radical -B-R5 and which can additionally have attached to it one or more of the following substituents:
nitro, halogen, cyano, unsubstituted or substituted alkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, formyl or a radical R5;
B is oxygen, sulfur, SO, S02;
35 X is oxygen or sulfur;
Y is nitrogen or C-H;
Z is nitrogen or a group C-R4;
Rl is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino and/or dialkylamino;
R2 is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino and/or dialkylamino;
R3 is hydrogen;
a succinyliminooxy group;
a S-membered heteroaromatic ring containing one to three nitrogen atoms which can have attached to it one to four halogen atoms and/or one to two of the following radicals: alkyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
a radical oR6;
a radical (~)m - N
~0 where R7 and R8 can be identical or different and where m can assume the values 0 or 1;
or a radical o Il O
R4 is hydrogen, alkyl, halogen;
35 R5 is unsubstituted or substituted alkyl, dialkylamino or unsubstituted or substituted phenyl;
R6 is hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
an alkyl group which can have attached to it one to five halogen atoms and/or one or two of the following radicals: alkoxy, alkylthio, cyano, alkylcarbonyl, alkoxycarbonyl, cycloalkyl, a radical -0-N=CR10Rll, phenyl, phenoxy, or phenylcarbonyl, it being possible for the aromatic radicals, in turn, to have attached to them one to five halogen atoms and/or one to three of the following radicals: al:kyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
an alkyl group which can have attached to it one to five halogen atoms, and a 5-membered heteroaromatic ring containing one to three nitrogen atoms, or a 5-membered heteroaromatic ring containing one to three nitrogen atoms and additionally one sulfur or oxygen atom in the ring, it being possible for these to have attached to them one to four halogen atoms and/or one to two of the following radicals: alkyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
an alkyl group which has attached to it in the 2-position one of the following radicals: alkoxyimino, alkenyloxyimino, haloalkenyloxyimino or benzyloxyimino;
an alkenyl or an alkynyl group, it being possible for these groups, in turn, to have attached to them one to five halogen atoms;
phenyl which is unsubstituted or mono- to trisubstituted by nitro, alkyl or alkoxy or mono- to pentasubstituted by halogen;
a radical -N=CRl0R1l where Rl~ and Rll can be identical or different;
a 5-membered aromatic heterocycle bonded via a nitrogen atom and having one to four nitrogen atoms in the ring or a benzo-fused 5-membered aromatic heterocycle bonded via a nitrogen atom and having one to three nitrogen atoms in the ring, it being possible for these to be substituted by halogen, alkyl, haloalkyl;
R7,R8 are hydrogen;
alkyl, alkenyl, alkynyl, it being possible for each of these radicals to have attached to it one to five halogen atoms and/or one to two of the following groups: alkoxy, alkylthio, cyano, alkylcarbonyl, alkoxycarbonyl, bis-dialkylamino, cycloalkyl;
phenyl or substituted phenyl;
together are a cycli2ed alkylene chain or together are a cyclized alkylene chain having a hetero atom, which can be oxygen, sulfur or ni.trogen, it being possible for each of these to haYe attached to it one to three alkyl substituents;
or a group CH ~
~--R13 15 R9 is alkyl or phenyl, which can have attached to them one to four of the following substituents: halogen, nitro, cyano, alkyl;
R10,Rll are alkyl which can have attached to it a phenyl radical, an alkoxy and/or an alkylthio group, or are cycloalkyl, phenyl, or together are an alkylene chain which can have attached to it one to five alkyl groups and which can be bridged by an alkylene chain;
25 R12 is hydrogen or alkyl which can be substituted by hydroxyl, amino, hydrogen sulfide, alkylthio, carboxyl, carbamoyl, guanidinyl, phenyl, hydroxyphenyl, imidazolyl or indolyl radicals, or together with R7 is linked via an alkylene chain to form a ring;
Rl3 is alkyl, alkenyl or a:Lkynyl;
where 35 sub~tituted alkyl, substituted alkoxy, substituted alkylthio, sub~tituted alkylsulfinyl, substituted alkylsulfonyl, substituted alkylamino and substituted dialkylamino are to be understood as meaning in each case that the alkyl groups can be substituted by one up to the maximum possible number of halogen atoms and/or can 40 have attached to them one to three of the following radicals:
nitro, cyano, haloalkoxy, alkyl.thio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three hal.oqen atoms or one to three methyl groups, or phenoxy or phenoxy which is substituted by one to 45 three halogen atoms or one to t.hree methyl groups, substituted phenyl, substituted phenoxy, substituted phenylthio and substituted phenylsulfonyl are to be understood as meaning in each case that the phenyl ring can have attached to it one to five halogen atoms, one to three alkyl or alkoxy groups and/or 5 one to three of the following radicals: nitro, cyano, haloalkyl, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three halogen atoms or one to three methyl groups, or phenoxy or phenoxy which i8 substituted by one to three halogen atoms or one 10 to three methyl groups.
Preferred salicylic acid derivatives of the formula I are those where the substituents have the following meanings:
15 A is a 5-membered heteroaromatic ring having one oxygen, nitrogen or sulfur atom or h~ving one to four nitrogen atoms or having one to two nitrogen atoms and additionally one sulfur or oxygen atom in the ring which has attached to it at ].east one radical -B-R5 and which can additionally have attached to it one or more of the following substituents: nitro, halogen, cyano, unsubstituted or substi.tuted Cl-C6-alkyl, C1-C4-alkylthio, C1-C4-alkylsulfonyl, C1-C4-alkylsulfinyl, formyl or a radical R5; a 6-membered heteroaromatic ring having two to three nitrogen atoms in the ring which has attached to it at least one radical -B-R5 and which can additionally have attached to it one or more of the following sub~tituents: nitro, halogen, cyano, unsubstituted or substituted Cl-C6-alkyl, Cl-C4-alkylthio, Cl-C4-alkylsulfonyl, C1-C4-alkylsulfinyl, formyl or a radical R5; preferably a 5 -mhered heteroaromatic ring having one oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one to two nitrogen atoms and additionally one sulfur or oxygen atom in the ring which has attached to it at least one radcial -o-R5 or a 6-membered heteroaromatic ring having two to three nitrogen atoms in the ring which has attached to it at least one radical -o-R5;
40 B is oxygen, sulfur, SO or SO2;
X is oxygen or sulfur;
Y is nitrogen or C-H, preferably nitrogen;
Z is nitrogen or a group C-R4, preferably a group C-H or nitrogen;
Rl is halogen, Cl-C6-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl-C4-alkylthio, Cl-C4-alkylamino and/or di-Cl-C4-alkylamino; preferably halogen, Cl-C4-alkyl, Cl-C4 -alkoxy, Cl-C 4- haloalkoxy;
R2 is halogen, Cl-C6-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl-C4--alkylthio, Cl-C4-alkylamino and/or di-Cl-C4-alkylamino, preferably halogen, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, especially preferably Cl-C2-alkoxy and C1-C2-haloalkoxy;
15 R3 is hydrogen;
a succinyliminooxy group;
a 5 s ~ered heteroaromatic ring containing one to three nitrogen atoms which can have attached to it one to four halogen atoms and/or one to two of the following radical~: Cl-C6-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy and/or Cl-C4-alkylthio;
a radical oR6;
a radical (~)m - N
where R7 and R8 can be identical or different and where m can assume the values () or l;
or a radical o preferably hydrogen, a radical oR6, a radical ~(o)m-NR7R8, especially preferably a radical oR6;
R4 is hydrogen, C1-C4-alkyl, halogen;
R5 is unsubstituted or substituted C1-C6-alkyl, di-C1-C4-alkylamino or unsubstituted or substituted phenyl; especially preferably unsubstituted or substituted C1-C4-alkyl;
R6 i8 hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
a Cl-C8-alkyl group which can have attached to it one to five halogen atoms and/or one or two of the following radicals: Cl-C4-alkoxy, Cl-C4-alkylthio, cyano, Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl, C3-c6-cYcloalkyl~ a radical -O-N=CR1OR11 where R10 and can be identical or diiferent, phenyl, phenoxy, or phenylcarbonyl, it being possible for the aromatic radicals, in turn, to have attached to them one to five halogen atoms and/or one to three of the following radicals: C1-C6-alkyl, Cl-C4-haloalkyl, C1-C4-alkoxy, Cl-C4-haloalkoxy and/or C1-C4-alkylthio;
a C1-C6-alkyl group which can have attached to it one to five halogen atoms, and a 5-membered heteroaromatic ring containing one to three nitrogen atoms, or a 5-membered heteroaromatic ring containing one to three nitrogen atoms and additionally one sulfur or oxygen atom in the ring, it being possible for these to have attached to them one to four halogen atoms and/or one to two of the following radicals: Cl-C4-alkyl, C1-C4-haloalkyl, Cl-C4-alkoxy, C1-C4-haloalkoxy and/or Cl-C4-alkylthio;
a Cl-C6-alkyl group which has attached to it in the 2-position one of the following radicals:
Cl-C4-alkoxyimino, Cl-C4-alkenyloxyimino, Cl-C4-haloalkenyloxyimino or benzyloxyimino;
a C3-C6-alkenyl or a C3--C6-alkynyl group, it being possible for these groups, in turn, to have attached to them one to five halogen atoms;
.
OOS0/~6245 phenyl which is unsubstituted or mono- to trisubstituted by nitro, Cl-Cg-alkyl or Cl-C4-alkoxy or mono- to pentasubstituted by halogen;
a radical -N=CRl~Rll where Rl~ and Rll can be identical or different;
a 5-membered aromatic heterocycle bonded via a nitrogen atom and having one to four nitrogen atoms in the ring or a benzo-fused 5 ;~ ~ered aromatic heterocycle bonded via a nitrogen atom and having one to three nitrogen atoms in the ring, it being possible for these to be substituted by halogen, Cl-C6-alkyl, Cl-C4-haloalkyl;
15 R7,R8 are hydrogen;
Cl-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, it being possible for each of these radicals to have attached to it one to five halogen atoms and/or one to two of the following groups: Cl-Cg-alkoxy, Cl-C4-alkylthio, cyano, Cl-C4-alkylcarbonyl, C~-C4-alkoxycarbonyl, bis-di-Cl-Cg-alkylamino, cyclo-C3-C6-alkyl;
phenyl or substituted phenyl;
together are a cyclized Cl-C6-alkylene chain or together are a cyclized Cl-C6-alkylene chain having a hetero atom, which can be oxygen, sulfur or nitrogen, it being possible for each of these to have attached to it one to three Cl-C4-alkyl subsl:ituents;
or a group - CH
\~--R13 40 R9 is Cl-C6-alkyl or phenyl, which can have attached to them one to four of the following substituents: halogen, nitro, cyano, Cl-C4-alkyl;
Rl~,Rll are Cl-C6-alkyl which can have attached to it a phenyl radical, a Cl-C4-alkoxy and/or a Cl-Cg-alkylthio group, or are C3-C6-cycloalkyl, phenyl, or together are a Cl-C6-alkylene chain which can have attached to it one to five Cl-C4-alkyl groups and which can be bridged by a Cl-C6-alkylene chain; especially preferably are Cl-C4-alkyl, and together a Cl-C5-alkylene chain;
5 R12 i9 hydrogen or Cl-C6-alkyl which can be substituted by hydroxyl, amino, hydrogen sulfide, alkylthio, carboxyl, carbamoyl, guanidinyl, phenyl, hydroxyphenyl, imidazolyl or indolyl radicals, or together with R7 is linked via a Cl-C4-alkylene chain to form a ring;
Rl3 is Cl-C6-alkyl, Cl-C4-a].kenyl or Cl-C4-alkynyl;
where 15 substituted alkyl, substituted alkoxy, substituted alkylthio, substituted alkylsulfinyl, substituted alkylsulfonyl, substituted alkylamino and substituted dialkylamino are to be understood as meaning in each case that the a:Lkyl groups can be substituted by one up to the ~ possible number of halogen atoms and/or can 20 have attached to them one to three of the following radicals:
nitro, cyano, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three halogen atoms or one to three methyl groups, or phenoxy or phenoxy which is substituted by one to 25 three halogen atoms or one to three methyl groups, and substituted phenyl, substituted phenoxy, substituted phenylthio and substituted phenylsulfonyl are to be understood as meaning in each case that the phenyl ring ~_an have attached to it one to 30 five halogen atoms, one to three alkyl or alkoxy groups and~or one to three of the following radicals: nitro, cyano, haloalkyl, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three halogen atoms or one to three methyl groups, or phenoxy or 35 phenoxy which is substituted by one to three halogen atoms or one to three methyl groups.
Preferred salicylic acid derivatives of the formula I are those where the substituent R6 has the following meanings:
R6 is hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
a Cl-C4-alkyl group which can have attached to it one to five halogen atoms and~or one or two of the following radicals: Cl-C4-alkoxy, Cl-C4-alkylthio, cyano, Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl, .
C3-C6-cycloalkyl, a radical -0-N=CR10Rll where Rl~ and R
can be identical or different, phenyl, phenoxy, or phenylcarbonyl, it being possible for the aromatic radicals, in turn, to have attached to them one to five halogen atoms and/or one to three of the following radicals: Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy and~or Cl-C4-alkylthio;
a C2-C4-alkenyl or a C2--C4-alkynyl group, it being possible for these groups, in turn, to have attached to them one to five halogen atoms;
phenyl which is unsubstituted or mono- to trisubstituted by nitro, alkyl or alkoxy or mono- to pentasubstituted by halogen;
a radical -N=CRl~Rll where R10 and Rll can be identical or different;
20 and the remaining substituents have the abovementioned meanings.
~urthermore preferred salicylic acid derivatives of the formula I
are those where the substituents R7 and R8 have the following meanings:
R7,R8 are hydrogen;
Cl-C4-alkyl, Cl-C4-alkenyl, Cl-C4-alkynyl;
phenyl or substituted phenyl;
together are a cyclized C1-C6-alkylene chain or together are a cyclized Cl-C6-alkylene chain having a hetero atom, which can be oxygen, sulfur or nitrogen, it being possible for each of these to have attached to it one to three alkyl substituent:s;
and the remaining substituents have the abovementioned meanings.
40 ~urthermore preferred salicylic acid derivatives of the formula I
are those where the substituent R6 has the following meanings:
R6 i5 hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
1~
a Cl-C2-alkyl group which can have attached to it one to five halogen atoms and~or one of the following radicals:
alkoxy, alkylthio, phenyl;
5 and the remaining substituents have the abovementioned -Anings Other preferred salicylic acid derivatives of the formula I are those where the substituents R6, R7 and R8 have the following ~AningS:
R6 is hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
a Cl-C4-alkyl group which can have attached to it one to lS five halogen atoms and/or one or two of the following radicals: C1-C4-alkoxy, Cl-C4-alkylthio, cyano, Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl, C~-C6-cycloalkyl, a radical -O-N=CR10R11 where R10 and R
can be identical or different, phenyl, phenoxy, or phenylcarbonyl, it being possible for the aromatic radicals, in turn, to have attached to them one to five halogen atoms and/or one to three of the following radicals: C1-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy and/or Cl-C4-alkylthio;
a C2-C4-alkenyl or a C2-C4-alkynyl group, it being possible for these groups, in turn, to have attached to them one to five halogen atoms;
phenyl which is unsubstituted or mono- to trisubstituted by nitro, alkyl or alkoxy or mono- to pentasubstituted by halogen;
a radical -N=CRl~Rll where Rl~ and Rll can be identical or ~5 different;
R7,R8 are hydrogen;
Cl-C4-alkyl, Cl-C4-alkenyll Cl-C4-alkynyl;
phenyl or substituted phenyl;
together are a cyclized C1-C6-alkylene chain or together are a cyclized C1-C6-alkylene chain having a hetero atom, which can be oxygen, slllfur or nitrogen, it being possible for each of these to have attached to it one to three alkyl substituents;
and the remaining substituents have the abovementioned meanings.
Also preferred salicylic acid derivatives of the formula I are those where the substituents R6, R7 and R8 have the following meanings:
10 R6 is hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
a C1-C2-alkyl group which can have attached to it one to five halogen atoms and/or one of the following radicals:
alkoxy, alkylthio, phenyl;
R7,R8 are hydrogen;
Cl-C4-alkyl, Cl-C4-alkenyl, Cl-C4-alkynyl;
phenyl or substituted phenyl;
together are a cyclized C1-C6-alkylene chain or together are a cyclized Cl-C6-al.kylene chain having a hetero atom, which can be oxygen, sulfur or nitrogen, it being possible for each of these to have attached to it one to three alkyl substituents;
and the remaining substituents have the abovementioned meanings.
Especially preferred salicylic acid derivatives of the formula I
are those where the substituents Rl, R2 and Y have the following meanings:
35 Rl,R2 are alkoxy and Y is nitrogen and the remaining substituents have the abovementioned -Anings.
Other especially preferred salicylic acid derivatives of the formula I are those where the substituents Rl, R2, Y and R3 have the following meanings:
45 Rl,R2 are alkoxy, Y is nitrogen, Z is C-H and 5 R3 is hydroxyl and the remaining substituents have the abovementioned meanings.
Very especially preferred salicylic acid derivatives of the 10 formula I are those where the substituents Rl, R2, Y, R3 and A
have the following meanings:
Rl,R~ are alkoxy, 15 Y is nitrogen, R3 is hydroxyl and A is a 5 ~ - 'ered heteroaromatic ring having one oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one to two nitrogen atoms and additionally one sulfur or oxygen atom in the ring which has attached to it at least one radical -~-R5 and which can additionally have attached to it one or more of the following substituents; nitro, halogen, cyano, unsubstituted or substituted alkyl, alkylthio, alkylsulfonyl, alkylswlfinyl, formyl or a radical R5, and the remaining substituents have the abovementioned meanings.
Patent Applications Wo 91/13065 and DE-A 39 19 435 disclose herbicidally active salicylaldehyde derivatives and salicylic acid derivatives, respectively, which have a heterocyclic substituent. The activity of the compounds known from the 35 literature is not always satisfactory with a view to herbicidal action, crop plant selectivity or bioregulatory action.
It is therefore an object of the present invention to provide heterocycle-substituted salicylaldehyde and salicylic acid 40 derivatives which have an improved biological activity.
Accordingly, we have found that this object is achieved by the heterocycle-substituted salicylic acid derivatives I defined at the outset. The novel compounds I have an outstanding herbicidal 45 action combined with an improved selectivity in crop plants.
We have furthermore found processes for the preparation of the compounds I and their use as herbicides and growth regulators.
The compounds of the formula I are accessible via a plurality of 5 routes. Particularly advantageous is the route via the benzo[l,3]-dioxinones IV which can be prepared by known processes from the heterocyclic tin compounds II and the benzodioxinones III with palladium catalysis (EP 657 441) and which are first opened with a nucleophile R3-H in a manner known per se in the 10 presence or absence of a base to give the salicylic acid derivatives V, which are then reacted with heterocycles of the type VI in a manner known per se in the presence or absence of a base:
base Pd~/pdII ~ R3 - H ~
SnR123 + Rl6 ~ X A ~ X A ~ XH
0 ~ o ~ 0 ~ o ~ ~ ~ R3 II III IV V
~
N ~ Z N ~ Z
A ~ X Y R2 Rl4 ~ Y ~ R2 o R3 I VI
The radicals have the abovement:ioned meanings, Rl2 is Cl-C6-alkyl and Cl-C6-cycloalkyl, Rl6 is a halogen atom, preferably bromine or 35 iodine, or a trifluoromethylsulfonyloxy group, Rl4 is a nucleofugic leaving group such as halogenf alkyl- or arylsulfonyl.
Furthermore, a derivative A-R16 can be reacted with a 40 tin-substituted benzoic acid of the formula VII where Rl5 is unsubstituted or substituted benzyl, Cl-C4-alkyl, dihydropyranyl, trialkylsilyl, alkoxyalkyl and dialkoxyalkyl with palladium catalysis and the resulting benzoic acid VIII can be converted in a manner known per se into the salicylic acids Va where 45 R3 = hydrogen:
A - R16 + R123Sn ~ , R15 ~ , R15 ~ OH
OH O OH O OH
VII VIII Va 10 A catalytically active palladium compound i9 employed in each of the two abovementioned processes. Any palladium salts or complexes which are at least partially soluble in the reaction mixture are suitable. The oxidation level of the palladium can be 0 or 2. Suitable counterions for the palladium salts are, inter 15 alia, the following: chloride, bromide, iodide, sulfate, acetate, trifluoroacetate, acetylacetonate or hexafluoro-2,4-pentadionate.
A large number of different palladium complexes can be used. The only prerequisite is that the ligands of the palladium can be displaced by the substrate under the reaction conditions.
20 Especially suitable ligands are phosphine ligands, eg.
aryl-alkylphosphines such as, inter alia, methyldiphenylphosphine, isopropyldiphenylphosphine, triarylphosphines such as, inter alia, triphenylphosphine, tritolylphosphine, trixylylphosphine, trihetarylphosphines, such 25 as trifurylphosphine, or dimer:ic phosphines. Substances which are also well suited are olefinic ligands, such as, inter alia, dibenzylideneacetone or its saLts, cycloocta-1,5-diene or amines such as trialkylamines (eg. triethylamine, tetramethylethylenediamine, N-methylmorpholine) or pyridine.
The complex used can be employed directly in the reaction. This procedure can be followed using, for example, tetrakistriphenylphosphinepalladium(0), bistriphenylphosphinepalladium dichloride, 35 bistriphenylphosphinepalladium diacetate, a dibenzylideneacetone/palladium(0) complex, tetrakismethyl-diphenylphosphinepalladium(0) or bis(1,2-diphenylphosphinoethane)palladium dichloride. It is also possible to use a palladium salt and additionally a suitable 40 ligand, and the catalytically active complex is formed in situ only then. This procedure is suitable, for example, for the abovementioned salts and phosphine ligands, eg. trifurylphosphine or tritolylphosphine. Palladium complexes, eg.
tris~dibenzylideneacetone)dipalladium, 45 bis(dibenzylideneacetone)palladium or 1,5-cyclooctadienepalladium dichloride can also be further activated by the addition of ligands, eg. trifurylphosphine or tritolylphosphine.
As a rule, 0.001 to 10 mol%, in particular 0.005 to 5 mol%, of 5 the palladium compound (salt or complex) is used, based on the compounds II or VII. Higher amounts are possible, but tend to be uneconomical. The amount of II or VII based on the reactants III
and A-R13, respectively, is generally from 0.8 to 3, preferably 0.95 to 1.5, mole equivalents. All solvents which do not react l0 themselves with the substrates used are suitable for the reaction. Polar solvents accelerate the reaction. Especially suitable are ethers such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, amides such as dimethylformamide, dimethylacet:amide, N-methylpyrrolidone, lS dimethylpropyleneurea, or amines such as triethylamine. The use of mixtures, eg. of ethers with amides, is frequently advantageous. Other suitable components for mixtures are alkyl alcohols and water, especially when the radical B contains a boron atom. The addition of te1:raalkylammonium halides or alkali 20 metal halides, eg. lithium chloride, is frequently useful and particularly recommended when X is a sulfonyloxy radical. It is frequently useful to add an organic or inorganic base, such as potassium carbonate, sodium carbonate, calcium carbonate, calcium hydroxide, sodium hydroxide, potassium hydroxide, potassium 25 phosphate, sodium phosphate, pyridine or an amine, such as triethylamine, especially when the radical B contains a boron atom.
The reaction temperature is from -20 to 200 C, preferably from 50 30 to 160 C. The reaction times are usually from a few minutes to 50 hours, in most cases 0.5 to l0 hours. When using low-boiling solvents, it is sometimes useful to carry out the reaction in the autoclave under inherent pressure.
35 The organotin compounds of the formula VII are prepared by metallating the benzoic acid on which they are based with a suitable base at low temperatures and subsequently reacting the product with a trialkyltin compound to give VII:
COOH COOH
R1s~ ~ 1) base R1s~ ~ SnR123 VII
Suitable bases are mainly cycloalkyl- or alkyllithium compounds, especially suitable being the commercially available butyl- and hexyllithium isomers. It is frequently expedient to add an auxiliary to aid metalation. Suitable substances are ethers, 5 alcoholates, eg. potassium tert-butylate, or amines such as tetramethylethylene~i ~ri ne The metalation can be effected at from (-130) C to 0 C, preferably from ~-100) to ~-50) C. All solvents which are normally used for metalation reactions are also suitable for this reaction, diethyl ether, methyl tert-butyl 10 ether, tetrahydrofuran and simple hydrocarbons being especially suitable; it may be advantageous to use mixtures of these. The reaction times for the metalation can be from a few minutes to a few hours. The trialkyltin compound is subsequently added, R13 being the customary leaving groups, preferably chlorine or 15 bromine. As regards the temperature during the addition and the subsequent reaction time, what has been described above also applies here. This may be followed by aqueous or non-aqueous work-up; it may be useful in the first case to keep constant the pH of the aqueous phase by means of a buffer. The yield may be 20 increased considerably when a substance which is suitable for destroying excess base is added at low temperatures prior to work-up. Suitable substances are, for example, carbon dioxide, water, alkyl halides or benzyl halides. If required, the organotin compounds of the formula I can be purified further, for 25 example by chromatography on silica gel. They prove to be stable during work-up and also to water at various pH values and can be stored at room temperature.
Another possibility of synthesizing active ingredients of the 30 formula I is to convert a heterocyclic formyl compound IX by known methods into the corresponding crotonaldehyde X, which is then reacted in a manner known per se ~EP 402 751) via the cyclohexenone XI and the salicylic acid derivative XII to give the active ingredient.
O O
5 o ~ A H ~ ~ ~ ~ oR6 ~B=CH3 or Ph3P=CH) IX X XI
R
N ~ Z
Rl R14Y ~ R2 OH O
A ~ ~ VI ~ oR6 o OR6 Ib XII
20 Benzoic acid derivatives, ie. compounds I where R3 is an OH group, can also be synthesized by con~erting a suitable precursor I
where R3 is oR6 into the free acid Ia by means of hydrolysis or hydrogenation.
Rl R
¦ hydrolysis or ~ N'~z hydrogenation ~ N ~ z A ~ X Y ~ R2 A ~ X Y ~ R2 30~ ~ R3 0 OH
I Ia Compounds of the formula I can also be synthesized by starting from the free acids Ia, ie. substances where R3 is OH, and 35 converting them into an activated form, such as a halide or an imidazolide, which are then reacted with a nucleophile R3-H in the presence or absence of a base. Alternatively, it is also possible first to activate the salicylic acids III and then to react the resulting derivatives V with heterocycles IV to give the active 40 ingredients I.
A ~ O~ ~ N 1 z OH O OH
III-OH Ia 1. activation 1. activation 102. R3-H ~2. R3-H
Rl A ~ OH ~ A ~ X Y R2 o R3 III I
20 In the description, the substituents mentioned preferably have the following meanings:
Cl-C4-alkyl: methyl, ethyl, l-p:ropyl, 2-propyl, l-butyl, 2-butyl, 2-methyl-propyl, l,l-dimethyl-ethyl;
Cl-C6-alkyl: C1-C4-alkyl and 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-butyl, 3-methyl-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 1,1-dimethylpropyl, 1,2-dimethyl-propyl, 2,2-dimethylpropyl, l-hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl, 30 3-methylpentyl, 4-methylpentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl.butyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 3,3-dimethyl.-2-butyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, in particular 35 methyl, ethyl, propyl, 2-propy]., butyl, 2-butyl, l,l-dimethylethyl, pentyl, 2,2-dimethylpropyl, hexyl;
Cl-C4-haloalkyl: chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, 40 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 1,1,2,2-tetrafluoroethyl, 2,2,~-trifluoroethyl, 2-chloro-1,1,2-trifluoroethyl and pentafluoroethyl, decafluorobutyl, l,1-bis-trifluoromethyl-2,2,2-trifluoroethyl, preferably difluoromethyl, trifluoromethyl, trichloromethyl and 45 chlorodifluoromethyl;
C3-C8-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, especially preferably cyclopropyl, cyclopentyl and cyclohexyl;
5 C3-Cl2-cycloalkyl: C3-C8-cycloalkyl and cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl, especially pre~erably cyclopropyl, cyclopentyl and cyclohexyl;
Cl-C4-alkylcarbonyl: acetyl, propionyl, l-propylcarbonyl, 10 2-propylcarbonyl, l-butylcarbonyl, 2-butylcarbonyl, 2-methyl-propylcarbonyl, l,1-dimethyl-ethylcarbonyl;
Cl-C4-alkoxycarbonyl: ethoxycarbonyl, propoxycarbonyl, l-propyloxycarbonyl, 2-propyloxycarbonyl, l-butyloxycarbonyl, 15 2-butyloxycarbonyl, 2-methyl-propyloxycarbonyl, l,l-dimethyl-ethoxycarbonyl;
C3-C6-alkenyl: propenyl, l-butenyl, 2-butenyl, 2-methylpropenyl, pentenyl, 2-pentenyl, 2-methy.lbutenyl, 3-methylbutenyl, 20 2-methyl-2-butenyl, hexenyl, 2-hexenyl, 3-hexenyl, 2-methylpentenyl, 3-methylpentenyl, 4-methylpentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 2,3-dimethylbutenyl, 2-ethylbutenyl, 3,3-dimethylbutenyl, 2,3-dimethyl-2-butenyl;
C3-C6-alkynyl: propynyl, butynyl, 2-butynyl, pentynyl, 2-pentynyl, 3-methylbutynyl, hexynyl, 2-hexynyl, 3-hexynyl, 3-methyl-pentynyl, 4-methyl-pentynyl, 4-methyl-2-pentynyl;
30 Cl-C4-alkoxy: methoxy, ethoxy, propoxy, l-methylethoxy, butoxy, 2-butoxy, l-methylpropoxy, 2-methylpropoxy, l,l-dimethylethoxy, in particular methoxy, ethoxy, l-methylethoxy;
Cl-C6-alkoxy: Cl-C4-alkoxy and pentoxy, 2-pentoxy, 3-pentoxy, 35 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methyl-2-butoxy, 3-methyl-2-butoxy, l,l-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 40 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, in particular methoxy, ethoxy, 1-methylethoxy;
45 Cl-C8-alkoxy: Cl-C6-alkoxy and heptoxy, octoxy, 2-ethylhexoxy;
0050~46245 Cl-C4-haloalkoxy: difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, l-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy and S pentafluoroethoxy, 1,1,2,3,3,3-hexafluoropropoxy, heptafluoro-propoxy, decafluorobutoxy, 1,1-bis-trifluoromethyl-2,2,2-trifluoroethoxy, preferably difluoromethoxy, trifluoromethoxy and chlorodifluoromethoxy;
0 Cl-C12-cyc loalkoxy: cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy, cyclodecyloxy, cycloundecyloxy and cyclododecyloxy, especially preferably cyclopropoxy, cyclopentoxy and cyclohexyloxy;
15 Cl-C4-alkylcarbonyloxy: acetoxy, propionyloxy, l-propylcarbonyloxy, 2-propylcarbonyloxy, l-butylcarbonyloxy, 2-butylcarbonyloxy, 2-methyl-propylcarbonyloxy, l,1-dimethyl-ethylcarbonyloxy;
20 Cl-C4-alkylthio: methylthio, ethylthio, propylthio, l-methylethylthio, butylthio, ~-butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, in particular methylthio, ethylthio, 1-methylethylthio;
25 C1-C4-alkylsulfinyl: methylsulfinyl, ethylsulfinyl, propylsulfinyl, l-methylethylsulfinyl, butylsulfinyl, 2-butylsulfinyl, l-methylpropylsulfinyl, 2-methylpropylsulfinyl, l,l-dimethylethylsulfinyl, in particular methylsulfinyl, ethylsulfinyl, l-methylethylsulfinyl;
Cl-C4-alkylsulfonyl: methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 2-butylsulfonyl, l-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, in particular methylsulfonyl, 35 ethylsulfonyl, 1-methylethylsulfonyl;
Cl-C4-alkylamino: methylamino, ethylamino, propylamino, l-methylethylamino, butylamino r 2-butylamino, 1-methylpropylamino, 2-methylpropylamino, l,l-dimethylethylamino, 40 in particular methylamino, ethylamino, 1-methylethylamino;
di-Cl-C4-alkylamino: dimethylamino, N-methyl-N-ethylamino, diethylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, dipropylamino, diisopropylamino, N-isopropyl-N-methylamino, 45 N-ethyl-N-isopropylamino, N-isopropyl-N-propylamino, dibutylamino, di-2-methylpropy:Lamino, di-l-methylpropylamino, N-butyl-N-methylamino and isomers, N-butyl-N-ethylamino and isomers, N-butyl-N-propylamino and isomers;
C3-C6-alkylene chain: propylene r butylene, pentylene, hexylene;
5-membered heteroaromatics which may be mentioned are mainly the following heterocycles: 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, l-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, l-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, l-imidazolyl, 2-imidazolyl, 10 4-imidazolyl, 5-imidazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 1,2,3-triazol-1-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, ~lH)1,2,4-triazol-1-yl, 15 (lH)1,2,4-triazol-3-yl, (lH)1,2,4-triazol-5-yl, (4H)1,2,4-triazol-2(5)-yl, (4H~1,2,4-triazol-4-yl, l-tetrazolyl, 5-tetrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 20 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 3(4)-furazanyl, 1,3,4-oxadiazol-2(5)-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,2,5-thiadiazol-3-yl, 1,3,4-thiadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl.
6 - ~cred heteroaromatics which may be mentioned are mainly the following heterocycles: 2-pyrimidinyl, 4(6)-pyrimidinyl, 5-pyrimidinyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 30 1,2,4-triazin-6-yl, 1,2,4,5-tetrazin-3(6)-yl.
The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. The herbicidal compositions comprising I
35 are very good at controlling vegetation on non-crop areas, particularly at high application rates. They act against broad-leaved weeds and grass weeds in crops such as wheat, rice, maize, soya beans and cotton without appreciably damaging the crop plants. This effect is observed mainly at low application 40 rates.
Depending on the particular application method, the compounds I, or compositions comprising them, can additionally be used in a further number of crop plants for eliminating undesirable plants.
45 Suitable crops are, for example, the following:
.
Allium cepa, pnAn~5 comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris ssp~ altissima, Beta vulgaris ssp.
rapa, ~rassica napus var. napus, Brassica napus var.
napobrassica, Brassica rapa var. silvestris, Camellia sinensis, 5 Carth~ s tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), 10 Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa , Phaseolus lunatus, 15 Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus c n;s, Ribes sylvestre, Ricinus c~ lnis, Saccharum officinarum, Secale cereale, Solanum, tuberosum, Sorghum bicolor ~s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia 20 faba, Vitis vinifera, Zea mays.
In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides as a result of breeding including genetic engineering methods.
The herbicidal compositions or the active ingredients can be applied pre- or post-emergence If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are 30 sprayed, with the aid of the spraying equipment, in such a way that they come into as little contact as possible with the leaves of the sensitive crop plants, while the active ingredients reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).
The compounds I, or the herbicidal compositions comprising them, can be applied, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil 40 dispersions, pastes, dusts, materials for spreading, or granules, by means of spraying, atomizing, dusting, scattering or pouring.
The use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.
Suitable inert additives are essentially as follows: mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg.
5 paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols, such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones, such as cyclohexanone, or strongly polar solvents, eg.
amines, such as N-methylpyrrolidone or water.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substances, either as such or dissolved in an 15 oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is also possible to prepare concentrates comprising active ingredient, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution 20 with water.
Suitable surfactants (adjuvants) are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and 25 dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, 30 condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene 35 oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose.
40 Powders, materials for spreading and dusts can be prepared by mixing or grinding the active ingredients together with a solid carrier.
Granules, eg. coated granules, impregnated granules and 45 homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of 5 vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.
The concentrations of the active ingredients I in the ready-to-use preparations can be varied within wide ranges. In lO general, the formulations comprise from 0.001 to 98% by weight, preferably from 0.1 to 95~ by weight, of active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
15 The compounds I according to the invention can be formulated, for example, as follows:
I 20 parts by weight of compound No. 50 are dissolved in a mixture composed of 80 part~ by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueou~
dispersion comprising ().02% by weight of the active ingredient.
30 II 20 parts by weight of compound No. 5 are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,()00 parts by weight of water and finely distributing it therein gives an aqueous dispersion comprising 0.02~ by weight of the active ingredient.
0050~46245 III 20 parts by weight of active ingredient No. 3 are dissolved in a mixture composed of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280 C and 10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion comprising 0.02% by weight of the active ingredient.
IV 20 parts by weight of active ingredient No. 6 are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalenesulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture comprising 0.1% by weight of the active ingredient.
V 3 parts by weight of active ingredient No. S0 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust comprising 3% by weight of the active ingredient.
VI 20 parts by weight of active ingredient No. 5 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dispersion.
VII 1 part by weight of compound 3 is dissolved in a mixture composed of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gives a stable emulsion concentrate.
~0 VIII 1 part by weight of compound 6 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Emulphor EL (ethoxylated castor oil).
This gives a stable emulsion concentrate.
~5 To widen the spectrum of action and to achieve synergistic effects, the substituted salicylic acid derivatives I can be mixed with a large number of representatives of other groups of ' 0050/46245 herbicidal or growth-regulating active ingredients and are then applied concomitantly. Suitable components for mixtures are 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and derivatives thereof, aminotriazoles, anilides, 5 (Het)aryloxyalkanoic acid and derivatives thereof, benzoic acid and derivatives thereof, benzothiadiazinones, 2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and derivatives thereof, 10 chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and derivatives thereof, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, bipyridyls, halocarboxylic acids and derivatives thereof, ureas, 3-phenyluracils, imidazoles, 15 imidazolinones, N-phenyl-3,4,5,6-tetrahydronaphthalimides, oxadiazoles, oxiranes, phenols, aryloxy- or heteroaryloxyphenoxypropionic esters, phenylacetic acid and derivatives thereof, phenylpropionic acid and derivatives thereof, pyrazoles, phenylpyrazoles, pyridazines, 20 pyridinecarboxylic acid and derivatives thereof, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
It may furthermore be advantageous to apply the compounds I, 25 alone or in combination with other herbicides or growth regulators, together with further crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are employed for treating nutrient 30 and trace element deficiencies. Nonphytotoxic oils and oil concentrates may also be added.
Depending on the control aim, the season, the target plants and the stage of growth, the active ingredient application rates are ~5 from 0.001 to 3.0, preferably 0~01 to 1.0, kg of active ingredient (a.i.)/ha.
Use Examples 40 The herbicidal action of the substituted salicylic acid derivatives of the formula I was demonstrated by greenhouse experiments:
The culture containers used were plastic pots containing loamy 45 sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.
.
In the case of pre-emergence treatment, the active ingredients, which were suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles.
The containers were irrigated gently to promote germination and 5 growth and subsequently covered with translucent plastic hoods until the plants had rooted. This cover resulted in uniform germination of the test plants, unless germination was adversely affected by the active ingredients.
10 For the post-emergence treatment, the test plants were first grown to a plant height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which were suspended or emulsified in water. The test plants were either sown directly and grown in the same containerR, or first 15 grown separately as seedlings and transplanted to the test containers a few days prior to treatment. The application rate for the post-emergence treatment is from 0.0312 to 0.0156 kg of a.i./ha.
20 The plants were kept at from 10 to 25 C or 20 to 35 C, depending on the species. The test period extended over 2 to 4 weeks.
During this time, the plants were tended, and their response to the individual treatments was evaluated.
25 The plants were evaluated using a scale of from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal course of growth.
30 The plants used in the greenhouse experiments belonged to the following species:
Scientific Name Common Name 35 Amaranthus retrofelux redroot pigweed Chenopodium album lambsquarters ~goosefoot) Echinochloa crus-galli barnyardgrass Oryza sativa rice 40 Sinapis alba white mustard Solanum nigrum black nightshade Veronica spp. speedwell Table 1 - Selective herbicidal activity, post-emergence treatment in the greenhouse ' 0050/46245 N ~ S ~ o O OH
o \
Ex. No. 50 10Application rate 0.0312 1 0.0156 (kg of a.i./ha~ l Test plants Damage in %
Table 2 - Herbicidal activity, post-emergence treatment in the greenhouse / ~ ~ N
N ~ N~o ~ ~ ~ O ~ OH
; N o o \
Ex. No. 5 30Application rate 0.0312 ¦ 0.0156 Test plants Damage in %
40 Synthesis Examples The protocols given in the Synthesis Examples below were used for obtaining other compounds I by using different starting compounds. The resulting compounds are listed in the Table which 45 follows together with physical data. Compounds without these data can be synthesized from the corresponding educts in a similar manner. The structures given in the Table describe especially preferred active ingredients of the formula I.
Those 2,2-dimethyl-4H-(1,3)benzodioxin-4-ones, used as starting 5 material, which have not been described in EP 657 441 are accessible by methods similar to those described in that publication.
1. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2-methoxythia-zol-5-yl)benzoic acid (Example No. 50): the starting material was obtained in the customary manner by coupling 2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-~1,3)benzo-dioxin-4-one with the tin compound obtained by metallation and stannylation of 2-methoxythiazole. 1.7 g (5.8 mmol) of 2,2-dimethyl-5-(2-methoxythiazol-5-yl)-4H-(l~3)benzodioxin-4-one were refluxed for 4 hours in 80 ml of water together with 241 mg (5.8 mmol) of 97% pure sodium hydroxide and 0.2 ml of a 40% strength tetrabutylammonium hydroxide solution. After filtration, the mixture was concentrated in vacuo and then extracted by boiling with toluene 5 times at 70 C under slightly subatmospheric pressure. The product (1.57 g~ was treated in 80 ml of dimethyl sulfoxide with a small amount of molecular sieve (4 Angstrom) and 646 mg (5.8 mmol) of potassium tert-butylate, and the mixture was stirred for 1 hour at room temperature. 1.26 g (5.8 mmol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine were subsequently added and the mixture was stirred overnight at room temperature. The reaction mixture was transferred to water which had been acidified using phosphoric acid, and the mixture was extracted repeatedly using ethyl acetate. The combined organic phases were washed repeatedly with water, dried over sodium sulfate and concentrated in vacuo. Yield 2.05 g. Melting point 150 to 153~C.
2. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-pyrimidin-5-yl)benzoic acid (Example No. 69):
a) 2,4-Dimethoxy-5-tributylstannylpyrimidine: 45 ml of a 1.6 M solution o~ n-butyllithium in hexane were added dropwise at -70 C to lS.0 g (68.5 mmol) of 2,4-dimethoxy-5-bromopyrimidine in 400 ml of diethyl ether, and stirring was continued for 1.5 hours at -75 CO
23.2 g (68.5 mmol) of 96% pure tributylstannyl chloride were then added dropwise to the yellow suspension at this temperature, the mixture was allowed to come to room temperature, and stirring was continued for 1 hour. After concentration in vacuo, there remained 36.6 g of a crude product which was directly employed further. lH NMR
(CDCl3): ~ = 0.85 (t); 1.05 (t); 1.22 (m); 1.50 (m); 3.95 (s); 4.00 (s); 8.12 (s).
b) 2,2-Dimethyl-5-~2,4-dimethoxy-pyrimidin-5-yl)-4H-(1,3)benzodioxin-4-one: in an autoclave, 12.1 g (37 mmol) of 2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(1,3)benzo-dioxin-4-one, 20.0 g of the above-described tin compound, 4.72 g (111 mmol) of lithium chloride, 855 mg (0.74 mmol) of tetrakistriphenylphosphinepalladium(0) and 50 mg of 2,6-bis-tert-butyl-4-methylphenol were heated for 6 hours at 140 C in 140 ml of dioxane. The mixture was subsequently concentrated in vacuo, chromatographed on silica gel using toluene/ethyl acetate mixtures and then stirred with cyclohexane. Yield 3~5 g. Melting point 194-196 C.
c) 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-pyrimidin-5-yl)benzoic acid: 1.5 g (4.8 mmol) of 2,2-dimethyl-5-(2,4-dimethoxypyrimidin-5-yl)-4H-(1,3)-benzodioxin-4-one were refluxed for 8.5 hours in 60 ml of water together with 196 mg of 97% pure sodium hydroxide and 0.16 ml of 40% strength tetrabutylammonium hydroxide solution. The mixture was filtered, the filtrate was concentrated in vacuo, and the product was extracted by boiling 7 times with toluene at 75 C under slightly subatmospheric pressure and then dried in vacuo. The product (1.41 g) was transferred into 70 ml of dimethyl sulfoxide, 532 mg ~4.7'i mmol) of potassium tert-butylate were added at room temperature, and stirring was continued for 1 hour. ]..04 g (4.75 mmol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine were then added and the mixture was stirred overnight at room temperature. The reaction mixture was transferred into water which had been acidified with phosphoric acid and extracted repeatedly using ethyl acetate. The com~ined organic phases were washed repeatedly with water, dried over sodium sulfate and concentrated in vacuoO Yield 0.9 g. Melting point 161 to 162 C.
3. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-pyrimidin-6-yl)benzoic acid (Example No. 68):
0050~46245 a) 2,4-Dimethoxy-6-tributylstannylpyrimidine: 27 ml of a 1.4 M solution of sec-butyllithium in hexane (38 mmol) were added dropwise at -100~C to 7.55 g (34.5 mmol) of 2,4-dimethoxy-6-bromopyrimidine in 120 ml of diethyl ether and 120 ml of tetrahydrofuran, and stirring was continued for 5 minutes at -100 C. At this temperature, 11.7 g (34.5 mmol) of 96% pure tributylstannyl chloride were then added dropwise, stirring was continued for 30 minutes at -80 C, and the mixture was allowed to come to room te perature. After concentration in vacuo, there remained 18.9 g of a crude product which was directly employed further. lH NMR (CDCl3): ~ = 0.90 (t); 1.07 (t);
1.32 ~m); 1.58 (m); 3.92 (s); 3.97 (s); 6.55 (s).
b) 2,2-Dimethyl-5-(2,4-dimethoxy-pyrimidin-6-yl)-4H-~1,3)benzodioxin-4-one: in an autoclave, 7.07 g (21.7 mmol~ of 2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(l,~)benzo dioxin-4-one, 18.6 g of the above-described tin compound, 2.77 g (65 mmol) of lithium chloride, 502 mg (0.43 mmol) of tetrakistriphenylphosphinepalladium(0) and 40 mg of 2,6-bis-tert-butyl-4-methylphenol were heated for 3 hours at 140 C in 200 ml of dioxane. The mixture was subsequently concentrated in vacuo, chromatographed on silica gel using toluene/ethyl acetate mixtures and then stirred with cyclohexane. Yield 2.5 g. Melting point 1~4~C.
c) 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-pyrimidin-6-yl)benzoic acid: 1.5 g (4,8 mmol) of 2,2-dimethyl-5-(2,4-dimethoxy-pyrimidin-6-yl)-4H-(1,3)benzodioxin-4-one were refluxed for 6 hours in 60 ml of water together with 196 mg of 97%
pure sodium hydroxide and 0.16 ml of 40% strength tetrabutylammonium hydroxide solution. The mixture was acidified and extracted, and the extract was dried over sodium sulfate and concentrated in vacuo. The product (1.07 g, 3.88 mmol) was transferred into 50 ml of dimethyl sulfoxide, 870 mg (7.77 mmol) of potassium tert-butylate were added at room temperature, and stirring was continued for 0.5 hour. 848 mg (3.89 mmol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine were then added and the mixture was stirred overnight at room temperature. The react:ion mixture was subsequently transferred into water which had been acidified with phosphoric acid and extracted repeatedly using ethyl acetate. The combined organic phases were washed .
OOS0/~6245 repeatedly with water, dried over sodium sulfate and concentrated in vacuo. Yield 0.95 g. Melting point 140-143 C.
5 4. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(1-methoxypyra-zol-5-yl)benzoic acid (Example No. 3):
a) 5-Tributylstannyl-l-methoxy-pyrazole: 15 g (153 mmol) of l-methoxypyrazole (prepared in accordance with DE 34 09 317) were dissolved in 280 ml of dry ether and the solution was cooled to -70 C. 96.8 ml (163 mmol) of a 1.7-molar solution of tert-butyllithium in he~Ane were added dropwise, stirring was continued for 1.5 hour, and 49.8 g (153 mmol) of tributyltin chloride were then added. The mixture was allowed to come to room temperature slowly, and stirring was continued overnight.
Then, the mixture was hydrolyzed using 150 ml of water, the organic phase was separated off, washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated. The residue which L- ~ined was freed from low-boiling substances by distillation. 55 g of the product remained (GC purity: 93%).
b) 2,2-Dimethyl-5-(1-methoxypyrazol-5-yl)-4H-(1,3)benzo-dioxin-4-one: in an autoclave, 23.1 g (71 mmol) of 2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(1,3)benzo-dioxin-4-one, 26 g of t:he above-described tin compound, 9.45 g (220 mmol) of lithium chloride, 1.7 g of tetrakistriphenylphosphinepalladium(0) and 90 mg of 2,6-bis-tert-butyl-4-methylphenol were heated for 6 hours at 140 C in 100 ml of dioxane. The mixture was subsequently concentrat:ed in vacuo, chromatographed on silica gel using toluene/ethyl acetate mixtures and then stirred with hexane. Yi.eld: 5 g of colorless oil.
c) 6-(1-Methoxypyrazol-5-yl)salicylic acid: 3.0 g (11 mmol) of the above-described compound were dissolved in 40 ml of acetone, and the solution was added to a solution of 1.77 g (32 mmol) of KO~I and 3 drops of tetrabutylammonium hydroxide solution in 40 ml of water. The mixture was stirred for 4 hours at room temperature, concentrated to half its bulk and extracted using MTBE. The aqueous phase was acidified using phosphoric acid and extracted three times by shaking with ~TBE. The combined organic phases were washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated.
There remained 1.9 g of a colorless solid, m.p. 208 to 218 C.
d) 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(1-methoxypyrazol-5-yl)benzoic acid: 1.61 ~ (6.9 mmol) of the product of c) were transferred into 50 ml of dimethyl sulfoxide, 1.55 g (13.8 mmol) of potassium tert-butylate were added at room temperature, and stirring was continued for 0.5 hour.
1.5 g (6.9 mmol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine were then added and the mixture was stirred overnight at room temperature. The reaction mixture was subsequently poured into water which had been acidified with phosphoric acid, and the solid which precipitated was filtered off with fiuction. The solid was washed with water and dried in a vacuum drying oven at 50 C. Yield 2.07 g. Melting point 182 to 185VC.
5. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(1-ethoxypyra-zol-4-yl)benzoic acid (Example No. s):
a) l-Ethoxypyrazole: 104.8 g (0.76 mol) of potassium carbonate and a solution of 60.1 g (0.385 mol) of ethyl iodide in 200 ml of acetone are added to a solution of 29.4 g (0.35 mol) of l-hydroxypyrazole (prepared in accordance with EP 567 827) in 200 ml of acetone, and the mixture is refluxed for four hours. After cooling, the precipitate is filtered off with suction and washed using acetone. The acetone is first distilled off from the filtrate at atmospheric pressure using a short column, and the distillation is then continued under reduced pressure, the product distilling over at 75 C/78 mm in the form of a colorless liquid. This gives 35.6 g of product in a purity of 99.8~ (GC).
b) 4-Bromo-l-ethoxy-pyrazole 20.1 g (178 mmol) of l-ethoxypyrazole were dissolved in 120 ml of carbon tetrachloride, and a solution of 28.5 g (178 mmol) of bromine in 122 ml of glacial acetic acid was added dropwise at 0 to 5 C while passing through a gentle stream of nitrogen. Stirring was continued for 30 minutes at this temperature, the reaction mixture was then allowed to come to room temperature in the course of one hour and then refluxed for 2.5 hours. After cooling, the mixture was poured into 500 ml of ice-water, the organic phase was separated off and the aqueous phase was extracted three more times using dichloromethane. The combined organic phases were extracted by shaking with water, 5% strength sodium bicarbonate solution, again with water and with sat;urated sodium chloride solution and dried over sodium sulfate, and the methylene chloride was distilled off on a rotary evaporator. The residue was distilled over a 15 cm Vigreux column, 33.3 g of the product distilling over at 52 to 54 C/0.5 mm (GC purity:
97.8%)-c) 5-Tributylstannyl-l-ethoxypyrazole: 3.81 g (157 mmol) of magnesium filings were placed in 10 ml of dry THF and the mixture was activated using grains of iodine. The mixture was refluxed, the cooling equipment was removed, and a solution of 27 g (142 mmol) of 4-bromo-1-ethoxypyrazole in 160 ml of dry THF was added dropwise in such a manner that the reflux conditions were retained. The mixture was kept under reflux for a further 3 hours, during which process most of the magnesium dissolved. The mixture was allowed to cool to roorn temperature, a solution of 43 g (132 mmol) of tributyltin chloride in 30 ml of dry THF
was then added dropwise, and the mixture was refluxed for 2 hours. After cooling,, the batch was poured into 500 ml of 5% strength ammonium chloride solution, and the aqueous phase was extracted four more times using methylene chloride. The combined organic phases were washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated. The residue which remained was pur:ified on silica gel (deactivated using hex~ ?thyldisalazane~ using hexane/acetone. This gives 21.8 g of colorless oil (GC purity: 84%).
d) 5-(1-Ethoxypyrazol-4-yl)-2,2-dimethyl-4H-(1,3)benzodio-xin-4-one: in an autocLave, 13.3 g (40 mmol) of 2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(1,3)benzo-dioxin-4-one, 20.1 g of the above-described tin compound, 5.23 g (125 mmol) of lithium chloride, 0.94 g of tetrakistriphenylphosphinepalladium(0) and 39 mg of 2,6-bis-tert-butyl-4-methylphenol were heated for 6 hours at 140 C in 100 ml of dioxane. The mixture was subsequently concentrated in vacuo, chromatographed on silica gel using hexane/acetone and then stirred with hexane. Yield: 4.6 g of a colorless oil.
e) 6-(1-Ethoxypyrazol-4-yl)salicylic acid: 2.9 g (10 mmol) of the above-described compound were dissolved in 40 ml of acetone, and the solution was added to a solution of .
1.6 g (29 mmol) of KOH and 3 drops of tetrabutylammonium hydroxide solution in 40 ml of water. The mixture was stirred for 2.5 hours at room temperature, concentrated to half its bulk and extracted using MTBE. The aqueous phase was acidified using phosphoric acid and extracted three times by shaking with MTBE. The combined organic phases were washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated. 2.27 q of a colorless resin remained.
f) 6-(1-Ethoxypyrazol-4-yl)-2-(4,6-dimethoxypyrimidin-2-yl-oxy)benzoic acid: using a protocol similar to the one given above for the l-methoxypyrazol-5-yl derivative, 1.76 g of the product of melting range 57 to 74 C were obtained from 1.55 g l6 mmol) of 6-(1-ethoxypyrazol-4-yl)salicylic acid, 1.35 g (12 mmol) of potassium tert-butylate and 1.31 g (6 mmol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine.
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The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. The herbicidal compositions comprising I
35 are very good at controlling vegetation on non-crop areas, particularly at high application rates. They act against broad-leaved weeds and grass weeds in crops such as wheat, rice, maize, soya beans and cotton without appreciably damaging the crop plants. This effect is observed mainly at low application 40 rates.
Depending on the particular application method, the compounds I, or compositions comprising them, can additionally be used in a further number of crop plants for eliminating undesirable plants.
45 Suitable crops are, for example, the following:
.
Allium cepa, pnAn~5 comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris ssp~ altissima, Beta vulgaris ssp.
rapa, ~rassica napus var. napus, Brassica napus var.
napobrassica, Brassica rapa var. silvestris, Camellia sinensis, 5 Carth~ s tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), 10 Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa , Phaseolus lunatus, 15 Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus c n;s, Ribes sylvestre, Ricinus c~ lnis, Saccharum officinarum, Secale cereale, Solanum, tuberosum, Sorghum bicolor ~s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia 20 faba, Vitis vinifera, Zea mays.
In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides as a result of breeding including genetic engineering methods.
The herbicidal compositions or the active ingredients can be applied pre- or post-emergence If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are 30 sprayed, with the aid of the spraying equipment, in such a way that they come into as little contact as possible with the leaves of the sensitive crop plants, while the active ingredients reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).
The compounds I, or the herbicidal compositions comprising them, can be applied, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil 40 dispersions, pastes, dusts, materials for spreading, or granules, by means of spraying, atomizing, dusting, scattering or pouring.
The use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.
Suitable inert additives are essentially as follows: mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg.
5 paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols, such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones, such as cyclohexanone, or strongly polar solvents, eg.
amines, such as N-methylpyrrolidone or water.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substances, either as such or dissolved in an 15 oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is also possible to prepare concentrates comprising active ingredient, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution 20 with water.
Suitable surfactants (adjuvants) are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and 25 dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, 30 condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene 35 oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose.
40 Powders, materials for spreading and dusts can be prepared by mixing or grinding the active ingredients together with a solid carrier.
Granules, eg. coated granules, impregnated granules and 45 homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of 5 vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.
The concentrations of the active ingredients I in the ready-to-use preparations can be varied within wide ranges. In lO general, the formulations comprise from 0.001 to 98% by weight, preferably from 0.1 to 95~ by weight, of active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
15 The compounds I according to the invention can be formulated, for example, as follows:
I 20 parts by weight of compound No. 50 are dissolved in a mixture composed of 80 part~ by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueou~
dispersion comprising ().02% by weight of the active ingredient.
30 II 20 parts by weight of compound No. 5 are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,()00 parts by weight of water and finely distributing it therein gives an aqueous dispersion comprising 0.02~ by weight of the active ingredient.
0050~46245 III 20 parts by weight of active ingredient No. 3 are dissolved in a mixture composed of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280 C and 10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion comprising 0.02% by weight of the active ingredient.
IV 20 parts by weight of active ingredient No. 6 are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalenesulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture comprising 0.1% by weight of the active ingredient.
V 3 parts by weight of active ingredient No. S0 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust comprising 3% by weight of the active ingredient.
VI 20 parts by weight of active ingredient No. 5 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dispersion.
VII 1 part by weight of compound 3 is dissolved in a mixture composed of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gives a stable emulsion concentrate.
~0 VIII 1 part by weight of compound 6 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Emulphor EL (ethoxylated castor oil).
This gives a stable emulsion concentrate.
~5 To widen the spectrum of action and to achieve synergistic effects, the substituted salicylic acid derivatives I can be mixed with a large number of representatives of other groups of ' 0050/46245 herbicidal or growth-regulating active ingredients and are then applied concomitantly. Suitable components for mixtures are 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and derivatives thereof, aminotriazoles, anilides, 5 (Het)aryloxyalkanoic acid and derivatives thereof, benzoic acid and derivatives thereof, benzothiadiazinones, 2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and derivatives thereof, 10 chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and derivatives thereof, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, bipyridyls, halocarboxylic acids and derivatives thereof, ureas, 3-phenyluracils, imidazoles, 15 imidazolinones, N-phenyl-3,4,5,6-tetrahydronaphthalimides, oxadiazoles, oxiranes, phenols, aryloxy- or heteroaryloxyphenoxypropionic esters, phenylacetic acid and derivatives thereof, phenylpropionic acid and derivatives thereof, pyrazoles, phenylpyrazoles, pyridazines, 20 pyridinecarboxylic acid and derivatives thereof, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
It may furthermore be advantageous to apply the compounds I, 25 alone or in combination with other herbicides or growth regulators, together with further crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are employed for treating nutrient 30 and trace element deficiencies. Nonphytotoxic oils and oil concentrates may also be added.
Depending on the control aim, the season, the target plants and the stage of growth, the active ingredient application rates are ~5 from 0.001 to 3.0, preferably 0~01 to 1.0, kg of active ingredient (a.i.)/ha.
Use Examples 40 The herbicidal action of the substituted salicylic acid derivatives of the formula I was demonstrated by greenhouse experiments:
The culture containers used were plastic pots containing loamy 45 sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.
.
In the case of pre-emergence treatment, the active ingredients, which were suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles.
The containers were irrigated gently to promote germination and 5 growth and subsequently covered with translucent plastic hoods until the plants had rooted. This cover resulted in uniform germination of the test plants, unless germination was adversely affected by the active ingredients.
10 For the post-emergence treatment, the test plants were first grown to a plant height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which were suspended or emulsified in water. The test plants were either sown directly and grown in the same containerR, or first 15 grown separately as seedlings and transplanted to the test containers a few days prior to treatment. The application rate for the post-emergence treatment is from 0.0312 to 0.0156 kg of a.i./ha.
20 The plants were kept at from 10 to 25 C or 20 to 35 C, depending on the species. The test period extended over 2 to 4 weeks.
During this time, the plants were tended, and their response to the individual treatments was evaluated.
25 The plants were evaluated using a scale of from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal course of growth.
30 The plants used in the greenhouse experiments belonged to the following species:
Scientific Name Common Name 35 Amaranthus retrofelux redroot pigweed Chenopodium album lambsquarters ~goosefoot) Echinochloa crus-galli barnyardgrass Oryza sativa rice 40 Sinapis alba white mustard Solanum nigrum black nightshade Veronica spp. speedwell Table 1 - Selective herbicidal activity, post-emergence treatment in the greenhouse ' 0050/46245 N ~ S ~ o O OH
o \
Ex. No. 50 10Application rate 0.0312 1 0.0156 (kg of a.i./ha~ l Test plants Damage in %
Table 2 - Herbicidal activity, post-emergence treatment in the greenhouse / ~ ~ N
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Ex. No. 5 30Application rate 0.0312 ¦ 0.0156 Test plants Damage in %
40 Synthesis Examples The protocols given in the Synthesis Examples below were used for obtaining other compounds I by using different starting compounds. The resulting compounds are listed in the Table which 45 follows together with physical data. Compounds without these data can be synthesized from the corresponding educts in a similar manner. The structures given in the Table describe especially preferred active ingredients of the formula I.
Those 2,2-dimethyl-4H-(1,3)benzodioxin-4-ones, used as starting 5 material, which have not been described in EP 657 441 are accessible by methods similar to those described in that publication.
1. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2-methoxythia-zol-5-yl)benzoic acid (Example No. 50): the starting material was obtained in the customary manner by coupling 2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-~1,3)benzo-dioxin-4-one with the tin compound obtained by metallation and stannylation of 2-methoxythiazole. 1.7 g (5.8 mmol) of 2,2-dimethyl-5-(2-methoxythiazol-5-yl)-4H-(l~3)benzodioxin-4-one were refluxed for 4 hours in 80 ml of water together with 241 mg (5.8 mmol) of 97% pure sodium hydroxide and 0.2 ml of a 40% strength tetrabutylammonium hydroxide solution. After filtration, the mixture was concentrated in vacuo and then extracted by boiling with toluene 5 times at 70 C under slightly subatmospheric pressure. The product (1.57 g~ was treated in 80 ml of dimethyl sulfoxide with a small amount of molecular sieve (4 Angstrom) and 646 mg (5.8 mmol) of potassium tert-butylate, and the mixture was stirred for 1 hour at room temperature. 1.26 g (5.8 mmol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine were subsequently added and the mixture was stirred overnight at room temperature. The reaction mixture was transferred to water which had been acidified using phosphoric acid, and the mixture was extracted repeatedly using ethyl acetate. The combined organic phases were washed repeatedly with water, dried over sodium sulfate and concentrated in vacuo. Yield 2.05 g. Melting point 150 to 153~C.
2. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-pyrimidin-5-yl)benzoic acid (Example No. 69):
a) 2,4-Dimethoxy-5-tributylstannylpyrimidine: 45 ml of a 1.6 M solution o~ n-butyllithium in hexane were added dropwise at -70 C to lS.0 g (68.5 mmol) of 2,4-dimethoxy-5-bromopyrimidine in 400 ml of diethyl ether, and stirring was continued for 1.5 hours at -75 CO
23.2 g (68.5 mmol) of 96% pure tributylstannyl chloride were then added dropwise to the yellow suspension at this temperature, the mixture was allowed to come to room temperature, and stirring was continued for 1 hour. After concentration in vacuo, there remained 36.6 g of a crude product which was directly employed further. lH NMR
(CDCl3): ~ = 0.85 (t); 1.05 (t); 1.22 (m); 1.50 (m); 3.95 (s); 4.00 (s); 8.12 (s).
b) 2,2-Dimethyl-5-~2,4-dimethoxy-pyrimidin-5-yl)-4H-(1,3)benzodioxin-4-one: in an autoclave, 12.1 g (37 mmol) of 2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(1,3)benzo-dioxin-4-one, 20.0 g of the above-described tin compound, 4.72 g (111 mmol) of lithium chloride, 855 mg (0.74 mmol) of tetrakistriphenylphosphinepalladium(0) and 50 mg of 2,6-bis-tert-butyl-4-methylphenol were heated for 6 hours at 140 C in 140 ml of dioxane. The mixture was subsequently concentrated in vacuo, chromatographed on silica gel using toluene/ethyl acetate mixtures and then stirred with cyclohexane. Yield 3~5 g. Melting point 194-196 C.
c) 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-pyrimidin-5-yl)benzoic acid: 1.5 g (4.8 mmol) of 2,2-dimethyl-5-(2,4-dimethoxypyrimidin-5-yl)-4H-(1,3)-benzodioxin-4-one were refluxed for 8.5 hours in 60 ml of water together with 196 mg of 97% pure sodium hydroxide and 0.16 ml of 40% strength tetrabutylammonium hydroxide solution. The mixture was filtered, the filtrate was concentrated in vacuo, and the product was extracted by boiling 7 times with toluene at 75 C under slightly subatmospheric pressure and then dried in vacuo. The product (1.41 g) was transferred into 70 ml of dimethyl sulfoxide, 532 mg ~4.7'i mmol) of potassium tert-butylate were added at room temperature, and stirring was continued for 1 hour. ]..04 g (4.75 mmol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine were then added and the mixture was stirred overnight at room temperature. The reaction mixture was transferred into water which had been acidified with phosphoric acid and extracted repeatedly using ethyl acetate. The com~ined organic phases were washed repeatedly with water, dried over sodium sulfate and concentrated in vacuoO Yield 0.9 g. Melting point 161 to 162 C.
3. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-pyrimidin-6-yl)benzoic acid (Example No. 68):
0050~46245 a) 2,4-Dimethoxy-6-tributylstannylpyrimidine: 27 ml of a 1.4 M solution of sec-butyllithium in hexane (38 mmol) were added dropwise at -100~C to 7.55 g (34.5 mmol) of 2,4-dimethoxy-6-bromopyrimidine in 120 ml of diethyl ether and 120 ml of tetrahydrofuran, and stirring was continued for 5 minutes at -100 C. At this temperature, 11.7 g (34.5 mmol) of 96% pure tributylstannyl chloride were then added dropwise, stirring was continued for 30 minutes at -80 C, and the mixture was allowed to come to room te perature. After concentration in vacuo, there remained 18.9 g of a crude product which was directly employed further. lH NMR (CDCl3): ~ = 0.90 (t); 1.07 (t);
1.32 ~m); 1.58 (m); 3.92 (s); 3.97 (s); 6.55 (s).
b) 2,2-Dimethyl-5-(2,4-dimethoxy-pyrimidin-6-yl)-4H-~1,3)benzodioxin-4-one: in an autoclave, 7.07 g (21.7 mmol~ of 2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(l,~)benzo dioxin-4-one, 18.6 g of the above-described tin compound, 2.77 g (65 mmol) of lithium chloride, 502 mg (0.43 mmol) of tetrakistriphenylphosphinepalladium(0) and 40 mg of 2,6-bis-tert-butyl-4-methylphenol were heated for 3 hours at 140 C in 200 ml of dioxane. The mixture was subsequently concentrated in vacuo, chromatographed on silica gel using toluene/ethyl acetate mixtures and then stirred with cyclohexane. Yield 2.5 g. Melting point 1~4~C.
c) 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-pyrimidin-6-yl)benzoic acid: 1.5 g (4,8 mmol) of 2,2-dimethyl-5-(2,4-dimethoxy-pyrimidin-6-yl)-4H-(1,3)benzodioxin-4-one were refluxed for 6 hours in 60 ml of water together with 196 mg of 97%
pure sodium hydroxide and 0.16 ml of 40% strength tetrabutylammonium hydroxide solution. The mixture was acidified and extracted, and the extract was dried over sodium sulfate and concentrated in vacuo. The product (1.07 g, 3.88 mmol) was transferred into 50 ml of dimethyl sulfoxide, 870 mg (7.77 mmol) of potassium tert-butylate were added at room temperature, and stirring was continued for 0.5 hour. 848 mg (3.89 mmol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine were then added and the mixture was stirred overnight at room temperature. The react:ion mixture was subsequently transferred into water which had been acidified with phosphoric acid and extracted repeatedly using ethyl acetate. The combined organic phases were washed .
OOS0/~6245 repeatedly with water, dried over sodium sulfate and concentrated in vacuo. Yield 0.95 g. Melting point 140-143 C.
5 4. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(1-methoxypyra-zol-5-yl)benzoic acid (Example No. 3):
a) 5-Tributylstannyl-l-methoxy-pyrazole: 15 g (153 mmol) of l-methoxypyrazole (prepared in accordance with DE 34 09 317) were dissolved in 280 ml of dry ether and the solution was cooled to -70 C. 96.8 ml (163 mmol) of a 1.7-molar solution of tert-butyllithium in he~Ane were added dropwise, stirring was continued for 1.5 hour, and 49.8 g (153 mmol) of tributyltin chloride were then added. The mixture was allowed to come to room temperature slowly, and stirring was continued overnight.
Then, the mixture was hydrolyzed using 150 ml of water, the organic phase was separated off, washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated. The residue which L- ~ined was freed from low-boiling substances by distillation. 55 g of the product remained (GC purity: 93%).
b) 2,2-Dimethyl-5-(1-methoxypyrazol-5-yl)-4H-(1,3)benzo-dioxin-4-one: in an autoclave, 23.1 g (71 mmol) of 2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(1,3)benzo-dioxin-4-one, 26 g of t:he above-described tin compound, 9.45 g (220 mmol) of lithium chloride, 1.7 g of tetrakistriphenylphosphinepalladium(0) and 90 mg of 2,6-bis-tert-butyl-4-methylphenol were heated for 6 hours at 140 C in 100 ml of dioxane. The mixture was subsequently concentrat:ed in vacuo, chromatographed on silica gel using toluene/ethyl acetate mixtures and then stirred with hexane. Yi.eld: 5 g of colorless oil.
c) 6-(1-Methoxypyrazol-5-yl)salicylic acid: 3.0 g (11 mmol) of the above-described compound were dissolved in 40 ml of acetone, and the solution was added to a solution of 1.77 g (32 mmol) of KO~I and 3 drops of tetrabutylammonium hydroxide solution in 40 ml of water. The mixture was stirred for 4 hours at room temperature, concentrated to half its bulk and extracted using MTBE. The aqueous phase was acidified using phosphoric acid and extracted three times by shaking with ~TBE. The combined organic phases were washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated.
There remained 1.9 g of a colorless solid, m.p. 208 to 218 C.
d) 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(1-methoxypyrazol-5-yl)benzoic acid: 1.61 ~ (6.9 mmol) of the product of c) were transferred into 50 ml of dimethyl sulfoxide, 1.55 g (13.8 mmol) of potassium tert-butylate were added at room temperature, and stirring was continued for 0.5 hour.
1.5 g (6.9 mmol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine were then added and the mixture was stirred overnight at room temperature. The reaction mixture was subsequently poured into water which had been acidified with phosphoric acid, and the solid which precipitated was filtered off with fiuction. The solid was washed with water and dried in a vacuum drying oven at 50 C. Yield 2.07 g. Melting point 182 to 185VC.
5. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(1-ethoxypyra-zol-4-yl)benzoic acid (Example No. s):
a) l-Ethoxypyrazole: 104.8 g (0.76 mol) of potassium carbonate and a solution of 60.1 g (0.385 mol) of ethyl iodide in 200 ml of acetone are added to a solution of 29.4 g (0.35 mol) of l-hydroxypyrazole (prepared in accordance with EP 567 827) in 200 ml of acetone, and the mixture is refluxed for four hours. After cooling, the precipitate is filtered off with suction and washed using acetone. The acetone is first distilled off from the filtrate at atmospheric pressure using a short column, and the distillation is then continued under reduced pressure, the product distilling over at 75 C/78 mm in the form of a colorless liquid. This gives 35.6 g of product in a purity of 99.8~ (GC).
b) 4-Bromo-l-ethoxy-pyrazole 20.1 g (178 mmol) of l-ethoxypyrazole were dissolved in 120 ml of carbon tetrachloride, and a solution of 28.5 g (178 mmol) of bromine in 122 ml of glacial acetic acid was added dropwise at 0 to 5 C while passing through a gentle stream of nitrogen. Stirring was continued for 30 minutes at this temperature, the reaction mixture was then allowed to come to room temperature in the course of one hour and then refluxed for 2.5 hours. After cooling, the mixture was poured into 500 ml of ice-water, the organic phase was separated off and the aqueous phase was extracted three more times using dichloromethane. The combined organic phases were extracted by shaking with water, 5% strength sodium bicarbonate solution, again with water and with sat;urated sodium chloride solution and dried over sodium sulfate, and the methylene chloride was distilled off on a rotary evaporator. The residue was distilled over a 15 cm Vigreux column, 33.3 g of the product distilling over at 52 to 54 C/0.5 mm (GC purity:
97.8%)-c) 5-Tributylstannyl-l-ethoxypyrazole: 3.81 g (157 mmol) of magnesium filings were placed in 10 ml of dry THF and the mixture was activated using grains of iodine. The mixture was refluxed, the cooling equipment was removed, and a solution of 27 g (142 mmol) of 4-bromo-1-ethoxypyrazole in 160 ml of dry THF was added dropwise in such a manner that the reflux conditions were retained. The mixture was kept under reflux for a further 3 hours, during which process most of the magnesium dissolved. The mixture was allowed to cool to roorn temperature, a solution of 43 g (132 mmol) of tributyltin chloride in 30 ml of dry THF
was then added dropwise, and the mixture was refluxed for 2 hours. After cooling,, the batch was poured into 500 ml of 5% strength ammonium chloride solution, and the aqueous phase was extracted four more times using methylene chloride. The combined organic phases were washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated. The residue which remained was pur:ified on silica gel (deactivated using hex~ ?thyldisalazane~ using hexane/acetone. This gives 21.8 g of colorless oil (GC purity: 84%).
d) 5-(1-Ethoxypyrazol-4-yl)-2,2-dimethyl-4H-(1,3)benzodio-xin-4-one: in an autocLave, 13.3 g (40 mmol) of 2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(1,3)benzo-dioxin-4-one, 20.1 g of the above-described tin compound, 5.23 g (125 mmol) of lithium chloride, 0.94 g of tetrakistriphenylphosphinepalladium(0) and 39 mg of 2,6-bis-tert-butyl-4-methylphenol were heated for 6 hours at 140 C in 100 ml of dioxane. The mixture was subsequently concentrated in vacuo, chromatographed on silica gel using hexane/acetone and then stirred with hexane. Yield: 4.6 g of a colorless oil.
e) 6-(1-Ethoxypyrazol-4-yl)salicylic acid: 2.9 g (10 mmol) of the above-described compound were dissolved in 40 ml of acetone, and the solution was added to a solution of .
1.6 g (29 mmol) of KOH and 3 drops of tetrabutylammonium hydroxide solution in 40 ml of water. The mixture was stirred for 2.5 hours at room temperature, concentrated to half its bulk and extracted using MTBE. The aqueous phase was acidified using phosphoric acid and extracted three times by shaking with MTBE. The combined organic phases were washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated. 2.27 q of a colorless resin remained.
f) 6-(1-Ethoxypyrazol-4-yl)-2-(4,6-dimethoxypyrimidin-2-yl-oxy)benzoic acid: using a protocol similar to the one given above for the l-methoxypyrazol-5-yl derivative, 1.76 g of the product of melting range 57 to 74 C were obtained from 1.55 g l6 mmol) of 6-(1-ethoxypyrazol-4-yl)salicylic acid, 1.35 g (12 mmol) of potassium tert-butylate and 1.31 g (6 mmol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine.
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Claims (10)
1. A salicylic acid derivative of the formula I
where the substituents have the following meanings:
A is a 5-membered heteroaromatic ring having one oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one to two nitrogen atoms and additionally one sulfur or oxygen atom in the ring which has attached to it at least one radical -B-R5 and which can additionally have attached to it one or more of the following substituents: nitro, halogen, cyano, unsubstituted or substituted alkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, formyl or a radical R5; a 6-membered heteroaromatic ring having two to three nitrogen atoms in the ring which has attached to it at least one radical -B-R5 and which can additionally have attached to it one or more of the following substituents: nitro, halogen, cyano, unsubstituted or substituted alkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, formyl or a radical R5;
B is oxygen, sulfur, SO, SO2;
X is oxygen or sulfur;
Y is nitrogen or C-H;
Z is nitrogen or a group C-R4;
R1 is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino and/or dialkylamino;
R2 is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino and/or dialkylamino;
R3 is hydrogen;
a succinyliminooxy group;
a 5-membered heteroaromatic ring containing one to three nitrogen atoms which can have attached to it one to four halogen atoms and/or one to two of the following radicals: alkyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
a radical OR6;
a radical where R7 and R8 can be identical or different and where m can assume the values 0 or 1;
or a radical R4 is hydrogen, alkyl, halogen;
R5 is unsubstituted or substituted alkyl, dialkylamino or unsubstituted or substituted phenyl;
R6 is hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
an alkyl group which can have attached to it one to five halogen atoms and/or one or two of the following radicals: alkoxy, alkylthio, cyano, alkylcarbonyl, alkoxycarbonyl, cycloalkyl, a radical -O-N=CR10R11, phenyl, phenoxy, or phenylcarbonyl, it being possible for the aromatic radicals, in turn, to have attached to them one to five halogen atoms and/or one to three of the following radicals: alkyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
an alkyl group which can have attached to it one to five halogen atoms, and a 5-membered heteroaromatic ring containing one to three nitrogen atoms, or a 5-membered heteroaromatic ring containing one to three nitrogen atoms and additionally one sulfur or oxygen atom in the ring, it being possible for these to have attached to them one to four halogen atoms and/or one to two of the following radicals: alkyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
an alkyl group which has attached to it in the 2-position one of the following radicals:
alkoxyimino, alkenyloxyimino, haloalkenyloxyimino or benzyloxyimino;
an alkenyl or an alkynyl group, it being possible for these groups, in turn, to have attached to them one to five halogen atoms;
phenyl which is unsubstituted or mono- to trisubstituted by nitro, alkyl or alkoxy or mono- to pentasubstituted by halogen;
a radical -N=CR10R11 where R10 and R11 can be identical or different;
a 5-membered aromatic heterocycle bonded via a nitrogen atom and having one to four nitrogen atoms in the ring or a benzo-fused 5-membered aromatic heterocycle bonded via a nitrogen atom and having one to three nitrogen atoms in the ring, it being possible for these to be substituted by halogen, alkyl, haloalkyl;
R7,R8 are hydrogen;
alkyl, alkenyl, alkynyl, it being possible for each of these radicals to have attached to it one to five halogen atoms and/or one to two of the following groups: alkoxy, alkylthio, cyano, alkylcarbonyl, alkoxycarbonyl, bis-dialkylamino, cycloalkyl;
phenyl or substituted phenyl;
together are a cyclized alkylene chain or together are a cyclized alkylene chain having a hetero atom, which can be oxygen, sulfur or nitrogen, it being possible for each of these to have attached to it one to three alkyl substituents;
or a group R9 is alkyl or phenyl, which can have attached to them one to four of the following substituents: halogen, nitro, cyano, alkyl;
R10,R11 are alkyl which can have attached to it a phenyl radical, an alkoxy and/or an alkylthio group, or are cycloalkyl, phenyl, or together are an alkylene chain which can have attached to it one to five alkyl groups and which can be bridged by an alkylene chain;
R12 is hydrogen or alkyl which can be substituted by hydroxyl, amino, hydrogen sulfide, alkylthio, carboxyl, carbamoyl, guanidinyl, phenyl, hydroxyphenyl, imidazolyl or indolyl radicals, or together with R7 is linked via an alkylene chain to form a ring;
R13 is alkyl, alkenyl or alkynyl;
where substituted alkyl, substituted alkoxy, substituted alkylthio, substituted alkylsulfinyl, substituted alkylsulfonyl, substituted alkylamino and substituted dialkylamino are to be understood as meaning in each case that the alkyl groups can be substituted by one up to the maximum possible number of halogen atoms and/or can have attached to them one to three of the following radicals: nitro, cyano, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three halogen atoms or one to three methyl groups, or phenoxy substituted phenyl, substituted phenoxy, substituted phenylthio and substituted phenylsulfonyl are to be understood as meaning in each case that the phenyl ring can have attached to it one to five halogen atoms, one to three alkyl or alkoxy groups and/or one to three of the following radicals: nitro, cyano, haloalkyl, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three halogen atoms or one to three methyl groups, or phenoxy or phenoxy which is substituted by one to three halogen atoms or one to three methyl groups.
where the substituents have the following meanings:
A is a 5-membered heteroaromatic ring having one oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one to two nitrogen atoms and additionally one sulfur or oxygen atom in the ring which has attached to it at least one radical -B-R5 and which can additionally have attached to it one or more of the following substituents: nitro, halogen, cyano, unsubstituted or substituted alkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, formyl or a radical R5; a 6-membered heteroaromatic ring having two to three nitrogen atoms in the ring which has attached to it at least one radical -B-R5 and which can additionally have attached to it one or more of the following substituents: nitro, halogen, cyano, unsubstituted or substituted alkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, formyl or a radical R5;
B is oxygen, sulfur, SO, SO2;
X is oxygen or sulfur;
Y is nitrogen or C-H;
Z is nitrogen or a group C-R4;
R1 is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino and/or dialkylamino;
R2 is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino and/or dialkylamino;
R3 is hydrogen;
a succinyliminooxy group;
a 5-membered heteroaromatic ring containing one to three nitrogen atoms which can have attached to it one to four halogen atoms and/or one to two of the following radicals: alkyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
a radical OR6;
a radical where R7 and R8 can be identical or different and where m can assume the values 0 or 1;
or a radical R4 is hydrogen, alkyl, halogen;
R5 is unsubstituted or substituted alkyl, dialkylamino or unsubstituted or substituted phenyl;
R6 is hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
an alkyl group which can have attached to it one to five halogen atoms and/or one or two of the following radicals: alkoxy, alkylthio, cyano, alkylcarbonyl, alkoxycarbonyl, cycloalkyl, a radical -O-N=CR10R11, phenyl, phenoxy, or phenylcarbonyl, it being possible for the aromatic radicals, in turn, to have attached to them one to five halogen atoms and/or one to three of the following radicals: alkyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
an alkyl group which can have attached to it one to five halogen atoms, and a 5-membered heteroaromatic ring containing one to three nitrogen atoms, or a 5-membered heteroaromatic ring containing one to three nitrogen atoms and additionally one sulfur or oxygen atom in the ring, it being possible for these to have attached to them one to four halogen atoms and/or one to two of the following radicals: alkyl, haloalkyl, alkoxy, haloalkoxy and/or alkylthio;
an alkyl group which has attached to it in the 2-position one of the following radicals:
alkoxyimino, alkenyloxyimino, haloalkenyloxyimino or benzyloxyimino;
an alkenyl or an alkynyl group, it being possible for these groups, in turn, to have attached to them one to five halogen atoms;
phenyl which is unsubstituted or mono- to trisubstituted by nitro, alkyl or alkoxy or mono- to pentasubstituted by halogen;
a radical -N=CR10R11 where R10 and R11 can be identical or different;
a 5-membered aromatic heterocycle bonded via a nitrogen atom and having one to four nitrogen atoms in the ring or a benzo-fused 5-membered aromatic heterocycle bonded via a nitrogen atom and having one to three nitrogen atoms in the ring, it being possible for these to be substituted by halogen, alkyl, haloalkyl;
R7,R8 are hydrogen;
alkyl, alkenyl, alkynyl, it being possible for each of these radicals to have attached to it one to five halogen atoms and/or one to two of the following groups: alkoxy, alkylthio, cyano, alkylcarbonyl, alkoxycarbonyl, bis-dialkylamino, cycloalkyl;
phenyl or substituted phenyl;
together are a cyclized alkylene chain or together are a cyclized alkylene chain having a hetero atom, which can be oxygen, sulfur or nitrogen, it being possible for each of these to have attached to it one to three alkyl substituents;
or a group R9 is alkyl or phenyl, which can have attached to them one to four of the following substituents: halogen, nitro, cyano, alkyl;
R10,R11 are alkyl which can have attached to it a phenyl radical, an alkoxy and/or an alkylthio group, or are cycloalkyl, phenyl, or together are an alkylene chain which can have attached to it one to five alkyl groups and which can be bridged by an alkylene chain;
R12 is hydrogen or alkyl which can be substituted by hydroxyl, amino, hydrogen sulfide, alkylthio, carboxyl, carbamoyl, guanidinyl, phenyl, hydroxyphenyl, imidazolyl or indolyl radicals, or together with R7 is linked via an alkylene chain to form a ring;
R13 is alkyl, alkenyl or alkynyl;
where substituted alkyl, substituted alkoxy, substituted alkylthio, substituted alkylsulfinyl, substituted alkylsulfonyl, substituted alkylamino and substituted dialkylamino are to be understood as meaning in each case that the alkyl groups can be substituted by one up to the maximum possible number of halogen atoms and/or can have attached to them one to three of the following radicals: nitro, cyano, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three halogen atoms or one to three methyl groups, or phenoxy substituted phenyl, substituted phenoxy, substituted phenylthio and substituted phenylsulfonyl are to be understood as meaning in each case that the phenyl ring can have attached to it one to five halogen atoms, one to three alkyl or alkoxy groups and/or one to three of the following radicals: nitro, cyano, haloalkyl, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is substituted by one to three halogen atoms or one to three methyl groups, or phenoxy or phenoxy which is substituted by one to three halogen atoms or one to three methyl groups.
2. A salicylic acid derivative of the formula I as claimed in claim 1, where R1,R2 are alkoxy and Y is nitrogen.
3. A salicylic acid derivative of the formula I as claimed in claim 1, where R1,R2 are alkoxy, Y is nitrogen, Z is CH and R3 is hydroxyl.
4. A salicylic acid derivative of the formula I as claimed in claim 1, where R1,R2 are alkoxy, Y is nitrogen, R3 is hydroxyl and A is a 5-membered heteroaromatic ring having one oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one to two nitrogen atoms and additionally one sulfur or oxygen atom in the ring which has attached to it at least one radical -B-R5 and which can additionally have attached to it one or more of the following substituents: nitro, halogen, cyano, unsubstituted or substituted alkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, formyl or a radical R5.
5. A herbicidal composition, comprising a herbicidally active amount of at least one compound of the formula I as claimed in claim 1 and at least one inert liquid and/or solid carrier and, if desired, at least one adjuvant.
6. A method of controlling undesirable vegetation, which comprises allowing a herbicidally active amount of a compound of the formula I as claimed in claim 1 to act on plants, their environment or their seed.
7. The use of a compound of the general formula I as claimed in claim 1 as a herbicide.
8. A process for the preparation of salicylic acid derivatives of the formula I as claimed in claim 1, which comprises reacting heterocyclic tin compounds of the formula II with benzo[1,3]dioxinones of the formula III with palladium catalysis and opening the resulting benzo[1,3]dioxinones IV
with a nucleophile R3-H in the presence or absence of a base to give the salicylic acid derivatives V, which are reacted with heterocycles of the type VI in the presence or absence of a base:
the substituents R1, R2 and R3 having the meanings given in claim 1 and R12 being alkyl and cycloalkyl, R13 a halogen atom or a trifluoromethylsulfonyloxy group and R14 halogen, alkyl- or arylsulfonyl.
with a nucleophile R3-H in the presence or absence of a base to give the salicylic acid derivatives V, which are reacted with heterocycles of the type VI in the presence or absence of a base:
the substituents R1, R2 and R3 having the meanings given in claim 1 and R12 being alkyl and cycloalkyl, R13 a halogen atom or a trifluoromethylsulfonyloxy group and R14 halogen, alkyl- or arylsulfonyl.
9. A process for the preparation of salicylic acid derivatives of the formula Ia as claimed in claim 1, which comprises reacting derivatives A-R13 with tin-substituted benzoic acids of the formula VII where R15 is unsubstituted or substituted benzyl, alkyl, dihydropyranyl, trialkylsilyl, alkoxyalkyl and dialkoxyalkyl with palladium catalysis and converting the resulting benzoic acids VIII into the salicylic acids Va where R3 = hydrogen, which are then reacted with compounds of the formula VI to give the active ingredients Ia where R3 = hydrogen.
10. A process for the preparation of salicylic acid derivatives of the formula I as claimed in claim 1, which comprises converting a heterocyclic formyl compound IX into the corresponding crotonaldehydes X, which are then reacted via the cyclohexenones XI and the salicylic acid derivatives XII
to give the active ingredients of the formula Ib.
to give the active ingredients of the formula Ib.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19536809.6 | 1995-10-02 | ||
| DE19536809A DE19536809A1 (en) | 1995-10-02 | 1995-10-02 | Heterocyclically substituted salicylic acid derivatives |
| PCT/EP1996/004204 WO1997012879A1 (en) | 1995-10-02 | 1996-09-26 | Heterocyclically substituted salicylic acid derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2231493A1 true CA2231493A1 (en) | 1997-04-10 |
Family
ID=7773901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002231493A Abandoned CA2231493A1 (en) | 1995-10-02 | 1996-09-26 | Heterocycle-substituted salicylic acid derivatives |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0873318A1 (en) |
| JP (1) | JP2000500122A (en) |
| KR (1) | KR19990063924A (en) |
| CN (1) | CN1202158A (en) |
| CA (1) | CA2231493A1 (en) |
| DE (1) | DE19536809A1 (en) |
| WO (1) | WO1997012879A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8748627B2 (en) * | 2006-02-15 | 2014-06-10 | Abbvie Inc. | Acetyl-CoA carboxylase (ACC) inhibitors and their use in diabetes, obesity and metabolic syndrome |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10132725A1 (en) | 2001-07-05 | 2006-08-03 | Grünenthal GmbH | Substituted γ-lactone compounds |
| DE10137487A1 (en) * | 2001-08-03 | 2003-03-27 | Gruenenthal Gmbh | Substituted 5,6,6a, 11b-tetrahydro-7-oxa-6-aza-benzo [c] fluorene-6-carboxylic acid derivatives |
| CA2641766A1 (en) | 2006-02-15 | 2007-08-23 | Abbott Laboratories | Novel acetyl-coa carboxylase (acc) inhibitors and their use in diabetes, obesity and metabolic syndrome |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3919435A1 (en) * | 1989-06-14 | 1990-12-20 | Basf Ag | SALICYLALDEHYDE AND SALICYLSAEED DERIVATIVES AND THEIR SULFUR ANALOGUE, PROCESS FOR THEIR MANUFACTURE AS HERBICIDES AND BIOREGULATORS |
| WO1991013065A1 (en) * | 1990-02-20 | 1991-09-05 | Fmc Corporation | 6-aryl-2-substituted benzoic acid herbicides |
| DE4126937A1 (en) * | 1991-08-10 | 1993-02-11 | Basf Ag | SALICYL (THIO) ETHER DERIVATIVES, METHODS AND INTERMEDIATE PRODUCTS FOR THEIR PREPARATION |
| DE4337323A1 (en) * | 1993-11-02 | 1995-05-04 | Basf Ag | Substituted pyridylsalicylaldehyde or salicylic acid derivatives, process for their preparation and their use as herbicides |
-
1995
- 1995-10-02 DE DE19536809A patent/DE19536809A1/en not_active Withdrawn
-
1996
- 1996-09-26 EP EP96932599A patent/EP0873318A1/en not_active Withdrawn
- 1996-09-26 WO PCT/EP1996/004204 patent/WO1997012879A1/en not_active Application Discontinuation
- 1996-09-26 CA CA002231493A patent/CA2231493A1/en not_active Abandoned
- 1996-09-26 CN CN96198318A patent/CN1202158A/en active Pending
- 1996-09-26 KR KR1019980702397A patent/KR19990063924A/en not_active Application Discontinuation
- 1996-09-26 JP JP9513945A patent/JP2000500122A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8748627B2 (en) * | 2006-02-15 | 2014-06-10 | Abbvie Inc. | Acetyl-CoA carboxylase (ACC) inhibitors and their use in diabetes, obesity and metabolic syndrome |
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990063924A (en) | 1999-07-26 |
| CN1202158A (en) | 1998-12-16 |
| WO1997012879A1 (en) | 1997-04-10 |
| EP0873318A1 (en) | 1998-10-28 |
| JP2000500122A (en) | 2000-01-11 |
| DE19536809A1 (en) | 1997-04-03 |
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