DE3800267A1 - Substituted pyrimidines - Google Patents

Abstract

Substituted pyrimidines of the formula (I) <IMAGE> in which R is alkyl, their acid addition salts, and their use in pesticides. Formula (I) provides a definition of the novel substituted pyrimidines, which can be prepared by analogous processes, for example from suitable pyrimidine-5-carboxylic acids and pyrazole.

Description

The invention relates to new substituted pyrimidines, a process for their manufacture and their use as a pesticide.

It is known that certain substituted pyrimidines, such as the compound 4- (4-t-butylphenoxy) -2- isobutylthiopyrimidine-5-carboxylic acid piperidide fungicides Have properties (see DE-OS 33 38 859).

The effectiveness of these previously known compounds is however, especially at low application rates and Concentrations are not completely in all areas of application satisfactory.

There were new substituted pyrimidines of the general Formula (I),

in which
R represents alkyl,
as well as their acid addition salts found.

Furthermore, it was found that the new substituted ones Pyrimidines of the general formula (I),

in which
R represents alkyl,
and their acid addition salts are obtained if pyrimidine-5-carboxylic acids of the formula (II),

in which
R represents alkyl,
with pyrazole in the presence of a condensing agent, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, and if appropriate subsequently subsequently adding an acid.

Finally it was found that the new ones were substituted Pyrimidines of the formula (I) and their acid addition salts have a good effect against pests.

Surprisingly, the substituted ones according to the invention show Pyrimidines of the general formula (I) a considerably better fungicidal activity than that from the Substituted pyrimidines known in the prior art, such as the compound 4- (4-t-butylphenoxy) - 2-isobutylthiopyrimidine-5-carboxylic acid piperidide, which chemically and functionally obvious compounds are.

The substituted pyrimidines according to the invention are generally defined by the formula (I). Compounds of the formula (I) in which
R represents straight-chain or branched alkyl having 1 to 4 carbon atoms.

Compounds of the formula (I) in which
R represents n-propyl, i-propyl, n-butyl or i-butyl.

Compounds of the formula (I) in which
R represents n-propyl or i-propyl.

Preferred compounds according to the invention are also addition products from acids and those substituted Pyrimidines of the formula (I) in which the substituent R has the meanings that are already preferred for this Substituents were called.

The acids that can be added include plant-compatible acids, preferably hydrohalic acids, such as B. hydrochloric acid and Hydrobromic acid, especially hydrochloric acid, also phosphoric acid, nitric acid, sulfuric acid, mono-, bi- and trifunctional carboxylic acids and Hydroxycarboxylic acids, such as. B. acetic acid, maleic acid, Succinic acid, fumaric acid, tartaric acid, citric acid, Salicylic acid, sorbic acid and lactic acid, sulfonic acids,  such as B. p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid as well as saccharin or thiosaccharin.

For example, if 4- (4-t-butylphenoxy) -2-n- propylthiopyrimidine-5-carboxylic acid and pyrazole as starting materials, and N, N′-dicyclohexylcarbodiimide as the condensing agent, the reaction sequence of the method according to the invention by the following formula represent:

To carry out the method according to the invention Pyrimidine-5-carboxylic acids required as starting materials are generally defined by formula (II). In this Formula (II) R preferably represents those Leftovers already related to the description the substances of the formula (I) according to the invention are preferred for these substituents.  

The pyrimidine-5-carboxylic acids of the formula (II) are known (see DE-OS 33 38 859).

The process according to the invention is carried out in the presence of a suitable condensing agent. As such all usually come to form an amide bond usable condensing agent in question. With carbodiimides, for example, are particularly preferably used N, N'-dicyclohexylcarbodiimide.

As a diluent for carrying out the invention Process come inert organic solvents in question. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated Hydrocarbons, such as gasoline, benzene, Toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, Dichloromethane, chloroform, carbon tetrachloride, Ethers, such as diethyl ether, dioxane, tetrahydrofuran or Ethylene glycol dimethyl or diethyl ether, ketones such as Acetone or butanone, nitriles, such as acetonitrile or propionitrile, Amides, such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, Esters, such as ethyl acetate or sulfoxides such as dimethyl sulfoxide.

The process according to the invention is preferably carried out in the presence a suitable reaction auxiliary. Organic bases in particular come as such in question. These include, for example, tertiary amines, such as triethylamine, N, N-dimethylaniline, pyridine, N, N-dimethylaminopyridine, 4- (1-pyrrolidino) pyridine, diazabicyclooctane  (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be carried out of the method according to the invention in a larger area can be varied. Generally one works at Temperatures between -20 ° C and 120 ° C, preferably at temperatures between 0 ° C and 80 ° C.

To carry out the method according to the invention is set per mole of pyrimidine-5-carboxylic acid of the formula (II) generally 1.0 to 3.0 mol, preferably 1.0 to 1.5 moles of pyrazole, 1.0 to 2.0 moles, preferably 1.0 to 1.5 moles of condensing agent and optionally 0.01 to 1.0 mol, preferably 0.1 to 0.3 mol Reaction aids. The implementation of the reaction, workup and isolation the reaction products are carried out according to generally customary methods Methods (see the manufacturing examples).

The acid addition salts of the compounds of formula (I) can be made in a simple manner using conventional salt formation methods, such as B. by loosening a connection Formula (I) in a suitable inert solvent and Adding the acid such as B. hydrochloric acid, be obtained and in a known manner, e.g. B. by filtering, isolated and optionally by washing cleaned with an inert organic solvent will.  

The active compounds according to the invention have a strong effect against pests and can be used to combat unwanted harmful organisms can be used practically. The active ingredients are for use as pesticides particularly suitable as fungicides.

Fungicides in crop protection are used for Control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Some pathogens are exemplary but not limiting of fungal diseases listed below Generic terms fall, called:

Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the concentrations necessary to combat plant diseases allows treatment from above ground Parts of plants, of seedlings, and des Floor.  

The active compounds according to the invention can also be used particularly good success in combating powdery mildew (Erysiphe graminis).

The active ingredients can depend on their respective physical and / or chemical properties in usual formulations are transferred, such as solutions, Emulsions, suspensions, powders, foams, pastes, granules, Aerosols, very fine encapsulations in polymers Substances and in coating compositions for seeds, as well as ULV cold and warm fog formulations.

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, under pressure liquefied gases and / or solid carriers, optionally using surfactants Agents, ie emulsifiers and / or dispersants and / or foam-generating agents. In case of Use of water as an extender can e.g. Belly organic solvents used as auxiliary solvents will. Essentially come as liquid solvents in question: 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 cyclohexanone, strongly polar Solvents such as dimethylformamide and dimethyl sulfoxide,  as well as water; with liquefied gaseous Extenders or carriers are such liquids meant, which at normal temperature and below Normal pressure are gaseous, e.g. B. aerosol propellants, such as Halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; come as solid carriers in question: e.g. B. natural stone powder, such as kaolins, Clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; come in as solid carriers for granules Question: e.g. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well synthetic granules from inorganic and organic Flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-generating agents come into question: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene Fatty alcohol ethers, e.g. B. alkylaryl polyglycol Ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and Protein hydrolyzates; as dispersants are: e.g. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can mineral and vegetable oils.  

Dyes such as inorganic pigments, e.g. B. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, Boron, copper, cobalt, molybdenum and zinc can be used.

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

The active compounds according to the invention can be used in the formulations in a mixture with other known active ingredients are present such as fungicides, insecticides, acaricides and herbicides as well as in mixtures with fertilizers and growth regulators.

The active ingredients as such, in the form of their formulations or the application forms prepared from it such as ready-to-use solutions, suspensions, wettable powders, Pastes, soluble powders, dusts and granules be applied. The application is done in the usual way Way, e.g. B. by pouring, spraying, spraying, scattering, Dusting, foaming, brushing, etc. It it is also possible to use the active ingredients according to the ultra-low Apply volume procedure or drug preparation or inject the active ingredient into the soil yourself. It can also treat the seeds of the plants will.  

When treating parts of plants, the drug concentrations can in the application forms in one larger range can be varied. They generally lie between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

When treating seeds, amounts of active ingredient are generally used from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g is required.

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

Manufacturing examples Example 1

To 2.4 g (0.0069 mol) of 4- (4-t-butylphenoxy) -2-n-propyl- thiopyrimidine-5-carboxylic acid, 0.52 g (0.0076 mol) pyrazole and 0.1 g (0.0006 mol) of 4- (1-pyrrolidino) pyridine in 45 ml of dichloromethane are added at room temperature Stir and exclude moisture 1.56 g (0.0075 mol) N, N'-dicyclohexylcarbodiimide, then stirred 16 Hours at room temperature, filtered, the filtrate is concentrated in a vacuum and chromatograph the residue Silica gel (mobile phase: cyclohexane / ethyl acetate 30: 7.5).

A second chromatography on silica gel with the eluent mixture diisopropyl ether / cyclohexane 3: 1 provides 1.2 g (44% of theory) of 4- (4-t-butylphenoxy) -2-n-propylthiopyrimidine-5-carboxylic acid pyrazolide as an oil.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 6.5 (dd, 1H), 7.8 (m, 1H) ppm.

Preparation of the starting compound Example II-1

To 20.8 g (0.056 mol) of 4- (4-t-butylphenoxy) -2-n-propylthiopyrimidine 5-carboxylic acid ethyl ester (cf. DE-OS 33 38 859) in 50 ml of 80% aqueous ethanol 3.1 g dropwise at room temperature with stirring (0.056 mol) potassium hydroxide in 50 ml 80% aqueous Ethanol, stir for an hour after the addition is complete Room temperature, then gives the reaction mixture in Water, acidified with dilute aqueous hydrochloric acid, extracted twice with dichloromethane, dried combined organic phases over sodium sulfate, concentrated in a vacuum and the remaining oil crystallizes by stirring with petroleum ether.

13.9 g (71.7% of theory) of 4- (4-t-butylphenoxy) - 2-n-propylthiopyrimidine-5-carboxylic acid from Melting point 189 ° C-193 ° C.  

Examples of use

In the following application example, the one below listed compound used as a reference substance:

4- (4-t-Butylphenoxy) -2-isobutylthiopyrimidine-5-carboxylic acid piperidide (known from DE-OS 33 38 859).  

Example A

Erysiphe test (barley) / protective
Solvent: 100 parts by weight of dimethylformamide
Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective effectiveness, young people are sprayed Plants with the active ingredient preparation dewy. To The plants will dry with the spray coating Spores of Erysiphe graminis f. sp. hordei pollinated.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of about 80% set up to develop Favor mildew pustules.

Evaluation is carried out 7 days after the inoculation.

A clear superiority in effectiveness over the prior art shows in this test z. B. the connection according to production example: (1).

Claims (9)

1. Substituted pyrimidines of the formula (I) in which
R represents alkyl,
as well as their acid addition salts. 2. Substituted pyrimidines according to claim 1, wherein in the formula (I)
R represents straight-chain or branched alkyl having 1 to 4 carbon atoms. 3. Substituted pyrimidines according to claim 1, wherein in the formula (I)
R represents n-propyl, i-propyl, n-butyl or i-butyl. 4. Substituted pyrimidines according to claim 1, wherein in the formula (I)
R represents n-propyl or i-propyl. 5. Process for the preparation of substituted pyrimidines of the formula I. in which
R represents alkyl,
and their acid addition salts, characterized in that pyrimidine-5-carboxylic acids of the formula (II) in which
R represents alkyl,
with pyrazole in the presence of a condensing agent, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, and if appropriate subsequently subsequently adding an acid. 6. Pesticides, characterized by a content of at least one substituted Pyrimidine of formula (I) according to claims 1 and 5. 7. Use of substituted pyrimidines Formula (I) according to claims 1 and 5 for combating of pests. 8. Pest control method, thereby characterized in that a substituted pyrimidine of formula (I) according to claims 1 and 5 affect pests and / or their habitat leaves. 9. Process for the preparation of pesticides, characterized in that one a substituted pyrimidine of formula (I) claims 1 and 5 with extenders and / or surface active agents mixed.