Derivative benzotriazole and their salts formed by the addition of acids, fungicidal vehicle and method of controlling undesirable fungi in the protection of plants and materials

 

(57) Abstract:

Describes the new derivative benzotriazole General formula (1), where X1is hydrogen, halogen, nitro or halogenated with 1-6 carbon atoms and 1 to 3 halogen atoms, X2is hydrogen, halogen, alkyl with 1-8 carbon atoms, nitro, halogenoalkane or halogenated with 1-6 carbon atoms and 1 to 3 halogen atoms, X3is hydrogen, halogen, alkyl with 1-8 carbon atoms, halogenated with 1-6 carbon atoms and 1 to 3 halogen atoms or a radical of the formula - O-R3, R3to 6-membered nitrogen-containing heterocyclic radical, substituted by halogenation with 1-6 carbon atoms and 1 to 3 halogen atoms, X2and X3together signify unsubstituted or substituted by alkyl with 1-8 carbon atoms alkylenes chain with 3-4 links or alkilinity chain with 3-4 links, in which two lesosecnyh carbon atom is replaced by oxygen atoms, substituted by 1-4 halogen atoms, or X2and X3together denote a residue of formula II, where X4is hydrogen or halogen, R - isoxazolyl, mono - or disubstituted amino, alkyl with 1-8 carbon atoms or cycloalkyl with 3-6 carbon atoms, pyrazolyl substituted by halogen and alkyl with 1-8 carbon atoms, thienyl, unsubstituted or samisen thiazolyl, substituted by alkyl with 1-8 carbon atoms, and their salts formed by the addition of acids. The compounds exhibit fungicidal activity, higher in comparison with analogues. Describes fungicidal vehicle and method of controlling undesirable fungi in the protection of plants and materials. 3 S. and 1 C.p. f-crystals, 5 PL.

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The invention relates to new derivatives of triazole with microbicide activity, in particular derivatives of benzotriazole and their salts formed by the addition of acids, fungicidal tool and method of controlling undesirable fungi in the protection of plants and materials.

Known derivative benzotriazole with microbicide activity (see application EP N 0 238 824, published 29.03.1988 year).

The objective of the invention is the expansion of the Arsenal derivatives benzotriazole with microbicide activity, in particular fungicidal activity.

The problem is solved proposed derivatives benzotriazole General formula (I)

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where X1is hydrogen, halogen, nitro or halogenated with 1-6 carbon atoms, substituted by 1 to 3 halogen atoms;

X2is hydrogen, halogen, Alilaguna;

X3is hydrogen, halogen, alkyl with 1-8 carbon atoms, halogenated with 1-6 carbon atoms, substituted by 1-3 halogen atoms, or a radical of the formula-O-R3;

R3to 6-membered nitrogen-containing heterocyclic radical, substituted by halogenation with 1-6 carbon atoms and 1 to 3 halogen atoms:

or X2and X3together signify unsubstituted or substituted by alkyl with 1-8 carbon atoms alkylenes chain with 3-4 links or alkilinity chain with 3-4 links, in which two lesosecnyh carbon atom is replaced by oxygen atoms, substituted by 1-4 halogen atoms,

or X2and X3together denote a residue of the formula

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X4hydrogen or halogen:

R - isoxazolyl, mono - or disubstituted amino, alkyl with 1-8 carbon atoms or cycloalkyl with 3-6 carbon atoms, pyrazolyl substituted by halogen and alkyl with 1-8 carbon atoms, thienyl, unsubstituted or substituted with halogen, alkyl with 1-8 carbon atoms or alkoxycarbonyl with 1-4 carbon atoms in the alkyl part, or thiazolyl substituted by alkyl with 1-8 carbon atoms,

and their salts formed by the addition of acids.

Preferred derivatives benzotriazole General formula I are compounds, the mi fluorine;

X2is hydrogen, chlorine, alkyl with 1-4 carbon atoms, nitro, halogenoalkane or halogenated with 1-2 carbon atoms, substituted by 1-3 fluorine atoms;

X3is hydrogen, chlorine, bromine, alkyl with 1-4 carbon atoms, halogenated with 1-2 carbon atoms, substituted by 1-3 fluorine atoms, or a radical of the formula-O-R3where R3mean 6-membered nitrogen-containing heterocyclic radical, substituted by halogenation with 1-4 carbon atoms and 1 to 3 halogen atoms;

X2and X3together signify unsubstituted or substituted by alkyl with 1-4 carbon atoms alkylenes chain with 3-4 links or substituted by 1 to 4 fluorine atoms alkylenes chain with 3-4 links, in which two lesosecnyh carbon atom is replaced by oxygen atoms,

or X2and X3together denote a residue of the formula

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X4is hydrogen, chlorine,

R - isoxazolyl, mono - or disubstituted amino, alkyl with 1-4 carbon atoms or cyclopropyl, pyrazolyl substituted by chlorine and alkyl with 1-4 carbon atoms, thienyl, unsubstituted or substituted by chlorine, bromine, alkyl with 1-4 carbon atoms or alkoxycarbonyl with 1-2 carbon atoms in the alkyl part or thiazolyl substituted by alkyl with 1-4 carbon atoms,

and their salts, formed by what means, for example, benzotriazol General formula (II)

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in which X1X2X3and X4have the above values,

subjected to interaction with a halide of General formula (III)

Gal-SO2-R (III)

in which R has the above meaning, and

Gal means chlorine or bromine,

optionally, in the presence of acid binding means, and a diluent, and, if necessary, to the resulting compound of formula (I) added acid.

If used as starting compounds 6,6-debtor-[1,3]dioxolo-[4,5-f] -1H-benzotriazol and 3,5-dimethyl-isoxazol-4-sulphonylchloride, the reaction can be represented by the following scheme:

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Benzotriazole formula (II) and halides of the formula (III) are known or can be derived principally known methods.

As a diluent for use with all conventional inert organic solvents. Preferred are aliphatic, cycloaliphatic and aromatic, possibly halogenated, hydrocarbons, such as benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform or carbon tetrachloride; and that is whether the diethyl ether of ethylene glycol, next, ketones, such as acetone or butanone or methyl isobutyl ketone; NITRILES, such as acetonitrile, propionitrile or benzonitrile, or esters, for example methyl or ethyl ester of acetic acid.

If the reaction is preferably run in the presence of acid binding means. As such, use all customary inorganic or organic bases. Preferably apply hydroxide of alkali or alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide, or ammonium hydroxide, carbonates of alkali metals such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, acetates, alkali or alkaline earth metals such as sodium acetate, potassium acetate, calcium acetate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclo, Diisobutylene or databaseconnect.

The reaction temperature can vary in a wide interval. Typically operate at temperatures from 0 to 150oC, preferably from 20 to 120oC. the Reaction is usually carried out under normal dawk benzotriazole formula (II) take 1.0 to 2.0 mol, preferably 1.0 to 1.3 mol, of a halide of formula (III) and optionally 1.0 to 2.0 mol, preferably 1.0 to 1.3 mol, acid binding means. Carrying out the reaction, the processing of the reaction mixture and the reaction product is carried out by known methods (see also examples receipt).

Salts of compounds (I) with acids get a simple way by conventional methods, for example by dissolving the compounds of formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid and was isolated in a known manner, for example by filtration, and optionally purified by washing inert organic solvent.

As mentioned above, derivatives benzotriazol the above General formula (I) exhibit fungicidal activity and therefore they can be an active substance fungicidal agent, which is an additional object of the invention.

Offer fungicidal agent may be any standard drug and obtained from him a working form, such as, for example, solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, nonconception in polymeric substances form and I am cold and hot way. These drugs and uniforms get in a known manner, for example by mixing the active substances with extenders or liquid solvents, pressurized gases and/or carriers, optionally with the use of surface-active agents, i.e. emulsifiers and/or dispersants and/or foam. In the case of using water as a filler can also be used as an aid in organic solvents. As liquid solvents are mainly used aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol and also their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents such as dimethylformamide and dimethylsulfoxide, and water. Under liquefied gaseous extenders or carriers understand such liquids at normal temperature and normmaking carbon. As solid carriers use the grinding of natural rocks such as kaolin, alumina, talc, chalk, quartz, montmorillonite or diatomaceous earth, and the grinding of synthetic rocks, such as highly dispersed silicic acid, alumina and silicates. As solid carriers for granules are used crushed and fractionated natural rocks such as calcite, marble, pumice, thick, dolomite, and also synthetic granules of inorganic and organic grinding, and also granules of organic material such as sawdust, coconut husk, corn cobs and stalks of tobacco. As emulsifying and foaming means is used, for example, nonionic and anionic emulsifiers, such as esters of polyoxyethylene and fatty acids, ethers of polyoxyethylene and fatty alcohols, for example alkylarylsulphonates simple ether, alkyl sulphonates, alkyl sulphates, arylsulfonate and protein hydrolysates. As a dispersant is used, for example, ligninolytic liquor and methylcellulose.

The preparations may also contain binders, such as carboxymethylcellulose, natural and synthetic poroshkoobraz the native phospholipids, for example Catalina and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

You can also use colorants such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyanide blue, and organic dyestuffs, such as alizarin, azo and metallophthalocyanine dyes, and trace elements in the form of salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The tool usually contains from 0.1 to 95 wt.% the active substance, preferably from 0.5 to 90%.

Thanks fungicidal activity derived benzotriazol the above General formula (I) can be used in the method of controlling undesirable fungi in the protection of plants and materials, which consists in applying to the fungi and/or their habitat of these compounds or their salts formed by the addition of acids. This method is another object of the invention.

When the unwanted mushrooms derivative benzotriazol the above General formula (I) and their salts can be used as such or in the form of the above mentioned drugs and working forms. However, their application in the normal way, neprimena ultrascalable method or composition with active early or very active substance incorporated into the soil. You can also process the seed.

When processing parts of plants the concentration of the active substance in the work form vary in a wide interval: usually, they range from 1 to 0.0001 wt.%, preferably from 0.5 to 0.001 wt.%.

When the seed treatment, the amount of active substance is usually from 0.001 to 50 g per kg of seed, preferably from 0.01 to 10 g

During cultivation, the concentration of active substance in the applications is from 0.00001 to 0.1 wt.%, preferably from 0.0001 to 0.02 wt.%.

Used for protection of technical materials, products contain active substances, usually in an amount of from 1 to 95%, preferably from 10 to 75%.

Under the technical materials see materials intended for use in the technique. Such technical materials protected from alteration or destruction mushrooms are, for example, adhesives, glues, paper and cardboard, textiles, leather, wood, masonry paints and plastics and other materials that may be damaged or destroyed by fungi. Under be protected materials also understand parts of industrial installations, for example, for circulation of cooling vadania as technical materials preferably should be called adhesive substance, glues, paper and cardboard, leather, wood, paint paint, refrigerants and fluids in heat exchangers, particularly preferably wood.

Concentration when using substances depends on the type and origin of fungi, as well as on the composition of the protected material. The optimal number is determined by a number of experiments. Usually the concentration of application range from 0.001 to 5 wt.% to 1.0 wt.%, counting on the protected material.

The invention is illustrated by the following examples.

Example 1

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A mixture of 2.0 g (10 mmol) of 6,6-debtor[1,3]dioxolo[4,5-f]- 1H-benzotriazole and 40 ml of absolute tetrahydrofuran is mixed at room temperature and mixed with 0.3 g (10 mmol) of sodium hydride (80%) and then stirred for 10 minutes at room temperature. Then added to 1.9 g (10 mmol) of 3,5-dimethylisoxazol-4-sulphonylchloride and stirred for 16 hours at 60oC. For handling poured the reaction mixture in 20 ml of water. The resulting mixture was twice extracted with 50 ml ethyl acetate. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The obtained residue chromatographic on silica gel using methylene chloride as the eluting means. This mod is f colorless solids with so pl. 120-123oC.

Example 2

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A mixture of 2.7 g (10 mmol) 4-bromo-6-trifluoromethyl-1H - benzotriazole and 40 ml of absolute tetrahydrofuran is mixed at room temperature under stirring with a 0.30 g (10 mmol) of sodium hydride (80%) and then stirred for 10 minutes at room temperature. Then added 3.4 g (10 mmol) of 4,5-dibromo-thiophene-2-sulphonylchloride and stirred for 16 hours at 60oC. For handling pour the reaction mixture into 200 ml of water. The resulting mixture was twice extracted with 50 ml ethyl acetate. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The obtained residue chromatographic on silica gel using methylene chloride. Obtain 2.8 g (52% of theory) of 1-(3,4-dibromo-Tien-2-yl-sulfonyl)-4-bromo-6-trifluoromethyl - 1H-benzotriazole in the form of a colourless solid with so pl. 192-195 (in Russian)oC.

Similarly receive are shown in table 1 compounds of the formula

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Example I

Test protection material

For evidence of activity against fungi determine the minimum concentration of inhibition (ICB) of the compounds according to the invention.

Agar, which was obtained by the use of malt extract, mixed with connections tours Penicillium brevicaule, Chaetomium globosum and Aspergillus niger. After two weeks of incubation at 28oC and 60-70% relative humidity determine the minimum concentration of inhibition (ICB). The MKT value means the lowest concentration of active substance at which no growth of the applied microorganisms.

The active substance and the test results are presented in table 2.

Example II

Test the protective activity against Phytophthora on tomatoes

1 weight. some of the listed in table 3, the active substance is mixed with 4.7 weight. including acetone as solvent and 0.3 weight. including alkylarylsulphonates ether as an emulsifier and dilute the concentrate with water to the concentrations indicated in tables 3, 4.

To test for protective activity, young plants are sprayed with the active composition to the formation of droplets. After drying plaque plants inoculant aqueous spore suspension of Phytophthora infestans and leave in the incubation chamber at 20oC and 100% relative humidity.

Later, 3 days after inoculation estimate. 0% means the degree of activity, which corresponds to the control, and the degree of activity of 100% means that it was not observed nestable in tables 3, 4.

Example III

Test the protective activity against Plasmopara in the vine

1 weight. some of the listed in table 5 of the active substance is mixed with 4.7 weight. including acetone as solvent and 0.3 weight. including alkylarylsulphonates ether as a concentrate and diluted with water to a concentration listed in table 5.

To test for protective activity, young plants are sprayed with the active composition to the formation of droplets. After drying plaque plants inoculant aqueous spore suspension Plasmopara viticola and leave it in a humid chamber for one day at 20-22oC and 100% relative humidity.

Then the plants are placed in a greenhouse at 21oC and a relative humidity of about 90% for 5 days. Then plants moisturize and 1 day incubated in a humid chamber.

Later, 6 days after inoculation estimate. 0% means the degree of activity, which corresponds to the control, and the degree of activity of 100% means that there was no destruction.

Active substances, their concentrations and the results are shown table 5.

1. Derivative benzotriazole General formula I

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where X1is hydrogen, the, lcil with 1 to 8 carbon atoms, nitro, halogenoalkane or halogenated with 1 to 6 carbon atoms and 1 to 3 halogen atoms;

X3is hydrogen, halogen, alkyl with 1 to 8 carbon atoms, halogenated with 1 to 6 carbon atoms and 1 to 3 halogen atoms, or a radical of the formula-O-R3;

R3- 6-teleny nitrogen-containing heterocyclic radical, substituted by halogenation with 1 to 6 carbon atoms and 1 to 3 halogen atoms; or

X2and X3together signify unsubstituted or substituted by alkyl with 1 to 8 carbon atoms alkylenes chain with 3 to 4 parts or alkilinity chain with 3 to 4 parts, in which two lesosecnyh carbon atom is replaced by oxygen atoms, substituted by 1 to 4 atoms of halogen,

or X2and X3together denote a residue of the formula

< / BR>
X4hydrogen or halogen;

R - isoxazolyl, mono - or disubstituted amino, alkyl with 1 to 8 carbon atoms or cycloalkyl with 3 to 6 carbon atoms, pyrazolyl substituted by halogen and alkyl with 1 to 8 carbon atoms, thienyl, unsubstituted or substituted with halogen, alkyl with 1 to 8 carbon atoms or alkoxycarbonyl with 1 to 4 carbon atoms in the alkyl part, or thiazolyl substituted by alkyl with 1 to 8 carbon atoms,

and their salts, formed the chlorine, bromine, nitro or halogenated with 1 to 2 carbon atoms and 1 to 3 fluorine atoms; X2is hydrogen, chlorine, alkyl with 1 to 4 carbon atoms, nitro, halogenoalkane or halogenated with 1 to 2 carbon atoms and 1 to 3 fluorine atoms; X3is hydrogen, chlorine, bromine, alkyl with 1 to 4 carbon atoms, halogenated with 1 to 2 carbon atoms and 1 to 3 fluorine atoms, or a radical of the formula-O-R3where R3mean 6-membered nitrogen-containing heterocyclic radical, substituted by halogenation with 1 to 4 carbon atoms and 1 to 3 halogen atoms;

X2and X3together signify unsubstituted or substituted by alkyl with 1 to 4 carbon atoms alkylenes chain with 3 to 4 parts or substituted by 1 to 4 fluorine atoms alkylenes chain with 3 to 4 parts, in which two lesosecnyh carbon atom is replaced by oxygen atoms, or

X2and X3together denote a residue of the formula

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X4is hydrogen, chlorine,

R - isoxazolyl, mono - or disubstituted amino, alkyl with 1 to 4 carbon atoms or cyclopropyl, pyrazolyl substituted by chlorine and alkyl with 1 to 4 carbon atoms, thienyl, unsubstituted or substituted by chlorine, bromine, alkyl with 1 to 4 carbon atoms or alkoxycarbonyl with 1 to 2 carbon atoms in the alkyl part or thiazolyl, substituted Alky lby with unwanted mushrooms, containing derivative benzotriazole as the active substance, characterized in that as a derivative benzotriazole it contains a compound of General formula I on p. 1 or its salt, formed by the joining of acid.

4. The method of combating unwanted fungi in the protection of plants and materials by drawing on them and/or their habitat derived benzotriazole, characterized in that as a derivative benzotriazole used as a compound of General formula I on p. 1 or its salt, formed by the joining of the acid.

 

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