Fungicide agent and production method of its effective compound

CZECHOSLOVAKIA SOCIALIST REPUBLIC (W) DESCRIPTION OF THE INVENTORY TO THE PATENT 247095 (11) (B2) t (22) Entered 24 01 85 (21) (PV 494-85) (32) 84 01424) France (40) Published 13 03 8G (51) Int Cl.4 A 01 N 43/653 Issued by 15 08 88 (72)

Author of invention DEBOURGE JEAN-CLAUDE, CHAMPAGNE AU MT D'OR GREINERALFRED, LYON (France) (73)

Proprietor of RHONE-POULENC AGROCHIMIE, LYON (France) (54) Fungicide! The present invention relates to a fungicidal plant protection agent which contains as an active ingredient a novel compound containing the remainder of the triazole and oligo-ether residues. The invention also relates to a process for the preparation of the novel compounds as well as to their use in plant protection, in particular the action of parasitic fungus, as well as the regression of plant growth.

It is already known a number of compounds that comprise Huji-triazole radical, especially fungicidů.Cílem present invention was to dispozicinové compounds which are suitable košetřování plant new ways.

Another object was to obtain such single compounds having a high insecticidal activity particularly against rusts and mildew, and particularly for anti-mildew on cereals.

Another objective was to obtain compounds with a polyvalent effect, especially against Botrytis, leaf blotch, pigmentation and seed diseases.

Further objects and advantages of the invention will be further elucidated in the following description.

It has now been found that these targets can be achieved using novel compounds,

. which corresponds to formula (I)

Crush

In which X is chloro or fluoro, n is an integer of 1 or 2, R 1 is hydrogen or C 1 -C 6 alkyl, R 2 is hydrogen or C 1 -C 8 alkyl, C 3 -C 7 cycloalkyl, allyl, phenyl or benzyl, which groups are optionally substituted by halogen atoms, C 1 -C 3 alkoxy groups or C 1 -C 3 alkoxy groups, or chlorophenoxy groups.

For the purpose of using pigmentation, preferred compounds of formula I are those wherein n is 2.

The compounds of the above general formula I may exist in one or several forms of optical isomers depending on the number of asymmetric centers in the molecule. The present invention encompasses both optical isomers as well as their racemic mixtures and the corresponding diastereoisomers. The separation of the diastereoisomers and / or optical isomers may be accomplished by known methods.

Also included within the scope of the present invention are the salts of the compounds of formula I, especially hydrochlorides, sulfates, oxalates and nitrates. An object of the present invention is a fungicidal composition which is characterized in that it contains as active ingredient at least one compound of the above defined formula (I) or an acid addition salt thereof. The subject of the present invention is also a process for the preparation of compounds of general formula I and salts thereof.

According to the invention, compounds of formula (I) and their salts are prepared by reacting compounds of formula (II)

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in which Z represents a chlorine atom or a bromine atom, X, R @ 1, R @ 2 and R @ 3 are as defined in sub-section I, in reaction with an alkali metal triazole derivative, for example, a potassium salt or a potassium salt.

This reaction is usually carried out in an aprotic polar solvent, and may also be catalyzed, for example by addition of an alkali metal iodide. The temperature is generally between 50 and 250 ° C, preferably between 70 and 230 ° C. For economic reasons, the most commonly used concentrations of all reactive components are between 1 and 50%.

The compounds of formula (II) which are used as starting materials can be prepared by reacting an alcohol of general formula

R2-OH in which R2 is as defined in formula (I)

with a compound of the formula (III)

X1, X1, X1, X2, X1, X1, X2, X2, X1, X2, X3, X2, X2, together form a divalent organic group, especially a lower alkylene group.

The acid used in this reaction as a catalyst may be protic or aprotic acid. Protic acids include: hydrochloric acid, sulfuric acid, trifluoroacetic acid, perchloric acid, benzenesulfonic acid, toluenesulfonic acid and methanesulfonic acid.

Protic acids include Lewis acids such as boron trifluoride, aluminum chloride, and stannic chloride. If a hydrochloric acid hydrocarbon catalyst is used, the acid may be released, for example, by the addition of acyl chloride, in particular acetyl chloride, which reacts with the alcohol in the presence of the released hydrogen chloride.

This reaction is usually carried out by simply heating the reactants. The temperature generally ranges from 50 ° C to the boiling point of the reaction mixture. An alcohol of the formula R2 OH may typically take on the role of the solvent in the reaction medium. Such inert auxiliary solvent, especially aliphatic, alicyclic or aromatic hydrocarbon, which may optionally be halogenated, or ether, may be added.

Compounds of formula (III) are typically prepared by reacting a carbonyl derivative of formula (IIIa)

(X) r 2 / W

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CO-C (O) Z (IIIa) 217033 in which X, Z have the same meanings as above, with an organomagnesium compound prepared from a compound of the formula Iub R1 OR3

Wherein Z is a halogen atom, preferably atom bromide, and R 1 and R 3 are as defined above.

An organomagnesium compound can be prepared by a known method by treatment with a 3-haloaldehydeacetal in a solvent medium. This + haloaldehyde acetalsalamate can be prepared by known methods, for example by G. Buchi and H. Wuesta, Org. Chem. 34, 1222 (1969) and H. Meerwein, Houben Weyl, Methoden der Org. Chem., Vol. Vl / 3, page 204, 4th edition (1965).

The reaction of a compound of formula (I) with an organomagnesium compound of formula (IUb) is most often carried out at temperatures between -70 ° C and +100 ° C, preferably between -50 ° C and -50 ° C. As the solvent that can be used in the reaction, ethers, in particular diethyl ether and tetrahydrofuran, or aliphatic, alicyclic or aromatic hydrocarbons, or mixtures thereof, can be used.

In addition to the above described process, the fungicidally effective compounds of formula (I) can be prepared by reacting a general alcohol alcohol

R2 -OH in which

R2 is as defined above, with a compound of formula IV

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similar reaction conditions for the preparation of compounds of formula II.

Compounds of formula (IV) may be obtained by reacting a triazole with a compound of general formula (V)

(X) wherein X, n, R 1 and R 3 are as defined above.

The triazole is optionally used wholly or preferably in the form of an alkali metal salt.

This reaction is usually carried out at temperatures between room temperature (20 ° C) and reflux temperature, preferably at temperatures between +50 ° C and +130 ° C, as solvents which can be used in the protuto reaction , especially alcohols, ethers and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide are contemplated.

Under conditions similar to those described for the preparation of compounds of general formula IV from compounds of formula V, compounds of formula IV can also be prepared from compounds of general formula III by reaction with alkali metal triazole derivatives.

Compounds of formula V can be obtained by hydrohalogenation of compounds of formula III. This reaction is usually carried out by reacting an organic or preferably an inorganic base at a temperature of 0 and 100 ° C. The aqueous medium and / or solvent-containing medium, such as a hydrocarbon or ether, an alcoholic or polar solvent, may serve as the reaction medium. The following examples further illustrate the invention without limiting its scope in any way. Examples 1 to 3 and Table I illustrate in particular the processes for the preparation of compounds of general formula I according to the invention, and illustrate the compounds themselves. The physical properties reported for these compounds represent NMR chemical shift values ​​of protons (o) in the acetal group: -O-CH-O-. in which

These shifts are measured in ppm and are expressed relative to tetramethylsilane as an internal standard. NMR spectra are measured at 100 MHz in deuterated chloroform. Example 1

The organo-magnesium compound is prepared with X, n, R1 and R3 as defined above, in the presence of an acid catalyst.

An acid catalyst can be used as a catalyst which has already been specified in connection with the preparation of the compounds of formula (II).

Other reaction conditions are also carried out on a silica gel column, yielding 4.1 g of an oil which contains a mixture of substantially equal parts of the two diastereoisomers

structural formula VIII

by reacting 9.7 g (0.4 mol) of magnesium with 0.5 mmol of dibromoethane in 10 ml of anhydrous tetrahydrofuran. While maintaining the temperature below 15 ° C, a solution of 47 ml (0.4 moles) of 2- (3-bromomethyl) -1,3-dioxolane in 200 ml of tetrahydrofuran is added dropwise. The addition is completed in 15 minutes, cooled to -45 DEG C. and a solution of 56.7 g (0.3 mole) of chloromethyl p-chlorophenyl ketone in 150 ml of tetrahydrofuran is added, keeping the temperature at -45 DEG. After half an hour the mixture is neutralized by the addition of 120 ml of pure acetic acid and then poured into 1 liter. Extraction is carried out with ethyl acetate. The ethyl acetate solution is then dried and the solvent is evaporated. 100 g of chlorohydrin is obtained, m.p. 99 DEG C. (after crystallization from cyclohexane) of formula VI

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(wine)

OH p-C1-C4-C (O) (See)

A mixture of 0.1 ml of acetyl chloride and a solution of 6 g (0.02 mol) of the compound of formula VI in 30 ml of methanol is heated under reflux for 2 hours. The reaction mixture is then poured into an aqueous solution containing 5% by weight. sodium carbonate solution. The mixture was extracted with ethyl acetate, the ether solution was dried and then ethered. An oil was obtained which was distilled at 140 DEG C. under an absolute pressure of 5.3 Pa. 4.7 g of an oily product of the formula VII

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Vil

A mixture obtained by adding 4.2 g (0.016 mole) of the compound of formula VII to 40 ml of dimethyl sulfoxide containing triazole sodium salt prepared from 1.6 g (0.024 mole) of triazole and 0.7 g (0.024 mole) of sodium hydride in 80% oil suspension is heated for 3 hours at 170 ° C under an inert gas atmosphere. The solution is poured into 200 ml of water.

The mixture is then extracted with ethyl ether, the ether solution is dried and the ether is evaporated.

The residue after evaporation is purified by chromatography

The compound of formula IX and / or (VII)

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(IX) is prepared in a manner similar to that described in Example 1, but using chloromethyl-o, p-dichlorophenyl ketone as the reactant instead of chloromethyl p-chlorophenyl ketone.

A mixture of 0.3 mol of the compound of formula IX with 400 ml of 15% (w / w) aqueous sodium hydroxide solution was stirred for 12 hours at room temperature. The organic phase is then diluted with diethyl ether, separated by decantation, washed with water, dried and evaporated.

By distillation at a boiling point of 147-150 ° C with a pressure of 2.7 Pa, 64 g of a colorless viscous oil is obtained, which contains compound X

Cl

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(*) 247095 10

A mixture of a solution of 5.8 g (0.02 mole) of the compound of formula X in 20 ml of n-butanol, 1.4 g (0.02 mole) of triazole and 0.09 g (0.01 moles) triazole sodium salt is heated at 110 DEG C. for 6 hours.

After this time, the mixture was cooled to room temperature, diluted with water and extracted with ethyl acetate. The ether solution is concentrated by evaporation. The residue is purified by chromatography on a silica gel column using a mixture of methanol, ethyl acetate and hexane (5: 47.5: 47.5) as the eluent.

There are obtained 5.1 g of a compound having the melting point of 131 DEG C., which has the following formula XI

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A mixture of acetyl chloride (0.10 ml) and a solution of 3.1 g of the compound of formula (XI) in absolute ethanol (30 ml) was heated to reflux for 4 hours. The crystals formed are filtered and washed with cold ethanol. 1.2 g of white crystals, melting at 162 DEG C., corresponding to the more polar diastereomer (based on thin layer chromatography) of compound XII

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The mother liquors from this filtration are concentrated, the residue is diluted with 1 ml of ethanol and 2 ml of iso-propyl ether, and the resulting crystals are separated. There are thus obtained 0.2 g of the same diastereomer, m.p. 164 ° C.

Chromatography of the residual oil from crystallisation on silica gel gives a second, less polar diastereomer, m.p. 61 ° C. Example 3

Using the procedures similar to those described in Example 1 and Examples 2 and 9, various other compounds corresponding to Formula XIII

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(XH) The meanings of the substituents in the formula XIIIa for some of the physical characteristics of compounds 1 to 49 are summarized in the following Table 1, which also includes the compounds prepared according to Examples 1, 2 and 9 (cf. , 11 and 291.

With respect to Compound No. 49, this compound contains the p-fluorophenyl group substituted with the X1-substituted p-chlorophenyl group in the ortho-position by the X1 residue in the th-position. When R @ 1 is hydrogen, the compounds contain two asymmetric carbon atoms and the two diastereoisomers can be separated by means of a thin layer of silica gel using methanol / ethyl acetate / hexane (5: 20: 75 by volume) as the solvent system. The less polar diastereoisomer moves faster on the chrome-matogram and is called A. The more polar diastereoisomer was moved more slowly over the chromatogram and indicated as B.

If R 1 is other than a hydrogen atom, then the compounds contain three asymmetric carbon atoms and occur in four diastereoisomers. These diastereoisomers are referred to as A, B, C, and D. Chromatographic data may sometimes be difficult to divide, but if this division is feasible, A is the least polar, D is the most polar, and B a C has a polarity between them. 247095

(CC) 5 NMR C + D oil 4,91 / 4,66 5,05 / 4,91 A + B (CH 2 CH 2) + C + D oil 4,90 / 4,66 A + B oil 5,09 / 4,95 A 107 5,29 B 158 5,14 A + BA + B 57 171 5,30 / 5,14 A -1 - B + C + D 152 A + B oil 5.24 5.08 The following Examples 4 to 7 illustrate the fungitic properties of the compounds of the invention as well as their use. In these examples, spraying with solutions or suspensions of the active compound is carried out so that a spray of a solution or suspension of concentration of 1 g of active ingredient per liter corresponds to the average application of approximately 2% of the active ingredient per 1 cm2 of plant leaves. 08 The following Examples 4 to 7 illustrate the fungicidal properties of the compounds of the invention as well as their use. In these examples, spraying with solutions or suspensions of the active compound is carried out so that a spray of a solution or suspension of concentration of 1 g of active ingredient per liter corresponds to the average application of approximately 2% of the active ingredient per 1 cm2 of plant leaves. 08 The following Examples 4 to 7 illustrate the fungicidal properties of the compounds of the invention as well as their use. In these examples, spraying with solutions or suspensions of the active compound is carried out so that a spray of a solution or suspension of concentration of 1 g of active ingredient per liter corresponds to the average application of approximately 2% of the active ingredient per 1 cm2 of plant leaves.

Under the conditions of Examples 4 to 7, the tested compounds do not show phytotoxicity. In these examples, the test substance is considered to provide a complete protection against fungal disease if the protection is at least 95%; protection is considered good if it is at least 80% (but less than 95% is protection) considered to be relatively good if at least 70% (but less than 80% J and finally the protection is considered to be average if at least 50% (but less than 70%) is present in the invention. except in the cases where it is stated otherwise and with the exception of the yields, is meant the percentage by weight, in the case of percentages related to the stoichiometry, this is molar, with respect to the concentrations, some are expressed in ppm (the number of parts per one million), which corresponds to the mg / liter concentration

The test for grass (Erysiphe graminis) injection (in vivo)

An aqueous emulsion of the active ingredient with a dispersive dispersion having the following composition: active compound tested 40 mg of a surfactant based oleic acid ester compound with polycondensation product of ethylene oxide and sorbitan "Tween 80" diluted to 10% preparation in water 0.4 ml water 40 ml

This aqueous emulsion is further diluted with water to obtain the desired concentration.

Plants of barley sown in pots to clay soil are treated at plant height 10 centimeters by spraying with an aqueous emulsion (also referred to as a spray mixture) containing the concentration of the active ingredient below. The experiment is repeated twice. After 48 h, barley plants are infested with grasshoppers (Erysiphe graminis), which are infested with already fed plants. The results of the test are scored for 8 to 12 days of amnesia.

Under these conditions, the following results were found: - at a dose of 1 g / liter, good or total protection was achieved by means of compounds I, 2, 4, 5, 6, 7, 8, 17, 18, 19 and 20; a dose of 0.33 g / liter was obtained by means of Compounds Nos. 8, 14, 16 and 27. - at a dose of 0.11 g / liter, complete protection was achieved by means of Compounds Nos. 12, 13, 15 and 28. a dose of 0.033 g / liter was fully protected by Compounds 9 and 10. Example 5

Puccinia recondita-induced cerebrovascular disease (brown incision of cereals) (in vivo)

Plants of wheat grown in potted clay soil are treated by spraying water emulsions (referred to as spraying mixtures) which have been prepared as described in Example 4 and which contain varying concentrations of the active ingredients according to the present invention at a height of about 10 cm. The experiment is repeated twice for each concentration.

After 48 hours, the treated plants are infused with an aqueous suspension of rust (Puccinia recondiata) containing approximately 50,000 spores in ml and prepared from already infected plants. The plants are then placed 48 hours in the incubation chamber at about 18 degrees Celsius and at 100% relative humidity. 247095 13

After these two days, the relative humidity drops to 60%. Eleven to fifteen days after infestation, the condition is assessed by the plant with the untreated control plants.

Under these conditions, the addition of 1 g / liter was found to be a good protection against the compounds of Nos. 4, 5, 6, 7, 9, 13, 14, 15, 16, 17, 18 and 21; at a dose of 0.33 g / liter complete protection was achieved by means of Compounds Nos. 10 and 11. Example 6

Test for gray mold (Botrytis cinerea) nayčeti

Tomato seedlings (30-day-old greenhouse cultivars grown in the greenhouse) are treated twice with aqueous emulsions (also referred to as spraying mixtures) of the same composition as described in Example 4 and at various concentrations of the test organism, Ascomycetes, Adelomycetes.

After 24 or 48 hours, leaves are cut off and placed on two petri dishes (11 cm in diameter), on the bottom of which was previously placed a roll of moist filter paper (5 lozenges per bowl).

The inoculum is then applied by spraying the spore suspension using a syringe (3 drops per 1 place). This spore suspension (Botrytis cinerea) was obtained from a 15-day culture which was suspended in the nutrient solution (80,000 spores / ml).

Evaluation is performed 3 days after infection by comparison with untreated controls.

Under these conditions, good or complete protection was observed at a dose of 1 g / liter of Compound No. 8, 1p and 16. Example 7

Assay for seed-infested fungi and soil-attacking fungi (in vitro) The effect of the compounds of the invention 14 is tested in this test on the following types of fungi that cause secondary cereal diseases:

Cercosporella herpotrichoides (CERC) Helminthosporium gramineum (HELM G) Pyrenophorae avenae (PYRE)

Septoria nodorum (SEPT N)

Helminthosporium teres (HELM T)

Fusarium roseum (FUS ROS)

Fusarium nivale (FUS NIV)

Fusarium culmorum (FUS CULM) Rhizoctonia cerealis (RHIZ C)

Abbreviations in brackets are used to designate these mushrooms in Table II.

Each of the experiments is carried out as follows: Potable broth, glucose and agar (PDA soil) are dosed into a series of Petri dishes (20 milliliters per dish) after sterilization in the autoclave.

As soon as the dishes are filled, the acetone solution of the active ingredient is added to the pre-cooled broth using the syringe until it reaches the desired final concentration.

As a control, Petri dishes similar to those described above were dosed with the same amount of nutrient medium but without the addition of the active substance.

After 24 or 48 hours, each disorder is infected with a piece of mycelium obtained from a previous culture of the species.

The dishes are maintained for 2 to 10 days (depending on the type of test fungi) at a temperature of 22 degrees Celsius, and the growth of the sponge mushroom containing the test compound is compared with the growth of the same sponge in the dish serving as a control.

For each test compound, a lower dose is determined which allows the growth of the fungi to be inhibited to 80-100%. The lameness is referred to as the &amp; quot; minimal inhibitory dose &amp; quot ;.

These minimum inhibitory doses, expressed in ppm, are summarized in Table II, wherein the abbreviations used are as defined above. 247G95

Minimum inhibition dose in ppm

CERC HELM HELM PYRE HELM SEPT FUS FUS FUS RHIZ

nina no. GTN ROS NIV CULM C

OOOOO rH r r r r r r r r r r r r r r r r r r r r r r r r r r o r o r co r oo r o r co r oo

rH 00 00 00 00 0000 00 00 co oo 00 00 00 00 oo oo

rH oo

rH

00 o CO 00 00 00 rH O CO CO CO oo oo O O CO CO CO CO CO 00 CO O CO CO CO CO OO O O rH rH rH rH rH oo o o o

OOCOOOtHOOOOOOOO

OOOOOOrHOOOOOOOO oo

rH oooooo

rH rH rH 00 00 00 co 00 oo

OO ^ rHCo "rH

OO

OO

CO oo "oo ooo o 00 00 00 oo" 00 oo

O rHO rHrH

O

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CO CO-COCO CO CO CO T-4 co

CO rH CO

COOH RH O ORH rH

OOOOOO rH O CO rO r r r r r r r r r r r r r r r r

OOO OO oo OH H rH H

H COCO H O H H (CO CO Hg grH CO OO r r S rH Co CO CO rH S

<NCO ^ OOCO [> ​​COOOrHC \ JinOb * OOOOrHC \\\\\\\\\\\\\\\\ "

The compounds according to the invention can be used both preventively and curatively to control various kinds of fungi, in particular fungi of the classes of BaSidiomycetes, Ascomycetes, Adelomycetes, or Fungi imperfecti, in particular fungus, rust, powdery mildew, pigmentation, fusarios, helmenthosporeios, septorios and rhizoctonos generally on vegetables and plants, especially on cereals such as wheat, barley, rye, oats and hybrids thereof, as well as on rice and maize.

The compounds of the present invention are particularly important due to their wide spectrum of cereal diseases (mildew, rust, pigmentation, helminthosporiosis, septoriosia, especially fusariosas, which are difficult to control plants) .These compounds are also very valuable in their effect on mold gray (Bo-trytis) and cercosporios, and also because they can be used on a variety of crops such as grapevine, market gardening and forestry.

Finally, it is to be noted that the compounds of the invention have excellent selectivity to crops.

The compounds of the invention are advantageously used at dosages of from 0.02 to 5 kg / ha, in particular at doses of 0.05 and especially particularly from 0.1 to 2 kg / ha. In practice, the compounds of the invention are sometimes used alone, but most often form part of suitable compositions. These compositions, which can be used to control plants against fungal diseases or plant growth regulating compositions, contain as active ingredient the above-described compound of the invention in combination with the solid or liquid carriers required in agriculture and surface active agents, also usable in agriculture. For this purpose, especially inert carriers and customary surfactants may be used. The above agents are the subject of the present invention.

These compositions may also contain all possible types of other ingredients such as, for example, protective colloids, adhesives, thickeners, thioxotropic agents, penetration agents, stabilizers, complexing agents, and the like, as well as other known active ingredients with pesticidal properties fungicidal or fungicidal properties), plant growth promoting agents (especially fertilizers) or plant growth regulators. In general, the compounds of the invention may be combined with any solid or liquid additives as is customary in the art for the manufacture of such compositions.

The dosage employed of the compounds according to the invention as fungicides may vary within wide limits, particularly depending on fungal toxicity and climatic conditions.

Generally, compositions containing 0.5 to 5,000 ppm of active ingredient are suitable. These values ​​are given for the means that serve 16 for direct application. The term "ppm" refers to the number of parts per million. A range of 0.5 to 5,000 ppm corresponds to a range of 5 X 10-5% to 0.5% (w / w).

With regard to the compositions suitable for glass and transport, such compositions contain more preferably from 0.5 to 95% by weight of the active ingredient.

The compositions according to the invention for agricultural use may contain the active ingredients according to the invention in an amount varying very widely from 5 to 10% to 95% by weight. Accordingly, the compounds used in the sense of the invention are generally combined with the carriers and, optionally, the surfactants. The term &amp; quot; carrier &amp; quot; means an organic or inorganic, natural or synthetic material with which the active substance is combined to facilitate its application to the plant, its seeds or soil. This carrier is therefore generally inert and must be usable in agriculture - especially it must be acceptable for the treated plant. The carrier may be solid (alums, natural or synthetic silicates, crystals, resins, waxes, solids, etc.) or liquid (water, alcohols, ketones,

The surfactant may be a binder, dispersant or wetting agent of the ionogen or nonionic type. Examples are polyacrylic acid salts, lignosulfonic acid salts, solifenolsulfonic or naphthalenesulfonic acids, polycondensation products of ethylene oxide with fatty acids or amine fatty acids, substituted phenols (especially alkylphenols or arylphenols), salts of esters of sulfosuccinic acid, taurine derivatives (especially alkyl taurates ), esters of phosphoric acid with condensation products of ethylene oxide with alcohols or phenols. The presence of one surfactant is generally necessary if the active agent and / or the inert carrier are not soluble in water and the water serves as a medium for preparing the dosage form. Thus, for general applications, compounds of formula I are generally used in the form of compositions. These compositions according to the invention can occur in very wide palette or liquid forms. (in which the content of the active substance of the formula (I) can be up to 100%) and granules, in particular grains obtained by extrusion, compression, impregnation of the granular support or powder preparation (the content of the compound of formula (I) in these granules may range between 1 and 80% for the latter cases. 17 impregnating the granular support or powder preparation (the content of the compound of formula (I) in these granules may vary between 1 and 80% for the latter cases. 17 impregnating the granular support or powder preparation (the content of the compound of formula (I) in these granules may vary between 1 and 80% for the latter cases. 17

Liquid compositions or compositions which are converted to liquid preparations are such solutions as water-soluble concentrates, emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders, (or spray powders) and pastes.

The emulsifiable or soluble concentrates most often contain 10 to 80% of the active ingredient, and the emulsions or solutions intended for administration contain from 0.01 to 20% of the active ingredient. In addition to the solvent, the emulsifiable concentrates may, if necessary, contain from 2 to 20% of suitable additives such as stabilizers, surfactants, penetrants, co-inhibitors, dyes and adhesives. Example F 1 Active ingredient 400 g / l of dodecylbenzene sulfonic acid alkali metal salt 24 g / l of condensation product of ethylene oxide with nonyl phenol (10: 1) 16 g / l of cyclohexanone 200 g / l of solvent aromatic hydrocarbon) to 1 liter

Another example of an emulsifiable concentrate of the following composition: Example F 2 Active ingredient 250 g epoxidized vegetable oil 25 g mixture of alkylarylsulfonate and polyglycol ether of fatty alcohols 100 g dimethylformamide 50 g xylene 575 g Using these concentrates, by dilution with water, emulsions of each desired concentration, particularly suitable for application to plant leaves.

Sprayable suspension concentrates are formulated to produce a stable, liquid release product which usually contains 10 to 75% of the active ingredient, from 0.5 to 15% of surfactants, from 0.1 to 10 % of thioxotropic agents, from 0 to 10% of suitable additives, as antifoaming agents, corrosion inhibitors, stabilizers, penetrants and adhesives, and as a carrier water or organic liquid in which the active ingredient is only slightly soluble or insoluble. The carrier can dissolve certain organic solids or inorganic salts which are intended to assist in preventing sedimentation or to act as anti-freezing agents. 18

Wettable powders (or spraying powders) are typically formulated to contain from 20 to 95% of the active ingredient and generally contain a solid carrier of 0 to 5% wetting agent, 3 to 10% dispersant and optionally 0 to 10% of one or more stabilizers or other additives such as penetration agents, adhesives, anti-caking agents, coloring agents. A few examples of wettable powder formulations are given below: Example F3 Active ingredient 50% Calcium lignosulfonate (deflocculant) 5% Isopropyl naphthalenesulfonate (anionic surfactant) 1% Silicate anti-caking 5% Cauliflower 39%

Another example of a 70% wettable powder composition: Example F 4 Active ingredient 700 g Sodium dibutyl fistylsulphonate 50 g Condensation product of naphthalenesulfonic acid, phenylsulphonic acid and formaldehyde (2: 2: 1) 30 g of kaolin 100 g of chalk

Another example of the composition of 40% wettable powder: Example F5 Active ingredient 400 g Sodium lignosulfonate 50 g Natri-butynynaphthalenesulfonate 10 g Silica 540 g

EXAMPLE F 6 Active Ingredient 250 g Lignosulfonic Acid Salt 45 g A mixture of the same weight parts of Cream and Hydroxyethyl Cellulose 19 g Sodium Dibutylnaphthalene Sulphate 15 g Silica 195 g Chalk Champagne 195 g kaolin 281 g

EXAMPLE F7 Active ingredient 250 g isooctylyleneoxyethylene ethanol 25 g mixture of equal parts of Champagne and hydroxyethyl cellulose 17 g sodium aluminosilicate 543 g diatomaceous earth 165 g Another example of the composition of 10% wettable powder : Example F8 Active ingredient 100 g Sodium salt of sulfated saturated fatty acids 30 g Condensation product of naphthalenesulfonic acid and formaldehyde 50 g of kaolin 820 g To prepare these wettable or dispersible powders, the active ingredients are thoroughly ground with other materials in suitable mixing devices and the mixture is crushed with mist or other suitable grinding equipment. In this way powders are obtained with preferred wettability and suspendability. These powders can be suspended in the desired concentration at any desired concentration, and the suspension can be used very advantageously, especially for application to plant leaves. Instead of wettable powders, pastes can also be prepared. The conditions and methods for the preparation of these traps as well as their use are similar to those in the case of wettable powders.

As already mentioned above, the present invention also includes compositions in the form of aqueous dispersions and aqueous emulsions, such as those obtained by dilution with water, wettable powders or emulsifiable concentrates according to the invention. The emulsions may be water-in-oil or oil-in-water and may also have a thick consistency, such as consistency of the isoniazone.

Granules which are intended to be applied in the extruder are usually prepared in a size of 0.1 to 2 mm, which can be produced by means of a barrier or impregnation. Preferably, these granules comprise 0.5 to 25% of the active ingredient and 0 to 10% of the additives, as stabilizers, slow release agents, binders and solvents. The following is an example of the composition of the granulate: Example F 9 active ingredient 50 g epichlorohydrin 2.5 g cetyl polyglycol ether 2.5 g polyethylene glycol 35 g kaolin (particle size: 0.3 to 0.8 mm) 910 g In this in particular, the active ingredient is mixed with epichlorohydrin and the mixture is dissolved in 60 g of acetone, polyethylene glycol and cetyl polyglycol ether are added, the kaolin is wetted with the solution and the acetone is evaporated in vacuo. .

The compounds of formula I can be used as a powder in the form. The composition suitable for use includes, for example, 50 g of active ingredient and 950 g of talc. Another suitable agent is a composition comprising 20 gelling components, 10 g of finely dispersed silica and 970 g of talc. The ingredients are mixed and the mixture is milled and the mixture obtained is sprayed. In the next section, the results are presented. The following types of fungi were used in these experiments, which are indicated in the tables with the appropriate abbreviations:

Gray mold (Botrytis cinerea) Grasshopper (Erysiphe ERYG graminis)

wheatgrass (Puccinia PUCR recondita)

Peronospora Grapevine PLA (Plasmopara viticola)

Piricularia oryzae PIR

Cerco-CBET spora beticola

peronospora tobacco PERO

(Peronospora tabacina) Pulp (Puccinia PUCS striiformis) Cucumber powdery mildew (Erysiphe cyrloracoracearum)

fusarium rot of onion FUS OX (Fusarium oxysporum) (melon)

Pytnium spp PYT

Pyrenospora avenae PYR

(SEPT T toria tritici) scab (Venturia VENTinaequalis)

Whetzelinia sclerotiorum WHE

Monilia laxa MON

Mycosphaerella fijiensis MSPH

Marssonina panattoniana MARS

brown spotted brambo- ALT leaves (Alternaria solani) 247095 21

aspergillus onion bulb ASP (Aspergillus niger) beetroot (Cercospo- CARA ra arachidicolaj Cladosporium herbarum CLAD Helminthosporium oryzae HELM OR penicillin PEN (Penicillium expansum) Pestalozzia spp PES Phialophora cinerescens PHI Pboma betae PHB Phoma foveata PHF Phom flute rot PHL (Phoma lingam) Ustilago USI maydis Verticillium dahliae VERT pea ASCO (Ascochyta pisi) Guignardia bidellii GUIG Corticium rolfsii CRO Phomopsis viticola PHV Sclerotinia Sclerotinia minor SCL Sclerotinia minor Phytophthora cinnamomi PHY Cl Phytophthora cactorum PHY CC

Phytophthora capsici (Phytophthora capsici) Phytophthora rot (Phyto-PHY INphthora infestans)

Phytophthora parasitica PHY PA

Phytophthora megasperma PHY ME

Phytophthora syringae PHY SY

Coryneum cardinal. CORY

potato rootstock RHIZ S (Rhizoctonia solani) symbol> indicates "greater than" symbol g indicates "less than" or "same as"

Pigmentation is termed Cerco-sporella herpotrichoides, although it is commonly referred to as Pseudocercosporella herpotrichoides.

Tables III, IV and VI contain a minimal inhibitory dose (in vitro) of different compounds for different types of fungi, depending on the application used in this example.

Table V contains the minimum in vivo dose (in vivo) of different compounds for different types of fungi, depending on the mode of application used in Examples 4 to 6.

Table VII shows the effect of different compounds in the field trial.

Minimum inhalation doses in ppm

Type of fungi Compound No. Minimal Inhibition Dose ALT 29 30 ASP 29 100 BOT (resistant to Iprodion) 29 10 CBET 29 100 CARA 29 3 CLAD 29 30 FUS CULM 29 30 FUS OX 29 100 HELM OR 29 100 PEN 29 100 PES 29 30 PHI 29 30 PHB 29 10 PHF 29 100 PHY 29 29 PHY 29 29 PHY 29 100 PHY 29 100 PHY 29 100 PHY 29 100 PHY 29 100 PHY 29 29 PHY 29 29 PHY 29 29 PHY 29 29 PHY 29 29 3 Compound No.

Minimum inhibitory dose

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Compound No. 45 29 12 35 9 28 47 48 Type of sponge: BOT 30 10 100 10 30 10> 100 100 (0) FUS CULM 100 30 100 30 11 30 100> 100 (80) FUS NIV 100 30 100 100 33 30> 100 30 FUS ROS 100 100> 100 30 33 30> 100> 100 (80) (50) CERC 30 <1 30 10 10 10 10 10 HELM G 30 10 100 10 11 10> 100 30 PYRE 10 3 30 10 3 , 3 10> 100 30 HELM T 3 3 10 10 3.3 3 100 10 RHIZ C 10 <1 30 10 11 30> 100 30 SEPT N 3 <1 30 10 3.3 3 100 10 Table VII Type Compound Dose% napa -% infected Method of evaluation of sponges number g / ha of cobs of leaves of leaves of PUCS results (control) 0 40 23 days after treatment; 45 250 17.5 determined at a total of 45 500 16.3 infected plants at 29 250 7.9 Stage 4 leaves 29 500 6.3 PUCS (control) 0 82.3 14 days after treatment; 45 125 3.4 observed on 3rd sheet 29 125 · 1.2 PUCS (control) 0 25.9 15 days after 1st treatment; 45 125 6, 7 observed on 1st sheet 29 125 3.5. , _______r,., ERYG (control) 0 25.9 14 days after treatment; 45 250 4.7 Observed on 3rd leaf 29 250 1.0 PUCS (control) 0 100 47.7 22 days after 2nd treatment 12 125 88 5.8 for ears; 7 days after 28 125 64 0.8 2. Treatment for Verification of the second leaf ERYG (control) 0 10.3 20 days after 2nd treatment; 12 1.25 0.9 1st leaf verification 28 125 0.1 PUCS (control) 0 96 24 days of treatment 45 125 74 45 250 74 29 125 54 29 250 46 12 125 91 12 250 87 28 125 39 28 250 46 247095 23 24

Table VII - continued

Type of sponge Compound No. Dose g / ha CERC (control) 0 45 500 45 1000 29 500 29 1 000 12 500 12 1000 28 500 28 1 000 The following sections describe the conditions under which the greenhouse test (in vivo) against Cercospora beticola (Example 8) as well as field hypocusis conditions (Example 8a). Example 8

Sugar beet seedlings with a height of 7 to 10 cm preventively treated postřikovousměsí containing the test compound, wherein when-used spray-mixture is prepared not in the same way as described in non-limitative examples 4. Each experiment was repeated dvakrátpro each concentration. 24 hours after treatment, sprouts of sprouts were injected by spraying an aqueous suspension of 0.2 g / ml of mycelium Cercospora betico-la. Does incubation continue after the time? 72 ° C at 25 ° C and 100% relative humidity, and after 3 days the seedlings were placed in the light (10,000 lux, 14 hours / day). The evaluation of the condition of the plants is carried out 14 days after infection and expressed as% of the efficacy compared to the untreated control plants. The effect on the control trial is 0%. The total protection crop is 100%. Example 8a

The main conditions of the various tests are set out in Table VII. The general conditions are as follows: the tests are repeated four times; area plots for the field trial range from 3 to 5 m2. Incestation is natural erosion (Erysophe graminis) (ERYG) and artificial for Cercosporella hespotrichoides (CERC) wheat rust (Puccinia recondita) (PUCR). Plants are treated with a spray mixture, applying a spray rate of 500 to 1000 liters / ha under a pressure of 0.3 MPa. The treatment was preventive for grass mildew and wheat rust (treatment repeated for every 15 days) and curative for Cercospo-

Percent Method of evaluation of strain results of straws 93 96 90 56 days after treatment; 82 verification on the main stem 72 93 85 82 63 rella herpotrichoides. The results are observed in a sample of 25 leaves for grass and downy mildew (per cent of the leaf area infected with the disease) or a sample of 25 stones for Cercosporella herpotrichoides (the percentage of affected stalks is determined). Example 9

A solution of 296 g (4.23 mol) in 1 liter of dichloromethane is cooled to 0 ° C. Thereafter, 343 g of gaseous broth are introduced into the solution while keeping the temperature at 0 ° C. After 15 minutes, 0.9 L of methanol is added at 0 ° C and the temperature of the reaction mixture is kept for 3 hours. Then add 2 liters of water containing 100 ml of concentrated (aqueous) ammonia solution. The mixture is decanted, the organic phase is separated off and the aqueous phase is extracted with 200 ml of dichloromethane. The organic phases are combined and washed with aqueous sodium bisulfite. The mixture is concentrated and then distilled in the presence of diethylaniline. 452 g of bromoacetal of the formula are obtained

Br-CH2-CH2 (CH2) -CH (OCH3) 2 Yield: 54% of theory.

Boiling point 44 to 50 ° C / 533 Pa.

An organomagnesium compound is prepared by adding a solution of bromoacetal (19.7 g) in magnesium (40 ml) tetrahydrofuran at a temperature between 15 and 22 ° C and in the presence of 1,2-dibromoethane (5 drops).

40 ml of tetrahydrofuran are then added, the mixture is cooled to -20 DEG C. and then 20.1 g of trichloroacetophenone dissolved in 50 ml of tetrahydrofuran is added dropwise. The temperature is maintained at -20 DEG C. 6 ml of acetic acid are then added and poured into 500 ml of water at room temperature. The mixture is extracted with ether, the organic solution is dried and concentrated. 30 g of a yellow oil containing mainly chloro-hydrin of formula 247095 are obtained

Z &amp; lt; / RTI &amp; gt;

(This process for the preparation of the non-cyclic acetal is the same as given for the preparation of the compounds of Example 3, wherein R 1 is other than hydrogen)

To a solution of 442 g of chlorohydrin in 1.5 l of ethanol was added a solution of 1 mol of potassium hydroxide in 200 ml of methanol, whereupon the reaction mixture was made alkaline for up to 25 or 30 hours. The mixture was concentrated in vacuo, diluted with ether, washed with water, dried over sodium sulfate, evaporated and the residue distilled under reduced pressure (121-140 ° C / 1.3 Pa). Thus, 138 g of a mixture of two diastereoisomers of the general formula C1,

<img img-format="tif" img-content="drawing" file="CS247095B2D00211.tif" id="idf0011" />

CH 2 CH (OCH 3) 2 To a solution of 126.5 g of this epoxide in 500 ml of dimethylformamide was added 57.2 g of triazole and then 172 g of potassium carbonate. The mixture is heated at 120 DEG C. for 4 hours, then filtered, the filtrate is washed with DMF and evaporated. The residue is poured into 2 liters of water, extracted with chloroform, the chloroform solution is washed with water, dried over sodium sulfate and evaporated in vacuo. To obtain 148.2 g of a light brown oil which was triturated in 100 ml of heptane. The mixture was filtered to give 117.5 g of a beige powder having a melting point of 117 ° C. Yield: 782% of theory.

The product contains a mixture of two diastereoisomers of the formula

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(OH) -CH (CH 2) 2 -CH

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From the chemical shifts of the NMR spectrum (d) at 100 MHz in deuterated chloroform to detect the protons of the methoxy group. Displacements at 3.23 and 3.19 ppm were observed for the diastereoisomer, and shifts at 3.38 and 3.20 ppm were observed for the second diastereoisomer. To a solution of 75 g of this hydroxytriazole in 7 ml of ethanol, 7.3 g of hydrogen chloride are added and the mixture is heated under reflux for 15 hours. Ethanol is evaporated in vacuo. The residue is taken up in ethyl acetate, the ethyl acetate extract is washed with aqueous sodium bicarbonate solution, washed with water and dried over sodium sulphate. Solvent separates. 68.6 g of a light brown oil are obtained. Yield: 96% of theory of compound of formula

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Of the compounds of the formula I according to the invention, those compounds in which R1 is R10 are preferred, with R10 being alkyl.

These compounds represent a group having particularly advantageous properties. In conjunction with these compounds, intermediate products of the formulas II, III, IUb, IIIc, 247095, 2728 IV and V in which R1 is R10, are preferred intermediates. Similar procedures by which these various compounds can be prepared according to the methods described above, but using R10 instead of R1, are particularly advantageous.

Even more preferably, in these various preferred compounds and processes for their production, R10 is lower alkyl of 1 to 4 carbon atoms, in particular methyl. The various procedures described above are used for various compounds of Formulas I to V, although R 1 is hydrogen even though R 1 is R 10. However, the preparation of compounds of formula III of the compounds of formulas IIIa and IIIb differs from whether R1 is hydrogen or R1 is R10. When R1 is hydrogen, then the reactant of formula (IIIb) is a compound of formula (IIIb) wherein Z 'is as defined above and two radicals R3 may be either (identical or different) , or they may optionally (and this variant is preferred) form a single divalent residue;

When R @ 1 is R @ 10, the reaction component of formula IIIb is a compound of formula IIIb2Z'-CH2 -CH-CH-OR30 R10 OR30 (IIIb2) wherein Z1 and R10 are as defined above, and R30 is as defined for R3 with the exception that the two residues R must be separate (and can not form any single divalent residue).

H. Wuest, J. Org. Chem. 34, 122 (1969) refers to compounds of the general formula IIIb, in which the two radicals R3 form a single trivalent residue. Data in Houben-Weyl Publishing, Vol. VI / 3, p. 204, 4th edition, 1965, relate to compounds IIIb2 in which the two radicals R30 are separated (each separately).

The present invention therefore also relates to compounds of the formula I wherein R2 is a halogen substituted alkyl group, especially a chlorine or fluorine-substituted alkyl group.

The present invention also relates to the use of various compounds of the formula I in which R 1 and R 2, as well as other substituents as defined above, are used to control the fungal attack of cereals.

In addition to the previously described application possibilities, the compounds of the invention have excellent biocidal efficacy with respect to many other different types of microorganisms which can be stated without the need for fungus, such as fungi of the genus:

Pullularia, for example Pullularia pullulans,

Cheatomium, for example, Chaetomium globosum, Aspergillus, e.g. Aspergillus niger and Coniophora, e.g. Coniophora puteana.

The compounds according to the invention enable their biocidal effects by combating microorganisms, the proliferation of which causes many problems in agriculture as well as in the industry. For these purposes, the compounds of the invention are particularly suitable for the protection of plants or industrial products such as wood, leather, paints, paper, oil, plastics and water-based water systems. In particular, it is well suited for the protection of lignocellulosic products, in particular building timber, furniture wood or sawn wood intended for a variety of uses, such as wood fencing, timber for pine and pine wood for railway sleepers.

The compounds of the present invention used in the treatment of the plant may optionally be mixed with one or several known biocidal agents such as pentachlorophenol, solvates, in particular the salts of copper, manganese, cobalt, chromium and zinc derived from inorganic or carboxylic acids (heptanoic, octanoic and naphthenic acids), organic tin complexes and mercaptobenzothiazoles. Example 10 below illustrates the biocidal activity of the compounds of the invention. Example 10 Microsuspension of the test substance is prepared to determine its fungicidal activity threshold. The following procedure is carried out: In a bead mill, each tube is filled with: 6 ml of an aqueous solution containing two softeners (4% polyglycol 400 and 0.4% Tween 80), 5 g glass beads with a diameter of 3 mm 3 g glass balls with a diameter of 5 mm.

This charge is stirred until homogeneous microsuspension is formed.

The given amount of microsphere thus obtained is added to the agar-containing medium