CA2093105A1 - Salts of 2-benzoylcyclohexanediones, selective herbicidal agents, process for their preparation, and their use for controlling weeds - Google Patents
Salts of 2-benzoylcyclohexanediones, selective herbicidal agents, process for their preparation, and their use for controlling weedsInfo
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- CA2093105A1 CA2093105A1 CA002093105A CA2093105A CA2093105A1 CA 2093105 A1 CA2093105 A1 CA 2093105A1 CA 002093105 A CA002093105 A CA 002093105A CA 2093105 A CA2093105 A CA 2093105A CA 2093105 A1 CA2093105 A1 CA 2093105A1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/45—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group
-
- 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
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/24—Sulfones; Sulfoxides having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
- C07C49/835—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups having unsaturation outside an aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Abstract Salts of 2-benzoylcyclohexanediones, selective herbicidal agents, process for their preparation, and their use for controlling weeds Compounds of the formula I
(I)
(I)
Description
2~3~
HOECHST AKTIENGESEI.LSCHAFT HOE 92/F 087 Dr. ~E/PP
Desc.ripl:ion Salts of 2-benzoylcyclohexanediones, selective herbi~idal agents, process for their preparation, and their use for controlling weed~
EP-A 137 963, EP-A-186 118, EP-A 274 634, ~P-A 298 680 and VS-4,780,127 disclose 2-benzoylcyclohexanedione deri-iatives which are described as agents for controlling a broad range of mono- and dicotyledon weeds.
WO 91/05470 discloses 2-benzoylcyclohexanedione deriva-tives which are selectiv2 in rice plants when applied at low dosage rates of active substance.
JP-A-3063-248 describes ammonium salts of 2-(2,4-di-chlorobenzoyl)cyclohexanedione and 2-(2-nitro-4-chloro-~nzoyl)cyclohexanedione which have a better ~electivity in rice when applied at do~age rates from 32 to 63 gha than 2-t2-nitro-4-chlorobenzoyl)c:yclohexanedione. The~e ammonium salts are highly phytotoxic at dosage rates above 63 g/ha. At the ~ame time, a broad action again~t weeds i~ only reached at dosage rAtes from 125 to 250 g/ha.
Surprisingly, it has now been found that salts of speci-fically ~ubstituted cyclohexanedione derivatives have an outstanding selectivity in rice and an excellent broad-range action against the harmful plants which occur typically in rice species. The broad ran~e of selectivity in rice allows even higher dosage rates of active ~ub-~tance to be used, resulting in a very broad control of weeds. Moreover, it has been found that the~e salts can be used highly selectively a~ainst some important harmful plants in other crops such as cereals and maize. The 2-benzoylcyclohexanediones on which they are based, in contrast, are not sufficiently effectiv2 in important useful crops such as maiæe and rice again~t the harmful 2~3 1~
plants which are typical in these ~ 80 that in ~ome cases only synergistic mixtures allow the 2-benzoylcyclo~
hexanedione derivatives ~o be used adequately (cf.
EP-A-274,634; WO 91/05469).
The compounds according to the invention control, in particular, perennial weeds which can be f ound in rice fields and which are frequently difficult to control, for example Sagittaria spec., Cyperus serotinus, Scirpus maritimus, Eleocharis 6pec. and Scirpus juncoides, as well as a broad range of annual weeds.
The present invention therefore relates to salts of 2-benzoylcyclohexanediones of the formula I
R ~ 7 x+ (I) in which Rl is halogen, (Cl-C4)alkoxy, (C~C4)alkyl, ( Cl-C4 ) halo-alkyl, -NO2, -CN or S~O~Rl;
R2 and R3 independently of one another are hydrogen, halogen, (C1-C4)alkyl, (Cl-C4)alkoxy, (Cl-C4)halo-alkoxy, (Cl-C4)haloalkyl, -CN, -NO2, -S(O~m-Rll, -NRl2Rl3, NRl4-co-Rl5, _co_R16;
R4, R6, R7, R8 and R9 independently of one another àre hydrogen or t Cl-C4 ) alkyl;
R5 is hydrogen, ( Cl-C4 ) alkyl or -CO-O-( C~-C4 ) alkyl;
R10 is ( Cl-C4 ) alkyl, ( C~-C4 ) haloalkyl or (C~-C4~alkoxy; 5 Rl1 is (Cl-C4~alkyl, (C~-C~)haloalkyl, phenyl, benzyl or _NRl7RlB;
2~31~
Rl2 and Rl3 independently of one another are hydrogen or (C~-C4)alkyl;
R14 is hydrogen or ( Cl-C4 ) alkyl;
R1~ is (C1-C4)alkyl;
Rl~ is hydrogen, (C1-C4)alkyl, (cl-c4)haloalkyl or ( C~-C4 ) alkoxy;
R17 and R1~ independently of one another are hydrogen or ~ C~-C4 ) alkyl and n and m independently of one another are 0, 1 or 2, and X+ is a metal cation equivalent such as, for example, an alkali me~al cation or alkaline earth metal cation equivalent, or, i~ appropriate, a ~ubstituted ammonium or phosphonium ion of the formula II
R19 y+ R21 (I~) in which Y i~ nitrogen or phosphoru~, R1~ is hydrogen, ~C~-C20)alkyl, ((7-C?n~alk Y 1 7~
alkoxy, it being possible for the last-mentioned radicals to be optionally monosu~stituted or poly-substituted by halogen, alkoxy, alkylthio or mono-or dialkylamino;
RZ, R2l and R22 independently of one another are hydrogen, (Cl-C20)alkyl, (C~~C~Q)alkenyl or (C~-C~o)aU~nyl, it being possible for these aliphatic radicals to ~e monosubstituted or poly3ub~tituted by halogen, amino, alkylamino or dialkylamino or to be inter-rupted once or more than once by heteroatom~ or heteroatom groups such as oxygen, sulfur, -N~- or -N(C1~C1~ yl; hy~(C1-C2~)alh~l, hydroxy(C2-C20)aIkenyl or -alkynyl, ~Cl-Cl2~alkylsulfonyl-(C~ 2)al~Yl, ~3-Clz)-cycloalkyl or tC3~Cl2)cycloalkenyl, it being po~si~le ~J ~
for these cycloaliphatic radicals to be monosub-stituted or polysubstituted by halogen, amino, alkylamino or dialkylamino, ~C~-Cl2)alXyl~ulfonyl, hydroxyl or (C~-C1a)alkoxy and/or to be intPrrupted once or more than once by heteroatoms or heteroatom groups ~uch as oxygen, sulfur, -N~-or-N(C1-C12)alkyl, or R2D, R21 and R22 independently of one another are a radical of the formula ( R 2 3 ~(CH2)q ~
in which p and q are 0, 1 or 2 and R23 i~ hydrogen, ( Cl-Cl2 ) alkyl, ( Cl-Cl2 ) alkoxy, ( Cl-C12 ) alkylthio~
(Cl~Cl2)alkylsulfonyl, CN, NO~, halogen, (C~-C~2)halo-alkyl, (C~-C 12 ) haloalkoxy, ~mino, (Cl-Cl2)alkylamino or tcl-cl2)dialkylamin or, in the event that Y is N, the radicals R20 and R
together with the nitrogen atom form a cycloali-phatic four- to twelve-membered ring sy~tem which i~
optionally monounsaturated or polyunsa~urated and which is optionally monosubstituted or polysubsti-tuted by halogen, (Cl-Ca)alkyl, (C3-C8)alkenyl (Cl-Ca)alkoxy, amino, (Cl-Ca)alkylamino, (Cl-C~)dial~
kylamino, phenyl, benzyl or hydroxyl and/or inter-rupted once or more than once by heteroatoms or heteroatom groups such as oxygen, sul~ur, ~NH- or -N~C1-C1z)alkyl;
or a sulfonium or ~ulfoxonium equivalent of the formula III
()r I
Rl9 S~ R21 ( III ) I
R~
in which R19, R20 and R2l have the abovementioned meaning and r i~ 0 or 1, and tautomeric forms thereof, with the exception of thoqe compounds in which R1 i8 chlorine or nitro, R2 is chlorine and R3 to ~9 are hydrogen.
Alkyl radicals are to be understood as meaning radicals with the stated number of carbon atoms. The radicals can be straight-chain or branched. The most common radicals are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl or tert.-butyl. Halogen is to be understood as meaning fluorine, chlorine, bromine or iodine. Haloalkyl radicals can be monosubstituted or polysubstituted by halogen, i.e. they can also be per-halogenated.
Preferred compounds of the abovementioned ~ormula (I) arethose in which Rl is fluorine, chlorine, bromine, iodine, methsxy, nitro, cyano or -S(0) nRl;
R2 and R3 independently of one another are hydrogen, fluorine, chlorine, bromine, iodine, methyl, meth-oxy, trifluoromethoxy, difluoromethoxy, cyano, nitro, trifluoromethyl, S02R~ NR12Rl3 -N(CH3)-Co-Rl5 or ~C0-0-~Cl-C4)-alkyl and R4, R5, R6, R7, R8 and R9 independently of one another ~re hydrogen or methyl and the remaining radicals h ve the abovementioned meanings.
2 ~ 9 31~ ~
Particularly preferred compounds of the formula (I) are those in which R2 and R3 independently of one another are hydrogen, fluorine, chlorine, bromine, -N(CH3~ 2 ~ methoxy, nitro, -SO2CH3, -SO2C2H5, -SO2CH2Cl, -SO2N(C~3)2, trifluoromethyl or difluoromethoxy.
Particularly suitable compounds of th~ form~la (I) according to the invention are ~he compounds in which 2-t2-chloro-4-methylsulfonylbenzoyl)-1,3-cyclohexane-dione, 2-~2-chloro-4-ethylsulfonyl~enzoyl)-1,3-cyclohexanedione, 2-(2-nitrobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione, 2-(2~chloro-4-ethylsulfonylbenzoyl)-5,5-dimethyl-1,3-cyclohexanedione, 2-~2-nitro--4-chlorobenzoyl)-4-(1-methylethyl) 1,3-cyclo-hexanedione, 2-(2-nitro-4-chlorobenzoyl)-4,4-d~methyl-1,3-cyclohexane-dione, 2-(2-chloro-4-methylsulfonylberlzoyl)-4,4-dimethyl-6-methyl-1,3-cyclohexanedione, 2-(2-nitro-4-methylsulfonylbenzoyl)-4,4-dimethyl-1,3-cyclohexanedione, 2-(2-nitro-4-di~luoromethoxybenzoyl)-1,3-cyclohexanedione or 2-(2-nitro-4-difluoromethoxybenzoyl)-4,4-dimethyl-1,3-cyclohexanedione are uset as a benzoylcyclohexanedione component.
The compounds of the formula (I) can exist in various tautomeric structures ~keto-enol tautomerism), the formula I describes only one of the tautomeric forms which are possible:
2~331~
R~ ~ R
I Ia ~7 :~-Ib The invention furthermore relates to a process for the preparation of compounds of the formula I, which com-prises replacing, in compounds of the formula IV
R2 ~ (IV) which also exist in various tautomeric structures, the acidic hydrogen atom by a cation of the formula X~
which is suitable for use in her~icides, by reacting them with the inorganic or organic bases on which the radical X+ is based.
Solvents which are generally used are protic or aprotic solvents such as, for sxample, water, msthanol, ethanol, isopropanol, n-butanol, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, acetone, ' 2~3 1~
methyl isobutyl ketone, dioxane, tetrahydrofuran or mixture~ of theRe ~olvent~, and the process is carried out at temperatures between -25C and ths reflux tempera-ture of the ~olvent, in particular between 0C and 60C.
The sequenc~ in which the reactant~ are added i~ not important. The educt~ are generally employed in ~toichio-metric amounts, depending on the valency of the cation.
Bases which are suitable for preparing the ~alts accord-ing to the invention are, for example, alkali metal carbonates such as potassium carbonate, alkali metal hydroxides and alkaline earth metal hydroxide~, ammonia, ethanolamine, triethylamine, diethylamine, piperidine, morpholine, diethanolamine, diallylamins, tri-n-propyl-amine, decylamine and dodecylamine.
The 2-benzoylcyclohexanedione derivatives of the form-ula (I) have been disclosed, ~ee, for example, EP-A-137,963, 186,118, 274,634 and 298,680, all of which have been mentioned above; UOS~ Patent 4,780,127, WO 91/13548 and EP 92,103,664.6, or they can be prepared ~y the methods described in these publications.
The present invention furthermore relates to a proces~
for the selective control of harmful plants in Grops o useful plants such as cereals, maize and, in particular, in rice crops, which comprises applying an effective amount of one or more compound~ of the formula I to the area under cultivation containing harmful plants and crop plants or their seeds. Active substance concentrations which are suitable are, for example, 0.001 to 0.5 kg/ha, preferably 0.01 to 0.25 kg/ha, in particular 0.02 to 0.20 kgtha, in rice crops and 0.01 to 2 kg/ha, preferably 0.05 to 1.0 kg/ha, in cereal~ or maizeO
The compounds employed according o the invention have an excPllent herbicidal activity against a broad range of economically important monocotyledon and dicotyledon ~ Q~
~ ~t9 ~3 _ ~ _ harmful plants. ~he active substances also act efficiPntly on perennial weeds which produce shoots from rhizomes, root stocks and other perennial organs and which are difficult to control. In this context, it does not matter whether the ~ubstance~ are applied pre-plant-ing, preemergence or post-emergence. Application pre-emergence and/or early post-emergence i8 preferred.
Specifically, examples may be mentioned of 80me repre-sentatives of the monocotyledon and dicotyledon weed flora which can be controlled by the agents according to the invention, without this mention being intended as a restriction to certain species.
Examples of monocotyledon weed species on which the active substance acts effectively are, from the annual group, Cyperus species and, from amongst the perennial species, perennial Cyperus species, Scirpus ~pecies and Eleocharis species.
The active substances to be employed according to the invention effect an outstanding control on weeds which occur under the specific agronomical conditions of rice such as, for example, Sagittaria, Alisma, Eleocharis, Scirpus, Cyperus etc..
In the case of the dicotyledon weed ~pecies, the spectrum of action extends, for example, to Rotala, Sphenoclea, Eclipta, Potamogeton, ~eteranthera, Aeschynomene and Ammania.
In addition, the active substance acts on weed species which can be found mainly in other crops such as cereal~
and maiza: examples of weed species on which the active substance acts effectively are, from among~t the mono-cotyledon weed species, for example, Avena, Lolium, Alopecurus, Ph~laris, Echinochloa, Di~itaria, Setaria a~
well as Cyperus species from the annual group and, from amongst the perennial specie~ Agropyron, Cynodon, 10 - ~
Imperata a8 well a~ Sorghum and al~o perennial Cyperus BpeCies. In the case of the dicotyledon weed specie~, the spectrum of action extends ~o species ~uch as, for example, Galium, Viola, Veronica, Lamium, St~llaria, ~maranthus, 5inapi~, Ipomoea, Matricaria, Abutilon and Sida from amongst the annuals as well as Convolvulus, Cirsium, Rumex and Axtemisia in ~he case of the perennial weed~.
If the compounds employed according to the invention are applied to the 80il ~urface before germination, then the weeds grow until they have reached the cotyledon stage but then their grow~h stops and, eventually, after three to four weeks have elapced, they die completely.
If the compounds of the formula (I) are applied post-emergence to the green parts of the plants, growthsimilarly ~tops drastically a very ~hort time after the treatment and the weed plants remain at the growth stage at the point of time of applica'tion, Qr they die com-pletely after a certain time, B0 that, in th.i~ manner~
competition by the weeds, which is harmful to the crop plants, is eliminated by the use of the compound~ of the formula ~I) according to the invention at a very early point in time and in a sustained manner.
Although the compounds employed according to the inven-tion have an outstanding herbicidal activity a~ainstmonocotyledon and dicotyledon weeds, crop plants of economically important CXOp8 such as, for example, wheat, barley, rye, maize, sugar beet, cotton and 80ya, and, in particular, rice crops of sown or transplanted rice, are not damayed at all, vr only to a negligible extent. For these reasons, the compounds of the formula 5I) are highly suitable for selectively controlling harmful plant9 in areas used for agricultural crop production~
preferably in cereals, maize and rice.
2~c~3~ ~5 The application rates of the compounds of the formula ~I) depend on the environment in terms of climate and ~oil and on the ~pecific harmful plants, the crops and the varieties in question, for example rice varieties. Late pre-emergence or early post-emergence application is particularly preferred.
The compounds of the formula (I) can be f~rmulated in various ways, depending on the prevailing biological and/or ~hemico-phy~ical parameters. Examples of possible formulations which are suitable ar~: wettable powders (WP), water-soluble powder~ (SP), emulsifiable concen-trate~ (EC), aqueous solutions or concentrates (SL), emulsions (EW) such as oil-in-water and water-in oil emulsions, sprayable solutions, capsule suspensions (CS), dispersions on an oil or water basi~, suspoemulsions, suspension concentrates (SC), dusts (DP), o:Ll-miscible solutions (OL), seed-dressing agents, granules (GR) in the form of microgranules, spray granules, coated gran-ules and adsorption granules, granules for soil applica-tion and for broadca~ting, wate~r-dispersible granules (WG), ULV formulations, microcapsules or waxes.
These individual formulation types are known in principle and described, for example, in:
Winnacker-Kuchler, ~'Chemische Technologie" [Chemical Technology], Volume 7, C. ~auser Verlag ~unich, 4th Ed.
1986; van ~alkenbur~, "Pesticides Formulations" Marcel Dekker, N.Y., 2nd Ed. 1972-1973; K. Narten3, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
The necessary formulation auxiliaries such as inert materials, urfactants, solvents and other additives are also known and described, for example, in: Watkins, "Handbook o~ Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; ~.v. Olphen, "Introduction to Clay Colloid Chemistxy"; 2nd Ed., J~
Wiley & sonB~ N.Y.; Mar~den, "Solvents Guide", 2nd Ed., 3 1 ~ ~
Inter cience, N.Y. 1950; McCutcheon~s ~Detergents and Emulsifiers Annual", ~C Publ. Corp., Ridgewood N.J.;
Sisley and Wood, ~Encyclopedia of Surface Active Ag~nts", Chem. Publ. Co. Inc., N.~ 64; Schonfeldt, "Grenzflàchenaktive ~thylenoxidaddukte" [Surface-active Ethylene oxide adduct6], Wis~ Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler, ~Chemi~che Technologie" tChem-ical Technology], Volume 7, C. ~auser Verlag, Nunich, ~th Ed., 1986.
Based on these formulations, it iB also possible to prepare combinations with other pesticidally active substances, such as other herbicides, fungicide~ or insecticides, or else safeners, fertilizers and/or growth regulators, for example in the form of a readymix or a tank mix.
Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also contain wetting agents, for example polyoxethylated alkylphenols, polyoxalkylated fatty alcohols, polyoxalkylated fatty~ amines, alkane- or alkylsulfonylbenzenesulfates, and dispersing agents, for example sodium ligninsulfonate, sodium 2,2'-dinaphthyl-methane-6,6'-disulfonate, sodium dibutylnaphthalenesul-fonate and also sodium oleoylmethyltaurate, in addition to a diluent or inert substance.
Emulsifia~le concentrates are pr~pared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene and also higher-boiling aromatic~ or hydrocarbons, wi~h the addition of one or more emulsifier~. Emulsifiers which can be used are, for example. calcium salts of alkylaryl-sulfonic acids, such as calcium dodecylbenzsnesulfonate or non-ionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyylycol ethers, propylene o~ide~ethylene oxid~
2~3~5 cond~nsation products, alkyl polyethers, ~orbitan fatty acid e~ters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.
Dusts are obtained by grinding the active substance with finely divided solid substances, for example talc or natural clays ~uch a8 kaolin~ bentonite, pyrophyllite, or diatomaceous earth.
Granules can be produced either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates onto the surface of carriers such as sand, kaolinites or of granulated inert material, by means of binder~, ~or example polyvinyl alcohol, sodium polyacrylate or alter-natively mineral oils.
Suitable active substance~ can also be granulated in the manner which iB conventional Eor the production of fertilizer granules, if desire~d in a mixture with fertilizer~.
As a rule, water-disper~ible granules are prepared by the customary methods ~uch as spray drying, fluidized-be~
granulation, disk granulation, mixing with high-speed stirrers and extrusion without 601id inert material.
The agrochemical preparations generally compri~e 0.1 to 99 percent by weight, in particular 0.1 to 95% by weight, of active ~ubstance of the formula (I~.
The active substance concentration in wettabla powders i6, for example, about 10 to 90~ by weight; the remainder to 100% by weight is composed of conventional formulation components. In th case of emulsifiable concentrates, the active substance concentration can be about 1 to 90%, preferably 5 to 80%, by weight. ~ormulations in the form of dusts contain 1 to 30, preferably in most cases 5 to X~13 ~ ~
20% by weight of active substance, ~prayable ~olutions about 0.05 to 80, preferably 2 to 50% by weight. In the case of water-dispersible granules, the active sub~tance content depends partly on whether the active compound i8 liquid or solid and on which granulation auxiliarie~, fillers etc. are u~ed. It i8 generally between 1 and 95, preferably between 10 and 80% by weight in the case of the water-dispersible granules.
In addition, the act.ive substance formulations mentioned comprise, if appropriate, the adhesives, wetting agents, dispersing agents, emulsifiers, penetrants, pr2serva-tives, anti-freeze agents, solv~nts, fillers, carriers, colorants, antifoam agents, ~vaporation inhibitors and p~
and viscoslty regulators which are conventional in each case.
A. Formulation example~
a) A dust is obtained by mixin~ 10 parts by weight of a compound of the formula (I) and 90 part~ by weight of talc as inert ~ubstanc~3 and comminuting the mixture in a hammer mill.
b) A wettable powder which is readily disper~ible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin-containing quartz as inert substance, 2~ 10 parts by weight of potassium ligninsulfonate and 1 part by weight of ~odium oleoylmethyltaurate a~
wetting and dispersing agent, and grinding the mixture in a pinned disk mill.
c) A di~persion concentrate which is readily di~pers-ible in water i8 obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight o~ alkylphenol polyglycol ether (~Triton X 207), 3 parts by weight of isotride~anol ~3~5 polyglycol ether (8 E0) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, approx. 255 to above 277C) and ~rinding the mixture in a ball mill to a finene~s of below S micron d) An emulsifiable concentrate i~ obtained from 15 parts by wPight of a compound of the formula (I), 75 parts by weight of cyclohexanone as ~olvent and 10 part~ by weight of oxethylated nonylphenol as emulsifier.
e) Water-dispersible granules are obtained by mixing parts by weight of active substance of the formula (I), 10 part~ by weight of calcium ligninsulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin, grinding the mixture in a pinned disk mill and granulating the powder in a ~Eluidized bed by ~pray-ing on water as granulation llqu~d.
~0 f) Water-disparsible granules are also obtained by homogenizing and precomminuting 25 parts by weight of active ~ubstance of the formula (I), 5 parts by weight of ~odium 2,2'-dinapthylmethane-6,6'-disul~onate, 2 parts by weight of sodium oleoylmethyltaurate, 1 part by weight of polyvinyl alcohol, 17 part by weight of calcium carbonate and 50 parts by weight of water in a colloi~ mill, subsequently grinding the mixture in a bead mill, and atomizing and drying th~
~ 3~3 resulting suspension in a sE)ray tower by means of a Gingle-sub~tance nozzle~
B. Chem-cal examples 1. Isopropylammonium ~alt of 2-(2-chloro-4-methyl~ul-fonylbenzoyl)-1,3-cyclohexanedione 1.6 g (0.0049 mol) of2-t2-chloro-4-methylsulfonyl)~
1,3-cyclohexanedione and 0.42 mol ~0.048 mol) of isopropylamine are combined at room temperature in 20 ml of dichloromethane and, after 2 hour~, the mixture i6 evaporated. 1.9 g ~100 % of theory) of the isopropylammonium salt of 2-(2-chloro-4-methyl-sulfonylbenzoyl)-1,3-cyclohexanedione of melting point 112C are obtained.
2. Sodium salt of2-(2-nitro-4-difluoromethoxyben20yl)-4,4-dimethyl-1,3-cyclohexanedione 2.13 g (0.006 mol) of 2-(2-nitro-4-difluoromethoxy-benzoyl)-4,4-dimathyl-1,3-cyclohsxanedione in 50 ml of methanol are combined, at room temperature, with 0.24 g (0.006 mol) NaOH dissolved in 5 ml of H20.
After 1 hour, the mixture i8 evaporated. 2.35 g (99 % of theory) of the sodium salt of 2-(2-nitro-~-difluoromethoxybenzoyl)-4,4-dLmethyl-1,3-cyclohex-anedione of melting point 160C are obtained.
The compounds listed in Table 1 are obtained analogously:
2 ~
~ 17 ~
_= =--_ _ e = _ ~ N ~ _ ¦~ ~ Y~ l = ~ T T I I = T
a~a: ~: I I I :1: I I
+ _ -~ _ _ :~ _ _ x 1~ I __ I :C I I I
1~: I __ O O O I I
o ~~ ~T ~ ~
~C I T I I T :C; I
NC O ~U~ T u~ O
~ _ I O ~ O Z oN o D w O _ C~J _ _ SD t~
E~
2 ~ ,s - la-= - = == - - :- - - =
~_ o ~ a:~ ~ r-_ _ . N _------ T - ----cna: I I I I I I I I I I I :~:
. __ . _ _ I I I I I :I: I I T T I
: I I I I I I I I I I t~
_ _ _ _ :r: I :C I I I I I :~: O ) I
Ul~r I I I I I I I ~.) I :1: I
~ __ _ _ ____ _ I I I I I I t~ I S~) I
1:1: :1: ~: S I :1: I I T 1 I ~
~ oN oN ~ ~ ~~ o o O ~~ ~ V l l L~= _ _ O ~,._ N C~) ~ Lf~ OE~ .- _ ,_ r -~ =~ =~ _ = =__ =
~r _ a'a: I I I T I I t.) :IC :i:
__ _ _ _ _ _ _ c~ I I I X t.~) O C~ I I
_ __ _ _ .
~ I $ I I I I I T
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U'a: I I I I I I I I
_ ._ ___ ul~r I I I I O I t:\ O
-- I . _ I I I I ~ ~ t ) . _ _ _ "'a: T I X ~ I :C I :1: T
_ . - _ _ .
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~3~`.3 C. Biological examples 1. Pre-emergence effect on weeds SePds or rhi20me pieces of monocotyledon and dicoty-ledon weed plants were placed in sandy loam soil in plastic pots and covered with soil. The active substances of the formula (I) which were fQr~ulated in the form of wettable powders or emulaion concen-trates were then applied to the surface o~ the 80il cover in the form of aqueous suspensions or emul-sion~ at an application rate of 600 to 800 1 of water/ha ~converted), at various dosage rates. After the treatment, the pots were placed in gre nhouse and kept under good growth conditions for the weeds.
After the test plants had emerged, the damage to the plants or the negative effect on plant emergence was scored visually after 3 to 4 week~ by comparison with untreated controls.
The damage to tha weed plants, or the compatibility with the crop plants, wa~ scored using a key in which the effectivene~s i8 expre~sed by ~igures from 0 to 5. The rigures denote:
0 = no effect 1 = 0 to 20 ~ effect or damase 2 = 20 to 40 ~ effect or damage 3 ~ 40 to 60 % effect or damage 4 = 60 to 80 ~ effect or damage 5 - 80 to 100 ~ effect or damage The active substances employed according to the invention showed a good herbicidal pre-emergence activity against a broad ran~e of gras~ weeds and broad-leaf weeds, while the rice plants ~uffered little damage, or none at all. ~ome re~ults ar~
compiled in Table 2.
2~3~
Table 2: Pre-emergence effect Ex. Dosage ~ idal activity No. rAte (kg of a. 9 ./ha) STME C~SE SIAL hOMU ECCR AVSA
1 1.25 5 5 5 5 5 4 . _ 2 1.~5 5 5 5 5 5 5 _ _ ____ _ 3 1.25 5 5 5 5 5 4 _ _ ~ 1~25 5 5 5 5 5 5 _ 1.25 5 5 5 5 5 5 _ 6 1.25 5 5 5 5 5 5 _ _ _ 7 1.25 5 5 5 5 5 5 _ 8 1.25 5 5 c; 5 5 4 _ _ _ _ 9 1.25 5 5 ~j 5 5 5 _ _ 1.25 5 5 c, 5 5 5 11 1.25 5 5 5 5 5 5 _ _ 12 1.25 5 5 5 5 5 5 30 ~ - ~ _ ~ _ ____~
Abbreviations:
STME = Stellaria media CHSE = Chrysanthemum segetum SIAL = Sinapis alba LOMU = Lolium multi~lorum ECCR = Echinochloa crus-galli ~VSA = Avena sativa a.~. - active substance 2 ~ 3 ~
2. Post~emergence effect on weeds Seeds or rhizome pieces of monocotyledon and dicoty-ledon weed plants were pl ced in sandy loam 80il in plastic pots and grown in the greenhouse under good growth condition~. Three weeks after sowing, the test plants are treated in the three-leaf ~tage.
The active substances of the formula (I) which were formulated as wettable powders or emulsion concen-trates are sprayed, at various dosage rates, onto the gxeen parts of the plants at an application rate of 300 to 600 l of water/ha (converted) and, after the test plants had remained in the greenhouse for approx. 3 to 4 weeks under optimum growth condi-tions, the effect of the preparations was scored visually by compari~on with untreated controls. The agents according to the invention al~o showed a good herbicidal po~t-emergence activity against a ~road range of economically important grass weeds and broad-leaf weeds (cf. Table 3).
2 ~ s Table 3: Post-emergence activity ~_ Ex. Dosage ~erbicidal activity No. rate (kg of a.s./ha) STME C~S~ SIAL ECCR
1 1.25 5 55 5 2 1.25 5 55 4 3 1.25 5 5-5 5 4 1.25 4 55 5 1.25 5 55 4 6 1.25 5 55 5 7 1.2~ 4 55 5 8 1.25 5 55 5 _ _ 9 1.25 5 55 5 ._ . _ 1.25 5 55 5 1.25 5 - 55 5 3. Effect on weeds and ~electivity in rice Weeds encountered specifically in rice growing as well as rice plants were grown in waterlogged soil.
The active sub~tance~ o the ormula (I~ formulated in the form of we table powder~ or emul6ion ~ ~ 9 3 ~ ¢ ~
concentrates were then applied to these plant~ at various do~age rates in the fo~m of aqueous ~uspen-sions or emulgiong at an application rate of 600 to 800 1 of water~ha (converted). After the treatment, S the pot~ were placed in ~he ~reenhouse. After the test plants had emerged after 3 to 4 weeks, they were scored visually by comparison with untreated controls.
The active substances employed according to the invention showed a good herbicidal pre-emerg~nce activity against a broad range of grass weeds and broad-leaf weeds, while the rice plants suffered little damage, or none at all. Some xesults are compiled in Table 4.
J3~5 Table 4 Pro- Dosage Herbicidal activity duct. rate ~kg S No. of a.s./ha) S~PY ELAC CYMO ORSA-V
1 o l25 5 5 5 2 o 125 5 5 55 _ 6 o 215~ 5 5 5 8 o 2125 55 55 55 _ 9 0.25 5 5 . 2 0.12 5 4 5 0 _ _ 0.25 5 5 5 0.12 5 4 ~ 0 11 o0 2152 5 45 s5 0 _ 12 ~ S S _ Abbreviations:
SAPY = Sagittaria pygmaea ~LAC = Eleocharis aciculariR
CYMO = Cyperus monti (= serotinus) ORSA-V = Oryza sativa (planted)
HOECHST AKTIENGESEI.LSCHAFT HOE 92/F 087 Dr. ~E/PP
Desc.ripl:ion Salts of 2-benzoylcyclohexanediones, selective herbi~idal agents, process for their preparation, and their use for controlling weed~
EP-A 137 963, EP-A-186 118, EP-A 274 634, ~P-A 298 680 and VS-4,780,127 disclose 2-benzoylcyclohexanedione deri-iatives which are described as agents for controlling a broad range of mono- and dicotyledon weeds.
WO 91/05470 discloses 2-benzoylcyclohexanedione deriva-tives which are selectiv2 in rice plants when applied at low dosage rates of active substance.
JP-A-3063-248 describes ammonium salts of 2-(2,4-di-chlorobenzoyl)cyclohexanedione and 2-(2-nitro-4-chloro-~nzoyl)cyclohexanedione which have a better ~electivity in rice when applied at do~age rates from 32 to 63 gha than 2-t2-nitro-4-chlorobenzoyl)c:yclohexanedione. The~e ammonium salts are highly phytotoxic at dosage rates above 63 g/ha. At the ~ame time, a broad action again~t weeds i~ only reached at dosage rAtes from 125 to 250 g/ha.
Surprisingly, it has now been found that salts of speci-fically ~ubstituted cyclohexanedione derivatives have an outstanding selectivity in rice and an excellent broad-range action against the harmful plants which occur typically in rice species. The broad ran~e of selectivity in rice allows even higher dosage rates of active ~ub-~tance to be used, resulting in a very broad control of weeds. Moreover, it has been found that the~e salts can be used highly selectively a~ainst some important harmful plants in other crops such as cereals and maize. The 2-benzoylcyclohexanediones on which they are based, in contrast, are not sufficiently effectiv2 in important useful crops such as maiæe and rice again~t the harmful 2~3 1~
plants which are typical in these ~ 80 that in ~ome cases only synergistic mixtures allow the 2-benzoylcyclo~
hexanedione derivatives ~o be used adequately (cf.
EP-A-274,634; WO 91/05469).
The compounds according to the invention control, in particular, perennial weeds which can be f ound in rice fields and which are frequently difficult to control, for example Sagittaria spec., Cyperus serotinus, Scirpus maritimus, Eleocharis 6pec. and Scirpus juncoides, as well as a broad range of annual weeds.
The present invention therefore relates to salts of 2-benzoylcyclohexanediones of the formula I
R ~ 7 x+ (I) in which Rl is halogen, (Cl-C4)alkoxy, (C~C4)alkyl, ( Cl-C4 ) halo-alkyl, -NO2, -CN or S~O~Rl;
R2 and R3 independently of one another are hydrogen, halogen, (C1-C4)alkyl, (Cl-C4)alkoxy, (Cl-C4)halo-alkoxy, (Cl-C4)haloalkyl, -CN, -NO2, -S(O~m-Rll, -NRl2Rl3, NRl4-co-Rl5, _co_R16;
R4, R6, R7, R8 and R9 independently of one another àre hydrogen or t Cl-C4 ) alkyl;
R5 is hydrogen, ( Cl-C4 ) alkyl or -CO-O-( C~-C4 ) alkyl;
R10 is ( Cl-C4 ) alkyl, ( C~-C4 ) haloalkyl or (C~-C4~alkoxy; 5 Rl1 is (Cl-C4~alkyl, (C~-C~)haloalkyl, phenyl, benzyl or _NRl7RlB;
2~31~
Rl2 and Rl3 independently of one another are hydrogen or (C~-C4)alkyl;
R14 is hydrogen or ( Cl-C4 ) alkyl;
R1~ is (C1-C4)alkyl;
Rl~ is hydrogen, (C1-C4)alkyl, (cl-c4)haloalkyl or ( C~-C4 ) alkoxy;
R17 and R1~ independently of one another are hydrogen or ~ C~-C4 ) alkyl and n and m independently of one another are 0, 1 or 2, and X+ is a metal cation equivalent such as, for example, an alkali me~al cation or alkaline earth metal cation equivalent, or, i~ appropriate, a ~ubstituted ammonium or phosphonium ion of the formula II
R19 y+ R21 (I~) in which Y i~ nitrogen or phosphoru~, R1~ is hydrogen, ~C~-C20)alkyl, ((7-C?n~alk Y 1 7~
alkoxy, it being possible for the last-mentioned radicals to be optionally monosu~stituted or poly-substituted by halogen, alkoxy, alkylthio or mono-or dialkylamino;
RZ, R2l and R22 independently of one another are hydrogen, (Cl-C20)alkyl, (C~~C~Q)alkenyl or (C~-C~o)aU~nyl, it being possible for these aliphatic radicals to ~e monosubstituted or poly3ub~tituted by halogen, amino, alkylamino or dialkylamino or to be inter-rupted once or more than once by heteroatom~ or heteroatom groups such as oxygen, sulfur, -N~- or -N(C1~C1~ yl; hy~(C1-C2~)alh~l, hydroxy(C2-C20)aIkenyl or -alkynyl, ~Cl-Cl2~alkylsulfonyl-(C~ 2)al~Yl, ~3-Clz)-cycloalkyl or tC3~Cl2)cycloalkenyl, it being po~si~le ~J ~
for these cycloaliphatic radicals to be monosub-stituted or polysubstituted by halogen, amino, alkylamino or dialkylamino, ~C~-Cl2)alXyl~ulfonyl, hydroxyl or (C~-C1a)alkoxy and/or to be intPrrupted once or more than once by heteroatoms or heteroatom groups ~uch as oxygen, sulfur, -N~-or-N(C1-C12)alkyl, or R2D, R21 and R22 independently of one another are a radical of the formula ( R 2 3 ~(CH2)q ~
in which p and q are 0, 1 or 2 and R23 i~ hydrogen, ( Cl-Cl2 ) alkyl, ( Cl-Cl2 ) alkoxy, ( Cl-C12 ) alkylthio~
(Cl~Cl2)alkylsulfonyl, CN, NO~, halogen, (C~-C~2)halo-alkyl, (C~-C 12 ) haloalkoxy, ~mino, (Cl-Cl2)alkylamino or tcl-cl2)dialkylamin or, in the event that Y is N, the radicals R20 and R
together with the nitrogen atom form a cycloali-phatic four- to twelve-membered ring sy~tem which i~
optionally monounsaturated or polyunsa~urated and which is optionally monosubstituted or polysubsti-tuted by halogen, (Cl-Ca)alkyl, (C3-C8)alkenyl (Cl-Ca)alkoxy, amino, (Cl-Ca)alkylamino, (Cl-C~)dial~
kylamino, phenyl, benzyl or hydroxyl and/or inter-rupted once or more than once by heteroatoms or heteroatom groups such as oxygen, sul~ur, ~NH- or -N~C1-C1z)alkyl;
or a sulfonium or ~ulfoxonium equivalent of the formula III
()r I
Rl9 S~ R21 ( III ) I
R~
in which R19, R20 and R2l have the abovementioned meaning and r i~ 0 or 1, and tautomeric forms thereof, with the exception of thoqe compounds in which R1 i8 chlorine or nitro, R2 is chlorine and R3 to ~9 are hydrogen.
Alkyl radicals are to be understood as meaning radicals with the stated number of carbon atoms. The radicals can be straight-chain or branched. The most common radicals are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl or tert.-butyl. Halogen is to be understood as meaning fluorine, chlorine, bromine or iodine. Haloalkyl radicals can be monosubstituted or polysubstituted by halogen, i.e. they can also be per-halogenated.
Preferred compounds of the abovementioned ~ormula (I) arethose in which Rl is fluorine, chlorine, bromine, iodine, methsxy, nitro, cyano or -S(0) nRl;
R2 and R3 independently of one another are hydrogen, fluorine, chlorine, bromine, iodine, methyl, meth-oxy, trifluoromethoxy, difluoromethoxy, cyano, nitro, trifluoromethyl, S02R~ NR12Rl3 -N(CH3)-Co-Rl5 or ~C0-0-~Cl-C4)-alkyl and R4, R5, R6, R7, R8 and R9 independently of one another ~re hydrogen or methyl and the remaining radicals h ve the abovementioned meanings.
2 ~ 9 31~ ~
Particularly preferred compounds of the formula (I) are those in which R2 and R3 independently of one another are hydrogen, fluorine, chlorine, bromine, -N(CH3~ 2 ~ methoxy, nitro, -SO2CH3, -SO2C2H5, -SO2CH2Cl, -SO2N(C~3)2, trifluoromethyl or difluoromethoxy.
Particularly suitable compounds of th~ form~la (I) according to the invention are ~he compounds in which 2-t2-chloro-4-methylsulfonylbenzoyl)-1,3-cyclohexane-dione, 2-~2-chloro-4-ethylsulfonyl~enzoyl)-1,3-cyclohexanedione, 2-(2-nitrobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione, 2-(2~chloro-4-ethylsulfonylbenzoyl)-5,5-dimethyl-1,3-cyclohexanedione, 2-~2-nitro--4-chlorobenzoyl)-4-(1-methylethyl) 1,3-cyclo-hexanedione, 2-(2-nitro-4-chlorobenzoyl)-4,4-d~methyl-1,3-cyclohexane-dione, 2-(2-chloro-4-methylsulfonylberlzoyl)-4,4-dimethyl-6-methyl-1,3-cyclohexanedione, 2-(2-nitro-4-methylsulfonylbenzoyl)-4,4-dimethyl-1,3-cyclohexanedione, 2-(2-nitro-4-di~luoromethoxybenzoyl)-1,3-cyclohexanedione or 2-(2-nitro-4-difluoromethoxybenzoyl)-4,4-dimethyl-1,3-cyclohexanedione are uset as a benzoylcyclohexanedione component.
The compounds of the formula (I) can exist in various tautomeric structures ~keto-enol tautomerism), the formula I describes only one of the tautomeric forms which are possible:
2~331~
R~ ~ R
I Ia ~7 :~-Ib The invention furthermore relates to a process for the preparation of compounds of the formula I, which com-prises replacing, in compounds of the formula IV
R2 ~ (IV) which also exist in various tautomeric structures, the acidic hydrogen atom by a cation of the formula X~
which is suitable for use in her~icides, by reacting them with the inorganic or organic bases on which the radical X+ is based.
Solvents which are generally used are protic or aprotic solvents such as, for sxample, water, msthanol, ethanol, isopropanol, n-butanol, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, acetone, ' 2~3 1~
methyl isobutyl ketone, dioxane, tetrahydrofuran or mixture~ of theRe ~olvent~, and the process is carried out at temperatures between -25C and ths reflux tempera-ture of the ~olvent, in particular between 0C and 60C.
The sequenc~ in which the reactant~ are added i~ not important. The educt~ are generally employed in ~toichio-metric amounts, depending on the valency of the cation.
Bases which are suitable for preparing the ~alts accord-ing to the invention are, for example, alkali metal carbonates such as potassium carbonate, alkali metal hydroxides and alkaline earth metal hydroxide~, ammonia, ethanolamine, triethylamine, diethylamine, piperidine, morpholine, diethanolamine, diallylamins, tri-n-propyl-amine, decylamine and dodecylamine.
The 2-benzoylcyclohexanedione derivatives of the form-ula (I) have been disclosed, ~ee, for example, EP-A-137,963, 186,118, 274,634 and 298,680, all of which have been mentioned above; UOS~ Patent 4,780,127, WO 91/13548 and EP 92,103,664.6, or they can be prepared ~y the methods described in these publications.
The present invention furthermore relates to a proces~
for the selective control of harmful plants in Grops o useful plants such as cereals, maize and, in particular, in rice crops, which comprises applying an effective amount of one or more compound~ of the formula I to the area under cultivation containing harmful plants and crop plants or their seeds. Active substance concentrations which are suitable are, for example, 0.001 to 0.5 kg/ha, preferably 0.01 to 0.25 kg/ha, in particular 0.02 to 0.20 kgtha, in rice crops and 0.01 to 2 kg/ha, preferably 0.05 to 1.0 kg/ha, in cereal~ or maizeO
The compounds employed according o the invention have an excPllent herbicidal activity against a broad range of economically important monocotyledon and dicotyledon ~ Q~
~ ~t9 ~3 _ ~ _ harmful plants. ~he active substances also act efficiPntly on perennial weeds which produce shoots from rhizomes, root stocks and other perennial organs and which are difficult to control. In this context, it does not matter whether the ~ubstance~ are applied pre-plant-ing, preemergence or post-emergence. Application pre-emergence and/or early post-emergence i8 preferred.
Specifically, examples may be mentioned of 80me repre-sentatives of the monocotyledon and dicotyledon weed flora which can be controlled by the agents according to the invention, without this mention being intended as a restriction to certain species.
Examples of monocotyledon weed species on which the active substance acts effectively are, from the annual group, Cyperus species and, from amongst the perennial species, perennial Cyperus species, Scirpus ~pecies and Eleocharis species.
The active substances to be employed according to the invention effect an outstanding control on weeds which occur under the specific agronomical conditions of rice such as, for example, Sagittaria, Alisma, Eleocharis, Scirpus, Cyperus etc..
In the case of the dicotyledon weed ~pecies, the spectrum of action extends, for example, to Rotala, Sphenoclea, Eclipta, Potamogeton, ~eteranthera, Aeschynomene and Ammania.
In addition, the active substance acts on weed species which can be found mainly in other crops such as cereal~
and maiza: examples of weed species on which the active substance acts effectively are, from among~t the mono-cotyledon weed species, for example, Avena, Lolium, Alopecurus, Ph~laris, Echinochloa, Di~itaria, Setaria a~
well as Cyperus species from the annual group and, from amongst the perennial specie~ Agropyron, Cynodon, 10 - ~
Imperata a8 well a~ Sorghum and al~o perennial Cyperus BpeCies. In the case of the dicotyledon weed specie~, the spectrum of action extends ~o species ~uch as, for example, Galium, Viola, Veronica, Lamium, St~llaria, ~maranthus, 5inapi~, Ipomoea, Matricaria, Abutilon and Sida from amongst the annuals as well as Convolvulus, Cirsium, Rumex and Axtemisia in ~he case of the perennial weed~.
If the compounds employed according to the invention are applied to the 80il ~urface before germination, then the weeds grow until they have reached the cotyledon stage but then their grow~h stops and, eventually, after three to four weeks have elapced, they die completely.
If the compounds of the formula (I) are applied post-emergence to the green parts of the plants, growthsimilarly ~tops drastically a very ~hort time after the treatment and the weed plants remain at the growth stage at the point of time of applica'tion, Qr they die com-pletely after a certain time, B0 that, in th.i~ manner~
competition by the weeds, which is harmful to the crop plants, is eliminated by the use of the compound~ of the formula ~I) according to the invention at a very early point in time and in a sustained manner.
Although the compounds employed according to the inven-tion have an outstanding herbicidal activity a~ainstmonocotyledon and dicotyledon weeds, crop plants of economically important CXOp8 such as, for example, wheat, barley, rye, maize, sugar beet, cotton and 80ya, and, in particular, rice crops of sown or transplanted rice, are not damayed at all, vr only to a negligible extent. For these reasons, the compounds of the formula 5I) are highly suitable for selectively controlling harmful plant9 in areas used for agricultural crop production~
preferably in cereals, maize and rice.
2~c~3~ ~5 The application rates of the compounds of the formula ~I) depend on the environment in terms of climate and ~oil and on the ~pecific harmful plants, the crops and the varieties in question, for example rice varieties. Late pre-emergence or early post-emergence application is particularly preferred.
The compounds of the formula (I) can be f~rmulated in various ways, depending on the prevailing biological and/or ~hemico-phy~ical parameters. Examples of possible formulations which are suitable ar~: wettable powders (WP), water-soluble powder~ (SP), emulsifiable concen-trate~ (EC), aqueous solutions or concentrates (SL), emulsions (EW) such as oil-in-water and water-in oil emulsions, sprayable solutions, capsule suspensions (CS), dispersions on an oil or water basi~, suspoemulsions, suspension concentrates (SC), dusts (DP), o:Ll-miscible solutions (OL), seed-dressing agents, granules (GR) in the form of microgranules, spray granules, coated gran-ules and adsorption granules, granules for soil applica-tion and for broadca~ting, wate~r-dispersible granules (WG), ULV formulations, microcapsules or waxes.
These individual formulation types are known in principle and described, for example, in:
Winnacker-Kuchler, ~'Chemische Technologie" [Chemical Technology], Volume 7, C. ~auser Verlag ~unich, 4th Ed.
1986; van ~alkenbur~, "Pesticides Formulations" Marcel Dekker, N.Y., 2nd Ed. 1972-1973; K. Narten3, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
The necessary formulation auxiliaries such as inert materials, urfactants, solvents and other additives are also known and described, for example, in: Watkins, "Handbook o~ Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; ~.v. Olphen, "Introduction to Clay Colloid Chemistxy"; 2nd Ed., J~
Wiley & sonB~ N.Y.; Mar~den, "Solvents Guide", 2nd Ed., 3 1 ~ ~
Inter cience, N.Y. 1950; McCutcheon~s ~Detergents and Emulsifiers Annual", ~C Publ. Corp., Ridgewood N.J.;
Sisley and Wood, ~Encyclopedia of Surface Active Ag~nts", Chem. Publ. Co. Inc., N.~ 64; Schonfeldt, "Grenzflàchenaktive ~thylenoxidaddukte" [Surface-active Ethylene oxide adduct6], Wis~ Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler, ~Chemi~che Technologie" tChem-ical Technology], Volume 7, C. ~auser Verlag, Nunich, ~th Ed., 1986.
Based on these formulations, it iB also possible to prepare combinations with other pesticidally active substances, such as other herbicides, fungicide~ or insecticides, or else safeners, fertilizers and/or growth regulators, for example in the form of a readymix or a tank mix.
Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also contain wetting agents, for example polyoxethylated alkylphenols, polyoxalkylated fatty alcohols, polyoxalkylated fatty~ amines, alkane- or alkylsulfonylbenzenesulfates, and dispersing agents, for example sodium ligninsulfonate, sodium 2,2'-dinaphthyl-methane-6,6'-disulfonate, sodium dibutylnaphthalenesul-fonate and also sodium oleoylmethyltaurate, in addition to a diluent or inert substance.
Emulsifia~le concentrates are pr~pared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene and also higher-boiling aromatic~ or hydrocarbons, wi~h the addition of one or more emulsifier~. Emulsifiers which can be used are, for example. calcium salts of alkylaryl-sulfonic acids, such as calcium dodecylbenzsnesulfonate or non-ionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyylycol ethers, propylene o~ide~ethylene oxid~
2~3~5 cond~nsation products, alkyl polyethers, ~orbitan fatty acid e~ters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.
Dusts are obtained by grinding the active substance with finely divided solid substances, for example talc or natural clays ~uch a8 kaolin~ bentonite, pyrophyllite, or diatomaceous earth.
Granules can be produced either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates onto the surface of carriers such as sand, kaolinites or of granulated inert material, by means of binder~, ~or example polyvinyl alcohol, sodium polyacrylate or alter-natively mineral oils.
Suitable active substance~ can also be granulated in the manner which iB conventional Eor the production of fertilizer granules, if desire~d in a mixture with fertilizer~.
As a rule, water-disper~ible granules are prepared by the customary methods ~uch as spray drying, fluidized-be~
granulation, disk granulation, mixing with high-speed stirrers and extrusion without 601id inert material.
The agrochemical preparations generally compri~e 0.1 to 99 percent by weight, in particular 0.1 to 95% by weight, of active ~ubstance of the formula (I~.
The active substance concentration in wettabla powders i6, for example, about 10 to 90~ by weight; the remainder to 100% by weight is composed of conventional formulation components. In th case of emulsifiable concentrates, the active substance concentration can be about 1 to 90%, preferably 5 to 80%, by weight. ~ormulations in the form of dusts contain 1 to 30, preferably in most cases 5 to X~13 ~ ~
20% by weight of active substance, ~prayable ~olutions about 0.05 to 80, preferably 2 to 50% by weight. In the case of water-dispersible granules, the active sub~tance content depends partly on whether the active compound i8 liquid or solid and on which granulation auxiliarie~, fillers etc. are u~ed. It i8 generally between 1 and 95, preferably between 10 and 80% by weight in the case of the water-dispersible granules.
In addition, the act.ive substance formulations mentioned comprise, if appropriate, the adhesives, wetting agents, dispersing agents, emulsifiers, penetrants, pr2serva-tives, anti-freeze agents, solv~nts, fillers, carriers, colorants, antifoam agents, ~vaporation inhibitors and p~
and viscoslty regulators which are conventional in each case.
A. Formulation example~
a) A dust is obtained by mixin~ 10 parts by weight of a compound of the formula (I) and 90 part~ by weight of talc as inert ~ubstanc~3 and comminuting the mixture in a hammer mill.
b) A wettable powder which is readily disper~ible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin-containing quartz as inert substance, 2~ 10 parts by weight of potassium ligninsulfonate and 1 part by weight of ~odium oleoylmethyltaurate a~
wetting and dispersing agent, and grinding the mixture in a pinned disk mill.
c) A di~persion concentrate which is readily di~pers-ible in water i8 obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight o~ alkylphenol polyglycol ether (~Triton X 207), 3 parts by weight of isotride~anol ~3~5 polyglycol ether (8 E0) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, approx. 255 to above 277C) and ~rinding the mixture in a ball mill to a finene~s of below S micron d) An emulsifiable concentrate i~ obtained from 15 parts by wPight of a compound of the formula (I), 75 parts by weight of cyclohexanone as ~olvent and 10 part~ by weight of oxethylated nonylphenol as emulsifier.
e) Water-dispersible granules are obtained by mixing parts by weight of active substance of the formula (I), 10 part~ by weight of calcium ligninsulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin, grinding the mixture in a pinned disk mill and granulating the powder in a ~Eluidized bed by ~pray-ing on water as granulation llqu~d.
~0 f) Water-disparsible granules are also obtained by homogenizing and precomminuting 25 parts by weight of active ~ubstance of the formula (I), 5 parts by weight of ~odium 2,2'-dinapthylmethane-6,6'-disul~onate, 2 parts by weight of sodium oleoylmethyltaurate, 1 part by weight of polyvinyl alcohol, 17 part by weight of calcium carbonate and 50 parts by weight of water in a colloi~ mill, subsequently grinding the mixture in a bead mill, and atomizing and drying th~
~ 3~3 resulting suspension in a sE)ray tower by means of a Gingle-sub~tance nozzle~
B. Chem-cal examples 1. Isopropylammonium ~alt of 2-(2-chloro-4-methyl~ul-fonylbenzoyl)-1,3-cyclohexanedione 1.6 g (0.0049 mol) of2-t2-chloro-4-methylsulfonyl)~
1,3-cyclohexanedione and 0.42 mol ~0.048 mol) of isopropylamine are combined at room temperature in 20 ml of dichloromethane and, after 2 hour~, the mixture i6 evaporated. 1.9 g ~100 % of theory) of the isopropylammonium salt of 2-(2-chloro-4-methyl-sulfonylbenzoyl)-1,3-cyclohexanedione of melting point 112C are obtained.
2. Sodium salt of2-(2-nitro-4-difluoromethoxyben20yl)-4,4-dimethyl-1,3-cyclohexanedione 2.13 g (0.006 mol) of 2-(2-nitro-4-difluoromethoxy-benzoyl)-4,4-dimathyl-1,3-cyclohsxanedione in 50 ml of methanol are combined, at room temperature, with 0.24 g (0.006 mol) NaOH dissolved in 5 ml of H20.
After 1 hour, the mixture i8 evaporated. 2.35 g (99 % of theory) of the sodium salt of 2-(2-nitro-~-difluoromethoxybenzoyl)-4,4-dLmethyl-1,3-cyclohex-anedione of melting point 160C are obtained.
The compounds listed in Table 1 are obtained analogously:
2 ~
~ 17 ~
_= =--_ _ e = _ ~ N ~ _ ¦~ ~ Y~ l = ~ T T I I = T
a~a: ~: I I I :1: I I
+ _ -~ _ _ :~ _ _ x 1~ I __ I :C I I I
1~: I __ O O O I I
o ~~ ~T ~ ~
~C I T I I T :C; I
NC O ~U~ T u~ O
~ _ I O ~ O Z oN o D w O _ C~J _ _ SD t~
E~
2 ~ ,s - la-= - = == - - :- - - =
~_ o ~ a:~ ~ r-_ _ . N _------ T - ----cna: I I I I I I I I I I I :~:
. __ . _ _ I I I I I :I: I I T T I
: I I I I I I I I I I t~
_ _ _ _ :r: I :C I I I I I :~: O ) I
Ul~r I I I I I I I ~.) I :1: I
~ __ _ _ ____ _ I I I I I I t~ I S~) I
1:1: :1: ~: S I :1: I I T 1 I ~
~ oN oN ~ ~ ~~ o o O ~~ ~ V l l L~= _ _ O ~,._ N C~) ~ Lf~ OE~ .- _ ,_ r -~ =~ =~ _ = =__ =
~r _ a'a: I I I T I I t.) :IC :i:
__ _ _ _ _ _ _ c~ I I I X t.~) O C~ I I
_ __ _ _ .
~ I $ I I I I I T
_ .
U'a: I I I I I I I I
_ ._ ___ ul~r I I I I O I t:\ O
-- I . _ I I I I ~ ~ t ) . _ _ _ "'a: T I X ~ I :C I :1: T
_ . - _ _ .
C~~ O" oN ~o~N ~ ~æ ~'~ oN ~~
_ _ . .
-a: ~ ~ ~ ~ ~ o ~ ~ ~
_ _ _ _ _ __ ~ _ ~ ___ ~ ~n æ ._ ~
~3~`.3 C. Biological examples 1. Pre-emergence effect on weeds SePds or rhi20me pieces of monocotyledon and dicoty-ledon weed plants were placed in sandy loam soil in plastic pots and covered with soil. The active substances of the formula (I) which were fQr~ulated in the form of wettable powders or emulaion concen-trates were then applied to the surface o~ the 80il cover in the form of aqueous suspensions or emul-sion~ at an application rate of 600 to 800 1 of water/ha ~converted), at various dosage rates. After the treatment, the pots were placed in gre nhouse and kept under good growth conditions for the weeds.
After the test plants had emerged, the damage to the plants or the negative effect on plant emergence was scored visually after 3 to 4 week~ by comparison with untreated controls.
The damage to tha weed plants, or the compatibility with the crop plants, wa~ scored using a key in which the effectivene~s i8 expre~sed by ~igures from 0 to 5. The rigures denote:
0 = no effect 1 = 0 to 20 ~ effect or damase 2 = 20 to 40 ~ effect or damage 3 ~ 40 to 60 % effect or damage 4 = 60 to 80 ~ effect or damage 5 - 80 to 100 ~ effect or damage The active substances employed according to the invention showed a good herbicidal pre-emergence activity against a broad ran~e of gras~ weeds and broad-leaf weeds, while the rice plants ~uffered little damage, or none at all. ~ome re~ults ar~
compiled in Table 2.
2~3~
Table 2: Pre-emergence effect Ex. Dosage ~ idal activity No. rAte (kg of a. 9 ./ha) STME C~SE SIAL hOMU ECCR AVSA
1 1.25 5 5 5 5 5 4 . _ 2 1.~5 5 5 5 5 5 5 _ _ ____ _ 3 1.25 5 5 5 5 5 4 _ _ ~ 1~25 5 5 5 5 5 5 _ 1.25 5 5 5 5 5 5 _ 6 1.25 5 5 5 5 5 5 _ _ _ 7 1.25 5 5 5 5 5 5 _ 8 1.25 5 5 c; 5 5 4 _ _ _ _ 9 1.25 5 5 ~j 5 5 5 _ _ 1.25 5 5 c, 5 5 5 11 1.25 5 5 5 5 5 5 _ _ 12 1.25 5 5 5 5 5 5 30 ~ - ~ _ ~ _ ____~
Abbreviations:
STME = Stellaria media CHSE = Chrysanthemum segetum SIAL = Sinapis alba LOMU = Lolium multi~lorum ECCR = Echinochloa crus-galli ~VSA = Avena sativa a.~. - active substance 2 ~ 3 ~
2. Post~emergence effect on weeds Seeds or rhizome pieces of monocotyledon and dicoty-ledon weed plants were pl ced in sandy loam 80il in plastic pots and grown in the greenhouse under good growth condition~. Three weeks after sowing, the test plants are treated in the three-leaf ~tage.
The active substances of the formula (I) which were formulated as wettable powders or emulsion concen-trates are sprayed, at various dosage rates, onto the gxeen parts of the plants at an application rate of 300 to 600 l of water/ha (converted) and, after the test plants had remained in the greenhouse for approx. 3 to 4 weeks under optimum growth condi-tions, the effect of the preparations was scored visually by compari~on with untreated controls. The agents according to the invention al~o showed a good herbicidal po~t-emergence activity against a ~road range of economically important grass weeds and broad-leaf weeds (cf. Table 3).
2 ~ s Table 3: Post-emergence activity ~_ Ex. Dosage ~erbicidal activity No. rate (kg of a.s./ha) STME C~S~ SIAL ECCR
1 1.25 5 55 5 2 1.25 5 55 4 3 1.25 5 5-5 5 4 1.25 4 55 5 1.25 5 55 4 6 1.25 5 55 5 7 1.2~ 4 55 5 8 1.25 5 55 5 _ _ 9 1.25 5 55 5 ._ . _ 1.25 5 55 5 1.25 5 - 55 5 3. Effect on weeds and ~electivity in rice Weeds encountered specifically in rice growing as well as rice plants were grown in waterlogged soil.
The active sub~tance~ o the ormula (I~ formulated in the form of we table powder~ or emul6ion ~ ~ 9 3 ~ ¢ ~
concentrates were then applied to these plant~ at various do~age rates in the fo~m of aqueous ~uspen-sions or emulgiong at an application rate of 600 to 800 1 of water~ha (converted). After the treatment, S the pot~ were placed in ~he ~reenhouse. After the test plants had emerged after 3 to 4 weeks, they were scored visually by comparison with untreated controls.
The active substances employed according to the invention showed a good herbicidal pre-emerg~nce activity against a broad range of grass weeds and broad-leaf weeds, while the rice plants suffered little damage, or none at all. Some xesults are compiled in Table 4.
J3~5 Table 4 Pro- Dosage Herbicidal activity duct. rate ~kg S No. of a.s./ha) S~PY ELAC CYMO ORSA-V
1 o l25 5 5 5 2 o 125 5 5 55 _ 6 o 215~ 5 5 5 8 o 2125 55 55 55 _ 9 0.25 5 5 . 2 0.12 5 4 5 0 _ _ 0.25 5 5 5 0.12 5 4 ~ 0 11 o0 2152 5 45 s5 0 _ 12 ~ S S _ Abbreviations:
SAPY = Sagittaria pygmaea ~LAC = Eleocharis aciculariR
CYMO = Cyperus monti (= serotinus) ORSA-V = Oryza sativa (planted)
Claims (10)
1. A salt of a 2-benzoylcyclohexanedione of the formula I
(I) in which R1 is halogen, (C1-C4)alkoxy, (C1-C4)alkyl, (C1-C4)halo-alkyl, -NO2, -CN or S(O)nR10;
R2 and R3 independently of one another are hydrogen, halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)halo-alkoxy, (C1-C4)haloalkyl, -CN, -NO2, -S(O)m-R11, -NR12R13, -NR14-CO-R15 -CO-R16;
R4, R6, R7, R8 and R9 independently of one another are hydrogen or (C1-C4)alkyl;
R5 is hydrogen, (C1-C4)alkyl or -CO-O-(C1-C4)alkyl;
R10 is (C1-C4)alkyl, (C1-C4)haloalkyl or (C1-C4)alkoxy;
R11 is (C1-C4)alkyl, (C1-C4)haloalkyl, phenyl, benzyl or -NR17R18;
R12 and R13 independently of one another are hydrogen or (C1-C4)alkyl;
R14 is hydrogen or (C1-C4)alkyl;
R15 is (C1-C4)alkyl;
R16 is hydrogen, (C1-C4)alkyl, (C1-C4)haloalkyl or (C1-C4)alkoxy;
R17 and R18 independently of one another are hydrogen or (C1-C4) alkyl and n and m independently of one another are 0, 1 or 2, and X+ is a metal cation equivalent, or an unsubstituted or substituted ammonium or phosphonium ion of the formula II
(II) in which Y is nitrogen or phosphorus, R19 is hydrogen, (C1-C20)alkyl, (C2-C20)alkenyl or (C1-C20)-alkoxy, it being possible for the last-mentioned radicals to be optionally monosubstituted or poly-substituted by halogen, alkoxy, alkylthio or mono-or dialkylamino;
R20, R21 and R22 independently of one another are hydrogen, (C1-C20)alkyl, (C2-C20)alkenyl or (C2-C20)alkenyl, it being possible for these aliphatic radicals to be monosubstituted or polysubstituted by halogen, amino, alkylamino or dialkylamino or to be inter-rupted once or more than once by heteroatoms or heteroatom groups; or are hydroxy(C1-C20)alkyl, hydroxy(C2-C20)alkenyl or -alkynyl, (C1-C12)alkylsulfonyl-(C1-C12)alkyl, (C3-C12)-cycloalkyl or (C3-C12)cycloalkenyl, it being possible for these cycloaliphatic radicals to be monosubsti-tuted or polysubstituted by halogen, amino, alkyl-amino or dialkylamino, (C1-C12)alkylsulfonyl, hydroxyl or (C1-C12)alkoxy and/or to be interrupted once or more than once by heteroatoms or heteroatom groups, or R20, R21 and R22 independently of one another are a radical of the formula in which p and q are 0, 1 or 2 and R23 is hydrogen, (C1-C12)alkyl, (C1-C12)alkoxy, (C1-C12)alkylthio, (C1-C12)alkylsulfonyl, CN, NO2, halogen, (C1-C12)halo-alkyl, (C1-C12)haloalkoxy, amino, (C1-C12)alkylamino or (C1-C12)dialkylamino, or, in the event that Y is N, the radicals R20 and R21 together with the nitrogen atom form a cycloali-phatic four- to twelve-membered ring system which is optionally monounsaturated or polyunsaturated and which is optionally monosubstituted or polysubsti-tuted by halogen, (C1-C8)alkyl, (C3-C8)alkenyl, (C1-C8)alkoxy, amino, (C1-C8)alkylamino, (C1-C8)dial-kylamino, phenyl, benzyl or hydroxyl and/or inter-rupted once or more than once by heteroatoms or heteroatom groups, or are a sulfonium or sulfoxonium equivalent of the formula III
(III) in which R19, R20 and R21 have the abovementioned meaning and r is 0 or 1, and tautomeric forms thereof, with the exception of those compound in which R1 is chlorine or nitro, R2 is chlorine and R3 to R9 are hydrogen.
(I) in which R1 is halogen, (C1-C4)alkoxy, (C1-C4)alkyl, (C1-C4)halo-alkyl, -NO2, -CN or S(O)nR10;
R2 and R3 independently of one another are hydrogen, halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)halo-alkoxy, (C1-C4)haloalkyl, -CN, -NO2, -S(O)m-R11, -NR12R13, -NR14-CO-R15 -CO-R16;
R4, R6, R7, R8 and R9 independently of one another are hydrogen or (C1-C4)alkyl;
R5 is hydrogen, (C1-C4)alkyl or -CO-O-(C1-C4)alkyl;
R10 is (C1-C4)alkyl, (C1-C4)haloalkyl or (C1-C4)alkoxy;
R11 is (C1-C4)alkyl, (C1-C4)haloalkyl, phenyl, benzyl or -NR17R18;
R12 and R13 independently of one another are hydrogen or (C1-C4)alkyl;
R14 is hydrogen or (C1-C4)alkyl;
R15 is (C1-C4)alkyl;
R16 is hydrogen, (C1-C4)alkyl, (C1-C4)haloalkyl or (C1-C4)alkoxy;
R17 and R18 independently of one another are hydrogen or (C1-C4) alkyl and n and m independently of one another are 0, 1 or 2, and X+ is a metal cation equivalent, or an unsubstituted or substituted ammonium or phosphonium ion of the formula II
(II) in which Y is nitrogen or phosphorus, R19 is hydrogen, (C1-C20)alkyl, (C2-C20)alkenyl or (C1-C20)-alkoxy, it being possible for the last-mentioned radicals to be optionally monosubstituted or poly-substituted by halogen, alkoxy, alkylthio or mono-or dialkylamino;
R20, R21 and R22 independently of one another are hydrogen, (C1-C20)alkyl, (C2-C20)alkenyl or (C2-C20)alkenyl, it being possible for these aliphatic radicals to be monosubstituted or polysubstituted by halogen, amino, alkylamino or dialkylamino or to be inter-rupted once or more than once by heteroatoms or heteroatom groups; or are hydroxy(C1-C20)alkyl, hydroxy(C2-C20)alkenyl or -alkynyl, (C1-C12)alkylsulfonyl-(C1-C12)alkyl, (C3-C12)-cycloalkyl or (C3-C12)cycloalkenyl, it being possible for these cycloaliphatic radicals to be monosubsti-tuted or polysubstituted by halogen, amino, alkyl-amino or dialkylamino, (C1-C12)alkylsulfonyl, hydroxyl or (C1-C12)alkoxy and/or to be interrupted once or more than once by heteroatoms or heteroatom groups, or R20, R21 and R22 independently of one another are a radical of the formula in which p and q are 0, 1 or 2 and R23 is hydrogen, (C1-C12)alkyl, (C1-C12)alkoxy, (C1-C12)alkylthio, (C1-C12)alkylsulfonyl, CN, NO2, halogen, (C1-C12)halo-alkyl, (C1-C12)haloalkoxy, amino, (C1-C12)alkylamino or (C1-C12)dialkylamino, or, in the event that Y is N, the radicals R20 and R21 together with the nitrogen atom form a cycloali-phatic four- to twelve-membered ring system which is optionally monounsaturated or polyunsaturated and which is optionally monosubstituted or polysubsti-tuted by halogen, (C1-C8)alkyl, (C3-C8)alkenyl, (C1-C8)alkoxy, amino, (C1-C8)alkylamino, (C1-C8)dial-kylamino, phenyl, benzyl or hydroxyl and/or inter-rupted once or more than once by heteroatoms or heteroatom groups, or are a sulfonium or sulfoxonium equivalent of the formula III
(III) in which R19, R20 and R21 have the abovementioned meaning and r is 0 or 1, and tautomeric forms thereof, with the exception of those compound in which R1 is chlorine or nitro, R2 is chlorine and R3 to R9 are hydrogen.
2. A compound as claimed in claim 1, wherein R1 is fluorine, chlorine, bromine, iodine, methoxy, nitro, cyano or -S(O)nR10;
R2 and R3 independently of one another are hydrogen, fluorine, chlorine, bromine, iodine; methyl, meth-oxy, trifluoromethoxy, difluoromethoxy, cyano, nitro, trifluoromethyl, -SO2R11, -NR12R13 -N(CH3)-CO-R15 or -CO-O-(C1-C4)-alkyl and R4, R5, R6, R7, R8 and R9 independently of one another are hydrogen or methyl.
R2 and R3 independently of one another are hydrogen, fluorine, chlorine, bromine, iodine; methyl, meth-oxy, trifluoromethoxy, difluoromethoxy, cyano, nitro, trifluoromethyl, -SO2R11, -NR12R13 -N(CH3)-CO-R15 or -CO-O-(C1-C4)-alkyl and R4, R5, R6, R7, R8 and R9 independently of one another are hydrogen or methyl.
3. A compound as claimed in claim 1 or 2, wherein R2 and R3 independently of one another are hydrogen, fluorine, chlorine, bromine, -N(CH3)2, methoxy, nitro, -SO2CH3, -SO2C2H5, -SO2CH2Cl, -SO2N(CH3)2 trifluoromethyl or difluoromethoxy.
4. A process for the preparation of compounds of the formula I as defined in claim 1, which comprises replacing, in compounds of the formula IV, (IV) the acidic hydrogen atom by a cation of the formula X+
which is suitable for use in herbicides, by reacting them with the inorganic or organic bases on which the radical X+ is based.
which is suitable for use in herbicides, by reacting them with the inorganic or organic bases on which the radical X+ is based.
5. The process as claimed in claim 4, wherein one of the compounds below is used as compound of the formula IV:
2-(2-chloro-4-methylsulfonylbenzoyl)-1,3-cyclohexane-dione, 2-(2-chloro-4-ethylsulfonylbenzoyl)-1,3-cyclohexanedione, 2-(2-nitrobenzoyl)-4,4-dimethyl-1,3-cyclohaxanedione, 2-(2-chloro-4-ethylsulfonylbenzoyl)-5,5-dimethyl-1,3-cyclohexanedione, 2-(2-nitro-4-chlorobenzoyl)-4-(1-methylethyl)-1,3-cyclo-hexanedione, 2-(2-nitro-4-chlorobenzoyl)-4,4-dimethyl-1,3-cyclohexane-dione, 2-(2-chloro-4-methylsulfonylbenzoyl)-4,4-dimethyl-6-methyl-1,3-cyclohexanedione, 2-(2-nitro-4-methylsulfonylbenzoyl)-4,4-dimethyl-1,3-cyclohexanedione, 2-(2-nitro-4-difluoromethoxybenzoyl)-1,3-cyclohexanedione or 2-(2-nitro-4-difluoromethoxybenzoyl)-4,4-dimethyl-1,3-cyclohexanedione.
2-(2-chloro-4-methylsulfonylbenzoyl)-1,3-cyclohexane-dione, 2-(2-chloro-4-ethylsulfonylbenzoyl)-1,3-cyclohexanedione, 2-(2-nitrobenzoyl)-4,4-dimethyl-1,3-cyclohaxanedione, 2-(2-chloro-4-ethylsulfonylbenzoyl)-5,5-dimethyl-1,3-cyclohexanedione, 2-(2-nitro-4-chlorobenzoyl)-4-(1-methylethyl)-1,3-cyclo-hexanedione, 2-(2-nitro-4-chlorobenzoyl)-4,4-dimethyl-1,3-cyclohexane-dione, 2-(2-chloro-4-methylsulfonylbenzoyl)-4,4-dimethyl-6-methyl-1,3-cyclohexanedione, 2-(2-nitro-4-methylsulfonylbenzoyl)-4,4-dimethyl-1,3-cyclohexanedione, 2-(2-nitro-4-difluoromethoxybenzoyl)-1,3-cyclohexanedione or 2-(2-nitro-4-difluoromethoxybenzoyl)-4,4-dimethyl-1,3-cyclohexanedione.
6. An agent for the selective control of harmful plants in crops of useful plants, which comprises a selectively effective amount of a compound of the formula I as claimed in claim 1, 2 or 3 and formulation auxiliaries which are conventionally used in crop protection.
7. A method of controlling harmful plants in crops of useful plants, which comprises applying, to the area under cultivation, one or more compounds of the formula I
as claimed in any one of claims 1 to 3 in an amount suitable for obtaining a selective-herbicidal activity.
as claimed in any one of claims 1 to 3 in an amount suitable for obtaining a selective-herbicidal activity.
8. The method as claimed in claim 7, wherein the com-pounds of the formula I are applied in rice crops at a concentration of 0.001 to 0.5 kg/ha.
9. The method as claimed in claim 7, wherein the com-pounds of the formula I are applied in cereal or maize crops at a concentration of 0.01 to 2 kg/ha.
10. The use of compounds of the formula I as claimed in any one of claims 1 to 3 as herbicides for controlling harmful plants in crops of useful plants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4210583.8 | 1992-03-31 | ||
| DE4210583 | 1992-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2093105A1 true CA2093105A1 (en) | 1993-10-01 |
Family
ID=6455554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002093105A Abandoned CA2093105A1 (en) | 1992-03-31 | 1993-03-30 | Salts of 2-benzoylcyclohexanediones, selective herbicidal agents, process for their preparation, and their use for controlling weeds |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0563817A3 (en) |
| JP (1) | JPH0665135A (en) |
| KR (1) | KR930019617A (en) |
| CN (1) | CN1077449A (en) |
| CA (1) | CA2093105A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6479436B1 (en) | 1996-09-20 | 2002-11-12 | Basf Aktiengesellschaft | Hetaroyl cyclohexanedione derivatives with herbicidal effect |
| CN103119020A (en) * | 2010-07-21 | 2013-05-22 | 拜耳知识产权有限责任公司 | (4-trifluormethyl-3-thiobenzoyl) cyclohexanediones and use thereof as herbicides |
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|---|---|---|---|---|
| US5506195A (en) * | 1994-11-01 | 1996-04-09 | Zeneca Limited | Selective 1,3-cyclohexanedione corn herbicide |
| US5668089A (en) * | 1996-04-08 | 1997-09-16 | Zeneca Limited | Selective corn herbicide |
| UA72992C2 (en) * | 2000-06-13 | 2005-05-16 | Сінджента Лімітед | Method of selective inhibition of undesired vegetation in the fields |
| DE10117503A1 (en) | 2001-04-07 | 2002-10-17 | Bayer Cropscience Gmbh | Derivatives of benzoylcyclohexanediones and their use as herbicides |
| WO2003062195A1 (en) * | 2002-01-25 | 2003-07-31 | Nippon Soda Co.,Ltd. | Substituted phenylhydrazine derivatives and herbicides |
| KR101767519B1 (en) * | 2009-07-29 | 2017-08-11 | 바이엘 인텔렉쳐 프로퍼티 게엠베하 | 2-(3-Alkylthiobenzoyl)cyclohexanediones and their use as herbicides |
| CN204681616U (en) * | 2012-11-22 | 2015-09-30 | 三菱电机株式会社 | Induction heating cooking instrument |
| WO2015054887A1 (en) * | 2013-10-18 | 2015-04-23 | 浙江省诸暨合力化学对外贸易有限公司 | Triketone ammonium salt compound, and preparation method and application thereof |
| WO2015070392A1 (en) * | 2013-11-13 | 2015-05-21 | 迈克斯(如东)化工有限公司 | Preparation method for cyclohexanetrione compound |
| CN111559965B (en) * | 2019-02-14 | 2022-11-18 | 东莞市东阳光农药研发有限公司 | Substituted benzoyl compounds and application thereof in agriculture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4797150A (en) * | 1986-06-09 | 1989-01-10 | Stauffer Chemical Company | Certain 2-(2-substituted benzoyl)-1,3,5-cyclohexanetriones |
| IL77349A (en) * | 1984-12-20 | 1990-07-12 | Stauffer Chemical Co | 2-(2'-nitrobenzoyl)-1,3-cyclohexanediones,their preparation and their use as herbicides |
| KR890003680A (en) * | 1986-10-16 | 1989-04-17 | 죤 알.페넬 | 2- (2-substituted benzoyl) -4- (substituted) -1,3-cyclohexanedione and methods for preparing the same and methods for inhibiting compositions and plants using the same |
| ATE108764T1 (en) * | 1987-11-28 | 1994-08-15 | Nippon Soda Co | CYCLOHEXENONE DERIVATIVES. |
| HUT50312A (en) * | 1988-02-01 | 1990-01-29 | Sandoz Ag | Herbicide composition containing new dion-compounds and process for producing these compounds |
-
1993
- 1993-03-26 EP EP19930105014 patent/EP0563817A3/en not_active Withdrawn
- 1993-03-30 JP JP5072288A patent/JPH0665135A/en not_active Withdrawn
- 1993-03-30 KR KR1019930005130A patent/KR930019617A/en not_active Application Discontinuation
- 1993-03-30 CN CN93103695A patent/CN1077449A/en active Pending
- 1993-03-30 CA CA002093105A patent/CA2093105A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6479436B1 (en) | 1996-09-20 | 2002-11-12 | Basf Aktiengesellschaft | Hetaroyl cyclohexanedione derivatives with herbicidal effect |
| CN103119020A (en) * | 2010-07-21 | 2013-05-22 | 拜耳知识产权有限责任公司 | (4-trifluormethyl-3-thiobenzoyl) cyclohexanediones and use thereof as herbicides |
| CN103119020B (en) * | 2010-07-21 | 2015-08-12 | 拜耳知识产权有限责任公司 | (4-trifluoromethyl-3-thiobenzoyl) cyclohexanedione and the purposes as weedicide thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1077449A (en) | 1993-10-20 |
| EP0563817A3 (en) | 1993-11-03 |
| JPH0665135A (en) | 1994-03-08 |
| EP0563817A2 (en) | 1993-10-06 |
| KR930019617A (en) | 1993-10-18 |
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