CA2085148A1 - Combination of als inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agents - Google Patents
Combination of als inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agentsInfo
- Publication number
- CA2085148A1 CA2085148A1 CA 2085148 CA2085148A CA2085148A1 CA 2085148 A1 CA2085148 A1 CA 2085148A1 CA 2085148 CA2085148 CA 2085148 CA 2085148 A CA2085148 A CA 2085148A CA 2085148 A1 CA2085148 A1 CA 2085148A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- alkoxy
- hydrogen
- halogen
- radicals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
Abstract
Abstract Combination of ALS inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agents.
The invention relates to mixtures or application combina-tions which contain ALS inhibitor herbicides and other plant-protection agents such as insecticides or her-bicides having different mechanisms of action, indepen-dently of whether these preparations are applied together or in succession, in particular one or more herbicides from the sulfonylurea, imidazolinone and pyrimidine or triazine derivative group and other agents such as insecticides and herbicides and one or more compounds of the formulae B1 and B2, (B1) (B2) in which the radicals are as defined in the description.
It has been found that damage to the crop plants can be reduced or entirely prevented if these mixtures or application combinations are applied.
The invention relates to mixtures or application combina-tions which contain ALS inhibitor herbicides and other plant-protection agents such as insecticides or her-bicides having different mechanisms of action, indepen-dently of whether these preparations are applied together or in succession, in particular one or more herbicides from the sulfonylurea, imidazolinone and pyrimidine or triazine derivative group and other agents such as insecticides and herbicides and one or more compounds of the formulae B1 and B2, (B1) (B2) in which the radicals are as defined in the description.
It has been found that damage to the crop plants can be reduced or entirely prevented if these mixtures or application combinations are applied.
Description
208~48 HOECHST AXTIENGESELLSCHAFT HOE 91tF 391 Dr. AB/PL
Description Combination of ALS inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agents The invention relates to the technical field of plant-protection agents, in particular combinations of herbi-cides of the ALS inhibitor type with insecticides or other foliar-active herbicides.
German Patent Application P 40 41 120.6 has proposed to make available acetolactate synthase tALS) inhibitors, which could formerly not be employed selectively in gramineous crops such as cereals or maize, in combination with certain herbicide safeners tantidotes) for selective use in such crops.
Surprisingly, it has now been found that these antidotes can also prevent the damage to crop plants which arises when ALS inhibitors and other plant-protection agents, such as insecticides and herbicides, are applied together or in succession to a crop plant population.
Novel herbicides from the sulfonylurea group tALS
inhibitors) are increasingly also employed in maize crops for the selective control of weeds and weed grasses, since they have already been of importance for years in cereal and rice crops. Such herbicides are, for example, primisulfuron, nicosulfuron, DPX-E-9636 rimsulfuron and other sulfonylurea derivatives, or mixtures of these compounds with one another.
Although the selectivity of these herbicides in maize cultures is normally good, their use can lead to damage of the crop plants if these are treated beforehand or at - 2 - 2~
the same time or afterwards with an insecticide, such as, for example, terbufos, or other insecticides from the org~nophosphate, pyrethroid or carbamate groups. Even if such treatments are up to 20 days or more apart, damage to the crop plants can still ari~e. Herbicides, such as, for example, bentazone or bromoxynil, can also cause damage if maize crops or other crops are treated together or alternatively at separate tLmes with such compounds and sulfonylurea herbicides. In this case, the type of treatment i8 not important, it can be spraying of the leaves or soil, or the insecticides or herbicides can be applied to the seed as granules on or in the soil, or the seed~ can be dressed. It is only crucial that when all is said and done the various active substances act in the crop plant or begin to interact there in the plant metabolism. The presence of these compounds prevents or reduces the plant metabolism of ALS inhibitor (sulfonylurea) herbicides, so that discolorations, chloroses or even leaf deformations and severe growth disorders occur, which can also severely damage the yield of the crop plants.
The mentioned incompatibilities are an economic problem for the user, since he must not apply various agents together or must not treat crop plants, such as, for example, maize, with certain preparations which, for example, are very effective or very good value.
Surprisingly, however, it has now been found that ~uch damage to crop plants can be reduced or entixely pre-vented if, at the s~me time as the herbicide or ALS
inhibitor, plant-protecting agent~ are app ied such as have been proposed in German Patent Application P 40 41 120.6, which act as antidotes or safeners.
The invention therefore relates to mixtures or applica-tion combinations which contain ~ 3 - 208S~8 A) ALS inhibitor herbicides and other plant-protection agents such as insecticides or herbicides with different mechani~ms of action, independently of whether these preparations are applied together or S in succession, in particular one or more herbicides from the sulfonylurea, imidazolinone and pyrimidine or triazine derivative group and other agents such as insecticides and herbicides and B) one or more compounds of the formulae B1 and B2 (X)n ~ W ~`Z (B1) ~( X )n (B2) O~ "C O
in which X is hydrogen, halogen, C1-C4-alkyl, Cl-C4-alkoxy, nitro or C1-C4-haloalkyl, 15 Z is OR1, SR1, NR1R, where R is H, C1-C~-alkyl, C1-C6-alkoxy or optionally ~ubstituted phenyl, or a saturated or unsaturatQd 3- to 7-membered hetero-cycle having at least one nitrogen atom and up to 3 hetero atoms, which is bonded to the carbonyl group 2 0 via the nitrogen atom and is unsub6tituted or substituted by radicals from the group comprising C1-C4-alkyl, C1-C4-alkoxy and optionally sub6tituted phenyl, preferably a radical of the formula OR1, NHR
or N(CH3), in particular of the formula OR1, _ 4 _ 208~8 R is a Cl-C2-alkylene chain which can additionally be substituted by one or two C1-C4-alkyl radicals, preferably -CH2-, Rl is hydrogen, Cl-Cl8-alkyl, C3-Cl2-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubsituted or mono- or polysubstituted by radicals from the group compri~ing halogen, hydroxyl, C1-CB-a1kOXY~ C1-C8_a1kY1thiO, C2-C8-a1k~nY1thiO, C2-C8-alkynylthio, C2-CB-alkenyloxy, C2-C8-alXynyloxy, C3-C7-cycloalkyl, C3-C7-cycloalkoxy, cyano, mono~ and di-Cl-C4-alkylamino, Cl-C8-alkoxycarbonyl, C2-C8-alkenyloxycarbonyl, Cl-C8-alkylthiocarbonyl, C2-C8-alkynyloxycarbonyl, Cl-C8-alkylcarbonyl, C2-C8-alkenylcarbonyl, C2-C8-alkynylcarbonyl, Cl-C8-alkylcarbonylamino,C2-C8-alkenylcarbonylamino, C2-C8-alkynylcarbonylamino, aminocarbonyl, Cl-C8-alkylaminocarbonyl, Di-Cl-C6-alkylaminocarbonyl, C2-C6-alkenylaminocarbonyl, C2-C6-alkynylamino-c arbonyl, C1-C8- alkoxyc arbonyl amino, Cl-C8-alkylaminocarbonylamino,Cl-C6-alkylcarbonyloxy which is unsubstituted or substituted by halogen, NO2, Cl-C4-alkoxy or optionally substituted phenyl, C2-C6-alkenylcarbonyloxy, C2-C6-alkynylcarbonyloxy, C1-C8-alkylsulfonyl, phenyl, phenyl-C1-C6-alkoxy, phenyl-C1-C6-alkoxycarbonyl, phenoxy, phenoxy-C1-C6-alkoxy, phenoxy-C1-C6-alkoxycarbonyl, phenylcar-bonyloxy, phenylcarbonylamino, phenyl-Cl-C6-alkyl-carbonylamino, where the last-mentioned 9 radicals in the phenyl ring are unsubstituted or mono- or polysubstituted by radicals from the group com-prising halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloa:lkoxy and nitro, and radicals of the formulae -SiR'3, -O-SIR'3, (R')3Si-C1-C6-alkoxy, -CO-O-NR' 2 ~ _O-N=cR ~ 2 ~ -N=CR' 2 ~
-O-NR~2-CH(OR~ )2 and -O-~CH2)m-CH(OR'2)2, in which R' in said formulae independently of one another are 20~5~4~
hydrogen, C1-C4-alkyl, phenyl which is unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C4-alkyl, C~-C4-alkoxy, C1-C4-haloalkoxy and nitro, or in pairs are a C2-C6-alkylene chain and m = 0 to 6, and a radical of the formula R"O-CHR (OR")-Cl-C6-alkoxy, in which the radicals R" independently of one another are C1-C4-alkyl or together are a C1-C6-alkylene radical and R is hydrogen or C1-C4-alkyl, 10 n is an integer from 1 to 5, preferably 1 to 3, W is a divalent heterocyclic radical having 5 ring atoms, of the formula Wl to W4 ~N~ N~
R2 ~J
CooR3 (W1) (W2) N/ \
N - CH
(W3) (W4) in which R2 is hydrogen, C1-C~-alkyl, C1-Ca-haloalkyl, C3-C12-cycloalkyl or optionally substituted phenyl and R3 is hydrogen, C1-C3-alkyl, Cl-Ca-haloalkyl, Cl-C4-alkoxy-Cl-C4-alkylI Cl-C6-hydroxyalkyl, C3-Cl2-20cycloalkyl or tri-(C1-C4-alkyl)silyl, or the salts of said compounds.
- 6 - 6~
Herbicidal agents according to the invention of par-ticular interest are those where, in the compounds of the formulae Bl and B2, Rl is hydrogen, C1-C12-alkyl or C3-C7-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubstituted or mono- or polysubstituted by halogen or mono- or disubsti-tuted, preferably monosubstituted by radicals from the group comprising hydroxyl, Cl-C4-alkoxy, Cl-C4-alkylthio, C2-C4-alkenyloxy, C2-C6-alkynyloxy, mono-and di-(Cl-C2-alkyl)-amino, (Cl-C4-alkoxy)carbonyl, C2-C4-alkenyloxycarbonyl, C2-C4-alkynyloxycarbonyl, Cl-C4-alkylcarbonyl, C2-C4-alkenylcarbonyl, C2-C4-alkynylcarbonyl,C1-C4-alkylsulfonyl, phenyl,phenyl-C1-C4-alkoxycarbonyl, phenoxy, phenoxy-Cl-C4-alkoxy, phenoxy-(Cl-C4-alkoxy)carbonyl, where the last-mentioned 6 radicals in the phenyl ring are unsub-stituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C2-alkyl, Cl-C2-alkoxy, Cl-C2-haloalkyl, C1-C2-haloalkoxy and nitro, and radicals of the formulae -SIR'3, -O-N=CR'2, -N=CR~2, -N=CR'2 and -O-NR'2, in which the R' in said formulae independently of one another are hydrogen, Cl-C2-alkyl, phenyl which is unsubstituted or mono-or polysubstituted by radicals from the group comprising halogen, Cl-C2-alkyl, Cl-C2-alkoxy, Cl-C2-haloalkyl, Cl-C2-haloalkoxy and nitro, or in ~airs are a C4-C5-alkanediyl chain.
Herbicidal agent~ according to the invention also of particular interest are those where, in the compounds of the formulae Bl and B2, X i6 hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or Cl-C2-haloalkyl, preferably hydrogen, halogen or Cl-C2-haloalkyl.
- 7 - 2~8~$~
Preferred herbicidal agents according to th~ invention are those where, in the compounds of the formula Bl, X is hydrogen, halogen, nitro or Cl-C4-haloalkyl, n is a number from 1 to 3, Z is a radical of the formula ORl, R1 is hydrogen, C1-C8-alkyl or C3-C7-cycloalkyl, where the above C-containing radicals are unsub-stituted or mono- or polys~bstituted by radicals from the group comprising halogen or mono- or disubstituted, preferably unsubstituted or monosub-stituted, by radicals from the group comprising hydroxyl, Cl-C4-alkoxy, (C1-C4-alkoxy)carbonyl, C2-C6-alkenyloxycarbonyl, (C2-C6~alkynyloxy)carbonyl and radicals of the formulae -SiR'3, -O-N=CR'2, -N=CR'2 and -O-NR'2, in which the radicals R' in said formulae independently of one another are hydrogen or Cl-C4-alkyl or in pairs are a C4-C5-alkylene chain, R2 is hydrogen, Cl-Ce-alkyl, Cl-C6-haloalkyl, C3-C7-cycloalkyl or phenyl and 0 R3 is hydrogen, Cl-C8-alkyl, Cl-C8-haloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl, Cl-C6-hydroxyalkyl, C3-C7-cyclo-alkyl or tri-(Cl-C4-alkyl)silyl.
Preferred herbicidal agents according to the invention are also those where, in the compounds of the formula B2, X is hydrogen, halogen or Cl-C4-haloalkyl and n is a number from 1 to 3, pxeferably (X)n = 5-Cl, Z is a radical of the formuls OR1, R is CH2 and Rl is hydrogen, Cl-C8-alkyl, Cl-C8-haloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl or ~Cl-C4-alkenyloxy)-Cl-C4-alkyl, prefexably Cl-C8-alkyl.
Particularly preferred herbicidal agent~ according to the invention are those containing compounds of the formula ~1, in which 208~ ~%
W is Wl, X is H, halogen or C1~C2-haloalkyl and n = 1 - 3, in particular (X) n = 2 ~ 4 -C12 ~
Z is a radical of the formula OR1, R1 is hydrogen, C1-C8-alkyl, C1-C4-haloalkyl, Cl-C4-hydroxyalkyl, C3-C7-cycloalkyl, (cl-c4-alkoxy)-cl-c4-alkyl or tri-(C1-C2-alkyl)-silyl, preferably Cl-C4-alkyl, R2 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl or C3-C7-cycloalkyl, preferably hydrogen or C1-C4-alkyl, and R3 is hydrogen, C1-CB-alkyl, C1-C4-haloalkyl, C1-C4-hydroxyalkyl, C3-C7-cycloalkyl, (C1-C4-alkoxy)-C1-C4-alkyl or tri-(C1-C2-alkyl)silyl, preferably hydrogen or C1-C4-alkyl.
15 Particularly preferred herbicidal agents according to the invention are also those containing compounds of the formula Bl, in which W is W2~
X is H, halogen or C1-C2-haloalkyl and n = 1 - 3, in particular (X) n = 2~4 -C12, Z is a radical of the formula OR1, R1 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl, C1-C4-hydroxyalkyl, C3-C7-cycloalkyl, (C1-C4-alkoxy)-C1-C4-alkyl or tri-(C1-C2-alkyl)silyl, preferably C1-C4-alkyl and R2 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl, C3-C7-cycloalkyl or phenyl, preferably hydrogen or Cl-C4-alkyl.
Particularly preferred herbicidal agents according to the invention are also those containing compounds of the formula Bl, in which W is W3, X is H, halogen or C1-C2-haloalkyl and n = 1 - 3, in particular (X) n = 2 ~ 4-Cl2 ~ 5 Z is a radical of the formula OR1, 208~ 48 Rl is hydrogen, C~-C8-alkyl, C1-C4-haloalkyl, Cl-C4-hydroxyalkyl, C3-C7-cycloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl or tri-(Cl-C2-alkyl)silyl, preferably Cl-C4-alkyl and R2 is Cl-C8-alkyl or Cl-C4-haloalkyl, preferably Cl-haloalkyl.
Particularly preferred herbicidal agents a~cording to the invention are also those containing compounds of the formula B1, in which W is W4, X is hydrogen~ halogen, nitro, Cl-C4-alkyl or Cl-C2-haloalkyl, preferably CF3, or Cl-C4-alkoxy, n is l to 3, Z is a radical of the formula ORl, 5 R1 is hydrogen, Cl-C4-alkyl or (C1-C4-alkoxy)carbonyl-Cl-C4-alkyl, preferably (cl-c4-alkoxy)-co-cH2-~( alkoxy)-CO-C(CH3)H-, HO-CO-CH2- or HO-CO-C(CH3)H-.
In the formulae, alkyl, alkenyl and alkynyl are straight-chain or branched; the same applies to substituted alkyl, alkenyl and alkynyl radicals such a haloalkyl, hydroxy-alkyl, alkoxycarbonyl etc.; alkyl is, for example, methyl, ethyl, n- and i-propyl, n-, i-, t- and 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1,3-di-methylbutyl, heptyls, such as n-heptyl, l-methylhexyl and 1,4-dimethylpentyl; alkenyl is, for example, allyl, l-methylprop-2-en-l-yl, but-2-en-l-yl, but-3-en-1-yl, l-methylbut-3-ene and 1-methylbut-2-ene; alkynyl i~, for example, propargyl, but-2-yn-1-yl, but 3-yn-l-yl, l-methyl-but-3-yne; halogen iB fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine; haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl substituted by halogen, for example such as CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CCl3, CHCl2, CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF20, CF3CH20;
optionally substituted phenyl is, for example, phenyl 2a~ 8 which is unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 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.
The compounds of the formula Bl are disclosed in EP-A-333 131, EP-A-269 806, EP-A-346 620, International Patent Application PCT/EP gO/01966 and International Application No. PCT/EP 90/02020 and literature cited therein or can be prepared by or analogously to the processes described therein. The compounds of the formula B2 are disclosed in EP-A-86 750, EP-A-94 349 and EP-A-l91 736 and literature cited therein or can be prepared by or analogously to the processes described therein. ~hey are additionally proposed in German Patent Application P 40 41 121.4.
Suitable mixed combinations of the type A are ALS in-hibitor herbicides according to the invention, such as sulfonylureas and imidazolinones, as well as substituted pyrimidines and triazones which can be employed in a mixture or applied separately with other plant-protection agents, such as insecticides, for example organo-phosphates, or herbicides.
Such ALS inhibitors of the 6ulfonylurea type are, forexample, the known compounds priml~ulfuron-methyl, nicosulfuron, DPX-E-9636, amidosulfuron, thiameturon-methyl, NC319 (EP-A-282 613) and other disclosed active substances and pyridylsulfonylureas (German Patent Application P 40 30 577.5) and alkoxyphenoxysulfonylureas (EP-A-342 569) and mixtures of said active substances with one another.
~8~
Suitable compounds are pyridylsulfonylureas of the formula Al or their salts, R~
~ ~ R R6 Rs ~ //\\ ~ ~ ~ ~ (A1) in which R is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or ~rialkylammonium, E is CH or nitrogen, R4 is halogen or NR9R10, R5 is hydrogen, halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy,C1-C3-haloalkyl,C1-C3-haloalkoxy,C1-C3-alkyl-thio, (C1-C3-alkoxy)-C1-C3-alkyl, (C1-C3-alkoxy)carbonyl, mono- or di(C1-C3-alkyl)amino, Cl-C3-alkylsulfinyl or sulfonyl, SO2-NR4Rb or CO-NRaRb, R6 is hydrogen or CH3, R7 is halogen, C1-C2-alkyl,Cl-C2-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy or OCH2CF3, R8 is C1-C2-alkyl, C1-C2-haloalkoxy or C1-C2-alkoxy and R9 is Cl-C4-alkyl and R10 is C1-C4-alkylsulfonyl or R9 and Rl together are a chain of the formula -(CH2)3S02- or -(CHz)4SO2-r or alkoxyphenoxysulfonylureas of the formula A2 or their salts, Rl4 ( R 1 2 ) ~ ~S~ ~ 1N--1R 15 1.... 1,~
R R
in which 12 2~8~8 R"" is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium, E is CH or nitrogen, Rl1 is methoxy, ethoxy, propoxy, isopropoxy or Cl-C4-alkoxycarbonyl, RlZ is hydrogen, halogen, NO2, CF3, CN, C1-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio or (Cl-C3-alkoxy)-carbonyl, n is 1, 2 or 3, Rl3 is hydrogen, Cl-C4-alkyl or C3-C4-alkenyl, R14 and Rl5 independently of one another are halogen, Cl-C2-alkyl, Cl-Cz-alkoxy, Cl-C~-haloalkyl, Cl-C2-halo-alkoxy or (Cl-C2-alkXY)-cl-c2-al~yl-ALS inhibitors of the imidazolinone type are imazethapyr, 15 imazaquin, imazethamethapyr (AC-263222) and other related compounds and mixtures thereof.
Suitable substituted pyrimidines and triazines have the formula C
N ~ R2~
N ~ (C) in which X' is oxygén, sulfur or NR24, Y' is nitrogen or CH, R22 and R23 independently of one another are hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, Cl-C4-alkylmer-25 capto, C~-C4-alkylamino or di-Cl-C4-alkylamino, R2l is a substituted aryl or heteroaryl radical of the formula - 13 - 20~4~
R 2 s~( w ) n ~R26 or ~ ~ ~ ~502R
n~ is 0 or 1, W' is -O-, -NR24-, -S-, -ON(R31)- or -o-N=C(R31), X' is N, N~O or CR24, S R24 is defined as R22 or R23, RZ5 is halogen, cyanor nitro, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Cl-C4-alkoxy, haloalkyl or haloalkoxy, R26 is C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, alkali metal or 1 equivalent of alkaline earth metal, alkylammonium, aryl, CF3 or (CHR33)m.CHR27R2B where m' = 0 or 1, R27 and R33 independently of one another are hydrogen, Cl-C4-alkyl or Cl-C4-alkoxy, R2~ is C1-C4-alkoxycarbonyl, cyano, halogen, acetyl, pivaloyl, benzoyl, C1-C4-alkoxy, aryloxy, halo-acetoxy, methanesulfonyloxy, hydroxyl, C1-C4-alkyl-mercapto,C1-C4-alkylsulfonyl,arylmercapto,di-C1-C4-alkylamino, pyridyl, aryl or CoNR2aR30, R29 and R30 independently of one another are hydrogen, C1-C4-alkyl, C~-C4-alkenyl, aryl or benzyl, R31 is hydrogen ox C1-C4-alkyl or R26 and R31 together are methylene, ethanediyl or pro-panediyl and aryl i8 phenyl or naphthyl, each of which i~ unsubsti-tuted or mono- or disubstituted by halogen, Cl-C4-alkyl, C1-C4-alkoxy, phenoxy, nitro and/or C1-C4-alkoxycarbonyl, or R11 is a radical of the formula 2085~48 - ~4 -R~200~ ~ or ~ ~9 R34 iB hydrogen, halogen, halo-Cl-C4-alkyl, C1-C4-cyclo-alkyl, Cl-C4-alkylmercapto-C1-C4-alkyl, hydroxyl-Cl-C4-alkyl, hydroxyl, cyano, aryloxyalkyl, thienyl, aryl, dihydronaphthyl or ,R
( CH2 )m~
where aryl is as defined above, R40 is hydrogen, halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy or S(O)p.R , R41 is alkyl, p' is a 0, 1 or 2, m" is a 0, 1 or 2, R3s and R36 independently of one another are hydrogen or C1-C4-alkyl, or these, together with the carbon atom, are a 3-, 4-, 5- or 6-membered cycloalkane ring, in which a methylene group can be replaced by oxygen and which can be substituted by one or two C1-C4-alkyl groups, R37 and R3~ independently of one another are hydrogen or Cl-C4-alkyl, R39 is Cl-C4-alkyl or phenyl, or R38 and R3~ are -(CH2)l- where l = 3 or 4, which can be substituted by one or two C1-C4-alkyl groups, R42 is hydrogen, C1-C4-alkyl,C1-C4-alkenyl, C1-C4-alkynyl, phenyl, C1-C4-alkylidenamino, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, halo-C1-C4-- 15 _ 2~8~ ~ ~8 alkyl, cycloalkyl, nitro-substituted phenylmercapto-Cl-C4-alkyl, halogen or benzyl which can be substi-tuted by Cl-C4-alkyl or Cl-C4-alkoxy, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium.
The various types of ALS inhibitors can also be mixed with one another. Other active substance structures which inhibit the enzyme ALS, for example herbicidal sulfona-mides such as flumetsulam (DE-498) and the like are also possible here. Possible combination components in the ~mixture~ of the type A are the following plant-protec-tion agents, where the indiYidual components can be applied toge~her or separately from one another at an interval of time of up to several weeks:
1.) Insecticidal preparations such as organophosphates, for example terbufos (~Counter~, fonofos (~Dyfonate), phorate (~Thimet), chlorpyrifos (Reldan) and other rela~éd active substances, insecticidal carbamates such as, for example, carbofuran (0Furadan) and others; as well as pyrethroid insecticides such as, for example, tefluthrin (~Force), deltamethrin (~Decis) and tralomethrin (Scout) and others; as well as other insecticidal agents having a different mechanism of action.
5 2.) Herbicides which are employed as components, in order to widen the spectrum of action of ALS
inhibitors and to improve the activity, such a~, for example, bentazone, cyanazine, bromoxynil or other herbicides which are absorbed through the leaf.
The following groups of compounds have proven suitable as safeners for the abovementioned product combinations:
a) Compounds of the dichlorophenylpyrazoline-3-car-boxylic acid type (i.e. of the formula ~1, in which - 16 - ~8~8 W = Wl and (X)n = 2,4-Cl2), preferably compounds such as ethyl l-(2,4-dichlorophenyl)-5-(ethoxycarbonyl-5-methyl-2-pyrazoline-3-carboxylate (Bl-l) and related compounds, such as are described in Inter-national Application PCT/EP 90/02020, b3 Derivatives of dichlorophenylpyrazolcarboxylic acid (i.e. of the formula Bl, in which W = W2 and (X)n =
2,4-C12), preferably compounds ~uch as ethyl l-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (B1-2), ethyl 1-(2,4-dichlorphenyl)-5-isopropyl-pyrazole-3-carboxylate (Bl-3), ethyl l-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (B1-4), ethyl 1~(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate ~Bl-5) and related compounds, such as are described in EP-A-0 333 131 and EP-A-0 269 806.
c) Compounds of the triazolecarboxylic acid type (i.e.
of the formula B1 in which W = W3 and (X)n =
2~4-Clz)~ preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-(lH)-1,2,4-tria-zole-carboxylate (Bl-6, fenchlorazole) and related compounds (see EP-A-0 174 562 and EP-A-0 346 620);
d) Compounds of the dichlorobenzyl-2-isoxazoline-3-carboxylic acid type (i.e. of the formula B1, in which W = W4 and (X)~ = 2,4-Cl2), preferably com-pounds such as ethyl 5-(2,4-dichlorohenzyl)-2-iso-axazoline-3-carboxylate (B1-7) and related com-pounds, such as are described in International Application PCT/EP 90/01966.
0 e) Compounds of the (5-chloro-8-quinolinoxy)acetic acid type (i.e. of the formula B2, in which (X)n = 5-Cl, Z = OR1, R = CH2), preferably compounds such as l-methylhex-l-yl (5-chloro-8-quinolihoxy)acetate (B2-l), 1,3-dimethylbut-1-yl (5-chloro-8-quino-- 17 _ 2~ 8 linoxy)acetate (B2-2), 2-allyloxy-1-methylethyl (5-chloro-8-quinolinoxy)acetate (B2-3) and related compounds, such as are described or have been proposed in EP-A-86 750, EP-A-94 349 and EP-A-l91 736 and German Patent Application P 40 41 121.4.
The safeners (antidotes) of the above groups a) to e) reduce or suppress phytotoxic effects which can occur when using the product combinations in productive plant crops, without impairing the activity of the herbicides against harmful plants. By this means, the field of use of the mixtures can be very considerably widened and extended, for example, to crops such as maize, wheat, barley and other gramineous crops in which until now use 1~ of the combinations has not been possible or only restri-ctively possible, i.e. at low doses with not very wide action.
The herbicidal ALS inhibitors and their combination components and the safeners mentioned can be applied together (as a finished formulation or in a tank-mix process) or in any desired sequence in succession. The weight ratio safener: herbicide (ALS inhibitor) can vary within wide limits and is preferably in the range from 1:10 to 10:1, in particular from 1:10 to S:l. The optimum amounts of herbicide and safener in each case are depen-dent on the type of herbicide used or on the safener used and on the nature of the plant population to be treated and can be determined from case to case by appxopriate preliminary experiments. The application rate of the insecticide or herbicide additionally employed is depen-dent on its activity alone and corresponds to the general product recommendations.
Principal fields of use for the application of the safeners are, in particular, maize and cereal crops, (wheat, rye, barley, oats), rice and sorghum, but also - 18 ~ 8 cotton and soybean, preferably maize.
Depending on their properties, the safeners of the type B can be used for the pretreatment of the seeds of the crop plant (dressing of the seeds) or introduced into the seed furrows before the seed or applied together with the herbicide before or after the emergence of the plants.
Pre-emergence treatment includes both the treatment of the cultivation areas before sowing and the treatment of the sown, but not yet covered cultivation surfaces.
Application together with the herbicide is preferred, i.e. with the ALS inhibitor. Tank mixtures or finished formulations can be employed for this.
The required application rates of the safeners can vary within wide limits depending on the indication and herbicide used and are as a rule in the range from 0.001 to l kg, preferably 0.005 to 0.2 kg, of acti~e substance per hectare.
The present invention therefore also relates to a process for the protection of crop plants from phytotoxic side effects of herbicide combinations, which comprises applying to the plants, plant seeds or the cultivation surface an effective amount of a compound of said type B) before, after or at the same time as the herbicide of said type A) in combination with an insecticide or herbicide.
The compounds of the type B) and their combinations with one or more of said herbicides (ALS inhibitors) can be formulated in various ways, depending on which biological and/or chemico-physical parameters are specified. Suit-able formulation possibilities are, for example:
Wettable powders (WP), emulsifiable concentrates (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 2~8~48 emulsions, capsule suspensions (CS), dispersions on an oil or water basis (SC), suspoemulsions, suspension concentrates, dusting agents (DP), oil-miscible solutions (OL), dressing agents, granules (GR) in the form of micro granules, spray granules, coated granules and adsorption granules, granules for application to the soil or scat-tering, water-soluble granules (SG), water-dispersible granules (NG), ULV formulations, microcapsules and waxes.
These individual formulation types are known in principle and are described, for example, in: Winnacker-Ruchler, "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 required formulation auxiliaries such as inert materials, surfactants, solvents and other additives are likewise known and are 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, "Grenzflach-enaktive Athylenoxidaddukte" (Surface-active Ethylene Oxide Adducts), Wiss. Verlagsgesell., Stuttgart 1976;
Winnacker-Kuchler "Chemische Technologie" tChemical Technology) Vol./4th Ed, 7, C. Hauser Verlag Munich, 1986.
On the basis of these formulations, combinations with other pesticidally active substances, such as insecticides, fungicides, fertilizers and/or growth regulators, can be prepared, for example in the form of ~o~ 8 a finished formulation or as a tank-mix.
Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also contain wetting agents, for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols and fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates or alkylarylsulfonates and dispersing agents, for example sodium ligninsulfonate, sodium 2,2-dinaphthylmethane-6-6~-disulfonate, sodium dibutylnaphthalenesulfonate or alternatively sodium oleoylmethyltauride in addition to a diluent or inert substance.
Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or alternatively higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. Examples of emulsifiers which can be used are: alkylarylsulfonic acid calcium salts such as Ca dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide conden-sation products ~for example block polymers), alkyl polyethers, sorbitan fatty acid estars, polyoxyethylene-sorbitan fatty acid esters of polyoxyethylenesorbitolesters.
Dusting agents can be obtained by grinding the active substance with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophillite, or diatomaceous earth.
Granules can be produced either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates to the surface of carriers, such as sand, kaolinites or granulated inert - 21 - 208~48 material, by means of binders, for example polyvinyl alcohol, sodium polyacrylate or alternatively mineral oils. Suitable active substances can also be granulated in the manner which is customary for the production of fertilizer granules, if desired in a mixture with fer-tilizers.
The agrochemical preparations as a rule contain 0.1 to 99 ~ by weight, in particular 0.1 to 95 % by weight, of active substances of type B) or of antidote/herbicide active substance mixture A) and B) and 1 to 99.9 % by weight, in particular 5 to g9.~ % 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.
The concentration of active substance in wettable powders is, for example, about 10 to 90 % by weight; the remainder to 100 % by weight is composed of customary formulation component In the case of emulsifiable concentrates, the active substance concentration is about 1 to 80 ~ by weight of active substances. Formulations in the form of dusts contain about 1 to 20 % by weight of active substances, sprayable solutions about 0.2 to 20 %
by weight of active substances. In the case of granules such as water-dispersable granules, the active substance content depends partly on whether the active substance is liquid or solid. As a rule, the contents in the case of the water-dispersable granules is between 10 and 90 % by weight.
In addition, said active sub~tance formulations optionally contain the tackifiers, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers customary in each case.
For use, the formulations, present in commercially available form, are diluted, i~ appropriate, in a customary manner, for example by means of water in the 2~
case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in the form of dusts, granules and sprayable solutions are customarily not further diluted with other inert substances before use. Particularly good activitieæ of the agents according to the invention can be achieved if other wetting agents in concentrations of 0.1 to 0.5 % by weight are added in the tank-mix process to the surfac-tants contained in the formulations, for example nonionic 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 required applica-tion rate of the "safener" varies with the external conditions such as temperature, humidity, the nature of the herbicide used and the like.
The following examples serve to illustrate the invention without restricting it thereto:
A. Formulation examples a) A dusting agent is obtained by mixing 10 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B) and 90 parts by weight of talc as inert substance and comminuting the mixture in a hammer mill.
b) A wettable powder which is readily dispersible in water is obtained by mixing 25 part~ by weight of a substance of type B) or of an active substance mixture type A) and a safener of type B), 64 parts by weight o~ kaolin-containing quartz as inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltauride as a wetting and dispersing agent and grinding the mixture in a pinned-disk mill.
2 ~
c) A dispersion concentrate which is readily disper-sible in water is obtained by mixing 20 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 6 parts by weight of alkylphenol polyglycol ether ~registered trademark ~Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 E0) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to over 277C), and grinding the mixture in a ball mill to a fineness of less than 5 microns.
d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated nonyl-phenol as an emulsifier.
e) Water-dispersable granules are obtained by mixing 75 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 10 " of calcium ligninsulfonate, 5 " of sodium lauryl sulfate 25 3 " of polyvinyl alcohol and 7 " of kaolin, grinding the mixture in a pinned-di0k mill and granulating the powder in a fluidized bed by spraying water as a granulating fluid.
0 f) Water-dispersable granules are also obtained by homogenizing 25 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type 2a8~8 B), o f s o d i u m 2 , 2 ~ -dinaphthylmethane-6,6'-disulfonate, 2 parts by weight of sodium oleoylmethyltauride, 1 " of polyvinyl alcohol, 17 ~I of calcium carbonate and 50 " of water in a colloid mill and precomminuting, then grinding the mixture in a bead mill and atomizing and drying the suspension thus obtained in a spray tower by means of a single substance nozzle.
The insecticides or herbicides additionally used can be added both in the tank-mix process, or applied separately from the finished formulation composed of ALS inhibitor and safener of the type B.
The active substance mixture A is in each case composed of an ALS inhibitor and an insecticide and/or another herbicide.
B. Biological examples The crop plants were cultivated up to the 4-leaf stage in open ground or in a greenhouse in plastic pots and then treated according to the invention with compoundæ of type A) and B) post-emergence. The compounds of type A) and B) were in this case applied in the form of aqueous suspensions br emulsions at a water application rate of, after conversion, 300 l/ha. 4 week~ after treatment, the plant6 were visually as6e~sed for any typ~ of damage due to the applied herbicides, the extent of prolonged inhibition of growth being taken particularly into account. Assessment was carried out in percentage values in comparison with untreated controls.
The result~ in the following tables illustrate that the compounds of type B) employed according to the invention 2~8~
can effectively reduce severe damage to crop plants. Even very severe damage is markedly reduced and slight damage is completely abolished. Combinations of ALS inhibitors and mixture components and compounds of type B) are therefore outstandingly suitable for the selective control of weeds in maize.
Example 1 Type A Type B Type A Type B
Herbicide combination Safener g of AS/ha g of AS/ha X damage (ALS inhibitor) to thQ
crop plant maize Hl + terbufos - 25 + 500 0 100 12 + 500 0 80 primisulfuron - 100 + 500 0 100 + terbufos 50 + 500 0 70 nicosulfuron - 200 + 500 0 90 + terbufos 100 + 500 0 80 terbufos - 500 0 0 primisulfuron B2-1 100 + 500 100 70 50 + 500 50 40 Hl + terbufos B2-2 25 + 500 25 50 12 + 500 12 20 nicosulfuron B2-3 200 + 500 200 40 + terbufos 100 + 500 100 30 Hl ~ 25 0 40 primisulfuron - 100 0 50 nicosulfuron - 200 0 30 Greenhouse experiment with 4 repetitions.
2o8~8 Sowing of maize in a pure sand culture. Terbufos was scattered on the soil surface as granules immediately after sowing. All other treatments were carried out in the 4-leaf stage. Naize variety "~FELIX".
H1 = CH
1 ~
CO/ ~<N~
S Example 2:
OCH~
Type AS~ha ~ damag~ to maize varieties FELIX DEA
bentazone 2.0 0 0 1.0 0 0 0.5 0 0 bromoxynil 1.0 20 30 0.5 20 30 0.25 10 15 15 primisulfurone 0.100 25 20 0.050 10 8 0.025 5 5 bentazone + 2.0 + 0.05 30 35 + prlmisulfuron 1.0 -~ 0.05 15 20 20 bentazone + 2.0 ~ 0.05 + 0.1 10 15 + primisulfuron 1.0 + 0.05 + 0.1 0 5 + Hl bromoxynil + 1.0 + 0.05 55 50 + primisulfuron 0.5 + 0.05 40 35 20~5~48 bromoxynil + 1.0 + 0.05 + 0.1 lS 15 + primisulfuron 0.5 + 0.05 + 0.1 5 0 + Hl Application in the 4-leaf stage cf the maize, height 23 - 26 cm.
Assessment: 4 weeks aftsr treatment
Description Combination of ALS inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agents The invention relates to the technical field of plant-protection agents, in particular combinations of herbi-cides of the ALS inhibitor type with insecticides or other foliar-active herbicides.
German Patent Application P 40 41 120.6 has proposed to make available acetolactate synthase tALS) inhibitors, which could formerly not be employed selectively in gramineous crops such as cereals or maize, in combination with certain herbicide safeners tantidotes) for selective use in such crops.
Surprisingly, it has now been found that these antidotes can also prevent the damage to crop plants which arises when ALS inhibitors and other plant-protection agents, such as insecticides and herbicides, are applied together or in succession to a crop plant population.
Novel herbicides from the sulfonylurea group tALS
inhibitors) are increasingly also employed in maize crops for the selective control of weeds and weed grasses, since they have already been of importance for years in cereal and rice crops. Such herbicides are, for example, primisulfuron, nicosulfuron, DPX-E-9636 rimsulfuron and other sulfonylurea derivatives, or mixtures of these compounds with one another.
Although the selectivity of these herbicides in maize cultures is normally good, their use can lead to damage of the crop plants if these are treated beforehand or at - 2 - 2~
the same time or afterwards with an insecticide, such as, for example, terbufos, or other insecticides from the org~nophosphate, pyrethroid or carbamate groups. Even if such treatments are up to 20 days or more apart, damage to the crop plants can still ari~e. Herbicides, such as, for example, bentazone or bromoxynil, can also cause damage if maize crops or other crops are treated together or alternatively at separate tLmes with such compounds and sulfonylurea herbicides. In this case, the type of treatment i8 not important, it can be spraying of the leaves or soil, or the insecticides or herbicides can be applied to the seed as granules on or in the soil, or the seed~ can be dressed. It is only crucial that when all is said and done the various active substances act in the crop plant or begin to interact there in the plant metabolism. The presence of these compounds prevents or reduces the plant metabolism of ALS inhibitor (sulfonylurea) herbicides, so that discolorations, chloroses or even leaf deformations and severe growth disorders occur, which can also severely damage the yield of the crop plants.
The mentioned incompatibilities are an economic problem for the user, since he must not apply various agents together or must not treat crop plants, such as, for example, maize, with certain preparations which, for example, are very effective or very good value.
Surprisingly, however, it has now been found that ~uch damage to crop plants can be reduced or entixely pre-vented if, at the s~me time as the herbicide or ALS
inhibitor, plant-protecting agent~ are app ied such as have been proposed in German Patent Application P 40 41 120.6, which act as antidotes or safeners.
The invention therefore relates to mixtures or applica-tion combinations which contain ~ 3 - 208S~8 A) ALS inhibitor herbicides and other plant-protection agents such as insecticides or herbicides with different mechani~ms of action, independently of whether these preparations are applied together or S in succession, in particular one or more herbicides from the sulfonylurea, imidazolinone and pyrimidine or triazine derivative group and other agents such as insecticides and herbicides and B) one or more compounds of the formulae B1 and B2 (X)n ~ W ~`Z (B1) ~( X )n (B2) O~ "C O
in which X is hydrogen, halogen, C1-C4-alkyl, Cl-C4-alkoxy, nitro or C1-C4-haloalkyl, 15 Z is OR1, SR1, NR1R, where R is H, C1-C~-alkyl, C1-C6-alkoxy or optionally ~ubstituted phenyl, or a saturated or unsaturatQd 3- to 7-membered hetero-cycle having at least one nitrogen atom and up to 3 hetero atoms, which is bonded to the carbonyl group 2 0 via the nitrogen atom and is unsub6tituted or substituted by radicals from the group comprising C1-C4-alkyl, C1-C4-alkoxy and optionally sub6tituted phenyl, preferably a radical of the formula OR1, NHR
or N(CH3), in particular of the formula OR1, _ 4 _ 208~8 R is a Cl-C2-alkylene chain which can additionally be substituted by one or two C1-C4-alkyl radicals, preferably -CH2-, Rl is hydrogen, Cl-Cl8-alkyl, C3-Cl2-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubsituted or mono- or polysubstituted by radicals from the group compri~ing halogen, hydroxyl, C1-CB-a1kOXY~ C1-C8_a1kY1thiO, C2-C8-a1k~nY1thiO, C2-C8-alkynylthio, C2-CB-alkenyloxy, C2-C8-alXynyloxy, C3-C7-cycloalkyl, C3-C7-cycloalkoxy, cyano, mono~ and di-Cl-C4-alkylamino, Cl-C8-alkoxycarbonyl, C2-C8-alkenyloxycarbonyl, Cl-C8-alkylthiocarbonyl, C2-C8-alkynyloxycarbonyl, Cl-C8-alkylcarbonyl, C2-C8-alkenylcarbonyl, C2-C8-alkynylcarbonyl, Cl-C8-alkylcarbonylamino,C2-C8-alkenylcarbonylamino, C2-C8-alkynylcarbonylamino, aminocarbonyl, Cl-C8-alkylaminocarbonyl, Di-Cl-C6-alkylaminocarbonyl, C2-C6-alkenylaminocarbonyl, C2-C6-alkynylamino-c arbonyl, C1-C8- alkoxyc arbonyl amino, Cl-C8-alkylaminocarbonylamino,Cl-C6-alkylcarbonyloxy which is unsubstituted or substituted by halogen, NO2, Cl-C4-alkoxy or optionally substituted phenyl, C2-C6-alkenylcarbonyloxy, C2-C6-alkynylcarbonyloxy, C1-C8-alkylsulfonyl, phenyl, phenyl-C1-C6-alkoxy, phenyl-C1-C6-alkoxycarbonyl, phenoxy, phenoxy-C1-C6-alkoxy, phenoxy-C1-C6-alkoxycarbonyl, phenylcar-bonyloxy, phenylcarbonylamino, phenyl-Cl-C6-alkyl-carbonylamino, where the last-mentioned 9 radicals in the phenyl ring are unsubstituted or mono- or polysubstituted by radicals from the group com-prising halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloa:lkoxy and nitro, and radicals of the formulae -SiR'3, -O-SIR'3, (R')3Si-C1-C6-alkoxy, -CO-O-NR' 2 ~ _O-N=cR ~ 2 ~ -N=CR' 2 ~
-O-NR~2-CH(OR~ )2 and -O-~CH2)m-CH(OR'2)2, in which R' in said formulae independently of one another are 20~5~4~
hydrogen, C1-C4-alkyl, phenyl which is unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C4-alkyl, C~-C4-alkoxy, C1-C4-haloalkoxy and nitro, or in pairs are a C2-C6-alkylene chain and m = 0 to 6, and a radical of the formula R"O-CHR (OR")-Cl-C6-alkoxy, in which the radicals R" independently of one another are C1-C4-alkyl or together are a C1-C6-alkylene radical and R is hydrogen or C1-C4-alkyl, 10 n is an integer from 1 to 5, preferably 1 to 3, W is a divalent heterocyclic radical having 5 ring atoms, of the formula Wl to W4 ~N~ N~
R2 ~J
CooR3 (W1) (W2) N/ \
N - CH
(W3) (W4) in which R2 is hydrogen, C1-C~-alkyl, C1-Ca-haloalkyl, C3-C12-cycloalkyl or optionally substituted phenyl and R3 is hydrogen, C1-C3-alkyl, Cl-Ca-haloalkyl, Cl-C4-alkoxy-Cl-C4-alkylI Cl-C6-hydroxyalkyl, C3-Cl2-20cycloalkyl or tri-(C1-C4-alkyl)silyl, or the salts of said compounds.
- 6 - 6~
Herbicidal agents according to the invention of par-ticular interest are those where, in the compounds of the formulae Bl and B2, Rl is hydrogen, C1-C12-alkyl or C3-C7-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubstituted or mono- or polysubstituted by halogen or mono- or disubsti-tuted, preferably monosubstituted by radicals from the group comprising hydroxyl, Cl-C4-alkoxy, Cl-C4-alkylthio, C2-C4-alkenyloxy, C2-C6-alkynyloxy, mono-and di-(Cl-C2-alkyl)-amino, (Cl-C4-alkoxy)carbonyl, C2-C4-alkenyloxycarbonyl, C2-C4-alkynyloxycarbonyl, Cl-C4-alkylcarbonyl, C2-C4-alkenylcarbonyl, C2-C4-alkynylcarbonyl,C1-C4-alkylsulfonyl, phenyl,phenyl-C1-C4-alkoxycarbonyl, phenoxy, phenoxy-Cl-C4-alkoxy, phenoxy-(Cl-C4-alkoxy)carbonyl, where the last-mentioned 6 radicals in the phenyl ring are unsub-stituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C2-alkyl, Cl-C2-alkoxy, Cl-C2-haloalkyl, C1-C2-haloalkoxy and nitro, and radicals of the formulae -SIR'3, -O-N=CR'2, -N=CR~2, -N=CR'2 and -O-NR'2, in which the R' in said formulae independently of one another are hydrogen, Cl-C2-alkyl, phenyl which is unsubstituted or mono-or polysubstituted by radicals from the group comprising halogen, Cl-C2-alkyl, Cl-C2-alkoxy, Cl-C2-haloalkyl, Cl-C2-haloalkoxy and nitro, or in ~airs are a C4-C5-alkanediyl chain.
Herbicidal agent~ according to the invention also of particular interest are those where, in the compounds of the formulae Bl and B2, X i6 hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or Cl-C2-haloalkyl, preferably hydrogen, halogen or Cl-C2-haloalkyl.
- 7 - 2~8~$~
Preferred herbicidal agents according to th~ invention are those where, in the compounds of the formula Bl, X is hydrogen, halogen, nitro or Cl-C4-haloalkyl, n is a number from 1 to 3, Z is a radical of the formula ORl, R1 is hydrogen, C1-C8-alkyl or C3-C7-cycloalkyl, where the above C-containing radicals are unsub-stituted or mono- or polys~bstituted by radicals from the group comprising halogen or mono- or disubstituted, preferably unsubstituted or monosub-stituted, by radicals from the group comprising hydroxyl, Cl-C4-alkoxy, (C1-C4-alkoxy)carbonyl, C2-C6-alkenyloxycarbonyl, (C2-C6~alkynyloxy)carbonyl and radicals of the formulae -SiR'3, -O-N=CR'2, -N=CR'2 and -O-NR'2, in which the radicals R' in said formulae independently of one another are hydrogen or Cl-C4-alkyl or in pairs are a C4-C5-alkylene chain, R2 is hydrogen, Cl-Ce-alkyl, Cl-C6-haloalkyl, C3-C7-cycloalkyl or phenyl and 0 R3 is hydrogen, Cl-C8-alkyl, Cl-C8-haloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl, Cl-C6-hydroxyalkyl, C3-C7-cyclo-alkyl or tri-(Cl-C4-alkyl)silyl.
Preferred herbicidal agents according to the invention are also those where, in the compounds of the formula B2, X is hydrogen, halogen or Cl-C4-haloalkyl and n is a number from 1 to 3, pxeferably (X)n = 5-Cl, Z is a radical of the formuls OR1, R is CH2 and Rl is hydrogen, Cl-C8-alkyl, Cl-C8-haloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl or ~Cl-C4-alkenyloxy)-Cl-C4-alkyl, prefexably Cl-C8-alkyl.
Particularly preferred herbicidal agent~ according to the invention are those containing compounds of the formula ~1, in which 208~ ~%
W is Wl, X is H, halogen or C1~C2-haloalkyl and n = 1 - 3, in particular (X) n = 2 ~ 4 -C12 ~
Z is a radical of the formula OR1, R1 is hydrogen, C1-C8-alkyl, C1-C4-haloalkyl, Cl-C4-hydroxyalkyl, C3-C7-cycloalkyl, (cl-c4-alkoxy)-cl-c4-alkyl or tri-(C1-C2-alkyl)-silyl, preferably Cl-C4-alkyl, R2 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl or C3-C7-cycloalkyl, preferably hydrogen or C1-C4-alkyl, and R3 is hydrogen, C1-CB-alkyl, C1-C4-haloalkyl, C1-C4-hydroxyalkyl, C3-C7-cycloalkyl, (C1-C4-alkoxy)-C1-C4-alkyl or tri-(C1-C2-alkyl)silyl, preferably hydrogen or C1-C4-alkyl.
15 Particularly preferred herbicidal agents according to the invention are also those containing compounds of the formula Bl, in which W is W2~
X is H, halogen or C1-C2-haloalkyl and n = 1 - 3, in particular (X) n = 2~4 -C12, Z is a radical of the formula OR1, R1 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl, C1-C4-hydroxyalkyl, C3-C7-cycloalkyl, (C1-C4-alkoxy)-C1-C4-alkyl or tri-(C1-C2-alkyl)silyl, preferably C1-C4-alkyl and R2 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl, C3-C7-cycloalkyl or phenyl, preferably hydrogen or Cl-C4-alkyl.
Particularly preferred herbicidal agents according to the invention are also those containing compounds of the formula Bl, in which W is W3, X is H, halogen or C1-C2-haloalkyl and n = 1 - 3, in particular (X) n = 2 ~ 4-Cl2 ~ 5 Z is a radical of the formula OR1, 208~ 48 Rl is hydrogen, C~-C8-alkyl, C1-C4-haloalkyl, Cl-C4-hydroxyalkyl, C3-C7-cycloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl or tri-(Cl-C2-alkyl)silyl, preferably Cl-C4-alkyl and R2 is Cl-C8-alkyl or Cl-C4-haloalkyl, preferably Cl-haloalkyl.
Particularly preferred herbicidal agents a~cording to the invention are also those containing compounds of the formula B1, in which W is W4, X is hydrogen~ halogen, nitro, Cl-C4-alkyl or Cl-C2-haloalkyl, preferably CF3, or Cl-C4-alkoxy, n is l to 3, Z is a radical of the formula ORl, 5 R1 is hydrogen, Cl-C4-alkyl or (C1-C4-alkoxy)carbonyl-Cl-C4-alkyl, preferably (cl-c4-alkoxy)-co-cH2-~( alkoxy)-CO-C(CH3)H-, HO-CO-CH2- or HO-CO-C(CH3)H-.
In the formulae, alkyl, alkenyl and alkynyl are straight-chain or branched; the same applies to substituted alkyl, alkenyl and alkynyl radicals such a haloalkyl, hydroxy-alkyl, alkoxycarbonyl etc.; alkyl is, for example, methyl, ethyl, n- and i-propyl, n-, i-, t- and 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1,3-di-methylbutyl, heptyls, such as n-heptyl, l-methylhexyl and 1,4-dimethylpentyl; alkenyl is, for example, allyl, l-methylprop-2-en-l-yl, but-2-en-l-yl, but-3-en-1-yl, l-methylbut-3-ene and 1-methylbut-2-ene; alkynyl i~, for example, propargyl, but-2-yn-1-yl, but 3-yn-l-yl, l-methyl-but-3-yne; halogen iB fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine; haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl substituted by halogen, for example such as CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CCl3, CHCl2, CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF20, CF3CH20;
optionally substituted phenyl is, for example, phenyl 2a~ 8 which is unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 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.
The compounds of the formula Bl are disclosed in EP-A-333 131, EP-A-269 806, EP-A-346 620, International Patent Application PCT/EP gO/01966 and International Application No. PCT/EP 90/02020 and literature cited therein or can be prepared by or analogously to the processes described therein. The compounds of the formula B2 are disclosed in EP-A-86 750, EP-A-94 349 and EP-A-l91 736 and literature cited therein or can be prepared by or analogously to the processes described therein. ~hey are additionally proposed in German Patent Application P 40 41 121.4.
Suitable mixed combinations of the type A are ALS in-hibitor herbicides according to the invention, such as sulfonylureas and imidazolinones, as well as substituted pyrimidines and triazones which can be employed in a mixture or applied separately with other plant-protection agents, such as insecticides, for example organo-phosphates, or herbicides.
Such ALS inhibitors of the 6ulfonylurea type are, forexample, the known compounds priml~ulfuron-methyl, nicosulfuron, DPX-E-9636, amidosulfuron, thiameturon-methyl, NC319 (EP-A-282 613) and other disclosed active substances and pyridylsulfonylureas (German Patent Application P 40 30 577.5) and alkoxyphenoxysulfonylureas (EP-A-342 569) and mixtures of said active substances with one another.
~8~
Suitable compounds are pyridylsulfonylureas of the formula Al or their salts, R~
~ ~ R R6 Rs ~ //\\ ~ ~ ~ ~ (A1) in which R is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or ~rialkylammonium, E is CH or nitrogen, R4 is halogen or NR9R10, R5 is hydrogen, halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy,C1-C3-haloalkyl,C1-C3-haloalkoxy,C1-C3-alkyl-thio, (C1-C3-alkoxy)-C1-C3-alkyl, (C1-C3-alkoxy)carbonyl, mono- or di(C1-C3-alkyl)amino, Cl-C3-alkylsulfinyl or sulfonyl, SO2-NR4Rb or CO-NRaRb, R6 is hydrogen or CH3, R7 is halogen, C1-C2-alkyl,Cl-C2-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy or OCH2CF3, R8 is C1-C2-alkyl, C1-C2-haloalkoxy or C1-C2-alkoxy and R9 is Cl-C4-alkyl and R10 is C1-C4-alkylsulfonyl or R9 and Rl together are a chain of the formula -(CH2)3S02- or -(CHz)4SO2-r or alkoxyphenoxysulfonylureas of the formula A2 or their salts, Rl4 ( R 1 2 ) ~ ~S~ ~ 1N--1R 15 1.... 1,~
R R
in which 12 2~8~8 R"" is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium, E is CH or nitrogen, Rl1 is methoxy, ethoxy, propoxy, isopropoxy or Cl-C4-alkoxycarbonyl, RlZ is hydrogen, halogen, NO2, CF3, CN, C1-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio or (Cl-C3-alkoxy)-carbonyl, n is 1, 2 or 3, Rl3 is hydrogen, Cl-C4-alkyl or C3-C4-alkenyl, R14 and Rl5 independently of one another are halogen, Cl-C2-alkyl, Cl-Cz-alkoxy, Cl-C~-haloalkyl, Cl-C2-halo-alkoxy or (Cl-C2-alkXY)-cl-c2-al~yl-ALS inhibitors of the imidazolinone type are imazethapyr, 15 imazaquin, imazethamethapyr (AC-263222) and other related compounds and mixtures thereof.
Suitable substituted pyrimidines and triazines have the formula C
N ~ R2~
N ~ (C) in which X' is oxygén, sulfur or NR24, Y' is nitrogen or CH, R22 and R23 independently of one another are hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, Cl-C4-alkylmer-25 capto, C~-C4-alkylamino or di-Cl-C4-alkylamino, R2l is a substituted aryl or heteroaryl radical of the formula - 13 - 20~4~
R 2 s~( w ) n ~R26 or ~ ~ ~ ~502R
n~ is 0 or 1, W' is -O-, -NR24-, -S-, -ON(R31)- or -o-N=C(R31), X' is N, N~O or CR24, S R24 is defined as R22 or R23, RZ5 is halogen, cyanor nitro, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Cl-C4-alkoxy, haloalkyl or haloalkoxy, R26 is C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, alkali metal or 1 equivalent of alkaline earth metal, alkylammonium, aryl, CF3 or (CHR33)m.CHR27R2B where m' = 0 or 1, R27 and R33 independently of one another are hydrogen, Cl-C4-alkyl or Cl-C4-alkoxy, R2~ is C1-C4-alkoxycarbonyl, cyano, halogen, acetyl, pivaloyl, benzoyl, C1-C4-alkoxy, aryloxy, halo-acetoxy, methanesulfonyloxy, hydroxyl, C1-C4-alkyl-mercapto,C1-C4-alkylsulfonyl,arylmercapto,di-C1-C4-alkylamino, pyridyl, aryl or CoNR2aR30, R29 and R30 independently of one another are hydrogen, C1-C4-alkyl, C~-C4-alkenyl, aryl or benzyl, R31 is hydrogen ox C1-C4-alkyl or R26 and R31 together are methylene, ethanediyl or pro-panediyl and aryl i8 phenyl or naphthyl, each of which i~ unsubsti-tuted or mono- or disubstituted by halogen, Cl-C4-alkyl, C1-C4-alkoxy, phenoxy, nitro and/or C1-C4-alkoxycarbonyl, or R11 is a radical of the formula 2085~48 - ~4 -R~200~ ~ or ~ ~9 R34 iB hydrogen, halogen, halo-Cl-C4-alkyl, C1-C4-cyclo-alkyl, Cl-C4-alkylmercapto-C1-C4-alkyl, hydroxyl-Cl-C4-alkyl, hydroxyl, cyano, aryloxyalkyl, thienyl, aryl, dihydronaphthyl or ,R
( CH2 )m~
where aryl is as defined above, R40 is hydrogen, halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy or S(O)p.R , R41 is alkyl, p' is a 0, 1 or 2, m" is a 0, 1 or 2, R3s and R36 independently of one another are hydrogen or C1-C4-alkyl, or these, together with the carbon atom, are a 3-, 4-, 5- or 6-membered cycloalkane ring, in which a methylene group can be replaced by oxygen and which can be substituted by one or two C1-C4-alkyl groups, R37 and R3~ independently of one another are hydrogen or Cl-C4-alkyl, R39 is Cl-C4-alkyl or phenyl, or R38 and R3~ are -(CH2)l- where l = 3 or 4, which can be substituted by one or two C1-C4-alkyl groups, R42 is hydrogen, C1-C4-alkyl,C1-C4-alkenyl, C1-C4-alkynyl, phenyl, C1-C4-alkylidenamino, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, halo-C1-C4-- 15 _ 2~8~ ~ ~8 alkyl, cycloalkyl, nitro-substituted phenylmercapto-Cl-C4-alkyl, halogen or benzyl which can be substi-tuted by Cl-C4-alkyl or Cl-C4-alkoxy, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium.
The various types of ALS inhibitors can also be mixed with one another. Other active substance structures which inhibit the enzyme ALS, for example herbicidal sulfona-mides such as flumetsulam (DE-498) and the like are also possible here. Possible combination components in the ~mixture~ of the type A are the following plant-protec-tion agents, where the indiYidual components can be applied toge~her or separately from one another at an interval of time of up to several weeks:
1.) Insecticidal preparations such as organophosphates, for example terbufos (~Counter~, fonofos (~Dyfonate), phorate (~Thimet), chlorpyrifos (Reldan) and other rela~éd active substances, insecticidal carbamates such as, for example, carbofuran (0Furadan) and others; as well as pyrethroid insecticides such as, for example, tefluthrin (~Force), deltamethrin (~Decis) and tralomethrin (Scout) and others; as well as other insecticidal agents having a different mechanism of action.
5 2.) Herbicides which are employed as components, in order to widen the spectrum of action of ALS
inhibitors and to improve the activity, such a~, for example, bentazone, cyanazine, bromoxynil or other herbicides which are absorbed through the leaf.
The following groups of compounds have proven suitable as safeners for the abovementioned product combinations:
a) Compounds of the dichlorophenylpyrazoline-3-car-boxylic acid type (i.e. of the formula ~1, in which - 16 - ~8~8 W = Wl and (X)n = 2,4-Cl2), preferably compounds such as ethyl l-(2,4-dichlorophenyl)-5-(ethoxycarbonyl-5-methyl-2-pyrazoline-3-carboxylate (Bl-l) and related compounds, such as are described in Inter-national Application PCT/EP 90/02020, b3 Derivatives of dichlorophenylpyrazolcarboxylic acid (i.e. of the formula Bl, in which W = W2 and (X)n =
2,4-C12), preferably compounds ~uch as ethyl l-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (B1-2), ethyl 1-(2,4-dichlorphenyl)-5-isopropyl-pyrazole-3-carboxylate (Bl-3), ethyl l-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (B1-4), ethyl 1~(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate ~Bl-5) and related compounds, such as are described in EP-A-0 333 131 and EP-A-0 269 806.
c) Compounds of the triazolecarboxylic acid type (i.e.
of the formula B1 in which W = W3 and (X)n =
2~4-Clz)~ preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-(lH)-1,2,4-tria-zole-carboxylate (Bl-6, fenchlorazole) and related compounds (see EP-A-0 174 562 and EP-A-0 346 620);
d) Compounds of the dichlorobenzyl-2-isoxazoline-3-carboxylic acid type (i.e. of the formula B1, in which W = W4 and (X)~ = 2,4-Cl2), preferably com-pounds such as ethyl 5-(2,4-dichlorohenzyl)-2-iso-axazoline-3-carboxylate (B1-7) and related com-pounds, such as are described in International Application PCT/EP 90/01966.
0 e) Compounds of the (5-chloro-8-quinolinoxy)acetic acid type (i.e. of the formula B2, in which (X)n = 5-Cl, Z = OR1, R = CH2), preferably compounds such as l-methylhex-l-yl (5-chloro-8-quinolihoxy)acetate (B2-l), 1,3-dimethylbut-1-yl (5-chloro-8-quino-- 17 _ 2~ 8 linoxy)acetate (B2-2), 2-allyloxy-1-methylethyl (5-chloro-8-quinolinoxy)acetate (B2-3) and related compounds, such as are described or have been proposed in EP-A-86 750, EP-A-94 349 and EP-A-l91 736 and German Patent Application P 40 41 121.4.
The safeners (antidotes) of the above groups a) to e) reduce or suppress phytotoxic effects which can occur when using the product combinations in productive plant crops, without impairing the activity of the herbicides against harmful plants. By this means, the field of use of the mixtures can be very considerably widened and extended, for example, to crops such as maize, wheat, barley and other gramineous crops in which until now use 1~ of the combinations has not been possible or only restri-ctively possible, i.e. at low doses with not very wide action.
The herbicidal ALS inhibitors and their combination components and the safeners mentioned can be applied together (as a finished formulation or in a tank-mix process) or in any desired sequence in succession. The weight ratio safener: herbicide (ALS inhibitor) can vary within wide limits and is preferably in the range from 1:10 to 10:1, in particular from 1:10 to S:l. The optimum amounts of herbicide and safener in each case are depen-dent on the type of herbicide used or on the safener used and on the nature of the plant population to be treated and can be determined from case to case by appxopriate preliminary experiments. The application rate of the insecticide or herbicide additionally employed is depen-dent on its activity alone and corresponds to the general product recommendations.
Principal fields of use for the application of the safeners are, in particular, maize and cereal crops, (wheat, rye, barley, oats), rice and sorghum, but also - 18 ~ 8 cotton and soybean, preferably maize.
Depending on their properties, the safeners of the type B can be used for the pretreatment of the seeds of the crop plant (dressing of the seeds) or introduced into the seed furrows before the seed or applied together with the herbicide before or after the emergence of the plants.
Pre-emergence treatment includes both the treatment of the cultivation areas before sowing and the treatment of the sown, but not yet covered cultivation surfaces.
Application together with the herbicide is preferred, i.e. with the ALS inhibitor. Tank mixtures or finished formulations can be employed for this.
The required application rates of the safeners can vary within wide limits depending on the indication and herbicide used and are as a rule in the range from 0.001 to l kg, preferably 0.005 to 0.2 kg, of acti~e substance per hectare.
The present invention therefore also relates to a process for the protection of crop plants from phytotoxic side effects of herbicide combinations, which comprises applying to the plants, plant seeds or the cultivation surface an effective amount of a compound of said type B) before, after or at the same time as the herbicide of said type A) in combination with an insecticide or herbicide.
The compounds of the type B) and their combinations with one or more of said herbicides (ALS inhibitors) can be formulated in various ways, depending on which biological and/or chemico-physical parameters are specified. Suit-able formulation possibilities are, for example:
Wettable powders (WP), emulsifiable concentrates (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 2~8~48 emulsions, capsule suspensions (CS), dispersions on an oil or water basis (SC), suspoemulsions, suspension concentrates, dusting agents (DP), oil-miscible solutions (OL), dressing agents, granules (GR) in the form of micro granules, spray granules, coated granules and adsorption granules, granules for application to the soil or scat-tering, water-soluble granules (SG), water-dispersible granules (NG), ULV formulations, microcapsules and waxes.
These individual formulation types are known in principle and are described, for example, in: Winnacker-Ruchler, "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 required formulation auxiliaries such as inert materials, surfactants, solvents and other additives are likewise known and are 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, "Grenzflach-enaktive Athylenoxidaddukte" (Surface-active Ethylene Oxide Adducts), Wiss. Verlagsgesell., Stuttgart 1976;
Winnacker-Kuchler "Chemische Technologie" tChemical Technology) Vol./4th Ed, 7, C. Hauser Verlag Munich, 1986.
On the basis of these formulations, combinations with other pesticidally active substances, such as insecticides, fungicides, fertilizers and/or growth regulators, can be prepared, for example in the form of ~o~ 8 a finished formulation or as a tank-mix.
Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also contain wetting agents, for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols and fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates or alkylarylsulfonates and dispersing agents, for example sodium ligninsulfonate, sodium 2,2-dinaphthylmethane-6-6~-disulfonate, sodium dibutylnaphthalenesulfonate or alternatively sodium oleoylmethyltauride in addition to a diluent or inert substance.
Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or alternatively higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. Examples of emulsifiers which can be used are: alkylarylsulfonic acid calcium salts such as Ca dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide conden-sation products ~for example block polymers), alkyl polyethers, sorbitan fatty acid estars, polyoxyethylene-sorbitan fatty acid esters of polyoxyethylenesorbitolesters.
Dusting agents can be obtained by grinding the active substance with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophillite, or diatomaceous earth.
Granules can be produced either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates to the surface of carriers, such as sand, kaolinites or granulated inert - 21 - 208~48 material, by means of binders, for example polyvinyl alcohol, sodium polyacrylate or alternatively mineral oils. Suitable active substances can also be granulated in the manner which is customary for the production of fertilizer granules, if desired in a mixture with fer-tilizers.
The agrochemical preparations as a rule contain 0.1 to 99 ~ by weight, in particular 0.1 to 95 % by weight, of active substances of type B) or of antidote/herbicide active substance mixture A) and B) and 1 to 99.9 % by weight, in particular 5 to g9.~ % 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.
The concentration of active substance in wettable powders is, for example, about 10 to 90 % by weight; the remainder to 100 % by weight is composed of customary formulation component In the case of emulsifiable concentrates, the active substance concentration is about 1 to 80 ~ by weight of active substances. Formulations in the form of dusts contain about 1 to 20 % by weight of active substances, sprayable solutions about 0.2 to 20 %
by weight of active substances. In the case of granules such as water-dispersable granules, the active substance content depends partly on whether the active substance is liquid or solid. As a rule, the contents in the case of the water-dispersable granules is between 10 and 90 % by weight.
In addition, said active sub~tance formulations optionally contain the tackifiers, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers customary in each case.
For use, the formulations, present in commercially available form, are diluted, i~ appropriate, in a customary manner, for example by means of water in the 2~
case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in the form of dusts, granules and sprayable solutions are customarily not further diluted with other inert substances before use. Particularly good activitieæ of the agents according to the invention can be achieved if other wetting agents in concentrations of 0.1 to 0.5 % by weight are added in the tank-mix process to the surfac-tants contained in the formulations, for example nonionic 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 required applica-tion rate of the "safener" varies with the external conditions such as temperature, humidity, the nature of the herbicide used and the like.
The following examples serve to illustrate the invention without restricting it thereto:
A. Formulation examples a) A dusting agent is obtained by mixing 10 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B) and 90 parts by weight of talc as inert substance and comminuting the mixture in a hammer mill.
b) A wettable powder which is readily dispersible in water is obtained by mixing 25 part~ by weight of a substance of type B) or of an active substance mixture type A) and a safener of type B), 64 parts by weight o~ kaolin-containing quartz as inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltauride as a wetting and dispersing agent and grinding the mixture in a pinned-disk mill.
2 ~
c) A dispersion concentrate which is readily disper-sible in water is obtained by mixing 20 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 6 parts by weight of alkylphenol polyglycol ether ~registered trademark ~Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 E0) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to over 277C), and grinding the mixture in a ball mill to a fineness of less than 5 microns.
d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated nonyl-phenol as an emulsifier.
e) Water-dispersable granules are obtained by mixing 75 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 10 " of calcium ligninsulfonate, 5 " of sodium lauryl sulfate 25 3 " of polyvinyl alcohol and 7 " of kaolin, grinding the mixture in a pinned-di0k mill and granulating the powder in a fluidized bed by spraying water as a granulating fluid.
0 f) Water-dispersable granules are also obtained by homogenizing 25 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type 2a8~8 B), o f s o d i u m 2 , 2 ~ -dinaphthylmethane-6,6'-disulfonate, 2 parts by weight of sodium oleoylmethyltauride, 1 " of polyvinyl alcohol, 17 ~I of calcium carbonate and 50 " of water in a colloid mill and precomminuting, then grinding the mixture in a bead mill and atomizing and drying the suspension thus obtained in a spray tower by means of a single substance nozzle.
The insecticides or herbicides additionally used can be added both in the tank-mix process, or applied separately from the finished formulation composed of ALS inhibitor and safener of the type B.
The active substance mixture A is in each case composed of an ALS inhibitor and an insecticide and/or another herbicide.
B. Biological examples The crop plants were cultivated up to the 4-leaf stage in open ground or in a greenhouse in plastic pots and then treated according to the invention with compoundæ of type A) and B) post-emergence. The compounds of type A) and B) were in this case applied in the form of aqueous suspensions br emulsions at a water application rate of, after conversion, 300 l/ha. 4 week~ after treatment, the plant6 were visually as6e~sed for any typ~ of damage due to the applied herbicides, the extent of prolonged inhibition of growth being taken particularly into account. Assessment was carried out in percentage values in comparison with untreated controls.
The result~ in the following tables illustrate that the compounds of type B) employed according to the invention 2~8~
can effectively reduce severe damage to crop plants. Even very severe damage is markedly reduced and slight damage is completely abolished. Combinations of ALS inhibitors and mixture components and compounds of type B) are therefore outstandingly suitable for the selective control of weeds in maize.
Example 1 Type A Type B Type A Type B
Herbicide combination Safener g of AS/ha g of AS/ha X damage (ALS inhibitor) to thQ
crop plant maize Hl + terbufos - 25 + 500 0 100 12 + 500 0 80 primisulfuron - 100 + 500 0 100 + terbufos 50 + 500 0 70 nicosulfuron - 200 + 500 0 90 + terbufos 100 + 500 0 80 terbufos - 500 0 0 primisulfuron B2-1 100 + 500 100 70 50 + 500 50 40 Hl + terbufos B2-2 25 + 500 25 50 12 + 500 12 20 nicosulfuron B2-3 200 + 500 200 40 + terbufos 100 + 500 100 30 Hl ~ 25 0 40 primisulfuron - 100 0 50 nicosulfuron - 200 0 30 Greenhouse experiment with 4 repetitions.
2o8~8 Sowing of maize in a pure sand culture. Terbufos was scattered on the soil surface as granules immediately after sowing. All other treatments were carried out in the 4-leaf stage. Naize variety "~FELIX".
H1 = CH
1 ~
CO/ ~<N~
S Example 2:
OCH~
Type AS~ha ~ damag~ to maize varieties FELIX DEA
bentazone 2.0 0 0 1.0 0 0 0.5 0 0 bromoxynil 1.0 20 30 0.5 20 30 0.25 10 15 15 primisulfurone 0.100 25 20 0.050 10 8 0.025 5 5 bentazone + 2.0 + 0.05 30 35 + prlmisulfuron 1.0 -~ 0.05 15 20 20 bentazone + 2.0 ~ 0.05 + 0.1 10 15 + primisulfuron 1.0 + 0.05 + 0.1 0 5 + Hl bromoxynil + 1.0 + 0.05 55 50 + primisulfuron 0.5 + 0.05 40 35 20~5~48 bromoxynil + 1.0 + 0.05 + 0.1 lS 15 + primisulfuron 0.5 + 0.05 + 0.1 5 0 + Hl Application in the 4-leaf stage cf the maize, height 23 - 26 cm.
Assessment: 4 weeks aftsr treatment
Claims (13)
1. A herbicidal agent, which comprises A) one or more herbicides from the sulfonylurea, im-idazolinone and pyrimidine or triazine derivative group and other agents such as insecticides and herbicides and B) one or more compounds of the formulae B1 and B2, (B1) (B2) in which X is hydrogen, halogen, C1-C4 alkyl, C1-C4-alkoxy, nitro or C1-C4-haloalkyl, Z is OR1, SR1, NR1R, where R is H, C1-C6-alkyl, C1-C6-alkoxy or optionally substituted phenyl, or a saturated or unsaturated 3- to 7-membered hetero-cycle having at least one nitrogen atom and up to 3 hetero atoms, which is bonded to the carbonyl group via the nitrogen atom and is unsubstituted or substituted by radicals from the group comprising C1-C4-alkyl, C1-C4-alkoxy and optionally substituted phenyl, R is a C1-C2-alkylene chain which can additionally be substituted by one or two C1-C4-alkyl radicals, R1 is hydrogen, C1-C18-alkyl, C3-C12-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen, hydroxyl, C1-C8-alkoxy, C1-C8-alkylthio, C2-C8-alkenylthio, C2-C8-akynylthio, C2-C8-alkenyloxy, C2-C8-alkynyloxy, C3-C7-cycloalkyl, C3-C7-cycloalkoxy, cyano, mono- and di-C1-C4-alkylamino, C1-C8-alkoxycarbonyl, C2-C8-alkenyloxycarbonyl, C1-C8-alkylthiocarbonyl, C2-C8-alkynyloxycarbonyl, C1-C8-alkylcarbonyl, C2-C8-alkenylcarbonyl, C2-C8-alkynylcarbonyl, C1-C8-alkylcarbonylamino,C2-C8-alkenylcarbonylamino, C2-C8-alkynylcarbonylamino, aminocarbonyl, C1-C8-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C2-C6-alkenylaminocarbonyl, C2-C6-alkynylamino-carbonyl, C1-C8 alkoxycarbonylamino, C1-C8-alkylaminocarbonylamino, C1-C6-alkylcarbonyloxy, which is unsubstituted or substituted by halogen, NO2, C1-C4-alkoxy or optionally substituted phenyl, C2-C6-alkenylcarbonyloxy, C2-C6-alkynylcarbonyloxy, C1-C8-alkylsulfonyl, phenyl, phenyl-C1-C6-alkoxy, phenyl-C1-C6-alkoxycarbonyl, phenoxy, phenoxy-C1-C6-alkoxy, phenoxy-C1-C6-alkoxycarbonyl, phenylcar-bonyloxy, phenylcarbonylamino, phenyl-C1-C6-alkylcar-bonylamino, where the last-mentioned 9 radicals in the phenyl ring are unsubstituted or mono- or poly-substituted by radicals from the group comprising halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy and nitro, and radicals of the formulae -SiR'3, -O-SiR'3, (R')3Si-C1-C6-alkoxy, -CO-O-NR'2, -O-N=CR'2, -N=CR'2, -O-NR'2-CH(OR')2 and -O-(CH2)m-CH(OR'2)2, in which the R' in said formulae independently of one another are hydrogen, C1-C4-alkyl, phenyl which is unsubstituted or mono- or polysubstituted by radicals from the group com-prising halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and nitro, or in pairs are a C2-C6-alkylene chain and m = O to 6, and a radical of the formula R"O-CHR'"(OR")-C1-C6-alkoxy, in which the radical R" independently of one another are C1-C4-alkyl or together are a C1-C6-alkylene radical and R'" is hydrogen or C1-C4-alkyl, n is an integer from 1 to 5, W is a divalent heterocyclic radical having 5 ring atoms, of the formula W1 to W4 (W1) (W2) (W3) (W4) in which R2 is hydrogen, C1-C8-alkyl, C1-C8-haloalkyl, C3-C12-cycloalkyl or optionally substituted phenyl and R3 is hydrogen, C1-Ca-alkyl, C1-C8-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C6-hydroxyalkyl, C3-C12-cycloalkyl or tri-(C1-C4-alkyl)silyl, or the salts of said compounds.
2. An agent as claimed in claim 1, wherein R1 is hydrogen, C1-C12-alkyl or C3-C7-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubstituted or mono- or polysubstituted by halogen or mono- or disubsti-tuted, preferably monosubstituted by radicals from the group comprising hydroxyl, C1-C4-alkoxy, C1-C4-alkylthio, C2-C4-alkenyloxy, C2-C6-alkynyloxy, mono-and di-(C1-C2-alkyl)-amino, (C1-C4-alkoxy)carbonyl, C2-C4-alkenyloxycarbonyl, C2-C4-alkynyloxycarbonyl, C1-C4-alkylcarbonyl, C2-C4-alkenylcarbonyl, C2-C4-alkynylcarbonyl, C1-C4-alkylsulfonyl, phenyl,phenyl-C1-C4-alkoxycarbonyl, phenoxy, phenoxy-C1-C4-alkoxy, phenoxy-(C1-C4-alkoxy)carbonyl, where the last-men-tioned 6 radicals in the phenyl ring are unsubsti-tuted or mono- or polysubstituted by radicals from the gxoup comprising halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy and nitro, and radicals of the formulae -SiR'3, -O-N=CR'2, -N=CR'2 and -O-NR'2, in which the R' in said formulae independently of one another are hydrogen, C1-C2-alkyl, phenyl which is unsubstituted or mono- or polysubstituted by radicals from the group com-prising halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy and nitro, or in pairs are a C4-C5-alkenyl chain.
3. An agent as claimed in claim 1 or 2, wherein in the compounds of the formula B1, X is hydrogen, halogen, nitro or C1-C4-haloalkyl, n is a number from 1 to 3, Z is a radical of the formula OR1, R1 is hydrogen, C1-C8-alkyl or C3-C7-cycloalkyl, where the above carbon-containing radicals are unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen or mono-or disubstituted, preferably unsubstituted or monosubstituted, by radicals from the group comprising hydroxyl, C1-C4-alkoxy, (C1-C4)-alkoxy)carbonyl, C2-C6-alkenyloxy)carbonyl, (C2-C6-alkynyloxy)carbonyl and radicals of the formulae -SiR'3, -O-N=CR'2, -N=CR'2 and -O-NR'2, in which the radicals R' in said formulae independently of one another are hydrogen or C1-C4-alkyl or in pairs are a C4-C5-alkanediyl chain, R2 is hydrogen, C1-C8-alkyl, C1-C6-haloalkyl, C3-C7-cycloalkyl or phenyl and R3 is hydrogen, C1-C8-alkyl, C1-C8-haloalkyl, (C1-C4-alkoxy)-C1-C4-alkyl, C1-C6-hydroxyalkyl, C3-C7-cyclo-alkyl or tri-(C1-C4-alkyl)silyl.
4. An agent as claimed in one or more of claims 1 to 3, wherein in the compounds of the formula B2, X is hydrogen, halogen or C1-C4-haloalkyl and n is a number from 1 to 3, preferably (X)n = 5-Cl, Z is a radical of the formula OR1, R* is CH2 and R1 is hydrogen, C1-C8-alkyl, C1-C8-haloalkyl, (C1-C4-alkoxy)-Cl-C4-alkyl or (Cl-C4-alkenyloxy)-Cl-C4-alkyl, preferably C1-C8-alkyl.
5. An agent as claimed in one or more of claims 1 to 4, which contains one or more herbicides from the group c o m p r i s i n g p h e n y l s u l f o n y l u r e a s , thienylsulfonylureas, pyrazolsulfonylureas, sulfondiamide derivatives, pyridylsulfonylureas, alkoxyphenoxysulfonylureas, imidazolinones and pyrimidine or triazine derivatives in combination with other insecticides and herbicides.
6. An agent as claimed in one or more of claims 1 to 5, which contains one or more herbicides from the group comprising nicosulfuron, DPX-E-9636, amidosulfuron, thiameturon-methyl, NC 319, primisulfuron-methyl, pyridylsulfonylureas of the formula Al, (A1) in which R is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium, E is CH or nitrogen, R4 is halogen or NR9R10, R5 is hydrogen, halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy,C1-C3-haloalkyl,C1-C3-haloalkoxy,C1-C3-alkyl-thio, (C1-C3-alkoxy)-C1-C3-alkyl, (C1-C3-alkoxy)carbonyl, mono- or di(C1-C3-alkyl)amino, C1-C3-alkylsulfinyl or sulfonyl, SO2-NRaRb or CO-NRaRb, R6 is hydrogen or CH3, R7 is halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy or OCH2CF3, R8 is C1-C2-alkyl, C1-C2-haloalkoxy or C1-C2-alkoxy and R9 is C1-C4-alkyl and R10 is C1-C4-alkylsulfonyl or R9 and R10 together are a chain of the formula -(CH2)3SO2- or -(CHZ)4SO2-, alkoxyphenoxysulfonylureas of the formula A2 (A2) in which R"" is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium, E is CH or nitrogen, R11 is ethoxy, propoxy or isopropoxy, R12 is hydrogen, halogen, NO2, CF3, CN, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or (C1-C3-alkoxy)carbonyl, n is 1, 2 or 3, R13 is hydrogen, C1-C4-alkyl or C3-C4-alkenyl, R14 and R15 independently of one another are halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl, C1-C2-halo-alkoxy or (C1-C2-alkoxy)-C1-C2-alkyl, or the salts of said compounds.
7. An agent as claimed in one or more of claims 1 to 6, which contains at least one active substance from the pyrimidine and triazine series, of the formula C
(C) in which X' is oxygen, sulfur or NR24, Y' is nitrogen or CH, R22 and R23 independently of one another are hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, C1-C4-alkylmer-capto, C1-C4-alkylamino or di-C1-C4-alkylamino, R21 is a substituted aryl or heteroaryl radical of the formula or n' is O or 1, W' is -O-, -NR24-, -S-, -oN(R31)- or -n-N=C(R31)-, Z' is N, N-O or CR24, R24 is defined as R22 or R23, R25 is halogen, cyano, nitro, C,-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4alkoxy, haloalkyl or haloalkoxy, R26 is C1-C4-alkyl, C2-C4alkenyl, C2-C4-alkynyl, alkali metal or 1 equivalent of alkaline earth metal, alkyl ammonium, aryl, CF3 or (CHR33)mCHR27R28 where m' = O
or 1, R27 and R33 independently of one another are hydrogen, C1-C4-alkyl or C1-C4-alkoxy, R28 is C1-C4-alkoxycarbonyl, cyano, halogen, acetyl, pivaloyl, benzoyl, C1-C4-alkoxy, aryloxy, halo-acetoxy, methanesulfonyloxy, hydroxyl, C1-C4-alkyl-mercapto,C1-C4-alkylsulfonyl,arylmercapto,di-C1-C4-alkylamino, pyridyl, aryl or CONR28R30, R29 and R30 independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, aryl or benzyl, R31 is hydrogen or C1-C4-alkyl or R26 and R31 together are methylene, ethanediyl or pro-panediyl and aryl is phenyl or naphthyl, each of which is unsubsti-tuted or mono- or disubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, phenoxy, nitro and/or C1-C4-alkoxycarbonyl, or R11 is a radical of the formula or R34 is hydrogen, halogen, halo-C1-C4-alkyl, C1-C4-cyclo-alkyl, C1-C4-alkylmercapto-C1-C4-alkyl, hydroxyl-C1-C4-alkyl, hydroxyl, cyano, aryloxyalkyl, thienyl, aryl, dihydronaphthyl or where aryl is as defined above, R40 is hydrogen, halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy or S(O)pR41, R41 is alkyl, P' is a 0, 1 or 2, m" is a 0, 1 or 2, R35 and R36 independently of one another are hydrogen or C1-C4-alkyl, or these, together with the carbon atom, are a 3-, 4-, 5- or 6-membered cycloalkane ring, in which a methylene group can be replaced by oxygen and which can be substituted by one or two C1-C4-alkyl groups, R37 and R38 independently of one another are hydrogen or C1-C4-alkyl, R39 is C1-C4-alkyl or phenyl, or R38 and R39 are -(CH2)1- where 1 = 3 or 4, which can be substituted by one or two C1-C4-alkyl groups, R42 is hydrogen, Cl-C4-alkyl, C1-C4-alkenyl, C1-C4-alkynyl, phenyl, C1-C4-alkylidenamino, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, halo-C1-C4-alkyl, cycloalkyl, nitro-substituted phenylmercapto-C1-C4-alkyl, halogen or benzyl which can be substi-tuted by C1-C4-alkyl or C1-C4-alkoxy, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium.
(C) in which X' is oxygen, sulfur or NR24, Y' is nitrogen or CH, R22 and R23 independently of one another are hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, C1-C4-alkylmer-capto, C1-C4-alkylamino or di-C1-C4-alkylamino, R21 is a substituted aryl or heteroaryl radical of the formula or n' is O or 1, W' is -O-, -NR24-, -S-, -oN(R31)- or -n-N=C(R31)-, Z' is N, N-O or CR24, R24 is defined as R22 or R23, R25 is halogen, cyano, nitro, C,-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4alkoxy, haloalkyl or haloalkoxy, R26 is C1-C4-alkyl, C2-C4alkenyl, C2-C4-alkynyl, alkali metal or 1 equivalent of alkaline earth metal, alkyl ammonium, aryl, CF3 or (CHR33)mCHR27R28 where m' = O
or 1, R27 and R33 independently of one another are hydrogen, C1-C4-alkyl or C1-C4-alkoxy, R28 is C1-C4-alkoxycarbonyl, cyano, halogen, acetyl, pivaloyl, benzoyl, C1-C4-alkoxy, aryloxy, halo-acetoxy, methanesulfonyloxy, hydroxyl, C1-C4-alkyl-mercapto,C1-C4-alkylsulfonyl,arylmercapto,di-C1-C4-alkylamino, pyridyl, aryl or CONR28R30, R29 and R30 independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, aryl or benzyl, R31 is hydrogen or C1-C4-alkyl or R26 and R31 together are methylene, ethanediyl or pro-panediyl and aryl is phenyl or naphthyl, each of which is unsubsti-tuted or mono- or disubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, phenoxy, nitro and/or C1-C4-alkoxycarbonyl, or R11 is a radical of the formula or R34 is hydrogen, halogen, halo-C1-C4-alkyl, C1-C4-cyclo-alkyl, C1-C4-alkylmercapto-C1-C4-alkyl, hydroxyl-C1-C4-alkyl, hydroxyl, cyano, aryloxyalkyl, thienyl, aryl, dihydronaphthyl or where aryl is as defined above, R40 is hydrogen, halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy or S(O)pR41, R41 is alkyl, P' is a 0, 1 or 2, m" is a 0, 1 or 2, R35 and R36 independently of one another are hydrogen or C1-C4-alkyl, or these, together with the carbon atom, are a 3-, 4-, 5- or 6-membered cycloalkane ring, in which a methylene group can be replaced by oxygen and which can be substituted by one or two C1-C4-alkyl groups, R37 and R38 independently of one another are hydrogen or C1-C4-alkyl, R39 is C1-C4-alkyl or phenyl, or R38 and R39 are -(CH2)1- where 1 = 3 or 4, which can be substituted by one or two C1-C4-alkyl groups, R42 is hydrogen, Cl-C4-alkyl, C1-C4-alkenyl, C1-C4-alkynyl, phenyl, C1-C4-alkylidenamino, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, halo-C1-C4-alkyl, cycloalkyl, nitro-substituted phenylmercapto-C1-C4-alkyl, halogen or benzyl which can be substi-tuted by C1-C4-alkyl or C1-C4-alkoxy, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium.
8. An agent as claimed in claims 1 to 7, which additionally contains insecticides such as terbufos, fonofos, phorate, chlorpyrifos or other insecticides and/or herbicides such as bentazone, cyanazine, bromoxynil, dicamba, pyridate, 2,4-D, bromofenoxim or other herbicides of different active substance classes, which can be selectively employed in maize, where insecticides and herbicides can both be applied together with the ALS inhibitors or separately from them at an earlier or later time.
9. An agent as claimed in one or more of claims 1 to 8, wherein the weight ratio safener: herbicide is in the range from 1 : 10 to 10 : 1.
10. An agent as claimed in one or more of claims 1 to 9, which contains 0.1 to 99 % by weight of active substances of the type B) or of the antidote/herbi-cide active substance mixture A) and B) and 1 to 99.9 % by weight of a solid or liquid additive and 0 to 25 % by weight of a surfactant.
11. A process for the protection of crop plants from phytotoxic side effects of herbicides, which com-prises applying an effective amount of one or more compounds (safeners) of the type B) defined in claim 1 before, after or at the same time as the herbicide of the type A) as claimed in claim 1 to the plants, plant seeds or the cultivation surface, an insecticide and/or a herbicide as claimed in claim 7 or 8 being co-applied beforehand, afterwards or at the same time.
12. The process as claimed in claim 11, wherein the safener of the type B) is applied at an application rate of 0.001 to 2 kg/ha of active substance and in a weight ratio safener: herbicide in the range from 1 : 10 to 10 : 1.
13. The process as claimed in claim 11 or 12, wherein the crop plants are maize plants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4141247 | 1991-12-14 | ||
| DEP4141247.8 | 1991-12-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2085148A1 true CA2085148A1 (en) | 1993-06-15 |
Family
ID=6447038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2085148 Abandoned CA2085148A1 (en) | 1991-12-14 | 1992-12-11 | Combination of als inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agents |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0547546A1 (en) |
| CA (1) | CA2085148A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5541148A (en) * | 1992-07-08 | 1996-07-30 | Ciba-Geigy Corporation | Selective safened herbicidal composition comprising 2-ethoxycarbonyl-3-(4,6-dimethoxypyrimidine-2-yl) oxy-pyridine and an acylsulfamoylphenyl-urea safener |
| GB2334887A (en) * | 1998-03-05 | 1999-09-08 | Rhone Poulenc Agriculture | Antidotes for the herbicide pyribenzoxim [benzophenone O-(2,6-bis[(4,6-dimethoxy-2-pyrimidyl)oxy]benzoyl)oxime], especially cloquintocet & fenchlorazole |
| CN1318978A (en) * | 1998-07-16 | 2001-10-24 | 阿温提斯作物科学有限公司 | Herbicidal agents with substituted phenoxysulfonylureas |
| US6201897B1 (en) | 1998-11-09 | 2001-03-13 | Earth Resource Mapping | Transformation and selective inverse transformation of large digital images |
| DE102004035132A1 (en) * | 2004-07-20 | 2006-02-16 | Bayer Cropscience Ag | Insecticides based on selected insecticides and safeners |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE196591T1 (en) * | 1990-12-21 | 2000-10-15 | Aventis Cropscience Gmbh | MIXTURES OF HERBICIDES AND ANTIDOTES |
| EP0565593B1 (en) * | 1990-12-31 | 1999-03-03 | Monsanto Company | Reducing pesticidal interactions in crops |
-
1992
- 1992-12-11 CA CA 2085148 patent/CA2085148A1/en not_active Abandoned
- 1992-12-14 EP EP92121257A patent/EP0547546A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0547546A1 (en) | 1993-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU1836012C (en) | Method to protect cereals against phytotoxic action of phenoxapropethyl | |
| CN1764374B (en) | Use of aromatic hydroxy compounds as safeners | |
| CA2058284C (en) | Mixtures of herbicides and antidotes | |
| KR100913892B1 (en) | Herbicides | |
| EP0820227B1 (en) | Synergistic herbicidal compositions of metolachlor | |
| CA2442316C (en) | Synergistic herbicidal compositions comprising mesotrione | |
| US7098169B2 (en) | Herbicide-safener combination based on isoxazoline carboxylate safeners | |
| UA66743C2 (en) | Substituted isoxazolines, a method of obtaining thereof, a means on the basis thereof and a method of protecting plants | |
| SK4722003A3 (en) | Agrochemical compositions with quinoline safeners and use thereof | |
| CZ300185B6 (en) | Herbicidal agent, process for its preparation, method of controlling undesired plants and use of such herbicidal agent | |
| AU2002311427A1 (en) | Synergistic herbicidal compostions comprising mesotrione | |
| US5461019A (en) | Synergistic herbicidal combinations, process for their preparation, and use of said compositions as herbicidal agents | |
| CA2086491C (en) | Combinations of herbicides and crop-protecting substances | |
| RU2302113C2 (en) | Herbicidal agent containing benzoylpyrazoles and protective components, and a method of controlling weeds in cultural plants | |
| US6271177B1 (en) | Selective herbicidal composition | |
| CA2096115C (en) | Synergistic herbicidal compositions | |
| AU2002242701A1 (en) | Herbicide-safener combination based on isoxozoline carboxylate safeners | |
| JP3350779B2 (en) | Herbicidal synergistic composition and method for controlling weeds | |
| US5622910A (en) | Mixtures of herbicides and antidotes | |
| CA2085148A1 (en) | Combination of als inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agents | |
| CA2013301A1 (en) | Pesticidal compositions with enhanced activity | |
| JPH0687706A (en) | Synergistic herbicide and toxicity relaxing agent | |
| CA2055886A1 (en) | Synergistic composition, and method for selective control of weeds | |
| US5342822A (en) | Herbicidal agents | |
| JPH07215808A (en) | Synergetically active composition for controlling undesirable plant in cropping |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |