LT3236B - Novel sulfonylcarbamides - Google Patents

Abstract

The invention relates to compounds of formula (I) in which E is -CH= or -N=, and with the proviso that a) at least one of the radicals R3, R4, R5, R6 and R7 is C1-C4 alkyl, b) E is -CH= when X is halogen and c) E is -CH= when X or Y are -OCHF2 or -SCHF2, and in which the meanings of the other substituents are given in the description, and to their use for controlling weeds, or for regulating and inhibiting the growth of plants.

Description

The present invention relates to novel sulfonylureas having a herbicidal and plant growth regulating activity, to a process for their synthesis, to a preparation containing these compounds as active substances, and to their use in combating weeds, in particular for selective use in crop applications or for regulating or inhibiting plant growth.

Urea compounds, triazine compounds and pyrimidine compounds having herbicidal activity are well known. Such compounds are described, for example, in European Patent Application Ser. 0 007 687, 0 030 138, 0 073

562 and 0 126 711, as well as U.S. Pat. A-4,618,363.

Currently, new sulfonylureas having herbicidal and plant growth regulating activity have been found.

The present invention relates to compounds of the formula

Q-so ₂ -nh-co-nr

X

To where

Q is a residue of formula A or B

A or

R is hydrogen or methyl,

X is C? -C? -Alkyl, C _r -C _THE alkoxy,

C _x -C ₄ -halogenalkoksilas C ₁ -C ₄ -haloalkyl,

C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylthio radical, halogen, C ₂ -C ₅ alkoxyalkyl, C ₂ -C ₅ alkoxyalkoxy, C ₁ -C ₄

alkylamino or di- (C ₁ -C ₃ -alkyl) aminoradikalas, Y is C ₁ -C ₄ -alkyl, _Ο τ -Ο ₄ alkoxy, C ₁ -C ₄ -halogenalkoksilas C ₁ -C ₄ -halogenalkiltio- , C ₁ -C ₄ alkylthio, C ₂ -C ₅ alkoxyalkyl, C ₂ -C ₅ alkoxyalkoxy, C ₂ -C ₅ alkylthioalkyl or cyclopropyl,

E is -CH = or -N =,

_Al R is hydrogen, halogen, - (Z) n _o -NO _2, -NR ₂ R ₃ C = CR _4, -O-CHR ₅ -C = CR _4, or -COOR _6,

R _a2 is hydrogen, fluorine, chlorine or methyl,

R _b is hydrogen, fluorine, chlorine, methyl or methoxyl,

Z is O, S, SO or SO ₂ , n is O or 1,

R ₄ is C ₁ -C ₄ alkyl, and C ₁ -C ₄ -alkyl substituted by 1, 2, 3 or 4 halogen atoms, C₁-C₄ alkoxy or C _r C ₃ -alkiltioradikalais C ₂ -C ₄ alkenyl or C ₂ -C ₄ alkenyl substituted with 1, 2, 3 or 4 halogen atoms,

R ₂ is hydrogen or C 1 -C 8 alkyl,

R ₃ is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy,

R ₄ is hydrogen or C ₁ -C ₄ alkyl,

R ₅ is hydrogen or methyl and

R ₆ is C ^ Cg alkyl or C ₃ -C ₆ -cycloalkyl, as well as salts of these compounds, in addition to the residue of the formula A, in position 2 is a substituent R _al oksetaniloksiradikalas or, in the case where _Al is R -COOR ₆ , this substituent occupies position 2 of the residue of formula A, and when X is halogen, or X or Y is -OCHF ₂ or -SCHF ₂ , -E is CH =.

More preferred are compounds of formula I, characterized in that Q is a residue of formula A, wherein R _al is hydrogen, chloro, -CO ₂ CH _3, -CO ₂ C ₂ H _5, -CH ₂ CH ₂ CF _3, CH = CH-CF ₂ -CH ₃ or -C = CH 10

R ₂ is hydrogen or methyl. More preferred are compounds where R _al and R ₂ is hydrogen. When Q is such a residue of Formula A, more preferred values for R are hydrogen, X is methyl, methoxyl, chlorine, -OCHF ₂ or -OCH ₂ CF _3, and Y is methyl, methoxyl, chlorine, -OCHF _2, or -N ( CH ₃ ) ₂ .

In another group of particularly preferred compounds of formula I, radical Q is a residue of formula B. In this case, R _b is hydrogen. More preferred compounds are those wherein R is hydrogen, X is methyl, methoxyl, ethoxyl, -OCHF ₂ or -OCH ₂ CF ₃ and Y is methyl, methoxyl, chloro, -N (CH ₃ ) _2, or cyclopropyl. Particularly suitable compounds are when X and Y are independently methyl or methoxyl.

Another group of particularly active compounds of formula I is that R is hydrogen.

Another group of particularly suitable compounds of Formula I is substituted with a radical of the formula Q,

where R _b has the given values. Therefore, compounds wherein R _b is hydrogen are particularly suitable.

Of particular importance is the compound

having the formula IA.

By the above definitions, halogen means fluorine, chlorine, bromine and iodine, more preferably fluorine, chlorine and bromine.

Substituted alkyl groups may be straight or branched, such as methyl, ethyl, npropyl, iso-propyl, n-butyl, sec-butyl, isobutyl or tert-butyl. Alkylated groups having 1-3 carbon atoms are more suitable.

Alkenyl may be straight or branched alkenyl such as vinyl, allyl, metalyl, 1-methylvinyl or but-2-en-1-yl. More preferred are alkenyl radicals having from 2 to 4 carbon atoms in the chain.

Halogenalkyl may be, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl and 2,2,2-trichloroethyl and 3,3,3-trifluoropropyl; more preferred are trichloromethyl, difluorochloromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy may be, for example, methoxy, ethoxy, propyloxy, i-propyloxy, η-butyloxy, iso-butyloxy, sec-butyloxy and tert-butyloxy, more preferred are methoxy and ethoxy.

Haloalkoxyl may be, for example, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2-difluoroethoxy, more preferred are difluoromethoxy- , 2-chloroethoxy, trifluoromethoxy and 3,3,3trifluoropropyloxy.

Alkylthio radicals may be, for example, methylthio, ethylthio, propylthio, isopropylthio, η-butylthio, isobutylthio, sec-butylthio or tert-butylthio radicals, more preferably methylthio and ethylthio radicals.

Alkoxyalkoxyls may include methoxymethoxy, methoxyethoxy, methoxypropyloxy, ethoxymethoxy, ethoxyethoxy as well as propyloxymethoxy.

Alkylamino radicals may be methylamino, ethylamino, n-propylamino or iso-propylamino radicals.

Dialkylamino radicals may be, for example, dimethylamino, methylethylamino, diethylamino or n-propylmethylamino radicals.

The invention also encompasses salts which may form compounds of formula I with amines, alkali and alkaline earth metal hydroxides and quaternary ammonium bases.

The alkali and alkaline earth metal hydroxide forming salts include lithium, sodium, potassium, magnesium or calcium hydroxides, in particular sodium and potassium hydroxides.

Examples of amines suitable for the formation of salts may be primary, secondary, tertiary aliphatic and aromatic amines such as methylamine, ethylamine, npropylamine, iso-propylamine, four isomeric butylamines, n-amylamine, iso-amylamine, hexylamine, nonamine, octamine , decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-isopropylamine, methyl-hexylamine, methyl-nylamine, methyl-octadecylamine, methyl-octadecamine, ethyl-heptylamine, ethylheptylamine, ethylheptylamine, ethylheptylamine, ethylheptylamine, -propylamine, di-n-butylamine, di-n-amylamine, di-isoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, iso-propanolamine, N, N-diethanolamine, n-ethylpropanolamine, n-butyl ethanolamine, , n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hex senyl-2-amine, propylenediamine, diethanolamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-iso-butylamine, tri-sec-butylamine, tri-n-amylamine; heterocyclic amines such as pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines such as aniline, methoxyaniline, ethoxyaniline, o-, m-, p-toluidine, phenylenediamine, benzidine, naphthylamine and o-, m-, p-chloroaniline; especially suitable are ethyl, propyl, diethyl and triethylamine, in particular isopropylamine and diethanolamine.

Examples of quaternary amines are usually ammonium halide cations such as tetramethylammonium cation, trimethylbenzylammonium cation, triethylbenzylammonium cation, tetraethylammonium cation, trimethylethylammonium cation as well as ammonium cation.

The compounds of formula I described in the invention can be synthesized by reacting the corresponding sulfonamides with the corresponding pyrimidine or triazine derivatives. For example, by reacting a compound of formula

Q-SO ₂ -NH ₂ II with a compound of formula

O-CO-NR

m

III 'X or

Appropriate end products can be obtained from the GOI. Substituted sulfonamides, for example, having the formula

Q-SO2-NH-COORc by reaction with a compound of formula λ

N />

n ² h

VI

X may also form a compound of formula I of the invention.

In formulas II to VI, the radicals Q, R, X, Y and E have the meanings given above; R _c is phenyl which may be substituted.

The synthesis of compounds of formula I is preferably carried out in an aprotic, inert organic solvent. Such solvents include hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran , acetonitrile or propionitrile, amides such as dimethylformamide, diethylformamide or N-methylpyrrolidone. A more suitable reaction temperature is from -20 to 120 ° C.

The reactions are slightly exothermic and can be carried out at room temperature. In order to shorten the reaction time or to initiate the reaction, it is expedient to boil the reaction mixture briefly. The reaction time is also shortened by the addition of a few drops of base, which catalyzes the reaction. 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 are particularly suitable as bases. -diazabicyclo [5.4.0] -undec-7-ene. Inorganic bases may also be used as bases, for example hydrides such as sodium or calcium hydride, hydroxides such as sodium or potassium hydroxide, carbonates such as sodium and potassium carbonate or bicarbonate such as sodium and potassium bicarbonate.

The final compounds of Formula I may be isolated by concentration and / or evaporation of the solvent and purified by recrystallization or dispersion of the solid residue in a solvent in which they are poorly soluble, such as ether, aromatic hydrocarbons or chlorinated hydrocarbons.

Phenylsulfonamides of the formula

VIII are novel compounds which, as intermediates, have been specifically designed and synthesized to produce the active compounds of Formula I. They are the subject of the present invention.

Compounds of formula VII may be synthesized, for example, by the following methods:

(a) by treatment with a compound of the formula

Rd

H

with a compound of formula

b) acting on a compound of the formula

HAL

H

SO ₂ NH ₂

Compound XI of the formula

O

OH

Reactions of this type are described in U.S. Patent No. A-4,523,944.

Another embodiment which can be applied to the synthesis of said intermediates is described in Acc.Chem.Res. 12,146 (1979) and Synthesis 312 (1983) and 253 (1985) and essentially involves the conversion of compounds of formula VII to other derivatives:

(c) acting on a compound of the formula

so ₂ nh ₂

H

XIII o

a compound of formula A-B in the presence of a palladium catalyst to give a compound of formula

XIV.

Another method of synthesis is described in EP A-336 587

d) acting on a compound of the formula

X \ / ^z

SRy xv

COOR, chlorine and ammonia in a two-step process, a home compound of formula

XVI

Compounds of formula VIII may be quenched, for example, in the following ways:

) by reacting a compound of the formula / SO ₂ NH ₂ ^R b -N-OH with a compound of formula X and

XVII

XVIII

f) acting on a compound of the formula

HAL

SO ₂ NH ₂ compound of formula XII.

Reactions of this type are described, for example, in U.S. Pat. 92/00555.

Other methods for the synthesis of the corresponding type of sulfonylureas are described in U.S. Pat. A-4,537,618 and 5,041,603; B-120 814.

In the above formulas, the substituents R _aX , R _a2 and R _b have the meanings given. R _d represents methyl, phenyl or substituted phenyl, R _x represents bromine or iodine, R ' _al represents CT _X = CT ₂ T ₃ , C = CR ₄ or -COOR ₆ , where T _x represents hydrogen or C _x -C ₅ alkyl. , T ₂ is hydrogen or C _x -C ₅ alkyl or halogen and T ₃ is hydrogen or halogen substituted C ₁ -C ₅ alkyl, R _y is isopropyl or benzyl and HAL represents halogen. AB is a compound of the formula HT _X C = CT ₂ T ₃ or HC> CR ₄ or a combination of CO and R ₆ OH, where T _x , T ₂ , T ₃ , R ₄ and R ₆ have the meanings given.

Compounds of formulas X and XII are described, for example, in J. Org.Chem.48, 2953 (1983) and in Acta Chem. Scand. 28, 701 (1974).

The compounds of formulas IX and XI can be synthesized according to the methods described in EP-A-0404. A-205 348, 216 504, 336 587 and U.S. Pat. A-4,523,944; 4,618,363; and 4,981,509. Methods for synthesizing compounds of formulas XVII and XVIII are described in U.S. Pat. A-4,579,583 and Swiss Patent Application 895 / 91-6.

The most commonly used amount of active ingredient of formula I is from 0.001 to 2 kg / ha, more preferably from 0.005 to 1 kg / ha. The dose required to achieve the desired effect is determined experimentally. It depends on the nature of the action, the stage of development of the crop and the weed, as well as the conditions of use (place, time, method) and can therefore vary widely within these parameters.

The compounds of formula I possess growth inhibitory and herbicidal properties which allow them to be used effectively for crop applications, especially for cereals, cotton, soybean, rape, maize and rice, and are particularly suitable for soybean and cereal crops. In soy crops, weed control is better when the crop germinates. The compounds of formula I are particularly distinguished by their rapid degradation.

The invention also provides a preparation having herbicidal and plant growth regulating properties, comprising a new active ingredient of formula I, as well as a method for inhibiting plant growth.

Plant growth regulators are substances that cause agronomically desirable biochemical and / or physiological and / or morphological alterations to the plant.

The active ingredients in the compositions of the invention affect plant growth in a variety of ways, depending on the time of application, dosage, mode of application and environmental conditions. Plant growth regulators of formula I may, for example, inhibit the vegetative growth of plants. Substances with this effect are used in ornamental horticulture, fruit plantations, maintenance of lawns, street slopes, sports facilities and industrial sites, as well as specific inhibitions of armpit shoots, such as tobacco growing. In agriculture, inhibiting the growth of cereal crops strengthens the straw and therefore reduces the amount of seeding, a similar agronomic effect is observed in rape, sunflower, maize and other crops. In addition, by inhibiting vegetative growth, plants can be grown more densely. Growth inhibitors are also used for the selective control of soil cover plants where plant cover crops or broadleaf crops are not destroyed but can no longer compete with the parent crop, thereby maintaining their agronomically beneficial effects, such as suppressing erosion, fixing nitrogen and loosening soil.

Inhibition of plant growth herein is understood to mean controlling the natural development of a plant without altering the genetically conditioned life cycle of the plant, i.e. without using mutations. The mode of growth regulation is applied at a particular stage of plant development. The active compounds of the formula I may be applied, for example, before or after emergence, to seeds or seedlings, roots, tubers, shoots, leaves, flowers or other parts of the plant. This can be done by treating the plant itself with the active substance or its preparation and / or by treating the plant's nutrient medium (soil).

There are various methods and technologies for the use of compounds of formula I or preparations containing them for use in the control of plant growth, for example:

(i) Seed treatment

(a) Seed treatment of the active substance in the form of a wettable powder by shaking the seeds in a container until the powder uniformly covers the surface of the seeds (dry staining). Up to 4 g of the active ingredient of formula I are used per kg of seed (up to 8 g of wettable powder in a 50% formula).

(b) Seed treatment with an emulsion concentrate of the active substance or an aqueous solution of a powder of the compounds of formula I prepared by method (a) (wet staining).

(c) soaking by immersing the inoculum for 1 to 72 hours in a working solution containing 1000 ppm of the active substance of formula I followed by drying the seeds (wet soaking, seed soaking).

Seed treatment of seedlings or treatment of infected seedlings is, of course, more appropriate methods of application, since all the active substance is applied to the plant for which it is intended. Usually between 0.001 g and 4.0 g of active substance is used per kg of seed, however, one can use deviations (re-staining) according to the methods using additives of other active substances or micro-fertilizers.

(ii) Controlled dosing of active substances

The active substance adsorbed in solution on a mineral granular carrier or polymeric granulate (urea / formaldehyde) is dried. Sometimes the granules are coated with a film (granules with a coating), which results in prolonged action of the active substance.

The compounds of formula I are used in the form as they are synthesized or, more preferably, in admixture with conventional excipients, which are used in the preparation of formulations and converted into emulsifiable concentrates for spray application or dilution solutions, diluted emulsions, powders, soluble powders, dust materials, granules, and capsules of polymeric materials, for example.

Methods of application - Spraying, aerosol spraying, dusting, wetting, sprinkling or dispensing, as well as the type of formulation, as well as the form of the substance, are selected according to the intended purposes and the circumstances.

The recipe, i.e. a preparation containing the active compound of the formula I and, where appropriate, one or more solid or liquid additives, the composition of which is prepared in a known manner, for example by mixing and / or grinding the active ingredient with a neutral excipient such as a solvent, a solid carrier and, where appropriate, a surfactant (tenside).

Solvents may be aromatic hydrocarbons, especially C ₈ -C ₁₂ fractions, for example alkylbenzene mixtures such as xylene mixtures or alkylnaphthalenes; aliphatic and cycloaliphatic hydrocarbons such as 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, dimethylsulfoxide or water; vegetable oils and their esters, such as rapeseed, castor or soybean oil; as well as silicone oils.

Solid carriers, such as dusts and dispersible powders, may include natural ground rock such as calcite, talc, kaolin, montmorillonite, or atapulgite. Physical Properties pageLT 3236 B

Fine swelling silica gel or fine dispersing polymeric materials with high absorption may be added to the swelling. The granular, granular adsorbent carriers may be porous materials such as pumice, crushed bricks, sepiolite or bentonite, examples of non-abrasive materials may be calcite or sand. In addition, many materials can be used before being granulated, such as dolomite or crushed plant residues.

The surfactant compounds may be nonionic, cationic and / or anionic surfactants suitable for the formulation comprising the active ingredient of formula I and having good emulsifying, dispersing and coating properties. The term surfactants includes mixtures of surfactants.

Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surfactants.

Soaps may contain salts of higher fatty acids (C ₁₀ C ₂₂ ) and alkaline, earth alkaline or optionally substituted ammonium salts such as oleic or stearic acid or natural fatty acids such as coconut oil or tallow sodium or potassium. Also mentioned are the salts of methylturin and fatty acids.

So-called synthetic surfactants, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates, are quite commonly used.

The fatty alcohol sulfonates or sulfates usually contain alkali, earth alkaline or optionally substituted ammonium salts having an alkyl radical of 8 to 22 carbon atoms, and alkyl also includes the alkyl moiety of the acyl radical, such as lignin sulfonic acid, dodecyl sulfuric acid ester or fatty alcohols. sodium or calcium salts of natural fatty acids. This group also includes salts of sulfuric esters and salts of sulfonic acid esters with fatty alcohol-ethylene oxide adducts. Among the sulfonated benzimidazole derivatives, compounds having two sulfonic acid groups and one fatty acid radical having from 8 to 22 carbon atoms are more suitable. Alkylarylsulfonates may be, for example, sodium, calcium or triethanolamine salts of the condensation product of dodecylbenzene sulfuric acid, dibutyl phthalic sulfuric acid or naphthalene sulfonic acid and formaldehyde.

Corresponding phosphates may be, for example, salts of phosphate acid and esters of p-nonylphenol- (4-14) -ethylene oxide adduct or phospholipids.

Nonionic surfactants may include, in particular, derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols with polyglycol ethers, which may have from 3 to 30 glycol ether groups, from 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical. of alkyl atoms of the alkyl phenol of carbon atoms.

Other suitable nonionic surfactants are water-soluble polyethylene oxide derivatives having from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups with polypropylene glycol, ethylenediamine polypropylene glycol and alkyl polypropylene glycol having from 1 to 10 carbon atoms in the alkyl chain. The aforementioned compounds typically contain from 1 to 5 ethylene glycol moieties per propylene LT 3236 B fragment.

Non-ionic surfactants include nonylphenolpolyethoxyethanol, castor oil polyglycol ether, polypropylene and polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Also mentioned are esters of polyoxyethylene sorbitan and fatty acids, such as polyoxyethylene sorbitan trioleate.

In the case of cationic surfactants, the quaternary ammonium salts in which at least one N-substituent is an alkyl radical having from 8 to 22 carbon atoms are to be mentioned; other substituents are small, optionally halogenated alkyl, benzyl or small hydroxyalkyl radicals. Preferred salts are halides, methyl or ethyl sulfates such as stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) -ethylammonium bromide.

Preparation methodologies utilize the surfactants described in the following publications:

-Mc Cutcheon ¹ s Detergent and Emulsifiers Annual, Mc Publishing Corp., Glen Rock, New Jersey, 1988. -M. and J. Ash, Encyclopedia of Surfactants,

Vol. I-III, Chemical Publishing Co., New York, 19801981.

-Dr. Helmut Stache Tensid-Taschenbuch, Carl Hanser Verlag, Muenchen / Wien 1981.

The pesticide in ready-to-use form will generally contain from 0.1 to 99%, in particular from 0.1 to 95%, of the active ingredient of formula I, from 1 to 99% of liquid or solid additives and from 0 to 25%, preferably from 0, 1 to 25% tensides.

Concentrated preparation is more commercially available, whereas the final consumer usually uses a diluted preparation. The formulation may also contain other additives such as stabilizers such as epoxidized vegetable oils (epoxidised coconut oil, rapeseed or soybean oil), foam extinguishing agents such as silicone oil, preservatives, viscosity regulators, binders, lipicides. substances as well as fertilizers or other active substances for specific effects.

The most suitable formulas are:

(% = percentage by weight)

Emulsifiable concentrates:

Active substance:

Surfactant:

Liquid carrier:

Dust:

Active substance:

Solid Carrier:

Suspension concentrate:

Active substance:

1 to 20%,

better from 5 to 10% from 5. to 30% better from 10 to 20% since 15th to 94% better from 70 to 85%

0.1 to 10%, preferably 0.1 to 1%, 99.9 to 90%, preferably 99.9 to 99%, 5 to 75%, preferably 10 to 50%, 94 to 24%, preferably 88 to 30% 1 to 40%, preferably 2 to 30%

Water:

Surfactant:

Coating Powder:

Active substance:

Surfactant:

Solid Carrier:

Granules:

Active substance:

Solid Carrier:

Examples of synthesis:

0.5 to 90%, preferably 1 to 80%, 0.5 to 20%, preferably 1 to 15%, 5 to 95%, preferably 15 to 90%, 0.5 to 30%, preferably 3 to 15% 99.5 to 70%, preferably 97 to 85% example:

Synthesis of 2- (Oxetan-3-yloxy) phenylsulfonamide

A mixture of 28.8 g of 2-hydroxyphenylsulfonamide, 40.0 g of 4-methylphenylsulfonyl-oxetan-3-yl ester, 23.5 g of potassium carbonate and 100 ml of dimethylformamide is stirred for 24 hours at 100-105 ° C. It is then poured into water, neutralized with hydrochloric acid (10%), extracted with ethyl acetate, dried and concentrated to crystallization. 14.3 g of the title compound are obtained, m.p. mp 180-182 ° C.

example:

Synthesis of 2- (2-chloroethoxy) -5-hydroxyphenylsulfonamide

Dissolve 11.4 g of 2- (2-chloroethoxy) -5-methoxyphenylsulfonamide in 500 ml of methylene chloride, add 54 g of boron tribromide in ice-cooled solution and keep at room temperature for 30 minutes. The reaction mixture is poured into a mixture of 1000 ml of ice water and 500 ml of methylene chloride, washed to neutral with a saturated saline solution, the aqueous phase is mixed with 350 g of sodium chloride and extracted with ethyl acetate. The organic phase is washed again with saturated brine and dried over sodium sulfate. Evaporation and recrystallization from chloroform-hexane afforded 8.0 g of the title compound, m.p. mp 146-147 ° C.

example:

Synthesis of N- [2- (Oxetan-3-yloxy) phenylsulfonyl] -N'- (4-methoxy-6-methyl-pyrimidin-2-yl) urea

A mixture of 2.0 g of 2- (oxetan-3-yl) phenylsulfonamide, 2.2 g of (4-methoxy-6-methyl-pyrimidin-2-yl) phenylcarbamate and 30 ml of absolute dioxane is added dropwise at 20-25 ° C. At temperature C, a mixture of 1.33 g of diazabicyclo [5.4.0] -undec-7-ene (1.5-5) and 10 ml of absolute dioxane is stirred for 2 hours at 20-25 ° C. Pour into water, add 10% HCl to pH5, filter, wash with water. 3.0 g of the title compound ch ₃ '0 are obtained, m.p. 195-197 ° C.

example:

Synthesis of 3- (Oxethan-3-yloxy) pyridin-2-ylsulfonamide Sodium hydride. (55, 6% suspension in oil) A solution of 115 g of dimethylformamide in 115 ml of dimethylformamide was maintained at a temperature not exceeding 30 ° C. . After stirring for 10 minutes, within 15 minutes. 12.33 g of 3-fluoropyridine-2-sulfonamide dissolved in 35 ml of dimethylformamide were added dropwise at 22-32 ° C. The suspension is stirred for 2 hours at 60 ° C, then another 1.4 g of oxetan-3-ol is added and stirred for another hour at 60 ° C. A thick suspension is obtained which is diluted with 50 ml of acetonitrile. Under cooling, the mixture is mixed with 15 ml of trifluoroacetic acid, stirred for 10 min at 10-15 ° C, filtered and evaporated. The residue was purified by silica gel chromatography eluting with ethyl acetate-methanol (5: 1) to give 11.2 g of the title compound, m.p. mp 178-181 ° C.

example:

Synthesis of N - [(3-Oxetan-3-yloxy) pyridin-2-ylsulfonyl] -N '- (4,6-dimethoxypyrimidin-2-yl) urea

To a solution of 2.76 g of 3- (oxetan-3-yloxy) pyridin-2-ylsulfonamide in 40 ml of acetonitrile are added 3.47 g of N- (4,6-dimethoxy-pyrimidin-2-yl) phenylcarbamate and 1.96 ml of 1 , 5-diazabicyclo- [5.4.0] -undec-7-ene and stirred for 90 min. at room temperature. The mixture is then concentrated and the residual oil is removed with 8 ml of hydrochloric acid (2N) and water, filtered, washed with ether, water and dried. 4.5 g of the title compound are obtained

The compounds of formula I and their intermediates in the following tables may be synthesized analogously.

table

> ₂ NH-CO-N

N.

Ύ '

Y

No. R R _a2 Doors- aniloxy position Ral X Y E mp (° C) 101 H H 2 H ch ₃ and ₃ N 142-145 102 H H 2 H and ₃ and ₃ CH 207-209 103 H H 2 H and ₃ and ₃ N 153-156 104 H H 2 H and ₃ C _L CH 201-203 105 H H 2 H ch ₃ ch ₃ CH 176-178 106 H H 2 H ch ₃ and ₃ CH 195-197 107 H H 5 2-COOCH ₃ ch ₃ and ₃ CH 108 H H 5 2-COOCH ₃ ch ₃ ch ₃ CH 109 H H 5 2-COOCH ₃ and ₃ Ci CH 110 H H 5 2-COOCH ₃ and ₃ ochf ₂ CH 111 H H 5 2-COOCH ₃ ochf ₂ ochf ₂ CH 112 H H 4 2-COOCH ₃ and ₃ and ₃ CH 113 H H 4 2-COOCH ₃ and ₃ and ₃ N 114 H H 4 2-COOCH ₃ and ₃ ch ₃ CH 115 H H 4 2-COOCH ₃ ch ₃ ch ₃ CH 116 H H 5 2-COOCH ₃ ch ₃ ch ₃ CH 117 H H 5 2-COOCH ₃ ch ₃ and ₃ N 118 H H 5 2-COOCH ₃ and ₃ and ₃ N 119 H H 5 2-COOCH ₃ and ₃ and ₃ CH 120 H ch ₃ 5 2-COOCH ₃ and ₃ and ₃ CH 121 H ch ₃ 5 2-COOCH ₃ och ₂ cf ₃ N (CH ₃ ) ₂ n ' 122 H H 5 2-C1 ch ₃ and ₃ N 195-198 123 H H 5 2-C1 ch ₃ and ₃ CH 181-184 124 H H 5 2-C1 and ₃ and ₃ CH 125 H H 5 2-C1 and ₃ and ₃ N - 126 H H 5 2-CH ₂ CH ₂ CF ₃ and ₃ and ₃ N 127 H H 5 2-CH ₂ CH ₂ C ₃ and ₃ and ₃ CH 128 H H 5 2-CH ₂ CH ₂ CF ₃ and ₃ ch ₃ N

table (continued)

No. R Ka2 Doors- aniloxy position Ral X Y E mp (° C) 129 H H 5 2-CH ₂ CH ₂ CF ₃ ch ₃ ch ₃ CH 130 H H 5 2-CH = CH-CF ₂ - ch ₃ ch ₃ ch ₃ CH 131 H H 5 2-CH = CH-CF ₂ - ch ₃ ch ₃ och ₃ - N 132 H H 5 2-CH = CH-CF ₂ - ch ₃ and ₃ and ₃ CH 133 H H 5 2-CH = CH-CF ₂ - ch ₃ and ₃ ch ₃ CH 134 H H 5 2-C = CH and ₃ ch ₃ CH 135 H H 5 2-CsCH and ₃ and ₃ CH 136 H H 5 2-CsCH ch ₃ and ₃ N 137 H H 5 2-OCH and ₃ and ₃ N 138 H H 2 5-C = CH and ₃ and ₃ N 139 H H 2 5-C = CH and ₃ and ₃ CH 140 H H 2 5-C = CH and ₃ ch ₃ CH 141 H H 2 5-C = CH ch ₃ ch ₃ CH 142 H H 5 2-COOC ₂ H ₅ ch ₃ ch ₃ CH 143 H H 5 2-COOC ₂ H ₅ ch ₃ and ₃ CH 144 H H 5 2-OCH ₃ ch ₃ and ₃ N 160-162 145 H H 5 2-OCH ₃ ch ₃ and ₃ CH 155-157

table

so ₂ nh—

CO-N-to ^ Y '

No. -so ₂ nh- position Oxetanil oxy position R ^R b X Y E i.e. (° C) 201 3 2 H H and ₃ and ₃ CH 167-169 202 3 2. H H and ₃ ch ₃ N 166-170 203 3 2 H H and ₃ and ₃ N - 204 3 2 H H ch ₃ ch ₃ CH - 205 2 3 H H and ₃ and ₃ CH 168-169 206 2 3 H H and ₃ ch ₃ N 108-110 207 2 3 H H and ₃ Cl CH 172-175 208 2 3 H H and ₃ ch ₃ CH 163-165 209 2 3 H H ch ₃ ch ₃ CH 161-163 210 2 3 H H ochf ₂ and ₃ CH - 211 2 3 H H och ₂ cf ₃ N (CH ₃ ) ₂ N 158-161 212 2 3 H H och ₂ ch ₃ N 178-181

table

No. Ral R _a2 The position of oxetanyloxy i.e. (° C) 301 H H 2 180-182 302 2-COOCH ₃ H 5 303 2-COOC ₂ H ₅ H 5 304 2-COOCH3 H 4 306 2-C1 H 5 158-162 307 2-CH ₂ CH ₂ CF ₃ H 5 308 2-CH = CH-CF ₂ - 1 ch ₃ H 5 309 2-OCH H 5 310 5-OCH H 2 311 2-COOCH ₃ CH ₃ 5 312 2-OCH ₃ H 5 155-157

table

No. ^R b -SO ₂ NH ₂ position Oxetanilox position i.e. (° C) 401 H 2 3 178-181 402 H 3 2 147-149

Examples of formulas containing the active ingredient of formula I (% -wt%)

F1. Spray powder a) b) c) Active substance according to Tables 1-3 20% 50% 0.5% Well lignin sulfonate 5% 5% 5% Well lauryl sulfate 3% - - Well diisobutylnaphthalenesulfonate - 6% 6% Octylphenolpolyethylene glycol ether - 2% 2% (7-8 mol EO) Fine disperse silica 5% 27% 27% Kaolin 67% - - Sodium chloride - - 59.5%

The active ingredient is mixed with the additives and well ground in a suitable mill. This gives a sprayable powder which can be diluted with water to the desired concentration of the suspension.

F2. Water dispersible granules a) b) Active substance according to Tables 1-3 75% 5% Well dibutylnaphthalenesulfonate 2% 0.5% Gum Arabic 1% 1% Sodium sulphate 5% 3% Well lignin sulfonate 17% 15% Kaolin - 75.5%

Dilution of such concentrate with water gives emulsions of the desired concentration.

F3. Dust preparations a) b) Active substance according to Tables 1-3 0.1% 1% Talk 99.9% - Kaolin 99%

Dust preparations are prepared by carefully mixing the active ingredients with the excipients.

F4. Extruded granulate a) b) Active substance according to Tables 1-3 10% 1% Well lignin sulfonate 2% 2% Carboxymethylcellulose 1% 1% Kaolin 87% 96%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then air-dried.

F5. Felted granulate

Active substance according to Tables 1-3 3%

Polyethylene glycol (MG 200) 3%

Kaolin 94%

The finely divided active ingredient is uniformly poured into the polyethylene glycol moistened kaolin in the blender. In this way, a dust-free coated granulate is obtained.

F6. Suspension concentrate a) b) Active substance according to Tables 1-3 5% 40% Ethylene glycol 10% 10%

Nonylphenolpolyethylene glycol ether (15 mol EO) 1% 6% Well lignin sulfonate 5% 10% Carboxymethylcellulose 1% 1% 37% aqueous formaldehyde 0.2% 0.2% solution Silicone oil (75% aqueous 0.8% 0.8 emulsions a) Water 77% 32%

The finely divided active ingredient is thoroughly mixed with the additives. The concentrate thus obtained can be diluted with water to give a suspension of the desired concentration.

F7. Saline solution

Active substance according to Tables 1-3 5% Isopropylamine 1%

Octylphenolpolyethylene glycol ether 3% (78 mol EO)

Water

91%

Biological samples

Example B1: Herbicidal activity before germination of plants

Plastic cups are filled with swollen vermiculite (density: 0.135 g / cm ³ , water adsorption: 0.565 1/1). After saturation of non-adsorbable vermiculite with an aqueous emulsion of the active ingredient in deionized water (active substance concentration 70 ppm), seeds of the following plants are sown: Nasturtium officinalis, Agrostis tenuis, Stellaria media and Digitaria sanguinalis. The test vessels are further stored in an incubator at 20 ° C, 20 kLi illumination and 70% relative humidity. During the germination phase, the cups are covered with clear material and watered with deionized water for four to five days to increase local humidity. After five days, 0.5% of standard liquid fertilizer is added to the water for irrigation. Twelve days after sowing, the test results and effects on test plants are evaluated on the following scale:

- the plants have not germinated or died

2-3 - Very strong effect

4-6 - Moderate effect

7-8 - Weak effect

- no effect (as in control group)

Table Bl: Operation before germination:

The concentration of the active substance is 70 ppm

Plants to be tested: Nasturtium Stellaria Agrostis Digitaria

Active substance

101 2

102 2

103 2

104 2

105 2

106 2

122 3

123 3

144 3

145 3

201 2

202 2

205 2

206 2

207 3

208 3

209 2

211 3

212 3

Example B2: Herbicidal effect on germination of plants

Monocotyledonic and dicotyledic weeds are sprayed after emergence (at 4-6 leaf stage) with an aqueous dispersion of the active ingredient (8-500 g of active ingredient per ha) prepared according to Example F6 and stored at 24-26 ° C and 45-60% RH. for humidity. Test results are evaluated 15 days after treatment. 3 weeks after treatment, herbicide exposure is evaluated on a 9-point scale (1 = plant dying, 9 = no effect) compared to control. Bonites 1 to 4 (especially 1 to 3) mean good and very good herbicidal activity. Bonitets 6 to 9 (especially 7 to 9) imply good herbicide tolerance (especially for crop plants).

In this test, compounds of formula I exhibit potent herbicidal activity. The same results are obtained when the compounds of Formula I are used in the formulations in Examples F1-F5 and F7.

Claims (9)

Compounds of the formula q-so ₂ -nh-co-nr i, \ Y wherein Q is a residue of formula A or B, Ra A 'N ^v In which R is hydrogen or methyl, X is C ₁ -C ₄ alkyl, C _x -C ₄ alkyl, C ₁ -C ₄ haloalkoxyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylthio radical, halogen, C ₂ -C ₅ alkoxyalkyl, C ₂ -C ₅ alkoxyalkoxy, A C ₁ -C ₃ alkylamino or a di- (C ₁ -C ₃ alkyl) amino radical, Y is C ₁ -C ₄ alkyl, C _x -C ₄ alkoxy, C ₁ -C ₄ haloalkoxyl, C ₁ -C ₄ haloalkylthio, Ο ₄ -Ο -alkiltioradikalas _four C ₂ -C ₅ -alkoksialkilas C ₂ -C ₅ -alkoksialkoksilas C ₂ -C ₅ -alkiltioalkilas or cyclopropyl E is -CH = or -N =, _Al R is hydrogen, halogen, - (Z) _n -R _x, -NO _2, -NR ₂ R _3, -CsC-R ,, -O-CHR ₅ -C = CR _4, or -COOR _6, R _a2 is hydrogen, fluorine, chlorine or methyl, R _b is hydrogen, fluorine, chlorine, methyl or methoxy radical, Z is O, S, SO or SO ₂ , n is 0 or 1, R ₄ is C ₁ -C ₆ -alkyl as well as C ₁ -C ₄ -alkyl substituted 1, 2, 3 or 4 halogen atoms, 0 _χ -0 ₃ alkoxyls or C ₁ -C ₃ alkylthio radicals, C ₂ -C ₄ alkenyl or C ₂ -C ₄ alkenyl substituted with 1, 2, 3 or 4 halogen atoms, R ₂ is hydrogen or C ₁ -C ₃ alkyl, R ₃ is hydrogen, C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, R ₄ is hydrogen or C ₁ -C ₄ alkyl, R ₅ is hydrogen or methyl and R ₆ is Ci-Ci alkyl or C ₃ -C ₆ -cycloalkyl, as well as salts of these compounds, in addition to the residue of the formula A 2-position substituent R _al oksetaniloksiradikalas or, in the case where _Al is R -COOR ₆ , this substituent takes up the residue of formula A, position 2, and when X is halogen, or X or Y is -OCHF ₂ or -SCHF ₂ , -E is CH =. 2. Compounds according to claim 1, characterized in that Q is a moiety of formula A, wherein R _al is hydrogen, chloro, -CO ₂ CH _3, -CO ₂ C ₂ H _5, CH ₂ CH ₂ CF _3, - CH = CH-CF ₂ -CH _3, or -C = CH and R ₂ is hydrogen or methyl. 3. Compounds according to claim 2, characterized tys in which R _al and R ₂ is hydrogen. Process for the synthesis of compounds of formula I according to claim 1, characterized in that the compound of formula O-SO ₂ -NH ₂ II acts on a compound of the formula sinkad or X or a compound of the formula Q-SO ₂ -NH-COOR _c V acts on a compound of formula X Y wherein Q, R, X, Y and E have the meanings defined in claim 1 and R _c is phenyl or substituted phenyl. 5. Compounds of the formula vn in which ^R ai There is hydrogen, halogen - (Z) _n -R _x , nitro, -NR ₂ R ₃ , - c = cr ₄ , -O-CHR ₅ -C = CR ₄ , -COO-R _fi , -CH ₂ CH ₂ CF ₃ or -CH = CH- cf ₂ -ch ₃ and R _a2 is hydrogen, fluorine, chlorine or methyl Compounds of the formula wherein R _b is hydrogen, fluorine, chlorine, methyl or methoxyl. 7. A herbicidal and plant growth inhibitory preparation according to claim 1, characterized in that it contains one or more compounds which matches I formula according to 1 . 8. Fighting with unwanted plant growth mode, b e - s i s k i in action the fact that the plants or their environment processes efficient the amount of active compound, of Formula I, or an effective amount of a formulation containing the active compound. 9. A method of inhibiting the growth of a plant, comprising treating the plants or their environment with an effective amount of an active ingredient according to claim 1 of the formula I or an effective amount of a preparation containing said active substance. Use of a preparation according to claim 7, for selective control of weeds in cultivated crops before and after emergence.