MXPA99007920A - Saccharine-5-carbonyl-cyclohexane-1,3,5-trione derivatives, their preparation and their use as herbicides - Google Patents

Abstract

The invention concerns saccharine-5-carbonyl-cyclohexane-1,3,5-trione derivatives of formula (I), in which the substituents have the following meanings:L is C1-C3 alkyl, C1-C3 alkoxy;Z is C1-C4 alkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, C3-C5 alkinyl, benzyl or phenyl, the phenyl rings each optionally being substituted one or a plurality of times by C1-C4 alkyl, C1-C3 alkoxy or halogen;M is hydrogen, C1-C3 alkyl, C1-C3 alkoxy, fluorine, chlorine, cyano, nitro or trifluoromethyl;and R1, R2, R3, R4 are C1-C4 alkyl. The invention further concerns salts of compound (I) which can be used in agriculture.

Description

DERIVATIVES OF SACARIN-5-CARBONIL-CICLOHEXAN-l, 3,5-TRIONA.

Description The subject of the present invention are derivatives of saccharin-5-carbo-nyl-cyclohexane-1,3,5-trione of the formula I wherein the substituents have the following meanings: L C? -C3-alkyl, Ci-C3-alkoxy; Z C1-C4-alkyl, C3-Cs-cycloalkyl, C3-C6-alkenyl, C3-Cs-alkyl-quinyl, benzyl or phenyl, whose phenyl rings are optionally mono- or polysubstituted by C1-C-alkyl, C? -C3 -alkoxy or halogen; M hydrogen, C? -C3 -alkyl, C? -C3-alkoxy, fluoro, chloro, cyano, nitro or trifluoromethyl; R1, R2, R3, R4 Ci-C4-alkyl; as well as the salts useful in agriculture of compound I.

In addition, the herbicidal products containing compounds I, as well as methods for controlling the growth of unwanted plants with saccharin derivatives i, are objects of the invention.

Known saccharincarbonyl-cyclohexanedione derivatives of herbicidal action are known from WO 96/05182. EP-A 252 298 describes benzoyl-1, 3, 5-herbicidal cyclohexanthrones which, however, do not have a saccharin structure.

In addition, it is known to use saccharin derivatives as fungicides, for example JP 72/00419 and 73/35457 and in the pharmaceutical field, eg EP-A 594 257.

However, the herbicidal properties of the known compounds, as well as the compatibility with the crop plants, are only partly satisfactory.

The object was to find saccharin derivatives with improved properties.

Therefore, saccharin-5-carbonyl-cyclohexane-1,3,5-rione derivatives of the general formula I were found.

The compounds of the formula I are obtained according to scheme 1, by acylation of cyclohexane-1, 3, 5-riones of the formula II- with a saccharin-5-carboxylic acid chloride of the formula III and rearrangement of the enol ester obtained of formula IV, in the presence of a catalyst, giving the active substance of formula I.

In Scheme 1 above, the substituents R1 through R4, L, M and Z have the meanings indicated above.

The first step in the course of the reaction depicted in Scheme 1 is performed by the addition of the acid chloride III to the solution or suspension of the cyclohexane-1,3,5-trione II in the presence of an auxiliary base. The reaction components and the auxiliary base are preferably used in equimolar amounts, but it can also be advantageous to use a slight excess of 1.2 to 1.5 mol equivalents of the auxiliary base. As solvents, methylene chloride, tetrahydrofuran, ethyl acetate, toluene or, preferably, acetonitrile can be used. As an auxiliary base, alkali carbonates, pyrirdine or tertiary alkylamines are suitable, with triethylamine being preferred. During the addition of the acid chloride, the reaction mixture is preferably cooled to 0 to 10 ° C, then stirred at a temperature of 20 to 70 ° C, especially 25 to 40 ° C, until the reaction is complete. finished The enol ester IV can be isolated before transposition, but it is preferred to carry out the reaction in such a way that two to four, preferably 2.5, equivalents of triethylamine are added to the reaction mixture and then added at 25 ° C. 2 to 10, in particular 3 mol% of a cyano compound, for example acetonianehydrin, or, preferably, trimethylsilyl cyanide and then stirred at a temperature of 20 to 40 ° C, preferably at 25 ° C, until enol ester IV and is not present. ' Examples of the transposition of enol esters of cyclohexane-1, 3, 5-triones catalyzed by cyanide are found in EP-A 252 298.

Further processing is carried out by acidifying the reaction mixture with 5% hydrochloric acid or sulfuric acid and then extracting with a solvent, such as, for example, ethyl acetate or methylene chloride. After drying the extract over sodium sulfate or magnesium sulfate, the solvent is distilled in a vacuum and the raw product is subjected, if necessary., to a pu-rification. For its purification, the reaction product can be subjected, for example, to chromatography (silica gel, cyclohexane / ethyl acetate) or recrystallization (methanol / water or glacial acetic acid / water). Another purification method is the extraction of the reaction product with a solution of ethyl acetate with an aqueous solution of alkali carbonate, the final product passing into the aqueous phase. By acidifying the aqueous solution and further extraction, after the solvent has been dried and removed, the final product is obtained in a purer form. The cyclohexane-1, 3, 5-triones of formula II used as starting materials are conodic and can be prepared in a manner known per se [see Spitzer, Monatshefte der Chemie 11, 104 (1890), Riedl et al., Liebigs Ann. Chem. 585, 209 (1954) and Murin et al. Chem. Ber. 92, 2033 (1959)]. A process for the preparation of the especially preferred 2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione is described in EP-A 283 152.

The acid chlorides of formula III used as starting materials are also known. They are obtained by reaction of a saccharin-5-carboxylic acid substituted in appropriate form with thionyl chloride. The synthesis of saccharin-5-carboxylic acids is described, for example, in DE 44 27 996.

In the above-mentioned definitions of compounds I, collective tea generally representative of the following groups were used: I rent; linear or branched alkyl groups with 1 to 4 carbon atoms, for example C 4 -C alkyl, such as, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl und 1, 1-Dimethylethyl; alkoxy: linear or branched alkyl groups with 1 to 3 carbon atoms, such as, for example, those mentioned above, which are linked via an oxygen atom (-0-) to the backbone, for example C? C3-alkoxy, such as, for example, methyloxy, ethyloxy, propyloxy and 1-methylethyloxy; cycloalcryl; monocyclic alkyl groups with 3 to 8 ring carbon members, eg cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; Alanenil; linear or branched alkenyl groups with 2 to 6 carbon atoms and a double bond in an arbitrary position, for example C2-Ce-alkenyl, such as, for example, ethenyl, 1-propenyl, 2-propenyl, 1- Methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1- pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2- methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1-dimethyl-2- propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3- hexenyl, 4-hexe-nyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2 pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl , 4-methyl-3-pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, l-dimethyl-2-butenyl , 1, l-di-methyl-3-butenyl, 1,2-dimethyl-l-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl -l-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2, 3 -dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3, 3-dimethyl-1-butenyl, 3, 3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl -2-butenyl, l-ethyl-3-butenyl, 2-ethyl-l-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, - ethyl-l-methyl-2-propenyl, l-ethyl-2-methyl-l-propenyl and l-ethyl-2-methyl-2-propenyl; alsuinyl; linear or branched alkynyl groups with 3 to 5 carbon atoms and a triple bond in an arbitrary position, for example C3-Cs-alkynyl, such as, for example, 2-propynyl, 2-butynyl, 3-butynyl, l- methyl-2-propinyl, 2-pentynyl, 3-pentynyl, 4-pentyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, l, l- dimethyl-2-propynyl and l-ethyl-2-propynyl; halogen; fluorine, chlorine, bromine and iodine.

With respect to the use intended as herbicides, derivatives of saccharin-5-carbonyl-cyclohexane-1,3,5-trione of the formula I are preferred, in which the substituents have the following meanings: L methyl, ethyl, methoxy or ethoxy; in addition, preferably methyl and methoxy and most preferably methyl; Z C? -C4-alkyl, C3-C8-cycloalkyl, C3-Ce-alkenyl, C3-Cs-Alkynyl, benzyl and phenyl; in addition, preferably methyl, ethyl, i-propyl, i-butyl, t-butyl, cyclopropyl; cyclohexyl, allyl, propargyl, phenyl and benzyl; most preferably methyl, ethyl and phenyl and even more preferably methyl; M hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, cyano, nitro and trifluoromethyl; in addition, preferably hydrogen, methyl, ethyl, methoxy and chloro; most preferably hydrogen, methyl and chlorine; R1, R2, R3, R4 methyl, ethyl, n-propyl, n-butyl; in addition, preferably methyl and ethyl; very preferably methyl.

Also preferred are combinations of the abovementioned ingredients as preferred.

Saccharin derivatives of the formula I are very preferred, wherein the substituents L and R1 to R4 mean methyl, means methyl and M means hydrogen, methyl or chlorine.

The compounds I can be present in the form of their salts useful in agriculture, the type of salt in question generally being unimportant. Generally, the salts of those bases that do not adversely affect the herbicidal action of I are appropriate.

Suitable basic salts are those of the alkali metals, preferably the sodium and potassium salts, of the alkaline earth metals, preferably the calcium, magnesium and barium salts and of the transition metals, preferably the salts of manganese, copper, zinc and iron, as well as ammonium salts which can carry one to three substituents C? -C4-alkyl, hydroxy-C1-C4-alkyl and / or a phenyl or benzyl substituent, preferably the salts of diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, and trimethyl- (2-hydroxyethyl) ammonium, the salts of phosphonium, the salts of sulfonium, preferably the salts of tri- (C 1 -C 4) alkylsulfonium, and the salts of sulfoxonium, preferably the salts of tri- (C1) -C4-) alkylsulfoxonium.

The compounds I and their salts useful in agriculture are suitable - both in the form of isomeric mixtures, and also in the form of pure isomers - and herbicides. The products containing I are excellently able to combat the growth of plants in areas not intended for cultivation, especially in high application quantities. In crops, such as wheat, rice, corn, soybean and cotton, they are active against weeds and unwanted grasses without causing damage worth mentioning in crop plants. This effect is obtained mainly with low amounts of application.

Depending on the respective application method, the compounds I or the products containing them can be used in other additional plant cultures to eliminate the undesired plants therein. For example, the following crops are included: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissi a, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus lemon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirs tum, ( Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec. , Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre, Ricinus communis, Saccharum officinarum, Sécale cereale, Solanum tuberosum, Sorghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

In addition, compounds I can also be used in crops which have been made tolerant to the action of herbicides by culture or genetic engineering methods.

The products or the herbicidal substances can be applied before or after the emergency. When the active substances are less tolerated by the crop plants, then application methods may be used in which the herbicidal products are sprayed with the aid of spraying apparatus in such a way that they do not fall on the leaves of the sensitive crop plants, but only on the leaves of unwanted plants that grow below the first ones or on the ground covered with unwanted plants (post-directed, lay-by). The compounds I or the herbicidal products containing them can be used, for example, in the form of aqueous solutions, powders directly sprayable suspensions, also in the form of suspensions, dispersions or emulsions aqueous, oleic or otherwise, dispersions of oil, pastes, spraying, dusting or granulating agents, by means of spraying, spraying, spraying, sprinkling or spraying. The forms of application depend on the purpose of the use; In any case, they must guarantee the finest possible distribution of the active substances of the invention. Suitable as inert additives are fractions of oil from the average boiling point to high, such as kerosene or diesel oil, in addition, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic hydrocarbons and aromatics, such as paraffin, tetrahydronaphthalate. alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexa-nol, cyclohexanone or strongly polar solvents, such as N-methylpyrrolidone or water. Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders or granules dispersible in water by the addition of water. To obtain emulsions, pastes or oil dispersions, the substances can be homogenized as such or dissolved in an oil or solvent, by means of wetting agents, tackifiers, dispersants or emulsifiers, in water. However, it is also possible to prepare, from the active substance, a humectant, adherent, dispersant or emulsifier and, optionally, a solvent or an oil, concentrates which can be diluted with water.

Suitable surfactants are: alkali metal, alkaline earth metal, ammonium salts of aromatic sulphonic acids, eg lignin sulphonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalene sulphonic acid, as well as fatty acids, alkyl and alkylaryl sulphonates, alkyether sulfates, . lau-ryl ether and fatty alcohol, as well as the sulfated salts of hexa, hepta and octadecanols, as well as glycol ethers of fatty alcohol, sulfonated naphthalene condensates and their derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylenectyl-phenol ethers, isooctylphenol, octylphenol or nonylphenol ethoxylates, alkylphenol polyglycol ethers, tributylphenylpolyglycol ethers, alkylaryl polyether alcohols, isothri-decyl alcohol, fatty alcohol-ethylene oxide condensates, castor oil ethoxylated, polyoxyethylene alkyl ethers, polyoxypropylene, acetal polyglycol ether lauryl alcohol, sorbitol esters, sulphite residual liquors and methylcellulose.

The spraying, spraying and atomizing agents can be obtained by mixing the active substances together with a solid support.

Granules, eg coated granules, impregnates and homogeneous granules can be prepared by bonding the active substances with solid supports. Suitable solid supports are mineral soils, such as silica gel, silicic acids, siliceous gels, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as stone powders, bark powders of trees, wood and nuts, cellulose powders or other solid supports.

The concentrations of the active substances I in the ready formulations can vary widely. The formulations generally contain from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight of at least one active substance. The active substances are used in a purity of 90% bis 100%, preferably 95% up to 100% (according to NMR spectrum). The compounds I of the invention can be formulated, for example in the following manner: I. 20 parts by weight of compound No. 1.1 are dissolved in a mixture containing 80 parts by weight of alkylated benzene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide to 1 mole of N - oleic acid monoethanolamide, 5 parts by weight of the calcium salt of dedecylbenzenesulfonic acid and 5 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100 000 parts by weight of water and distributing it finely therein, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

II. 20 parts by weight of compound No. 1.1 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 10 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100 000 parts by weight of water and distributing it finely therein, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

III. 20 parts by weight of the active substance No. 1.1 are dissolved in a mixture consisting of 25 parts by weight cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point of 210 to 280 ° C and 10 parts. by weight of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution in 100 000 parts by weight of water and distributing it finely therein, an aqueous dispersion containing 0 is obtained., 02% by weight of the active substance. IV. 20 parts by weight of compound No. 1.1 are intimately mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulphonic acid of a sulphite waste liquor and 60 parts by weight of powdery silica gel and ground in a hammer mill. By distributing the mixture finely in 20,000 parts by weight of water, a spray mixture containing 0.1% by weight of the active substance is obtained V. 3 parts by weight of the active substance No. 1.1 are mixed with 97 parts by weight of finely particulated kaolin. In this way, a spray agent containing 3% by weight of the active substance is obtained. SAW. 20 parts by weight of the active substance No. 1.1 are intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol-polyglycol ether, 2 parts by weight of the sodium salt of a condensate of phenolsulfonic acid-urea-formaldehyde and 68 parts by weight of a paraffinic mineral oil. A stable oleic dispersion is obtained. VII. 1 part by weight of compound 1.1 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained. VIII, 1 part by weight of compound 1.1 is dissolved in a mixture consisting of 80 parts by weight of cyclohexanone, 20 parts by weight of Wettol® EM 31 (nonionic emulsifier based on ethoxylated castor oil). A stable emulsion concentrate is obtained.

In order to broaden the spectrum of action and to achieve synergistic effects, the compounds I can be mixed with numerous representatives of other groups of hervicidal active substances and growth regulators and applied in conjunction with these. Examples of suitable mixing components are 1, 2, 4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anuides, (het) aryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2- aroyl-1, 3-cyclohexandiones, hetaryl-aryl-ketones, benzisoxazole-zolidinones, meta-CF 3 -phenyl derivatives, carbamates, quinolincarboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1, 3-dione derivatives, diacines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halogenated carboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3, 4,5, 6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryloxyphenoxy-propionates, phenylacetic acid and its derivatives, phenylpro-pionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridincar acid boxyl-ico and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.

In addition, it may be useful to apply the compounds I on their own or in combination with other herbicides also mixed with other plant protection products, for example products for controlling pests or phytopathogenic fungi or bacteria. Also interesting is the miscibility with solutions of mineral salts, which are used to alleviate nutrient deficiencies or microelements. Non-phytotoxic oils and oil concentrates can also be used.

The amounts of application in active substance amount, depending on the respective application end, of the season of the year, the target and growth plants, to 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance ( sa). Synthesis examples Active substance from 2, 2,, - tetramethyl-cyclohexane-1,3,3-trione and 2,4-dimethyl-saccharin-5-carboxylic acid chloride (No. 1 in Table 1) 0.91 g (0.005 mole) of 2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione in 25 ml of acetonitrile are suspended and 0.6 g (0.005 mole) of triethylamine are added. . Then, 1.37 g (0.005 mole) of 2,4-dimethylase-carin-5-carboxylic acid chloride is added at 25 ° C at once and the reaction mixture is stirred without cooling for 4 hours. Then 1.2 g (0.012 mole) of triethyloamine and then 10 drops of trimethylsilyl cyanide are again added and stirred for 16 hours at 25 ° C. To complete the transposition of the enol ether, it is still heated for 2 hours at 40 ° C.

For further processing, the reaction mixture is concentrated in the rotary evaporator to drynessThe residue is mixed with 30 ml of water, acidified with 5% HCl to pHl and extracted three times with ethyl acetate. After drying the extract over sodium sulfate, the solvent is removed in the rotary evaporator, obtaining 2.1 g of a solid. After recrystallization from a mixture of 5 parts of glacial acetic acid and 1 part of water, 0.9 g (43% of theory) of a white solid with m.p. 210 ° C.

In the same way, the following compounds of Table 1 are obtained: Table 1: Application examples The herbicidal action of the compounds of the formula I can be demonstrated by tests in the greenhouse: Plastic pots filled with clay sand with approx. 3.0% humus as substrate. The seeds of the test plants are sown separately according to the species.

In the treatment before the emergency, actibas substances suspended or emulsified in water are applied directly after sowing by means of fine distribution nozzles. The containers are irrigated slightly to encourage germination and growth, and then the pots are covered with transparent plastic bags until the plants have taken root. With this covering a uniform germination of the test plants is reached, as this is not counteracted by the active substances. The amount of application in the treatments before the emergency amount to 0.5 or 0.25 kg / ha of s.a. For the post-emergence treatment, the test pan is grown until it has reached a growth height of 3 to 15, depending on its growth pattern, and then treated with the active substances suspended or emulsified in water. For this purpose, the test plants are sown directly in the same containers in which they are grown, or they are sown in separate germination containers and the plants are planted some days before the treatment in the test vessels. The plants were maintained according to their species at temperatures of 10 to 25 ° C or 20 to 35 ° C. The trial period amounted to 2 to 4 weeks. During this time, the plants were taken care of and their reaction to the different treatments was evaluated.

The evaluation is based on a scale of 0 to 100, where 100 means no emergence or total destruction of at least the parts of the plants surfaced, and 0 means no damage or normal development of growth. The plants used in the trials in the greenhouse belong to the following species: Table 2 Selective herbicidal activity in treatments before emergence in the greenhouse Table 3 Selective herbicide activity in treatments before emergence in the greenhouse

Claims (1)

1. CLAIMS The saccharin-5-carbonylcyclohexan-1,3,5-trione derivatives of the formula I wherein: L is C? -C3 alkyl; Z is C? -C alkyl; M is hydrogen, C? -C3 alkyl; R1, R2, R3, R4 are each C? -C4 alkyl; And the salts of compound I useful in the agricultural area. The saccharin derivatives of the formula I as mentioned in claim 1, wherein L is methyl or ethyl. The saccharin derivatives of the formula I as mentioned in any of claims 1 to 2, wherein Z is methyl, ethyl, i-propyl, i-butyl or t-butyl. The saccharin derivatives of the formula I as mentioned in any of claims 1 to 3, wherein M is hydrogen, methyl or ethyl. The saccharin derivatives of the formula I as mentioned in any of claims 1 to 4, wherein R1 to R4 are each methyl, ethyl, n-propyl or n-butyl. The saccharin derivatives of the formula I as mentioned in any of claims 1 to 5, wherein R1 to R4 are each methyl or ethyl. The saccharin derivatives of the formula I as mentioned in claim 1, wherein L and R1 to R4 are each methyl, Z is methyl and M is hydrogen or methyl. A herbicidal composition containing at least one saccharin derivative of the formula I, as mentioned in claim 1, and customary inert additives.