DE2943631A1 - AZOLYLKETALS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS MICROBICIDES - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann - Or. F. Koer.igsberger Dipl.-Phys. R. Holzbauer - Dipl. -Ing. (". K:; ngsei3cn - Dr. F" Lumstein jun.

PATE NTA NWÄ LT E

βΟΟΟ Munich 2 BrauhausstraOe 4 Telephone Sammei No. 22 5341 Telegrams Zumpat ■ Telex S299 / O

• 5 ·

Case 5-12095 / 96 / =

Azolyl ketals, process for their preparation and their use as microbicides

The present invention relates to azolyl ketals of the formula I.

including their plant-compatible salts with inorganic ones or organic acids and metal complexes, in which R is tertiary butyl or optionally once or twice through

Halogen-substituted phenyl and R- optionally by 1 to 3 halogen atoms, C ^ - ^ - alkyl, Methoxy, cyano, nitro and / or phenoxy mean substituted phenyl or diphenyl, and

A is -CH CH- or -CH ₂ - ^ C _n --CH ₂ -,

R ₃ R ₄ R ₅ \ ₆

wherein R_, R ₇ , R _c and R, independently of one another, are hydrogen,

JHJ O

C, -C, -alkyl, C -ΰ, -Α ^ οχ ^ βΙΙ ^ Ι or phenoxym? '; Hyl or 16 Ib

R_ and R, together denote tetramethylene and X denotes CH or N.

Under alkyl or alkyl part tine other substituent are the following groups depending on the number of carbon atoms specified to understand: methyl, ethyl, propyl, butyl, pentyl or hexyl as well their isomers (such as iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-pentyl etc.)

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Halogen stands for fluorine, chlorine, bromine or iodine.

Examples of salt-forming acids are hydrochloric acid, Hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, Nitric acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, oxalic acid, benzenesulfonic acid, methanesulfonic acid.

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

With these various exemplary enumerations is no limitation connected.

Compounds of the formula I are very valuable active ingredients against phytopathogenic microorganisms.

A preferred subgroup of effective fungicides are those compounds of the formula I in which R is tertiary butyl or phenyl which is optionally substituted once or twice by fluorine or chlorine and R 'is optionally phenyl or diphenyl which is optionally substituted by 1 to 2 halogen atoms and A is -CH-CH- or -CH —-C _n -CH - is,

where R_, R, R_ and R, independently of one another, are hydrogen, CC- alkyl methoxymethyl or phenoxymethyl or R ,, and R _f together are tetramethylene and X is CH or N-

Another subgroup of effective fungicides are those compounds of the formula I in which R stands for tertiary butyl or 2,4-dichlorophenyi, & represents a pfeenyl radical optionally substituted by methyl, chlorine, methoxy, cyano or phenoxy and &"and S represent a tetramethylene bridge *

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Another subgroup of effective fungicides are those compounds of the formula I in which R is tertiary butyl or 2,4-dichlorophenyl R "represents a phenyl radical which is optionally substituted by methyl, chlorine, methoxy, cyano or phenoxy, and A is -CH (R) -CH (R) -, where R is hydrogen and R, C -C -alkoxymethyl or phenoxymethyl, where among the possible alkoxymethyl side chains the C -C alkoxymethyl groups are preferred.

A preferred subgroup of effective fungicides consists of those compounds of the formula I in which R is tertiary butyl or 2,4-dichlorophenyl, R "is mono- or disubstituted by chlorine A phenyl radical denotes, A forms an ethylene bridge which is optionally substituted by C -C -alkyl or methoxymethyl and X stands for CH or N.

Particularly preferred, however, are those fungicides which obey the formula I in which R denotes terti-butyl, R denotes a single or phenyl radical disubstituted twice by chlorine, A forms an ethylene bridge and X denotes CH or N.

The following individual compounds are particularly preferred:

2-tert-butyl-2- [1- (4-chlorophenoxy) -l- (1,2,4-triazol-1-y1] -methy1- -1,3-dioxolane

2-tert-butyl-2- [l- (4-chlorophenoxy) -l- (imidazol-l-yl)] - methyl-1,3 -dioxolane

2-tert-butyl-2- [l- (phenoxy) -l- (l, 2,4-triazol-l-yl)] - methyl-l, 3- -dioxolane

2-tert-butyl-2- [1- (4-fluorophenoxy) -l- (1,2,4-triazol-l-yl)] methyl -1,3-dioxolane

2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenoxy) -l- (1,2,4-triazol-l-yl)] - -methyl-1,3-dioxolane

2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -1- (1,2,4-triazol-1-yl)] - methyl-1,3-dioxolane.

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The compounds of formula I are according to a further The present invention prepared by adding a compound of the formula II

R— -JZ - CH - 0 - R (II)

with a compound of the formula III

MeN ^ j (III)

Χ = ·

converts ^ where R, R., X and A have the meanings given under formula I. have, Hai for halogen, preferably chlorine or bromine and Me for hydrogen or a metal cation, preferably an alkali or Erdatkali metal cation Xz.B. Potassium or sodium).

If appropriate, the process is carried out in the presence of aprotic polar solvents which are inert towards the reactants. Examples of such solvents are acetonitrile, dimethylsulfoxide, dimethylformamide, dimethylacetamide or _t Hexamethylphosphorsäuretriaffiid SuIfοlan.

In those cases where Me in the formula <III) is 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 hydrogen carbonates of alkali and alkaline earth metals and, for example, tert. Amines such as triethylamine, Triäthy lendiamiii, pyridine, 4-diniethylaminopyridine, 4-? Yrrolidylpyridin and diazabicyclooctane.

The process is carried out at temperatures between 0 and 150 ^s C and at normal pressure.

The starting ketals of formula IJ are prepared by

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J.

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a) a compound of the formula IV

₁ - CH ₂ OR ₂ (IV)

with a diol of the formula V

HO — A — OH (V)

reacts in the presence of an acid and b) the resulting ketal of the formula VI

R - C - CH 0 - R (VI)

halogenated.

Solvents that are inert towards the reactants are used, such as, for example, for reaction a) hydrocarbons such as Benzene, toluene and halogenated hydrocarbons (carbon tetrachloride, Chloroform, methylene chloride, dichloroethane etc.) or for reaction b) halogenated hydrocarbons (carbon tetrachloride, Chloroform, methylene chloride etc.), diethyl ether, tetrahydrofuran, Dioxane, etc.

Possible acids in process a) are, for example, mineral acids such as HBr, HCl and H ₂ SO, as well as p-toluenesulphonic acid and boron trifluoride etherate.

Possible halogenating agents in process b) are, for example, chlorine, sulfuryl chloride, bromine or N-bromosuccinimide, with the Use of N-bromosuccinimide or chlorine, catalysts (e.g. light, peroxide such as dibenzoyl peroxide or α, α'-azoiso-butyronitrile) are used can be.

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The reaction temperatures are in subsidiary step a) 40 ° to 150 ⁰ C, whereby worked advantageously with a water separator. In the process b) are the reaction temperatures from 0 ° to 100 ⁰ C, preferably 35 ° to 70 ⁰ C. The process steps a) and b) of the ketalization and the halogenation of the pinacolone-ether IV (R = tert-butyl) to intermediates of Formulas VI and II represent an independent further aspect of the present invention. This aspect is also an independent method for the preparation of pinacolin ether ketals of the formula VI and of halogenated ketals of the formula

The ketones on which the ketals of the formula I are formally based are in individual cases 4 by DE-OS 2,325,156; 2,705,676; DE-AS 2,201,063 and DE-OS 2,705,678 become known. However, they cannot be used as starting materials for the process steps described here.

The following examples serve to explain the invention in more detail without restricting the same. Temperatures are given in degrees Celsius, pressures in millibars. Percentages and parts are by weight AAF.

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_ΛΛ "2 9 Λ 3 B

Manufacturing examples

Example 1 : Preparation of 2-tert-butyl-2- [1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl)] methyl-1,3-dioxolane of the formula

, —Rψ Y CH - Ο— ^ O / " ^C1 (connection no. 18)

a) Preparation of 2-tert-butyl-2- [l- (4-chlorophenoxy)] - methy1-1,3- -dioxolane of the formula

ί ^Η 3 0 0
CH ₃ 1 V CH ₇ -O- (θ / " ^C1

40 g of 4-chlorophenoxypinacoline were mixed with 17 g of ethylene glycol Addition of 0.2 g of p-toluenesulfonic acid in 300 ml of toluene during 30 Hours. Heated refluxing on the water separator. The cooled toluene solution was successively washed with dilute bicarbonate solution and water, dried with sodium sulfate, filtered and concentrated in vacuo. The crystals thus obtained were made from petroleum ether crystallized and gave 35 g of the intermediate product, m.p. 68-70 ° C.

b) Production of 2-tert-butyl-2- [l- (4-chlorophenoxy) -l-bromo] - -methyl-l, 3-dioxolane of the formula

.300
, C V CH-O-

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24 g of the 4-chlorophenoxypinakolin -äthylenketal of stage a) were dissolved in 150 ml of carbon tetrachloride. At 40-5O ⁰ C approx. 16 g of bromine were slowly added dropwise. After stirring for 15 hours at this temperature, the bromine was consumed. After cooling, the carbon tetrachloride solution was washed with dilute bicarbonate solution, dried and concentrated. The residue gave 18 g of product from petroleum ether with a melting point of 115 ° -12O ° C.

c) final product.

3 g 1,2,4-triazole and 2 g 55% sodium hydride suspension in paraffin oil were added together in absolute dimethylformamide. After completion of hydrogen evolution for 1 h. At 80-100 ⁰ C was stirred. 11 g of 2-tertiarbutyl-2-il- (4-chlorophenoxy) -1-bromo] -methyl-1,3-dioxolane in dimethylformamide were then added dropwise and the reaction gas mixture was stirred at 100 ° -20 ° C. for 18 hours . The solvent was removed in vacuo and the oily residue was taken up in ether, washed with water, dried, filtered and evaporated. After evaporation, S g of a viscous oil were obtained from the ether solution? «Read was purified by chromatography on a silica gel column. In this way, colorless crystals of compound no. 18 with m.p. 103-105 ^e C. were obtained.

Example 2 ; Production of 2-tert-butyl-2-il- <4-ChlorpheBOxy) - -l- (ifflidazol-l-yl)] - methyl-1,3-dioxolane of the formula

Oy {verb no. 1}

I- a

End product.

g issidazole and 2 g 552 sodium hydride suspension in liquid paraffin

—C C CH — o—

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combined in absolute dimethylformamide. After completion of hydrogen evolution for 1 h. At 80-100 ⁰ C was stirred. Then, 11 g of 2-tert-butyl-2- [l- (4-chlorophenoxy) -l-bromo] -methyl-l, were added dropwise 3-dioxolane in dimethylformamide, and the reaction mixture stirred for 18 hrs. At 100-120 ⁰ C. The solvent was removed in vacuo 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 led to colorless crystals of compound no. Mp. 102-104 ⁰ C.

Example 3: Preparation of 2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl)] methyl-1,3-dioxolane the formula

(Verb. No.35)

a) Preparation of 2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenoxy)] methyl-1,3-dioxolane of the formula

/ ^C1

-CH ₂ -O

H ₂ -O-^ -Cl

• s «as

A mixture of 54 g of a- (p-chlorophenoxy) -2,4-dichloroacetophenone, 20 ml of ethylene glycol and 2 g of p-toluenesulfonic acid in 400 ml of toluene was refluxed on a water separator. After a reaction time of 10 hours in each case, a further 10 ml of ethylene glycol were added admitted. After 50 hours the reaction mixture was cooled to room temperature, once with sodium bicarbonate solution and washed twice with water, the toluene phase separated off, dried over sodium sulfate and concentrated. 61 g of one were obtained light yellow, viscous oil.

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b) Preparation of 2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenoxy) -l- bromo] methyl-1,3-dioxolane of the formula

ei— ^ y - ^ -? ^H - ° ~ \ / " ^C1

100 g of 2- (2,4-dichlorophenyl) -2- [l- (4-chlorophenoxy)] - methyl-l, 3- dioxolane were dissolved in 400 ml of absolute dioxane and allowed at 70 ⁰ C 46 g (15 ml) of bromine are added dropwise with 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 deposited oil was extracted with dichloromethane, and the organic phase was washed with aqueous sodium bicarbonate solution and dried over sodium sulfate. 130 g of a brown oil were obtained, which was taken up in 500 ml of hexane. From this solution, 78 g of beige crystals of mp. 100-104 ⁰ C separated out.

c) final product.

37 g of 1,2,4-triazole were added to a solution of 77 g of 2-125 4-dichlorophenyl) -2-II-14-chlorophenoxy) -! - bromo ] methyl-1,3-dioxolane in 500 ml of absolute dimethylformamide Added potassium and the reaction mixture was stirred at 100 ° C. for 15 hours. After removing the dimethyl pharmaceutical in vacuo, the brown residue was extracted with water and hexane / dichloromethane (8: 2 parts by volume). The organic extracts were dried over sodium sulfate and concentrated. This gave 62 g of a dark brown ÖIS, which after cleaning with a Äl * ffidniuffiGxLä- (Aktivltät 2-3) -Saule 30 g of a yellowish Cristal! Weight of compound no. 35, mp. 104-107 ⁰ C yielded.

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Example 4 : Preparation of 2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -1- (1,2,4-triazol-1-yl)] methyl-1,3-dioxolane of the formula

(Verb. No.26)

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

CH ₃ CC-CH-O- _N y -Cl

50 g of 2,4-dichlorophenoxypinacoline were mixed with 20 g of ethylene glycol and 0.5 g of p-toluenesulfonic acid in 300 ml of toluene for 24 hours Water separator heated under reflux. The solution, cooled to room temperature, was washed with aqueous sodium bicarbonate solution and then washed with water, dried with sodium sulfate and concentrated in vacuo. 55 g of colorless crystals were obtained M.p. 61-63 ° C.

b) Production of 2-tert-butyl-2- [l- (2,4-dichlorophenoxy) -l-bromo] - -methyl-l, 3-dioxolane of the formula

F ³ Ό ¹ K

C C - CH - 0 - ^ ^ -

200 g of the 2,4-dichlorophenoxypinakolinethylene ketal prepared according to a) were dissolved in 900 ml of absolute dioxane and 105 g of bromine were added dropwise ^{at 40-5O 0 C with stirring.} After stirring for 4 hours, the bromine was consumed. The mixture was stirred for a further 1 hour

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and then carried the reaction solution into 5 liters of ice water , the latter containing 50 g of sodium bicarbonate. The precipitated crystals were filtered off with suction, dried and recrystallized from hexane. So 130 g of colorless crystals were obtained, mp. 99-102 ⁰ C.

c) final product.

A solution of 15 g of 1,2,4-triazole potassium in 250 ml of dimethyl sulfoxide was mixed with 38.5 g of 2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -1-bromo] -methyl-1 ₅ 3-dioxolane and stirred for 15 hours at ⁰ C IOO. Then the reaction solution was cooled to room temperature and poured into water. The brown oil obtained was extracted with ethyl ether, dried over sodium sulfate and purified with a silica gel column. 17 g of a viscous oil _{5 were obtained} which could be made to crystallize by adding petroleum ether. The resulting crystals of the VerÜn4ung no. 26 were recrystallized from hexane / diethyl ether and had a mp. Of 106 108 ⁰ C.

In an analogous manner, the following compounds of the formula I are found getting produced:

(D

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Table I.

I ³ ί ⁴

(X = CH; A = -CH-CH-)

Verb,
No. ^R i ^R 2 ^R 3 ^R 4 H Phys. Rons t. 1 t-butyl -C ₆ H ₄ -Cl (4) H H C ₂ H ₅ M.p. 102-104 ° 2 t-butyl -C ₆ H ₄ -Cl (4) H H »l / 2 CuSO ₄ -CH ₂ OCH ₃ 3 t-butyl -C, H.-C1 (4)
6 4 CH ₃ CH ₃ H vise. OeI 4th t-butyl -CH-Cl (4)
6 4 H C ₃ H ₇ (n) C ₂ H ₅ 5 t-butyl -CH ₇ -Cl (A)
6 4 H -CH ₂ OCH ₃ C ₃ H ₇ (n) 6th t-butyl -C, H.-C1 (4)
6 4 -CH ₂ -CH ₂ - CH ₂ -CH ₂ - H 7th t-butyl -C ₆ H ₃ -Cl ₂ (2.4) H H 8th t-butyl -C ₆ H ₃ -Cl ₂ (2.4) H 9 t-butyl -CH -Cl, (2.4)
OJ I H 10 t-butyl - ^C 6 ^H 5 H vise. OeI 11 t-butyl -diphenyl H vise. OeI 12th -C ₅ H ₃ -C 1 ₂ (2.4) -C, H -CK4)
6 4 H 13th -C ₆ H ₄ -F (4) -C, H.-C1 (4)
0 H H resin L4 -C ₅ H ₃ -Cl ₂ (2.4) H

Table II (X = CH; A = -CH - - C _n -

^R 5 * 6

Verb, ^R l , 4) Y (4) ^R 5 ^R 6 Phys . Const. No. (4) 15th t-butyl "C ₆ H ₄ -Cl (4) H H 16 -C ₆ H ₃ -Cl ₂ (2nd -C, H, -Cl
6 4 CH ₃ CH ₃ Smp 82-84 "C 17th -C ₆ H ₄ - _F (4) -CxH-Cl
6 4 CH ₃ CH ₃ M.p. 150-151 °

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Table III

(X = N; A = -ςΗ — ςΗ-)

Verb. ^R i ^R 2 ^R 3 ^R 4 j Phys. Const. No. 18th t-butyl -C ₆ H ₄ -Cl (A) H H M.p. 103-105 ° 19th t-butyl -C, H -Cl (4)
6 4 H H-1/2 CuSO.
4th 195-198 ° 20th t-butyl -C ₆ H ₄ -Cl (4) H C ₂ H ₅ M.p. 110-115 ° 21st t-butyl -C, H.-C1 (4)
6 4 H C ₃ H ₇ (n) M.p. 90-92 ° 22nd t-butyl -CH-CK4)
6 4 CH ₃ CH ₃ vise. OeI 23 t-butyl -CH-CK4)
6 4 H -CH ₂ -O-CH ₃ 24 t-butyl -C, H.-C1 {4)
6 4 -CH ₂ -CH ₂ -CE ₂ -CH ₂ - M.p. 115-120 ° 25th t-butyl -CH-Cl (4)
6 4 H -CH ₂ -OC ₆ H ₅ vise. OeI 26th t-butyl -C ₅ H ₃ -Cl ₂ (2.4) H H M.p. 106-108 ° 27 t-butyl -G ₆ H ₃ -Cl ₂ <2.4) H H'l / '2Mn (NO ₃ ) ₂ 28 t-butyl -C ₆ H ₃ -Cl ₂ (2.4) H -C ₂ H ₅ vise. OeI 29 t-butyl -C ₆ H ₃ -Cl ₂ (2.4) H -CH ₂ -O-CH ₃ resin 30th
-j t-butyl "V ₅ H H vise. OeI 31 ι
j
-j t-butyl -C ₆ H ₄ -F (4) H H vise »OeI 32 y t-butyl -diphenyl H ^C 2 ^H 5 vise. OeI 33 y - ^C 6 ^H 5 -C ₆ H ₃ -Cl ₂ <2.4) H H 129-132 * 34 y -C ₆ H ₄ -F (4) -CH -Cl (4)
6 4 H H M.p. 115-116 ° 35 y -C _g H ₃ -Ci ₂ <2.4> -CH-CK4):
Q 4 H H S®p, 104-107 ^s 36 i -CH-Cl ₀ (2.4)
OJ Z -C ₆ H ₃ -Cl ₂ <2.4) ^ H H M.p. 94-97 ° 37 - € ₆ H ₃ -C1 ₂ {2.4) -C, H, -Cl (4)
6 4 H -CH ₅ -O-CH ₃ 38 y -C ₆ H ₃ -Cl ₀ (2.4) -CH-Cl (4)
Q 4 H C ₃ H ₇ (n)

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Table IV

(XN; A = -CH ₂ -Q-CH ₂ -)

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Verb.
No. ^R l ^R 2 CH ₃ ^R 6 Phys. Const. 39 t-butyl -C, H -Cl (4)
6 4 H CHy HCl vise. OeI 40 t-butyl -C ₆ H ₄ -Cl (4) CH ₃ H 41 -C ₆ H ₃ -Cl ₂ (2.4) -C ₆ H ₄ -ClU) CH ₃ CH ₃ M.p. 12S-131 ^e 42 -C ₆ H ₄ -F (4) -C ₅ H ₄ -Cl (4) CH ₃ M.p. 134-138 "

The compounds of the formula I can be used alone or together used with suitable supports and / or other aggregates will. Suitable carriers and aggregates can be solid or be liquid and correspond to the substances commonly used in formulation technology such as natural or regenerated mineral substances, Solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Active ingredients of the formula I can also be used in admixture with, for example, pesticidal or plant growth-improving preparations will.

The content of active ingredient in marketable products is between 0.0001 and 90%.

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

Fixed forms of processing :

Dusts and grit generally contain up to 10% of the active ingredient. A 5Ziges dust can for example consist of 5 parts

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of the active ingredient and 95 parts of an additive such as talc or from 2 parts of active ingredient, 1 part of highly disperse silica and 97 parts of talc. In addition, there are other mixtures with such and other carrier materials commonly used in formulation technology and aggregates are conceivable. In the manufacture of these dusts the active ingredients are mixed with the carriers and additives and grind and can be dusted in this form.

Granules such as coated granules, impregnating granules, homogeneous granules and pellets usually contain 1 to 8OZ of the active ingredient. For example, a 5Zig granulate can be composed of 5 parts of the active ingredient, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol and 91 parts of kaolin (preferred particle size 0.3-0.8 mm). You can proceed as follows to produce the granulate:

The active substance is mixed with epichlorohydrin and with 6 parts of acetone dissolved, then polyethylene glycol and cetyl polyglycol ether are added. The solution obtained in this way is sprayed onto kaolin, and then the acetone is evaporated in vacuo. Such a microgranulate is advantageous for combating soil- used mushrooms.

Liquid processing forms :

A distinction is generally made between active ingredient concentrates that are dispersible or soluble in water and aerosols. Among the water-dispersible active substance concentrates include, for example, wettable powder {wettable powders) and pastes, which are usually in the commercial packs 25 - contain 90f and in solutions ready for use from 0.01 to 15% of the active ingredient * Emulsion concentrates contain IG to 50Z and solution concentrates contain in the use solution 0., 0QOi to 2QZ active ingredient. For example, a TOZiges wettable powder can consist of 70 parts of the active ingredient, 5 parts of sodium dibutylnaphthylsulfonate,

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plus 3 parts of naphthalenesulfonic acids - phenolsulfonic acids - formaldehyde condensate (in a mixing ratio of 3: 2: 1), 10 parts of kaolin and 12 parts of champagne chalk. A 40% wettable powder can consist, for example, of the following substances: 40 parts of active ingredient, 5 parts of lignin sulfonic acid sodium salt, 1 part of dibutylnaphthalenesulfonic acid - Sodium salt and 54 parts of silica. A 25Zigen wettable powder can be produced in different ways. For example, this can be composed of: 25 parts of the active ingredient, 4.5 parts calcium lignosulfonate, 1.9 parts champagne chalk / Hydroxyethylene cellulose mixture 1: 1, 1.5 parts of sodium dibutylnaphthalene sulfonate, 19.5 parts of silica, 19.5 parts of Champagne chalk and 28.1 parts of kaolin. A 25% wettable powder can also exist, for example from 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 of sodium silicate, 16.5 parts of kieselguhr and 46 Share kaolin. A 10% wettable powder can be made from 10 parts of the active ingredient and 3 parts of a mixture of sodium salts of saturated fatty alcohol sulfonates, 5 parts of naphthalenesulfonic acid / formaldehyde condensate and 82 parts of kaolin. Other wettable powders can Mixtures represent from 5 to 30% of the active substance together with 5 parts of an absorbent carrier material such as silica, 55 to 80 Parts of a carrier material such as kaolin and a dispersant mixture, consisting of 5 parts of sodium aryl sulfonate and 5 parts Share an alkylaryl polyglycol ether. A 25Ziges emulsion concentrate may contain, for example, the following emulsifiable substances: 25 parts of the active ingredient, 2.5 parts of epoxidized vegetable oil, 10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture, 5 parts of dimethylformamide and 57.5 parts of xylene.

From such concentrations, emulsions of the desired application concentration can be prepared by diluting with water, which are particularly suitable for foliar application. In addition, you can other wettable powders with different mixing ratios or different ones

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Carrier materials and additives commonly used in formulation technology are produced. The active ingredients are intimately mixed with the additives mentioned in suitable mixers and ground in appropriate mills and rollers. The wettability and suspension properties obtained are wettable powders which can be diluted with water to form suspensions of the desired concentration and, in particular, used for foliar application. Such means also belong to the invention.

It has surprisingly been found that compounds of the structure of the formula I have a microbicide spectrum for protecting crop plants which is very favorable for practical needs. For the purposes of the present invention, crop plants are, for example: Grain: (wheat, barley, rye, oats, rice); Beet: (sugar beet and fodder beet); Pome, stone and berry fruit: (apples, pears, plums ^ peaches ^ almonds ^ cherries ^ earth- _t raspberries and blackberries); Legumes: (beans, lentils, peas, soy); Oil cultures: (rapeseed, mustard, poppy seeds, olives, sunflowers, coconut, castor, cocoa, peanuts); Cucumber plants: (pumpkin, cucumber, melons); Fiber plants (cotton, flax, hemp, jute); Citrus fruits: (oranges, lemons, grapefruits, mandarins); Vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers) or plants such as corn, tobacco, nuts, coffee, tea, sugar cane, grapevines, hops, banana and natural rubber plants as well as ornamental plants,

With the active ingredients of the formula I, the fungi that occur on plants or plant parts (fruits, flowers, foliage, stems, tubers, roots) of these and related useful crops can be contained or destroyed, with plant parts growing later also spared from such fungi stay. The active ingredients are effective against the phytopathogenic pilse belonging to the following classes: Ascoaycetes ίζ ,, Β »Erysifrtvaeeae, Fusariura, Helminthosporium, Venturia, Podosphaera); Basidiomycetes such as especially rust fungi (eg Puccinia, Tilletia, Hemileia); Fungi imperfecti (e.g. Moniliales ua _s Cerco-

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'3.3 -

spora as well as Botrytis and Verticillium) and those of the Phycomycetes class belonging to Oomycetes. In addition, the compounds of the formula I have a systemic effect. They can also be used as a mordant for treatment of seeds (fruits, tubers, grains) and plant cuttings to protect against fungal infections and against phytopathogens occurring in the soil Mushrooms are used.

The invention thus also relates to the use of the compounds of the formula I for combating phytopathogenic microorganisms or for preventive prevention of infestation on plants.

Biological examples

Example 5: Action against Erysiphe graminis on barley

a) Residual protective effect

Barley plants about 8 cm high were sprayed with a spray powder des Active ingredient prepared spray mixture (0.02% active ingredient) sprayed. After 3-4 hours, the treated plants with conidia des Pollinated mushroom. The infected barley plants were placed in a greenhouse at about 22 ° C. and the fungal attack after 10 days judged.

b) Systemic effect

A spray mixture made from wettable powder of the active ingredient was poured into barley plants about 8 cm high (0.006% active ingredient based on the earth's volume). Care was taken to ensure that the spray mixture did not come into contact with the above-ground parts of the plant came. After 48 hours, the treated plants were dusted with conidia of the fungus. The infected barley plants were in a Greenhouse set up at about 22 ° C and the fungal attack after 10 days judged.

030020/0676

2943S31

Example 6: Action against Puccinia graminis on wheat

a) Residual protective effect

Wheat plants were sprayed 6 days after sowing with a spray mixture (0.06Z active ingredient) prepared from wettable powder of the active ingredient. After 24 hours, the treated plants were infected with a uredospore suspension of the fungus. After incubation for 48 hours at 95-100% relative humidity and about 20 ° C, the infected plants were placed in a greenhouse at about 22 ⁰ C. The development of rust pustules was assessed 12 days after infection.

b) Systemic effect

A spray mixture prepared from wettable powder of the active ingredient was poured into wheat plants 5 days after sowing (0.006Z active ingredient based on the volume of the soil). After 48 hours, the treated plants were infected with a uredospore suspension of the fungus. After incubation for 48 hours at 95-100% relative atmospheric humidity and approx. 20 ^° C., the infected plants were placed in a greenhouse at approx. 22 ^° C. The development of rust pustules was assessed 12 days after infection.

Example 7i Action against Cercospora arachidicola on peanut plants Res idua1-protective effect

cm high groundnut plants are infected with a from a wettable powder 4p of active substance produced spray mixture (0,02f active substance) tesprüht and 48 hours later with a conidia suspension of the fungus "The infected plants were incubated for 72 hours at about 21 ^S C and high humidity and then to Set up in a greenhouse for the appearance of the typical leaf spots. The fungicidal effect was assessed 12 days after infection based on the number and size of the spots that occurred.

3 0020/0676

. _as . ^2iU3i ' ³

Example 8: Action against Venturia inaequalis on apple trees Residual protective effect

Apple seedlings with about 5 developed leaves were made with one Spray liquor (0.06% active ingredient) produced by spraying a wettable powder of the active ingredient. After 24 hours the treated plants were infected with a conidia suspension of the fungus. The plants were then incubated for 5 days at 90-100% relative humidity and placed in a greenhouse at 20-24 ° C. for 10 more days. The scab infestation was assessed 15 days after infection.

The compounds of the formula I according to the invention generally showed good fungicidal properties in the tests described above Effect. Thus, among others, the compounds listed below brought about an inhibition of the infestation to less than 20% in comparison with untreated but infected (= 100% infestation) control plants:

In Puccinia graminis: Verb.Nr. 1, 3, 11, 13, 18, 19, 20, 21, 22, 24,

26, 28, 29, 30, 31, 32, 34, 35, 39.

With Cercospora arachidicola: Verb.Nr. 1, 18, 20, 22, 26, 32, 35.

In Erysiphe graminis: Verb.Nr. 1, 3, 11, 13, 17, 18, 19, 20, 21, 22,

24, 25, 26, 28, 29, 30, 31, 32, 33, 34, 35, 36, 39.

In Venturia inaequalis: Verb.No. 1, 3, 13, 18, 19, 20, 21, 22, 25,

26, 28, 29, 30, 31, 32, 33, 34, 35, 39.

The following compounds of the formula I inhibited the infestation to 5% and less in the above experiments:

In Puccinia graminis: Verb.Nr. 1, 3, 13, 18, 19, 20, 22, 26, 28, 29,

30, 31, 35, 39.

030020/0676

With Cercospora arachidicola: Verb.Nr. 1, 18, 20, 22, 26, 35.

In Erysiphe graminis: Verb.Nr. 1, 3, 13, 18, 19, 20, 21, 22, 25, 26,

28, 29, 30, 31, 32, 33, 34, 35, 39.

In Venturia inaequalis: Verb.No. 1, 18, 22, 26, 29, 30, 31, 35, 39.

030020/0676

Claims (17)

Claims 1. y compounds of the formula I. (I) including their plant-compatible salts with inorganic or organic acids and metal complexes, in which R is tertiary butyl or optionally once or twice through Halogen-substituted phenyl and R ₂ denote phenyl or diphenyl optionally substituted by 1 to 3 halogen atoms, C.-C.-alkyl, methoxy, cyano, nitro and / or phenoxy, and A is -CH CH- or -CH ₂ - / C _n --CH ₃ , -, R ₃ R ₄ R ₅ \ ₆ wherein R-, R ,, R and R, independently of one another hydrogen, C -C alkyl, C -C alkoxymethyl or phenoxymethyl or Io Io R. and R, together represent tetramethylene and X represents CH or N. 2. Compounds of formula I according to claim 1, wherein R _{1 is} tertiary butyl or phenyl which is optionally substituted once or twice by fluorine or chlorine and R »is optionally phenyl or diphenyl which is optionally substituted by 1 or 2 halogen atoms and A is -CH — CH- or -CH ₂ -, C _n -CH ₂ -, CH-CH- or -CH ₂ -, C _n -R ₃ R ₄ R ₅ \ ₆ where R_, R ,, R and R, independently of one another hydrogen, C-C- -Alkyl, methoxymethyl or phenoxymethyl or R 1 and R 1 together Mean tetramethylene and X stands for CH or N. 030020/0676 3. Compounds of formula I according to claim 1, wherein R is tertiary butyl or 2,4-dichlorophenyl, R _{2 is} a phenyl radical optionally substituted by methyl, chlorine, methoxy, cyano or phenoxy and R and R together represent a tetramethylene bridge. 4. Compounds of formula I according to claim 1, wherein R. is tert-butyl or 2,4-dichlorophenyl, R_ is a phenyl radical optionally substituted by methyl, chlorine, methoxy, cyano or phenoxy, and A is -CH (R -) - CH (R ^) -, where R, hydrogen and R are C ₁ -C, alkoxymethyl or phenoxymethyl. 5 * Compounds of the formula I according to claim 1, wherein & for TertiMrbutyl or 2,4-dichlorophenyl, R- is one or two times A phenyl radical substituted by chlorine denotes an ethylene bridge optionally substituted by C -C alkyl or methoxymethyl and X is CH or N. 6. Compounds of formula I according to claim 5, wherein S is tertiary butyl means, R- is a phenyl radical which is mono- or disubstituted by chlorine, A forms an ethylene bridge and X is CH or N means. 7. The compound 2-tert-butyl-2- [l- (4-chlorophenoxy) -l- (l, 2,4, - -txiazol-1-yl) j-methyl-1,3-dioxolane according to Claim 1. The compound 2-tert-butyl-2- {1- {4-chlorophenoxy) -l-imidal-1,3-dioxolane according to claim 1. 9. The compound 2-tertiarbutyl-2-II- (phenoxy) -l- (1,2,4-triazol -1-yl)] - methyl-1,3-dioxolane according to claim 1. 030020/0676 10. The compound 2-tert-butyl-2- [l- (4-fluorophenoxy) -l- (l, 2,4, - -triazol-l-yl)] methyl-1,3-dioxolane according to claim 1. 11. The compound 2- (2,4-dichlorophenyl) -2- [l- (4-chlorophenyl) -l- - (l, 2,4-triazol-l-yl)] - methyl-l, 3-dioxolane according to claim 1. 12. The compound 2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -l- - (1,2,4-triazol-l-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 II il with a compound of the formula III (III) Me <J converts, where R., R-, X and A have the meanings given under formula I, Hal for halogen and Me for hydrogen or a Metal cation. 14. Pesticides to control phytopathogenic Microorganisms, characterized in that there is a compound of the formula I according to Claim 1 as at least one active component together with one or more suitable carriers. 15. Means according to claim 14, characterized in that it is as at least one active component contains a compound of the formula I according to any one of claims 2 to 12. 030020/0676 16. Use of compounds of the formula I according to claim 1 for combating and / or preventively preventing an attack by phytopathogens Microorganisms. 17. Use according to claim 16 of compounds of the formula I according to any one of claims 2 to 12. 0 3 0 0 2 0/0 67 €