CH634842A5 - 2-Phenyl-2-(1(H)-imidazolylmethyl)-1,3-dioxane derivatives, processes for their preparation, microbicides containing these active substances, and their use - Google Patents

Abstract

Compounds of the formula I <IMAGE> in which R1, R2 and R3 independently of one another denote halogen, and two of the three substituents also denote hydrogen, X denotes C1-C8-alkyl, Y denotes hydrogen or C1-C8-alkyl, and Z denotes hydrogen, C1-C8-alkyl or -CH2OH, with the total number of carbon atoms in the substituents X, Y and Z not exceeding the number 10, including their plant-tolerated salts with inorganic or organic acids and their metal complexes, are suitable as microbicides, in particular for the control of phytopathogenic fungi. They can be employed in the form of plant protection agents together with suitable carriers.

Description

** WARNING ** Beginning of DESC field could overlap end of CLMS **.

PATENT CLAIMS 1. Compound of formula I

wherein R1, R2 and R3 independently of one another halogen and two of the three substituents also hydrogen, X C1-C8 alkyl, Y is hydrogen or C1-Ca alkyl and Z denotes hydrogen, C1-C8 alkyl or -CH2OH, the total number of carbon atoms in the substituents X, Y and Z not exceeding 10, as well as their salts and their metal complexes.

2. Compounds according to claim 1, wherein R1 is hydrogen or halogen, R2 is halogen and R3 is hydrogen.

3. Compounds according to claim 2, wherein R1 is hydrogen or chlorine, R2 is chlorine and Rs is hydrogen.

4. Compounds according to claim 1, in which the alkyl chain does not have more than 3 carbon atoms in any of the substituents X, Y or Z.

5. Compounds according to claim 1, in which the dioxane ring is disubstituted in the 5-position by 2-alkyl groups.

6. Process for the preparation of compounds of the formula I, characterized by the reaction of the imidazole of the formula II

wherein Me represents hydrogen or a metal atom, with a halide of formula III

in which R1, R2, R3, X, Y and Z have the meanings given for formula I and Hal is halogen.

7. Microbicidal agent, characterized in that it contains a compound of the formula I as an active ingredient.

8. Agent according to claim 7, characterized in that it contains a compound according to claim 3.

9. Use of compounds of the formula I for combating fungi.

10. Use according to claim 9, characterized in that compounds according to claim 3 are used.

The present invention relates to substituted 2-phenyl-2- [1 (H) -imidazolylmethyl] -1,3-dioxane derivatives of the formula I and their salts with inorganic or organic acids and their metal complexes, the preparation of such compounds, and also microbicides Agents which contain compounds of the formula I as active ingredients and the use of compounds of the formula I for combating plant diseases.

In formula I.

mean the three substituents R1, R2 and R3 independently of one another halogen and two of the three substituents also hydrogen, X C1-C8 alkyl, Y is hydrogen or C1-C8 alkyl and Z is hydrogen, C1-C8 alkyl or -CH2OH, the total number of carbon atoms in the substituents X, Y and Z not exceeding 10.

The term halogen includes fluorine, chlorine, bromine and iodine. C1-C3-alkyl means methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. Butyl, tert. Butyl and the various isomers amyl, hexyl, heptyl and octyl.

Examples of inorganic acids are hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, phosphoric acid, phosphorous acid, nitric acid.

Examples of organic acids are acetic acid, trichloroacetic acid, oxalic acid, succinic acid, maleic acid, lactic acid, glycolic acid, aconitic acid, citric acid, benzoic acid, benzenesulfonic acid, methanesulfonic acid.

Metal complexes of formula I consist of the underlying organic molecule and an inorganic or organic metal salt, e.g. the hydrohalides, nitrates, sulfates, phosphates, tartrates, etc. of copper, manganese, iron, zinc and other metals. The metal cations can be present in the various valencies assigned to them.

There is no limitation associated with these various exemplary lists.

The compounds of the formula I have a microbicidal spectrum, which is very favorable for practical needs, for protecting crop plants without adversely affecting them by undesired side effects. For the purposes of the present invention, crop plants are, for example, cereals, corn, rice, vegetables, sugar beets, soy, peanuts, fruit trees, ornamental plants, vines, hops, cucumber plants (cucumbers, pumpkins, melons), solanaceae such as potatoes, tobacco and tomatoes, as well as banana plants. , Cocoa and natural rubber plants.

The active ingredients of the formula I can be used to contain or destroy the fungi that occur on plants or parts of plants (fruits, flowers, foliage, stems, tubers, roots) of these and related crops,

parts of plants that grow later remain spared from such fungi. The active ingredients are effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Erysiphaceae, Fusarium, Helminthosporium); Basisdiomycetes such as rust fungi in particular (e.g. Puccinia, Tilletia); Fugi imperfecti (e.g. Moniliales and others, Cercospora as well as Botrytis and Piricularia) and the Oomycetes belonging to the class of Phycomycetes such as Phytophthora or Plasmopara. In addition, the compounds of the formula I have a systemic effect. They can also be used as a dressing agent for the treatment of seeds (fruits, tubers, grains) and plant cuttings to protect against fungal infections and against phytopathogenic fungi occurring in the soil.

Preferred plant fungicides are above all compounds of the formula I and their salts or metal complexes in which R1 is hydrogen or halogen, R2 is halogen and R3 is hydrogen. This group shall be called compound group Ia. 4-chlorophenyl and 2,4-dichlorophenyl derivatives (= compound group Ib) are of particular interest here. In the compound groups Ia and Ib, such compounds are important plant fungicides in which the alkyl chain does not have more than 3 carbon atoms in any of the substituents X, Y or Z (= compound group Ic). Another important group of compounds are also those of the formulas I to Ic whose dioxane ring is disubstituted in the 5-position by 2 alkyl groups.

It has been shown in particular that imidazolyl compounds of the formula I have a pronounced Botrytis effect. Apparently similar links to the USP.

3,575,999, which are proposed as therapeutics and where X, Y and Z are simultaneously hydrogen, do not have this effect. It is therefore surprising that the active structure of the formula I leads to important plant fungicides which are able to combat gray mold rot and other plant diseases. Botrytis spp.

(B. cinerea, B. allii), with the gray mold rot on vines, strawberries, apples, onions and other types of fruit and vegetables, represent a significant economic pollutant.

The ketals of the formula I are produced by the reaction of imidazole of the formula II

wherein Me represents hydrogen or preferably a metal atom and particularly preferably an alkali metal atom, with a halide of the formula III

reacted, in which Rl, R2, R3, X, Y and Z have the meanings given for formula I and Hal is halogen, preferably chlorine or bromine (USP. 3,575,999). The reaction of II with III is preferably carried out in a polar, but reaction-inert solvent, e.g. Dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, benzonitrile and others. Such solvents can be used in combination with other inert solvents such as aliphatic or aromatic hydrocarbons (benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene, etc.). If Hal is chlorine or bromine, alkali iodide (such as NaI or KI) can be added to accelerate the reaction. Elevated temperatures of 30 to 220 ° C., preferably 80-170 ° C., are advantageous. The reaction mixture is expediently refluxed.

If the compounds of the formula I are obtained as bases, they can be converted into corresponding salts by means of inorganic or organic acids or into metal complexes of the formula I by means of preferably equimolar amounts of metal salts. Conversely, salts of the formula I can be converted into the free bases of the formula I, for example by reaction with an alkali (hydrogen) carbonate or alkali metal hydroxide.

The starting ketals of formula III can be derived from the underlying acetophenone derivative of formula IV

by reaction with the desired cx, y-diol in an inert solvent (such as benzene, toluene, xylene, etc.) and subsequent or simultaneous halogenation of the ketal. It is advantageous to add p-toluenesulfonic acid to accelerate the reaction. The diols are capable of forming trans forms of the formula III or cis forms or mixtures of cis / trans forms. Other isomers are possible. Correspondingly, isomeric end products of the formula I are formed from the intermediate products. The invention relates to all isomeric compounds, their salts and metal complexes. Indirect ways of preparation are also feasible by initially ketalizing the free ketone IV with another diol or alkanol and only then reacting the ring ketal or open ketal with the excess diol V

restructured. These methods for the preparation of intermediates of the formula III are in general use.

A production example is given below for illustration. The temperatures are given in degrees Celsius.

Example 1 Production of

1- [2- (2,4-dichlorophenyl) -5-ethyl-1,3-dioxan-2-ylmethyl] -1H -imidazole nitrate.

While stirring, 10.8 parts of irnidazole and 270 parts of dimethylformamide (DMF) are slowly added to a solution of 3.7 parts of sodium in 40 parts of methanol. The excess methanol is then distilled off and the reaction mixture is heated to 150.degree. 19 parts of 2-bromomethyl-2- (2,4-dichlorophenyl) -5-ethyl-1,3-dioxane are added and the reaction mixture is refluxed for 5 hours, cooled and poured into 600 ml of cold water. It is extracted three times with 150 ml of diethyl ether each time, the combined extracts are washed with water, dried over Na2SO4, filtered off and concentrated. The oily residue is purified by chromatography on a column of silica gel, using a mixture of 98% chloroform and 2% methanol for the elution. The eluate is concentrated and the residue is dissolved in a mixture of 4-methyl-2-pentanone and diisopropyl ether converted into nitrate. It is recrystallized once from this mixture: 5.8 parts of end product, melting point 145.1.degree In this way, the following compounds of the formula

produced (R, = 2-position), whereby isomeric forms are to be included: Comp. No. R1 R2 R3 X Z Salt Physical constant 1 Cl Cl H H 5-C2H5 - nD20 1.5659 2 Cl Cl H H 5-C2H5 NHO3 m.p. 145.10 3 Cl Cl H H 5-nC3H7 - 4 Cl Cl H H 5-n-butyl 5 Cl Cl H H 5-n-hexyl 6 H Cl H H 5-C2H5 - oil 7 Cl Cl 5-Cl H 5-C2H5 - oil 8 Cl H 6-Cl H 5C2H5 HNO3 9 Cl Cl H 5CH3 5-C2H5 - nD23 1.5502 10 Cl Cl H 5-C2H5 5-C2H5 - bp 180-190 / 0.04 torr 11 Cl Cl H 5-CH3 5-CH3 - bp 165-170 / 0.04 torr 12 H Cl H 5-CH3 5-C2H5-oil 13 H Cl H 5-CH3 5-nC8H1, -14 Cl Cl H 5-CH3 5-C2H17-15 H Br H 5-CH3 5-C2H5 - oil 16 HFH 5-CH3 5-C2H5 - oil 17 Cl H 6-Cl 5-CH3 5-C2H, - oil 18 Cl Cl H 5-CH3 5-nC3H7 - oil 19 H Cl H 5-CH3 5-n-C3H7 - oil 20 HFH 5-CH3 5-nC3H7 - m.p. 133-137 21 Cl Cl H 5-C2H5 5-CH2OH - m.p. 153-159 22 H Cl H 5-C2H5 5 -CH2OH - 23 HFH 5-C2H5 5-CH2OH - 24 HJH 5-C2H5 5-CH2OH connection no. R1 R2 R3 XZ salt physical constant 25 Cl Cl H 4-CH3 5-C2H5 26 Cl Cl H 4-C2H5 5 -C2H5 27 Cl Cl H 4-nC3H7 5-C2H5 - nD23 1.5486 28 Cl Cl H 5-CH3 5-CH2OH 29 H Cl H 5-CH3 5-CH2OH - 30 Cl Cl H 5-CH3 5-CH3 CuCl2 m.p. .> 300 (Z.) 31 Cl Cl H 5-CH3 5-CH, ZnCl2 32 Cl Cl H 5-CH3 5-CH3 Mn (NO3) 2 33 Cl Cl H 5-C2H5 5-nC4H9 - nD20 1.5565 34 Cl Cl H 5-C2H5 5-nC4H9 CuCl2 and the following compounds of the formula

Connection no. XY Salt 35 CH3 H 36 C2H5 H 37 nC3H7 H 38 nC4H9 H 39 nC8H17 H 40 CH3 CH3 41 C2H5 CH3 42 C2H5 C2H5 43 nC8H17 CH3 44 nC3H7 C2H5 45 CH3 CH3 HNO3 46 CH3 CH3 CuCI2 47 CH3 CH3 Mn (NO ) 2 48 CH3 CH3 ZnCl2 49 C2H5 C2H5 HNO3 50 C2H5 C2H5 CuCl2 51 C2H5 C2H, FeCl3 and the following compounds of the formula

Connection number R1 R2 R3 Salt 52 Cl Cl H HNO3 53 H Cl H - 54 Cl H 6-Cl 55 H F H - 56 Cl Cl H CuCl2 57 Cl Cl H Mn (NO3) 2 as well as the following compounds of the formula

Connection no.Ri R2 R3 Salt 58 H Cl H - 59 Cl Cl H - viscos 60 Cl Cl H HNO3 61 Cl Cl H Maleinate 62 Cl Cl H CuCl2 resin 63 Cl Cl H ZnCl2 64 Cl Cl H Mn (NO3) 2 65 Cl H 6-Cl HNO3 66 Cl Cl 5-Cl HNO3 67 HJH HCI 68 Cl Br H (COOH) 2 The compounds of the formula I can be used alone or together with suitable carriers and / or other additives. Suitable carriers and additives can be solid or liquid and correspond to the substances customary in formulation technology such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

The content of active ingredient in marketable products is between 0.1 and 90%.

For administration, the compounds of the formula I can be in the following working-up forms (the percentages by weight in brackets represent advantageous amounts of active ingredient): Solid forms of processing: dust and grit (up to 10%) granules, coated granules, impregnation granules and homogeneous granules, pellets (grains) (1 to 80%); Liquid processing forms: a) Active substance concentrates dispersible in water: Wettable powders and pastes (25-90% in the commercial pack, 0.01 to 15% in ready-to-use Solution); Emulsion and solution concentrates (10 to 50%; 0.01 to 15% in ready-to-use solution); b) solutions (0.1 to 20%); Aerosols.

The active ingredients of the formula I of the present invention can be formulated, for example, as follows: Dusts: The following substances are used to produce a) 5% and b) 2% dusts: a) 5 parts of active ingredient 95 parts of talc; b) 2 parts of active ingredient 1 part of highly dispersed silica, 97 parts of talc.

The active ingredients are mixed and ground with the carrier substances and can be dusted in this form for use.

Granules: The following substances are used to produce 5% granules: 5 parts of active ingredient 0.25 parts epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol 91 parts of kaolin (grain size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin, and the acetone is then evaporated in vacuo. Such microgranules are advantageously used to control soil fungi.

Wettable powder: The following are used to produce a) 70%, b) 40%, c) and d) 25%, e) 10% wettable powders Ingredients used: a) 70 parts of active ingredient 5 parts of sodium dibutylnaphthylsulfonate, 3 parts of naphthalenesulfonic acids-phenolsulfonic acids-formaldehyde condensate 3: 2: 1, 10 parts kaolin, 12 parts of champagne chalk; b) 40 parts of active ingredient 5 parts of lignin sulfonic acid sodium salt, 1 part sodium dibutylnaphthalenesulfonic acid, 54 parts of silica; c) 25 parts of active ingredient 4.5 parts calcium lignosulfonate, 1.9 parts of champagne chalk / hydroxyethyl cellulose Mixture (1: 1), 1.5 parts of sodium dibutyl naphthalene sulfonate, 19.5 parts of silica, 19.5 parts of champagne chalk, 28.1 parts of kaolin; d) 25 parts of active ingredient 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of champagne chalk / hydroxyethyl cellulose Mixture (1: 1), 8.3 parts sodium aluminum silicate, 16.5 parts kieselguhr, 46 parts of kaolin; e) 10 parts of active ingredient 3 parts mixture of the sodium salts of saturated Fatty alcohol sulfates, 5 parts of naphthalenesulfonic acid / formaldehyde Condensate, 82 parts of kaolin.

The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. The wettable powder obtained has excellent wettability and suspension properties, which can be diluted with water to form suspensions of the desired concentration and, in particular, can be used for foliar application.

Emulsifiable concentrates: The following substances are used to produce a 25% emulsifiable concentrate: 25 parts of active ingredient 2.5 parts epoxidized vegetable oil, 10 parts of an alkylarylsulfonate / fatty alcohol poly glycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene.

Such concentrates can be diluted with water to produce emulsions of the desired concentration, which are particularly suitable for foliar application.

Example 2 Action against Cercospora personata (= C. arachidicola) on peanut plants 3-week-old peanut plants were sprayed with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.02% active ingredient). After about 12 hours, the treated plants were dusted with a conidia suspension of the fungus. The infected plants were then incubated for approx. 24 hours at> 90% relative atmospheric humidity and then placed in the greenhouse at approx. 22 ° C.

The fungal attack was evaluated after 12 days.

Compared to the untreated control, plants which had been treated with active ingredients of the formula I showed little or almost no disease infestation. Compound No. 18, among others, also completely prevented the disease in a concentration of 0.006%.

Example 3 Action against Plasmopara viticola (Bert. Et Curt.) (Berl. Et DeToni) on vines residual preventive effect Vine cuttings of the Chasselas variety were grown in the greenhouse. At the 10-leaf stage, 3 plants were sprayed with a broth (0.06% active ingredient) prepared from the active ingredient formulated as a wettable powder. After the spray coating had dried on, the plants on the underside of the leaves were evenly infected with the spore suspension of the fungus. The plants were then kept in a humid chamber for 8 days. After this time, the control plants showed clear symptoms of disease. The number and size of the infection sites on the treated plants served as an assessment standard for the effectiveness of the substances tested.

Compounds Nos. 9, 18, 25, 27, 28 and others completely prevented the disease.

Example 4 Action against Erysiphe graminis on barley a) Residual protective action Approx. Barley plants 8 cm high were sprayed with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.02% active ingredient). After 3-4 hours, the treated plants were dusted with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22 ° C. and the fungal attack was assessed after 10 days.

b) Systemic effect A spray liquor made from wettable powder of the active ingredient was poured into barley plants about 8 cm high (0.006% active ingredient based on the volume of the soil). Care was taken to ensure that the spray mixture did not come into contact with the above-ground parts of the plant. After 48 hours, the treated plants were dusted with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 220 ° C. and the fungal attack was assessed after 10 days.

Experiment a): Compounds of the formula I were shown to be fully effective (no disease). Compounds nos. 9 to 13, 18, 21, 27 and others also showed full effect in a concentration of 0.006%.

Experiment b): Compound No. 18, among others, was found to be fully effective.

Example 5 Effect against Botrytis cinerea on beans. Residual protective effect Approx. Bean plants 10 cm high were sprayed with a spray mixture (0.02% active ingredient) prepared from a wettable powder formulation of the active ingredient. After 48 hours, the treated plants were infected with a conidia suspension of the fungus. After incubation of the infected plants for 3 days at 95-100% relative humidity and 21 ° C., the fungal infestation was assessed. The compounds of the formula I prevented the disease completely.

A large part of the connections, e.g. the compounds No. 9, 10, 11, 27, prevented the disease infestation even in a concentration of 0.006% and below.

Claims (10)

PATENT CLAIMS 1. Compound of formula I wherein R1, R2 and R3 independently of one another halogen and two of the three substituents also hydrogen, X C1-C8 alkyl, Y is hydrogen or C1-Ca alkyl and Z denotes hydrogen, C1-C8 alkyl or -CH2OH, the total number of carbon atoms in the substituents X, Y and Z not exceeding 10, as well as their salts and their metal complexes. 2. Compounds according to claim 1, wherein R1 is hydrogen or halogen, R2 is halogen and R3 is hydrogen. 3. Compounds according to claim 2, wherein R1 is hydrogen or chlorine, R2 is chlorine and Rs is hydrogen. 4. Compounds according to claim 1, in which the alkyl chain does not have more than 3 carbon atoms in any of the substituents X, Y or Z. 5. Compounds according to claim 1, in which the dioxane ring is disubstituted in the 5-position by 2-alkyl groups. 6. Process for the preparation of compounds of the formula I, characterized by the reaction of the imidazole of the formula II wherein Me represents hydrogen or a metal atom, with a halide of formula III in which R1, R2, R3, X, Y and Z have the meanings given for formula I and Hal is halogen. 7. Microbicidal agent, characterized in that it contains a compound of the formula I as an active ingredient. 8. Agent according to claim 7, characterized in that it contains a compound according to claim 3. 9. Use of compounds of the formula I for combating fungi. 10. Use according to claim 9, characterized in that compounds according to claim 3 are used. The present invention relates to substituted 2-phenyl-2- [1 (H) -imidazolylmethyl] -1,3-dioxane derivatives of the formula I and their salts with inorganic or organic acids and their metal complexes, the preparation of such compounds, and also microbicides Agents which contain compounds of the formula I as active ingredients and the use of compounds of the formula I for combating plant diseases. In formula I. mean the three substituents R1, R2 and R3 independently of one another halogen and two of the three substituents also hydrogen, X C1-C8 alkyl, Y is hydrogen or C1-C8 alkyl and Z is hydrogen, C1-C8 alkyl or -CH2OH, the total number of carbon atoms in the substituents X, Y and Z not exceeding 10. The term halogen includes fluorine, chlorine, bromine and iodine. C1-C3-alkyl means methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. Butyl, tert. Butyl and the various isomers amyl, hexyl, heptyl and octyl. Examples of inorganic acids are hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, phosphoric acid, phosphorous acid, nitric acid. Examples of organic acids are acetic acid, trichloroacetic acid, oxalic acid, succinic acid, maleic acid, lactic acid, glycolic acid, aconitic acid, citric acid, benzoic acid, benzenesulfonic acid, methanesulfonic acid. Metal complexes of formula I consist of the underlying organic molecule and an inorganic or organic metal salt, e.g. the hydrohalides, nitrates, sulfates, phosphates, tartrates, etc. of copper, manganese, iron, zinc and other metals. The metal cations can be present in the various valencies assigned to them. There is no limitation associated with these various exemplary lists. The compounds of the formula I have a microbicidal spectrum, which is very favorable for practical needs, for protecting crop plants without adversely affecting them by undesired side effects. For the purposes of the present invention, crop plants are, for example, cereals, corn, rice, vegetables, sugar beets, soy, peanuts, fruit trees, ornamental plants, vines, hops, cucumber plants (cucumbers, pumpkins, melons), solanaceae such as potatoes, tobacco and tomatoes, as well as banana plants. , Cocoa and natural rubber plants. The active ingredients of the formula I can be used to contain or destroy the fungi that occur on plants or parts of plants (fruits, flowers, foliage, stems, tubers, roots) of these and related crops, ** WARNING ** End of CLMS field could overlap beginning of DESC **.