DE4304864A1 - New sulphonyl-urea-triazine and -pyrimidine cpds. - useful as herbicides and plant growth regulators - Google Patents

Abstract

Sulphonylwea derivs of formula (I) and their amine, alkali(ne earth) metal base or ammonium base salts, are new: A=L4SO2N(Ls) or a gp. of formulae (i)-(vii): Q = COORa, NO2, halo, YR2, 1-6C haloalkyl, 1-6C haloalkenyl, 2-6C alkynyl, SO2N(T)2, SO2NHT, or a heterocycle (contg. 1-3 heteroatoms selected from O, N and S, which is linked via C and in which O and S may not be neighbouring atoms); Q1 = H, halo, MeO, F2CHO, Me or MeS; R = H or Me; R1, R8, R4, R11 = 1-6C alkyl, 3-6C cycloalkyl or a gp. of formulae n,m = 1,2 or 3, provided that n + m is not more than 4; R2, R10 = 1-6C alkyl, 3-6C cycloalkyl, 2-6C alkenyl, 3-6C alkenyl, 1-6C haloalkyl, 1-4C alkoxy-1-6C alkyl, 2-6C haloalkenyl or oxetan-3-yl; R3, R4, R5 = H or T; T= 1-4C alkyl; R6 = H, T or SO2R7; R7 = T; or R5 + R7 = a 2-6C alkylene chain; L = halo, XR10, COOR11, T, 1-4C haloalkyl, C(O)NR3R4 or NR5R6, L1 = H, T, halo, TO, 1-4C haloalkyl or 1-4C haloalkoxy; L2 = H, halo or Me; L3 = T or 2-pyridyl; L4 = T; L4 + L5 = a 2-6C alkylene chain; L6 = H, halo or Me; L7-L10= H or T; E=CH or N; x = 1-4C haloalkoxy, 1-4C haloalkyl, TO, T, halo, cyclopropyl, MeNH or N(Me)2. Certain intermediates are also claimed. USE/ADVANTAGE - (I) are herbicides which are esp. useful against weeeds in cotton, soya, rice, rape, corn and other cereal crops. (I) are also useful as plant growth regulators. Dosage of (I) is, e.g., by seed treatment, in doses of up to 4 g of active agent per kg of seeds. Alternatively, dosage of (I) is 0.001-2(esp. 0.005-1) kg/ha.

Description

The present invention relates to novel, herbicidally active and plant growth-regulating N-arylsulfonyl-N'-pyrimidinyl- and N'-triazinylureas, Process for their preparation, as agents containing them, as well as their Use for controlling weeds, especially selective in crops or to regulate and inhibit plant growth.

Urea compounds, triazine compounds and pyrimidine compounds with herbicidal Effect are well known. Such compounds are used for example in the European Patent Application Nos. 00 07 687, 00 30 138, 00 73 562 and 01 26 711 described.

There have now been new sulfonylureas with herbicidal and plant growth regulating Properties found.

The N-arylsulfonyl-N'-pyrimidinyl- and N'-triazinylureas according to the invention correspond to the formula I.

wherein

Q is COOR₉, nitro, halogen, Y-R₂, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, -SO₂N (C₁-C₄-alkyl) ₂, -SO₂NH (C₁-C₄-alkyl) or a carbon-bonded heterocycle having 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, wherein oxygen and sulfur can not be adjacent; Q₁ is hydrogen, halogen, methoxy, difluoromethoxy, methyl or methylthio;
R is hydrogen or methyl;
R₁, R₈, R₉ and R₁₁ independently of one another are C₁-C₆-alkyl, C₃-C₆-cycloalkyl or

n is 1, 2 or 3;
m is 1, 2 or 3;
in which
n and m together can not exceed 4;
R₂ and R₁₀ independently of one another represent C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-haloalkyl, C₁-C₄-alkoxy, C₁-C₆-alkyl, C₂- C₆-haloalkenyl or oxetan-3-yl;
R₃, R₄ and R₅ independently represent hydrogen or C₁-C₆-alkyl;
R₆ is hydrogen, C₁-C₄-alkyl or -SO₂-R₇;
R₇ is C₁-C₄alkyl; or
R₅ and R₇ together form a C₂-C₆ alkylene chain;
L is halogen, Y-R₁₀, COOR₁₁, C₁-C₄-alkyl, C₁-C₄-haloalkyl,

-N (R₅) R₆;
L₁ is hydrogen, C₁-C₄-alkyl; Halogen, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, or
C₁-C₆-haloalkoxy;
L₂ is hydrogen, halogen or methyl;
L₃ is C₁-C₄ alkyl or 2-pyridyl;
L₄ is C₁-C₄alkyl;
L₅ is hydrogen or C₁-C₄-alkyl; or L₄ and L₅ together form a C₂-C₆ alkylene chain;
L₆ is hydrogen, halogen or methyl;
L₇, L₈, L₉ and L₁₀ independently represent hydrogen or C₁-C₄-alkyl;
E for nitrogen or methine;
X is C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-alkyl, halogen, cyclopropyl, methylamino or dimethylamino, and the salts of these compounds with amines, alkali or alkaline earth metal bases or with quaternary ammonium bases.

The alkyl groups occurring in the substituent definitions can be straight-chain or are branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl. Preferably, as or in the Substituent occurring alkyl groups 1-3 carbon atoms.

By alkenyl is meant straight-chain or branched alkenyl, such as. Vinyl, allyl, Methallyl, 1-methylvinyl or but-2-en-1-yl. Alkenyl radicals having a chain length are preferred from 2 to 3 carbon atoms.

Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, Dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, trifluoromethyl and Dichlorofluoromethyl.

Alkoxy is for example methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy and tert -butyloxy; preferably methoxy and ethoxy.  

Haloalkoxy is z. Difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2-difluoroethoxy; preferably Difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Cycloalkyl is, for example, cyclopropyl, dimethylcyclopropyl, cyclobutyl, Cyclopentyl, methylcyclopentyl or cyclohexyl, but preferably cyclopropyl, Cyclopentyl or cyclohexyl.

Carbon-bonded heterocycles are within the scope of the present invention for example, thiophene, furan, tetrahydrofuran, pyrimidine, pyrrolidine, pyrroline, pyrrole, Imidazolidine, imidazoline, imidazole, piperazine, pyrimidine, pyrazine, thiazine, Oxazole, thiazole, piperidine and morpholine.

The invention also includes the salts containing the compounds of formula I with amines, Alkali and Eralkylimetallbasen or quaternary ammonium bases can form.

Among alkali metal and alkaline earth metal hydroxides as salt formers are the hydroxides of Emphasize lithium, sodium, potassium, magnesium or calcium, but especially that of sodium or potassium.

Examples of amines suitable for salt formation are primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethylamine, n-propylamine, iso- Propylamine, the four isomeric butylamines, n-amylamine, iso-amylamine, hexylamine, Heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, Heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, Methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, Ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, Dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, Di-n-amylamine, di-iso-amylamine, dihexylamine, diheptylamine, dioctylamine, Ethanolamine, n-propanolamine, iso-propanolamine, N, N-diethylethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2-amine, n-hexenyl-2-amine, Propylenediamine, diethanolamine, trimethylamine, triethylamine, tri-n-propylamine, tri- iso-propylamine, tri-n-butylamine, tri-iso-butylamine, tri-sec-butylamine, tri-sec-butylamine, tri-n-amylamine; heterocyclic amines such as. Pyridine, quinoline, iso-quinoline, morpholine, piperidine, Pyrrolidine, indoline, quinuclidine and azepine; primary arylamines such. Aniline,  Methoxyanilines, ethoxyanilines, o, m, p-toluidines, phenylenediamines, benzidines, Naphthylamines and o, m, p-chloroanilines; but especially ethyl, propyl, diethyl or Triethylamine, but especially iso-propylamine and diethanolamine.

Examples of quaternary ammonium bases are generally the cations of Haloammonium salts, e.g. The tetramethylammonium cation, the trimethylbenzylammonium cation, the triethylbenzylammonium cation, the tetraethylammonium cation, the trimethylethylammonium cation, but also the ammonium cation.

Below the compounds of formula I, those are preferred in which A is A₁, A₂, A₃, A₄, A₅ or A₇ is, but preferably A₁ or A₃. Including this Preferably, E is preferably nitrogen or methine, with R in particular stands for hydrogen.

Including these preferences is that group of compounds of formula I. to emphasize, in the X for C₁-C₄-alkyl, C₁-C₄-alkoxy or dimethylamino and Q for COOR₉ is particularly preferably A for A₁; R is hydrogen; X for methoxy, Dimethylamino or methyl; Q₁ is hydrogen or methyl and R₉ is methyl.

As a single compound from the scope of formula I is N- [2- (methoxycarbonyl) - phenylsulfonyl] -N '- [4-methoxy-6- (oxetan-3-yloxy) -1,3-pyrimidin-2-yl] -urea especially emphasized.

The compounds of formula I can be prepared by either

• a) a compound of formula II A-SO₂NH₂ (II) wherein A has the meaning given under formula I, with a compound of formula III wherein R, X and E have the meaning given under formula I and R₁₂ is phenyl which may be substituted by C₁-C₄-alkyl or halogen, is, or
• b) a compound of the formula IV A-SO₂-Z (IV) where A has the meaning given under formula I and ZN = C = O or -NH-COOR₁₃, wherein R₁₃ is phenyl which is substituted by C₁-C₄-alkyl or Halogen may be substituted, with a compound of formula V wherein X and E have the meaning given under formula I, reacted.

The reactions to compounds of the formula I are advantageously described in aprotic, inert organic solvents. Such solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, carbon tetrachloride or chlorobenzene, Ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as Dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably between -20 ° C and + 120 ° C.

The reactions are generally slightly exothermic and may occur at Room temperature to be performed. For the sake of abbreviation of the reaction time or also  to initiate the reaction will be expedient for a short time to the boiling point of Reaction mixture warmed up. The reaction times can also be adjusted by adding be shortened a few drops of base as a reaction catalyst. As bases are especially tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo- (2.2.2) -octane, 1,5-diazabicyclo (4.3.0) non-5-ene or 1,5-diazabicyclo (5.4.0) undec-7-ene suitable. As bases but can also organic Bases such as hydrides such as sodium or calcium hydride, hydroxides such as sodium and Potassium hydroxide, carbonates such as sodium and potassium carbonate or bicarbonates such as potassium and sodium bicarbonate can be used.

The end products of the formula I can be obtained by concentration and / or evaporation of the Solvent isolated and by recrystallization or trituration of the solid residue in solvents in which they do not dissolve well, such as ether, aromatic Hydrocarbons or chlorinated hydrocarbons.

The sulfonamides of the formula II can be prepared from the corresponding phenylsulfonyl chlorides by reaction with ammonia. Such reactions are known and the person skilled in the art.

The compounds of formulas III and V are new and also form an object of the present invention. The compounds of formula V, wherein X is for Difluoromethoxy can be prepared by reacting a compound of formula VI

with a compound of formula VII

implements. Such reactions are known and familiar to the person skilled in the art. links of formula VII and their preparation are known (see, for example, B. Lamm et al., Acta Chem. Scand. 28, 701 (1974) or J. Org. Chem. 48, 2953-2956 (1983)). The connection of Formula VI is known from USP 44 80 101.

The preparation of the compounds of the formulas II and IV and their conversion with the compounds of the formula III or V to compounds of the formula I, as well as the analogous preparation of compounds of the formula III and V is familiar to the expert and disclosed for example in the following patents :
DE-A-27 15 786, EP-A-00 04 163, EP-A-00 07 687, EP-A-00 13 480, EP-A-00 23 141, EP-A-00 23 422, EP-A A-00 30 139, EP-A-00 30 142, EP-A-00 35 893, EP-A-00 44 209, EP-A-00 44 210, EP-A-00 44 211, EP-A- 00 44 212, EP-A-00 44 213, EP-A-00 44 807, EP-A-00 44 808, EP-A-00 44 809, EP-A-00 48 143, EP-A-00 51 466, EP-A-00 57 456, EP-A-00 70 802, EP-A-00 72 347, EP-A-00 73 562, EP-A-00 79 683, EP-A-00 82 108, EP-A-00 83 975, EP-A-00 84 020, EP-A-00 84 224, EP-A-00 85 218, EP-A-00 85 476, EP-A-00 87 780, EP-A A-00 95 925, EP-A-00 96 002, EP-A-00 96 003, EP-A-00 96 593, EP-A-00 97 122, EP-A-01 02 925, EP-A- 01 03 537, EP-A-01 07 979, EP-A-01 08 708, EP-A-01 17 014, EP-A-01 20 814, EP-A-01 26 711, EP-A-01 69 815, EP-A-01 76 304, EP-A-01 84 385, EP-A-02 06 995, EP-A-02 37 292, EP-A-02 38 070, EP-A-02 62 096, EP-A-02 73 860, EP-A-03 27 251, EP-A-03 36 587, EP-A-03 42 456, EP-A-01 45 664, USP 47 74 337 and USP 46 18 363.

The active compounds of the formula I are generally used at rates of from 0.001 to 2 kg / ha, in particular 0.005 to 1 kg / ha used successfully. The for the desired Effect required dosage can be determined by experiment. It is dependent the type of effect, the stage of development of the crop and the weed as well as the application (location, time, method) and can, due to these parameters, vary within wide ranges.

The compounds of the formula I are distinguished by growth-inhibiting and herbicidal Characteristics that make them excellent for use in crops of crops, particular in cereals, cotton, soy, rape, maize and rice, the Use in soybean culture and grain is particularly favored. Preferably, the Weed control of weeds in soybean crops postemergence. In particular, the  Compounds of formula I by their good degradability.

The invention also relates to herbicidal and plant growth regulating agents which a new active substance of the formula I, as well as methods for the inhibition of the Plant growth.

Plant growth regulators are substances that are agronomic in / on the plant desired biochemical and / or physiological and / or morphological changes effect.

The active substances contained in the agents according to the invention influence this Plant growth depending on application time, dosage, mode of administration and Environmental conditions in different ways. Plant growth regulators of the formula I For example, they can inhibit the vegetative growth of plants. This kind of Effect is of interest on lawns, in ornamental plants, in orchards Straßenböschungen, on sports and industrial plants, but also in the targeted Inhibition of secondary drives as in tobacco. In agriculture, the inhibition of vegatative growth in cereals via a stalk gain to reduced stock, similar agronomic effects can be achieved in oilseed rape, sunflower, maize and other crops. Furthermore, by inhibiting vegetative growth the number of plants per area will be increased. Another application of growth inhibitors is the selective control of ground cover plants in plantations or wide-row crops by strong growth inhibition, without killing these ground cover, so that the competition against the main culture is eliminated, the agronomic positive effects such as erosion prevention, nitrogen fixation and soil loosening though remain.

Among a method for inhibiting plant growth is a control of to understand natural plant development, without that of genetic properties to change determined life cycles of the plant in the sense of a mutation. The Method of growth regulation will be determined on a case-by-case basis Development time of the plant applied. The application of the active ingredients of Formula I can be done before or after emergence of the plants, for example already on the seeds or the seedlings, on roots, tubers, stems, leaves, or flowers other plant parts. This can be z. B. by applying the drug itself or in Form of an agent on the plants and / or by treatment of the nutrient medium of  Plant (ground) happen.

For the use of the compounds of the formula I or compositions containing them Regulation of plant growth come in different methods and techniques Consider, such as the following:

i) Seed dressing

a) seed dressing with a formulated as a wettable powder by shaking in a container until evenly distributed on the seed surface (dry dressing). It uses up to 4 g of active ingredient of the formula I (in a 50% strength Formulation: up to 8.0 g of spray powder) per 1 kg of seed.

b) dressing the seeds with an emulsion concentrate of the active ingredient or with a aqueous solution of formulated as a wettable powder active ingredient of formula I by method a) (wet pickling).

c) staining by exchanging the seed in a broth containing up to 1000 ppm active substance Formula I for 1 to 72 hours and optionally subsequent drying of Seeds (dip dressing, seed soaking).

The dressing of the seeds or the treatment of the germinated seedling are natural the preferred methods of administration, because the drug treatment is completely focused on the target culture. As a rule, 0.001 g to 4.0 g are used Active substance per 1 kg of seed, depending on the methodology, which includes the additive other active substances or micronutrients, from the stated limit concentrations can deviate up or down (repeat stain).

ii) controlled release of active ingredient

The active ingredient is dissolved in solution on mineral granules or polymerized Granules (urea / formaldehyde) raised and allowed to dry. Possibly a coating can be applied (coating granules) which allows the Dosed active ingredient over a certain period of time.

The compounds of formula I are in unchanged form, as from the synthesis available, or preferably with the usual in formulation technology auxiliaries used and therefore z. B. emulsifiable concentrates, directly sprayable  or dilutable solutions, dilute emulsions, wettable powders, soluble powders, Dusts, granules, also encapsulations in z. B. polymeric substances in known Way processed. The application methods such as spraying, misting, dusting, Wetting, scattering or pouring are the same as the type of means desired Targeted and chosen according to the given circumstances.

The formulations, d. H. the active ingredient of the formula I and optionally one or several solid or liquid additives containing agents, preparations or Compositions are prepared in known manner, e.g. B. by intimate mixing and / or grinding the active ingredients with extenders, such as. With solvents, solid carriers and optionally surface-active compounds (Surfactants).

Suitable solvents are: Aromatic hydrocarbons, in particular the fractions C₈ to C₁₂, such as mixtures of alkylbenzenes, z. B. xylene mixtures or alkylated naphthalenes; aliphatic and cycloaliphatic hydrocarbons such Paraffins, cyclohexane or tetrahydronaphthalene; Alcohols, such as ethanol, propanol or butanol; Glycols and their ethers and esters, such as propylene glycol or dipropylene glycol ether, Ketones such as cyclohexanone, isophorone or diacetone alcohol, strong polar Solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or water; vegetable oils and their esters, such as rapeseed, castor oil or soybean oil; optionally also silicone oils.

As solid carriers, for. As for dusts and dispersible powders are in the Usually natural minerals used, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties can also be highly dispersed Silica or highly dispersed absorbent polymers are added. When granulated, adsorptive granules are porous types such. Pumice, broken brick, Sepiolite or bentonite, as non-sorptive carrier materials, for. B. calcite or sand in Question. In addition, a variety of pregranulated inorganic materials or organic nature such as in particular dolomite or crushed plant residues be used.

As surface-active compounds are formulated depending on the type Active ingredient of the formula I nonionic, cationic and / or anionic surfactants with good Emulsifying, dispersing and wetting properties into consideration. Among surfactants are also To understand surfactant mixtures.  

Suitable anionic surfactants may be both so-called water-soluble soaps and water-soluble ones be synthetic surface-active compounds.

As soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), such as. B. the Na or K salts of oleic or stearic acid, or called by natural fatty acid mixtures, the z. B. from coconut or Tallow oil can be obtained. Furthermore, the fatty acid methyl taurine salts are too mention.

More frequently, however, so-called synthetic surfactants are used, in particular fatty alcohol sulfonates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty alcohol sulfonates or sulfates are generally available as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical 8 to 22 carbon atoms, wherein alkyl also includes the alkyl moiety of acyl radicals, e.g. B. the Na or Ca salt of lignosulfonic acid, dodecylsulfuric acid ester or a fatty alcohol sulfate mixtures made from natural fatty acids. Also belong here the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethyl oxide Adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid residue having 8-22 C atoms. Alkylarylsulfonates are z. For example, the na Ca or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation product.

Furthermore, corresponding phosphates such. B. salts of phosphoric acid ester a p-nonylphenol (4-14) -Ethylenoxid adduct or phospholipids in question.

Nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and Alkylphenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of May contain alkylphenols.

Further suitable nonionic surfactants are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing polyethylene oxide adducts on polypropylene glycol, ethylenediaminopolypropylene glycol and  Alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The mentioned Compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, Polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, Polyethylene glycol and octylphenoxypolyethoxyethanol mentioned.

Also included are fatty acid esters of polyoxyethylene sorbitan such as the polyoxyethylene sorbitan trioleate into consideration.

The cationic surfactants are mainly quaternary ammonium salts, which contain as N-substituent at least one alkyl radical having 8 to 22 carbon atoms and as further substituents lower, optionally halogenated alkyl, benzyl or having lower hydroxyalkyl radicals. The salts are preferably in the form of halides, Methyl sulfates or ethyl sulfates, e.g. For example, the stearyltrimethylammonium chloride or Benzyldi (2-chloroethyl) ethylammonium bromide.

The surfactants commonly used in formulation technology are u. a. in the following publications described:

• "McCutcheon's Detergents and Emulsifiers Annual", McPublishing Corp., Glen Rock, New Jersey, 1988.
• M. and J. Ash, "Encyclopaedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
• - Dr. Helmut Stache "Surfactant Paperback", Carl Hanser Verlag, Munich / Vienna 1981.

The pesticidal preparations usually contain 0.1 to 99%, in particular 0.1 to 95%, active ingredient of the formula I, 1 to 99% of a solid or liquid additive and 0 to 25%, especially 0.1 to 25% of a surfactant.

While as a commodity rather concentrated funds are preferred, uses the Consumers usually diluted funds.

The agents may also contain other additives such as stabilizers z. B. optionally Epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), defoamers,  z. Silicone oil, preservatives, viscosity regulators, binders, adhesives as well as fertilizers or other active ingredients for achieving special effects.

In particular, preferred formulations are composed as follows: (% = Percent by weight)

Emulsifiable concentrates:
Active ingredient: 1 to 20%, preferably 5 to 10%
Surfactant: 5 to 30%, preferably 10 to 20%
liquid carrier: 15 to 94%, preferably 70 to 85%

Säube:
Active ingredient: 0.1 to 10%, preferably 0.1 to 1%
solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates:
Active ingredient: 5 to 75%, preferably 10 to 50%
Water: 94 to 24%, preferably 88 to 30%
Surfactant: 1 to 40%, preferably 2 to 30%

Wettable powders:
Active ingredient: 0.5 to 90%, preferably 1 to 80%
Surfactant: 0.5 to 20%, preferably 1 to 15%
solid support material: 5 to 95%, preferably 15 to 90%

granules:
Active ingredient: 0.5 to 30%, preferably 3 to 15%
solid carrier: 99.5 to 70%, preferably 97 to 85%

Preparation Examples example H1 Preparation of 2-amino-4-methoxy-6- (oxetan-3-yloxy) -1,3-pyrimidine (Compound No. 5.11)

To a mixture of 2.4 g of 50% sodium hydride dispersion and 50 ml of N-methylpyrrolidone Are added dropwise 4.8 g of 85% pure 3-hydroxy-oxetane. After completion of the Hydrogen evolution is given at a temperature of 20 ° C 8 g Added 2-amino-4-chloro-6-methoxy-1,3-pyrimidine. After 2 hours of stirring at a temperature from 50-55 ° C, the reaction mixture is poured into ice-water. After suction filtration, wash with Water and recrystallization from ethanol gives 5.9 g 2-Amino-4-methoxy-6- (oxetan-3-yloxy) -1,3-pyrimidine having a melting point of 159-160 ° C.

example H2 Preparation of N- [2- (methoxycarbonyl) phenylsulfonyl] -N '- [4-methoxy-6- (oxetan-3-yloxy) -1,3-pyrimidin-2-yl] urea (compound 1.025)

A mixture of 2.4 g of 2- (methoxycarbonyl) phenylsulfonyl isocyanate, 2.0 g 2-Amino-4-methoxy-6- (oxetan-3-yloxy) -1,3-pyrimidine and 30 ml of absolute dioxane are allowed to Stir at 60-65 ° C for one hour. After complete evaporation of the Reaction mixture and recrystallization of the residue from acetone gives 2.9 g N- [2- (methoxycarbonyl) -phenylsulfonyl] -N '- [4-methoxy-6- (oxetan-3-yloxy) -1,3-pyrimidin-2-yl] urea (Compound 1.025) having a melting point of 135-136 ° C.

Analogously, the connections listed in the attached tables are the Formula I and their intermediates produced.  

Table 1

Compounds of the formula Ia

Table 2

Compounds of the formula Ib

Table 3

Compounds of the formula Ic

Table 4

Compounds of the formula Id

Table 5

Compounds of formula Ie

Table 6

Compounds of the formula If

Table 7

Compounds of the formula Ig

Table 8

Compounds of the formula Ih

Table 9

Compounds of the formula Ii

Formulation Examples of Active Ingredients of the Formula I.

(% = Weight percent)

The active ingredient is mixed well with the additives and in a suitable mill well ground. One receives spraying powders, which become with water to suspensions each dilute the desired concentration.

From such concentrates, by diluting with water emulsions each desired concentration can be produced.

By intimately mixing the excipients with the active ingredient is used finished dusts.

The active ingredient is mixed with the additives, ground and treated with water moistens. This mixture is extruded and then dried in a stream of air.

5. Serving Granules Active ingredient according to Tables 1-7 3% Polyethylene glycol (MG 200) 3% kaolin 94%

The finely ground active substance is mixed with polyethylene glycol in a mixer moistened kaolin applied evenly. In this way you get dust-free Coated granules.

The finely ground active substance is intimately mixed with the additives. You get like that a suspension concentrate from which by dilution with water suspensions Any desired concentration can be produced.

7. saline solution Active ingredient according to Tables 1-7 5% isopropylamine 1% Octylphenol polyethylene glycol ether (78 moles of AeO) 3% water 91%

Biological examples Example B1: Herbicidal action before emergence of the plants

Plastic pots are filled with expanded vermiculite (density: 0.135 g / cm³, Water adsorption capacity: 0.565 L / L). After saturating the non-adsorptive Vermiculites with an aqueous emulsion of active ingredient in deionized water containing the Containing active ingredients in a concentration of 70 ppm, seeds are the following Plants sown on the surface: Nasturtium officinalis, Agrostis tenuis, Stellaria media and Digitaria sanguinalis. The test vessels are then in a Climate chamber at a temperature of 20 ° C, a lighting of about 20 kLux and maintained a relative humidity of 70%. During a germination phase of 4 to 5 Days are the pots to increase the local humidity with covered with translucent material and poured with deionized water. After this 5th day is added to the irrigation water 0.5% of a commercial liquid fertilizer. 12 Days after sowing the experiment is evaluated and the effect on the Test plants evaluated according to the following scale:

1: Plant not germinated or totally dead
2-3: very strong effect
4-6: medium effect
7-8: weak effect
9: no effect (like untreated control)

In this experiment, the compounds of formula I show strong herbicidal action.

Example B2: Post-emergent herbicidal action (contact herbicide)

A number of weeds, both monocots and dicots, were found after emergence (in the 4- to 6-leaf stage) with an aqueous active ingredient dispersion in a dosage of 8-500 g of active substance per hectare sprayed on the plants and this at 24 ° -26 ° C and 45-60% relative humidity maintained. 15 days after the treatment is the Trial evaluated.

After 3 weeks, the herbicidal action with a nine-stage (1 = complete Damage, 9 = no effect) Boniturschema compared in an untreated Control group evaluated. Credit notes from 1 to 4 (especially 1 to 3) indicate a good to very good herbicidal action. Credit notes from 6 to 9 (especially from 7 to 9)  indicate a good tolerance (especially for crops).

In this experiment, the compounds of formula I show strong herbicidal action.

Claims (19)

1. Compounds Formula I. Q is COOR₉, nitro, halogen, Y-R₂, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, -SO₂N (C₁-C₄-alkyl) ₂, -SO₂NH (C₁-C₄-alkyl) or a carbon-bonded heterocycle having 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, wherein oxygen and sulfur can not be adjacent;
Q₁ is hydrogen, halogen, methoxy, difluoromethoxy, methyl or methylthio;
R is hydrogen or methyl;
R₁, R₈, R₉ and R₁₁ independently of one another are C₁-C₆-alkyl, C₃-C₆-cycloalkyl or n is 1, 2 or 3;
m is 1, 2 or 3; where n and m together can not be more than 4;
R₂ and R₁₀ independently of one another are C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₂-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-haloalkyl, C₁-C₄-alkoxyC₁-C₆-alkyl, C₂-C₆- Haloalkenyl or oxetan-3-yl;
R₃, R₄ and R₅ independently represent hydrogen or C₁-C₄ alkyl;
R₆ is hydrogen, C₁-C₄-alkyl or -SO₂-R₇;
R₇ is C₁-C₄alkyl; or R₅ and R₇ together form a C₂-C₆ alkylene chain;
L is halogen, Y-R₁₀, COOR₁₁, C₁-C₄-alkyl, C₁-C₄-haloalkyl, or
-N (R₅) R₆;
L₁ is hydrogen, C₁-C₄-alkyl; Halogen, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, or C₁-C₆-haloalkoxy;
L₂ is hydrogen, halogen or methyl;
L₃ is C₁-C₄ alkyl or 2-pyridyl;
L₄ is C₁-C₄alkyl;
L₅ is hydrogen or C₁-C₄-alkyl; or L₄ and L₅ together form a C₂-C₆ alkylene chain;
L₆ is hydrogen, halogen or methyl;
L₇, L₈, L₉ and L₁₀ independently represent hydrogen or C₁-C₄-alkyl;
E for nitrogen or methine;
X is C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-alkyl, halogen, cyclopropyl, methylamino or dimethylamino, and the salts of these compounds with amines, alkali or alkaline earth metal bases or with quaternary ammonium bases. 2. Compounds of formula I according to claim 1, characterized in that A for A₁,  A₂, A₃, A₄, A₅ or A₇ stands. 3. Compounds of formula I according to claim 1, characterized in that A is A₃ stands. 4. Compounds of formula I according to claim 1, characterized in that A for A₁ stands. 5. Compounds of formula I according to any one of claims 1 to 4, characterized characterized in that E is methine. 6. Compounds of the formula I according to one of claims 1 to 4, characterized characterized in that E is nitrogen. 7. Compounds of formula I according to any one of claims 5 or 6, characterized characterized in that R is hydrogen. 8. Compounds of formula I according to any one of claims 5 or 6, characterized in that
X is C₁-C₄alkyl, C₁-C₄alkoxy or dimethylamino; and
Q stands for COOR₉. 9. Compounds of formula I according to claim 8, characterized in that
A for A₁;
R is hydrogen;
X is methoxy, dimethylamino or methyl;
Q₁ is hydrogen or methyl; and
R₉ is methyl. 10. A process for the preparation of the compounds of the formula I, characterized in that either

• a) a compound of formula II A-SO₂NH₂ (II) wherein A has the meaning given under formula I in claim 1, with a compound of formula III wherein R, X and E have the meaning given under formula I and R₁₂ is phenyl which may be substituted by C₁-C₄-alkyl or halogen, is, or
• b) a compound of formula IV A-SO₂-Z (IV) wherein A has the meaning given under formula I in claim 1 and ZN = C = O or -NH-COOR₁₃, wherein R₁₃ is phenyl which is C₁-C₄ Alkyl or halogen can be substituted, with a compound of formula V wherein X and E have the meaning given under formula I in claim 1, is reacted.

11. Compounds of the formula III wherein R, X and E have the meaning given under formula I in claim 1 and R₁₂ is phenyl which may be substituted by C₁-C₄-alkyl or halogen. 12. Compounds of the formula V wherein X and E have the meaning given under formula I in claim 1. 13. A herbicidal and plant growth-inhibiting agent, characterized by a Content of one or more sulfonylureas of the formula I, according to claim 1. 14. Composition according to claim 13, characterized in that it contains between 0.1% and 95% Active ingredient of the formula I according to claim 1 contains. 15. A method for controlling unwanted plant growth, characterized gekenn characterized in that an active ingredient of the formula I, according to claim 1, or a this Active substance-containing agent in an effective amount on the plants or their Habitat applied. 16. The method according to claim 15, characterized in that an active ingredient amount between 0.001 and 2 kg per hectare. 17. A method for inhibiting plant growth, characterized in that  an active ingredient of the formula I, according to claim 1, or a drug containing this active ingredient Apply agent in an effective amount to the plants or their habitat. 18. The method according to claim 15 for selective pre- or post-emergence control of weeds in crops. 19. Use of an agent according to claim 13 for selective pre- or post-emergence control of weeds in crops.