HU205904B - Fungicide compositions containing cyclopropane-carboxylic acid derivatives as active components and process for producing the active components - Google Patents

Abstract

Cyclopropane-carboxamides and -thiocarboxamides of the formulae (I) and (II) are new. Salts of (I) with inorganic and organic acids are also claimed. Z is gp.(i) R is H, alkyl, cycloalkyl, haloalkyl or othosubstd. alkyl, aryl, substd. aryl, heteroaryl, alkenyl, OR1, SR1 or -(CH2)nCO.OR1; n is 0-10; R1 is 1-4C alkyl; R2 is halogen, 1-3C alkoxy or 1-3C haloalkoxy; R3 is H or CH3; X is O or S; Y is O or S; or, when Y is O, Z can also be -SR9; R9 is haloalkyl; 1-8C alkyl; aryl opt. substd. by Cl, Br, F or NO2; aryl-(1-3C alkyl) opt. substd. by Cl, Br, F or NO2; alkanoyl, -SNR4R5; or NR4R5; R4 and R5 are each alkyl, alkanoyl, alkoxycarbonyl, benzyl or opt.substd. pyridyl. R6, R7 and R8 are each independently 1-6C alkyl. - N-(2-methoxy-5-pyridyl)- bis-(cyclopropane carbox)- imide; O-ethyl-N-(2-methoxy- 5-pyridyl-cyclopropane carboxyl) oxamate; N-(2-fluoro-1,1,2,2 tetrachloroethylthio) N-(2-methoxy-5-pyridyl)-cyc lopropane carboxamide are specifically claimed.

Description

(57) EXTRAS

The fungicidal compositions of the present invention comprise as active ingredient a pyridylcyclopropanecarboxylic acid derivative of formula (I) or a fungicidally acceptable organic or inorganic salt thereof, wherein

X

II

Z is -CR or -SR ₉ ,

R is hydrogen, C3-C5 cycloalkyl,

C 1-4 alkyl, C 1-4 alkoxy,

C 1-4 alkylthio, furanyl, phenyl substituted with halogen, or - (CH ₂ ) _n -C-OR 1;

II

A group of the formula O in which n is 0,1 or 2,

R 1 is C 1 -C 4 alkyl,

R ₉ is C 1 -C 5 alkyl, perhalogenated or substituted three times or five times with halogen, phenyl, mono- or di-substituted with chloro or nitro,

R ₂ is halogen or C 1-3 alkoxy,

R ₃ is hydrogen or methyl,

X is oxygen and Y is oxygen and contain a conventional inert carrier and / or diluent, optionally a surfactant and / or optionally an additive.

(I)

Scope of the description: 10 pages (including 1 page figure)

205 904 B

HU 205904 Β

FIELD OF THE INVENTION The present invention relates to fungicidal compositions containing pyridylcyclopropanecarboxylic acid derivatives and to the preparation of the active compounds.

Fungal infections of crops such as barley, rice, tomatoes, wheat, beans, roses, grapes and other agriculturally important crops cause severe losses and damage in agricultural products, both in quantity and quality. Therefore, there is a great need to prevent the occurrence of fungal infections and to prevent the development of fungi or to eradicate fungi. More effective spraying with commercially available fungicides would prevent the growth of fungi and inhibit the growth of fungi on agricultural crops. Therefore, it is desirable to develop fungicidal agents which kill fungi and eliminate their deleterious effects upon spraying after infection.

In the course of our work, we have discovered that certain novel pyridylcyclopropanecarboxylic acids are very effective as fungicidal agents, both for preventive use and for the control of fungal infections.

Reference is made to the following references for the state of the art of the present invention.

- No. 3,376,309. U.S. Pat.

In the formula

A is -NR ' ₂ or a non-aromatic branched hydrocarbon group; R' is the same or different, being hydrogen or a non-aromatic hydrocarbon group,

Z 'is oxygen or sulfur.

X 'is halogen or C 1-8 alkoxy,

Y 'is hydroxy, halogen, nitro, C 1-4 alkyl, C 1-8 alkoxy, amino, alkylamino, dialkylamino, amide, mercapto, alkylmercapto, cyano. , thiocyano or isothiocyano, n 'is 1,2 or 3, m' is zero, 1 or 2, however, the Y 'groups - if m is other than zero - and the X' groups are attached to a carbon atom of the pyridine ring which is not adjacent the site of attachment of the -NR'CZ'A group to the ring.

- No. 4,672,070. U.S. Pat.

In this formula

One of X 'and Y' being a methine group and the other being a nitrogen atom,

R 1 'represents a halogen atom, a group of the formula -WR ₃ ' or -NHCOOR 4 ', wherein

W is oxygen or sulfur,

R ₃ 'is lower alkyl, alkenyl or alkynyl, lower haloalkyl or lower alkoxy, lower alkyl, and

R ₄ 'is lower alkyl,

R ₂ 'is lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl or lower alkoxy (lower) alkyl other than methyl,

Z "is hydrogen, lower alkyl, alkenyl, alkynyl, lower alkoxycarbonyl (lower) alkyl, or a group of formula -COR ₅ " or -SR 4 "where R ₅ " is short lower alkyl, cyclo (lower) alkyl or phenyl and < 1 > is lower alkyl, phenyl, or lower alkoxycarbonyl;

"A" is oxygen or sulfur and

B is lower alkyl, alkenyl, lower cycloalkyl, phenyl or a group -W'R ₇ "where

W 'is oxygen or sulfur and

R ₇ 'is lower alkyl, alkenyl, alkynyl, halo-lower alkenyl or alkynyl, lower cycloalkyl, phenyl optionally substituted with at least one halogen or substituted lower alkyl.

The novel fungicidal pyridylcyclopropanecarboxylic acids correspond to formula ©. In this formula

R

II

Z is -CR or -SR ₉

R is hydrogen, C3-C5 cycloalkyl,

C 1-4 alkyl, C 1-4 alkoxy,

C1-C4 alkylthio, furanyl, halo-substituted phenyl, or - (CH3-, -C-OR3) wherein n is 0,1 or 2,

R 1 is C 1 -C 4 alkyl,

R ₉ is C 1 -C 5 alkyl, perhalogenated (or tri-or 5-substituted by halogen), phenyl, mono- or di-substituted by chloro or nitro,

R ₂ is halogen or C 1-3 alkoxy,

R ₃ is hydrogen or methyl,

X is O and Y is O.

Also effective as fungicidal agents are compounds of formula (I) which are acceptable as fungicides

Organic and inorganic salts thereof, which are also useful as preventive and curative agents in the control of fungal pests.

The term "fungicide" as used herein refers to a compound that inhibits fungal growth. The term "control / control" as used herein refers to the prevention, inhibition and control of fungal growth. The term "curative" refers to the use of a fungicidal agent after infection, which enables the fungus to be inhibited and prevents the development of harmful fungi in the crop.

The novel fungicidal active compounds, as mentioned above, are pyridylcyclopropanecarboxylic acid derivatives of the formula I and their organic or inorganic salts which are acceptable in the field of fungicides.

Compounds of formula I wherein Z is

X

II

-CR is generally prepared in a multi-step reaction. In the first step, 2-methoxy-5-aminopyridine is reacted with cyclopropanecarboxylic acid chloride in a polar solvent such as dichloromethane in a suitable reactor such as a glass vessel. It is desirable to use an acid acceptor such as pyridine in the reaction vessel. The reaction is usually carried out at room temperature but is carried out at a temperature in the range of -30 ° C to 80 ° C. The reaction is usually complete within 1-3 hours. The resulting intermediate is isolated by conventional means such as washing with an alkaline solution such as NaOH and water, drying over a conventional drying agent such as magnesium sulfate, washing with acetone and crystallization from hexane.

The resulting N- (2-methoxy-5-pyridyl) -cyclopropanecarboxamide is then reacted with an appropriately substituted acid chloride in the presence of NaH or another strong base in an inert solvent such as tetrahydrofuran (THF). Alternatively, N- (2-methoxy-5 pyridyl) -cyclopropanecarboxamide is reacted with a trialkylsilyl halide in which the alkyl moiety is a C 1-6 alkyl group in the presence of an acid acceptor such as triethylamine to silylate the amide, followed by reaction with an appropriately substituted acid chloride. The resulting silylamide is a novel compound having the formula (H). In this formula, R ₂ , R ₃ and Y are as defined above, while R 1, R ₇ and R 8 are C 1 -C 6 alkyl, preferably C 1 -C 4 alkyl, in particular methyl. This silylamide is then used to prepare the active ingredients of the fungicidal agents of the invention. An appropriately substituted 2-methoxy-5-pyridylcarboxamide may also be silylated and subsequently treated with cyclopropanecarboxylic acid chloride to give the desired product.

Compounds of formula I wherein Z is -SR ₉ can generally be prepared by a two step process. In the first step, 2-methoxy-5-aminopyridine is reacted with cyclopropanecarboxylic acid chloride in an inert solvent such as dichloromethane in a suitable reactor. It is expedient to use an acid acceptor such as pyridine in the reaction vessel. The reaction is usually carried out at room temperature but is carried out at a temperature in the range of -30 ° C to 80 ° C. The reaction is usually complete within 13 hours. The resulting product is isolated by conventional means, washed with an alkaline solution such as NaOH solution and water, dried with conventional drying agents such as magnesium sulfate and crystallized from hexane. The resulting N- (2-methoxy-5-pyridyl) -cyclopropanecarboxamide is then reacted with an appropriately substituted sulfenyl chloride in an inert solvent in the presence of a tertiary amine such as pyridine or triethylamine or the use of an inorganic base such as sodium hydride (NaH). next to. Salts of the various pyridylcyclopropanecarboxamides may be prepared in a conventional manner by reacting at least one mol of Lewis acid with a carboxamide. The reaction is preferably carried out in a solvent in which the carboxamide is soluble. The salt thus obtained is recovered from the reaction mixture by conventional means.

The pyridylcyclopropanecarboxamides prepared as described are bases. The proton-free nitrogen atom in the pyridine ring can be protonated with an acid such as an organic or inorganic acid. Suitable acids for this purpose are hydrochloric acid, nitric acid, hydrobromic acid, sulfuric acid, sulfamic acid and phosphoric acid, inorganic acids, and acetic acid, trifluoroacetic acid, benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, phenyl -phosphoric acid and organophosphoric acid from the organic acids. The salts are also fungicidal.

The invention is further illustrated by the following exemplary embodiments.

Example 1

Preparation of N- (2-methoxy-5-pyridyl) -cyclopropanecarboxamide

12.4 g (0.10 mol) of 5-amino-2-methoxypyridine and 10 ml of pyridine are mixed with 200 ml of dichloromethane in a reaction vessel. 9.1 (0.10 mol) cyclopropanecarboxylic acid chloride was then added over 2 minutes. The reaction is exothermic and the temperature rises to 34 ° C. The reaction mixture was allowed to stand at room temperature for one hour and then washed with 200 ml of 5% sodium hydroxide solution and 100 ml of water. The resulting organic phase was separated and dried over magnesium sulfate crystals. Crystals are formed, the mixture is filtered and washed with 300 ml of acetone and the filtrate is concentrated in vacuo. This gives a solid which is triturated with hexane and dried to give 16.7 g. The product was identified by IR and NMR spectroscopy.

130-131 ° C.

Example 2

Preparation of N- (methoxy-5-pyridyl) -bis (cyclopropanecarboxyl) imide

0.6 g of sodium hydride (NaH) and 50 ml of THF are mixed in a reaction vessel. thereafter

HU 205904 Β

3.6 g (0.02 mol) of the product of Example 1 are added with stirring to the THF / NaH mixture. The whole was stirred for 15 minutes and then cyclopropanecarboxylic acid chloride (1.82 ml) was added. The reaction is exothermic and the temperature rises to 30 ° C. Stirring was continued for one hour the reaction was washed three times with 200 ml of hexane and diluted with 150 to 150 ml of water and dried over MgSO ₄ and concentrated on a rotary evaporator. This gives a solid which is washed with pentane followed by 3: 10 v / v hexane / ether, filtered through florisil and evaporated. 0.4 g of a solid is thus obtained.

107-114 ° C. Nuclear magnetic resonance (NMR) analysis of the resulting material indicates that it is identical to the title compound. This compound is hereinafter designated as 1.

Example 3

0-ethyl-N- (2-methoxy-5-pyridyl cyclopropane) oxamate

In a 500 mL flask, 19.2 g (0.1 mol) of the compound prepared in Example 1 are mixed with 200 mL of benzene under a nitrogen atmosphere and then rapidly cooled to 5 ° C. Chloro-trimethylsilane (13 g, 0.12 mol) was then mixed in a addition funnel at 5 ° C with 12.3 g (0.12 mol) triethylamine in 25 ml benzene and cooled rapidly to 5 ° C. The addition funnel was added slowly in a 500 mL flask over 0.5 hour and the reaction mixture held at 5-10 ° C for an additional 0.5 hour. The reaction mixture was allowed to warm to room temperature, stirred for 2 hours and filtered. The filter cake was washed twice with 100 ml of benzene and dried on a rotary evaporator. The product was distilled at 118.0-120.0 ° C (0.66 x ^{10 3} Pa). In this way, a clear viscous material is obtained which solidifies on standing. The resulting material was identified as N- (2-methoxy-5-pyridyl) -cyclopropanecarboxy-N-trimethylsilylamide.

In a 100 mL round-bottomed flask, 2.64 g (0.01 mol) of the silylamide prepared as described above are mixed with 24 mL of dichloromethane and 1.25 mL (0.011 mol) of ethyl oxalyl chloride, and the whole is treated with 0.5 mL. stir for 1 hour until the reaction is complete. The reaction mixture was filtered through dicalite and the filter cake was stripped on a rotary evaporator, washed with 25 mL of hexane, filtered and dried in vacuo. This gave 2.39 g (81%) of a solid.

M.p .: 69-71 C. ^e

The product is identified by infrared, nuclear magnetic resonance and mass spectroscopy and is referred to hereinafter as Compound # 3. The composition of the solvent mixtures is characterized by volume ratios.

Example 4

N-trichloro-methylthio-N- (2-methoxy-5-pyridyl) cyclopropanecarboxamide

3.8 g (0.020 mol) of the compound prepared in Example 1 are dissolved in 25 ml of tetrahydrofuran in a 300 ml round-bottomed flask with stirring. NaH (0.60 g) was added with stirring. The reaction is exothermic and gas evolves. The reaction mixture was cooled to -60 ° C and 2.2 ml (0.020 mol) of trichloromethylsulfenyl chloride was added over 10 seconds and then allowed to warm to room temperature. After completion of the reaction, the reaction mixture was diluted with 150 mL of dichloromethane and washed three times with 150 150 ml water, dried over _MgSO4 and concentrated in vacuo. The resulting oil was dissolved in hexane, filtered, and evaporated to give 3.7 g of an oil which was identified as the title compound (Compound 14) by nuclear magnetic resonance spectroscopy.

Representative compounds of the compounds of formula I according to the invention and their properties are summarized in Table I below.

Table I Compounds of Formula I

X

II

A) Z is = CR

example Number R Ri r ₂ r ₃ X Y Physical properties n§ or op. C 1 (the group - -och ₃ H SHE SHE 107.0 to 114.0 2 H - -och ₃ H SHE SHE 1.5630 3 SHE II -CORj -c ₂ h ₅ -och ₃ H SHE SHE 69.0 to 71.0 4 SHE II -CHjCORj -c ₂ h ₅ -och ₃ H SHE SHE 95.0 to 98.0

HU 205 904 Β

example Number R Ri r ₂ rj X Y Physical properties ng or op. C 5 SHE II - (CH CORj -C ₂ H ₅ -och ₃ H SHE 0 semisolid 6 -sch ₃ - -och ₃ H SHE 0 137.0 to 138.0 7 -och ₃ - -och ₃ H SHE 0 120.0 to 122.0 8 -ch ₃ - -och ₃ H SHE 0 9 (b) group - -och ₃ H SHE 0 10 (c) group - -och ₃ H SHE 0 95.0 to 100.0 11 (the group - -och ₃ -ch ₃ SHE 0 12 the hydrochloride salt of compound 10 125 (decomposes) 13 (the group Cl H SHE 0 100.0 to 105.0

B) Z = -SR ₉ , Y = 0

Dry. number r ₉ RZ rj Rs R4 Physical properties Op. Or ng or Rf 14 -cci ₃ -och ₃ H - - Rf = 0.70 (thin layer chromatography 1) : 1: hexane / ethyl acetate) 15 -CC1 ₂ CC1 ₂ F -och ₃ H - - 16 -CC1 ₃ Cl H - - 60.0-65.0 ° C 17 -CC1 ₃ -och ₃ -ch ₃ - - 18 (d) group -och ₃ H - - 19 group (e) -och ₃ H 86.0-90.0 ° C 20 group (f) -och ₃ H - - 45.0-48.0 ° C

Example 5

Mole equivalent preventive spray estimation method Barley powdery mildew (BPM)

Northrup King Sunbar 401 varieties of barley seeds were sown in sandy-marl soils seven days before the test (12 seeds in 50 mm pots). The test compound was diluted with 50/50 acetone / water (0.004 M) to produce decreasing concentrations. The test solution was then sprayed onto barley plants by spraying.

After 20 hours, the experimental plants were transferred to an inoculation chamber equipped with a rotary vent. Barley seedlings, which were highly infected, were placed against the sporadic Erysiphe graminis fungus, a rotating vent, to release and disperse the spores. The vent was turned off after two minutes and the chamber was closed for another five minutes to allow the spores to settle. The inoculated plants were then placed in a greenhouse that provided automatic watering from below.

The results were determined seven days after inoculation and expressed as the percentage of damaged surface area relative to untreated control plants. The amount of drug that reduced infection by 90% (CO 90) was determined from the dose-dilution curve.

Leaf rust (LR)

Seven wheat grains of the Anza variety were sown in a sandy-marl soil in a 50 mm diameter vessel 12 days before the test. The test compound was diluted with 50/50 acetone / water (0.004 M) to produce decreasing concentrations. 12 ml of the solution was then sprayed onto the wheat plants with a spray gun.

A suspension of rust fungi spores of Puccinia recondita was prepared by releasing in vacuo spores of rust fungi and in a concentration of 10 ⁵ spores / ml deionized water, 0.4% Tween 20 [polyoxyethylene sorbitan mo5

A suspension was prepared with the addition of Nolaurate HU 205 904 B]. The plants were sprayed 24 hours after treatment to drip with the spore suspension and the sprayed plants were placed in a humid chamber. After 48 hours, the inoculated plants were then transferred to a greenhouse where bottom watering was possible.

The results were determined 10 days after inoculation and expressed as the percentage of reduction in the surface area affected compared to untreated control plants. The amount of drug that reduced infection by 90% (EC 90) was determined from the dose / dilution curves.

Budworm (BB)

Two petals of white rose petals were placed in a petri dish lined with wet filter paper. The test compound was diluted with 50/50 acetone / water (0.004 M) to produce decreasing concentrations. The petals are then sprayed with half a ml of such a solution and left to dry.

Subsequently, an inoculum was prepared by adding a 5 mm aliquot of two-week-old Botrytis cinerea cultured on Elliot's V-8 agar to 10 ml of sterile distilled water containing 0.5% by weight of grape juice. on each petal leaf. Petri dishes containing inoculated petal leaves were placed in sealed plastic containers where saturated air humidity was provided.

Results were determined four days after inoculation and expressed as percentage reduction in graft surface relative to acetone / aqueous control petals. The amount of drug that reduced infection by 90% (EC 90) was determined from dose / dilution curves.

The results are reported in Table H as an approximate EC 90 in ppm.

II. spreadsheet

compound Number BPM LR BB 1 > 750 > 750 30 2 > 750 > 750 70 3 200 600 30 4 750 750 30 5 750 > 750 80 6 - - 30 7 - - 250 8 - - 30 9 - - 20 10 - - 40 11 - - 80 12 - - 80 13 - - 750 14 200 200 70

compound Number BPM LR - BB 15 - - 30 16 - - 250 17 - - 750 18 - - 20 19 - - 80 20 - - 30

Example 6

Curative evaluation method

Leaf rust (LR)

Seven Anza-type wheat grains were seeded into a sandy-marl soil in a 50 mm diameter vessel 12 days before the test by suspending Puccinia recondita rye fungus cancers in vacuo to 10 ⁵ A suspension was added with the addition of Tween 20 (polyoxyethylene sorbitan monolaurate). The plants were then inoculated by spraying them with a spore suspension until dripping and placing the sprayed plants in a humidified chamber. After 48 hours, the plants were transferred to a greenhouse where bottom irrigation was possible.

The test compound was diluted with 50/50 acetone / water (0.075% w / w) to give decreasing concentrations. Fifty hours after inoculation, the plants were placed on rotatable plates and sprayed with a hand-held sprayer until the solution to be examined was dripped. Inoculation was calculated from the time the plants were placed in the humidity chamber.

The results were determined 10 days after inoculation and expressed as the percentage of the area of the lesion as compared to that of untreated control plants.

The results obtained are shown in ΠΙ. are summarized in Table.

III. spreadsheet

example Number LR 1 100 2 100 3 100 4 100 5 100 14 100

The fungicidal compositions of the present invention are particularly effective against both bud preventive and curative fungus-causing Botrytis fungi. To control ABotrytis and prevent infection, the compositions of the invention are applied to the foliage and have a more beneficial effect.

EN 205 904 B as known compositions. Fungicides against which the compositions of the present invention are particularly effective are Erysiphe graminis, Puccinia graminis and Piricularia oryzae.

The fungicidal compositions of the present invention can be used for both prophylaxis and treatment of fungal infections (both preventive and curative treatment) at different concentrations and by different methods. The fungicidal compositions of the present invention can be applied directly to the foliage of the crop and to the soil in which the crop is cultivated, or applied by irrigation in water to the roots of the crop or to the soil.

The compositions of the present invention are fungicidal compositions which are in practice mixtures containing an effective amount of a fungicidal active ingredient, excipient and excipients conventionally used in the preparation of pesticides, which promote, facilitate dispersion of the active ingredients and make them suitable for use in plant protection. the mode of administration of the compositions also greatly influences the efficacy of the active compounds in a given application.

The fungicidal compositions of the invention containing the active compounds of formula (I) may be formulated as wettable powders, emulsifiable concentrates, spray powders, or other known formulations, depending on the route of administration. Suitable applications for preventive and curative fungicidal use are wettable powders and emulsifiable concentrates.

These formulations may contain very little, e.g., from about 0.1% to about 95%, by weight, of the active ingredient. The effective amount of fungicide depends on the nature of the seeds or plants to be treated and the amount of active agent to be used is in the range of about 0.056 to 28 kg / ha, preferably 0.112 to 11.2 kg / ha.

Wettable powders are prepared in a finely divided form which is readily dispersible in water or other dispersants. The wettable powder is applied to the soil or plant as a dry powder or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller earth, kaolin chalk, silicon oxides and other readily wettable organic or inorganic diluents. Wettable powders are customarily formulated to contain from about 5 to about 95 weight percent of the active ingredient, and further include small amounts of wetting, dispersing, or emulsifying agents to facilitate wetting and dispersion.

Dry, free-flowing or water-dispersible granules are agglomerated wettable powders which are prepared by granulating in a cauldron or fluidized bed. The dry-flowing granules are applied to the soil or plant in the form of a dispersion in water or other liquid. These granules are dust-free and flow freely when dry and form homogeneous dispersions after dilution with water. Typical carriers for this purpose are dry, free-flowing granules, fuller earth, kaolin fets, silicas, and other readily wettable organic or inorganic diluents. Dry, free-flowing granules are usually formulated to contain from about 5% to about 95% by weight of an active ingredient and usually include small amounts of wetting, dispersing or emulsifying agents to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersants and contain the active ingredient together with a liquid or solid emulsifier, and may also contain liquid carriers such as xylene, heavy aromatic petroleum products, isophorone and other non-volatile solvents. For fungicidal use, these concentrates are dispersed in water or other liquid vehicle and usually sprayed onto the surface to be treated. The weight percentage of the actual active ingredient may vary depending on the mode of treatment and will typically contain from about 0.1% to about 95% by weight of the active ingredient in the fungicidal composition.

Typical wetting, dispersing or emulsifying agents used in agricultural compositions are, for example, alkyl or alkylaryl sulfonates and their sodium salts, polyhydroxy alcohols and other types of surfactants which are commercially available. Typically, the surfactant used will comprise from 0.1 to 15% by weight of the fungicidal composition.

Sprayable powders which flow freely are also suitable formulations for use in agriculture. These formulations contain the active ingredient in admixture with finely divided solids such as talc, chalk, flour and other organic or inorganic solids which act as dispersants and carriers for the active ingredient.

Pastes which are homogeneous suspensions of a finely divided solid in a liquid such as water or oil are used for special purposes. These formulations usually contain about 595% by weight of active ingredient and may also contain minor amounts of wetting, dispersing or emulsifying agents to aid dispersion. The pastes can be diluted as usual and applied to the affected surface.

Typical formulations

Oil Artist materials Crowd% Compound # 1 1 oil solvent-heavy aromatic petroleum product 99 100

HU 205 904 B

Emulsifiable Concentrate Ingredients crowd% Compound # 2 50 kerosene 45 emulsifier (mixture of long chain ethoxylated polyether with long chain sulfonate) 5 100

Emulsifying concentrate Ingredients crowd% Compound # 3 90 kerosene 5 emulsifier (mixture of long chain ethoxylated polyether with long chain sulfonate) 5 100

Sprayable Powders or Wettable Powders Ingredients crowd% crowd% crowd% Compound # 4 0.5 50.0 90.0 attapulgite chalk powder 93.5 44.0 4.0 Sodium lignin sulfonate 5.0 5.0 5.0 sodium dioctyl szulfoszukcl- sodium 1.0 1.0 1.0 100.0 100.0 100.0

Other formulations may also be contemplated for use as fungicides, such as solutions of the active ingredient in dispersants in which they are completely soluble in the desired concentration. Examples of such solvents are acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, such as aerosols, may also be used, in which the active compounds are in finely divided form and driven by evaporation of a low boiling point dispersant such as a propellant such as pheon.

The fungicidal compositions of the invention are applied to the plants in a conventional manner. Sprayable powders and liquid formulations may be applied to the affected surfaces by means of sprayers, hand or machine sprayers. The compositions of the present invention may also be applied by aerial spraying because they are effective in small amounts in the form of powder or spray.

Claims (5)

PATENT CLAIMS A process for preparing pyridylcyclopropanecarboxylic acid derivatives of the general formula (0) and their fungicidally acceptable organic or inorganic salts, wherein X il Z is -CR or -SR ₉ , R is hydrogen, C3-C5 cycloalkyl, C 1-4 alkyl, C 1-4 alkoxy, C1-C4 alkylthio, furanyl, halo-substituted phenyl, or - (CH3-C-OR3) wherein n is 0,1 or 2, R _t is C 1 -C 4 alkyl, R ₉ is C 1 -C 5 alkyl, perhalogenated or substituted three times or five times with halogen, phenyl, mono- or di-substituted with chloro or nitro, R ₂ is halogen or C 1-3 alkoxy, R ₃ is hydrogen or methyl, X is O and Y is O, characterized in that a 2-R2-5-aminopyridine benzofuran substituted hel _R3 mal cyclopropane carboxylic acid chloride in the presence, and N- _(2-R2 pyridin-5-yl) -cyclopropanecarboxamide intermediate a) for the preparation of a compound of the formula I in which Z is -C (X) R wherein R is as defined in the foregoing reaction, _t ) R-CO-Cl, or a2) a tri- (l) - with (C 6) alkylsilyl halide to form the silylamide of formula (Y) - in which Y, R ₂ and R ₃ are as defined in the preceding paragraph and R ₆ , R ₇ and R _g are C 1-6 alkyl and then reacting with R-CO-Cl, or b) reacting a compound of formula I wherein Z is-SR ₉ , wherein R ₉ is as defined herein, with R ₉ -S-Cl and optionally forming a salt. A process for the preparation of a compound of formula (I) according to claim 1, wherein: X II Z is -CR, R is (a), R ₂ is -OCH ₃ , X is oxygen, Y is oxygen and R _{3 is} hydrogen, wherein the appropriately substituted starting materials are used. A process according to claim 1 for the preparation of a compound of formula 0) wherein: X 0 II II Z is -CR, R is -COR 3, R ₁ - (¾), R ₂ is -OCH ₃ , X is oxygen, Y is oxygen, and R _{3 is} hydrogen, wherein the appropriately substituted starting materials are used. HU 205 904 B A process according to claim 1 for the preparation of compounds of formula I wherein Z is -SR ₉ , R ₉ is -CC ₁₂ CC ₁₂ F, R ₂ is -OCH ₃ , Y is O and R ₃ hydrogen, wherein the appropriately substituted starting materials are used. 5. A fungicidal composition, wherein the active ingredient is a compound according to any one of claims 1-3. A pyridylcyclopropanecarboxylic acid derivative of the formula (I) according to claim 1, or a fungicidally acceptable organic or inorganic salt thereof, wherein the substituents have the meaning given in the above-mentioned claims. 5 to 95% by weight, and 5 to 99.9% by weight of an inert carrier and / or diluent, optionally a surfactant and / or, if desired, other additives such as a dispersing or wetting agent. HU 205 904 B