DE4239728A1 - Thiocyanatomethylthiobenzthiazole derivatives - Google Patents

Abstract

Described are novel thiocyanatomethylthiobenzthiazole derivatives of formula (I), in which n is the number 0, 1 or 2 and X is a halogen, a method of preparing them and their use as pest-control agents.

Description

The invention relates to new thiocyanatomethylthiobenzthiazole derivatives, a process for their manufacture and their use as pesticides, in particular especially as fungicides.

It has already become known that 2-thiocyanatomethylthiobenzthiazole for Control of fungal pests can be used (cf. DE-AS 16 70 221, DE-OS 17 67 538, DE-OS 17 93 450 and DE-OS 19 39 031). The fungicidal However, this compound is not entirely effective at low application rates satisfactory.

There have now been new thiocyanatomethylthiobenzthiazole derivatives of the formula

in which
n stands for the numbers 0, 1 or 2 and
X represents halogen,

found.  

It was also found that thiocyanatomethylthiobenzthiazole derivatives of Formula (I) is obtained if

• a) Mercaptobenzthiazoles of the formula in which
  X has the meaning given above, with chloromethylthiocyanate of the formula Cl-CH ₂ -SCN (III), if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and if appropriate
• (b) the resulting compounds of the formula in which
  X has the meaning given above, with an oxidizing agent, optionally in the presence of a catalyst and optionally in the presence of a diluent.

Finally, it was found that the new thiocyanatomethylthiobenzthiazole Derivatives of formula (I) are very suitable as pesticides. they can preferably be used as fungicides, insecticides and acaricides.

Surprisingly, the substances according to the invention have a much stronger one fungicidal activity as the 2-thiocyanatomethylthiobenzthiazol, which a con is similar to a previously known active substance with the same direction of action.

The substances according to the invention are defined by the formula (I).
X preferably represents fluorine, chlorine, bromine or iodine.
n stands for the numbers 0, 1 or 2.

If 7-fluoro-2-mercaptobenzthiazole and chloromethylthiocyanate are used as the Aus materials, the course of the method according to the invention can follow through de Formula scheme are illustrated:

If 7-chloro-2-thiocyanatomethylthiobenzthiazol is used as starting material and Hydrogen peroxide as a reaction component, the amounts being so measured be that for 1 mole of 7-chloro-2-thiocyanatomethylthiobenzthiazol 2 moles Hydrogen peroxide are present, so the course of the second stage of method according to the invention illustrated by the following formula become:

The ver as starting materials in step (a) of the process according to the invention turning mercaptobenzothiazoles of formula (II) are known and / or can processes known per se (cf. J. Chem. Soc. 1965, 954-973,  especially 968; Bull. Soc. Chim. France 1973, 3044-3051 - cited in Chem. Abstracts 80; 82786z).

In step (a) of the process according to the invention, this continues as the starting compound tion to be used chloromethylthiocyanate of formula (III) is a known, han standard synthetic chemical.

Step (a) of the process according to the invention for producing the new compound The formula (I) is preferably used using diluents carried out. Practically all inert organi come as diluent solvent. Aliphatic and aroma can preferably be used tables, optionally halogenated hydrocarbons such as pentane, hexane, heptane, Cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, Ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, Ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, Tetrahydrofuran and dioxane, alcohols such as methanol, ethanol, n- and i-propanol, n-, i-, s- and t-butanol, ketones such as acetone, methyl ethyl, methyl isopropyl and Me thyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as. B. Acetonitrile and propionitrile, amides such as e.g. B. dimethylformamide, dimethylacetamide and N-methylpyrrolidone and dimethyl sulfoxide, tetramethylene sulfone and hexa methylphosphoric triamide.

All of them can be used as acid acceptors in step (a) of the process according to the invention Acid binders which can usually be used for such reactions are used become. Alkali metal and alkaline earth metal hydrides, such as Lithium, sodium, potassium and calcium hydride, alkali metal and alkaline earth metal hydroxides, such as lithium, sodium, potassium and calcium hydroxide, alkali metal and Alkaline earth metal carbonates and bicarbonates, such as sodium and potassium carbo nate or bicarbonate and calcium carbonate, alkali metal acetates such as Na trium and potassium acetate, alkali metal alcoholates, such as sodium and potassium methylate, -ethylate, -propylate, -isopropylate, -butylate, -isobutylate and tert-butoxide, also basic Nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributyl amine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohe xylamine, N, N-dimethylbenzylamine, N, N-dimethyl-aniline, pyridine, 2-methyl, 3-Me  ethyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 2-ethyl, 4-ethyl and 5-ethyl-2- methyl pyridine, 1,5-diazabicyclo [4,3,0] non-5-ene (DBN), 1,8-diazabicyclo- [5,4,0] - undec-7-ene (DBU) and 1,4-diazabicyclo [2,2,2] octane (DABCO).

The reaction temperatures in step (a) of the process according to the invention rens can be varied over a wide range. Generally one works at Tem temperatures between 0 ° C and 150 ° C, preferably at temperatures between 10 ° C and 100 ° C.

Step (a) of the process according to the invention is generally below normal printing done. However, it is also possible to increase or decrease it Pressure to work.

To carry out stage (a) of the process according to the invention, the the starting materials required in each case generally in approximately equimolar amounts used. However, it is also possible to use either of the two To use components in a larger excess. The reactions will be generally in a suitable diluent in the presence of a Acid acceptor performed, and the reaction mixture is at several hours the required temperature is stirred. The processing takes place after usual methods (see the manufacturing examples).

The starting materials in stage (b) of the process according to the invention Compounds of the formula (Ia) required are substances according to the invention. You can be prepared according to step (a) of the process according to the invention.

Step (b) of the process according to the invention is carried out using an oxidizing agent. Oxidizing agents suitable for use are preferably hydrogen peroxide (H ₂ O ₂ ), peracids or salts thereof, such as performic acid, peracetic acid, perpropionic acid, perbenzoic acid, 3-chloroperbenzoic acid, potassium hydrogen persulfate, potassium peroxodisulfate or sodium peroxodisulfate, or also their hypo-chloric acid solutions or also their hypochlorous acid solution Water.

Step (b) of the process according to the invention is optionally carried out under Ver using a catalyst. Here are preferred as catalysts wise salts of metals of IV., V. and VI. Subgroup of the periodic table of the Elements suitable. Examples include sodium (meta) vanadate, sodium called molybdate and sodium tungstate.

Step (b) of the process according to the invention is preferably carried out using a diluent. Here come as a diluent in addition to water, the organic solvents customary for oxidation reactions in Be dress. Chlorinated hydrocarbons such as methylene can preferably be used chloride, ethylene chloride, chloroform, carbon tetrachloride, 1,1,2-trichloroethane, chlorine benzene and o-dichlorobenzene, alcohols, such as methanol, ethanol, propanol, isopro panol, butanol, isobutanol and sec-butanol, carboxylic acids, such as formic acid, Acetic acid and propionic acid.

The reaction temperatures in step (b) of Ver driving can be varied over a wide range. Generally one works at Temperatures between -20 ° C and + 120 ° C, preferably at temperatures between 0 ° C and 80 ° C.

Step (b) of the process according to the invention is generally below normal printing done. However, it is also possible to increase or decrease it Pressure - generally between 0.1 bar and 10 bar - to work.

To carry out stage (b) of the process according to the invention, use 1 Moles of starting compound of the formula (Ia) generally between 1 and 5 moles, preferably between 1 and 3 moles of oxidizing agent, and optionally between 0.001 and 0.1 mol, preferably between 0.01 and 0.05 mol of a catalyst.

In a preferred embodiment of stage (b) of the process according to the invention rens becomes the starting compound of formula (Ia) and optionally a catalyst placed in a diluent and at room temperature with stirring the oxidizing agent metered. Then the reaction mixture, optionally at  elevated temperature, stirred until the end of the reaction. The workup can can then be carried out in the usual way (cf. the production examples).

The active compounds according to the invention are very suitable as pest control medium. They are preferably used as fungicides, insecticides and acaricides.

Fungicides are used in crop protection to combat Plasmodio phoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidio mycetes, Deuteromycetes.

Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas species, such as Xanthomonas oryzae;
Pseudomonas species, such as Pseudomonas lachrymans;
Erwinia species, such as Erwinia amylovora;
Pythium species, such as Pythium ultimum;
Phytophthora species, such as Phytophthora infestans;
Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as Plasmopara viticola;
Peronospora species, such as Peronospora pisi or P. Brassicae;
Erysiphe species, such as Erysiphe graminis;
Sphaerotheca species, such as Spaerotheca fuliginea;
Podosphaera species, such as Podosphaera leucotricha;
Venturia species, such as Venturia inaequalis;
Pyrenophora species, such as Pyrenophora teres or P. graminea;
(Conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as Cochliobolus sativus;
(Conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as Uromyces appendiculatus;
Puccinia species, such as Puccinia recondita;
Tilletia species, such as Tilletia caries;
Ustilago species, such as Ustilago nuda or Ustilago avenae;
Pellicularia species, such as Pellicularia sasakii;
Pyricularia species, such as Pyricularia oryzae;
Fusarium species, such as Fusarium culmorum;
Botrytis species, such as Botrytis cinerea;
Septoria species, such as Septoria nodorum;
Leptosphaeria species, such as Leptosphaeria nodorum;
Cercospora species, such as Cercospora canescens;
Alternaria species, such as Alternaria brassicae;
Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the control of plants Concentrations necessary for diseases allow treatment above ground Parts of plants, of seedlings, and of the soil.

The active compounds according to the invention are particularly suitable for combating Pyricularia oryzae on rice and for combating cereal diseases, such as Leptosphaeria nodorum, Cochliobolus sativus and Pyrenophora teres. Furthermore the substances according to the invention also have a very good action against venturi Species, such as Venturia inaequalis on apples. The invention Substances also have a good in vitro effect.

The active compounds according to the invention also have a favorable toxicity to warm-blooded animals and are suitable for controlling animal pests in crop protection as well in the field of animal husbandry and animal husbandry.

In crop protection, the substances according to the invention can be used as insecticides and acaricides be used.

In the field of animal husbandry and cattle breeding, the invention can Substances for controlling insects, mites, ticks and other animal pests be used. By fighting these pests you can do better Results, for example higher milk yield, higher weight, more beautiful animal fur, achieve longer lifespan etc.  

The active compounds according to the invention are used in this field in known way, such as by external application, for example in the form of dew chens (dipping), spraying (spraying), pouring on (pour-on and spot-on) and on powder.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, Active ingredient-impregnated natural and synthetic substances, very fine encapsulation in polymeric substances and in coating compositions for seeds, also in formulations with Fuel sets, such as smoking cartridges, cans, spirals, etc., as well as ULV cold and Warm lever formulations.

These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with diluents, i.e. liquid solvents, are under pressure Liquefied gases and / or solid carriers, optionally with Ver Use of surface-active agents, i.e. emulsifiers and / or dispersers yawing and / or foaming agents. In case of using water as an extender z. B. also organic solvents as auxiliary solvents be used. The following are essentially suitable as liquid solvents: Aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or Methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols such as butanol or glycol and their ethers and Esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexa non, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and Water; with liquefied gaseous extenders or carriers are such Liquids are meant, which at normal temperature and under normal pressure are gaseous, e.g. B. aerosol propellants, such as halogenated hydrocarbons and butane, Propane, nitrogen and carbon dioxide; as solid carriers come into question: B. natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; as solid carriers for Granules are possible: B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules  inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as an emulsifier and / or foam-generating agents are possible: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fat alcohol ether, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfo nates and protein hydrolyzates; as dispersants come into question: z. B. Lignin Leaches of sulfite and methyl cellulose.

Adhesives such as carboxymethylcellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholi pide, such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferrocy blue and organic dyes such as alizarin, azo and metal phthalocyanine substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, mo lybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be mixed with in the formulations other known active ingredients such as fungicides, insecticides, acaricides and Herbicides and in mixtures with fertilizers and growth regulators.

The active substances can be used as such, in the form of their formulations or in the form thereof rode application forms such as ready-to-use solutions, suspensions, spray powder ver, pastes, soluble powders, dusts and granules. The An Turn happens in the usual way, for. B. by pouring, spraying, spraying, Scattering, dusting, foaming, brushing, etc. It is also possible to use the Apply active ingredients according to the ultra-low-volume process or the active substance preparation or inject the active substance yourself into the soil. It can also the seeds of the plants are treated.  

In the treatment of parts of plants, the drug concentrations in the Application forms can be varied in a larger area. They are generally mean between 1 and 0.001% by weight, preferably between 0.5 and 0.001%.

In the seed treatment, amounts of active ingredient are generally from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g.

When treating the soil, active ingredient concentrations are from 0.00001 to 0.1 % By weight, preferably from 0.0001 to 0.02%, is required at the site of action.

The manufacture and use of the active compounds according to the invention start out the following examples.

Manufacturing examples example 1 (Process step (a))

5.9 g (55 mmol) of chloromethylthiocyanate become a Mi at 20 ° C. with stirring solution from 10.0 g (50 mmol) of 7-chloro-2-mercapto-benzothiazole, 2.7 g (50 mmol) of Na trium methylate and 100 ml of methanol. The reaction mixture then turns 60 Minutes at 50 ° C and 12 hours at 20 ° C and then on ice water poured. The crystalline product is isolated by suction.

12.0 g (88% of theory) of 7-chloro-2-thiocyanatomethylthio-benzothiazole are obtained melting point 87 ° C.

Example 2 (Process step (b))

A mixture of 27.2 g (100 mmol) 7-chloro-2-thiocyanatomethylthio-benzothiazole, 12.2 g of a 35% hydrogen peroxide solution in water (125 mmol H ₂ O ₂ ), 300 ml methanol and a spatula tip of sodium tungstate -Monohydrate is stirred at 20 ° C for 12 hours. After adding a further 2 g of hydrogen peroxide solution, the mixture is stirred for 2 hours at 40 ° C. to 45 ° C. and then poured onto ice water. The crystalline product is isolated by suction.

27.0 g (93% of theory) of 7-chloro-2-thiocyanatomethylsulfinlyl-benzothiazole are obtained melting point 174 ° C.

Analogous to Examples 1 and 2 and in accordance with the general description The manufacturing methods of the present invention are also those in the following Compounds of formula (I) listed in Table 1 are prepared.

Table 1

Examples of use

In the following usage examples, the verb below is used used as a reference substance:

2-thiocyanatomethylthiobenzthiazole
(known from DE-AS 16 70 221, example 1)

Example A Venturia test (apple) / protective

Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for prospective effectiveness, young plants are sprayed with the Active ingredient preparation to dripping wet. After the spray coating has dried on the plants with an aqueous conidia suspension of the apple scab pathogen (Ventu ria inaequalis) and then remain at 20 ° C and 100% relative for 1 day Humidity in an incubation cabin.

The plants are then in a greenhouse at 20 ° C and a relative humidity 70% installed.

Evaluation is carried out 12 days after the inoculation.

In this test, substances 1, 2, 3 and 4 according to the invention show at one concentration tration of 10 ppm in the spray liquid an efficiency of over 80%, while the efficiency of the reference substance (A) is below 70%.  

Example B Cockroach test

Test animal: Blattella germanica
Solvent: 35 parts by weight of ethylene glycol monomethyl ether
35 parts by weight of nonylphenol polyglycol ether

Three parts by weight are mixed to produce a suitable formulation Active ingredient with seven parts of the solvent-emulsifier mixture mentioned above and dilute the emulsion concentrate thus obtained with water to each desired concentration.

2 ml of this active ingredient preparation are pipetted onto filter paper dishes (⌀ 9.5 cm) animals that are in Petri dishes of appropriate size. After drying the Filter disks are 5 test animals at Blatella germanica and approx. 30 test animals at S. granarius transferred to the Petri dish and covered.

After 3 days, the effectiveness of the active ingredient preparation is determined. The Efficacy is expressed in%. 100% means that all cockroaches are killed were; 0% means that no cockroaches have been killed.

In this test, the compound (3) according to the invention shows at a concentration of 1000 ppm in the active ingredient preparation an effectiveness of 100%.

Claims (7)

1. Thiocyanatomethylthiobenzthiazol derivatives of the formula in which
n stands for the numbers 0, 1 or 2 and
X represents halogen. 2. Thiocyanatomethylthiobenzthiazol derivatives of formula (I) according to claim 1, in which
n stands for the numbers 0, 1 or 2 and
X represents fluorine, chlorine, bromine or iodine. 3. Process for the preparation of thiocyanatomethylthiobenzthiazole derivatives of the formula in which
n stands for the numbers 0, 1 or 2 and
X represents halogen,
characterized in that one

• a) Mercaptobenzthiazoles of the formula in which
  X has the meaning given above,
  with chloromethylthiocyanate of the formula Cl-CH₂-SCN (III) if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and if appropriate
• (b) the resulting compounds of the formula in which
  X has the meaning given above,
  with an oxidizing agent, optionally in the presence of a catalyst and optionally in the presence of a diluent.

4. pesticides, characterized by a content of minde least a thiocyanatomethylthiobenzthiazol derivative of the formula (I) according Claim 1.   5. Use of thiocyanatomethylthiobenzthiazole derivatives of the formula (I) according to claim 1 for combating pests. 6. A method for controlling pests, characterized in that Thiocyanatomethylthiobenzthiazol derivatives of formula (I) according to claim 1 on the pests and / or their habitat. 7. Process for the manufacture of pesticides, thereby characterized in that thiocyanatomethylthiobenzthiazole derivatives of Formula (I) according to claim 1 with extenders and / or surface-active Mixed fabrics.