NL7907953A - PROCESS FOR THE PREPARATION OF AZOLYL KETALS AND THE USE THEREOF AS MICROBICIDE. - Google Patents

Description

1 * N. 0.28.353>

Process for the preparation of azolyl ketals and their use as a microbicide

The present invention relates to a process for the preparation of azolyl ketals of the formula 1 including the plant tolerable salts with inorganic or organic acids and metal complexes, wherein a tert-butyl group or an optionally halogen-substituted phenyl group once or twice and

Hg represents a phenyl or diphenyl group optionally substituted by 1-3 halogen atoms, C 1 -C 8 alkyl, methoxy, cyano, nitro and / or phenoxy and 10 A is the group of the formula 2 or 3, wherein R 1, R 1 , R 1 and R 8 independently of one another represent hydrogen, C 1 -G 8 alkyl, -C 8 alkoxymethyl or phenoxymethyl, or R 1 and R 2 together represent tetramethylene and X represents the group CH or N.

Depending on the number of carbon atoms indicated, the alkyl or alkyl part of another substituent is understood to mean the following groups: methyl, ethyl, propyl, butyl, pentyl or hexyl and their isomers (such as iso-propyl, iso-butyl, sec.butyl , tert-butyl, iso-pentyl, etc.).

Halogen means fluorine, chlorine, bromine or iodine.

Examples of salt-forming acids are hydrochloric, hydrobromic, hydroiodic, sulfuric, phosphoric, nitric, acetic, trifluoroacetic, trichloroacetic, oxalic, benzenesulfonic and methanesulfonic acids.

Metal complexes of the formula I consist of the respective organic molecule and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, tartrates etc. of copper, manganese, iron, zinc and other metals. In addition, the metal cations can be present in the various associated dignities.

The compounds of the formula I are very valuable active substances against plant pathogenic micro-organisms.

A preferred subset of active fungicides are those compounds of formula I, wherein R 1 is a tert-butyl group or optionally a phenyl group substituted by fluorine or chlorine / a phenyl group once or twice and R 9 / optionally substituted by 1 - 2 halogen atoms. or diphenyl group and A is the group of formula 2 or 3, wherein R 1, R 1, R 1. and Rg independently represents hydrogen, C 1 -C 6 -alkyl, methoxymethyl or phenoxymethyl or R 1 and R 2 together tetramethylene and X represents the group CH or ET.

Another subset of active fungicides are those compounds of formula I wherein R1 represents a tert-butyl group or a 2,4-dichlorophenyl group, R2 is an optionally substituted phenyl radical by methyl, chlorine, methoxy, cyano or phenoxy and RT and E together represent a tetramethylene bridge. j 4

A further subset of active fungicides are those compounds of formula I wherein R 1 is a tert-butyl group or a 2,4-dichlorophenyl group, R g is an phenyl radical optionally substituted by methyl, chloro, methoxy, cyano or phenoxy and A is the group -C 1 (R 2) - CH (R 2) -, wherein R 1 represents hydrogen and R 1 C 1 -C 8 -alkoxy-methyl or phenoxymethyl, where among the possible alkoxymethyl side chains the C 1 -C 6 - alkoxymethyl groups are preferred.

A preferred subset of active fungicides consists of those compounds of formula I, wherein R 1 is tert. butyl group or a 2,4-dichlorophenyl group, Rg is a chlorine substituted phenyl group once or twice, A is an optionally C 1 -C 2 alkyl or methoxymethyl substituted ethylene bridge and X represents the group CH or H.

Particularly preferred, however, are those fungicides, which belong to the formula 1, in which R 1 represents a tert-butyl group, R 2 represents once or twice chloro-substituted phenyl radical, A represents an ethylene bridge and X represents the group CH or H.

The following individual compounds are particularly preferred: 2-tert-butyl-2- [1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl] -methyl-50 1,5 -dioxolan 2-tert, buty1-2- [1- (4-chlorophenoxy) -1- (imidazol-1-yl)] - methyl-1,3-dioxolan 2-tert-butyl-2- [1- (phenoxy ) -1- (1,2,4-triazol-1-yl)] - methyl-1,3-dioxolan 35 2-tert, butyl-2- [1- (4-fluorophenoxy) -1- (1,2 , 4-triazol-1-yl)] - methyl -1,3 "4ioxolan 2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenoxy) -1 - (1; 2,4-triazole -1-yl)] - methyl-1,3-dioxolan 2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -1- (1,2,4-triazol-1-yl) )] -40 methyl-1,3-dioxolan.

790 7 9 53.-3 *

The compounds of the formula I are prepared according to the invention by reacting a compound of the formula 4 with a compound of the formula 5, wherein R 1, X and A have the meaning indicated under formula 1, Hal halogen, preferably chlorine or bromine, and Me represent hydrogen or a metal cation, preferably an alkali or alkaline earth metal cation (eg, potassium or sodium).

The process is optionally carried out in the presence of aprotic polar solvents which are inert to the reactants. Examples of such solvents are acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric acid triamide or sulfolan.

In those cases where in the formula Me represents hydrogen, the process is carried out in the presence of a base. Examples of such bases are inorganic bases such as the oxides, hydroxides, hydrides, carbonates and bicarbonates of alkali and alkaline earth metals, as well as, for example, tert-amines such as triethyl amine, triethylenediamine, pyridine, 4-dimethylaminopyridine, 4-pyr- rolidylpiridine and diazabicycloctane.

The process is carried out at a temperature between 0 and 150 ° C and under normal pressure.

The starting metals of the formula IV are prepared by a) reacting a compound of the formula 6 with a diol of the formula 7 in the presence of an acid and b) halogenating the ketal of the formula 8 thus obtained.

Inert solvents are used with respect to the reactants, such as, for example, for reaction a) hydrocarbons such as benzene, toluene and halogenated hydrocarbons (carbon tetrachloride, chloroform, dichloromethane, dichloroethane, etc.) 50 or for reaction b) halogenated hydrocarbons (carbon tetrachloride) , chloroform, dichloromethane, etc.), diethyl ether, tetrahydrofuran, dioxane and so on.

Inorganic acids such as HBr, HCl and HgSO4, as well as p-toluenesulfonic acid and boron trifluoride etherate are suitable as acids in the process a).

Examples of suitable halogenating agents in process b) are chlorine, sulfuryl chloride, bromine or N-bromosuccinic acid imide, wherein in the use of IT broomide acid or chlorine, catalysts (e.g. light, peroxide such as 790 7 9 53 \ 4 dibenzoyl peroxide or α, α'-azoisobutyronitrile) can be used.

The reaction temperature at sub-stage a) is 40 - 150 ° C, advantageously with a water separator. In process b), the reaction temperature is 0-100 ° C, preferably 35-70 ° C. Process steps a) and b) of the ketalization and halogenation of the pinacoline ether of the formula 6 (E = tert-butyl) to intermediates of the formulas 8 and 4 are an independent part of the present invention. Bit aspect is also an independent method for the preparation of pinacolin ether ketals of the formula 8 and of halogenated ketals of the formula 4

The ketones of the formula 1 formally underlying ketones have been described in individual cases in the German Offenlegungsschrifts 2,325,156, 2,705,676, the German Auslege script 2.2OI.O63 and the German Offenlegungsschrift 1 2,705,678.

However, they cannot be used as starting materials for the process steps described here.

The invention is further elucidated by means of the following examples.

Preparation examples

Example I; Preparation of 2-tert-butyl-2- [1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl)] -methyl-1,3-dioxolane of the formula-9 (compound No. 18).

A) Preparation of 2-tert-butyl-2- [1- (4-chlorophenoxy)] -methyl-1,3-dioxolane of formula 10.

40 g of 4-chlorophenoxypinacoline were heated under reflux with 17 g of ethylene glycol with the addition of 0.2 g of p-toluenesulfonic acid in 300 ml of toluene on a water separator for 30 hours. The cooled toluene solution was washed successively with a dilute bicarbonate solution and water, dried with sodium sulfate, filtered and concentrated under reduced pressure. The crystals thus obtained were crystallized from petroleum ether to give 35 S of the intermediate, mp 68-70 ° C. B) Preparation of 2-tert-butyl-2- [1- (4-chlorophenoxy) -1-bromo] -methyl-1,3-dioxolane of formula 11; 24 g of the 4-chlorophenoxypinacoline ethylene ketal from step a) were dissolved in 150 ml of tetrachloromethane. At 40-50 ° C, about 16 g of bromine was slowly added dropwise. After stirring at this temperature for 15 hours, the bromine was used. After cooling, the tetrachloromethane solution was washed with dilute bicarbonate solution, dried and concentrated. The residue gave 18 g of product with a melting point of 118-120 ° C from petroleum ether.

c) Finished products.

3S of 1,2,4-triazole and 2 g of 55-P 2 -Cent sodium hydride suspension in paraffin oil were placed in absolute dimethylformamide.

After the hydrogen evolution had ended, the mixture was stirred for a further 1 hour at 80-100 ° C. Then, 11 g of 2-tert-butyl-2- [1- (4-chlorophenoxy) -1-bromo-methyl-1,3-dioxolan in dimethylformamide were added dropwise and the reaction mixture was added at 100-120 ° for 18 hours. C stirred. The solvent was removed under reduced pressure and the oily residue was taken up in ether, washed with water, dried, filtered and evaporated. After evaporation, 8 g of a viscous oil were obtained from the ether solution, which was purified by chromatography on a silica gel column.

In this way, colorless crystals of compound No. 18 having a melting point of 103-105 ° C were obtained.

Example II: Preparation of 2-tert-butyl-2- [1- (4-chlorophenoxy) -1- (imidazol-1-yl)] -methyl-1,3-dioxolane of the formula 12 (compound 20 No. 1 ) ·.

Final product: 3 g of imidazole and 2 g of 55-P-ocents sodium hydride suspension in paraffin oil were placed in absolute dimethylformamide. After the hydrogen evolution had ended, stirring was continued for 1 hour at 80-100 ° C. Then 11 g of 2-tert-butyl-2-[1- (4-chlorophenoxy) -1-bromo-methyl-1,3-dioxolan in dimethylformamide were added dropwise and the reaction mixture was added at 100-120 ° C for 18 hours. stirred. The solvent was removed under reduced pressure and the oily residue was taken up in ether, washed with water, dried, filtered and evaporated. After evaporation, 9 g of a viscous oil were obtained from the ether solution, which after recrystallization from hexane gave colorless crystals of the compound No. 1. Melting point 102-104 ° C.

Example III; Preparation of 2- (2,4-dichlorophenyl) -2- [1- (4-chloro-35-phenoxy) -1- (1,2,4-triazol-1-yl)] -methyl-1,3-dioxolane of the formula 13 (compound No. 35) · a) Preparation of 2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenoxy)] - methyl-1,3-dioxolane of the formula 14 ·

A mixture of 54 g of a- (p-chlorophenoxy) -2,4-dichloroacetophenone, 40 ml of ethylene glycol and 2 g of p-toluenesulfonic acid in 400 ml of toluene 790 7 9 53 β 6 was refluxed on a water separator.

After a reaction time of 10 hours, an additional 10 ml of ethylene glycol were added. After 50 hours, the reaction mixture was cooled to room temperature, washed once with sodium bicarbonate solution and twice with water, the toluene phase was separated, dried over sodium sulfate and concentrated. 61 g of a clear yellow, viscous oil were obtained, b) Preparation of 2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenoxy) -1-bromo] -methyl-1,3-dioxolane with the formula 15 · 10 100 g of 2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenoxy)] - methyl-1,3-dioxolan were dissolved in 400 ml of absolute dioxane and left at 70 ° C Add 46 g (15 ml) of bromine to the mixture while stirring. After 5 hours, the reaction mixture was cooled to room temperature and poured onto 2 liters of ice water, the latter containing 20 g of sodium bicarbonate. The separated oil was extracted with dichloromethane, the organic phase was washed with aqueous sodium bicarbonate solution and dried over sodium sulfate. 30 g of a brown oil, which was taken up in 500 ml of hexane, were obtained. From this solution 7-8 g of beige-colored crystals with a melting point of 110 DEG-104 DEG C. separate.

c) Finished product.

To a solution of 77 g of 2- (2,4-dichlorophenyl) -2- [1- (4-chloro-phenoxy) -1-bromo] -methyl-1,3-dioxolane in 500 ml of absolute dimethylformamide were added 37 g 1,2,4-triazole potassium was added and the reaction mixture was stirred at 100 ° C for 15 hours. After removal of the dimethylformamide under reduced pressure, the brown residue was extracted with water and a mixture of hexane and dichloromethane (8: 2 parts by volume). The organic extracts were dried over sodium sulfate and concentrated. 62 g of a dark brown oil were obtained, which after purification with an alumina (activity 2-3) column, 30 g of a yellowish crystal mass of the . .

bond No. 35 having a melting point of 104 DEG-107 DEG.

Example IV; Preparation of 2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -1- (1,2,4-triazol-1-yl)] - methyl-1,3-dioxolane of the formula 16 ( compound No. 26).

a) Preparation of 2-tert-butyl-2- [1- (2,4-dichlorophenoxy)] -methyl-1,3-dioxolane of formula 17.

50 g of 2,4-dichlorophenoxypinacoline were refluxed with 20 g of ethylene glycol and 0.5 g of p-toluenesulfonic acid in 300 ml of toluene at a water separator for 24 hours. The solution cooled to room temperature was filtered with aqueous sodium bicarbonate solution and then with water, dried with sodium sulfate and concentrated under reduced pressure. 55 S colorless crystals with a melting point of 61 - 63 ° C were obtained.

B) Preparation of 2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -1-bromo] -methyl-1,3-dioxolane of the formula 18.

200 g of the 2,4-dichlorophenoxypinacolinethylene ketal prepared according to a) were dissolved in 900 ml of absolute dioxane and mixed dropwise with 105 g of bromine at 40 DEG-50 DEG C. with stirring. After stirring for 4 hours, the bromine was consumed. Stirring was continued for 1 hour and the reaction solution was placed in 5 liters of ice water containing 50 g of sodium bicarbonate. The precipitated crystals were filtered off, dried and recrystallized from hexane. 130 g of colorless crystals with a melting point of 99 DEG-102 DEG C. were thus obtained.

C) Finished product.

A solution of 15 δ 1,2,4-triazole potassium in 250 ml dimethyl sulfoxide was mixed with 38> 5 δ 2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -1-bromo] -methyl -1,3-dioxolan mixed and stirred at 100 ° C for 15 hours. Then the reaction solution was cooled to room temperature and poured into water. The resulting brown oil was extracted with diethyl ether, dried over sodium sulfate and purified with a silica gel column. 17 g of a tough oil were obtained, which could be crystallized by adding petroleum ether. The resulting crystals of compound No. 26 were recrystallized from hexane / diethyl ether and had a melting point of 106-108 ° C.

The following compounds of the formula I can be prepared in an analogous manner: 790 7 9 53.

• 8 s ϊ3 ΐ4 TABLE A (X = CH; Α = -CH— CH-)

Verb. R R2 R ^ R ^ ', Physical, const.

No. '

1. t-Butyl -C, H-C1 (4) Η H m.p. 102-104 ° C

6 4 2 t-Butyl-C, H-C1 (4) H 'H »1/2 CuSO.

6.4 4 3 t-Butyl -C6H4-C1 (4) 0¾ CH3 visc. oil 4 t-Butyl -CH-CK4) HC, H_ (n) 6-4 3 7 5 t-Butyl -C H4-C1C4) H -CH2OCH3 6 t-Butyl -CgH ^ -Cl (4) -CH ^ CH ^ CH2-CH2-

7 t-Butyl -C H -Gl2 (2.4) Η H

8 t-Butyl -CfjH -Cl (2,4) H C2H5 9 t-Butyl -CfiH -Cl2 (2,4) H -CH2OCH3 10 t-Butyl -C ^ H ^ ® H visc. oil 11 t-Butyl-diphenyl H visc. oil 12 -rC H -C12 (2,4) -CgH -Cl (4) H C Η? (η) 13 -C.H -F (4) -OH.-Cl (4) Η H. resin 6 4 6 4

14 -C6H5 -C6H3-C12 (2.4) Η H

Table B (X = CH; A = -0 ^ - ^ 0--0 ^ -) R5 ^ 6

Verb R ^ R2 R ^ Rg Pys. const.

No.

15 t-Butyl -CcH.-Cl (4) ΗH

6 4

16 -C6H3-C19 (2.4) -C6H4-C1 (4) CH3 CH3 mp. 82-84 ° C

17 -CgH ^ -F (4) -C6H4-C1 (4) CH3 CH3 mp. 150-151 ° C

790 7 9 53 9 /

Table, S. (X = N; A = -CH — JH-) J ^ 4, i! j

Verb. R, j R-R. R. "Physical const.

.. 1 12 3 4 \

No. j

18 t-Butyl j -C, H -01 (4) Η H mp. 103-105 ° C

I o 4 "

19 t-Butyl -CgH ^ -Cl (4) H H * 1/2 CuS04 mp 195-198 ° C

T-Butyl-CH-C1 (4) H C-H- -1ini11.on

6 4 2 5 mp, 110-115 C

21 t-Butyl I-C, H-C1 (4) H C, H ^ (n) m.p. 90-92 ° C

6 4 3 7 22 t-Butyl I-0.11.-01 (4) CH. CH_ visk. oil [6 4 3 3 23 t-Butyl j -CH-Cl (4) H -CH -0-CH., O 4 _2_J_ 24 t-Butyl -C ^ H.-C1 (4) -OIL -CH-CH -CH 1 - mp, 115-120 ° σ 6 4 2 2 2 2 25 t-Butvl -C H-C1 (4) H -CH-0-C, Hc visc. oil 6 4 2 6 5 <

26 t-Butyl -0 / 8--01., (2.4) Η H mp 106-108 ° C

b J 2 J 2 28 t-Butyl -CH -01- (2,4) .HH «1 / 2Mn (N0 -) - b J 2 J 2 28 t-Butyl -0 ^^ - 01 ^ (2,4) H -C ^^ visk. oil 29 t-Butyl -C.H -01., (2,4) H -CH-O-CH., resin

o ό L L J

30 t-Butyl -C ^ H- Η H visc. oil 31 t-Butyl -C6H4-F (4) Η H visc. oil 32 t-Butyl-diphenyl H visc * oil 33 -C.H -C, H -01 ,, (2,4) Η H m.p. 129-132¾ b 5 b j 2

34 -C6H4-F (4) -C6H4-C1 (4) Η H mp. 115-116 ° C

35 -C6H3-C12 (2.4) -C6H4-C1 (4) Η H mp. 104-107 ° C

36 -C.H -01- (2.4) -C.H -01- (2.4) Η H mp. 94-97 ° C

bj 2 b 5 2 37 -CH -01- (2,4) -CH-Cl (4) H -CH - 0-CH, b J 2 6 4 2 3 38 -C6H3-C12 (2,4) - C6H4-C1 (4) H - C (n) --.__ L_J__ 790 7 9 53 ί 10 TABLE D (H; A = -CHg— ^ Gr — CHg-) - - 'i

Yerb. R „B0 Bc. H * Eys. const.

w 1 d $ o

No.

39 t-butyl -CgH 2 -Cl (4) CH 2 CH 2 HCl visc. oil

40 t-butyl -0 ^ -01 (4) Η H

41 -C6H3-C12 (2,4) -C6ï4-C1 (4) Cïï3 Cïï5 mp. 128-131 ° C

42 -CgH4-r (4) -CgH4-Cl (4) CH3 CH3 mp. 134-138 ° C

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 the formulation technique, such as, for example, natural or regenerated inorganic substances, solvent dispersants, wetting, adhering, thickening, binding or fertilizer materials. Active substances of the formula 1 can also be used in admixture with, for example, pesticides or the plant growth improving preparations.

The active substance content in the products to be marketed is between 0.0001 and 90% by weight.

For the application, the compounds of the formula I can be present in the following working-up forms:

Final reprocessing forms: 15 'Dusts and spreaders generally contain up to 10% by weight of the active compound. For example, a 5 percent dusting agent may consist of 5 parts by weight of the active ingredient and 95 parts by weight of an additive, such as talc, or 2 parts by weight of active ingredient, 1 part by weight of highly dispersed silica and 97% by weight .dln talk. In addition, further mixing with such and other carrier materials and additives customary in the formulation technique are conceivable. In the preparation of these dusts, the active substances are mixed with the carriers and additives and ground and can be sprayed in this form.

Granules such as coating granules, impregnating granules, homogeneous granules and pellets (= granules) usually contain 1-80% by weight of the active substance. For example, a 5% granulate can consist of 5 parts by weight of the active substance, 0.25 parts by weight of epichlorohydrin, 0.25 parts by weight of cetyl polyglycol ether, 3.50 parts by weight of polyethylene 790 7 9 53 -Μ glycol and 91 parts by weight of kaolin (preferred grain size 0.3-0.8 mm). The granulate can be prepared as follows:

The active substance is mixed with epichlorohydrin and dissolved in 5 parts by weight of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed on kaolin and then the acetone is evaporated under reduced pressure. Such a micro-granulate is advantageously used for controlling soil fungi.

10 Liquid excitation forms;

In general, a distinction is made between active substance concentrates, which are water-dispersible or soluble, and aerosols. Water dispersible active substance concentrates include, for example, wettable powders and pastes 15, which usually contain from 25 to 90% by weight in commercial packs and 0.01 to 15% by weight of the active substance in ready-to-use solutions. Emulsion concentrates contain 10-50% by weight and solution concentrates contain in the ready-to-use solution 0.0001-20% by weight of active substance. For example, a 70% spray powder may consist of 20 parts by weight of the active substance, 5 parts by weight of sodium dibutylnaphthyl sulfonate, and 3 parts by weight of naphthalene sulfonic acids - phenol sulfonic acids - formaldehyde condensate (in the mixing ratio 3 s2: 1), 10 parts by weight of kaolin and 12 parts by weight of champagne crayon are composed. For example, a 40 percent spraying powder may consist of the following materials: 40 parts by weight of active ingredient, 5 parts by weight of sodium salt of lignin sulfonic acid, 1 part by weight. sodium salt of dibutylnaphthalene sulfonic acid and 54 parts of silicic acid. The preparation of a 25% spray powder can be done in various ways. For example, it may be composed of: 25 parts of the active substance, 4> 5 parts of 30 calcium lignin sulfonate, 1.9 parts by weight: mixture of champagne chalk and hydroxyethylene cellulose in a ratio of 1: 1, 1 .5 parts by weight of sodium dibutylmbalenesulfonate, 19.5 parts by weight of silicic acid, 19 parts by weight of 5 parts by weight. parts of champagne crayon and 28.1 parts of kaolin. For example, a 25px spray powder may also consist of 25 parts of active ingredient, 2.5 parts of isoctylphenoxy-polyoxyethylene-ethano1, 1.7 parts of mixture of champagne crayon and hydroxyethyl cellulose in a ratio of 1: 1 8.3 parts of sodium silicate, 16.5 parts of diatomaceous earth and 46 parts of kaolin. For example, a 10 percent spray powder can be prepared from 10 parts of active ingredient, 3 parts of a mixture of 40 sodium salts of saturated fatty alcohol sulfonates, 5 parts of 790 7 9 53 t 12 naphthalene sulfonic acid / formaldehyde condensate, and 82 parts by weight of kaolin. Other spray powders may be mixtures of 5-50 wt% active substance together with 5 parts by weight of an absorbent carrier material, such as silicic acid, 55 - 80 parts by weight of a carrier material, such as kaolin, 5, and a dispersant mixture consisting of 5 wt. parts of sodium aryl sulfonate and 5 parts of an alkylaryl polyglycol ether. For example, a 25% concentrate of emulsion concentrate may contain the following emulsifiers: 25 parts of the active ingredient, 2.5 parts of epoxidized plant oil, 10 parts of a mixture of alkylarylsulfonate and fatty alcohol polyglycol ether, 5 parts of dimethylformamide and 57> 5 parts by weight of xylene.

Such concentrations can be prepared by diluting with water to obtain emulsions of the desired application concentration, which are particularly suitable for use on leaves.

In addition, other spray powders with different mixing ratios or other carrier materials and additives customary in the formulation technique can be prepared. The active ingredients are intimately mixed with the aforementioned additives in suitable mixers and milled on corresponding mills and rollers. Spray powders 20 with excellent wettability and floatability are obtained, which are diluted with water to form suspensions of the desired concentration and in particular can be used for application on leaves. Such means also belong to the invention.

It has been surprisingly found that compounds of the structure of the formula I have a microbicidal spectrum for the protection of cultivated plants which is very favorable for practical needs. For the purposes of the present invention, cultivated plants are for example cereals: (wheat, barley, rye, oats, rice); beets: (sugar and fodder beets); kernel, stone and berry fruits -50s: (apples, pears, plums, peaches, almonds, cherries, strawberry, raspberry and blackberry); legumes s (beans, lentils, peas, soy); oil cultures: (rapeseed, mustard, poppy, olives, sunflowers, coconut, castor bean, cocoa, groundnuts); cucumber crops: (pumpkins, gherkins, melons); fiber crops: (cotton, flax, hemp, jute); citrus fruits: (oranges, lemons, grapefruit, tangerines); vegetables: (spinach, cabbage lettuce, asparagus, cabbage varieties, carrots, onions, tomatoes, potatoes, paprika) or plants, such as corn, tobacco, nuts, coffee, tea, sugar cane, wine grapes, hops, banana and natural rubber crops as well as ornamental plants.

40 With the active substances of the formula 1, plants 790 7 9 53 Ί3 »or plant parts (fruits, blossom, foliage, stems, tubers, roots) of these and related useful cultures can be dammed or destroyed, with subsequent fungi growing plant parts of such fungi are kept clean. The active substances are active against the phyto-pathogenic fungi belonging to the following classes: ascomycetes (eg Erysiphaceae, Fusarium, HeInthosporium, Yenturia, Podosphaera); basidiomyoetes such as, in particular, rust fungi (eg Puccinia, Tilletia, Hemileia); Fungi imnerfeoti (for example, Moniliales and others, Geroosnora as-10 with Botrytis and Yerticillium) and the Oomyoetes belonging to the class of Phycomycetes. In addition, the compounds of the formula I work systemically. They can furthermore be used as a pickling agent for the treatment of seeds (fruits, tubers, grains) and plant cuttings for protection against infection by the fungus as well as against phytopathogenic fungi occurring in the soil.

The invention therefore further relates to the use of the compounds of the formula I for the control of phytopathogenic microorganisms or to the preventive prevention of an attack on plants.

20 Biological examples

Example Y: Action against Erysinhe graminis on barley a) Residual protective effect

Barley plants about 8 cm high were sprayed with a spray suspension (0.02 wt.% Active substance) prepared from a spray powder of the active substance. After 5-4 hours, the treated plants were pollinated with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22 ° C and fungal infestation was assessed after 10 days.

b) Systemic action A spray suspension prepared from spray powder of the active substance was poured into approximately 8 cm high barley plants (0.006% by weight of active substance, based on the volume of soil). In doing so, care was taken that the spray suspension did not come into contact with the plant parts above the earth. After 48 hours, the treated plants were pollinated with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22 ° C and fungal infestation was assessed after 10 days.

è 790 7 9 53 i Λ- 14 'Example VI ί Action against .. Pncoinia graminis bii wheat a) Residual-no effect

Wheat plants were sprayed 6 days after sowing with a spray suspension (0.06% w / w active substance) prepared from a spray powder of the active ingredient. After 24 hours, the treated plants were infected with a uredosporal suspension of the fungus. After an incubation for 48 hours at a relative humidity of air of 95-100% and a temperature of about 20 ° C, the infected plants were placed in a greenhouse at 22 ° C. The assessment of rust pimple development took place 12 days after infection.

b) Systemic operation

For wheat plants, a spray suspension prepared from spray powder of the active substance was poured 5 days after sowing (0.006% by weight of active substance, based on the volume of the soil). After 48 hours, the treated plants were infected with a uredosporous suspension of the fungus. After an incubation for 48 hours at a relative humidity of air of 95-100% and a temperature of about 20 ° C, the infected plants were placed in a greenhouse at 22 ° C. Rust pimple development was assessed 12 days after infection.

Example 711; Effect against Cercosuora arachidicola bi.i groundnut • plants ♦

Residual protective effect 10-15 cm high groundnut plants were sprayed with a spray suspension (0.02 wt.% Active substance) prepared from a spray powder of the active substance and infected 48 hours later with a conidial suspension of the fungus. The infected plants were incubated at about 21 ° 0 and high humidity for 72 hours and then placed in a greenhouse until the typical leaf spots occur. The fungicidal activity was assessed 12 days after infection, based on the number and size of the spots occurring.

Example Till: Action against Venturia inaequalis oy apple trees 35 Residual uroteotic effect

Young apple plants with about 5 developed leaves were sprayed with a spray suspension (0.06% by weight of active ingredient) prepared from a spray powder of the active substances. After 24 hours, the treated plants were infected with a conidian suspension of the fungus. The plants were then incubated at 790 7 9 53 15% relative humidity of 90-100% for 5 days and further placed in a greenhouse at 20-24 ° C for 10 days. Scab infestation was assessed 15 days after infection.

The compounds of the formula I according to the invention generally showed good fungicidal activity in the tests described above. For example, the compounds listed below effected an inhibition of infestation to less than 20% compared to untreated but infected (= 100% infestation) control plants: For Puccinia graminis: Yerb. Hr. 1, 5 »11» 13 »18» 19 »20, 21, 22, 24, 26, 28, 29, 30, 31, 32, 34, 35, 39-

At Cercospora arachidicola: Yerb. Hr. 1, 18, 20, 22, 26, 32, 35

Bi.i Erysiphe graminis: Yerb. Hr. 1, 3 »11» 13, 17, 18, 19, 20, 21, 22, 24, 25, 26, 28, 29, 30, 31, 32, 33, 34, 15 35, 36, 39-

At Yenturia inaequalis: Yerb. Hr. 1, 3 »13» 18, 19 »20, 21, 22, 25, 26, 28, 29, 30, 31, 32, 33, 34, 35, 39-A brake of the infestation to 5% or less effected in the above tests the following compounds of the formula:

At Puccinia graminis: Yerb. Hr. 1, 3 »13, 18, 19, 20, 22, 26, 28, 29, 30, 31, 35, 39-

At Oeroospora arachidicola: Yerb. Hr. 1, 18, 20, 22, 26, 35

At Erysiphe graminis: Yerb. Hr. 1, 3, 13 »18, 19» 20, 21, 22, 25 »'25 26, 28, 29, 30, 51, 32, 33, 34, 35, 39

At Yenturia inaequalis: Yerb. Hr. 1, 18, 22, 26, 29, 30, 31 »35,39 · 790 7 9 53

Claims (3)

16. it * * • s 1. "Compounds of the formula 1, including the plant tolerable salts with inorganic or organic acids and metal complexes, in which R 1 represents a tert-butyl group or an optionally phenyl group substituted once or twice by halogen and Rg an optionally substituted by 1-3 halogen atoms, C 1-8 alkyl, methoxy, cyano, nitro and / or phenoxy group, and 10. is the group of formula 2 or 3, wherein R 1, R 1, R 1, and R 2 independently of one another are hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxymethyl or phenoxymethyl or R 1 and R 2 together tetramethylene and X is the group CE or I. J5 2. A compound of the formula 1 according to claim 1, characterized in that R 1 is a tert-butyl group or an phenyl group optionally substituted once or twice by fluorine or chlorine and Rg an phenyl or diphenyl group optionally substituted by 1 or 2 halogen atoms and A is the group of formula 2 or 3, wherein R 1, R 2, R 1 and R 8 independently of one another are hydrogen, C 1 -C 20 alkyl, methoxymethyl or phenoxymethyl or R 1 and R 2 together tetramethylene and X is the group CH or N. 3. A compound of the formula 1 according to claim 1, characterized in that R 1 is a tert-butyl group or a 2,4-dichlorophenyl group, R g is an phenyl group optionally substituted by methyl, chlorine, methoxy, cyano or phenoxy and R 1 and R 2 together form a tetramethylene bridge. A compound of the formula 1 according to claim 1, characterized in that R 1 is a tert-butyl group or a 2,4-dichlorophenyl group, R g is an phenyl group optionally substituted by methyl, chlorine, methoxy, cyano or phenoxy and A is the group -CH (R 1) -CH (R 1) -, wherein R 1 represents hydrogen and R 1 C 1 -C 8 -alkoxymethyl or phenoxymethyl. 5. A compound of the formula 1 according to claim 1, characterized in that R 1 represents a tert-butyl group or a 2,4-dichlorophenyl group, Rg is a phenyl radical substituted once or twice, A an optional ethylene bridge substituted by C 1 -C 2 alkyl or methoxymethyl and X represents the group CH or N. 6. Compound of formula 1 according to claim 5> 790 7 9 53 17 '* characterized in that E ^ is a tert. Butyl group, Rg is a chlorine substituted once or twice, A forms an ethylene bridge and X represents the group GH or N. The compound 2-tert-butyl-2- [1- (4-chlorophenoxy) -1- (1,2,4-5-triazol-1-yl)] -methyl-1,3-dioxolane according to claim 1. The compound 2-tert-butyl-2- [1- (4-chlorophenoxy) -1- (imidazol-1-yl)] -methyl-1,3-dioxolane according to claim 1. The compound 2-tert-butyl-2- [1- (phenoxy) -1- (1,2,4-triazol-1-yl)] -methyl-1,3-dioxolane according to claim 1. 10. The compound 2-tert-butyl-2- [1- (4-fluoro-phenoxy) -1- (1,2,4-triazol-1-yl)] -methyl-1,3-dioxolane according to claim 1. The compound 2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenyl) -1, 2,4-triazol-1-yl)] -methyl-1,3-dioxolane according to claim 1. The compound 2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -1-15 (1,2,4-triazol-1-yl)] -methyl-1,3-dioxolane according to claim 1. 13. Process for the preparation of compounds according to claim 1, characterized in that a compound of the formula 4 is reacted with a compound of the formula 5, wherein R. j, Eg, X and A have the meanings indicated for formula 1, 20 Halogen and * Me represent hydrogen or a metal cation. 14. A process for the preparation of a preparation for controlling phytopathogenic micro-organisms, characterized in that this preparation is made up of at least one compound of the formula 1 according to claim 1 as active component together with one or more suitable carriers. Preparation according to claim 14, characterized in that it contains, as at least one active component, a compound of the formula 1 according to one or more of claims 2-12. 790 7 953 l L A R -c-ffl-ll -CH-OH- - «2 — Λ — wr 1 o () 0 X = l« 3 m R5 Bi A Rj ii AR, - 0— OH— 0 — R, / “¥» _ “'<> ί, αΐ 2 H <JR —0-CH2O-R2 A * il HO— A — OH R4 ~ C \ ~ CH2—0 - R2 V 10. 9. ~~? H3 0 0 yr ^ f / 0 CH, - CV-CH — 0- c 'VCI CH3-CC-CHg-OH; ^ Cl o vj sy = .- i = <I · <* s = ¾ Ji. ft. CH I pu! I P ° w ° P ° w ° / \ CH, —C-C-CH-0- ^> -Cl CH, -; C-C-CH-0 -? VCl 3. I '<* «/ 3 I Λ W CH, Bi-CH," / \ 3. P] 3. / 1 | -1 o. P Cl-y ~ CH-o-c V-ci N W P 790 7 9 53 «. A Ϋ -i .ei I-i / r-4. 0 0 Cl- /> —V — ch2 — o— ^ Vci! L I-1 0. .0 0 ~ ^ ci— / ch — o— / V-egg W 'IW' 8r! K CH f-1 CLv I 3 0 0 CH4 CC "- CH — 0—4 VCI 3. N CH3 Λ N-8 \ l CH I-1 Clv, 3 0W0 V- ^ s ch * —c - c — ch9-o- ^ Vci 3 I 2 s »/ ch3 li CH 1-1 Cl I 3 ° o y ^ CH — c-C— CH — 0— ^ VCI 3. I W '790 7 9 53 c »3 B'