CA2138924A1 - Bicyclic heteroaryl compounds, processes for their preparation, compositions comprising them, and their use as safeners - Google Patents

Abstract

Bicyclic heteroaryl compounds, processes for their prepartion, compositions comprising them, and their use as safeners.

Compounds of the formula (I) and salts thereof (I) in which W1 is N or CR* and W2 is O, S, NH, NR**, N=N, N=CR* or CR*=N and the total of the hetero ring atoms of the groups W1 and W2 is 2 or 3, and A is a divalent hydrocarbon radical having 1 to 12 carbon atoms, B1 and B2 are carboxyl, or derivatives thereof, or formyl or derivatives thereof, or an acyl radical of the formula -CO-R, in which R is an aliphatic, arali-phatic or aromatic radical which can additionally comprise other functional groups and can have a total of up to 24 carbon atoms, n is 0 or 1, R* in each case independently of the other radicals R*
is H, Hal, (C1-C8)-haloalkyl, (C1-C8)-haloalkoxy, (C1-C8)-alkyl, (C1-C8)-alkoxy, NO2, NH2 or amino which is substituted by 1 or 2 radicals selected from the group consisting of (C1-C4)-alkyl and acyl having 1-10 carbon atoms, or CN, (C1-C8)-alkylthio or (C1-C8)-alkylsulfonyl or (substituted) phenyl, and R** is (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C8)-alkyl-thio, (C1-C8)-alkoxy, (C1-C8)-haloalkoxy, (C1-C8)-alkylsulfonyl, cyano-(C1-C8)-alkyl, [(C1-C8)-alkyl]-carbonyl or [(C1-C8)-alkoxy]-carbonyl and which are defined in greater detail in claim 1 are suitable according to the invention as safeners for reducing phytotoxic effects of crop protection products (for example herbicides) on crop plants. The compounds, some of which are novel and some of which are known, can be prepared analogously to known processes.

Description

Z~38924 --- HOECHST AK~ SELLSCHAFT HOE 93/F 418 Dr.WE/wo Description Bicyclic heteroaryl compounds, processes for their preparation, compositions comprising them, and their use as safeners.

The invention relates to the technical field of crop protection products, in particular to combinations of active substance and antidote which are outstAn~;ngly suitable for use against competing harmful plants in crops of useful plants.

When crop treatment products, in particular herbicides, are used, undesirable damage may occur on the treated crop plants. A large number of herbicides are not fully tolerated (selective) by some important crop plants such as maize, rice or cereals, 80 that their use is limited to a narrow range. In some cases, they cannot be employed at all, or only at such low application rates that the desired broad herbicidal activity against the harmful plants is not guaranteed.

EP-A-154 153 discloses aryloxy compounds as safeners for phenoxyphenoxy herbicides and heteroaryloxyphenoxy herbicides.

EP-A-293 062 describes the use of aryloxy compounds as safeners for cyclohexanedione herbicides.

EP-A-94 349 discloses the use of quinoline-8-oxyalkane-carboxylic acid esters as safeners for herbicides belong-ing to a variety of structural classes.

DE-2637886 has already disclosed the use of 3-pyridyloxy-alk~nAm;des as safeners for herbicides from the triazine, carbamate and haloacetanilide series.

It has now been found that, surprisingly, bicyclic _ heteroaryl derivatives of the formula (I) below are outstAn~;ngly suitable for protecting crop plants against harmful effects of aggressive agrochemicals, in par-ticular herbicides.

The invention therefore relates to the use of the com-pounds of the formula (I) or salts thereof ( Bl 2 ) n B 1_A--O
~W

R R

in which W1 is N or CR and W2 is O, S, NH, NR , N=N, N=CR or CR =N and the total of the hetero ring atoms of groups Wl and w2 is 2 or 3, and A is a divalent hydrocarbon radical having 1 to 12, preferably 1 to 8, carbon atoms, for example (C1-C6)-alkanediyl or (C2-C8)-alkenediyl, B1 and B2 in each case independently of one another are carboxyl, carboxyl derivatives from the group con-sisting of esters, thioesters, nitriles, imides, anhydrides, halide, amides, hydrazides, imidic acid, hydrazonic acid, hydroxamic acid, hydroximic acid, amidine, amide oxide and derivatives of the last-mentioned 9 functional radicals which are further substituted on the nitrogen atom or the hydroxyl group, or formyl, formyl derivatives from the group consisting of acetals, thioacetals, imines, hydrazone, oxime and derivatives of the last-mentioned 3 functional radicals which are further substituted on the nitrogen atom or on the hydroxyl group, or an acyl radical of the formula -CO-R in which R is an aliphatic, araliphatic or aromatic radical which can additionally have further functional groups and can comprise, in total, up to 24 carbon atoms, n i8 0 or 1, R in each case independently of the other radicals R
iæ hydrogen, halogen, halo-(C1-C8)-alkyl, halo-(C1-C8)-alkoxy, (C1-C8)-alkyl, (C1-C8)-alkoxy, nitro, amino or amino which is substituted by one or two radicals selected from the group consisting of (C1-C4)-alkyl and acyl having 1 to 10 carbon atoms, or cyano, (C1-C8)-alkylthio, (C1-C8)-alkylsulfonyl or optionally substituted phenyl, preferably hydrogen, halogen, (C1-C6)-haloalkyl such as trifluoromethyl, (C1-C6)-haloalkoxy such as difluoromethoxy, (C1-C6)-alkyl, (C1-C6)-alkoxy, (C1-C6)-alkylthio, (C1-C6)-alkylsulfonyl, nitro, amino, mono-(Cl-C4)-alkylamino, di-(C1-C4)-alkyl-amino, (C1-C4)-alkanoylamino, N-(C1-C4)-alkanoyl-N-( Cl - C4 ) - alkylamino, benzoylamino, benzyloxy-carbonylamino, cyano or optionally substituted phenyl, and R is (C1-C8)-alkyl, halo-(C1-C8)-alkyl, (C1-C8)-alkyl-thio, (C1-C8)-alkoxy, halo-(C1-C8)-alkoxy, (C1-C8)-alkylsulfonyl, cyano-(C1-C8)-alkyl, [(C1-C8)-alkyl]-carbonyl or [(C1-C8)-alkoxy]-carbonyl as safeners for avoiding or reducing phytotoxic effects of crop protection products on crop plants.

Examples of suitable safeners are compounds of the formula (I) according to the invention in which A is (C1-C6)-alkanediyl or (C3-C8)-alkenediyl, B1 and B2 in each case independently of one another are a radical of the formula -COORl, -COSRl, -co-oN=cR2R3 -Co-NR4N=CR2R3 __ - 4 -- CoNRlR4 ~
-CO-R1 or I ~ R~ T ~ R6 ' ~ or ~ ~ R

R1 is hydrogen, (cl-cl8)-alkyl~ (C3-Cl2)-cYcloalkyl~
(C3-C12)-heterocyclyl, (C2-Cl8)-alkenyl, (C2-C8)-5alkynyl, aryl or heteroaryl, in which each of the abovementioned carbon-containing radicals are unsubstituted or mono-substituted or polysubstituted by identical or different substituents selected from the group consisting of halogen, halo-(C1-C8)-alkoxy, nitro, cyano, hydroxyl, (C1-C8)-alkoxy and (C1-C8)-alkoxy in which one or more non-adjacent CH2 groups are replaced by oxygen, as well as (C1-C8)-alkyl and halo-(C1-C8)-alkyl, the latter two only in the case of cyclic radicals, (C1-C8)-alkylthio, (C1-C6)-alkylsulfinyl, (C1-C6)-alkyl-sulfonyl, (C2-C8)-alkenylthio, (C2-C8)-alkynyl-thio, (C2-C8)-alkenyloxy, (C2-C8)-alkynyloxy, (C3-C7)-cycloalkyl, (C3-C7)-cycloalkoxy, (Cl-C8)-alkoxycarbonyl, (C2-C8)-alkenyloxycarbonyl, (C2-C8)-alkynyloxycarbonyl, (Cl-C8)-alkylthio-carbonyl, (C1-C8)-alkylcarbonyl, formyl, (C2-C8)-alkenylcarbonyl, (C2-C8)-alkynylcarbonyl, hydroxyimino, (C1- C4)- alkylimino, (C1- C4)- alkoxy-imino, (C1-C8)-alkylcarbonylamino, (C2-C8)-alkenylcarbonylamino, (C2-C8)-alkynylcarbonyl-amino, carbamoyl, (C1-C8)-alkylcarbamoyl, di-(C1-C6)-alkylcarbamoyl, (C2-C6)-alkenylcarbamoyl, (C2-C6)-alkynylcarbamoyl, (Cl-C8)-alkoxycarbonyl-amino, (C1-C8)-alkylaminocarbonylamino, di-(C1-C8)- alkylaminocarbonylamino, (C1-C 8)- alkoxy-carbonyloxy, (C1-C8)-alkylcarbonyloxy which is unsubstituted or ~ubstituted by halogen, nitro, 213892~

.
(Cl-C4)-alkoxy or optionally substituted phenyl, or (C2-C6)-alkenylcarbonyloxy, (C2-C6)-alkynyl-carbonyloxy, phenyl, phenyl-(Cl-C6)-alkoxy, phenyl-(Cl-C6)-alkoxycarbonyl, phenoxy, phenoxy-(Cl-C6)-alkoxy, phenoxycarbonyl, phensYy-(cl-c6)-alkoxycarbonyl, phenylcarbonyloxy, phenyl-carbonylamino,phenyl-(Cl-C6)-alkylcarbonylamino, the last-mentioned 10 radicals being unsubsti-tuted or mono- or polysubstituted, preferably up to trisubstituted, in the phenyl ring by identi-cal or different radicals selected from the group consisting of halogen, (Cl-C4)-alkyl, (Cl-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy and nitro, as well as radicals of the formulae -SiR2R3R4, -o-SiR2R3R4, R2R3R4Si-(C1-C6)-alkoxy, - Co-o-NR2R3 ~ -o-N=cR2R3 ~ -N=CR2R3, o-(CH2)m-CH(oR2)oR3, R'O-CHR''-CH(OR')-(C1-C6)-alkoxy, -NR2R3, -Co-NR2R3, -o-Co-NR2R3 and a three-to seven-membered saturated or unsaturated heterocyclic radical having up to three identical or different hetero atoms selected from the series consisting of S, O and N which is optionally benzo-fused and optionally sub-stituted, preferably up to trisubstituted by halogen and/or (C1-C4)-alkyl, R' radicals independently of one another are (Cl-C4)-alkyl or, in pairs together, are (Cl-C6)-alkanediyl radical and R'' is hydrogen or (Cl-C4)-alkyl, R2 and R3 in each case independently of one another are hydrogen, optionally substituted (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, phenyl-(Cl-C4)-alkyl or phenyl, the last-mentioned two radicals being unsubstituted or substituted in the phenyl radical, or R2 and R3 together are an optionally substituted (C2-C6)-alkanediyl chain, R4 is hydrogen or optionally substituted (C1-C4)-alkyl, or R1 and R4 together are an ~lkane~;yl chain having 2 to 5 carbon atoms in which one CH2 group can optionally be replaced by 0, NH or N-(Cl-C4)-alkyl, R5 and R6 are identical or different and independently of one another are hydrogen or (C1-C6)-alkyl, R7 and R5 are identical or different and independently of one another are hydrogen or (Cl-C6)-alkyl which can be substituted by halogen, (Cl-C4)-alkoxy or phenyl, R9 and Rl are identical or different and independently of one another are hydrogen or (Cl-C6)-alkyl which can be substituted by halogen, (Cl-C4)-alkoxy or OH, 5 T radicals independently of one another are oxygen or sulfur and m i~ an integer from O to 6.

In the abovementioned compounds of the formula (I) and hereinbelow, unle~s otherwise specified in individual cases, alkyl, alkenyl and alkynyl are straight-chain or br~nche~; this also applie~ analogously to the substi-tuted alkyl, alkenyl and alkynyl radicals such as halo-alkyl, hydroxyalkyl, alkoxycarbonyl etc. (C1-C4)-alkyl i~
alkyl having 1 to 4 carbon atoms. In the composite terms such as (C1-C4)-alkylcarbonyl, the number of the carbon atoms only refers to the alkyl radical and not to the total of the carbon atom~ of alkyl radical and the carbonyl group attached thereto; this also applies analogously to other composite terms. Alkyl is, for example, methyl, ethyl, n- and i-propyl, n-, i-, t- and 2-butyl, pentyl radical~, hexyl radicals such as n-hexyl, i-hexyl and 1,3-dimethylbutyl, heptyl radicals such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methyl-but-3-enyl and 1-methylbut-2-enyl; alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-ynyl.

Substituted alkyl or alkanediyl is to be understood as meaning alkyl or alkanediyl which is mono- or poly-substituted, preferably up to trisubstituted, in par-ticular monosubstituted, by identical or different radicals selected from the group consisting of halogen, hydroxyl and (Cl-C6)-alkoxy.

Halogen is fluorine, chlorine, bromine or iodine, pre-ferably fluorine, chlorine or bromine, in particular fluorine or chlorine. Haloalkyl, haloalkenyl and halo-alkynyl are alkyl, alkenyl or alkynyl which is partiallyor fully substituted by halogen, for example CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CC13, CHCl2, CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF20, OCH2CF3.
This also applies analogously to haloalkenyl and other halogen-substituted radicals.

Aryl is, for example, phenyl, naphthyl, tetrahydro-naphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl; aryloxy is preferably the oxy radicals which correspond to the abovementioned aryl radicals, in particular phenoxy.

A three- to seven-membered heterocyclic radical as mentioned above (or heterocyclyl) is preferably derived from benzene, of which at least one CH is replaced by N
or at least two adjacent CH by NH, S or 0. The radical can be benzo-fused. It is optionally partially or fully hydrogenated. Suitable radicals are, in particular, oxiranyl, pyrrolidyl, piperidyl, dioxolanyl, pyrazolyl, morpholyl, furyl, tetrahydrofuryl, indolyl, azepinyl, triazolyl, thienyl and oxazolyl.

Heteroaryl or heteroaryl in heteroaryloxy is, for example, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, but also bicyclic or polycyclic aromatic or araliphatic radicals, for example quinolyl, benzoxa-zolyl, etc.

- 2~38924 .
Substituted aryl or aryloxy, heteroaryl, heteroaryloxy, phenyl, phenoxy, benzyl, benzyloxy or substituted bicyclic radicals having aromatic moieties are, for example, a substituted radical derived from the unsubsti-tuted skeleton, the substituents being, for example, oneor more, preferably 1, 2 or 3, radicals selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, hydroxyl, amino, nitro, cyano, alkoxy-carbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, mono- and dialkylamino, alkyl-sulfinyl and alkylsulfonyl and, in the case of radicals having carbon atoms, those having 1 to 4 carbon atoms, in particular 1 or 2, being preferred. Preferred are, as a rule, substituents selected from the group consisting of halogen, for example fluorine and chlorine, C1-C4-alkyl, preferably methyl or ethyl, Cl-C4-haloalkyl, preferably trifluoromethyl, C1- C4 - alkoxy, preferably methoxy or ethoxy, C1-C4-haloalkoxy, nitro and cyano. Particularly preferred are the substituents methyl, methoxy and chlorine.

Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals selected from the group consisting of halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-halo-alkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl radicals, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro and -trichlorophenyl, 2,4-, 3,5-, 2,5-and 2,3-dichlorophenyl, and o-, m- and p-methoxyphenyl.

An aliphatic, araliphatic or aromatic radical i8 pre-ferably a saturated or mono- or polyunsaturated hydro-carbon radical, aryl, arylalkyl, heteroaryl or hetero-arylalkyl, the radica:! optionally being additionally substituted.

Acyl is, for example, formyl, alkylcarbonyl such as (C1-C4-alkyl)-carbonyl, or phenylcarbonyl, it being g possible for the phenyl ring to be substituted, for example as shown above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl and other acyl radicals of organic acids.

Some compounds of the formula (I) have one or more asymmetric carbon atoms or double bonds, which are not mentioned specifically in the general formula (I).
However, formula (I) embraces all stereoisomers which are defined by their specific spatial structure, such as enantiomers, diastereomers and E and Z isomers, and their mixtures.

The compounds of the formula (I) can form salts in which the radical Rl is replaced by an eguivalent of an agri-culturally suitable cation. Examples of these salts are metal salts, in particular alkali metal salts or alkaline earth metal salts, but also ammonium salts or salts with organic amines, or else salts which have sulfonium or phosphonium ions as cations.

Particularly suitable as salt formers are metals and organic nitrogen bases, especially quaternary ammonium bases. Suitable metals for salt formation are alkaline earth metals such as magnesium or calcium, but especially alkali metals, such as lithium and, in particular, potassium and sodium.

Examples of nitrogen bases which are suitable for salt formation are primary, secondary or tertiary, aliphatic and aromatic amines which are optionally hydroxylated under hydrocarbon radical, such as methylamine, ethyl-amine, propylamine, isopropylamine, the four butylamine isomers, dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline, isoquinoline and also methanolamine, ethanolamine, propanolamine, dimethanolamine, diethanolamine or ,, -- 10 triethanolamine.

Examples of quaternary ~mmo~; um bases are tetraalkyl-~mmo~; um cations in which the alkyl radicals indepen-dently of one another are straight-chain or branched (C1-C6)-alkyl groups, such as the tetramethylammonium cation, the tetraethylammonium cation or the trimethyl-ethylammonium cation, and furthermore the trimethyl-benzylammonium cation, the triethylbenzyla-mmonium cation and the trimethyl-2-hydroxyethylammonium cation.

Particularly preferred as salt formers are the ammonium cation and di- as well as trialkylammonium cations in which the alkyl radicals independently of one another are straight-chain or branched (C1-C6)-alkyl groups which are optionally substituted by a hydroxyl group, such as, for example, the dimethylammonium cation, the trimethyl-~mm9~; um cation, the triethylammonium cation, the di-(2-hydroxyethyl)-~mmo~;um cation and the tri-(2-hydroxyethyl)-ammonium cation.

Preferred safeners are compounds of the formula (I) in 20 which A is (C1- C4 ) - alkanediyl or (C3-C6)-alkenediyl, such as CH2, CH(CH3), CH2CH2, CH2CH2CH2 or C(CH3)2~
R radicals in each case independently of the other radicals R are hydrogen, halogen, halo-(C1-C6)-alkyl, halo-(cl-c6)-alkoxy~ (Cl-c8)-alkYl~ (C1 C8) alkoxy, nitro, amino or amino which is substituted by one or two radicals selected from the group consisting of (C1-C4)-alkyl and acyl having 1 to 10 carbon atoms, or cyano, (C1-C6)-alkylthio or (C1-C8)-alkylsulfonyl, preferably hydrogen, halogen, tri-fluoromethyl, 2-chloroethyl, difluoromethoxy, (C1-C4)-alkyl, (Cl-C4)-alkoxy, (Cl-C4)-alkylthio, (Cl-C4) -alkylsulfonyl, nitro, amino, mono-(C1-C4)-alkyl-amino, di-(C1-C4)-alkylamino, (C1-C4)-alkanoylamino, N-(C1-C4)-alkanoyl-N-(C1-C4)-alkylamino, benzoyl-amino, benzyloxycarbonylamino or cyano, in particular hydrogen, R1 is hydrogen, (Cl-C12)-alkyl, (C3-C8)-cycloalkyl, (C3-C8)-heterocyclyl, (C2-Cl2)-alkenyl, (C2-C8)-alkynyl or phenyl, each of the above carbon-containing radicals being unsubstituted or substituted by one or more, preferably by not more than three identical or different substituents selected from the group consisting of halogen, halo-(Cl-C8)-alkoxy, nitro, cyano, hydroxyl, (Cl-C8)-alkoxy, in which one or more non-adjacent CH2 groups can be replaced by oxygen, or (Cl-C8)-alkyl and halo-(Cl-C8)-alkyl, the latter two substituents only in the case of cyclic radicals, (Cl-C8)-alkyl-thio, (Cl-C6)-alkylsulfinyl, (Cl-C6)-alkyl-sulfonyl, (C2-C8)-alkenylthio, (C2-C8)-alkynyl-thio, (C2-C8)-alkenyloxy, (C2-C8)-alkynyloxy, (C3-C7)-cycloalkyl, (C3-C7)-cycloalkoxy, (Cl-C8)-alkoxycarbonyl, (C2-C8)-alkenyloxycarbonyl, (C2-C8)-alkynyloxycarbonyl, (Cl-C8)-alkylthio-carbonyl, (Cl-C8)-alkylcarbonyl, (C2-C8)-alkenyl-carbonyl, (C2-C8)-alkynylcarbonyl, hydroxyimino, (Cl-C4)-alkylimino, (Cl-C4)-alkoxyimino, (Cl-C8)-alkylcarbonylamino,(C2-C8)-alkenylcarbonylamino, (C2-C8)-alkynylcarbonylamino, carbamoyl, (Cl-C8)-alkylcarbamoyl, di-(Cl-C6)-alkylcarbamoyl, (C2-C6)-alkenylcarbamoyl, (C2-C6)-alkynyl-carbamoyl-(Cl-C8)-alkoxycarbonylamino, (Cl-C8)-alkylaminocarbonylamino, (Cl-C 8 ) - alkoxycarbonyl-oxy, (Cl-C8)-alkylcarbonyloxy which is unsubsti-tuted or substituted by halogen, nitro, (Cl-C4)-alkoxy or optionally substituted phenyl, or (C2-C6)-alkenylcarbonyloxy, (C2-C6)-alkynylcarbonyl-oxy, phenyl, phenyl-(Cl-C6)-alkoxy, phenyl-(Cl-C6)-alkoxycarbonyl, phenoxy, phenoxy-(('1-C6)-alkoxy, phenoxycarbonyl, phenoxy-(Cl-C6)-alkoxy-carbonyl,phenylcarbonyloxy,phenylcarbonylamino, phenyl-(Cl-C6)-alkylcarbonylamino, the last-mentioned 10 radicals being unsubstituted or - 2~389?4 mono- or polysubstituted, preferably up to tri-substituted, in the phenyl ring by identical or different radicals selected from the group con-sisting of halogen, (Cl-C4)-alkyl, (C1-C4)-alkoxy, (Cl-C4)-haloalkyl, (C1-C4)-haloalkoxy, and nitro, and radicals of the formula -SiR2R3R4, -o-SiR2R3R4, R2R3R4Si-(Cl-C6)-alkoxy, -Co-o-NR2R3, - o -N=CR2R3, -N=CR2R3, -NR2R3, - CoNR2R3, - oCoNR2R3, -o-(CH2)~-CH(oR2)oR3, R'O-CHR''-CH(OR')-(Cl-C6)---alkoxy and a five- to six-membered saturated or unsaturated heterocyclic radical having up to three identical or different hetero atoms from the series consisting of S, O and N which is optionally benzo-fused and optionally substi-tuted, preferably up to trisubstituted, by halogen and/or (Cl-C4)-alkyl, R' independently of one another are (Cl-C4)-alkyl or, in pairs together, a (Cl-C6)-alkanediyl radical, R'' is hydrogen or (Cl- C4 ) - alkyl, R2 and R3 radicals independently of one another are hydrogen, (Cl-C4)-alkyl or optionally substi-tuted phenyl or, together, an unbranched ( C2 - C4 ) - alkanediyl chain, and m is an integer from 0 to 6.

Other compounds of the formula (I) which are preferred as safeners are those in which R is as defined above and at least two radicals R~ on the benzene ring are hydrogen, Rl is hydrogen, (Cl-Cl2)-alkyl, (C3-C8)-cycloalkyl, (C3-C8)-heterocyclyl, (C2-Cl2)-alkenyl, (C2-C8)-alkynyl, each of the abovementioned carbon-containing radicals being unsubstituted or substituted by one or more, preferably by not more than two, in particular by not more than one, substituent selected from the group consisting of hydroxyl, (Cl-C8)-alkoxy, alkoxypoly-alkyleneoxy having a total of 2 to 8 carbon 21:~89~4 ~_ - 13 -atoms, (C1- C4 ) - alkylthi O ~ ( C2 - C4 ) - alkenylthio, (C2-C4)-alkynylthio, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, mono- and di-(Cl-C2)-alkylamino, (C1- C4 ) - alkoxycarbonyl, ( C2 - C4 ) -alkenyloxycarbonyl, (C2-C4)-alkynyloxy-carbonyl, (C1-C4)-alkylcarbonyl, (C2-C4)-alkenylcarbonyl, ( C2 - C4 ) - alkynylcarbonyl, (Cl-C4)-alkylcarbonylamino, (C2-C4)-alkenyl-carbonylamino, carbamoyl, (Cl-C8)-alkyl-carbamoyl, di-(Cl-C6)-alkylcarbamoyl, (Cl-C4)-alkoxycarbonyloxy, (Cl-C4)-alkylcarbonyloxy which is unsubstituted or substituted by one or two radicals selected from the group con-sisting of halogen and (C1-C4)-alkoxy, or (C2-C4)-alkenylcarbonyl, (C2-C4)-alkynyl-carbonyloxy, phenyl, phenyl-(Cl-C4)-alkoxy, phenyl-(Cl-C4)-alkoxycarbonyl, phenoxy, phenoxy-(Cl- C4 ) - alkoxy, phenoxycarbonyl, phenoxy-(Cl-C4)-alkoxycarbonyl, phenyl-carbonyloxy, the last-mentioned 8 radicals being unsubstituted or substituted in the phenyl ring by one or more radicals selected from the group consisting of halogen, (Cl-C2)-alkyl, (Cl-C2)-alkoxy, (Cl-C2)-haloalkyl, (Cl-C2)-haloalkoxy and nitro, and radicals of the formula -SiR2R3R4, -o-SiR2R3R4, R2R3R4Si-(Cl-C4)-alkoxy, -o-N=cR2R3~ -N=CR2R3, o-(CH2)m-CH(oR2)oR3, R'O-CHR''-CH(OR')-(Cl-C6)-alkoxy, NR2R3, -CoNR2R3 and -oCoNR2R3, R' radicals independently of one another are (Cl-C4)-alkyl or, in pairs together, are (Cl-C6)-alkanediyl radical and R'' is hydrogen or (Cl-C4)-alkyl, R2 and R3 are identical or different and independently of one another are hydrogen, (Cl-C4)-alkyl or optionally substituted phenyl, or together are an optionally substituted (C2-C4)-alkanediyl chain, R5 and R6 are identical or different and independently 21389~4 of one another are hydrogen or (C1-C4)-alkyl, R7 and R8 are identical or different and independently of one another are hydrogen or (C1-C4)-alkyl, R9 and R10 independently of one another are hydrogen or (C1-C4)-alkyl and m is an integer from O to 2.

Preferred safeners of the formula (I) according to the invention are those in which the group B1-A(B2)n-O- is in the ~-position relative to a bridgehead atom of the bicycle, the bridgehead atom being linked to a nitrogen atom from the group consisting of wl = N or w2 = N=N or N=CR .

Especially preferred safeners are tho6e which are based on the bicyclic systems benzothiazole, benzoxazole, quinoxaline, but also benzimidazole, cinnoline, quinazoline and benzo-1,2,4-triazine, in particular the following compounds of the formulae (Ia) to (Ih) BlA(B2) n ~ BlA(B2) -O
R ~cN R ~N

( la) ( Ib) B1A(B 2 ) n ~ BlA(B 2 ) _ O

R '~ N~ R R .~ N
( I c) ( Id) B 1 A ( B2 ) n~B 1 A ( B2 ) _0 R ~R R ~

( I e ) ( I f ) B 1 A ( B 2 ) n ~ B 1 A ( B 2 ) _ O

R ,~NN~\~R ' R ~N1R
( Ig) ( Ih) Particularly preferred safeners are thoæe of the formulae (Ia), (Ib) and (Ic) in which n = 0 or 1 and B1 and B2 are from the group of the carboxylic esters.

Some compounds of the formula (I) are already known or some of the structural classes in question have been described in general form; cf., for example, Hawaiian Sugar Technologists' Rept. 24, 152 (1965); Symp. Soc.
Exptl. Biol. 17, 98 (1963); JP-A-04-028893 (1992), JP-A-02-306916 (1990). However, the safener action of the compoundæ (I) has not hitherto been disclosed.

The invention therefore also relates to the chemical compounds of the abovementioned formula (I) and the salts thereof in which A, Bl, B2, n, R , wl and w2 are as defined above, with the exception of those compounds (I) which are already known.

The compounds of the formula (I) can be prepared by, or analogously to, generally known processes (Brettle, J.
Chem. Soc. (1956) 1891; Eckstein, Roczniki Chem. 30 (1956) 633; US 2 697 708; Newman et al., J. Am. Chem.

2~38924 Soc. 69 (1947) 718; M.P. Cava, N.R. Bhattacharw a, J.
Org. Chem. 23 (1958) 1614; D. Heilmann, G. Kempter, Wis8.
Z. Padagog. Hochsch. "Rarl Liebknecht", Po~tdam 25 (1981) 35; Ger 1 099 544; US 3 010 962).

For example, the compounds of the formula (I) according to the invention can be prepared by a procedure which comprises a) reacting a compound of the formula H O

R ~ ~ R ( I I ) R R

with a compound of the formula (III) (~B2)n Bl-A-L ( I I I ) in which n is a leaving group, or b) in the event that n = 0 and Bl = a carboxyl deriva-tive, reacting or amidating a compound of the formula (IV) R ~ '~[ `'C - R . ( I V ), R R

preferably with alcohols R1-OH, thioalcohols RlSH or amines NR1R4, to give acid derivatives of the 2l38924 formula (I), n = 0, c) in the event that B1 and B2 are carboxylic acid derivative groups, transesterifying or amidating a compound of the formula (I') ( B ~ ) n B A O

R [~[~ R ( I ' ) R R

in which B and B' are defined analogously to B1 and B2 to give compounds of the formula (I), the radicals A, B1, B2, n, R and W1 and w2 in formulae (II), (III), (IV) and (I') being as defined in formula (I).

The reactions in accordance with variant a) are pre-ferably carried out in dipolar aprotic ~olvents such as dimethyl sulfoxide, N,N-dimethylformamide, diethyl ether or acetone, in the presence of a base such as alkali metal alcoholate, alkali metal hydride or alkali metal carbonates, for example potassium carbonate. The optimum temperature conditions of the reactions also depend on the solvent and can be determined in preliminary experi-ments. A slightly elevated temperature, for example between 50 and 80C, has frequently proved expedient in the case of reactions in dimethyl sulfoxide or N,N-di-methylformamide.

The reactions in accordance with variant b) are either carried out with acid cataly~is, preferably using sulfuric acid, or in the presence of a reagent which activates the carboxyl group, for example thionyl chloride, dicyclohexylcarbodiimide or N,N'-carbonyldiimidazole, in dipolar aprotic solvents or halogenated hydrocarbons, for example chloroform or tetrachloromethane, at temperatures from room temperature to the boiling point of the reaction mixture, in particular at reflux temperature.

The transesterification or amidation reactions in accord-ance with variant c) are preferably carried out in such a manner that a compound of the formula (V) i8 reacted--with the alcohols, or the amines, in the presence of titanium alcoholates as catalyst at elevated temp-eratures, in particular at reflux temperature of the reaction mixture.

The compounds of the formula (II) are known or can be prepared by, or analogously to, generally known processes (J.H. Musser, J. Med. Chem. 30 (1987) 62, for example for benzoxazoles; A. Albert, A. Hampton J. Chem. Soc. 4985 (1952), for example for ~-;noYAlines~ cinnolines and quinazolines; U. Holstein, G.E. Krisov, Org. Magn. Reson.
14 (1980) 300, for example for ~l;noYAlines; C.F.H.
Allen, J. Van Allan, Org. Synth. Coll. Vol. 3, 76, for example for benzothiazoles; E.C. Wagner, M.H. Millett, Org. Synth. Coll. Vol. 2, 65, for example for benzimida-zoles; H. Neuhoefer in Comprehensive Heterocyclic Chemistry 3, 430, for example for benzotriazines; P.A.
Grieco, J. Am. Chem. Soc. 99 (1977) 5773 and Organikum, l9th Edition 1993, for example for conversions of func-tional groups.

If the compounds of the formula (I) according to the invention are applied in subtoxic concentrations together with the herbicidal active substances, or else in any desired sequence, they are capable of reducing, or completely compensating for, the phytotoxic side effects of these herbicides without, however, reducing the activity of the herbicides against the harmful plants.

This allows the field of application of conventional crop protection products to be widened considerably. Examples of herbicides whose phytotoxic side effects on crop plants can be reduced by means of compounds of the formula (I) are carbamates, thiocarbamates, halo-acetanilides, substituted phenoxy-, naphthoxy- and phenoxy-phenoxycarboxylic acid derivatives and also heteroaryloxyphenoxyalkanecarboxylic acid derivatives, such as quinolyloxy-, ~-; noyA lyloxy-, pyridyloxy-, benzoxalyloxy- and benzothiazolyloxy-phenoxyAlkAne-carboxylic esters, cyclohexanedione derivatives, imidazo-linones, pyrimidyloxypyridinecarboxylic acid derivatives, pyrimidyloxybenzoic acid derivatives, sulfonylureas, triazolopyrimidinesulfonamide derivatives and S-(N-aryl-N-alkylcarbamoylmethyl)dithiophosphoricesters.Preferred are esters and salts of phenoxyphenoxy- and heteroaryl-oxyphenoxycarboxylic acids, as well as sulfonylureas and imidazolinones.

A) Herbicides of the type of the (C1-C4)-alkyl, (C2-C4)-alkenyl and (C3-C4)-alkynyl phenoxyphenoxy- and hetero-aryloxyphenoxycarboxylates, such as A1) phenoxyphenoxy- and benzyloxyphenoxy-carboxylic acid derivatives, for example methyl 2-(4-(2,4-dichlorophenoxy)phenoxy)propionate (diclofop-methyl), methyl 2-(4-(4-bromo-2-chlorophenoxy)phenoxy)propionate (see DE-A-2601548), methyl 2-(4-(4-bromo-2-fluorophenoxy)phenoxy)propionate (see US-A-4808750), methyl 2-(4-(2-chloro-4-trifluoromethylphenoxy)phenoxy)-propionate (see DE-A-2433067), methyl 2-(4-(2-fluoro-4-trifluoromethylphenoxy)phenoxy)-propionate (see US-A-4808750), methyl 2-(4-(2,4-dichlorobenzyl)phenoxy)propionate (see DE-A-2417487), ethyl 4-(4-(4-trifluoromethylphenoxy)phenoxy)pent-2-enoate, methyl 2-(4-(4-trifluoromethylphenoYy)phenoxy)propionate - 2~38924 _ - 20 -(see DE-A-2433067), A2) "mononuclear" heteroaryloxyphenoxyalkanecarboxylic acid derivatives, for example ethyl 2-(4-(3,5-dichloropyridyl-2-oxy)phenoxy)propionate (see EP-A-2925), propargyl 2-(4-(3,5-dichloropyridyl-2-oxy)phenoxy)-propionate (EP-A-3114), methyl 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-phenoxypropionate (gee EP-A-3890), ethyl 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-phenoxy)propionate (see EP-A-3890) propargyl 2-(4-(5-chloro-3-fluoro-2-pyridyloxy)phenoxy)-propionate (EP-A-191736), butyl 2-(4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)-propionate (fluazifop-butyl), A3) "binuclear" heteroaryloxyphenoxyalkanecarboxylic acid derivatives, for example methyl and ethyl2-(4-(6-chloro-2-~inox~lyloxy)phenoxy) propionate (quizalofop-methyl and -ethyl), methyl 2-(4-(6-fluoro-2-quinoxalyloxy)phenoxy)propionate (see J. Pest. Sci. Vol. 10, 61 (1985)), 2-(4-(6-chloro-2-quinoxalyloxy)phenoxy)propionicacidand its 2-isopropylidene~m;nooxyethyl ester (propaquizafop and ester), ethyl 2-(4-(6-chlorobenzoxazol-2-yloxy)rh~nn~y)propionate (fenoxaprop-ethyl), its D(+) isomer (fenoxaprop-P-ethyl) and ethyl 2-(4-(6-chlorobenzothiazol-2-yloxy)phenoxy-propionate (see DE-A-2640730), fur-2-ylmethyl 2-(4-(6-chloroquinoxalyloxy)phenoxy-propionate (see EP-A-323 727), B) herbicides from the sulfonylurea series, such as, for example, pyrimidinyl or triazinylaminocarbonyl[benzene-, pyridine-, pyrazole-, thiophene- and (alkylsulfonyl)-alkylamino~sulfamides. Preferred substituents on thepyrimidine ring or triazine ring are alkoxy, alkyl, haloalkoxy, haloalkyl, halogen or dimethylamino, it being possible for all substituents to be combined with each other independently. Preferred substituent~ in the benzene, pyridine, pyrazole, thiophene or (alkyl-sulfonyl)alkylamino moiety are alkyl, alkoxy, halogen,nitro, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxyaminocarbonyl, alkyl, alkoxy-aminocarbonyl, haloalkoxy, haloalkyl, alkylcarbonyl, alkoxyalkyl, (alkanesulfonyl)alkylamino. Examples of suitable sulfonylureas are B1) phenyl- and benzylsulfonylureas and related com-pounds, for example 1-(2-chlorophenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea (chlorsulfuron), 1-(2-ethoxycarbonylphenylsulfonyl)-3-(4-chloro-6-methoxy-pyrimidin-2-yl)urea (chlorimuron-ethyl), 1-(2-methoxyphenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea (metsulfuron-methyl), 1-(2-chloroethoxyphenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea (triasulfuron), 1-(2-methoxycarbonylphenylsulfonyl)-3-(4,6-dimethyl-pyrimidin-2-yl)urea (sulfometuron-methyl), 1-(2-methoxycarbonylphenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-3-methylurea (tribenuron-methyl), 1-(2-methoxycarbonylbenzylsulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea (bensulfuron-methyl), 1-(2-methoxycarbonylphenylsulfonyl)-3-(4,6-bis(difluoro-methoxy)pyrimidin-2-yl)urea (primisulfuron-methyl), 3-(4-ethyl-6-methoxy-1,3,5-triazin-2-yl)-1-(2,3-dihydro-1,1-dioxo-2-methylbenzo[b]thiophene-7-sulfonyl)urea (see EP-A-79683), 3-(4-ethoxy-6-ethyl-1,3,5-triazin-2-yl)-1-(2,3-dihydro-1,1-dioxo-2-methylbenzo[b]thiophene-7- 8ul fonyl)urea (see EP-A-79683), the sodium salt of methyl 4-iodo-2-[3-(4-methoxy-6-methyl-1,3,5-triazinyl)ureidosulfonyl]benzoate (see WO-A-92/13845) 2'1 38924 B2) Thienylsulfonylureas, for example 1-(2-methoxy-carbonylthiophen-3-yl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea (thifensulfuron-methyl), B3) pyrazolylsulfonylureas, for example 1-(4-ethoxycarbonyl-1-methylpyrazol-5-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea (pyrazosulfuron-methyl), methyl 3-chloro-5-[4,6-dimethoxypyrimidin-2-ylcarbamoyl-sulfamoyl)-1-methylpyrazole-4-carboxylate (see EP 282613), methyl 5-(4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl)-1-(2-pyridyl)pyrazole-4-carboxylate (NC-330, seeBrighton Crop Prot. Conference - Weeds - 1991, Vol. 1, 45 ff.), B4) sulfonediamide derivatives, for example 3-(4,6-dimethoxypyrimidin-2-yl)-1-(N-methyl-N-methyl-sulfonylaminosulfonyl)urea (amidosulfuron) and structural analogs (see EP-A-0131258 and Z. Pfl. Krankh. Pfl. Schutz 1990, Special Issue XII, 489-497), B5) pyridylsulfonylureas, for example 1-(3-N,N-dimethylaminocarbonylpyridin-2-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea (nicosulfuron), 1-(3-ethylsulfonylpyridin-2-ylsulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea (DPX-E 9636, see Brighton Crop Prot.
Conf. - Weeds - 1989, page 23 et seq.), pyridylsulfonylureas as they are described in DE-A-4000503 and DE-A-4030577, preferably those of the formula ~ ~ 0 ~1~ N

in which E is CH or N, preferably CH, Rll is iodine or NRl6Rl7, Rl2 is H, halogen, cyano, (Cl-C3)-alkyl, (Cl-C3)-alkoxy, (Cl-C3)-haloalkyl, (Cl-C3)-haloalkoxy, (Cl-C3)-alkyl-thio, (Cl-C3)-alkoxy-(Cl-C3)-alkyl, (Cl-C3)-alkoxy-carbonyl, mono- or di-(Cl-C3)-alkylamino, (Cl-C3)-alkylsulfinyl or -sulfonyl, SO2-NRaRb or CO-NRaRb, in particular H, Ra and Rb independently of one another are H, (Cl-C3)-alkyl, (Cl-C3)-alkenyl, (Cl-C3)-alkynyl or together are -(CH2) 4- ~ - (CH2) 5- or (CH2)2-O-(CH2)2-, Rl3 is H or CH3, Rl4 is halogen, (Cl-C2)-alkyl, (Cl-C2)-alkoxy, (Cl-C2)-haloalkyl, preferably CF3, (Cl-C2)-haloalkoxy, preferably OCHF2 or OCH2CF3, Rl5 is (Cl-C2)-alkyl, (Cl-C2)-haloalkoxy, preferably OCHF2, or (Cl-C2)-alkoxy, and Rl6 iS ( Cl - C4 ) - alkyl and Rl7 is (Cl-C4)-alkylsulfonyl or Rl6 and Rl7 together are a chain of the formula -(CH2)3SO2- or -(CH2)4SO2~
for example 3-(4,6-dimethoxypyrimidin-2-yl)-1-(3-N-methylsulfonyl-N-methylaminopyridin-2-yl)sulfonylurea, or salts of these compounds, B6) alkoxyphenoxysulfonylureas as they are described in EP-A-0342569, preferably those of the formula ( R ~ 9 ) ~ \\5~/

in which E is CH or N, preferably CH, Rl3 is ethoxy, propoxy or isopropoxy, Rl9 is hydrogen, halogen, NO2, CF3, CN, (Cl-C4)-alkyl, (Cl-C4)-alkoxy, (Cl-C4)-alkylthio or (Cl-C3)-alkoxy-_ - 24 -carbonyl, preferably in the 6-position on the phenyl ring, n iB 1, 2 or 3, preferably 1, R20 is hydrogen, (C1-C4)-alkyl or (C3-C4)-alkenyl, R21 and R22 independently of one another are halogen, (Cl-C2)-alkYl~ (Cl-C2)-alkoxy, (Cl-C2)-haloalkyl, (C1-C2)-haloalkoxy or (C1-C2)-alkoxy-(C1-C2)-alkyl, preferably OCH3 or CH3, for example 3-(4,6-dimeth-oxypyrimidin-2-yl)-1-(2-ethoxyph~noYy)sulfonylurea, or salts of these compounds, and other related sulfonylurea derivatives and their mixtures, C) chloroacetanilide herbicides, such as N-methoxymethyl-2,6-diethylchloroacetanilide (alachlor), N-(3'methoxyprop-2'-yl)-2-methyl-6-ethylchloroacetanilide (metolachlor), N-(3-methyl-1,2,4-oxdiazol-5-ylmethyl)-2,6-dimethyl-chloroacetanilide, N-(2,6-dimethylphenyl)-N-(1-pyrazolylmethyl)chloro-acetamide (metazachlor), D) thiocarbamates such as S-ethyl N,N-dipropylthiocarbamate (EPTC) or S-ethyl N,N-diisobutylthiocarbamate (butylate), E) cyclohexanedione derivatives, such as methyl 3-(1-allyloxy; ;nohutyl)-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylate (alloxydim), 2-(1-ethoY; m; nobutyl)-5-(2-ethylthiopropyl)-3-hydr cyclohex-2-en-1-one (sethoxydim), 2-(1-ethoxy;m;nohutyl)-5-(2-phenylthiopropyl)-3-hydroxy-cyclohex-2-en-1-one (cloproxydim), 2-(1-(3-chloroallyloxy)iminobutyl)-5-[2-(ethylthio)-propyl]-3-hydroxycyclohex-2-en-1-one, 2-(1-(3-chloroallyloxy)iminopropyl)-5-[2-(ethylthio)-propyl]-3-hydroxycyclohex-2-en-1-one (clethodim), 2-(1-(ethoxyimino)-butyl)-3-hydroxy-5-(thian-3-yl)cyclo-_ - 25 -hex-2-enone (cycloxydim), or 2-(1-ethoxyiminopropyl)-5-(2,4,6-trimethylphenyl)-3-hydroxycyclohex-2-en-1-one (tralkoxydim), F) 2-(4-alkyl-5-oxo-2-imidazolin-2-yl)benzoic acid derivatives or 2-(4-alkyl-5-oxo-2-imidazolin-2-yl)-heteroarylcarboxylic acid derivatives such as, for example, methyl 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methylbenzoate and 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-4-methylbenzoic acid (imazamethabenz), 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)pyridine-3-carboxylic acid (imazethapyr), 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quino-line-3-carboxylic acid (imazaquin), 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)pyridine-3-carboxylic acid (imazapyr), 5-methyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)pyridine-3-carboxylic acid (imazethamethapyr), G) triazolopyrimidinesulfonamide derivatives, for example N-(2,6-difluorophenyl)-7-methyl-1,2,4-triazolo-(1,5-c)pyrimidine-2-sulfonamide (flumetsulam), N-(2,6-dichloro-3-methylphenyl)-5,7-dimethoxy-1,2,4-triazolo-(1,5-c)-pyrimidine-2-sulfonamide, N-(2,6-difluorophenyl)-7-fluoro-5-methoxy-1,2,4-triazolo-(1,5-c)pyrimidine-2-sulfonamide N-(2,6-dichloro-3-methylphenyl)-7-chloro-5-methoxy-1,2,4-triazolo-(1,5-c)pyrimidine-2-sulfonamide, N-(2-chloro-6-methoxycarbonyl)-5,7-dimethyl-1,2,4-triazolo-(1,5-c)pyrimidine-2-sulfonamide (see, for example, EP-A-343 752, US-4 988 812), H) benzoylcyclohexanedione derivatives, for example 2-(2-chloro-4-methylsulfonylbenzoyl)cycloh~Ane-1,3-dione (SC-0051, see EP-A-137963), 2-(2-nitrobenzoyl)-4,4-dimethylcycloheYAne-1,3-dione (see EP-A-274634), 2-(2-nitro-3-methylsulfonylbenzoyl)-4,4-dimethylcyclo-hexane-1,3-dione (see WO-91/13548), J) pyrimidinyloxypyrimidinecarboxylic acid derivatives or pyrimidinyloxybenzoic acid derivatives, for example benzyl 3-(4,6-dimethoxypyrimidin-2-yl)oxypyridine-2-carboxylate (EP-A-249 707), methyl 3-(4,6-dimethoxypyrimidin-2-yl)oxypyridine-2-carboxylate (EP-A-249 707), 2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoic acid (EP-A-321 846), 1-ethoxycarbonyloxyethyl 2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoate (EP-A-472 113) and K) S-(N-aryl-N-alkylcarbamoylmethyl)dithiophosphoric esters, such as S-[N-(4-chlorophenyl)-N-isopropylcarbamoylmethyl]
O,O-dimethyl dithiophosphate (anilofos).

The abovementioned herbicides of groups A to K are known to a person skilled in the art and, as a rule, described in "The Pesticide Manual", British Crop Protection Council, 9th Edition 1991, or 8th Edition 1987, or in "Agricultural Chemicals Book II, Herbicides", by W.T.
Thompson, Thompson Publications, Fresno CA, USA 1990 or in "Farm Chemicals ~An~hook '90", Meister Publishing Company, Willoughby OH, USA 1990. Imazethamethapyr is known from Weed Techn. 1991, Vol. 5, 430-438.

The herbicidal active substances and the abovementioned safeners can be applied together (as a readymix or by the tank mix method) or in succession, in any desired sequence. The ratio by weight of safener: herbicide can vary within wide limits and is preferably in the range of 1:10 to 10:1, in particular 1:10 to 5:1. The amounts of herbicide and safener which are optimal in each case depend on the type of the herbicide used or on the safener used as well as on the species of the plants to 2~38~4 be treated and can be determined in each individual case by suitable preliminary experiments.

The safeners are mainly employed in particular in cereal crops (wheat, rye, barley, oats), rice, maize, sorghum, but also cotton and soya bean, preferably cereals, rice and maize.

Dep~n~;ng on their properties, the safeners of formula (I) can be used for pretreating the seed of the crop plant (seed dressing), or they can be incorporated in the seed furrows prior to sowing, or used together with the herbicide prior to, or after, plant emergence. Pre-emergent treatment includes both the treatment of the area under cultivation prior to sowing and treatment of the areas under cultivation where seed has been sown but growth of the crop plant has not yet taken place. The use together with the herbicide is preferred. To this end, tank mixes or readymixes can be employed.

The application rates of safener required can vary within wide limits, depen~;ng on the indication and herbicide used, and are, as a rule, in the range from 0.001 to 5 kg, preferably 0.005 to 0.5 kg, of active substance per hectare.

The invention therefore also relates to a method of protecting crop plants against phytotoxic side-effects of herbicides, which comprises applying an effective amount of a compound of the formula (I) prior to, after or simultaneously with the herbicide to the plants, seeds of the plants or the area under cultivation.

The invention also relates to crop-protecting com-positions which comprise an active substance of the formula (I) and customary formulation auxiliaries, and to herbicidal compositions which comprise an active sub-stance of the formula (I) and a herbicide as well as formulation auxiliaries which are customary in the field _ - 28 -of crop protection.

The compounds of the formula (I) and their combinations with one or more of the herbicides mentioned can be formulated in a variety of ways, as predetermined by the biological and/or chemico-physical parameters. The following possibilities are therefore suitable for formulation: wettable powders (WP), emulsifiable concen-trates (EC), water-soluble powders (SP), water-soluble concentrates (SL), concentrated emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions or emulsions, capsule suspensions (CS), oil- or water-based dispersions (SC), suspoemulsions, suspension concentrates, dusts (DP), oil-miscible solutions (OL), seed-dresæing products, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, granules for soil application or broadcasting, water-soluble granules (SG), water-disper-sible granules (WG), ULV formulations, microcapsules and waxes.

These individual formulation types are known in principle and are described, for example, in Winnacker-Kuchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker N.Y., 1973; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.

The formulation auxiliaries required, such as inert materials, surfactants, solvents and other additives, are also known and described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; H. v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J.
Wiley ~ Sons, N.Y.; Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.;
Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenz-flachenaktive Athylenoxidaddukte" ~Surface-active Ethylene Oxide Adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Ed.
1986.

Combinations with other pesticidally active substances, fertilizers and/or growth regulators may also be prepared on the basis of these formulations, for example in the form of a readymix or a tank mix.

Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substances, also comprise ionic and/or non-ionic sur-factants (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols and fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates or alkylarylsulfonates, sodium lignosulfonate, sodium 2,2-~; n~ph thylmethane-6,6'-di-sulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleylmethyltauride, in addition to a diluent or inert substance.

Emulsifiable concentrates are prepared by dissolving the active substance or active substances in an organic solvent, for example butanol, cycloh~y~no~e~ dimethyl-formamide, xylene or else higher-boiling aromatics or hydrocarbons with the addition of one or more ionic and/or non-ionic surfactants (emulsifiers). Examples of emulsifiers which can be used are: calcium salts of an alkylarylsulfonic acid, such as calcium dodecylbenzene-sulfonate, or non-ionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensation products (for example block copolymers), alkyl polyethers, sorbitan fatty acid esters, polyoxy-ethylene sorbitan fatty acid esters or other polyoxyethy-lene sorbitan esters.

2~3~924 - ~ - 30 -Dusts are obtained by grinding the active substance or active substances with finely divided solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Granules can be produced either by spraying the active substance or active substances onto adsorptive, granu-lated inert material, or by applying active substance concentrates to the surface of carriers such as sand or kaolinite, or of granulated inert material, by means of binders, for example polyvinyl alcohol, sodium poly-acrylate or else mineral oils. Water-dispersible granules are generally prepared by the customary methods such as æpray drying, fluidized-bed granulation, disk granu-lation, m; ~; ng by means of high-speed mixers and extru-sion without solid inert material. Suitable active substances may also be granulated in the manner which is conventional for the production of fertilizer granules, if desired in a mixture with fertilizers.

As a rule, the agrochemical preparations comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active substances of the formula (I) (antidote) or of the herbicide/antidote active substance mixture and 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid additive and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant.

In wettable powders, the concentration of active sub-stance is, for example, approximately 10 to 90% by weight; the r- ~;n~er to 100% by weight iB composed of conventional formulation components. In the case of emulsifiable concentrates, the concentration of active substance is approximately 1 to 80% by weight. Formu-lations in the form of dusts comprise approximately 1 to 20% by weight of active substances, sprayable solutions approximately 0.2 to 20% by weight of active substances.
In the case of granules, such as water-dispersible granules, the active substance content depends partly on whether the active compound is in liquid or solid form.
As a rule, the content in the water-dispersible granules amounts to between 10 and 90% by weight.

In addition, the active substance formulations mentioned comprise, if appropriate, the adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers which are conventional in each case.

For use, the formulations, present in commercially available form, are diluted, if appropriate, in a custo-mary manner, for example using water in the case ofwettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in the form of dusts, granules and sprayable solutions are usually not further diluted with other inert substances before use. Particularly good activity rates of the compositions according to the invention can be achieved by adding, in addition to the surfactants in the formulations, further wetting agents at concentrations of 0.1 to 0.5% by weight in the tank mix method, for example non-ionic wetting agents or wetting agents of the fatty alcohol polyol ether sulfate type (see, for example, German Patent Application P 40 29 304.1). The application rate of the safeners required varies with the external conditions such as, inter alia, temperature, humidity, and the nature of the herbicide used.

Based on these formulations, it is also possible to prepare combinations with other substances which are active in crop management, for example pesticides, such as insecticides, acaricides, fungicides and herbicides and/or fertilizers and/or growth regulators, for example in the form of a readymix or a tank mix.

A. Formulation examples a) A dust is obtained by mixing 10 parts by weight of a compound of the formula (I) or of an active - 2~389Z4 ~- - 32 -substance mixture of a herbicide and a compound of the formula (I) and 90 parts by weight of talc as inert substance and comminuting the mixture in a hammer mill.

b) A wettable powder which i8 readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I) or of an active sub-stance mixture of a herbicide and a safener of the formula (I), 64 parts by weight of kaolin-cont~;n;ng quartz as inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as wetting agent and dispersant, and grinding the mixture in a pinned-disk mill.

c) A dispersion concentrate which is readily disper-sible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) or of an active substance mixture of a herbicide and a safener of the formula (I), 6 parts by weight of alkylphenol polyglycol ether (RTriton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range for example approximately 255 to above 277C) and gr;n~;ng the mixture in a ball mill to a fineness of below 5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I) or of an active ~ubstance mixture of a herbicide and a safener of the formula (I), 75 parts by weight of cycloheY~no~e as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier.

e) Water-dispersible granules are obtained by ~;Y; ng 75 parts by weight of a compound of the formula (I) or of an active substance mixture of a herbicide and a 2~38924 safener of the formula (I), 10 parts by weight of calcium lignosulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin, gr;nA~ ng the mixture in a pinned-disk mill and granulating the powder in a fluidizer bed by spray-ing on water as the granulation liquid.

f) Alternatively, water-dispersible granules are obtained by homogenizing and precomminuting, on a colloid mill, 25 parts by weight of a compound of the formula (I) or of an active substance mixture of a herbicide and a safener of the formula (I), 5 parts by weight of sodium 2,2'-dinaphthyl-methane-6,6'-disulfonate, 2 parts by weight of sodium oleoylmethyltaurate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water subsequently gr;nA;ng the mixture in a bead mill, and atomizing and drying the resulting suspension in a spray tower by means of a single-substance nozzle.

B. Preparation examples a) Ethyl 4-benzothiazolyloxyacetate Example 2-3 of Table 2 4 g (28 mmol) of 4-hydroxybenzothiazole were dis-solved in 210 ml of absolute tetrahydrofuran. 1.2 g (40 mmol) of sodium hydride (80% in mineral oil) were added in portions at 0C. The mixture wa stirred for 0.5 hour at room temperature and again cooled to 0C. At this temperature, a solution o$
7.5 g (45 mmol) of ethyl bromoacetate was added dropwise. After the dropwise addition had ended, the _ - 34 -mixture was stirred for 2 hours at room temperature.
For working up, the mixture was treated with 50 ml of 2N hydrochloric acid and 20 ml of water, and the phases were separated. The aqueous phase was extracted using ether, and the combined organic phases were dried over magnesium sul$ate. After the solvent had been distilled off, the residue was purified by column chromatography. This gave 6 g (25 mmol, 90% of theory) of ethyl 4-benzo-thiazolyloxyacetate as a colorless oil;
H NMR (CDCl3): ~ [ppm] = 8.85 (s, lH), 6.8-7.5 (m, 3H), 4.95 (s, 3H), 4.0-4.4 (q, 2H), 1.1-1.4 (t, 3H).

b) l-Methylhexyl 4-benzothiazolyloxyacetate Example 2-4 of Table 2 4.5 g (19 mmol) of ethyl 4-benzothiazolyloxyacetate were dissolved in 100 ml of 2-heptanol, 1 ml of titanium tetraisopropoxide was added, and the mixture was stirred overnight at 100C. The excess 2-heptanol was subsequently distilled off under an oil-pump vacuum, and the residue was purified by column chromatography. This gave 2.7 g (8.8 mmol, 46% of theory) of l-methylhexyl 4-benzothiazolyloxy-acetate as an oil;
lH NMR (CDC13): ~ [ppm~ = 8.82 (s, lH), 6.75-7.6 (m, 3H), 4.8-5.2 (m, lH), 4.9 (s, 3H), 0.6-1.8 (m, 14H).

c) Diethyl 4-benzothiazolyloxymalonate Example 2-6 of Table 2 1.6 g (11 mmol) of 4-hydroxybenzothiazole were dissolved in 100 ml of acetone. After 7.6 g (55 mmol) of potassium carbonate and 6.9 g (55 mmol) of diethyl chloromalonate had been added, the mixture was refluxed for 6 hours. It was subsequently filtered, and the filtrate was concentrated. The crude product obtained was purified by chromatography. This gave 1.5 g (5 mmol), 45% of theory) of diethyl 4-benzothia-zolyloxymalonate as an oil;
1H NMR (CDCl3): ~ [ppm] = 8.8 (8, lH), 7.0-7.7 (m, 3H), 6.0 (s, lH), 4.4-4.5 (q, 4H), 1.1-1.4 (t, 6H).

The examples given in Tables 1 to 10 below are obtained analogously to the above Examples a), b) and c) and to the processes described further above. The analogous carboxylic acids can be prepared from the correspo~i ng esters by methods known in principle.

Abbreviations in Tables 1 to 10: n-alkyl or alkyl (n) =
straight-chain alkyl; i-, 8-, t-alkyl = iso-alkyl, æecondary alkyl or tertiary alkyl; m.p. = melting point.
.

Table 1: Compounds of the formula (1) O - Z

~ \ ~ Y (t ) Ex. X Y Z m.p.~Cl:
CAS < Reg. No. >
l-l H H CH2CO2H

1-3 H H CH2CO2c2Hs 1-4 H H CH2co2-cH2-cH=cH2 1-5 H H CH2co2-cH(cH3~-(cH2~c-cH3 1-6 H H CH2co2-n-c8Hl7~n~
1-7 H H CH2CO2-C2Hs-O-C4Hgln) 1-8 H H CH2co2-cH(cH3l-cH2ocH2cH=cH2 1-9 H H CH2CO2-(CH2)2-O-cO-cHlcH3~2 1-10 H H CH2CO2-tCH2)2-O-cO-c(cH3)3 1-1~ H H CH2CO2-[CH2)3-O-cO-cH3 1-12 H H CH2-CO2-(CH2)3-O-cO-cF3 1-13 H H CH2C02 Na 1-15 H H CH2CO2NH~

1-16 H H CH2CO2NH2(CH312 . . _ Ex. X Y Z m.p.lC];
CAScReg.No.>
1-17 H H CH2-C02NH3(n-C7Hl5) 1-18 H H CH2-C02NH2(C2HsOH)2 1-19 H H CH2-CO2NH(c2HsOH)3 1-20 H H CHtCC2C2Hs~2 1-23 7-CI H CH2-C02-CH(CH3)-(cH2)4-cH3 1-24 7-CI H CHIC02C2Hs)2 1-27 7-CI CH3 CH2-C02-CH(CH3)-~cH2)4-cH3 1-28 7-CI CH3 CH(co2c2Hs)2 1-30 7-CI CN CH2-c02-cH3 1-31 7-CI CN CH2-co2-cH(cH3)-(cH2)4-cH3 1-32 7-CI CN CH(C02C2Hs)2 1-34 6-F H CH2-co2cH3 1-35 6-F H CH2-C02-CH(CH3)-(CH2)4-CH3 1-36 6-F H CH(C02C2Hs)2 1-37 H Cl CH2-c02-cH3 1-38 H Cl CH2-co2-cH(cH3)-(cH2)4-cH3 1-39 H Cl CH(C02C2Hs)2 _, Table 2: Compounds of the formula (2) O - Z

~ Y

Ex. X Y Z m.p.[C]:
CAS<Reg.No.>
2-1 H H CHzC02H <30172-80-6 2-3 H H CH2C02c2Hs oil 2-4 H H CH2-C02-CH(CH3)-lcH2)4-cH3 oil 2-5 H H CH2-C02-~CH2)2-0-cO-cH(cH3)2 2-6 H H CH(C02C2Hs)2 2-7 . 7-CI H CH2-C02H
2-8 7-CI H CH2-C02-C2Hs 86-87 2-9 7-CI H CH2-C02-CH(CH3)-(CH2)4-CH3 2-10 7-CI H CH(co2c2Hs)2 2-12 7-CF3 H CH2-C02-c2H5 2-13 7-CF3 H CH2-C02-CH(OH)3-(CHz)4~cH3 2-14 7-CF3 H CH(C02C2Hs)2 2-15 H Cl CH2-C02H
2-16 H Cl CH2-C02-c2H5 2-17 H Cl CH2-C02-CH(CH3)-(cH2)4-cH3 2-18 H Cl CH(C02~C2Hs)2 ,. ~ .

Ex. X Y Z m.p. [C];
CAS<Reg. No.>

2-21 7-CI 0-CH3 CH2-C02-CH(CH3)-~CH2)4-CH3 2-22 7-CI 0-CH3 CH~co2-c2Hs)2 2-24 6-CI F CH2-C02-C2Hs 2-25 6-CI F CH2-C02-CH(CH3~-(CH2~4-CH3 2-26 6-CI F CH(co2c2Hs~2 2-27 H H CH2-C02-CH2-cH = CH2 2-28 H H CH2-C02-n~C4Hs 2-29 H H CH2C02CH(CH3~-cH2-OCH2CH = CH2 2-30 H H CH2-C02-(cH2)2-O-co-cF3 2-31 H H C(CH312-COz-c2Hs 2-32 H H CH2-C02-(CH2)2-NH-C0-CH3 2-34 H H CH2-CO-N(CH3)2 2-37 H H CH2-C02 NH2(CH3~2 2-38 H H CH2-C02 NH(C2HsOH~3 2-39 H H CHIC02-CH~CH3~-(cH2l4-cH3l2 2-40 H H CH(CN~2 2-41 H H CH(C02H~2 2-42 H H CH(C0-cH3l2 2-43 H H CH(C02cH3~2 t 2138924 ~, Table 3: Compounds of the formula (3 ) ,~C ~Y ( ) Z - O

Ex. X Y Z m.p.[C];
CAS<Reg.No.>

3-3 H H CH2-C02-CH2-CH=cH2 3-4 H H CH2-C02-CH(CH3)-(CH2)4-CH3 3-5 H H CH2-co2-csH17 3-6 H H CH2-C02-C2H5-0-c4H8(n) 3-7 H H CH2-C02-(CH2)2-0-C0-CH3 3-8 H H CH(C02C2Hs)2 3-9 H Cl CH2-C02H
3-10 H Cl CH2-C02-C2H5 3-11 H Cl CH2-C02-CH(CH3)-(CH2)4-CH3 3-12 H Cl CHIC02C2Hs)2 3-14 H 0-CH3 CH2-C02-C2Hs 3-15 H 0-CH3 CH2-C02-CH(CH3)-(CH2)4-CH3 3-16 H 0-CH3 CH(co2-c2Hs)2 3-18 H -CN CH2-c02-c2Hs 3-19 H -CN CH2-C02-CH(CH3)-(CH2)4-cH3 3-20 H -CN CH(C02c2Hs)2 2~38924 Table 4: Compounds of the formula (4) O -~C ~Y ( ) X Y' Ex. X Y Y~ Z m.p.~C]:
CAS < Reg. No. >

4-2 H H CH3 CH2-c02-cH3 4-3 H H CH3 CH2-C02-c2H5 4-4 H H CH3 CH2-C02-CH2-CH=cH2 4-5 H H CH3 CH2-co2-cH~cH3)-(cH2)4cH3 4-6 H H CH3 CH2-C02-C8Hl7(n) 4-7 H H CH3 CH(C02C2Hs)2 4-9 H O-CH3 CH3 CH2-C02-c2Hs 4-10 H O-CH3 CH3 CH2-CO2-CH(CH3)-(CH2)4-CH3 4-11 H O-CH3 CH3 CH(C02C2Hs)2 4-14 7-CI H CH3 CH2-co2cH(cH3)-(cH2)4-cH3 4-15 7-CI H CH3 CH(C02C2Hs)2 4-18 H H -SO2-CH3 CH2-CO2-CH(CH3)-~CH2)4-CH3 2~38924 Ex. X Y Y~ Z m.p.[C];
CAS < Reg . No. >
4-19 H H -S02-CH3 CH(COZC2H5)2 4-20 H Cl -S02-CH3 CH2-C2H
4-21 H Cl -S02-CH3 CH2-co2-c2H6 4-22 H Cl -S02-CH3 CH2-C02-CH(CH3)-(CH 2)4-CH3 4-23 H Cl -S02-CH3 CH(C02C2H5)2 4-26 H H -CH2-CN CH2-C02-CH(CH2)4-CH3 4-27 H H -CH2-CN CH~C02C2H5)2 4-30 H CH3 -CH2-CN CH2-C02-CH~cH3)-(cH 2)4-CH3 4-31 H CH3 -CH2-CN CH(C02C2H5)2 - _ - 43 -Table 5: Compounds of the $ormula (5) o-7-~N X

Ex. X Y Y' Z m.p.[C];
CAS<Re~.No.>

5-4 H H H CH2-C02-CH2-CH=cH2 5-5 H H H CH2-co2-cH(cH3)-(cH2)4-cH3 5-6 H H H CH2-C02-n-C8H~7 5-7 H H H CH(COzC2Hs)2 5-10 8-CI H H CH2-C02-CH2-CH=CH2 5-11 8-CI H H CH2-C02-CH(CH3)-(CH2)4-CH3 5-12 8-CI H H CH(COC2H5)2 5-15 H CH3 H CH2-C02-CH(CH3)-(CH2)4-CH3 5-16 H CH3 H CH(C02C2H5)2 5-19 H CH3 CH3 CH2-co2-cH(cH3)(cH2)4-cH3 5-20 H CH3 CH3 CH(CO2C2Hs)2 213892~

Table 6: Compounds of the formula (6) O - Z

~ ~ (6) X Y' Ex. X Y Y' Z mp.[CI;
CAS < Reg. No. >

6-3 H H H CH2-CO2-CH(CH3)-~CH 2)4-CH3 6-4 H H H CH(CO2-C2Hs)2 6-6 5-CI H H CH2-CO2-c2Hs 6-7 5-CI H H CH2-C02-CH(CH3)-(CH 2)4-CH3 6-8 5-CI H H CH(CO2-C2Hs)2 6-11 5-F H H CH2-co2-cH(cH3)-(cH2)c-cH3 6-12 5-F H H CH(CO2c2Hs)2 6-14 5-CF3 H H CH2-C02-C2Hs 6-15 5-CF3 H H CH2-co2-cH(cH3)-(cH2)4-cH3 6-16 5-CF3 H H CH(CO2-C2Hs)2 Table 7: Compounds of the formula (7) O - Z

~ ~ (7) Ex. X Y Z m.p.lC];
CAS<Reg.No.>

7-3 H H CH2-C02-CH2-cH=cH2 7-4 H H CH2-co2-cH(cH31-(cH2)4-cH3 7-5 H H CH(C02-C2Hs)2 7-7 8-CI H CH2-C02-c2H5 7-8 8-CI H CH2-CO2-CH(CH3~-(CH2)4-cH3 7-9 8-CI H CH(CO2-C2Hs)2 7-11 8-F H CH2-C02-c2H5 7-12 8-F H CH2-CO2-CH(CH3)-(CH2)4-CH3 7-13 8-F H CH(CO2-C2Hs)2 7-15 7-CI H CH2-C02-c2H5 7-16 7-CI H CH2-co2-cH(cH3)-(cH2)4-cH3 7-17 7-CI H CH(CO2-C2Hs)2 . - 46 -.. _ Table 8: Compounds of the formula (8) O - Z
~N N

EX. X Y Z ~rl.p. ~C];
CAS~Reg.No.

8-2 H H CH2-C02-c2H5 8-3 H H CH2-C02-CH2-cH=cH2 8-4 H H CH2-CO2-CH(CH3)-(CH2)4-cH3 8-5 H H CH(CO2-C2Hs)2 8-7 5-CI H CH2-C02-C2Hs 8-8 5-CI H CH2-CO2-CH~CH3)-(CH2)4-cH3 8-9 5-CI H CHtC02~C2Hs)2 8-11 5-F H CH2-c02-c2Hs 8-12 5-F H CH2-CO2-CH(CH3)-~cH2)4-cH3 8-13 5-F H CH~CO2-C2Hs)2 8-16 6-CI H CH2-co2-cH~cH3)-~cH2)4-cH3 8-17 6-CI H CH~CO2-C2Hs)2 213~924 Table 9: Compounds of the formula (9) O - Z
~ (9) X Y' Ex. X Y Y' Z mp.lCl;
CAS<Reg. No.>

9-2 5-CH3 H H CH2-co2-c2H5 9-3 5-CH3 H H CH2-CO2-CH~CH3)-(cH 2)4-CH3 9-4 5-CH3 H H CH(CO2-C2Hs~2 9-7 H H H CH2-CO2-CH(CH3)-(CH2)4-cH3 9-8 H H H CH(CO2-C2Hs)2 9-10 5-CI H H CH2-CO2-C2Hs 9 11 5-CI H H CH2-CO2-CH(CH3)-(cH 2)4-CH3 9-12 5-CI H H CH(CO2C2Hs)2 9-15 5-F H H CH2-CO2-CH(CH3)-(cH2)4-cH3 9-16 5-F H H CH(CO2-C2Hs)2 C. Biological examples Example 1 In a greenhouse, wheat and barley were grown in plastic pots until they had reached 3- to 4-leaf-stage and then treated post-emergence in succession with the compounds according to the invention and the test herbicides. The herbicides and the compounds of the formula (I) were applied in the $orm of aqueous suspensions or emulsions at an application rate of 300 l of water/ha (converted).
3 to 4 weeks after the treatment, the plants were scored visually for any type of damage by the herbicides applied, taking into account the extent of prolonged growth inhibition. Assessment was by percentages in comparison with untreated controls.

Severe damage in the crop plants was reduced markedly and lesser damage compensated for completely, even when a massive overdose of the herbicide was used. Mixtures of herbicides and compounds according to the invention are therefore outstAn~;ngly suitable for selective weed control in cereal crops (cf. also Table 11).

Example 2 In the field or in the greenhouse, maize plants, broad-leaved weeds and grass weeds were grown in plastic pots until they had reached the 3- to 4-leaf-stage, and treated post-emergence in succession with herbicides and compounds of the formula (I) according to the invention.
The active substances were applied in the form of aqueous suspensions or emulsions at an application rate of 300 l of water/ha (converted). 4 weeks after the treatment, the plant were scored visually for any type of damage by the herbicides applied, t~k;ng into account in particular the extent of prolonged growth inhibition. The assessment was in percentages in comparison to untreated controls.

2~389~
_ - 49 -The results show that the compounds of the formula (I) according to the invention employed are capable of effectively reducing severe herbicide damage to the maize plants. Severe damage in the crop plants was reduced markedly and lesser damage compensated for completely, even when a massive overdose of the herbicide was used.
Mixtures of herbicides and compounds of the formula I
according to the invention are therefore outst~n~;ngly suitable for selective weed control in maize (cf. also Table 11).

Table 11: Crop-protecting action of compounds according to the invention Active Dose Herbicidal action in %
substances(kg of a.s./ha)HOVU ZEMV
Hl 0.2 80 H2 0.075 _ 75 Hl + S10.2 + 1.25 23 H2 + S20.075 + 1.25 - 30 Hl + S20.2 + 1.25 15 H2 + S20.075 + 1.25 - 35 Abbreviations in Table 11:
HOVU = Hordeum vulgare, ZEMV = Zea mays a.s. = active substance (based on pure active ingredient) Hl = Ethyl 2-(4-(6-chlorobenzoxazol-2-yloxy)phen propionate (fenoxaprop-ethyl) H2 = 3-(4,6-Dimethoxypyrimidin-2-yl)-1-[3-(N-methyl-sulfonylamino)-2-pyridylsulfonyl]urea Sl = Example 2-3 of Table 2, S2 = Example 2-4 of Table 2.

Claims (10)

1. The use of compounds of the formula (I) or salts thereof (I) in which W1 is N or CR* and W2 is O, S, NH, NR**, N=N, N=CR* or CR*=N and the total of the hetero ring atoms of groups W1 and W2 is 2 or 3, and A is a divalent hydrocarbon radical having 1 to 12 carbon atoms, B1 and B2 in each case independently of one another are carboxyl, carboxyl derivatives from the group consisting of esters, thioesters, nitriles, imides, anhydrides, halide, amides, hydrazides, imidic acid, hydrazonic acid, hydroxamic acid, hydroximic acid, amidine, amide oxide and deriva-tives of the last-mentioned 9 functional radicals which are further substituted on the nitrogen atom or the hydroxyl group, or formyl, formyl deriva-tives from the group consisting of acetals, thio-acetals, imines, hydrazone, oxime and derivatives of the last-mentioned 3 functional radicals which are further substituted on the nitrogen atom or on the hydroxyl group, or an acyl radical of the formula -CO-R in which R is an aliphatic, araliphatic or aromatic radical which can additionally have further functional groups and can comprise, in total, up to 24 carbon atoms, n is 0 or 1, R* in each case independently of the other radicals R* is hydrogen, halogen, halo-(C1-C8)-alkyl, halo-(C1-C8)-alkoxy, (C1-C8)-alkyl, (C1-C8)-alkoxy, nitro, amino or amino which is substituted by one or two radicals selected from the group consisting of (C1-C4)-alkyl and acyl having 1 to 10 carbon atoms, or cyano, (C1-C8)-alkylthio or (C1-C8)-alkylsulfonyl or optionally substituted phenyl, and R** is (C1-C8)-alkyl, halo-(C1-C8)-alkyl, (C1-C8)-alkylthio, (C1-C8)-alkoxy, halo-(C1-C8)-alkoxy, (C1-C8)-alkylsulfonyl, cyano-(C1-C8)-alkyl, [(C1-C8)-alkyl]-carbonyl or [(C1-C8)-alkoxy]-carbonyl as safeners for avoiding or reducing phytotoxic effects of crop protection products on crop plants.

2. The use as claimed in claim 1, wherein A is (C1-C6)-alkanediyl or (C3-C8)-alkenediyl, B1 and B2 in each case independently of one another are a radical of the formula -COOR1, -COSR1, -CO-ON=CR2R3, -CO-NR4N=CR2R3, -CONR1R4, -CO-R1 , , or , R1 is hydrogen, (C1-C18)-alkyl, (C3-C12)-cycloalkyl, (C3-C12)-heterocyclyl, (C2-C18)-alkenyl, (C2-C8)-alkynyl, aryl or heteroaryl, in which each of the abovementioned carbon-containing radicals are unsubstituted or monosubstituted or polysubsti-tuted by identical or different substituents selected from the group consisting of halogen, halo-(C1-C8)-alkoxy, nitro, cyano, hydroxyl, (C1-C8)-alkoxy and (C1-C8)-alkoxy in which one or more non-adjacent CH2 groups are replaced by oxygen, as well as (C1-C8)-alkyl and halo-(C1-C8)-alkyl, the latter two only in the case of cyclic radicals, (C1-C8)-alkylthio, (C1-C6)-alkylsulfinyl, (C1-C6)-alkylsulfonyl, (C2-C8)-alkenylthio, (C2-C8)-alkynylthio, (C2-C8)-alkenyloxy, (C2-C8)-alkynyloxy, (C3-C7)-cycloalkyl, (C3-C7)-cyclo-alkoxy, (C1-C8)-alkoxycarbonyl, (C2-C8)-alkenyloxy-carbonyl, (C2-C8)-alkynyloxycarbonyl, (C1-C8)-alkylthiocarbonyl, (C1-C8)-alkylcarbonyl, formyl, (C2-C8)-alkenylcarbonyl, (C2-C8)-alkynylcarbonyl, hydroxyimino, (C1-C4)-alkylimino, (C1-C4)-alkoxy-imino, (C1-C8)-alkylcarbonylamino, (C2-C8)-alkenyl-carbonylamino, (C2-C8)-alkynylcarbonylamino, carbamoyl, (C1-C8)-alkylcarbamoyl, di-(C1-C6)-alkylcarbamoyl, (C2-C6)-alkenylcarbamoyl, (C2-C6)-alkynylcarbamoyl, (C1-C8)-alkoxycarbonylamino, (C1-C8)-alkylaminocarbonylamino, di-(C1-C8)-alkyl-aminocarbonylamino, (C1-C8)-alkoxycarbonyloxy, (C1-C8)-alkylcarbonyloxy which is unsubstituted or substituted by halogen, nitro, (C1-C4)-alkoxy or optionally substituted phenyl, or (C2-C6)-alkenyl-carbonyloxy, (C2-C6)-alkynylcarbonyloxy, phenyl, phenyl-(C1-C6)-alkoxy, phenyl-(C1-C6)-alkoxy-carbonyl, phenoxy, phenoxy-(C1-C6)-alkoxy, phen-oxycarbonyl, phenoxy-(C1-C6)-alkoxycarbonyl, phenylcarbonyloxy, phenylcarbonylamino, phenyl-(C1-C6)-alkylcarbonylamino, the last-mentioned 10 radicals being unsubstituted or mono- or polysub-stituted, in the phenyl ring by identical or dif-ferent radicals selected from the group consisting of halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy and nitro, as well as radicals of the formulae -SiR2R3R4, -O-SiR2R3R4, R2R3R4Si-(C1-C6)-alkoxy, -CO-O-NR2R3, -O-N=CR2R3, -N=CR2R3, O-(CH2)m-CH(OR2)OR3, R'O-CHR''-CH(OR')-(C1-C6)-alkoxy, -NR2R3, -CO-NR2R3, -O-CO-NR2R3 and a three- to seven-membered saturated or unsatu-rated heterocyclic radical having up to three identical or different hetero atoms selected from the series consisting of S, O and N which is optionally benzo-fused and optionally substituted, R' radicals independently of one another are (C1-C4)-alkyl or, in pairs together, are (C1-C6)-alkanediyl radical and R'' is hydrogen or (C1-C4)-alkyl, R2 and R3 in each case independently of one another are hydrogen, optionally substituted (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, phenyl-(C1-C4)-alkyl or phenyl, the last-mentioned two radicals being unsubstituted or substituted in the phenyl radical, or R2 and R3 together are an optionally substituted (C2-C6)-alkanediyl chain, R4 is hydrogen or optionally substituted (C1-C4)-alkyl, or R1 and R4 together are an alkanediyl chain having 2 to 5 carbon atoms in which one CH2 group can option-ally be replaced by O, NH or N-(C1-C4)-alkyl, R5 and R6 are identical or different and independently of one another are hydrogen or (C1-C6)-alkyl, R7 and R8 are identical or different and independently of one another are hydrogen or (C1-C6)-alkyl which can be substituted by halogen, (C1-C4)-alkoxy or phenyl, R9 and R10 are identical or different and indepen-dently of one another are hydrogen or (C1-C6)-alkyl which can be substituted by halogen, (C1-C4)-alkoxy or OH, T radicals independently of one another are oxygen or sulfur and m is an integer from 0 to 6.

3. The use as claimed in claim 1 or 2, wherein A is CH2, CH(CH3), CH2CH2, CH2CH2CH2 or C(CH3)2, R* radicals in each case independently of the other radicals R* are hydrogen, halogen, halo-(C1-C6)-alkyl, halo-(C1-C6)-alkoxy, (C1-C8)-alkyl, (C1-C8)-alkoxy, nitro, amino or amino which is substituted by one or two radicals selected from the group consisting of (C1-C4)-alkyl and acyl having 1 to 10 carbon atoms, or cyano, (C1-C6)-alkylthio or (C1-C8)-alkylsulfonyl, R1 is hydrogen, (C1-C12)-alkyl, (C3-C8)-cycloalkyl, (C3-C8)-heterocyclyl, (C2-C12)-alkenyl, (C2-C8)-alkynyl or phenyl, each of the above carbon-con-taining radicals being unsubstituted or substi-tuted by one or more, identical or different substituents selected from the group consisting of halogen, halo-(C1-C8)-alkoxy, nitro, cyano, hydroxyl, (C1-C8)-alkoxy, in which one or more non-adjacent CH2 groups can be replaced by oxygen, or (C1-C8)-alkyl and halo-(C1-C8)-alkyl, the latter two substituents only in the case of cyclic rad-icals, (C1-C8)-alkylthio, (C1-C6)-alkylsulfinyl, (C1-C6)-alkylsulfonyl, (C2-C8)-alkenylthio, (C2-C8)-alkynylthio, (C2-C8)-alkenyloxy, (C2-C8)-alky-nyloxy, (C3-C7)-cycloalkyl, (C3-C7)-cycloalkoxy, (C1-C8)-alkoxycarbonyl, (C2-C8)-alkenyloxycarbonyl, (C2-C8)-alkynyloxycarbonyl, (C1-C8)-alkylthio-carbonyl, (C1-C8)-alkylcarbonyl, (C2-C8)-alkenyl-carbonyl, (C2-C8)-alkynylcarbonyl, hydroxyimino, (C1-C4)-alkylimino, (C1-C4)-alkoxyimino, (C1-C8)-alkylcarbonylamino, (C2-C8)-alkenylcarbonylamino, (C2-C8)-alkynylcarbonylamino, carbamoyl, (C1-C8)-alkylcarbamoyl,di-(C1-C6)-alkylcarbamoyl, (C2-C6)-alkenylcarbamoyl, (C2-C6)-alkynylcarbamoyl-(C1-C8)-alkoxycarbonylamino, (C1-C8)-alkylaminocarbonyl-amino, (C1-C8)-alkoxycarbonyloxy, (C1-C8)-alkyl-carbonyloxy which is unsubstituted or substituted by halogen, nitro, (C1-C4)-alkoxy or optionally substituted phenyl, or (C2-C6)-alkenylcarbonyloxy, (C2-C6)-alkynylcarbonyloxy,phenyl,phenyl-(C1-C6)-alkoxy, phenyl-(C1-C6)-alkoxycarbonyl, phenoxy, phenoxy-(C1-C6)-alkoxy, phenoxycarbonyl, phenoxy-(C1-C6)-alkoxycarbonyl, phenylcarbonyloxy, phenyl-carbonylamino, phenyl-(C1-C6)-alkylcarbonylamino, the last-mentioned 10 radicals being unsubstituted or mono- or polysubstituted in the phenyl ring by identical or different radicals selected from the group consisting of halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-halo-alkoxy, and nitro, and radicals of the formulae -SiR2R3R4, -O-SiR2R3R4, R2R3R4Si-(C1-C6)-alkoxy, -CO-O-NR2R3, -O-N=CR2R3, -N=CR2R3, -NR2R3, -CONR2R3, -OCONR2R3, -O-(CH2)m-CH(OR2)OR3, R'O-CHR''-CH(OR')-(C1-C6)-alkoxy and a five- to six-membered satu-rated or unsaturated heterocyclic radical having up to three identical or different hetero atoms from the series consisting of S, O and N which is optionally benzo-fused and optionally substituted, R' independently of one another are (C1-C4)-alkyl or, in pairs together, a (C1-C6)-alkanediyl radical, R'' is hydrogen or (C1-C4)-alkyl, R2 and R3 radicals independently of one another are hydrogen, (C1-C4)-alkyl or optionally substituted phenyl or, together, an unbranched (C2-C4)-alkane-diyl chain, and m is an integer from 0 to 6.

4. The use as claimed in any of claims 1 to 3, wherein at least two radicals R* of the benzene ring are hydrogen and R1 is hydrogen, (C1-C12)-alkyl, (C3-C8)-cycloalkyl, (C2-C12)-alkenyl, (C2-C8)-alkynyl, each of the abovementioned carbon-containing radicals being unsubstituted or substituted by one or more substituents selected from the group consisting of hydroxyl, (C1-C8)-alkoxy, alkoxypolyalkyleneoxy having a total of 2 to 8 carbon atoms, (C1-C4)-alkylthio, (C2-C4)-alkenylthio, (C2-C4)-alkynyl-thio, (C2-C4)-alkenyloxy, (C2-C4)-alkynyloxy, mono-and di-(C1-C2)-alkylamino, (C1-C4)-alkoxycarbonyl, (C2-C4)-alkenyloxycarbonyl, (C2-C4)-alkynyloxy-carbonyl, (C1-C4)-alkylcarbonyl, (C2-C4)-alkenylcarbonyl, (C2-C4)-alkynylcarbonyl, (C1-C4)-alkylcarbonylamino, (C2-C4)-alkenyl-carbonylamino, carbamoyl, (C1-C8)-alkylcarbamoyl, di-(C1-C6)-alkylcarbamoyl, (C1-C4)-alkoxy-carbonyloxy, (C1-C4)-alkylcarbonyloxy which is unsubstituted or substituted by one or two radicals selected from the group consisting of halogen and (C1-C4)-alkoxy, and (C2-C4)-alkenyl-carbonyloxy, (C2-C4)-alkynylcarbonyloxy, phenyl, phenyl-(C1-C4)-alkoxy, phenyl-(C1-C4)-alkoxy-carbonyl, phenoxy, phenoxy-(C1-C4)-alkoxy, phenoxycarbonyl, phenoxy-(C1-C4)-alkoxycarbonyl, phenylcarbonyloxy, the last-mentioned 8 radicals being unsubstituted or substituted in the phenyl ring by one or more radicals selected from the group consisting of halogen, (C1-C2)-alkyl, (C1-C2)-alkoxy, (C1-C2)-haloalkyl, (C1-C2)-haloalkoxy and nitro, and radicals of the formulae -SiR2R3R4, O-SiR2R3R4, R2R3R4Si-(C1-C4)-alkoxy, -O-N=CR2R3, -N=CR2R3, O-(CH2)m-CH(OR2)OR3, R'O-CHR''-CH(OR')-(C1-C6)-alkoxy, NR2R3, -CONR2R3 and -OCONR2R3 R' radicals independently of one another are (C1-C4)-alkyl or, in pairs together, are (C1-C6)-alkane-diyl radical and R'' is hydrogen or (C1-C4)-alkyl, R2 and R3 are identical or different and independently of one another are hydrogen, (C1-C4)-alkyl or optionally substituted phenyl, or together are an optionally substituted (C2-C4)-alkanediyl chain, R5 and R6 are identical or different and independently of one another are hydrogen or (C1-C4)-alkyl, R7 and R8 are identical or different and independently of one another are hydrogen or (C1-C4)-alkyl, R9 and R10 independently of one another are hydrogen or (C1-C4)-alkyl and m is an integer from 0 to 2.

5. A compound of the formula (I) or a salt thereof as defined in any of claims 1 to 4, with the exception of known compounds of the formula (I) or known salts of compounds of the formula (I).

6. A process for the preparation of compounds of the formula (I) or salts thereof as claimed in claim 5, which comprises a) reacting a compound of the formula (II) with a compound of the formula (III) (III) in which n is a leaving group, or b) in the event that n = 0 and B1 = a carboxyl derivative, reacting a compound of the formula (IV) (IV) to give acid derivatives of the formula (I), n = 0, or c) in the event that B1 and B2 are carboxylic acid derivative groups, transesterifying or amidating a compound of the formula (I') (I') in which B and B' are defined analogously to B1 and B2 to give compounds of the formula (I), the radicals A, B1, B2, n, R* and W1 and W2 in formulae (II), (III), (IV) and (I') being as defined in formula (I).

7. A herbicide-safener combination which comprises a safener of the formula (I) or a salt thereof as claimed in any of claims 1 to 5 and at least one herbicide.

8. A plant treatment product which comprises a safener of the formula (I) or a salt thereof, and customary formulation auxiliaries.

9. A method of protecting crop plants against phytotoxic side-effects of herbicides, which comprises applying, to the plants, parts of the plants, seeds of the plants or the areas under cultivation, an effective amount of a safener of the formula (I) or salt thereof as claimed in any of claims 1 to 5 before, after or simultaneously with, the herbicide.

10. A method for the selective control of harmful plants in crops of useful plants, which comprises applying pre- or post-emergence a herbicide-safener combination as claimed in claim 7 to the areas under cultivation.