CS240990B2

CS240990B2 - Bacteridical agent for plants diseases defeat and production method of efficient compound

Info

Publication number: CS240990B2
Application number: CS84312A
Authority: CS
Inventors: Willy Meyer; Werner Toepfl; Haukur Kristinsson; Wolfgang Eckhardt
Original assignee: Ciba Geigy Ag
Priority date: 1983-12-21
Filing date: 1984-01-16
Publication date: 1986-03-13
Also published as: IL70693A; PH20321A; CS31284A2

Description

ČUKOSLOVINSKA SOCIALISTICKÁ

RBPUBLIC (1 ·)

ADAD PROZY PROZYZYZY

AORJBVY

DESCRIPTION OF THE INVENTION

PATENT / 22 / Registered 16 01 84/21 / PV 312-84 / 32 / / 31 // 33 / Priority 21 21 83/563 841 / United States (40) Posted 13 06 85 (45) Released 14 08 87 240990 <M> (BS) (51) Int. Cl.4A Ol N 47/34 Meyer Willy; Ospfl Werner Dr., Dornach, 'KRISTINSSON HAUKUR dr. (72) Author BOTTMINGEN / Switzerland /, 'ECKHARDT WOLFGANG dr. The present invention relates to a bactericidal composition for the control of plant diseases, comprising a new N as an active ingredient. \ T (73) The proprietor of CIBA-GEIGY AG, BASILE (Switzerland) (54). The present invention further relates to a process for the preparation of these novel active compounds of the formula I and their use for combating harmful bacteria, in particular phytopathogenic species.

New compounds of formula I have been found

OCC1-CHCl

N-I / 1 / wherein X is oxygen or sulfur,

R 1 is hydrogen or alkyl of up to 3 carbon atoms, and

R 1 is hydrogen, C 1 -C 4 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl or C 1 -C 2 alkoxy, as well as salts of these compounds which have the ability to control harmful bacteria, in particular phyto-240990 240990 2 pathogenic types and can therefore be used as active ingredients of bactericidal compositions. The present invention provides a bactericidal composition for controlling plant diseases, characterized in that it comprises as active ingredient at least one N- [2- (1,2-dichloro-vinyloxy) -phenylsulfonyl] -thio / urea of the aforementioned and defined formula (I) or jejísůl. Within the compounds of formula I, ureas are preferred over thioureas. The present invention also encompasses salts which may form compounds of formula X with amines, basic alkali and alkaline earth metal compounds, or quaternary ammonium bases.

The alkali metal and alkaline earth metal hydroxides as salt-forming agents are hydroxides of lithium, sodium, potassium, magnesium or calcium, in particular sodium hydroxide or potassium hydroxide.

Examples of amines suitable for salt formation include primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethylamine, propylamine, isopropylamine, four isomeric butylamines, diraethylamine, diethylamine, diethanolamine, dipropylamine, diisopropylamine, di-n-butylamine, pyrrolidine , piperidine, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline and isoquinoline, especially ethylamine, propylamine, diethylamine or triethylamine, especially isopropylamine and diethanolamine. Further suitable are tricyclic nitrogenous bases such as 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [4.4], ojundec-7-ene or 1,5-diazabicyclo [4.3.1] non- 5-en.

Examples of quaternary ammonium bases include, but are not limited to, halo-ammonium salt cations such as tetramethylammonium salts, for example, tetramethylammonium cations, trimethylbenzylammonium cations, triethylbenzylammonium cations, triethylammonium cations, trimethyl-ethylammonium cations, but also ammonium cations.

Alkyl alone or as a constituent of another substituent, such as alkoxy, etc., according to the number of said carbon atoms, for example, are the following straight or branched groups: methyl, ethyl, propyl, butyl, as well as their isomers such as isopropyl, isobutyl, tert-butyl.

Alkenyl is understood to mean, for example, 1-propenyl, allyl, 1-butenyl, 2-butenyl or 3-butenyl. Alkinyl means, for example, 2-propynyl, propargyl, 1-butynyl, 2-butynyl, etc., preferably propargyl.

The compounds of formula I are at room temperature oils, resins, or predominantly crystalline solids, which have very valuable bactericidal properties.

These compounds can be used, for example, in agriculture or in related fields, for preventive and curative treatment of phytopathogenic bacteria, particularly Xanthomonas species. The active compounds of the formula I according to the invention exhibit high bactericidal activity and a wide range of activity over a wide range of applied concentrations and can be used without difficulty in particular agriculture.

Due to their marked bactericidal activity, in particular the phytobactericidal activity, the following groups of active ingredients are preferred: 24040

Group Ia:

Compounds of Formula I wherein X is oxygen or sulfur; R 1 is hydrogen or C 1 -C 3 alkyl; and R 2 is hydrogen, C 1 -C 4 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl or C 1 -C 2 alkoxy.

Group Ib:

Compounds of Formula I wherein X is oxygen or sulfur; R1 is hydrogen or (C1-C3) alkyl; and r 2 is C 1 -C 4 alkyl or C 1 -C 2 alkoxy.

Ic group:

Compounds of formula I wherein X is oxygen R 1 is hydrogen or alkyl of 1 to 3 carbon atoms; and R 2 is C 1 -C 4 alkyl.

Also interesting are the following subgroups:

Group Id;

Compounds of Formula I wherein X is oxygen or sulfur; R 1 is hydrogen or C 1 -C 3 alkyl, and r 2 is C 3 -C 4 alkenyl or C 3 -C 4 alkynyl.

Group Ie:

Compounds of Formula I wherein X is oxygen; R 1 is hydrogen or alkyl of 1 to 3 carbon atoms; and R 2 is C 3 -C 4 alkenyl or C 3 -C 4 alkynyl.

If group:

Compounds of formula I wherein X is oxygen and R1 and R2 are independently hydrogen, R2 is also C3 -C4 alkenyl or C3 -C4 alkynyl.

Particularly preferred individual compounds are, for example: N- [2- (1,2-dichloro-vinyloxy) -phenylsulfonyl-urea / Compound No. 1.1] N-N2- (1,2-dichloro-yloxy) -phenylsulfonyl-N'-methyl-urea / Compound No. 1, N 2 - (2- / 1,2-dichloro-yloxy) -phenylsulfonyl] -N'-isopropylurea / Compound No. 1,5 / 1 N- (2- (1,2-dichloro-vinyl) -phenylsulfonyl) -N'- n-butylurea / Compound No. 1.6 / N- [2- (1,2-Dichloro-vinyloxy) -phenylsulfonyl] -N'-methoxy-N '-methylurea / Compound No. 1.29 (N-β-2- (1,2-dichloro-vinyloxy) -phenylsulfonyl) N'-allylurea / Compound No. 1.20 / 240990 4 N - (1,2-Dichloro-vinyloxy) -phenylsulfonyl-N '-N'-dimethyl-urea / Compound No. 1.24 / N- (2·) N, 2-dichloro-vinyloxy (phenylsulfonyl) -N-methyl-N'-ethylurea / Compound No. 1.25 (N- [1,2-Dichloro-vinyloxy) -phenylsulfonyl] -N'-methyl-N'-allylurea / Compound No. 1.32 / NJ.2 - [1,2-dichloro-vinyloxy] -phenylsulfonyl-N '-methylthiourea / Compound No. 2.2 / N- [2- (1,2-dichloro-vinyloxy) -phenylsulfonyl-N' -isopropylthiourea / Compound No. 2.5 / N-N 2 - [1,2-Dichloro-vinyloxy] -phenylsulfonyl-N '-allylthiourea / Compound No. 2.20 /.

The preparation of the compounds of the formula I according to the invention is carried out in an organic solvent which is inert under the reaction conditions at temperatures between -20 and +120 ° C by the non-reacting of 2- (1,2-dichloro-vinyloxy) -phenylsulfonyl-iso-thio-cyanate. of formula II -so2-n / 11 /

OCC 1 - CHCl wherein X is as defined in Formula I,

preferably in the presence of a base, with an amine of the formula III h - y - R 1/111 / R 2 wherein R 1 and R 2 are as defined above.

This process of the invention will hereinafter be referred to as process a).

In addition, the compounds of formula (I) can also be prepared in that the seb / 2- (1,2-dichloro-vinyloxy) -phenylsulfonamide of formula (IV) <> so2 - nh2 / IV /

0CC1 = CHCl

is reacted in the presence of a base with a carbamoyl halide of formula V

X

II

Hal - C - N - R ./V/ 5 240990 in which

Hal represents a halogen atom, preferably chlorine or bromine, especially a chlorine atom, and X, R 1 and Rj are as defined above, or are

c) for the preparation of compounds of formula I wherein R 1 is hydrogen, reacts 2- / 1,2-dichloro-vinyloxy / phenylsulfonamide of the above formula IV, in the presence of a base, with iso / thio-cyanate of formula VI x> c = n - r 2 (wherein X and R 1 are as defined above). The ureas of formula I obtained can optionally be converted into salts by treatment with amines, hydroxides of alkali metals or alkaline earth metal hydroxides or quaternary ammonium bases. This reaction is effected, for example, using an equimolar amount of base and evaporation of the solvent.

The compounds of formulas III and VI are generally known or are produced by methods known per se. The compounds of formulas II and IV or their preparation are described in EP 44 807.

The above-mentioned reactions and /, b / ac / leading to compounds of formula I are preferably carried out in aprotic, inert, organic solvents or solvent mixtures. Suitable solvents or diluents are, for example, the following: aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, tetrachloromethane, tetrachlorethylene. ethers and ether compounds such as dialkyl ethers / diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc., ethylene glycol dimethyl ether, diethyl glycol dimethyl ether, anisole, dioxane, tetrahydrofuran nitriles such as acetonitrile, propionitrile, Ν-alkylated amides such as dimethylformamide; dimethylsulfoxide, ketones such as acetone, diethyl ketone, methyl ethyl ketone and mixtures of such solvents with each other. In many cases, the reactant may serve as a solvent.

Reaction temperatures are generally between -20 ° C and +120 ° C, preferably between 0 ° C and + 30 ° C. These reactions generally proceed slightly exotherm and can be carried out at room temperature.

In order to shorten the reaction time or also to initiate the reaction, it is expedient for a short period to heat up to the boiling point of the reaction mixture.

The reaction times may also be shortened by the addition of a few drops of the base as a reaction catarizer.

The bases used may be organic bases such as amines, for example tertiary amines (such as triethylamine, trimethylamine, tripropylamine, N-methylpiperidine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.1.0 < 2,7 > 4, ojundec-7-ene and the like, pyridine apyridine bases (such as 4-dimethylaminopyridine, 4-pyrrolidylaminopyridine, picolines, lutidine etc.), as well as inorganic bases such as hydrides such as sodium hydride or calcium hydride hydroxides, as sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate or hydrogen carbonates such as potassium bicarbonate and sodium bicarbonate. In a variant, the compound of formula III itself serves as a base. 240990 6

The end products can be isolated by concentration and / or evaporation of the solvent and can be purified by recrystallization or trituration of the solid residue in solvents where the thio compounds do not dissolve well, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons. The active compounds of the formula I are stable compounds. Handling of these substances does not require any safety precautions.

It has now surprisingly been found that the compounds of formula I have a very favorable spectrum of bactericidal activity against phytopathogenic bacteria for practical purposes. These substances are highly curative, in part also systemic and, in particular, preventive properties can be used to protect numerous crop plants.

With the active compounds of the formula I, the microorganisms which are present or destroyed can be destroyed or suppressed on plants or on parts of plants / fruits, flowers, leaves, stems, tubers, roots / various utility crops, and even later grown portions remain protected from such pests. plants. The active compounds of the formula I and their preparations are particularly effective against Pseudomonadeles, such as Pseudomonadeceae bacteria, such as Pseudomonas and Xanthomonas / Pseudomonas tomato, Pseudomonas tabaci, Pseudomonas mors-prunorum, Pseudomonas phaseolicola, Pseudomonas lachrymans, Xanthomonas capestris, Xantho -monas oryzae, Xanthomonas vesicatoria /. Accordingly, the present invention provides bactericidal compositions as well as their use and the use of compounds of formula I for controlling phytopathogenic bacteria, in particular Xanthomonas species which are harmful to plants, as well as preventively preventing plant infestation.

In addition, the present invention also encompasses the manufacture of agrochemical compositions comprising thoroughly mixing the active ingredient with at least one of the substances or groups of substances described herein. The invention also relates to a method of treating plants which comprises applying the compounds of formula (I) or novel compositions.

Like. cultural plants, for which the abovementioned amount of application applies, are coming For example, the following plant species may be considered within the scope of the invention: cereals / wheat, barley, rye, oats, rice, sorghum and related plants; beet / sugar beet and fodder beet; fruit trees fruiting with cores, seeds and berries / apple, pear, plum, peach, almond, cherry, strawberry, raspberry and blackberry /; legumes / beans, lentils, peas, soya /; oilseed / rape, mustard, poppy, olive tree, sunflower, coconut, castor, cacao, peanut /; cucurbits / pumpkins, cucumbers, melons /; fiber / cotton, flax, hemp, jute /; citrus / orange, lemon, largest lemon, tangerine /; various kinds of greens / spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers /; laurel plants / avocados, cinnamon, camphor / or other plants such as maize, tobacco, butternut, coffee, cane, tea, grapevine, hops, banana and cauliflower, as well as ornamental plants (Compositae), preferably rice and pepper. The active compounds of the formula I are usually used in the form of compositions and can be applied to the areas treated or to the plants simultaneously or sequentially with the other active ingredients. trace elements or other preparations that affect plant growth.

They may also be selective herbicides, insecticides, fungicides, bactericides, nematodes, molluscicides or mixtures thereof together with optionally other carrier substances, surfactants or other application-promoting additives used in the preparation of such compositions. 7 240990

Suitable carrier substances may be solid or liquid and correspond to substances used in the preparation of such compositions as, for example, natural or regenerated mineral substances, solvents, dispersants, wetting agents, adherents, thickeners, binders or putties. A preferred method of administering an active ingredient of the formula I or an agrochemical composition which contains at least one of these active ingredients is by application to the kerosene.

The number of applications is determined by the extent of infestation for the corresponding disease agent / species of fungus, but the active compounds of formula I can also be fed to the plant via soil and roots / systemic action by pouring a liquid preparation on the plant site or applying the active ingredients. into the soil in solid form, for example in the form of a granulate / soil application.

However, the compounds of formula (I) may also be applied to Coating by impregnating the semenabud with a liquid formulation of the active ingredient or forming a solid preparation layer thereon. In addition, other modes of application, such as deliberate treatment of plant stems or buds, are also possible in particular cases.

The compounds of formula X are used in this application unchanged or preferably together with the auxiliaries customary in the preparation of such compositions and are thus processed, for example, into emulsion concentrates, pastes which can be applied by brushing, direct sprayable or dilutable. solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and compositions encapsulated, for example, in polymeric materials in a conventional manner.

Application procedures, such as spraying, fogging, dusting, sprinkling, painting or watering, are chosen in accordance with the desired objectives and conditions. The preferred application rates are generally from 50 g to 5 kg of active ingredient per 1 ha, preferably from 100 g to 2 kg of active ingredient, in particular from 200 g to 600 g of active ingredient per ha.

Said compositions, i.e. compositions containing the active ingredient of the formula I and optionally solid or liquid additives, concentrates or dosage forms are prepared in a manner known per se, for example by thoroughly mixing and / or grinding the active ingredients with carriers such as solvents, solid carriers and optionally surfactant (s).

Suitable solvents may be: aromatic hydrocarbons, preferably 8 to 12 carbon atoms, such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as optionally epoxidized vegetable oils such as epoxidized coconut oil or oil or water .

As solid carriers, for example dusts and dispersible powders, natural stone meal such as limestone, talc, kaolin, montmorillonite or att-pulgite is used. Also, highly disperse acidic or highly disperse absorbent polymers can be added to improve the physical properties.

Suitable granular adsorptive carrier materials are porous types, such as, for example, pulp, brick, sepiolite or bentonite; for example, non-corrosive carriers weigh 240990 8 or sand. In addition, a variety of pre-granulated materials of inorganic or organic origin, such as dolomite or comminuted plant residues, can be used.

Particularly preferred application-promoting additives which can lead to a significant reduction in the amount used are natural / animal or vegetable / or synthetic phospho-lipids from a series of cephalins and lecithins such as phosphatidylethanolamine, phosphatidylserine, phosphatidylcholine, sphingomyelin, phosphatidylinosit, phosphatidylglycerin, lysolecithin, plasma-logen or cardiolipin, which can be obtained, for example, from animal or plant cells, especially from brain, heart, lung, liver, yolk, or soybean.

Useful compositions which are in the market are, for example, phosphatidylcholine mixtures. Synthetic phospholipids are, for example, dioctanoylphosphatidylcholine and dipalmitoylphosphatidylcholine.

Suitable surface-active compounds are, according to the type of active ingredient of the formula I to be treated, nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Tensides are also understood to mean mixtures of surfactants.

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

Examples of soaps are salts of higher fatty acids (C 10 -C 22) with alkali metals, alkaline earth metals or optionally substituted ammonium salts such as sodium or potassium oleic acid or stearic acid salts or mixtures of natural fatty acids. which are obtained, for example, from coconut oil or tallow. Introduce the necessary mixtures of methyltaurin with fatty acids. However, so-called synthetic surfactants, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates, are more commonly used.

Fatty sulphonates or sulphates generally occur in the form of alkali metal, alkaline earth metal or optionally substituted ammonium salts and contain an alkyl radical of 8 to 22 carbon atoms, the alkyl radical may also include an alkyl portion of acyl radicals such as for example, the sodium or calcium salt of ligninsulfonic acid, the dodecylsulfuric ester or the mixture of sulfated fatty alcohols that have been made from natural fatty acids.

Also included are salts of sulfuric acid esters and sulfonic acids of fatty alcohol adducts with ethylene oxide. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acids and the C8 -C22 fatty acid residue.

Alkylarylsulfonates are represented, for example, by the sodium, calcium or triethanol ammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or the condensation product of naphthalenesulfonic acid and formaldehyde. Also suitable are corresponding phosphates, such as salts of the phosphoric acid ester of an adduct of 4-14 moles of ethylene oxide with p-nonylphenol.

Suitable nonionic surfactants are, in particular, derivatives of polyglycol ethers of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids, and alkylphenols which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in aliphatic / hydrocarbon radicals and 6 to 18 atoms. carbon in the alkyl moiety of alkylphenols.

Other suitable nonionic surfactants are the water-soluble polyethylene oxide adducts propylene glycol, ethylenediaminopolypropylene glycol and alkyl polypropylene glycol having from 1 to 10 carbon atoms in the alkyl chain containing from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups. 9 240990

These compounds usually contain 1 to 5 units of ethylene glycol per propylene glycol unit.

Examples of nonionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene adducts with polyethylene oxide, tributylphenoxypolyethoxy ethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate. In particular, cationic surfactants are quaternary ammonium salts which contain at least one alkyl radical of 8 to 22 carbon atoms as the substituents on the nitrogen atom, and further substituents contain lower, optionally halogenated, alkyl, benzyl or lower hydroxyalkyl radicals.

These salts are preferably present in the form of halides, methylsulfates or ethylsulfates such as stearyltrimethylammonium chloride or benzyl-di- (2-chloroethyl / ethylammonium bromide).

The surfactants common in the preparation of such compositions are described, inter alia, in the following publications: "MC Cutcheon's Detergents and Emulsifiers Annual" BC Publishing Corp., Ringewood ·

New Jersey, 1981. Helmut Stache "Tensid-Taschenbuch" Carl Hauser-Verlag Munchen / W 1 ^ 81.

Generally, the agrochemical compositions contain from 0.1% to 99% of the active compound of the formula I, in particular from 0.1% to 95% of the active compound of the formula I, from 99.9% to 1%, in particular from 99.8% to 5%, of the solids and from 0-25% in particular 0.1 to 25% surfactants.

While concentrated compositions are preferred on the market, the end consumer generally uses diluted compositions. These compositions may also contain other additives such as stabilizers, antifoams, viscosity regulators, binders, adhesives, and fertilizers or other active ingredients to achieve special effects.

Such agrochemical compositions are part of the present invention. The following examples serve to illustrate the invention without limiting the scope of the invention in any way. Examples illustrating the preparation of the active compounds: Example 1 Production of N-1,2- (1,2-dichloro-vinyloxy) -phenylsulfonyl-N'-methyl-N'-ethyl-urea

so2-nh-co-n-c2h5

CH OCC 1 = CHCl 1 / Compound No. 1.25 / A solution of 2.1 g of N-methylethylamine in 50 ml of absolute dioxane is added dropwise at 20-25 ° to a solution of 10.3 g of 2- (1,2-dichloro-vinyloxy) phenyl isocyanate in 100 ml of absolute dioxane. C and the mixture was further stirred at room temperature for 15 hours. 240990 10

After the reaction mixture was evaporated, the residue was crystallized after addition of acetone-hexane. The product is filtered off and dried. Yield 7.5 g, mp 179-180 ° C. EXAMPLE H2 Production of N- [2- (2,2'-Dichloro-Vinyloxy) -phenylsulfonyl-N ', N'-dimethyl-urea SO2-NH-CO-N / CH3 / OCC1-CHCl / Compound No. 1.24 /

A solution of 10.7 g of 2- (1,2-dichloro-vinyloxy) -phenylsulfonamide, 12.2 g of 1,8-diazabicyclo-5,4,0undec-7-ene in 100 ml of dichloromethane is added dropwise at 20-25 ° C. 2 g of di-dimethylcarbamoyl chloride in 10 ml of dichloromethane and the mixture is heated to reflux.

Then the solvent is evaporated and the residue is dissolved in 5% sodium carbonate solution. The solution is filtered and acidified with 10% hydrochloric acid to precipitate the product in crystalline form. After filtration and drying, 12.1 g of N- [2- (1,2-dichloro-vinyl-oxy) -phenylsulfonyl] -N ', N'-dimethyl-urea are obtained. Mp 218-220 ° C. EXAMPLE 1 Production of dH3 N- [2- (1,2-dichloro-vinyloxy) -phenylsulfonyl] -N'-allyl-urea urea-2-h-co-nh-ch2ch = ch2 OCCl = CHCl # 1.20 /

compound r 1

A solution of 3.3 g of allyl isocyanate in 10 ml is added dropwise with stirring to a mixture of 10.7 g of 2- (1,2-dichloro-vinyloxy) -phenylsulfonamide and 6.1 g of 1,8-diazabicyclop, 4,0-jundec-7-ene in 100 ml of dichloromethane. dichloromethane.

After the exothermic reaction had subsided, the reaction mixture was further stirred for 1 hour at 20-25 ° C and then the solvent was evaporated. The residue was dissolved in 5% carbonate solution.

The solution is filtered and acidified with 10% hydrochloric acid to precipitate the product in crystalline form. After filtration and drying, 13.2 g of N2- (1,2-dichloro-vinyloxy) -phenylsulfonyl-N'-allylurea are obtained. Mp 187-188 ° C. Example H 4 Preparation of N, N '- (1,2-dichloro-vinyloxy) -phenylsulfonyl-N-methyl-thiourea

13.4 g of 2- (1,2-dichlorvinyloxy) phenylsulfonamide and 3.65 g of methyl isothiocyanate are dissolved in 50 ml of acetonitrile and under cooling at 0 to 5 ° C. and, while stirring, 7.8 g of 1,6-diazabicyclo 5.4.0 undec-7-ene is added. The resulting red reaction solution was allowed to stand for 24 hours, then 4.8 g of methanesulfonic acid was added thereto, and the mixture was diluted with water to a volume of 1 liter. The precipitated crystals are filtered off, washed with methanol and dried. Yield 15 g, m.p. 185 DEG-187 DEG C. (decomposition). EXAMPLE Preparation of N-1,2- (1,2-dichloro-vinyloxy) -phenylsulfonyl-N'-methyl-urea

To a suspension of 6.7 g of 2- (1,2-dichloro-vinyloxy) -phenylsulfonamide in 50 ml of dichloromethane, add 1.9 g of methyl isocyanate. 3.3 g of triethylamine are added dropwise over 10 minutes to the mixture at 20 to 25 ° C to give a clear solution.

The solution was further stirred for 1 hour and then evaporated to dryness. The residue was dissolved in 5% aqueous sodium carbonate solution and the solution was quenched with 10% hydrochloric acid to precipitate the product in crystalline form.

After filtration and drying, 7.8 g of N- [2- (1,2-dichloro-vinyloxy) -phenylsulfonyl] -N'-methyl-urea is obtained. Mp 228-229 ° C.

The following compounds of formula (I) are also prepared by analogous procedures to those described above:

Table l

Compounds of formula

OCCl-CHCl Compound No. 1.1 1.2 1.3 1.4 1.5

H

H CH. C2H5 physical constants / ° C / tt 219-221 tt 228-229 tt 169-173 tt 149-154 ο3η7-ι tt 156-160 240990 12 compound physical number R 1 R 2 constant / ° C / 1.6 H C 4 H 8 -n f t 123-126 1.7 HC ^ Hg-sek. 1.8H C4Hg-tert. 1.13 H och3 tt 154 - 156 1.14 H o c2h5 1.20 H ch2ch = ch2 tt 187 - 188 1.21 H ch2c = ch 1.22 H c / ch3 / 2c = ch tt 153 - 156 1.23 H CH2CH2CH-CH2 1.24 CH3 CH3 tt 218 - 220 1.25 ch3 C2H5 tt 179 - 180 1.26 CH3 C3H7 - n 1.27 ch3 Η3 - 7 - ί 1.28 C2H5 C2H5 1.29 ch3 och3 tt 154 - 156 1.30 CH3 OC2H5 1.32 Target3 CH2CH - CH2 tt 144 - 146 1.33 CH3 CH2CH2CH = CH2 1, 35 C2H5 CH2CH-CH2 1.36 C3H7 'n CH2CH = CH2 resin 1.37 C2.5 CH2C / CH3 / CH2 CH2 1.38-3-7 CH2C / CH3 CH2 = 1.39' CH3 CH2C / CH3 / CH2 1.40 H CH2C / CH3 / CH2 = 1.41 CH3 CH2CSCH semi-crystalline product 13 240990

Table 2

Compounds of formula

OCC1 = CHC1 compound physical number R1 r2 constant / ° C / 2.1 HH 2.2 H cb3 tt 185 - 187 2.3 H C2H5 2.4 H C3H7-n 2.5 H £ 3 ^ 7- ^ tt 146 - 148 2.6 H ^ 4 ^ 9 -n 2.7 HC ^ Hg-sec. 2.8 HC ^ Hg-tert. 2.13 H OCH3 Viscous oil 2.14 H OC2H5 semicrystalline product 2.20 H CH2CH = CH2 tt 129 - 131 2.21 H ch2c = ch 2.23 H CH2CH2CH = CE2 2.24 CH3 ch3 resin 2.25 CH3 C2H5 2.26 CH3 C2H5-n 2.27 CH3 C3H2-resin 2.28 C2H5 C2H5 '2.29 CH3 0CH3 2.30 CH3 OC2H5 2.33 CH3 CH2CH2CH = CH2 240990 14 continued

Compound No. R1 R2 2.35 C2H5 CH2CH-CH2 2.36 C3H2-n CH2CH = CH2 2.37 C2.5 CH2C / CH3 / CH. 2.38 C3H7-CH2C / CH3 / CH. 2.39 CH 3 CH 2 C / CH 3 / CH. 2.40 H CH 2 C / CH 3 / CH. 2.41 CH, CH, CBCH physical constants / ° C /

Examples illustrating the composition and preparation of compositions for a liquid active ingredient of formula I (%) by weight /

Fl. Emulsion concentrate a / b / c / active ingredient from Tables 25 »40% 50% calcium salt of dodecylbenzenesulfonic acid 5» 8 »6% polyethylene glycol ether of castor oil / 36 mol ethylene oxide / 5% - - tributylphenylpolyethylene glycol ether / 30 mol ethylene oxide / - 12% 4% cyclohexanone - 15% 20 i xylene blend 65% 25% 20% Each trace can be produced from such concentrates by diluting with water emulsion. F2. Solutions a / b / c / d / active ingredient from tables 80% 10% 5% 95% ethylene glycol monohydrate 20% - - polyethylene glycol / molecular weight 400 / - 70% - - N-methyl-2-pyrrolidone - 20 % - - epoxidized coconut oil benzine / boiling range160 to 190 ° C / 1% 5% 94% 15 240990

These solutions are suitable for P3. The granules of the active ingredient from tablecholine high-dispersion silicic acid attapulgite application in the form of minimal droplets a / b / 5% 10% 94% 1% 90% The active ingredient dissolved in the solvent is then evaporated in methylene chloride, the solution is sprayed onto the carrier in a vacuum. F4. Dust 4 / b / active ingredient from the table 2% high-dispersible silicic acid 1% talc 97% kaolin 5% 5% 90% By thoroughly mixing the carrier substances with the active ingredient, a directly usable dust is obtained. Examples illustrating the composition and preparation of solid carrier compositions of Formula I:% =% by weight / F5. Wettable powder a / b / c / active ingredient from table 25% ligninsulfonic acid sodium salt 5% sodium lauryl sulfate 3% sulfur adiisobutylnaphthalenesulfonateoctylphenolpolyethylene glycol ether / 7 to 8 moles ethylene oxide / high dispersion silicic acid 5 ikaolin 62% 50% 75% 5% 5% 6% 10% 2% 10% 10% 27% The active ingredient is well mixed to obtain a wettable powder that can be diluted with the additive, and the mixture is well ground in a suitable mill with water to suspend each desired concentration. F6. Emulsion concentrate active substance from table 10% octylphenolpolyethylene glycol ether / 4 to 5 moles of ethylene oxide / 3% calcium salt of dodecylbenzenesulfonic acid, 3 i polyglycol ether of castor oil / 35 moles of ethylene oxide / 4% cyclohexanone 30% mixture of xylenes 50% diluting with water the emulsion of each desired concentration. 240990 16 F7. Dust and / active ingredient from the table 5% talc 95% kaolin - The active ingredient is mixed with the carrier material to obtain a ready-to-use dust. • F8. Extruded granulate: active ingredient from table 10% ligninsulfonic sodium salt 2% carboxymethylcellulose 1% kaolin 87% b / 8% 92% blend in a suitable mill. Thus, the active ingredient is mixed with the ingredients, the mixture is ground and moistened with water. This mixture is processed on an extruder and then dried in a stream of air. F9. Coated granulate: active substance from table 3% polyethylene glycol / molecular weight 200/3% kaolin 94%

The finely divided active substance is uniformly applied to the kaolin moistened with polyethylene glycol in the mixer. In this way, a dust-free coated granulate is obtained. F10. Suspension concentrate. active substance from table 40% ethylene glycol 10% nonylphenolpolyethylene glycol ether / 15 mol ethylene oxide / 6% ligninsulfonic sodium salt 10% carboxymethylcellulose 1% 37% aqueous formaldehyde 0.2% silicone oil 75% aqueous emulsion 0.8% water 32%

The finely divided active ingredient is thoroughly mixed with the ingredients. In this way, a spenerate concentrate is obtained, from which a suspension of each desired concentration can be produced by dilution with water. 17 240990 Examples illustrating biological activity: Example B 1 Effect on Xanthomonas oryzae on rice a / Residual protective effect

"Caloro" or "S6" rice plants are sprayed with the test substance in the form of a spray suspension (0.06% active ingredient) after 3 weeks of cultivation in the greenhouse. After the spray layer has been dried for one day, the plants are placed in an air-conditioned room at 24 ° C and 75-85% relative humidity and are infected.

The infection is accomplished by cutting the tip of the leaves with scissors previously immersed in a suspension of Xanthomonas oryzae. After a 10-day incubation in the same space, the cut leaves fade, twist, and become necrotic. The extent of these symptoms is used to assess the residual efficacy of the test substance. b / Systemic effect

Rice plants. of the "Caloro" or "S6" species, after 3 weeks of cultivation in the greenhouse, pour the suspension of the test substance (0.006% of active ingredient by volume) and place the plants in an air-conditioned room at 24 ° C and 75-85% for three days. relative humidity and infect.

The infection is done by cutting the tips of the leaves with scissors that are previously immersed in the Xanthomonas oryzae suspension. After a 10-day incubation in the same room, the clippers wilt, curl, and become necrotic. The degree of these disease symptoms serves to assess the systemic efficacy of the test substance.

The compounds of the tables show good activity against Xanthomonas bacteria. Thus suppressing the residual protective and systemic treatment of the rice, among others, compounds No. 1.1, 1.2.1.5, 1.6, 1.13, 1.20, 1.22, 1.24, 1.25, 1.32, 2.2, 1.29, 2.5 and 2.20, the incidence of necrotic blood vessels is totally 0-5% / .

Compounds No. 1.2 and 1.25 completely prevent fungal attack (0%) even at an even lower application rate. Untreated but infected rice plants / control / show 100% necrosis. Example B2 Effect on Xanthomonas vesicatoria on paprika and / Residual-protective effect

"California Wonder" peppers are sprayed with the test substance as a spray suspension (0.06% active ingredient) after growing for 3 weeks in the greenhouse. After drying the spray layer for one day, the plants are placed in an air-conditioned room at 26 ° C and at 95-100% relative humidity and are infected by spraying the lower sides with a standard Xanthomonas vesicatoria suspension.

After a six-day incubation in the same room, round spots appear on the leaves whose appearance is first watery and later necrotic. The extent of these spots serves to assess the residual efficacy of the test substance.

B 24090 18 b / Systemic effect

"California Wonder" peppers are planted with a test substance slurry (0.006% active ingredient based on soil volume) after growing in a greenhouse for 3 weeks. Three days after this treatment, the plants are placed in an air-conditioned room at 26 ° C and at 95-100% relative humidity and are infected by spraying the lower sides of the leaves with a standard Xanthomonas vesicatoria suspension.

After a 6-day incubation in the same room, round spots appear on the leaves whose appearance is first watery and later necrotic. The extent of these spots serves to assess the systemic efficacy of the test substance. The compounds in both tables almost completely prevent the occurrence of these stains. In both experiments, the incidence of necrosis of the compound of Example B1 / Infestation 0 to 5% is almost completely suppressed. In the control experiment, the attack is 100%. Example B3 Effect against Pseudomonas tomato on tomatoes and / Residual-protective effect

"Rentita" tomato plants are sprayed with a spray suspension (0.06% active ingredient) after 3 weeks of growing in a greenhouse. After the spray layer has been dried for one day, the plants are placed in an air-conditioned room at 22 ° C and at 95-100% relative humidity and are infected by spraying the lower sides with a standard Pseudomonas tomato suspension.

After an 8-day incubation in the same space, small, black spots appear on the leaves with a yellowish court. The average number of spots per sheet serves as a basis for evaluating the efficacy of the test substance. b / Systemic effect

Tomato plants of the "Rentita" type are planted with suspending agents (0.006% of the active ingredient, based on the volume of the soil) after growing in a greenhouse for 3 weeks. Three days after this treatment, the plants are placed in a conditioned room at 22 ° C and at 95-100% relative humidity and are infected by spraying the lower sides of the leaves with a standard Pseudo-monas suspension.

After an 8-day incubation in the same space, small black spots with yellowfinch appear on the leaves. The average number of such spots per sheet serves as a basis for evaluating the efficacy of the test substance. In both assays, the compounds of Example B1 suppress the incidence of necrosis on the 0 to 5% total infestation. In the control experiment, the attack is 100%.

In the above-described Examples B1, B2 and B3, which illustrate biological activity, the following sulfonylureas have been simultaneously tested as reference substances:

/ compound known from De-OS 2 715 786/19 24.0990 OCH, B / II P = \ t

S02 - NH - C - NH - N

KC / CH3 cooch3 / a compound known from EP-7687 / O from CH3 1 | N = / so2 —NH-C-NH ΝΛ COOCH 3 · h 3 / a compound known from EP-7687 / OCH, D / o: SO 2 —NH - C - NH-

N = Z

IN

Cl OCH, a compound known from EP-4163 /

The specific test results obtained in Examples B1, B2 and B3 are summarized in the following table: tested tested by example / bactericidal effect in% / compound B1 B2 B3 number Xanthomonas Xanthomonas Pseudomonas oryzae vericatoria tornato 1.1 3-5 4-5 3-4 1.2 0 0 0 1.3 0 0 0 1.4 0 0 0 1.5 0 0 0 1.6 0 0 0 1.13 0 0 '1 1.20 3-5 4-4.5 3-5 1.22 5 5 4-5 1.24 4-5 4-5 5 1.25 0 0 0 1.29 0 0-1 0 1.32 3-5 '3-5 3-5. 1.36 5-7 6-7 5-7 1.38 5-7 5-10 8-10

Claims

240990 20 table continuation test compound number tested B1 Xanthomonas oryzae by example / bactericidal effect in% / B2 B3 Xanthomonas Pseudomonas vericatoria tomato 1.41 10 9-10 10 2.2 0 0 0 2.5 · 0-3 0 0-3 2.13 0 0 0 2.14 0 0 1 2.20 8-10 7-9 7-10 2.24 0 0 0 2.27 0 0 0 A 80-100 90-100 90-100 B 60-80 40-60 60-70 C 80-100 80-100 90-100 D 90-100 80-100 80-100 Control IOO 100 100 At low test, unlike the compounds, at least no effect at all. the compositions of the invention for practically unusable B, C and D effects, or B) A bactericidal composition for the control of plant diseases, characterized in that it contains agriculturally acceptable excipients and auxiliaries. the active ingredient is at least one of the compounds of the formula (IX) - (PO) - NH-CNR (1) OCC 1 -CHCl in which X is oxygen or sulfur, R 1 is hydrogen or (C 1 -C 3) alkyl and

21,240,990 R2 is hydrogen, C1 -C4 alkyl, C3 -C4 alkenyl, C3 -C4 alkynyl or C1 -C2 alkoxy, or a salt thereof.

2. A composition according to claim 1, wherein said compound is N- [2- (1,2-dichloro-vinyloxy) -phenylsulfonyl] -N'-methyl-urea.

3. A composition according to claim 1, wherein the active ingredient is a compound of formula (I) selected from the group consisting of N, N '- (1,2-dichloroquino) phenylsulfonylurea, N < 2 > 1,2-dichloro-vinyloxy-phenylsulfonyl-N'-isopropylurea, N- (2- (1,2-dichloro-vinyloxy) -phenylsulfonyl-N'-n-butyl-urea; N ' -methoxy-N ' -methylurea, N- [2- (1,2-dichloro-vinyloxy) -phenylsulfonyl] -N ' -allylurea, N-2- (1,2-dichloro-vinyloxy) -phenylsulfonyl] -N ' dimethylurea, N- [2- (1,2-dichloro-yloxy) -phenylsulfonyl] -N-methyl-11'-ethylurea, N-β2- (1,2-dichloro-vinyloxy) -phenylsulfonyl-N'-methyl-N ' - allylurea, N- [1,2- (1,2-dichloro-vinyloxy) -phenylsulfonyl] -N '-methylthiourea, N-η 2 - (1,2-dichloro-vinyloxy) -phenylsulfonyl-N' -isopropylthiurea and N- [2- (l), 2-dichloro-vinyloxy-phenylsulfonyl-N'-allylthiourea.

4. A process for the preparation of the active ingredient according to claim 1, characterized in that it is present in an organic solvent which is. inert under reaction conditions, allow to react at temperatures between -20 and +120 ° C 2- / 1,2-dichlorvinyloxy / phenylsulfonyliso / thio / cyanate of general formula II

In which X is as defined in 1, by an amine of formula III wherein němž - N - R 11 R 2/111 / R 1 and R 2 are as defined in point 1.