JPS60246302A - Use of amides for improving cultural plant resistance of herbicidal heteroaryloxyacetamides - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of known amides as antidotes to improve the tolerance of certain herbicidally active heteroaryloxyamides by crop plants.

The invention furthermore relates to new active compound compositions consisting of known amides and known herbicidally active heteroaryloxyacetamides and having particularly good selective herbicidal properties.

In the context of the present invention, an "antidote" (safety agent) is defined as a substance that is capable of clearly antagonizing the harmful effects of herbicides on crop plants, in other words that is capable of appreciably reversing the herbicidal action of the weed agent to be controlled. It should be understood as a substance that can protect crop plants without affecting them.

It is known that when various herbicide-active heteroaryloxyacetamides are used to control weeds in corn and other crops, they cause some damage to the crop plants.

It is also known that various amides are suitable for reducing the damage that can be caused to crop plants by herbicide active compounds, in particular thiocarbamates and acetanilides (e.g. Publication statement 2
, 218,097, German publication specification 82B, 265
, U.S. Patent No. 4,021,224, U.S. Patent No. 4.124.376 and U.S. Patent No. 4.137.
070).

However, the application of these substances as antidotes is highly dependent on the specific herbicidally active compound.

Formula (n) [wherein Het is a benzo-fused optionally substituted 5-membered heterocyclic % R8 and R4 are independently of each other hydrogen, alkyl, alkenyl, represents alkynyl, substituted alkyl, cycloalkyl, cycloalkenyl, alkoxy, alkenyloxy, alkoxyalkoxy, heterocyclyl or optionally substituted aryl, or R3 and R4 are herbicide-active heteroaryloxyacetamides taken together to represent an optionally substituted saturated or unsaturated heterocyclic group which may contain other heteroatoms. As an antidote to improve resistance, the formula (
1) [wherein R is hydrogen, halogen, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, bicycloalkyl, bicycloalkenyl, tricycloalkyl, aryl, heteroaryl , alkoxy, alkenyloxy, alkynyloxy, aryloxy, carbamoyl, alkoxycarbonyl or dithiolanyl, and R1 and R1 are, independently of each other, in each case hydrogen, formyl, chlorosulfonyl or in each case optionally substituted. Alkyl, alkenyl, alcadenyl, alkynyl, cycloalkyl, cycloalkenyl, which may be
represents alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, phenyl, phenoxy, phenylsulfonyl or heterocyclyl, or amino, alkylidenimino or optionally substituted alkylcarbonylamino or di(alkylcarbonyl)amino, or R1 and R2 together with the nitrogen atom to which they are attached are in each case optionally substituted alkylideneimino, pyrrolidinyl, piperidinyl, piperidonyl, perhydroazepinyl, perhydroazepinyl, dihydropyrazolyl , dihydro- or tetrahydro-pyridinyl, asahicyclononyl, morpholinyl,
perhydro-1,3-oxazinyl, l,3-oxazolidinyl, 1,4-piperazinyl, perhydro-1,4
It has now been found that the known amides of -diazepinyl, dihydro-, tetrahydro- or perhydro-quinolyl or monoisoquinolyl, indolyl or dihydro- or perhydro-indolyl] are very suitable.

The novel active compound compositions consisting of an amide of formula (I) and at least one herbicidal heteroaryloxyacetamide of formula (1) are highly suitable for the selective control of weeds in crops of useful plants. It was also found that

Surprisingly, tolerance by crop plants to herbicidal heteroaryloxyacetamides of formula (If) is expressed by formula (If).
A decisive improvement can be achieved by using the amides of 1) together. It was further unexpected that active compound compositions according to the invention consisting of an amide of formula (1) and a herbicidal heteroaryloxyacetamide of formula (It) would have better selectivity than the active compounds themselves. Ta.

Formula (1) provides a general definition of amides that can be used according to the invention. Suitable amides of formula (1) are those in which R represents hydrogen, fluorine, chlorine or bromine, where R5 and R6 are the same or different and in each case hydrogen or in each case a number of carbon atoms. represents a straight-chain or branched alkyl, alkenyl, alkynyl or cyanoalkyl in each case up to 8, or mono- or polysubstituted with optionally the same or different substituents having 1 to 20 carbon atoms. represents a straight-chain or branched alkyl which may be substituted with hydroxyl, halogen, fluorine, chlorine, bromine and iodine, cyano, cyanato and thiocyanato; in each case up to 6 carbon atoms. and optionally up to 9 identical or different halogen atoms, especially fluorine, chlorine and bromine,
In each case, a linear or branched alkoxy, alkylthio, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, halogenoalkoxy, nor\rogenohydroxyalkoxy, halogenoalkylcarbonyl, or 10genoalkoxycarbonyl,
halogenoalkylcarbonyloxy and halogenoalkenylcarbonyloxy; and in each case optionally phenyl, phenoxy, phenylthio and chenyl; and cycloalkyl and groups having 3 to 7 carbon atoms; , and possible substituents are hydroxyl, halogen, especially fluorine, chlorine and bromine, straight-chain or branched alkoxycarbonyl having up to 6 carbon atoms, and in each case optionally halogen, especially fluorine, phenyl and phenoxy which may be mono- or polysubstituted with the same or different substituents from the group consisting of chlorine and bromine, lower alkyl and lower alkoxy, or R is a straight chain or represents branched alkynyl, or cycloalkyl, cycloalkenyl, in which R has up to 12 carbon atoms in each case and may optionally be mono- or polysubstituted with the same or different substituents; represents bicycloalkyl, bicycloalkenyl or tricycloalkyl; possible substituents are straight-chain or branched alkyl having 1 to 4 carbon atoms, phenyl and groups, where Rfi and R6 have the above meanings; or R represents aryl having 6 to 10 carbon atoms and optionally mono- or polysubstituted with the same or different substituents, possible substituents being halogen, in particular fluorine, chlorine, bromine and iodine, nitro , carboxyl (also in the form of the carboxylate anion), in each case straight or branched, having up to 4 carbon atoms and optionally up to 5 identical or different halogen atoms, in particular fluorine, chlorine and bromine; alkyl, alkoxy,
halochenoalkyl, alkylcarbonyl, halogenoalkylcarbonyl and halogenoalkyl, in which R'' and fLa have the meanings given above, or R may optionally be mono- or polysubstituted in each case with the same or different substituents. represents furyl, chenyl, pyridyl or dithiolanyl, possible substituents are halogen, in particular fluorine, chlorine and bromine; a straight chain with up to 4 carbon atoms or in which 几ゝ and R6 have the abovementioned meaning or finally In each case straight-chain or branched alkoxy,
represents alkenyloxy, alkynyloxy, alkoxycarbonyl or phenoxy, and 1 and R2 are the same or different,
independently of one another hydrogen, formyl, chlorosulfonyl, or in each case optionally mono- or polysubstituted by the same or different substituents from the group consisting of halogen, in particular fluorine, chlorine and bromine, as well as lower alkyl; phenyl, phenoximodi or phenylsulfonyl, or straight-chain or branched alkyl having 1 to 12 carbon atoms and optionally mono- or polysubstituted with the same or different substituents; and possible substituents are hydroxyl, mercapto, cyano and halogen, in particular fluorine, chlorine, bromine and iodine; in each case up to 6 carbon atoms and optionally up to 5 identical or different halogen atoms, in particular fluorine, chlorine. and bromine, in each case straight-chain or branched alkoxy, alkoxyimino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy, alkylaminocarbonyloxy, halogenoalkylcarbonyloxy and alkylsulfonyloxy; alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenylaminocarbonyloxy and dialkenylaminocarbonyloxy with up to 6 carbon atoms in each individual straight-chain or branched alkyl or alkenyl moiety; and cycloalkyl moieties Charcoal Xfi inside is 3
cycloalkylaminocarbonyloxy, optionally mono- or polysubstituted with the same or different substituents from the group consisting of halogen, especially fluorine, chlorine and bromine, and lower alkyl, carbon cycloalkyl of 3 to 7 in number and optionally mono- or polysubstituted with the same or different substituents from the group consisting of halogen, especially fluorine, chlorine and bromine, and lower alkyl, optionally nitro, phenyl which may be mono- or polysubstituted with the same or different substituents from the group consisting of halogen, especially fluorine, chlorine and bromine, and lower alkyl and dioxyalkylene; and in each case optionally halogen, especially fluorine, furyl, tetrahydrofuryl, pyrazolyl, which may be mono- or polysubstituted with the same or different substituents from the group consisting of chlorine and bromine, and lower alkyl;
oxacylyl, inxazolyl, thiazolyl, thiadiazolyl, oxadiazolyl, pyridyl and pyrimidinyl; and optionally monosubstituted by the same or different substituents from the group consisting of lower alkyl, halogenoalkylcarbonyl, halogenophenoxyalkylcarbonyl and halogenoalkylcarbonylaminoalkyl in each case or amino which may be polysubstituted, or in each case 1 and R' have 3 to 8 carbon atoms and are optionally mono- or polysubstituted in each case with the same or different substituents. represents a straight-chain or branched alkenyl, alcadenyl or alkynyl, which may have a carbon number of up to 6, and possible substituents are halogen, in particular fluorine, chlorine and bromine, cyano and in each case straight, with up to 6 carbon atoms. chain or branched alkoxy, alkylcarbonyl or 1i alkoxycarbonyl,
or 141 and R2 in each case have 3 to 8 carbon atoms and are optionally mono- or polysubstituted in each case with the same or different substituents from the group consisting of halogen, in particular fluorine, chlorine and bromine, and lower alkyl; represents cycloalkyl or cycloalkenyl, which may be mono- or polysubstituted, optionally in each case with the same or different substituents, and/or which may be benzo-fused represents piperidyl, pyridyl, chenyl, oxasilyl, inxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, fluorenyl, phthalimidoyl or dioxanyl; possible substituents are halogen, in particular fluorine, chlorine and bromine, cyanide, and in each case 1 g of carbon.
~4 straight-chain or branched alkyl or alkanediyl, or in each case R1 and R2 have up to 6 carbon atoms and optionally up to 5 identical or different nitrogen atoms, especially fluorine, chlorine and bromine, in each case representing a linear or branched alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, halogenoalkylcarbonyl or genoalkoxycarbonyl, or R1 and R2 are optionally the same or different; represents an amine or an alkylidenimino which may be mono- or polysubstituted by substituents, the possible substituents having in each case 8 carbon atoms and optionally up to 5 identical or different atoms, in particular fluorine, chlorine and bromine, in each case straight-chain or branched alkyl, alkenyl, alkynyl, alkylcarbonyloyohhalogenoalkylcarbonyl, or in which R1 and R1 are the nitrogen atoms to which they are bonded; taken together, alkylideneamino, pyrrolidinyl, piperidinyl, piperidonyl, perhydroazepinyl, perhydroazepinyl, dihydropyrazolyl, optionally mono- or polysubstituted in each case with the same or different substituents; dihydro- or tetrahydro-pyridyl, azabicyclononyl, molporinyl,
perhydro-1,3-oxazinyl, l,3-oxazolidinyl, 1,4-piperazinyl, perhydro-1,4
-diazepinyl, dihydro-, tetrahydro- or perhydro-quinolyl or -inoquinolyl, indolyl, dihydro- or perhydro-indolyl, possible substituents being hydroxyl, halogen (in particular fluorine, chlorine and bromine), cyano and formyl; in each case In each case, straight-chain or branched, arbitrary [divalent, alkyl, alkanediyl, alkoxy, dioxyalkylene, alkylcarbonyl, alkoxycarbonyl and halogenoalkylcarbonyl, in each case with a carbon number of 8] and in each case straight-chain or branched alkylaminos and dialkylaminos with up to 4 carbon atoms in the individual alkyl moieties, in each case optionally halogens, especially fluorine, chlorine and bromine, nitro, and in each case phenyl, naphthyl, pyridyl and piperidinyl, optionally monosubstituted or polysubstituted with the same or different substituents from the group consisting of lower alkyl, halogenoalkyl, alkoxy, alkylcarbonyl and alkoxycarbonyl, and certain alkyl or alkenyl The number of carbon atoms in the moiety is up to 4 and optionally in each case mono- or polysubstituted by halogen, in particular fluorine, chlorine and bromine, the group consisting of lower alkyl and halogenoalkylcarbonyl, with the same or different substituents. straight-chain or branched cyclopropylalkyl, cyclohexylalkyl, hypericinylalkyl, phenylalkyl and phenylalkenyltheal, which may be straight-chain or branched.

Particularly preferred amides of 2) are those in which R represents hydrogen or chlorine, or in which R6 and R6 are the same or different and, independently of each other, in each case hydrogen, methyl, ethyl , allyl, glopargyl, but-1-yn-3-yl, 3-methylbut-1-yn-3-yl or 2-cyanopropyl
2-yl or 几 stands for straight-chain or branched alkyl having up to 15 carbon atoms, or having from 1 to 6 carbon atoms and from 1 to 9 identical or different halogen atoms, especially fluorine; ,chlorine,
represents a straight-chain or branched halogenoalkyl having bromine and iodine, or has 1 to 6 carbon atoms and is substituted with 7-, di-, or tri-substituents by the same or different substituents; Represents a branched alkyl group, and possible substituents include hydroxyl, fluorine, chlorine, bromine, cyanide, cyanato, thiocyanato, methoxy, ethoxy, methylthio, ethylthio, acetyl,
Propionyl, acetoxy, propionyloxy, methoxycarbonyl, ethoxycarbonyl, 1,1.3.3
-tetrachloro-2-hydroxy-prop-2-yloxy, 1.1゜1.3.3-pentachloro-2-hydroxyprop-2-yloxy, chloroacetyl, dichloroacetyl, chloroacetoxy, dichloroacetoxy,
pentachlorobutadien-1-ylcarbonyloxy,
and optionally in each case by the same or different substituents from the group consisting of chlorine, methyl or methoxy.
, optionally di- or tri-substituted phenyl,
phenoxy, phenylthio and chenyl, and cyclopropyl, cyclopentyl and cyclohexyl, and the radicals in which R6 and R6 are the same or different and in each case independently of one another hydrogen, methyl, ethyl, allyl, glopargyl, butylene; -1-in-
3-yl, 3-methyl-but-1-yn-3-yl or 2-cyanoprop-2-yl, or R has 2 to 5 carbon atoms and, by the same or different substituents, mono-, represents a straight-chain or branched alkenyl which is di- or tri-substituted; possible substituents are hydroxyl, fluorine, chlorine, bromine, methoxycarbonyl, ethoxycarbonyl, and in each case optionally fluorine, chlorine, methyl and phenyl and phenoxy which may be mono-, di- or tri-substituted with the same or different substituents from the group consisting of methoxy, or R is a straight-chain or branched alkynyl having 2 to 5 carbon atoms; or in each case optionally mono-, di-, tri-, tetra- or penta-substituted by the same or different substituents. represents butenyl, bicyclooctyl, bicyclononyl and tricyclodecyl, possible substituents being methyl, ethyl, phenyl and the radicals Bs and R6 are the same or different and in each case independently of each other hydrogen , methyl, ethyl,
allyl, glopargyl, but-1-yn-3-yl, 3
- methylbut-1-yn-3-yl or 2-cyanoprop-2-yl, or R represents phenyl, optionally mono-, di- or tri-substituted, with the same or different substituents; Substituents include fluorine, chlorine, bromine, iodine, nitro, methyl, ethyl, methoxy, ethoxy, carboxyl (also in the form of carboxylate anions), trifluoromethyl, chloroacetamide, dichloroacetamide and groups where R3 and R6 are the same. or different, and in each case independently of one another hydrogen, methyl, ethyl, allyl, glopargyl, but-1-yn-3
-yl, 3-methylbut-1-yn-3-yl or 2
-cyanoprop-2-yl or R represents furyl, chenyl, pyridyl or dithiolanyl, optionally mono-, di- or tri-substituted in each case by the same or different substituents;
Possible substituents are chlorine, methyl, in which R1 and R6 are the same or different, and in each case independently of each other hydrogen, methyl, ethyl, allyl, glopargyl, but-1-yn-3- yl, 3-methylbuty-1
-yn-3-yl or 2-cyanoprop-2-yl, or finally R is in each case optionally mono-, with the same or different substituents from the group consisting of fluorine, chlorine, bromine and phenyl; represents optionally di- or tri-substituted methoxy, ethoxy, allyloxy, glopargyloxy, butynyloxy, methoxycarbonyl, ethoxycarbonyl or phenyl, and R1 and R2 are the same or different and are independent of each other. mono-, with hydrogen, formyl, chlorosulfonyl, or optionally in each case with the same or different substituents from the group consisting of fluorine, chlorine, bromine and methyl;
represents phenyl, phenoxymodi or phenylsulfonyl which may be di- or tri-substituted, or has 1 to 8 carbon atoms and is optionally mono-, di- or tri-substituted with the same or different substituents; Represents a good straight-chain or branched alkyl,
Possible substituents are hydroxyl, mercapto, cyano, fluorine, chlorine, bromine, methoxy, ethoxy, propoxy, butoxy, methoximino, ethoximino, acetyl, glopionyl, acetoxy, glopionyloxy, methoxycarbonyl, ethoxycarbonyl, methoxycarbonyloxy, Ethoxycarbonyloxy, methylthiocarbonyloxy, ethylthiocarbonyloxy, chloroacetoxy, dichloroacetoxy, methylsulfonyloxy, ethylsulfonyloxy, methylaminocarbonyloxy, dimethylaminocarbonyloxy, ethylaminocarbonyloxy, diethylaminocarbonyloxy,
Propy is substituted by the same or different substituents from the group consisting of aminocarbonyloxy, butylaminocarbonyloxy, allylaminocarbonyloxy, diallylaminocarbonyloxy, cyclohexylaminocarbonyloxy, and optionally chlorine and methyl. or phenylaminocarbonyloxy, which may be tri-substituted, and in each case optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents from the group consisting of chlorine and methyl; cyclopropyl, cyclopentyl, cyclohexyl and cycloheptyl; phenyl optionally substituted with the same or different substituents from the group consisting of nitro, fluorine, chlorine, bromine, methyl and dioxymethylene; and furyl, tetrahydrofuryl, pyrazolyl, oxasilyl, isoxazolyl, thiazolyl, thiadiazolyl, which in each case may optionally be mono- or di-substituted by the same or different substituents from the group consisting of methyl, ethyl, propyl and chlorine; oxadiazolyl,
Pyridyl or pyrimidinyl: and optionally mono-substituted or di-substituted by the same or different substituents from the group consisting of methyl, ethyl, chloroacetyl, dichloroacetyl, chlorophenoxyacetyl, dichloroacetamidomethyl and dichloroacetamidoethyl. amine, or in each case 1 and 1lj2 have from 3 to 5 carbon atoms and in each case optionally the same or Straight-chain or branched alkenyl, alcadenyl or alkynyl, which may be mono- or di-substituted with different substituents; represents cycloglopyl, cyclopentyl, cyclohexyl, cyclohexenylmosy or cyclooctyl which may be mono-, di-, tri-, tetra- or penta-substituted, or in each case optionally fluorine, chlorine, bromine, cyanide, Piperidyl, pyridyl, chenyl which may be mono-, di- or tri-substituted and/or benzo-fused with the same or different substituents from the group consisting of methyl, ethyl, propyl, propanediyl and butanediyl , oxacylyl,
Represents isoxazolyl, thiadiazolyl, fluorenyl, phthalimidoyl or dioxanyl; or methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, acetyl, chloroacenal, dichloroacetyl, methoxycarbonyl, ethoxycarbonyl, chloroethoxycarbonyl or Amines or propylidenes representing bromoethoxycarbonyl or optionally mono- or disubstituted by the same or different substituents from the group consisting of methyl, ethyl, allyl, propargyl, acetyl, chloroacetyl and dichloroacetyl represents imino or R' and R2 taken together with the nitrogen atom to which they are attached are mono-, di-, tri-, tetra- or penta-, optionally in each case by the same or different substituents. optionally substituted methylideneimino, ethylidene amine, propylideneimino, pyrrolidinyl, piperidinyl, piperidonyl, perhydroazepinyl, perhydroazepinyl, dihydropyrazolyl, dihydro- or tetrahydro-pyridyl, azabicyclononyl, morpholinyl, perhydro-1,3-oxazinyl, l,
3-oxazolidinyl, 1,4-piperazinyl, perhydro-1,4-diazepinyl, dihydro-, tetrahydro- or perhydro-quinolyl or isoquinolyl, indolyl or dihydro- or perhydro-
Represents indolyl; possible substituents are hydroxyl, fluorine, chlorine, bromine, cyanide, formyl, methyl, ethyl,
Propyl, butyl, ethanediyl, gulono(ndiyl),
Methoxy, ethoxy, propoxybutoxy, dioxyethylene, dioxypropylene, dioxybutylene, acetyl, gropionyl, chloroacetyl, dichloroacetyl, α-chlorogropionyl, methoxycarbonyl,
from ethoxycarbonyl, methylamino, ethylamino, dimethylamino and diethylamino, and in each case optionally fluorine, chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxytrifluoromethyl, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl phenyl, naphthylamodi, hapiperidinyl which may be mono-, di- or tri-substituted by the same or different substituents from the group consisting of; cyclopropylmethyl, cyclohexylmethyl, piperidinylethyl, piperidinylethyl, benzyl, phenylethyl and phenylpropenyl which may be mono-, di- or tri-substituted with different substituents.

In the concept of the present invention, the terms "lower alkyl", "lower alkoxy" and the like refer to the corresponding groups having 1 to 4 carbon atoms. Particular mention may be made of the compounds of the following general formula (1): -11-11-1-1-41-11-11-41+1
Table 1 (Continued) H H @2 Amides of formula (1) which can be used according to the invention are known (for example German published specification IFZ8z8.zci5,
German Published Specification 3.228.007 or German Published Specification 2.218. (See 197).

They include amines of the formula (Ji) in which R+ and R2 have the above meanings;
optionally in the presence of an acid binder such as triethylamine, dimethylbenzylamine or pyridine and optionally a diluent such as methylene chloride or acetonyl, at a temperature between 08 and +120°C.
It can be produced by a method of reacting with an acyl chloride of the formula (IV) R-Co-CI (■) [wherein R has the above meaning].

The amine of formula (1) used in excess can simultaneously act as an acid binder in this reaction. In this case there is no need to add other acid binders.

As mentioned above, the amides of formula (1) which can be used according to the invention are suitable for improving the tolerance of herbicidally active heteroaryloxyacetamides of formula (It) by crop plants.

Formula (It) provides a general definition of herbicidally active heteroaryloxyacetamides that can be used according to the invention.

The herbicidal heteroaryloxyacetamides of formula (1) which can be preferably used represent a heterocyclic group of the formula in which Het may be optionally mono- or polysubstituted with the same or different substituents, where: In each case, X represents oxygen or sulfur, and the possible substituents are halogen, cyanide, nitro, in each case straight-chain or branched, with 1 to 8 carbon atoms in the individual alkyl moiety. Chain alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylcarbonyl and alkoxycarbonyl, in each case straight or branched, having in each case 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms halogenoalkyl, halogenoalkoxy and halogenoalkylthio, linear or branched dioxyalkylene optionally mono- or polysubstituted by the same or different halogen atoms, and in each case optionally halogen, cyanide, phenyl, phenoxy, phenylthio, benzyl, benzyloxy and benzylthio, which may be mono- or polysubstituted with the same or different substituents from the group consisting of nitro, lower alkyl and lower halogenoalkyl, and R' and R4 are In each case straight-chain or branched, independently of each other, the number of carbon atoms in the individual alkyl, alkenyl or alkynyl moiety is up to 0 and, as appropriate, has from 1 to 9 identical or different halogen atoms. alkyl, alkenyl, alkynyl, halogenoalkyl, cyanoalkyl, alkoxyalkyl, phenylalkyl, tetrahydrofurylalkyl, alkoxy, alkenyloxy or alkoxyalkoxy, or in each case cycloalkyl or cyclo having 3 to 8 carbon atoms; represents alkenyl or phenyl, naphthyl or morpholinyl, optionally mono- or polysubstituted in each case with the same or different substituents, the possible substituents being /% rogene, cyano, nitro, and in each case straight-chain or branched alkyl, alkanediyl, alkoxy, alkylthio, halogenoalkyl and halogenoalkyl having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms. pyrrolidinyl, piperidyl, which is alkoxy or R'' and R4 together with the nitrogen atom to which they are attached may be mono- or polysubstituted, optionally in each case with the same or different substituents; , perhydroazepinyl, perhydroazepinyl, dodecamethyleneimino, morpholinyl, 1,3-thiazolidinyl, 1,4-piperazinyl,
dihydro- or perhydro-indolyl, or dihydro-, perhydro- or tetrahydro-quinolyl or -isoquinolyl, in which possible substituents are halogen, in each case linear or branched, having from 1 to 4 carbon atoms; chain alkyl and alkoxy,
Monosubstituted or polysubstituted alkylenes and dioxyalkylenes having 1 to 4 carbon atoms, in each case divalent, and optionally in each case the same or different substituents from the group consisting of halogen, lower alkyl and lower alkoxy. is optionally substituted phenyl and benzyl.

Herbicidal heteroaryloxyacetamides of formula (It) which can be particularly preferably used include heterocyclic groups of the formula in which Net may be optionally substituted with 7-no, di- or tri-substituted substituents. where X is in each case oxygen or sulfur and the possible exchange groups here are fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, rho and I-propyl, n-1i
-1s- and t-butyl, methoxy, ethoxy, n-
and l-propoxy, n-1i-1S- and t-butoxy, methylthio, ethylthio, n- and 1-propylthio, n-1i-1S- and t-butylthio, methylsulfonyl, ethylsulfonyl, n-cICFi
-propylsulfonyl, n-1i-1S- and t-butylsulfonyl, acetyl, gropionyl, methoxycarbonyl, ethoxycarbonyl, n- and 1-propoxycarbonyl, trifluoromethyl, difluorochloromethyl, dichlorofluoromethyl, trichloromethyl, chloro Methyl, dichloromethyl, pentafluoroethyl, heptafluoropropyl, trifluoromethoxy,
trifluoromethylthio and dioxydifluoromethylene, and optionally in each case nine identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl and trifluoromethyl; optionally substituted phenyl, phenoxy, phenylthio, benzyl, benzyloxyoyohipendylthio, and R1 and R4 are PC independently of each other, methyl, ethyl,
n- and i-propyl, n-1i-1S- and t-
Butyl, n- or i-pentyl, n- or 1-
hexyl, n- or i-octyl, n- or i
-decyl, allyl, butenyl, clopargyl, futhynyl, pentynyl, hexynyl, trifluoromethyl, trifluoroethyl, cyanomethyl, cyanoethyl, methoxyethyl, ethoxyethyl, benzyl, phenylethyl, tetrahydrofurylmethyl, methoxy, ethoxy, n
- or i-Profoxy n-1i-1S- or t-butoxy, allyloxy, butenyloxy, methoxyethoxy, ethoxyethoxy, cyclopropoxy, cyclohexyl, cycloheptyl, cyclohexenyl or morpholinyl, or in each case the same or different substituents represents phenyl or naphthyl which may be mono-, di- or tri-substituted; possible substituents are fluorine, chlorine, bromine, cyanide, nitro, phenoxy, methyl, ethyl, n- and i-propyl, propanediyl, methoxy, ethoxy, n- and i-propoxy, methylthio, trifluoromethyl and trifluoromethoxy, or R3 and R4 together with the nitrogen atom to which they are attached, in each case optionally the same or represents a radical of the formula which may be mono-, di- or tri-substituted by different substituents, possible substituents being chlorine, methyl, ethyl,
n- and 1-propyl, methoxy, ethoxy and n
- and i-propoxy, and phenyl and benzyl optionally in each case mono-, di- or tri-substituted by the same or different substituents from the group consisting of fluorine, chlorine, methyl and methoxy,
Particular mention may be made of the compounds of the following general formula ([l):
'-00Q% O k 1%-r%+ Season 1 l I HHHH H--H UptI PQ Engineering Q 1 Akebonojiichi+++-t, -He-t 1 1 1 + 1-1 1-1 1 -I M M m + +-1+ + H Engineering I C 2 = 2 2 = 2 222 JP-A-6 (1-246302 (77)) The herbicide-active heteroaryloxyacetamides of Mr. (If) are known (For example, German published specifications 2, 8)
22,155, Su903,966, Su914,003.
3,018,075.3,038,652.3,038
．． 599.3,038, 608.3.03a635 and 3.218.482 or European Publication Specification 5,
501.18, 497.29, 171.29, 183.
60.426 or 94.541), or they are the subject of previous patent applications filed by Toyama Ganjin GmbH (for example German Patent Specification 3.228.131. of July 28, 1982). July 28, 1982
German Patent Specification 3,228.147 of June 29, 1983, German Patent Specification 3.323,334 of June 4, 1984, and German Patent Specification 3.400 of January 4, 1984.
．． 168).

They include, for example, chloroheteroaromatic compounds of the formula (2) % (%) in which Net has the meaning given above, optionally in the presence of an acid binder such as potassium carbonate or potassium hydroxide. and optionally in the presence of a diluent such as medelene chloride or acetonitrile, at a temperature between 00 and +120°C, glycolic acid amides of formula (vl)r, in which R3 and R4 have the meanings given above; Obtained by a method of reaction.

Amides of formula (1) which can be used as antidotes according to the invention include herbicidally active heteroaryls of formula (II) by important crop plants such as maize, soybean, cotton, sugar beet, cereals, rice and sugarcane. Particularly suitable for improving resistance to oxyacetamides.

The active compound compositions according to the invention exhibit very good activity against weeds and grass weeds in crops of a wide variety of useful plants. They can therefore be used to selectively control weeds in crops of a wide variety of useful plants. Cereals are to be understood here in the broadest sense as all plants that grow in undesirable locations.

The active compounds according to the invention can be used, for example, with respect to the following plant species: Dicotyledonous weeds of the following genera: Sinapis, Lepidium, Galium, Stel Iarja.
), Matricaria lj4, Anthemis, Galinsoga Jli
(Ga I insoga), Chenopodium (Cheno
podium), (Jrti-ca, Senecio, Amara-nt
hus), Portulaca, Xanthium, Convolvulus (C
onvolvu-1us), Ipomo spp.
ea), Po Iygonum, Sesbania, Arn
brosia), Cirsium, Carduus, Sonchus
), Solanum, (, R.
rippa), Rotala, Azena $
1i (Lindernia), Lamium 17mu (Lindernia)
ium), Veronica & (Veronica),・
Abutilon, Emex
), Datura Jl (Datura), Viola, Viola: +1I4 (Gale
Dicotyledonous cultivated plants of the following genera: Gossypium, Glycine, Beta,
Carrot genus (Daucus), Phaseolus genus (Pha)
-seolus), pisum, Solanum, 7-y Linum/, Ipomoea, Vicia
), Nicotiana, Tomato (L
ycopersicon), Arachis spp.
is), 7 Bra-ssica, Lactuca, Cucumi
s), and Cucurbits (Cucurbits).
a) Monocotyledonous weeds of the following genera: Bchinoch
loa), Setaria, Pan i-cum, Pan i-cum, Igit
aria), Phleum, Phleum genus (Poa), Poa genus Jll (Fe
stuca), Ohishiba J% (Ele-usine),
Brachiaria, Lolium, Bromus
), Avena, Cyperus (C
yperus), 8orghum, Agropyron, Cyn
odon), Monochor ia
), Flmbristylis, Sa-gittaria, Ble
ocharis), Scirpus, Paspalum, Platypus (I
schaemum), Speckrea (Spheno)
clea), Dactyloctenium (Da-ctylo
monocotyledonous cultivated plants of the following genera: Oryza, Zea, Triticum
m), Barley (Hordeum), Oat (
Ave-na), Secale, Moo
:l Sorghum, Panic
um), Saccharum, Ananas, ASpa
raguS), and Allium.

However, the use of the active compound compositions according to the invention is not restricted to this type, but can be extended in a similar manner to other plant species.

The active compound compositions according to the invention are particularly suitable for the selective control of weeds in corn, dive, cotton, sugar beet, cereals, rice and sugar cane.

The selective herbicidal activity of the active compound compositions according to the invention is particularly pronounced if the herbicidally active compound and the antidote are present in a particular ratio. However, the weight ratio of herbicidally active compound to antidote can be varied within a relatively wide range in the active compound compositions according to the invention. Generally, 1
2 parts by weight of herbicide active compound 0.01-1
00 parts by weight, preferably 0.1 to 20 parts by weight of the formula (1
) exists.

The antidote of the formula (r) which can be used according to the invention and the active compound composition consisting of the antidote of the formula (1) according to the invention and the herbicide active compound of the formula (It) can be prepared in the following manner:
For example, solutions, emulsions, wettable powders, suspensions, powders, dusting agents, coatings, soluble powders, granules, suspension-emulsion concentrates,
Very fine capsules in natural and synthetic materials, as well as polymeric materials, impregnated with the active compounds can be converted.

These formulations are prepared in a known manner, for example by combining the substances with liquid solvents and/or solid carriers, optionally using surfactants, ie emulsifiers and dispersants and/or blowing agents. It can be manufactured by mixing with

When using water as extender, organic solvents can be used as co-solvents, for example. The following are mainly suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylenes or methylene chloride. , aliphatic hydrocarbons such as cyclohexane, or paraffins,
For example petroleum distillates, mineral and vegetable oils, alcohols such as butanol or glycols, especially their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents. , such as dimethylformamide and dimethylsulfoxide, and water.

Solid carriers include, for example, ammonium salts, as well as ground natural minerals, such as kaolins, clays, talc, chalk, quartz, acpulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as e.g. Highly dispersed silicic acid, alumina and silicates are suitable. Solid carriers for granules include crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic powders, and granules of organic substances, For example, sawdust, coconut husks, male corncobs and tobacco stalks are suitable. As emulsifiers and/or blowing agents, nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyethylene fatty alcohol ethers,
For example, alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates and albumin hydrolysis products are suitable. Suitable dispersants are, for example, liqunin-sulfate waste liquor and methylcellulose.

Adhesives, such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules and latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalic and lecithins, and Synthetic phospholipids can be used in the formulation. Other adhesives are mineral oils and vegetable oils.

Colorants such as inorganic pigments such as iron oxide, titanium oxide and Prussian blue, as well as organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and micronutrients such as iron, manganese,
Salts of boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain o, i to 95% by weight of an antidote usable according to the invention or an active compound composition consisting of antidote and herbicide active compounds according to the invention,
And they preferably contain from 0.5 to 90% by weight.

The antidotes that can be used according to the invention and the active compound compositions according to the invention can be used as such or in the form of their preparations in mixtures with other known herbicides for the control of weeds. It can also be a finished formulation or a tank mixture. Other known active compounds, such as fungicides, insecticides, acaricides, nematicides, avicicides, growth factors, phytonutrients and soil structure improvers,
Mixtures of different types are also possible.

The antidotes which can be used according to the invention or the active compound compositions according to the invention (as such, or in the form of their preparations or prepared by further dilution from said preparations), such as application forms, e.g. They can be used in the form of suspensions, emulsions, powders, coatings and granules, which can be prepared in the usual manner, e.g. by scattering, spraying, spraying, etc.
Used by spraying, granulation, dusting, dry application, shaking application, slurry application or coating.

Antidotes that can be used in accordance with the present invention can be applied by conventional methods for such antidotes. Thus, the antidote that can be used according to the invention can be applied before or after the herbicide or together with the herbicide.

Furthermore, if the detoxifying agent is used before or after sowing, the crop plants can be better protected from damage than by treating (coating) the seeds with an antidote before sowing.

Another possible use is to apply the antidote into the sowing ridge during sowing. If the plants are seedlings, they can be treated with an antidote before transplanting.

The amount applied in the antidote does not in principle depend on the amount of herbicide or herbicidal active compound applied. Generally, the applied amount of antidote for surface treatment is 0.2”□ 20 J/
h a, preferably 0.5 to 5 kg 7 ha
During. For seed treatment, the amount of antidote applied is generally K.
Between O92 and zo01/yunotane, preferably 0.5 to 51
/kg A1 1I4j1. The application amounts of the active compound compositions according to the invention can vary within the following ranges. Generally they are 0.01-25ky/ha
between 0.05 and 15 kp/ha t7).

The applied amount of herbicide active compound is generally 0. 9 to O1-20
/ha, preferably it O, 05~] Okg/ha
Changes between.

Example A Pre-Emergence Test Method 1 Solvent: 5 Orthogonal Acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether active compound to prepare a suitable formulation of 1 part by weight of herbicide active compound or The mixture of antidote or herbicide active compound and antidote was mixed with the above amount of solvent, the above amount of emulsifier was added, and the concentrate was diluted with water to the desired concentration.

Method 2 Add an amount of antidote equal to 1/2% or 1/2% or other proportion of the glaze, along with 1,000 liters of IJ and 21 parts methanol per 100 y of corn. , and 2.3 seconds of lVJ was stirred in a disposable beaker. The methanol was then dried off within 2.3 minutes at room temperature.

Methods 1 and 2 Seeds of untreated test plants or those that have been applied with antidote according to method 2 are plowed into normal soil and after 24 hours herbicide preparations (methods 1 and 2) or antidote are applied. Preparations (Method 1) Preparations of antidote and herbicide active compounds (Methods 1 and 2) were sprayed. It is convenient to keep the amount of water per unit area constant.

After 3 weeks, the rate of plant growth inhibition was evaluated in comparison with untreated controls. The values are 100% (as for the untreated control without activity) - indicating complete inhibition of the growth of the above-ground parts of the plants.

The active compounds, application amounts and results are shown in Tables 1-5.

Claims (1)

[Claims] 1. Formula (It) [wherein )let represents an optionally substituted 5-membered heterocyclic group which may be benzo-fused, and R1 and R4 are Independently of each other, hydrogen, alkyl,
represents alkenyl, alkynyl, substituted alkyl, dichlorofurkyl, cycloalkenyl, alkoxy, alkenyloxy, alkoxyalkoxy, heterocyclyl or optionally substituted aryl, or R1 and R4 are the nitrogen atoms to which they are bonded; which together represent an optionally substituted saturated or unsaturated heterocyclic group which may contain other heteroatoms. Formula as an antidote to improve resistance by plants (
1) [wherein R is hydrogen, halogen, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, bicycloalkyl, bicycloalkenyl, tricycloalkyl, aryl, heteroaryl , alkoxy, alkenyloxy, alkynyloxy, aryloxy, carbamoyl, alkoxycarbonyl or dithiolanyl, and R1 and R2 are independently of each other in each case tomohydrogen, formyl, chlorosulfonyl or in each case optionally substituted. Alkyl, alkenyl, alcadenyl, alkynyl, cycloalkyl, cycloalkenyl,
represents alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, phenyl, phenoxy, phenylsulfonyl or heterocyclyl, or amine, alkylideneimino or optionally substituted alkylcarbonylamino or di(alkylcarbonyl)amine, or R1 and R2 together with the nitrogen atom to which they are attached are in each case optionally substituted alkylideneiminopyrrolidinyl, piperidinyl, piperidonyl, perhydroazepinyl, perhydroazocinyl,
dihydropyrazolyl, dihydro- or tetrahydro-pyridinyl, azabicyclononyl, morpholinyl, perhydro-1,3-oxazinyl, 1,3-oxazolidinyl, 1,4-piperazinyl, perhydro-], 4-
diazepinyl, dihydro-, tetrahydro- or perhydro-quinolyl or monoisoquinolyl, indolyl or dihydro- or perhydro-indolyl]. 2. A method characterized in that the amide of the formula (1) described in claim 1 is applied to crop plants and their environment together with a heteroaryloxyacetamide (II). A method for improving the herbicide activity and tolerance of teroaryloxyacetamides of formula (n) according to claim 1 by crop plants. 3. An amide of formula (1) according to claim 1 and at least one amide of formula (I) according to claim 1
A selective control agent for weeds in crops of useful plants, characterized in that it contains an active compound composition consisting of the herbicidal heteroaryloxyacetamide of t). 4. Patented for causing the active compound composition according to claim 3 to act on weeds or their environment;
Method for selective control of weeds in crops of useful plants. 5. Use of the active compound composition according to claim 3 for selectively controlling weeds in crops of useful plants. 6. Process for producing a selective control agent for weeds in crops of useful plants, characterized in that the active compound composition according to claim 3 is mixed with a filler and a surfactant. .