CS213386B2 - Means for killing the fytopatogennous fungi and method of making the active component of the said means - Google Patents

Abstract

The new 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, in which the total number of carbon atoms in the substituents X, Y and Z does not exceed 10 including their plant-compatible salts with inorganic or organic acids and their metal complexes, are suitable as microbicides, in particular for combating phytopathogenic fungi. They can be employed together with suitable carriers in the form of plant protection agents.

Description

Composition for controlling phytopathogenic fungi comprising, as active ingredient, a l- (2 - aryl-l, 3-dioxan-N - 2-ylmethyl (ethyl) -lH-imidazole and lH-l, ^2,4-triazol! US suitably substituted 1,3-dioxanoic ring having from 1 to 3 substituents of the formula

R ^z

R * and a process for the preparation of the active ingredient of the composition.

213386 3

BACKGROUND OF THE INVENTION 1. Field of the Invention phytopathogenic fungi. It also relates to the production of the active ingredient of the composition.

U.S. Pat. Nos. 3,575,999 and 4,079,062 disclose: 1- (2-aryl-1,3-dioxan-2-ylmethyl) -1H-imidazoles and 1H-1,2,4-triaaols; wherein the 1,3-dioxane residue is unsubstituted, wherein the compounds exhibit an antigenic and ahtibacterial effect.

The active ingredients of the present invention differ from the preceding compounds substantially by the presence of 1 to 3 alkyl substituents on the 1,3-dioxane moiety.

The present invention provides a composition for controlling phytopathogenic huibs comprising an inert carrier and an active ingredient. SUMMARY OF THE INVENTION The present invention provides as an active ingredient 1- (2-aryl-1,3-diioxan-2-ylmethyl) -1H-imidazole and 1H-1,2,4-triazole derivatives of the formula I as active ingredient and their phytopharmaceutically acceptable acid addition salts, metal salt complexes and stereochemically isomeric forms thereof.

The derivatives have the general formula I

wherein R ¹ , R ² and R ³ are each independently selected from hydrogen and halogen, provided that at least one of R ¹ , R ^2, and R ³ is halogen;

Q is a member selected from the group consisting of CH and N; and

X, Y and Z are each independently selected from hydrogen and C 1 -C 6 alkyl, provided that at least one, X, Y and Z is other than hydrogen.

Preferred compounds within the scope of the present invention are those wherein X, Y and Z together contain at most 10 carbon atoms and those wherein R ¹ and R ³ are hydrogen, chloro or bromo and R ² is chloro or bromo.

Particularly preferred compounds within the scope of the present invention are those in which X, Y and Z simultaneously contain at least 5 carbon atoms, those in which R ² is chlorine and R ¹ and R ³ are hydrogen, and those in which R ¹ and R ² are both chloro and R ³ is hydrogen.

even more preferred compounds within the scope of the present invention are those in which no X, Y and Z substituents have more than 3 carbon atoms.

The most preferred compounds within the scope of the present invention are those wherein R ¹ and R ² are chlorine, R ³ is hydrogen, optionally R ² is chlorine and R ¹ and R ³ are hydrogen and none of X, Y and Z is more than 3 carbon atoms and two of them are attached to the carbon atom at the 5-position of the 1,3-dioxane nucleus.

The following are particularly preferred. compounds:

1- [2- (2,4-dichlorophenyl) -5,5-diethyl-1,3-dioxan-2-ylmethyl] -1H-1,2,4-triazole and a pharmaceutically acceptable acid addition salt, metal salt complexes and their stereochemically isomeric forms,

1- [2- (2,4-dichlorophenyl) -5,5-dimethyl-1,3-dioxan-2-ylniethyl] -1H-1,2,4-triazole and pharmaceutically acceptable acid addition salts, metal complexes salts and their wall of cchemically isomeric forms,

1- [2- (2,4-dichlorophenyl) -5-methyl-5-propyl-1,3-dioxan-2-ylmethyl] -1H-1,2,4-triazole and pharmaceutically acceptable acid addition salts, metal salt complexes and their stereochemically isomeric forms,

1- [2- (2,4-dichlorophenyl) -4-methyl-1,3-dioxan-2-ylmethyl] -1H-1,2,4-triazole and pharmaceutically acceptable acid addition salts, metal salt complexes and their stereochemically isomeric forms,

1- [2- (2,4-Dichlorophenyl) -4,6-dimethyl-1,3-dioxan-2-ylmethyl-1H-1,2,4-triazole and pharmaceutically acceptable acid addition salts, metal salt complexes and stereochemically isomeric forms thereof.

As used in the foregoing definitions, halogen is a generic name for fluoro, chloro, bromo and iodo; the term C 1 -C 6 alkyl includes branched or unbranched hydrocarbon groups of one to eight carbon atoms such as methyl, propyl, pentyl, 1-methylethyl, 1,1-dimethylethyl, hexyl, heptyl, octyl and the like.

The present invention further provides a process for the preparation of an active ingredient of the above composition, wherein the compounds of formula I can generally be prepared by reacting an azole of formula II wherein Q is as previously described and Me is a tetrasubstituted ammonium ion, e.g. -C 6 -alkyl) ammonium, tri (C 1 -C 6 -alkyl), ammonium and the like or preferably a metal atom such as potassium, sodium and the like, with a halide of formula III wherein R ¹ , R ² , R ³ , X, Y and Z are as defined above and T is halogen, preferably chlorine, bromine or iodine.

The reaction of the compound of formula (II) with compound ( ^{1) of} formula (III) is preferably carried out in a Telaitively polar reaction-inert organic solvent, such as Ν, Ν-dimethylformamide, Ν, id-idimiethylacetamide, dimethylsulfoxide, ac-etcinitrile, benizonitrile etc. The solvent may be used in combination with other solvents inert to the reaction, for example with aliphatic or aromatic hydrocarbons such as benzene, methylbenzene, dimethylbenzene, hexane, petroleum ether, chloro benzene, nitrobenzene and the like. When T represents chlorine or bromine, it may be advantageous to carry out the reaction in the presence of an alkali metal joidide such as sodium joidide or potassium iodide to increase the reaction rate. Preferred are elevated temperatures of from about 30 to 220 ° C, preferably from about 80 to about 170 ° C, and usually are carried out under reflux.

When Me represents hydrogen, the reaction is carried out in the presence of a base. Suitable bases which may be used are alkali metal oxides, hydroxides, carbonates and bicarbonates, as well as tertiary amines such as N, N-diethylethamamine, pyridine and the like. In view of its intrinsic properties, the azole of formula II, when added to an excess, can be used to accelerate the reaction.

In these and subsequent preparations, the reaction products can be isolated from the environment and, if necessary, further purified by well-known methods such as extraction, elution, crystallization, chromatography and the like.

Suitable acid-forming acids are well tolerated by plants or are physiologically acceptable, such as, for example, from inorganic acids, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, nitric acid and the like; , methanesulfouic and similar acids.

Complexes of metal salts of formula (I) may be obtained by complex reactions of azoles of formula (I) with organic or inorganic metal salts, such as, for example, halides, nitrates, sulfates, phosphates, 2,3-hydroxybutanedioates and the like, copper, of manganese, zinc, iron and transient transition metals, which may be present in any of their possible effects.

Stoichiometrically defined metal salt complexes can be prepared by dissolving a compound of formula I in a water miscible solvent (e.g., warm ethanol, methanol, 1,4-dioxane or *, Ν-dimethylformamide) and adding to the aqueous solution. a solution of the desired metal salts, such as CuSO 4. . 5H 2 O, Mn (NO 3) 2 4H 2 O, FeCl 3. 6H2O and the like.

The foregoing is intended to illustrate and not to limit the present scope of the invention.

The intermediates of formula (II) used as starting materials in the foregoing reactions are well known in the art.

Intermediates of formula (III) may be prepared by known methods for preparing these or similar compounds, such as, for example, acetalizing a suitable acetophenone derivative of formula (IV) with the corresponding 1,3-diol of formula (V) by the following known acetalization procedures.

(IV)

HO HO

(IN)

In the preceding reaction scheme, R ¹ , R ² , R ³ , X, Y and Z are as previously defined and L is hydrogen or T. When L is hydrogen, this L group is converted to a halogen by the following known halogenation procedures before , during or after acetalization.

The acetylation reaction is readily accomplished by stirring and heating the reactants together in a suitable reaction-inert solvent, for example benzene, methylbenzene and the like, preferably in the presence of a catalytic amount of the appropriate acid, for example 4-methylbenzenesulfonic acid and the like. Most preferably, the reaction is carried out under azeotropic distillation of water which is released during the reaction. Alternatively, acetals of formula III may be derived from other cyclic or aliphatic acetals by this second reaction with an excess of 1,3-diol of formula V corresponding to the desired aceital.

It will be apparent from Formula I that the compounds of the present invention have at least one asymmetric carbon atom, and that some compounds have one or more other asymmetric carbon atoms within the 1-nitroBan nucleus due to the presence of X, Y and Z substituents and consequently they may exist in various stereochemically isomeric forms. Stereochemically isomeric forms of Formula I and phytopharmaceutically acceptable acid addition salts and metal salt complexes are included within the scope of this invention.

The diastereomeric racemates of formula I may be obtained separately by conventional methods. Suitable methods that may be advantageously employed herein include, for example, selective crystallization. and chromatographic preparation, for example, column chromatography.

Since the stereochemistry is already fixed in the intermediates of formula (III), it is also possible to separate the diastereomeric racemates at this stage, from which the corresponding forms of the formula (I) can be derived as outlined above. The separation of diastereomeric racemates of these intermediates can be carried out by conventional methods as previously described for the separation of diastereomeric racemates of the compounds of formula (I). AND.

The compounds of the formula I have a very advantageous antimicrobial spectrum, which makes them suitable for protection. crop without causing unwanted side reactions.

Examples of these crops are: cereals, corn, rice, vegetables, diabetes, soybeans, peanuts, fruit trees, ornamental plants, vines, hops, cucurbits (squashes, cucumbers, melons), eggplants such as potatoes, tobacco, tomatoes, as well as bananas, cacao, and rubber.

The compounds of formula I may be used to reduce or prevent fungal growth on plants of these or related crops or on parts of these plants, (e.g. on fruits, flowers, leaves, stems, tubers, roots), with newly emerging parts of these plants they are also protected from fungal attack. The compounds of the invention are active against phytopathogenic fungi belonging to the following classes: Ascomiycetes (eg, Erysiphaceae, Fusarium, Venturia, Helminthosporium); Basidiomycetes such as particularly rust · (e.g. imperfect fungi (e.g. Moniliales etc.., Cerospora and Botrytis) and Oomycetes belonging to the class P.byttomy.ícetes as Phyto ^p Phytophthora and Plasmopara. They may be further Mon. used for the protection «Seedlings (for example, fruits, tubers, grains) and cuttings before fungal infection and against fungi occurring in the soil.

Botrytis species (Botrytis cinerea, Botrytis is allíi) cause extensive economic damage to grapevines, strawberries, apples, berries and similar fruits and vegetables.

The compounds of formula II can be used alone or in admixture with suitable carriers and / or additives. Suitable carriers and additives may be solid or liquid and are generally known, such as natural and regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

The concentration of the active ingredient in commercial preparations may vary from about 0.1 to about 90%.

For administration, the compounds of formula (I) may be prescribed in the following forms (suitable concentrations of the active ingredient are indicated in parentheses):

Solid mixtures: powders (up to 10%), granules, coated granules, impregnated granules and homogeneous granules, iodine pellets 1 to 80%);

Liquid mixtures: a) water-dispersible concentrates: wettable powders and pastes (25 to 90% in commercial form, 0.01 to 15% in solution form); emulsion and solution concentrates (10 to 50%; 0.01 to 15% in solution form); b) solutions (0.1-20%); aerosols.

If desired, to broaden the spectrum of activity of Formula I, they may be combined with other suitable pesticides such as fungicides, bactericides, insecticides, acaricides, herbicides, growth regulators and the like.

The following examples are intended to illustrate - and not to. limitations on the scope of the present invention. All temperatures are in degrees Celsius.

A. Examples of chemical preparations

Example I

To a stirred solution of sodium methoxide prepared from 3.7 parts sodium in 40 parts methanol is added 10.8 parts 1H-imidazole and 270 parts Ν, Ν-dimethylformamide. The methanol was distilled off to an internal temperature of 150 ° C. Then 19 parts of N-N, N -Chromomethyl) -2- (2,4-dichlorophenyl) -5-ethyl-1, 3-dioxane were added and the whole was stirred ai. Heat at reflux for 5 hours. The reaction mixture was cooled and poured into water. The production is extracted three times with 1'-oxybenzoate. The combined extracts were washed with water, dried, filtered and evaporated. The residue was purified by silica gel column chromatography: the first fraction was obtained by eluting with a mixture of trichloromethane and 2% methanol. The eluent was evaporated and the residue was converted to the sodium salt in 4-methyl-6-peintanone-a-2,2'-o-o-benzylpropyl.

The salt is filtered off and crystallized from the mixture

4- ^ 10111-1-2 ^ (? 13110 ^ 1 and 2,2'-cybispropane) to give -5.8 parts (26.5 '%) of A- + B ^ 1- [2- (2, 4-Dichlorophenyl-1H-ethyl-1H-dioxan-2-yl.

methyl J-1H-imidazole nitrate; melting point 145.1 °

Celsius.

FHkua č

a) A mixture of 1- (2,4-dichlorophenyl) ethanol, 35 parts of 2-ethyl-1,3-hexanediol, 2 parts of 4-methylbenzenesulfonic acid and 400 parts of methylbenzene was heated to reflux with a water separator. After cooling, the reaction mixture is washed twice with 200 ml of water, dried over sodium sulphate, filtered and evaporated to a heated solution of the residual oil under reflux. 33.6 parts of bromine are slowly added in methylbenzene to such a degree that the reaction mixture is discolored then reflux for 1 hp. Cooling the reaction mixture was washed twice with water, dried, filtered and evaporated.

The residual oil containing 2- (bromomethyl) -2- (2,4-dichlorophenyl) -5-ethyl-4-propyl-1,3-dioxane is purified by distillation; boiling point 150 to 153 ^° C at 4 Pa.

(b) 23 parts of 2 '(отготтеШу1) -2- (2,4-η 10 -Oооphenyl) -5-ethyl-4-propyl-1,3-diolamine, 5.6 parts of imidazole and 100 parts of dimethyl sulfoxide are mixed with 9.3 parts of potassium tert-butoxide and the whole was stirred for 16 hours at 130 ° C. The cooled mixture was poured into 500 parts of water and extracted with 3 x 300 parts of Ι, Γ-oxy-bigethan. The combined organic layers were washed with 300 parts water, dried and evaporated. The residual oil was purified by column chromatography over silica gel using ethyl acetate as eluent. The pure fractions were combined and the eluent was evaporated to give a diastereomeric mixture of 1- [2- (2,4-dichlorophenyl) -5-ethyl-4-propyl]. -1,3-dioxan-2-ylmethyl] -1H-1H-azole as a brown oil; n _D ²³ - 1.5486. 7 "

Following the procedure described above and using equivalent amounts of starting materials, the following were prepared:

Merge. R ¹ R2 R ³ Χ, Υ, Ζ salt / base melting point: in ° C 1.1 Cl Cl H 5-СгНз, Η, H - olei / n > -1,559 145.1 1.2 Cl Cl H 5-C2 H5, H, H HNOs 1.3 Cl Cl H 5-C2 H5, H, H -. . ’. ’-Τ-: 1.4 Cl Cl H 5-C ₄ H 9, H, H - 1.5 Cl Cl H 5-COH 13, H, H -г— - - ~ - 1.8 H Cl H 5-C2H5, H.H. ask 1.7 Cl Cl S-Cl 5-C2 H5, H, H plej 1.8 Cl H 6-C1 5-C2 H5, H, H нш 1.9 Cl Cl H 5-S, 5-C2H5.H - Dlej / n _p ^ž ? = 1,5502 1.10 WHOSE Cl H 5-C2H5,3-C2N5, H - PG'U Учти AQM to 19075.32 Pa boiling point 165 1.11 Cl Cl H 5-СНз, 5-СНз, Ή - up to 170 / 5.32 Pa 1.12 H Cl H 5-СНз, б-СгНз, Η oil 1.13 H Br H 5-СНз, 5-С2Н5, Н - oil 1.14 H F H 5-СНз, 5-СгНз, Ή •Oil 1.15 Cl H 6-C1 5-СНз, 5-С2Н5, Н ^'Oil 1.16 Cl Cl H 5-СНз, 5-СзН7, Н -— oil 1.17 H Cl H 5-СНз, 5-СзН7, Н - oil 1.18 H F H 5-СНз, 5-СзН7, Н __ 133—137 1.19 Cl Cl H 4-СНз, 5-С2Н5, Н - ..— 1.20 Cl Cl H 4-СгНз 5-С2Н5. Н - 1.21 Cl Cl H 4-Cl7, 5-Cl5, Н oil / n _D ²³ -1, 5486 1.22 Cl Cl H 5-СНз, 5-СНз, Ή CuC.h 1.23 -NO. 1 Cl H 5-СНз, 5-СНз, Н ZnClz 1.24 Cl Cl H 5-СНз, 5-СНз, Н Ми (ЬЮз) 2 oil / n _p 2 ° == 1, 5565 1.25 Cl Cl H 5-С2Н5,5-С4Н9, Н «Ote] 1.26 Cl Cl H 5-С2Н5, 5-С4Н9, Н CuCh - 1.27 Cl Cl H 4-СНз, Η, Н -

Slcuč. ... /.- R1: ^R2. ·:. . R ³ X, Y, Z salt / base melting point in ° C

1.28 Cl Cl H 4-C2 H5, H, H. ... ..., - т - 1.29 Cl .. ..Cl H 4-СзН7, Η, Ή - 1.30 . ..Cl Cl. H 4-C 4 H 9, H, H - -. ... 1.31. whose..' Cl H 4-СНз, 6-СНз, H . - - 1.32. Cl. . Cl h ’: 4-C2H5, 6-h, h: - - 1.33 Cl Cl. H 4-C2 H5, 6-C2 H5, H - -. 1.34 . Cl Cl, H 4-C 3 H 7, 6-C 2 H 5, H • -. ·. 1.35 Cl :: . Cl . H 6-CH3, 6-CH3, H ^! ΗΝ03 . - 1.36 Cl Cl, H 4-S, 6-S, H. CuClz - ' 1.37 Cl :. whose 'H 4-СНз, 6-СНз, Η : (Η (Νθ3) 3.  ~~ ·. 1.38 Cl ...... Cl . H 4-СНз, 6-СНЗ, Н ZnC12 - '·. · 1.39. ... Cl ; ... ci H . 4-С2Н5.6-С2Н5, Н HN03 -r - ’·. 1.40 ' Cl Cl H ... 4-С2Н5,67C2H5, Ή CuC12 1.41 Cl : cl :, h 4-С2Н5,6-С2Н5, н FeCl3 i - 1.42 Cl Cl ... ... H 4-S, 5-S, 6-S HNOs 1.43,. H · Cl . H 4-S, 5-S, 6-S -. 1.44 ' : Cl H  6-C1 . . 4-S, 5-S, 6-S. - 1.45 H F - H 4-S, 5-S, 6-S - 1.46 Cl Cl H 4-S, 5-S, 6-S CUC12 1.47 ' Cl Cl H 4-S, 5-S, 6-S Mn (NO 3) 2 - 1.48 .. _r H Cl H 4-S, 4-S, 6-S - - 1.49, ý Cl Cl H 4-S, 4-S, 6-S - - 1.50 Cl Cl H 4-S, 4-S, 6-S HN03 - 1.51, '.:' · Cl Cl H 4-S, 4-S, 6-S CuClz - 1.52 Cl Cl H 4-S, 4-S, 6-S Zn.C12 - 1.53. , Cl Cl H 4-S, 4-S, 6-S Mn (NO 3) 2 - 1.5.4: Cl H 6-C1 4-S, 4-S, 6-S HN03 - 1.55; Cl Cl 5-C1 4-S, 4-S, 6-S HN03 - 1.5,6 .. H J H 4-S, 4-S, 6-S HCl - 1.57 Cl Br H 4-S, 4-S, 6-S (C00H) 2 - 1.58 Cl Cl H 5-СНз - Olei / n _D ²⁰ = l, 56B2 1.59 Cl Cl H 2-СН (СНз) 2 - oil / n. _D ²⁰ = l 5621 1.60 Cl Cl H 4-S7, 5-S7, 5-S7 - oil

Example d III - '........... 7 ='

Mixture ^: 2 parts of 2,2-dimethyl-1,3-propanediol, 1 part of 4-methylbenzenesulfonic acid. 90 parts of ethylbenzene were azeotropically over. tiluje dp! Dry for 1 hour: Then, 7.1 parts of 1- [2- (2,4-dichlorophenyl) -2,2; longer methoxycyclohexyl] -1H-1,2, Oriazole is added with 4-methyl zensulfurate. The reaction mixture was cooled, washed successively with dilute sodium hydroxide solution and water, dried, filtered and evaporated. The residue was converted to the nitrate salt in 2,2'-oxybispropane.

The salt was filtered off and dried, yielding 4.8 parts (79%) of [2- (2,4-dichlorophenyl) -5,5-dimethyl-1,3-dioixan-2-ylmethyl] -1H-1, 2,4- '. -triazole nitrate; mp 130.6 ° C.

Using the same procedure and using equivalent amounts of the respective starting materials, the following compounds were prepared:

Merge. R1 R2

C.

salt / base melting point in ° C

2.1 Cl Cl H 5-C2 H5, H, H - oil n _D ²⁰ = 1.557B 2.2 Cl Cl H 5-C2 H5, H, H HNO3 160.9 2.3 Cl Cl H 5-C 3 H 7, H, H - - 2.4 Cl Cl H 5-C 4 H 9, H, H - - 2.5 Cl Cl H 5-C 6 H 13, Η, H - - 2.6 H Cl H 5-C2 H5, H, H - oil 2.7 Cl Cl 5-C1 5-C 2 H 5, Η, H - oil 2.8 Cl H 6-C1 5-C2 H5, H, H HNO3 - 2.9 Cl Cl H 5-S, 5-C2H5, Η, H HNO3 134.7 2.10 Cl Cl H 5-C2 H5, 5-C2 H5, H HNO3 127.2 2.11 Cl Cl H 5-CH 3, 5-CH 3 HN03 130.6 2.12 H Cl H 5-N, 6-C2H5 - oil 2.13 H Br H 5-N, 6-C2H5 - oil 2.14 H F H 5-S, 5-C2H5 - oil 2.15 Cl H 6-C1 5-СНз 5-С2Н5 - oil 2.16 Cl Cl H 5-СНз 5-СЗН7 HN03 165.4 2.17 H Cl H 5-СНз 5-СЗН7 - Plej 2.18 H F H 5-S, 5-C3H7 - Plej 2.19 Cl Cl H 4-СНз 5-С2Н5 - plej 2.20 Cl Cl H 4-С2N5, 5-С2N5 .—. -. 2.21 Cl Cl H 4-С3Н7,5-С2Н5 - ole j / n _D23 = 1.512 2.22 Cl Cl H 5-S, 5-S CuCl? - 2.23 Cl Cl H 5-S, 5-S ZnC12 ’ - 2.24 Cl Cl H 5-S, 5-S (Ηι (Ν03) ζ - 2.25 Cl Cl H 5-С2Н5.5-С4Н9 - ole.j / n _D 20 = l 5419 2.26 Cl Cl H 5-С2Н5, 5-С4Н9 CuC12 - 2.27 Cl Cl H 4-СНз - oil / n _D 23 = 1.5505 2.28 '··· Cl Cl H 4-С2Н5 - - 2.29 Cl Cl H 4-СзН7 - - 2.30 Cl Cl H 4-С4Н9 - - 2.31 Cl Cl H 4-S, 6-S - - 2.32 Cl Cl H 4-С2Н5,6-СНз - - 2.33 Cl Cl H 4-СгНз 6-С2Н5 —- - 2.34 Cl Cl H 4-СзН7,6-С2Н5 - - -2.35 Cl Cl H 4-S, 6-S HNO3 - 2.36 Cl Cl H 4-S, 6-S CuC12 - 2.37 Cl Cl H 4-S, 6-S (Η (ΝΌ3) - 2.38 Cl Cl H 4-S, 6-S ZnC12 - 2.39 Cl Cl H 4-С2N5, 6-С2N5 HN03 - 2.40 Cl Cl H 4-С2N5, 6-С2N5 C11Cl2 - 2.41 Cl Cl H 4-С2N5, 6-С2N5 FeCh - 2.42 Cl Cl H 4-S, 5-S, 6-S HNO3 - 2.43 H Cl H 4-S, 5-S, 6-S - - 2.44 Cl H 6-C1 4-S, 5-S, 6-S - - 2.45 H F H 4-S, 5-S, 6-S - - 2.46 Cl Cl H 4-S, 5-S, 6-S Cu € 12 - 2.47 Cl Cl H 4-S, 5-S, 6-S Mm (NO3) 2 - 2.48 H Cl H 4-СНз, 6-СНз, 6-СНз - - 2.49 Cl Cl H 4-СНз, 6-СНз, 6-СНз - viscous 2.50 Cl Cl H 4-СНз, 6-СНз, 6-СНз HNOs -

13 213386 14 Merge. C. R ¹ R ² R ^{3 is} X, Y, Z salt / base melting point in ° C

2.51 Cl Cl H 4-СНз, 6-СНз, 6-СНз CUC12 - 2.52 Cl Cl H 4-СНз, 6-СНз, 6-СНз ZnClz - 2.53 Cl Cl H 4-СНз, 6-СНз, 6-СНз Мп (N03) 3 - 2.54 Cl H 6-C1 4-СНз, 6-СНз, 6-СНз HN03 - 2.55 Cl Cl 5-C1 4-СНз, 6-СНз, 6-СНз HN03 - 2.56 H AND H 4-СНз, 6-СНз, 6-СНз НС.1 - 2.57 Cl Br H 4-СНз, 6-СНз, 6-СНз (С00Н) 2 - 2.58 Cl Cl H 5-СНз - ole] / n _D ²⁰ = 1.5504 2.59 Cl Cl H 5-СН (СНз) г. - oil _D ²⁰ = 1.5-547 2.60 Cl Cl H 4-S7, 5-S7, 5-S7 - ^ole: j / n _D ²⁰ = l 5423

Example IV

a) A mixture of 56.7 parts of 1- (2,4-dichlorophenyl) ethanone, 32.4 parts. 1,3-butanedol · 2 parts of 4-methylbenzenesulfonic acid and 400 parts of methylbenzene were stirred and refluxed for 5 hours using a water separator. After cooling, the reaction mixture was washed with water, dried, filtered and evaporated. The oily residue which is taken up in 525 parts of refluxing trichloromethane is obtained and 49.6 parts of bromine are slowly added thereto. After the bromine addition was complete, the mixture was stirred and refluxed for 1 hour. After cooling, the reaction mixture was washed twice with water, dried, filtered and evaporated.

The residual yellow oil is crystallized from 500 parts cold petroleum ether (b.p. 40-60 ° C), digested at low temperature, filtered and washed with cold petroleum ether (bp 40-60 ° C) to give 2- (2,4) crystals. -dichlorophenyl) -2- (bromomethyl) -4-methyl-1,3-dioxane; diastereomeric mixtures; mp 69-75 ° C.

(b) Mixture of 10,8 parts of potassium carbonate,

5.4 parts of 1H-1,2,4-triazole, 20.5 parts of 2- (2,4-dichlorophenyl) -2- (broimmethyl) -4-methyl-1,3-dioxane, 0.2 parts sodium iodide and 100 parts of di-methylsulfoxide were stirred for 36 hours at 100 ° C, cooled and poured into 600 parts of water. The reaction mixture was extracted three times with ethyl acetate and the combined organic layers were washed with 200 parts water, dried, filtered and evaporated.

The residual oil was purified by column chromatography over silica gel using ethyl acetate as eluent. The pure fractions were collected and the eluent was evaporated to give 1- (- 2- (2,4-dichlorophenyl) -4-methyl-1,3-dioxan-2-ylmethyl] -1H-1,2,4 -triazole; n _D ²² : 1.5505.

B. Examples of compositions

Example V

Pills:

the following substances are used in the preparation

(a) 5%; and (b) 2% of powder:

(b) 2 parts active substance a part of highly dispersed silicic acid parts of a talc.

The active ingredients are mixed with carriers and ground and in this form can be used for powders for application.

Example VI

Granulate:

the following substances are used to prepare 5% granules of active ingredient parts

0.2.5 parts of epichlorohydrin

0.25 cetyl polyglycol ether

3.25 parts, polyethylene glycol parts kaolin (particle size 0.3-0.8 mm).

The active ingredient is admixed with epichlorohydrin and the mixture is dissolved in 6 parts of ZrgOronone. Then ethylene glycol and cetylpolyglycol ether are added. The resulting solution was sprayed onto kaolin and the 2-propanone was evaporated in vacuo.

This microgranulate is preferably used for controlling soil phytopathogenic fungi.

Example VII

AND

Wettable powders:

the following ingredients are used to prepare a) 70%, b) 40%, c and d) 25%, e) 10% wettable powder.

a) 70 parts of active substance parts of sodium dibutylnaphthylsulfonate parts of naphthalenesulfonic acid / phenolsulfonic acid / formaldehyde condensate (3: 2: 1) parts of kaolin and parts of champagne chalk

b) 40 parts of active substance parts of sodium lignin sulphonate part of sodium dibuylnaphthalenesulphonic acid parts of silicic acid

(a) 5 parts of active substance parts of talc;

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(c) 25 parts of active substance

4.5 parts of calciumignin sulphonate

1.9 parts · 1: 1 mixture of champagne chalk and iaydroxyethyicellulose

1.5 parts of sodium dibutylnaphthalenesulfonate

19.5 parts of silicic acid

19.5 episode · champagne chalk

28.1 parts of kaolin

(d) 25 parts of active substance

2.5 parts of isoocyleneenoxypolyethylene ethanol

1.7 parts of champagne chalk mixed with 1: 1 hydraxyethylcellulose

8.3 parts of sodium aluminum silicate

16.5 parts of kieselguhr parts of kaolin

e) 10 parts of active substance parts of a mixture of sodium salts of saturated fatty alcohol sulphates parts of naphthenenesulfonic acid mixed with formaldehyde condensate of parts of kaolin. '

The active substances are thoroughly mixed in suitable mixers with additives and ground in suitable mills and rollers. The wettable powders and the successive powders obtained have excellent wettability. These wettable powders may be diluted with water to obtain suspensions of the desired concentration and may be used, in particular, for foliar application.

Example VIII

Emu Ignitable Concentrates:

the following substances are used for the preparation

20 ·% of emulsifiable concentrate:

parts of the active substance

2.5 parts of epoxidized roslin oil 10 parts of a mixture of alkylarylsulfonate and polyglycol ether fatty alcohol parts of dimethylformamide

57.5 parts of dimethylbenzene.

By diluting this concentrate with water, it is possible to prepare emulsions of the desired concentration which are particularly suitable for foliar application.

C, Biological examples

Example IX

Activity against Gercospora personata (= Gercospora arachidicola) on peanut plants

Peanuts 3 weeks old are sprayed with a spray well (containing 0.02 percent active ingredient) prepared from a wettable powder of the active ingredient. After about 12 hours, the treated plants are infected by dusting the conidia suspension of the fungus. The infected plants are then incubated for about 24 hours at 22 ° C at high relative humidity (greater than 90%) and then placed in a greenhouse. Fungal infections are evaluated 12 days after infection based on the number and spread of emerging spots.

Compared to untreated plants, those treated with the compound of formula I showed limited or no growth at all.

Example X ......

Activity against Plasmopara viticola (Bert, and Cur-t.) (Berl. Et De Toni) on vines

The residual protective action of the vine seedlings (Chasseias species) having 10 leaves are sprayed with a spraying agent (containing 0.06% active ingredient) prepared from a wettable powder of the active ingredient.

After spray drying, the plants are infected with a spore sporangia on the lower surface of the leaves, and then the plants are allowed to stand in a humid room for 8 days. After this time the untreated plants show steady fungal growth. The degree of fungal infection is evaluated based on the number and spread of the spots.

Compounds of numbers 1.9, 1.16, 1.19, 1.21, 2.9, 2.10, 2.11 and 2.16 and similar compounds completely inhibit fungal growth.

EXAMPLE XI

Erysiphe graminis activity on barley

a) Residual protective action

Barley plants about 8 cm in height are sprayed with a spray drench (containing 0.02 percent active ingredient) prepared from a wettable powder of the active ingredient. After. The treated plants are dusted with conidia of the fungus for 3-4 hours. Infected barley plants are then placed in a greenhouse at about 22 ° C and fungal infestation is evaluated 10 days after the day of infection.

b) Systemic action

A spray drench (containing 0.006% active ingredient, proportional to the soil volume), prepared from a wettable powder of the active ingredient, is applied to barley plants about 8 cm high, taking care not to come into contact with the outer parts of the plants with spraying. After 48 hours, the treated plants are dusted with conidia of the fungus. Infected barley plants are placed in a greenhouse at 22 ° C and fungal infections are evaluated after 10 days.

Test. and)

The compounds of formula I completely inhibited fungal growth. Compounds No. 1.9, 1.10, 1.11 / 1.16, 1.21,

2.9, 2.10; 2.11, 2.16, 2.27, 2.31 and similar compounds show complete inhibition even at a concentration of 0.0006%.

'. Test b)

Compounds No. 1.16, 2.9, 2.11 and the like show complete inhibition of fungal growth. ·

The compounds of formula I, and in particular the 1H-1,2,4 / triazole derivatives, are particularly effective in protecting against powdery mildew (Erysiphe spp.

;. Example XII • Efficacy against Botrytis cinerea on horse beans.

Horse bean plants of about 10 cm in height are sprayed with a spray mixture (containing 0.02% active ingredient) prepared from a wettable powder of the active ingredient. After 48 hours, the treated plants are infected with a conidia suspension of the fungus. After incubating the infected plants for 3 days at 95 to 100% relative humidity and temperature. The fungal infection was evaluated at 21 ° C. .....

A large number of compounds of formula I, for example compounds Nos. 1.10, 1.9, 1.11 and 1.21 completely prevent the fungus from growing at a concentration. 0.006% even. lower. . .

Example XIII ·

Efficacy against Hemlleia vastatrix on coffee plants

Protective effect

Coffee plants with a height of about 15 cm are sprayed with a spray nozzle (containing 0.06% active ingredient) prepared from a wettable powder of the active ingredient. After. At 24 hours, treated trees are infected with a rust spore suspension. The infected coffee plants are allowed to stand in a humid room for 48 hours and then in a wet room. greenhouse at 22 ° C until rust blisters appear. (About 4 weeks.) Reduction of rust blisters is a measure of the effectiveness of the test substances.

The compounds of formula I show complete protective action at the indicated concentrations. Compounds No. 2.9, 2.10, 2.11, 2.16 and the like exhibit complete protective efficacy even at a concentration of 0.0000%.

P-Example XIV

Residual protective action against Venturia inaegualis on apple seedlings

Apple seedlings 10 to 20 cm high are sprayed with a spray well containing 0.01.6%. active substances, such as active compounds. wettable powder of the active ingredient. After 24 hours, the treated plants are infected with a conidia suspension of the fungus. The plants are then grafted at 90% to 100% relative humidity and then in a greenhouse at 20 to 24 ° C for 10 days. Fungal infections are evaluated 15 days after the day of infection.

The 1H-1,2,4-triazole derivatives of formula I exhibit the above. concentration 0.06. o / ₀ full protective effect. Even at very low concentrations, 0.006% of Compound # 1 was present.

2.9, 2.10, 12/11. 2.16 and similar compounds show complete efficacy.

Example XV

Efficacy against Puccinia graminis on wheat

(a) Residual protective action:

Wheat. the plants were sprayed 6 days after sowing by spraying (0.06% active ingredient) prepared from a wettable powder of the active ingredient. After. For 24 hours, the treated plants were infected with a uredospore suspension of fungi. . .After. incubation time. 48 hours at 95-100% relative humidity and at about 20 ° C were. the plants are kept in a greenhouse at a temperature of about 22 ° C. The development of rust blisters was evaluated 12 days after infection. .

The compounds of formula I show complete inhibition of fungal growth. Even at a low concentration of 0.006% of compound number 2.10, 2.16,

2.27 and 2.3 ^ 1 show complete inhibition.

(b) Systernic action:

On the day after sowing, the wheat plants are sprayed with a spray mixture (containing 0.006 percent active ingredient; the amount of spray being proportional to the soil volume) prepared from the wettable powder of the active ingredient. After 3 days, the treated plants are infected with a fungal uredospore suspension. After an incubation period of 48 hours at 95-100 ° C relative humidity and 20 ° C, the treated plants are allowed to stand at about 22 ° C in a greenhouse. The rust blisters were evaluated 12 days after the day of infection.

Certain compounds of formula I, for example compounds 2.9 and 2.10 completely prevent fungal growth by systemic action, and compounds 2.11 exhibit complete activity even at concentrations of 0.002%.

The results of biological examples IX to XV demonstrate an exceptional potency and a broad spectrum of activity of the compounds of formula I, in particular TH1: 1, 1, 2, 3, 3, 3, 3, 3, 3 and 4 (1). against biologically different plant pathogenic fungi.

Claims (5)

What is claimed is: 1. A composition for controlling phytopathogenic fungi comprising an inert carrier material comprising, as active ingredient, an effective antifungal amount of a compound selected from the group consisting of azole derivatives of formula I and phytopharmaceutically acceptable acid addition salts, metal salt complexes and stereochemically isomeric forms thereof; wherein R ¹ , R ² and R ³ are independently selected from hydrogen and halogen, provided that at least one of R ¹ , R ² and R ³ is halogen; Q is a member selected from the group consisting of CH and N; X, Y and Z are independently selected from the group consisting of hydrogen and C 1 to C 6 alkyl, provided that at least one of the substituents X, Y and Z is other than hydrogen. . 2. The composition of claim 1 wherein R ¹ and R ³ are hydrogen, chloro or bromo and R ² is chloro or bromo. 3. A composition according to claim 2, wherein each of X, Y and Z has no more than 3 'carbon atoms. 4. A composition according to claim 3, wherein two of Y, X and Z are C 1 to C 6 alkyl groups, both of which are attached at the 5-position of the dioxane ring. 5. A process for the preparation of an active ingredient of the formula I as claimed in claim 1, comprising reacting a compound of the formula II NV Me. (ID wherein Q is as defined above and -Me is hydrogen, a tetrasubstituted ammonium ion of the tri- (C 1 -C 6 alkyl) ammonium or metal atom with a compound of formula III wherein R ¹ , R ² , R ³ , X, Y and Z have and T is halogen, wherein the reaction between the compound of formula II and the compound of formula III is carried out in relatively polar, relative to the reaction of an inert organic solvent at elevated temperatures and when Me is hydrogen, the reaction is carried out in the presence bases and, optionally, phytopharmaceous acid addition salts, metal salt complexes or stereoisomeric forms of the product are prepared.