CS208149B2 - A fungicidal agent and a plant growth regulating agent and a method for preparing an active ingredient thereof - Google Patents

Abstract

The invention relates to heterocyclic compounds, namely imidazole or 1,2,4-triazole compounds, a method of their production, compositions containing these compounds, a method of controlling fungal diseases in plants using them and a method of regulating plant growth using them. The compounds according to the invention are compounds of the general formula I H OH where X represents a group of the formula =N- or =CH-, Rj represents a C2-4 alkenyl group or a benzyl group, optionally substituted in the ring by halogens, trifluoromethyl-, nitro-, cyano-, C^ alkyl-, C1-4 alkoxy-, C,_^ alkylenedioxy-, amino-, hydroxy-, phenyl- or phenoxy groups or/and optionally substituted on the alpha carbon atom by a phenyl- or C,_^ alkyl group, R2 represents a propyl- or butyl group and Rj represents hydrogen or their addition salts with acids.

Description

The invention relates to heterocyclic compounds, namely imidazole or 1,2,4-triazole compounds, a method of their production, compositions containing these compounds, a method of controlling fungal diseases in plants using them, and a method of regulating plant growth using them.

The compounds of the invention are compounds of general formula I

H OH

where

X represents a group of the formula =N- or =CH-,

Rj represents a C ₂ -4 alkenyl group or a benzyl group, optionally substituted in the ring by halogens, trifluoromethyl, nitro, cyano, C^ alkyl, C _1-4 alkoxy, C,_^ alkylenedioxy, amino, hydroxy, phenyl or phenoxy groups and/or optionally substituted on the alpha carbon atom by a phenyl or C,_^ alkyl group,

R ₂ represents a propyl or butyl group and

Rj represents hydrogen or their acid addition salts.

The compounds of the invention contain chiral centers. The compounds of the invention are usually obtained in the form of racemic mixtures. These or other mixtures can, however, be separated into their individual isomers by methods known per se, for example by chromatography. In many cases, the compounds can be prepared stereospecifically in the form of a single diastereoisomer.

The benzyl group may contain more than one substituent in the ring. Examples of polysubstituted groups include groups containing up to the highest possible number of substituents (especially containing 1, 2 or 3 substituents), such as halogen atoms, especially chlorine atoms, and/or nitro, methyl or methoxy groups.

Suitable salts are salts with inorganic or organic acids, for example hydrochloric, nitric, sulfuric, toluenesulfonic, acetic or oxalic acid.

Specific examples of compounds of the invention are given in Table 1.

Table 1 R number. Rp R, Y Melting point ^{£ J} (or boiling point) (°C) .

1 ^X ) p-ci-c ₆ h ₄ ch ₂ - target.Bu H =N- 162 to 164 2 ^{c6H5CH2- ​ ​} target.Bu H =N- 91 to 93 3 pfc ₆ h ₄ ch ₂ - target. Bu H =N- 137 to Γ42 4 ptc ₆ h ₄ ch ₂ - target. Bu Ue =N- 152 to 153 JX) P-C1-C ₆ H ₄ CH _z - target.Bu H =N- 133 to 134 6 p-Cl-CgH ₄ CH ₂ - Bu target Me =N- 176 to 178 7 P-C1-C ₆ H ₄ CH ₂ - tert.Bu H =CH- 179 to 181 8 p-no ₂ -c ₆ h ₄ ch ₂ tert.Bu H =N- 157 to 159 9 3,4-diCl-CgHgCHg target.Bu H =N- 186 to 188 10 ofc ₆ h ₄ ch ₂ target.Bu H =N- 100 to 102 11 2,4-diCl-CgHgCH ₂ tert.Bu H =N- 140 to 143 12 ch ₂ ch=ch ₂ target.Bu H =N- (110 to 120/13.3 Pa) 13 m-CF ₃ -C ₆ H ₄ CH ₂ tert.Bu H =N- 71 to 73 14 3-NO ₂ -4-Cl-CgH ₃ CH ₂ target.Bu H =N- 177 to 178 15 o-Cl-CgH ₄ CH ₂ target.Bu H =N- 100 to 102 16 p-Br-C ₆ H ₄ CH ₂ tert.Bu H =N- 181 to 183 17 mF-CgH ₄ CH ₂ target. Bu H =N- 110 to 113 18 m-Br-CgH ₄ CH ₂ target. Bu H =N- 133 to 136 19 2,4-diCl-CgH ₃ CH ₂ iso-Pr H =N- 127 to 130 20 p-Cl-C ₆ H ₄ CH ₂ iso-Pr H =N- 100 to 103 21 ^times ) p-Cl-CgH ₄ CH ₂ tert.Bu H =N- 138 to 140

continuation of table 1

Number ^R , ^R 2 ^R 3 Ϊ Melting point (or boiling point) (°C) 22 pfc ₆ h ₄ ch ₂ iso-Pr H =N- 74 to 78 23 2,6-di-Cl-C ₆ H ₃ CH ₂ tert.Bu H =N- 151 to 154 24 2-C1, 4-F-CgH ₃ CH ₂ tert.Bu H =N- 137 to .40 25 ofc ₆ h ₄ ch ₂ iso-Pr H =N- .22 to 127 26 C ₆ C1 ₅ C ^h 2 target.Bu H =N- 173 to .75 27 ' 2,4,5-triCl-C ₆ H ₂ CH ₂ tert.Bu H =N- 188 .to 192 28 2,3,6-triCl-C ₆ H ₂ CH ₂ tert.Bu H =N- 168 to .72 29 4-F-2-Cl-C ₆ H ₃ CH ₂ target.Bu H =N- 150 to .53 30 2-F-4-Cl-C ₆ H ₃ CH ₂ tert.Bu Me =N- 153 to 154 31 2,4-diF-C ₆ H ₃ CH ₂ target.Bu H =N- 111 to 114 32 pFC ₆ H ₄ CH(Me)- target.Bu H =N- 197 to 201 33°) 2,4-diCl-C ₆ H ₃ CH(Me) target.Bu H =N- 145 to .47 34 p-Cl-C ₆ H ₄ CH(Me) target.Bu H =N- .82 to 185 35 2_F-4-Br-CgH ₃ CH ₂ tert.Bu H =N- 171 to .74 36 2,4-diBr-CgH ₃ CH ₂ tert.Bu H =N- 157 to 160 37 o-MeO-CgH ₄ CH ₂ tert.Bu H =N- .41 to 144 38 o-Me-CgH ₄ CH ₂ target.Bu H =N- 123 to .25 39 p-Me-CgH ₄ CH ₂ tert.Bu H =N- 144 to 146 40 2,5-diMe-CgH ₃ CH ₂ target.Bu H =N- 1.4 to 117 41 2,4-diCl-CgH ₃ CH ₂ tert.Bu H =CH- 191 to .93 42 _CgH5CH2 ^​ target. Bu H =CH- '167 to 169 43 2-Cl-4-F-CgH ₃ CH ₂ target. Bu H =CH- 162 to 164 44 0-Cl-CgH ₄ CH ₂ target.Bu H =CH- .67 to .69 45 oF-CgH ₄ CH ₂ target. Bu H =CH- 164 to 165 46 pF-CgH ₄ CH ₂ tert.Bu H =CH- 164 to 166 47 p-Br-C ₆ H ₄ CH ₂ tert.Bu H =CH- 199 to 201 48 oFC ₆ H ₄ CH ₂ tert.Bu Me =CH- 146 to .49 49 p-Br-CgH ₄ CH ₂ tert.Bu Me =CH- .88 to .92 50 m-Cl-C ₆ H ₄ CH ₂ tert.Bu H =N- 127 to .29 51 p-MeO-CgH ₄ CH ₂ tert.Bu H =N- 116 to .18 52 2-MeO-5-Br-CgH ₃ CH ₂ tert.Bu H =N- 184 to .86

continuation of table 1

number ^R 1 r ₂ ^R 3 Y Melting point (or boiling point) (°C) 53 _p -ci-c ₆ h ₄ ch ₂ tert.Bu H =N- 109 to 111 54 c ₆ h ₅ ch<c ₆ h ₅ ) tert.Bu H =N- 55 p-(c ₆ h ₅ ch ₂ o)-c ₆ h ₄ ch ₂ tert.Bu H =N- 56 pC ₆ ^H 5-C ₆ ^H 4CH ₂ target.Bu H =N- 158 to 160 57 _p -EtO-CgH ₄ CH ₂ target. Bu H =N- 116 to 117 58 O-EtO-CgH ₄ CH ₂ target.Bu H =N- 152 to 154 59 2-NO ₂ -4-F-CgH ₃ CH ₂ tert.Bu H =N- 60 2,4-diCl-CgH ₃ CH ₂ tert.Bu H =N- 197 to 199 61 p-NH ₂ -CgH ₄ CH ₂ tert.Bu H =N- 146 to 148 62 o-Br-CgH ₄ CH ₂ tert.Bu H =N- .13 to 114.5 63 o-CN-CgH ₄ CH ₂ target. Bu H =N- 132 to .33 64 3-Br-4-MeO-CgH ₃ CH ₂ target.Bu H =N- 163 65 p-ci-c ₆ h ₄ ch ₂ iso-Bu H =N- 45 to 50 66 2,4-diCl-CgH ₃ CH ₂ iso-Bu H =N- 119 to 123 67 0-I-CgH ₄ CH ₂ tert.Bu H =N- ,17 to 119. 68 m-N0 ₂ -CgH ₄ CH ₂ target. Bu H =N- 170 to .72 69 p-(t-Bu)-C gH ₄ CH ₂ tert.Bu H =N- 90 70 3-Cl-4-MeO-CgH ₃ CH ₂ tert.Bu H =N- .48 71 2-Cl-6-F-CgH ₃ CH ₂ tert.Bu H =N- 120 to 122 72 p-CF ₃ -CgH ₄ CH ₂ target. Bu H =N- .39 to 141 73 pFC ₆ H ₄ CH ₂ Iso-Bu H =N- 74 m-Me-CgH ₄ CH ₂ target. Bu H =N- 124 75 p-Et-CgH ₄ CH ₂ tert.Bu H =N- 89 76 2-Cl-4-F-CgH ₃ CH ₂ iso-Bu H =N- 94 to 97 77 ^{c6H5CH2 ​ ​} iso-Bu H =N- oil 78 o-cf ₃ -c ₆ h ₄ ch ₂ target. Bu H =N- 105 79 m-EtO-C gH ₄ CH ₂ tert.Bu H =N- .06 to .08 80 3,4-diMe-CgH ₃ CH ₂ target.Bu H =N- 141 81 p-(i-Pr)-CgH ₄ CH ₂ target. Bu H »N- 82 p-HO-CgH ₄ CH ₂ target. Bu H =N- 83 o-HO-CgH ₄ CH ₂ tert.Bu H =N- 2.4 to 2.7

continuation of table 1

Number ^R , r ₂ ^H 3 Y Melting point (or boiling point) (°C) 84 p-Me-C ₆ H ₄ CH ₂ iso-Bu H =N- 70 to 73 85 ofc ₆ h ₄ ch ₂ iso-Bu H =N- 64 to 68

Notes: Compound No. 53 is in the acetate form.

^x ) Compounds 1 and 5 are diastereoisomers. X-ray analysis shows that in compound 1 the carbon bearing the triazole ring is in the S-configuration and the carbon bearing the hydroxy group is in the R-configuration. In compound 5 the carbon bearing the triazole ring is in the S-configuration and the carbon bearing the hydroxy group is in the S-configuration.

⁺ ) This compound is in the form of a complex with copper with the predicted structure

°) Nuclear magnetic resonance shows that compounds 22, 24, 25 and 33 are in the form of a mixture of stereoisomers. The weight ratio of the two isomers in each case is as follows.

Compound Weight ratio 22 9:1 24 7:1 25 4:1 33 1.5:1

The acetate of compound 1 was also prepared. This ester (compound 53), in its impure state, has a melting point of 125-128°C.

Compounds of formula I wherein R3 represents hydrogen or their salts may be prepared by reduction of a compound of formula II.

H

N ^: where

Y, R1 and Rg are as defined above, or salts thereof, preferably at a temperature of 0 to 100°C and for a period of 1 to 12 hours. Suitable reducing agents are sodium borohydride, lithium aluminium hydride or aluminium isopropoxide. If desired, catalytic hydrogenation using a suitable metal catalyst may be used. When the compound of formula II is a sterically hindered ketone, a Grignard reagent, for example a butylmagnesium halide (for example a bromide or iodide) may be used as the reducing agent. When reagents such as butylmagnesium halide are used, individual diastereoisomers are often obtained.

The reduction can be carried out by dissolving the reactants in a solvent such as diethyl ether or tetrahydrofuran (in the case of reduction with lithium aluminum hydride) or in a solvent containing hydroxyl groups (in the case of reduction with sodium borohydride). The reaction temperature depends on the reactants and solvent, but usually the reaction mixture is refluxed. After the reaction, the product can be isolated by extraction into a common solvent after acidification with dilute mineral acid. After removal of the solvent under vacuum, the product can be allowed to crystallize from the common solvent.

Compounds of formula I, wherein Rj represents a methyl or alkenyl group, or salts thereof, can be prepared by reacting a compound of formula II or a salt thereof with an appropriate Grignard reagent, for example a methyl or alkenyl magnesium halide, such as methyl or allyl magnesium bromide or iodide, preferably at 15 to 80°C for 6 to 12 hours. This reaction can be carried out by methods known per se.

The starting compound of general formula II can be prepared by reacting imidazole or 1,2,4-triazole or its salt with an alpha-haloketone of general formula III r ₂ c-ch-x (III) where

X represents halogen, preferably bromine or chlorine, and

R 1 and R ₂ have the meanings given above.

This process can be carried out by heating the reactants together, optionally in the presence of a solvent or diluent. Preferably, the process is carried out in the presence of a solvent.

Suitable solvents are those not containing hydroxyl groups such as acetonitrile, dimethylformamide, dimethylsulfoxide, sulfolane and tetrahydrofuran. Solvents containing hydroxyl groups such as methanol and ethanol may be used under certain conditions, provided that the presence of hydroxyl groups does not interfere with the course of the reaction. The process may be carried out in the presence of a base such as sodium hydride, sodium ethoxide, excess imidazole or triazole or an alkali metal carbonate (e.g. potassium carbonate). The reaction temperature depends on the choice of reagents, solvents and base, but usually the reaction mixture is heated to reflux.

Typically, the reaction components are first dissolved in a solvent and the product is isolated after the reaction has occurred by removing the reaction solvent in vacuo. Unreacted imidazole or triazole can be removed by extracting the product with a suitable solvent, which is then washed with water. If desired, crystallization or other purification can then optionally be carried out.

208.49

Alpha-haloketones can be prepared by known methods.

Compounds of formula II or their salts can also be prepared by alkenylation, alkynylation or aralkylation of a compound of formula IV.

where

Y and Rg are as defined above.

Further details of this reaction can be found in German published application number 2 6.0 022.

Salts, metal complexes, ethers and esters of compounds of formula I can be prepared from compounds of formula I by known methods. For example, complexes can be prepared by reacting the uncomplexed compound with a metal salt in a suitable solvent.

The compounds are effective fungicides, especially against the following diseases:

Piricularia oryzae on rice,

Puccinia recondita, Puccinia striiformis and other rusts on wheat,

Fuccinia hordei, Puccinia striiformis and other rusts on barley and rusts on other host plants, such as coffee, apple, vegetables and ornamentals,

Plasmopara viticola on grapevines,

Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildews on various host plants, such as Sphaerotheca fullginea on cucumbers, Podosphaera leucotricha on apple trees and Uncinula necator on grapevines,

Cercospora arachldicola on groundnut and other Cercospora species, for example on sugarcane, banana and soybean,

Botrytis cinerea (gray mold) on tomatoes, strawberries, grapevines and other host plants,

Phytophthora infestans (Potato late blight) on tomatoes and

Venturia inaqualis (scab) on apple trees.

Some of the compounds of the invention also have a broad spectrum of antifungal activity in vitro. They are active against various fruit diseases occurring on fruit after harvest (e.g. Penicillium digatatum and Penicillium italicum on oranges, Gloeosporium musaru on bananas. Some of the compounds are effective as seed dressings against Pusarium spp., Septoria spp., Tilletia spp. (seed-borne disease of wheat), Ustilago app., and Pyrenophora spp. on cereals.

The compounds of the invention can also be used as industrial (as opposed to agricultural) fungicides, for example as fungicides in paints.

The compounds of the invention also have a plant growth regulating effect.

The plant growth regulating effect of the compounds is manifested, for example, as an effect causing stunting of the vegetative growth of monocotyledonous or dicotyledonous herbs or woody plants. Such stunting may be useful, for example, in cereals or soybeans, where stem shortening may reduce the risk of lodging. Compounds causing stunting may also be useful in modifying the growth of sugarcane, since they increase the sugar concentration in the cane at harvest. Stunting in groundnuts may aid in the harvest. Retardation of grass growth may aid in the maintenance of turfgrasses. Examples of suitable grasses include Stenotaphrum secundatum, Cynosurus cristatus, Lolium multiflorum and Lolium perenne, Agrostis tenuis, Cynodon dactylon, Dactylis glomerata, Festuca spp. (e.g. Festuca rubra) and Poa spp. (e.g. Foa pratense). At least some of the compounds of the invention have an effect on the stunting of grasses without significant phytotoxic effects and without detrimentally affecting the appearance (e.g. grass color), which makes them attractive for use in the maintenance of ornamental lawns and grassy borders of flower beds, etc. The compounds can also cause stunting of weedy plant species present in these grasses, such as Cyperus spp. and dicotyledonous weeds. The compounds of the invention can also retard the growth of vegetation that is not cultivated, such as weedy plants or natural plant cover, which can be used in the maintenance of plantations or fields. The regulatory effect on plants can be manifested by an increase in yield.

Other regulatory effects of the compounds on plant growth include changing the leaf angle of plants and promoting tillering in monocots. Changing the leaf angle may be useful, for example, in changing the leaf orientation of potatoes, which allows more light to reach the growing plants, resulting in increased photosynthesis and tuber weight. Increasing tillering in monocots (e.g. rice) may increase the number of flowering shoots per unit area, resulting in increased overall grain yield in these crops. Treatment of plants with compounds of the invention may result in the leaves of the plants becoming a darker shade of green.

The compounds of the invention can also inhibit sugar beet flowering, which results in increased sugar yield. They can also reduce the size of sugar beet tubers without significantly reducing sugar yield, which allows for increased seeding density.

In regulating plant growth with the compounds of the invention, the amount of compound used depends on a number of factors, for example on the specific compound selected and on the type of plant whose growth is to be regulated. Generally, however, 0.1 to 15, preferably 0.1 to 5 kg of compound per hectare is applied. However, for certain plants, even applications in this range may have undesirable phytotoxic effects. In order to determine the optimum amount of a specific compound for each specific purpose for which the compound is to be used, it is often necessary to carry out routine tests.

The compounds of the invention also have algicidal, antibacterial and antiviral effects and herbicidal effects.

For controlling fungi or regulating plant growth, the compounds may be used as such, but they are conveniently used in the form of compositions. The invention provides a fungicidal composition and a plant growth regulating composition, characterized in that it comprises a compound of the general formula I as defined above or a salt, complex, ether or ester thereof and a carrier or diluent.

The invention also provides a method for controlling fungal diseases in plants, which comprises applying the above-defined compound according to the invention, its salt, complex, ether or ester, to the plants, the seeds of the plant or the place where the plants or seeds are located.

The invention also provides a method of controlling plants, characterized in that the compound of the invention, a salt, complex, ether or ester thereof, as defined above, is applied to plants, plant seeds or the location where the plants or seeds are located.

The compounds, salts, complexes, ethers and esters can be applied in various ways, for example they can be applied as such or in the form of compositions, either directly to the leaves of the plants, or also directly to the shrubs and trees or to the seeds or to the environment in which the plants, shrubs or trees grow or are to be grown. The compounds or compositions can be applied as sprays, dusts or as creams or pastes or can be applied in the form of vapors. They can be applied to any part of the plant, shrub or tree, for example to the leaves, stems, branches or roots or to the soil surrounding the roots or to the seeds before sowing.

The term "plant" includes both seedlings and shrubs and trees. The fungicidal effect according to the invention is preventive, protective, prophylactic or eradicating.

The compounds of the invention are preferably used in the form of compositions for agricultural and horticultural purposes. The type of composition used depends on the specific intended purpose.

The compositions may be in the form of powders or granules containing the active ingredient and a solid diluent or carrier, for example kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesium hydroxide, sphagnum, gypsum, Hewitt clay, diatomaceous earth and kaolin. The compositions for seed dressing may contain, for example, a substance to increase the adhesion of the composition to the seeds (for example, mineral oil). Alternatively, the active ingredient may be formulated into a composition for seed dressing with the aid of an organic solvent (for example, N-methylpyrrolidone or dimethylformamide).

The compositions may also be in the form of dispersible powders, granules or grains containing a wetting agent to facilitate the dispersion of the powders or grains in liquids. These compositions may also contain fillers and suspending agents.

Aqueous dispersions or emulsions can also be prepared by dissolving the active ingredient or ingredients in an organic solvent, optionally containing one or more wetting agents, dispersants or emulsifiers, and then adding water, optionally containing wetting agents, dispersants or emulsifiers, to the mixture. Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes, trichloroethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and glycol ethers (for example 2-ethoxyethanol and 2-butoxyethanol).

Compositions to be used as sprays may also be in the form of aerosols, in which the composition is maintained in a container under pressure in the presence of a propellant gas, for example fluorotrichloromethane or difluorodichloromethane.

The compounds can also be mixed in a dry state with a pyrotechnic mixture to form compositions suitable for generating smoke containing the compounds in enclosed spaces.

Alternatively, the compounds may be used in microencapsulated form.

Different compositions can be better adapted to different uses by adding suitable additives, for example additives to improve the distribution, adhesion or rain resistance of the compounds on the treated surfaces.

The compounds can be used in the form of mixtures with fertilizers (for example fertilizers containing nitrogen, potassium or phosphorus). Preference is given to such compositions which contain only fertilizer granules into which the compound according to the invention is introduced, for example by coating. Such granules conveniently contain up to 25% by weight of the compound. The scope of the invention therefore also includes fertilizers containing a compound of the general formula I or a salt, metal complex, ether or ester thereof.

The compositions may also be in the form of liquid preparations, which are used as dips or sprays. Such compositions are usually aqueous dispersions or emulsions,

containing the active ingredient in the presence of one or more wetting agents, dispersants, emulsifiers or suspending agents. These agents may be cationic, anionic or nonionic agents. Suitable cationic agents are quaternary aminium compounds, for example cetyltrimethylammonium bromide.

Suitable anionic agents are soaps, salts of aliphatic monoesters of sulfuric acid (for example, sodium lauryl sulfate) and salts of sulfonated aromatic compounds (for example, sodium dodecylbenzene sulfonate, sodium lignosulfonate, calcium or ammonium, the corresponding butyl naphthalene sulfonate and a mixture of sodium diisopropyl and triisopropyl naphthalene sulfonates).

Suitable nonionic agents are condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol or with alkylphenols such as octyl or nonylphenol and octylcresol. Other nonionic agents are partial esters derived from long-chain fatty acids and hexyl anhydrides, condensation products of these partial esters with ethylene oxide and lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose) and gums of vegetable origin (for example gum arabic and tragacanth).

Compositions intended for use in the form of aqueous dispersions or emulsions are usually supplied in the form of concentrates containing a high proportion of the active compound or compounds, the concentrate then being diluted with water before use. These concentrates often withstand long-term storage and after such storage they can be diluted with water to form aqueous compositions which are homogeneous for a period of time sufficient to enable them to be applied using conventional spraying equipment. The concentrates conveniently contain up to 95%, and preferably 10 to 25%, for example 25 to 60% by weight of the active ingredient or ingredients. After dilution with water to aqueous compositions, the resulting compositions may contain varying amounts of the active ingredient or ingredients, depending on the intended purpose of use. However, aqueous compositions containing 0.0005 or 0.01 to 10% by weight of the active ingredient or ingredients are usually used.

The compositions of the invention may also contain other compounds having a biological effect (for example other growth stimulants such as gibberellins (for example GAj, GA ₄ or GAj), auxins (for example indoleacetic or indolebutyric acid) and cytokinins (for example kinetin, diphenylurea, benzimidazole and benzyladenine) and other compounds with complementary fungicidal or insecticidal effect and stabilizers, for example epoxide compounds (for example epichlorohydrin). Other fungicidal compounds may be compounds) which are capable of controlling ear diseases in cereals, for example wheat, such as Septoria, Giberella, Helminthsporum and black mold. Examples of such compounds include benomyl, carbendazole (BCM) and captafol.

Alternatively, such a compound may be a compound capable of controlling seed-borne or soil-borne diseases. Examples of such compounds include Uaneb and Captan.

The following examples serve to further illustrate the invention.

The products identified by company names in the examples have this structure:

Tween 20: surfactant based on the condensate of sorbitan monolaureth and ethylene oxide

Aerosol OT: sodium dioctyl sulfosuccinate

Polyfon H: sodium lignin sulfonate

Diapersol T: a mixture of sodium sulfate and formaldehyde condensate with sodium salt of naphthalenesulfonic acid.

Example

1-tert-butyl-2-(1,2,4-triazol-1-yl)-2-p-chlorobenzylethanol (compound 1)

Stage 1

1,2,4-Triazole (33.4 g) and sodium ethoxide (sodium hydroxide /11.6 g/ and ethanol /250 ml/) were heated under reflux for 1 hour. Brompinacolone (87 g) was added to the solution at boiling point and heating was continued for another 2 hours. The mixture was then cooled to ambient temperature, the precipitated sodium bromide was filtered off and the solvent was removed in vacuo. The residue was extracted with chloroform (100 ml). The solution was washed with water (4 x 15 ml), dried (sodium sulfate) and filtered. Petroleum ether (b.p. 60-80 °C) was added and the solution was concentrated. Alpha-1,2,4-triazol-4-yl-pinacolone was obtained, melting point 176 °C. Further concentration of the solution yields alpha-1,2,4-triazol-1-ylpinacolone with a melting point of 63-65°C.

Grade II

Alpha-1,2,4-triazol-1-yl-pinacolone (3.3 g) in dimethylformamide (20 ml) was added dropwise to a suspension of sodium hydride (0.48 g, 100%) in dimethylformamide (10 ml) with stirring at room temperature. After stirring for 2 hours, p-chlorobenzyl chloride (3.2 g) in dimethylformamide (2-3 ml) was added dropwise and the reaction mixture was maintained at 5-10 °C for 2 hours. The solvent was removed in vacuo and water was added to the residue. The aqueous solution was extracted with methylene chloride, the organic layer was washed with water and dried (magnesium sulfate) and the solvent was evaporated. Recrystallization of the yellow solid gave alpha-p-chlorobenzyl-alpha-1,2,4-triazol-1-yl-pinacolone, mp 122-123 °C as a white crystalline solid.

Grade III

To a solution of the product from Step II' (2.0 g) in methanol (20 ml) was added sodium borohydride (0.26 g) portionwise. The reaction mixture was refluxed for 1 hour. The solvent was evaporated in vacuo and hydrochloric acid (1 N, 40 ml) was added to the residue. The white precipitate was filtered off, washed with water, dried and recrystallized from aqueous ethanol. The title compound was obtained as a white crystalline solid, mp 162-164 °C.

The starting material for stage 111 can be obtained by the following alternative method:

Grade I

4-Chlorobenzaldehyde (140.5 g) and pinacolone (100 g) in industrial grade methanol (IMS) (200 ml) were added dropwise over 25 minutes to sodium hydroxide (40 g) in water (70 ml) and IMS (150 ml) while the mixture was kept at 25 °C by external cooling with a mixture of water and ice. The resulting creamy suspension was stirred at 18 °C for a further 3 hours and then filtered. The residue was washed with aqueous IMS and dried. 4-chlorobenzaldehyde pinacolone, mp 83-84 °C, was obtained. The filtrate was concentrated under reduced pressure and allowed to stand for 2 days to obtain more chalcone product (mp 83-84 °C).

Grade II

Chalcone (22.25 g) is suspended in ethyl acetate (125 ml) and Raney nickel (6 g) washed with ethyl acetate (4 x 15 ml) is added to the suspension. The apparatus is evacuated with a water pump and hydrogen is brought to atmospheric pressure. The mixture is then shaken vigorously at room temperature. After 14.5 hours, the hydrogenation is stopped when the gas consumption is 2303 ml. The catalyst is filtered off, taking care not to leave the residue dry, and the filtrate is concentrated in vacuo.

Crude 4-chlorobenzylpinacolone is obtained.

Grade IXI

A solution of 4-chlorobenzylpinacolone (11.2 g) in tetrachloroethane (80 ml) was cooled to about 5 °C and at this temperature bromine (8 g) in tetrachloromethane (20 ml) was added dropwise over a period of 2 hours. Care was taken to ensure that a minimum amount of free bromine was present in the reaction mixture to avoid the formation of intermediates. Solution 3e was washed with saturated aqueous sodium bicarbonate solution and then with water, dried (magnesium sulfate) and concentrated in vacuo to give a white crystalline solid, which was crude 1-(4-chlorophenyl)-2-bromo-4,4-dimethylpentan-3-one, m.p. 48-50 °C.

Stage IV

The product (0.69 g) from Step III and 1,2,4-triazole (0.17 g) were mixed with potassium carbonate (0.52 g) in acetone (10 ml) and the mixture was refluxed for 2 hours. After cooling to room temperature, the inorganic material was filtered off and the filtrate was concentrated in vacuo to give crude alpha-p-chlorobenzyl-alpha-1,2,4-triazol-1-ylpinacolone.

Example 2

1-tert-butyl-2-(1,2,4-triazol-1-yl)-2-benzylethanol (compound 2)

Grade I

Pinacolone (10 g) in dry diethyl ether (30 ml) was slowly added to a suspension of sodium amide (4.1 g) in dry diethyl ether (15 ml). The mixture was stirred overnight at room temperature and then stirred and refluxed for 16 hours (at which time the mixture was orange in color). Benzyl chloride (13.2 g) was then added dropwise and the mixture was refluxed for 24 hours. Water (100 ml) was added, the ether layer was separated and washed with water, dilute hydrochloric acid and again with water and then dried (sodium sulfate). The ether was evaporated under reduced pressure and the residue was distilled. Alpha-benzylpinacolone was obtained, boiling at 78-80°C/8 Pa.

Grade II

Bromine (1.4 ml) was added dropwise to alpha-benzylpinacolone (5.2 g) in diethyl ether (80 ml) at about 10°C. The solution was then stirred for 1 hour at room temperature and the ether was evaporated under vacuum. The resulting red liquid was distilled in a flask. A slightly colored liquid was obtained, which was alpha-bromo-alpha-benzylpinacolone with a boiling point of 100/13.3 Pa.

Grade III

1,2,4-Triazole (0.28 g) in dimethylformamide (5 ml) was added dropwise to a suspension of sodium hydride (0.1 g 100%) in dimethylformamide (2 ml). The reaction mixture was stirred for 2 hours and then alpha-bromo-alpha-benzylpinacolone (1.0 g) in dimethylformamide (5 ml) was added. The reaction mixture was stirred overnight at room temperature and then poured into water (75 ml). Alpha-(1,2,4-triazol-1-yl)-alpha-benzylpinacolone was obtained as a white crystalline solid, melting at 69-71 °C.

Stage IV

To alpha-1,2,4-triazol-1-yl-alpha-benzylpinacolone (2.0 g) in methanol (20 ml) was added sodium borohydride (0.26 g) portionwise. The mixture was refluxed for 1 hour. The solvent was removed in vacuo and hydrochloric acid (1 N, 40 ml) was added to the residue. The white precipitate was filtered off, washed with water, dried and crystallized from aqueous ethanol to give the title compound as a white crystalline solid.

Example 3

1-(1,2,4-triazol-1-yl)-1-beta-fluorobenzyl-2-tert.butylpropan-2-ol (compound 4)

An ethereal solution of methylmagnesium iodide (prepared by reacting methyl iodide (6.2 g) with magnesium (1.1 g) in dry diethyl ether) was treated dropwise with alpha-1,2,4-triazol-1-yl-alpha-p-fluorobenzylpinacolone (4.0 g) in dry diethyl ether (30 ml). The mixture was then refluxed for 1 hour, cooled and treated with 10% sulfuric acid (20 ml). The insoluble material was filtered off, washed with dilute hydrochloric acid and water and then dried. After crystallization from aqueous ethanol, the title compound was obtained.

Example 4

1-tert-butyl-2-(1,2,4-triazol-1-yl)-2-p-chlorobenzylethanol (compound 5)

A solution of butylmagnesium bromide (prepared from butyl bromide (5.63 g) and magnesium (1.0 g) in dry diethyl ether) was treated dropwise with alpha-(1,2,4-triazol-1-yl)-alpha-p-chlorobenzyl chloride (4.0 g) in diethyl ether (30 ml) and the mixture was refluxed for 1 hour. The reaction mixture was treated with dilute sulfuric acid (20 ml). The ether layer was separated, washed with water and dried over sodium sulfate. After removal of the solvent in vacuo, a white solid was obtained, which was recrystallized from a mixture of diethyl ether and gasoline (60 to 80 degrees Celsius). The title compound was obtained.

Example 5

Copper complex of compound 1 (compound 21)

Copper chloride (0.9 g, 0.005 mol) dissolved in water (4 ml) was added dropwise to a solution of compound 1 (2.9 g, 0.01 mol) in ethanol (60 ml) and the resulting green solution was stirred for half an hour. The solvent volume was reduced by about 30 ml and water (30 ml) was added. A green oil was separated. The aqueous phase was decanted and the organic phase was stirred with isopropyl alcohol (50 ml) for 30 minutes. The resulting green solid was then filtered off and dried. After recrystallization from ethanol/water mixtures, the copper complex (1.6 g) was obtained.

Example 6

In this example, several compositions of the invention are shown.

1. Dispersible powder

2. Emulsifiable concentrate compound 1 aerosol OT Polyfon H kaolin %wt %wt 5 %wt 43 %wt compound 1 dodecylbenzenesulfonate amine 2-n-butoxyethanol

100 g/liter 400 g/liter up to 1 liter

3. Aqueous suspension

4. Dust

compound 1 250 g/liter compound 1 5% by weight Polyphone H 25 g/liter kaolin 95% by weight Bentonite 15 polysaccharide 0.75 water up to 1 liter and

5. Granulate 6. Solution in solvent compound 1 5% by weight compound 1 200 g/liter starch 5% by weight dimethylformamide up to 1 liter kaolin 90% by weight

Example 7

Compounds are tested against various foliar fungal diseases of plants. This testing technique is used.

Plants are grown in John Innes potting compost (No. 1 or Seed as appropriate) in 4 cm diameter mini-pots. A layer of fine sand is placed at the bottom of the pots to facilitate uptake of the test compound by the roots.

The test compounds are processed into a buS formulation by grinding them in a ball mill with aqueous Dispersol T or dissolving them in an acetone/ethanol mixture and diluting the resulting solution to the desired concentration just before use. For foliar diseases, a suspension with a concentration of 100 ppm active substance is sprayed onto the leaves and this suspension is introduced to the roots of the same plant through the soil. (The spray is applied to maximum retention and the root watering is done to a final concentration corresponding to about 40 ppm active substance, based on dry soil. Before spraying on cereals, Tween 20 is added to the formulation to a final concentration of 0.1%.

In most tests, the test compound is applied to the soil (roots) and to the leaves (spray) one or two days before inoculation of the plants with the diseases. The exception is the test with Erysiphe graminis, in which the plants are inoculated 24 hours before treatment. After inoculation, the plants are placed in a suitable environment that allows the infection to occur and then incubated until the disease can be evaluated. The period between inoculation and evaluation varies from 4 to 14 days depending on the disease and the environment.

Disease suppression is characterized by the following stages:

= no disease 3 = 0 to 5% = 6 to 25% = 26 to 60% more than 60%.

The results are shown in Table 2.

,5

Table 2

Compound number Poohinia recondita on wheat Erysiphe graminis on barley Plricularia oryzae on rice Plasmopara viticola on vine Phytophthora infestans on tomatoes Botrytis cinerea on tomatoes 1 4 4 3 3 0 3 2 4 4 2 0 0 3 3 4 4 3 0 0 2 4 4 4 3 0 0 0 5 4 4 1 4 0 3 6 2 4 3 0 2 7 4 4 0 0 0 4 8 4 4 0 1 0 2 9 4 4 0 0 0 1 10 4 4 3 3 0 2 11 4 4 1 1 0 3 12 4 4 1 3 0 0 13 4 4 2 0 0 0 14 2 4 0 0 2 15 4 4 3 0 3 16 4 3 3 0 0 4 17 3 3 4 0 18 3 4 0 0 2 19 1 0 0 0 0 3 20 3 3 1 0 3 1 21 3 4 3 4 3 22 4 4 1 0 0 0 23 4 4 3 0 0 2 24 4 3 0 0 0 2 25 3 4 1 0 0 1 26 1 4 2 0 0 1 27 1 4 0 0 0 3 28 3 0 1 0 0 3 29 4 3 1 0 3 3 30 2 3 0 0 3 2 31 3 3 3 4 0 2 32 4 4 1 1 0 3 33 4 4 0 0 0 2 34 - 4 4 0 0 0 3 35 4 3 0 0 0 2 36 4 4 1 0 0 1 37 4 4 2 0 0 3 38 0 0 0 4 39 0 0 4 40 4 4 1 0 0 0 41 2 4 1 0 0 2 42 0 0 0 0 43 1 0 1 0 44 4 1 0 1 1 45 4 0 0 0 3 46 3 4 1 0 0 2 47 3 4 0 0 0 3 48 1 4 0 3 49 3 4 0 0 4 50 4 4 0 0 1 3

208.49 continuation of table 2 .6

Compound number Puccinia recondita on wheat Erysiphe graminis on barley Piricularia oryzae on rice Plasmopara viticola on vine Phytophthora infestane on tomatoes Botrytis cinerea on tomatoes 51 4 4 3 0 2 4 52 4 4 1 0 2 53 3 4 1 0 2 2 54 2 4 0 0 0 0 55 3 4 0 0 2 3 56 1 4 2 0 0 3 57 4 1 3 0 0 3 58 3 4 1 0 4 3 59 4 4 3 0 3 2 60 2 4 2 0 0 61 3 4 0 0 3 1 62 4 4 3 0 0 63 4 4 3 1 0 64 3 4 1 0 0 0 65 4 4 3 0 0 2 66 4 4 1 0 0 3 67 4 4 0 0 0 ' 2 68 4 4 0 1 0 3 69 0 4 1 0 0 1 70 4 4 1 1 0 0 71 4 4 3 0 3 2 72 3 3 3 0 0 3 73 4 3 2 0 0 0 74 4 4 3 0 3 75 1 4 3 4 0 3 76 4 4 2 1 3 77 4 4 2 0 1 78 4 4 0 3 0 0 79 0 4 0 0 2 ’ 3 80 3 4 0 0 0 4

Example 8

This example illustrates the protective effect of the compounds (at a concentration of 50 ppm) against various fungal diseases of fruit.

The efficacy of the compounds against apple powdery mildew (Podosphaera leucotricha) and grape powdery mildew (Uncinula necator) is determined. The tests are carried out as follows:

Small Jonathan apple and grapevine plants about 3 weeks old, grown in small pots of 3 cm diameter, are first sprayed with a solution or suspension of the test compound, the coating is allowed to dry overnight in a greenhouse and the following day infection with disease spores is carried out by placing the plants in an enclosed space and allowing disease spores blown into the space to settle on the plants for 4 to 6 hours without the use of draft.

The percentage of plant leaf infestation by the disease is measured after 8 days for apple trees and after 9 to 10 days for grapevines.

Furthermore, tests of the efficacy of the compounds against apple scab (Venturia in17 aequalis) are carried out. These tests are carried out as follows:

Spores of Venturia inaequalis, an obligate parasite, are transmitted from plant to plant using an agar culture, which provides a highly pathogenic fungus.

Infected leaves are removed from the stock infested plants 13 days before inoculation. Spores are removed from the leaves by stirring in a small volume of deionized water, counted and then adjusted to 100,000 spores/ml. The suspension is sprayed onto the lower leaves of apple seedlings of one of the three susceptible varieties, Jonathan, Granny Smith and Red Delicious. The inoculated seedlings are immediately placed in a high humidity area at 19°C and kept there for 48 hours. After this incubation period, the plants are moved to a suitable growth area where the disease is allowed to develop. The disease is easily assessed 12 or 13 days after incubation.

The test compound is applied 24 hours after incubation.

The same scoring system as in Table 2 is used. The results are shown in Table 3.

Table 3

Compound number

Disease suppression

Podosphaera leuchotricha Uncinula necator Venturia inaequalis on apple trees on vines on apple trees

9

21 22

0 o o 1 2 2 0 2 0

1 0 2 0

4 4 4 2 1

0 4 to 4 0 «

about about

about about

up to 2 0 0 .0

continuation of table 3

Compound number Sweats Fodosphaera leuchotricha on apple trees Disease Uncinula necator on grapevine about b y Venturia inaequalis on apple trees 32 4 4 1 33 4 4 4 34 4 4 4 35 36 3 4 2 37 2 1 1 38 4 4 3 39 4 4 4 40 0 2 0 41 0 0 42 0 1 0 43 1 1 0

Example 9

The compounds are tested at a concentration of 50 ppm as a protective dip against Penicillium digitatum on oranges and Oloesporium musarum on bananas.

The oranges are washed and then rinsed with industrial methylated spirits and wiped. The peel is removed and discs are cut from them with a No. 6 cork borer. The discs are immersed in a solution of the test compound containing 0.1% Tween 20 as a wetting agent and then placed on the outermost side of the Repli-dishes. The discs are allowed to dry and then sprayed with a suspension of Penicillium digitatum spores at a concentration of 1x10^ spores/ml. The dishes are then stored in a humid environment at 19°C for 13 days.

Banana tests are performed in a similar manner using banana peels.

The discs are then rated using the classification system used in Table 2.

The results are shown in Table 4.

Table 4

Compound number

Disease suppression

P. digitatum O. musarum on oranges on bananas

9

I continuation of table 4

Compound number Control P. digitatum on oranges diseases G. musarum on bananas 13 14 0 1 15 0 4 16 17 18 4 0 19 20 21 22 23 4 24 25 26 27 28 1 29 30 4 2 to 4 31 32 4

Example

This example illustrates the regulatory effect of the compounds on plant growth. The compounds are applied as a solution in distilled water at a concentration of 5,000 ppm and the solution is applied to the leaves of young seedlings of wheat, barley, corn, rice, rye, soybean, cotton, peanut, lettuce, tomato, kidney bean and common bean. The experiments are repeated twice. 21 days after treatment, the plants are evaluated for the regulatory effect of the compounds on growth and phytotoxic symptoms.

Table 5 shows the effect of compounds on stunting vegetative growth of plants. This classification system is used.

= 20% retardation =21 to 40% retardation = 41 to 60% retardation = 61 to 80% retardation

If no number is given, the compound is essentially ineffective as an agent for achieving stunted growth.

Other plant growth regulating properties are indicated as follows:

G = darker green leaf color,

A = peak effect,

T = effect on tillering.

The symbol means that the compound has not been tested on a particular crop.

An asterisk (+) indicates that the compound is applied at a concentration of 4,000 ppm.

Table 5

·& Φ Ρ ο CJ +J ο φ φ •H Q) Xl) I X) β Φ About ► β The ο Φ about β •rl I θ'® ο K> •rl Φ >fj rM O β Φ β Λ4 +* Φ 3 β and p Φ (0 The Ν ·(□ S»xfl υ O ο About Φ >about Xsl H O •n ί» ΌΦ *ΦΗ •ο M CO Q) 3 '>> M β *o β The Η Φ Φ Φ φ what Λ T3 Λ β •r> and what β. O Λ W β See <Η 1 1G 1G 0 G 1GA 0 1 2G 1G ,Α GA 2 1 2G 0 G 1GA 0 3 2G 2GAT 2GA 1GA 3 2G 3G 1 1G 1G 1 3 3GA 2GA 1GA 1GA 4 5 1G ,G 0 G 1G 1 3 3GA 2Α 2Α 1GA 6 2GA 1 - A 0 ΙΑ 7 - - - - - - - - - - - - 8 1G ,G . 0 0 IGA G GA A 2Α 9 1GA G GA 2G 10 1GT G 2A 1G A 0 2GA ,1 2GA 2 GA 1GA ,2 1GA 1GA 2G 2 2GA 13 1 0 2 2GA G A GA 2Α 14 1GA 0 GA 15 0 1GA 1G GA GA A 1GA ,6 ,G 1G 0 1G 2GA G GA G A 3GA 17 ,G 1 0 0 2GAT 1G G A 3Α ,8 19 1 1 - 2Α 2 - 20 2 2 1 - 2GA 2GA 3Α - 2G 21 0 0 G 1GAT τ GA IGA 22 ⁺ - - 23 ⁺ - 3G 1GA 1 3GA - 3GA 24 ⁺ 2T 1 1G - 3GA A ΙΑ 3GA - 25 ⁺ - 3GA 2Α 3GA 26 ⁺ 27 - - 28 ⁺ 2 1G - 2Α 3GA - 29 ⁺ 2Z 2 2 1 - 3A 3 3GA 3 - 3GA ³⁰⁺ - 2GA 2Α A 2G - 31 - - «. — 32 ⁺ - - 33 - w 34 - - 35 ⁺ 2GT 2G 1 - 3GA 1 2G - 2GA 36 37 - - 38 ⁺ 2GT 2GT - 3GA ,Α ' 2G - 3GA 39 ⁺ 2 1 - 2 ΙΑ ,Α 1 - 1G

⁺

In the following examples, the compounds which form the active ingredient of the compositions according to the invention are compared with the compounds disclosed in DOS No. 2,407,143 (Bayer AG). It is clear that the compounds according to the invention have a higher fungicidal effect and a higher growth regulating effect (observed as an effect manifested by stunting of grass plants) compared with these standard compounds.

The tested compounds according to the invention and according to DOS No. 2,407,143 can be represented by the general formula

NN-CH—A—R ²

R ¹ where

2

R, R and A have the meanings given in this table:

Compound Example No. in DOS 2 407 143 Compounds according to the invention R ¹ R ² A B 18 Ph t-Bu C=0 C 26 Ue p-Cl-Ph CUOH D 27 p-Cl-Ph Ph CHW 11 2,4-diCl-PhCH ₂ t-Bu CHW 1 p-Cl-PhCH ₂ t-Bu CHW 2 PhCH ₂ t-Bu CHW

Example 11

The retarding effect of the above six compounds is compared in parallel experiments. The comparative experiments are carried out as follows:

Three species of grasses used for environmental improvement are used as test plants, namely Agrostis tenuis, Cynosurus cristatus and Dactylis glomerata. The grasses are grown in a greenhouse (environment: natural daylight, supplemented with a mercury fluorescent lamp of the MBFR type, temperature 23 °C during the day and 18 °C at night, day length 16 hours, water supply from below) and are placed in pots made of fibrous material containing peat-sand compost. The grasses are sprayed 14 days after sowing with the test compounds in the form of preparations with a concentration of 500,

000, 2,000, 4,000 and 8,000 ppm, with the amount of active ingredient chosen to correspond to 0.5, 1, 2, 4 and 8 kg of active ingredient per hectare. The test compounds are mixed with 1 ml of a mixture containing 95% cyclohexanone, 3.33% Synperonic NPE 1,800 and 1.67% Tween 85 and the mixture is diluted to 20 ml with distilled water before use. The volume of the applied product is chosen to correspond to 1,000 liters of the product per hectare. After 10 days from spraying, stunting of grasses and phytotoxicity are visually determined. Both effects are evaluated on a scale of 0 to 5, where grade 0 corresponds to control plants and grades 1, 2, 3, 4 and 5 indicate increasing intensity of the effect. For each grass species, the experiments are carried out twice and the average values are calculated. The overall effect on all three grass species is expressed as the sum of the values for each species (so in this case the highest possible score is 15). The results are shown in Table 6 (retardant effect on grass plants) and Table 7 (phytotoxicity).

Table 6

Compound Concentration (ppm) Agrostis Cynosurus Dactylys Total 1 500 2.0 3.0 3.5 8.5 1,000 3.0 3.0 4.0 10.0 2,000 3.5 3.0 3.5 10.0 4,000 5.0 3.0 4.5 12.5 8,000 5.0 4.0 4.0 13.0 2 500 4.5 3.0 3.0 10.5 1,000 4.5 4.0 4.0 12.5 2,000 5.0 4.5 4.0 13.5 4,000 5.0 5.0 4.0 14.0 8,000 5.0 4.0 5.0 14.0 1, 500 3.0 3.0 3.0 9.0 1,000 3.0 3.0 2.5 8.0 2,000 3.0 3.0 4.5 9.5 4,000 4.0 3.0 3.5 10.5 8,000 4.5 4.0 4.5 13.0 with 500 0.5 1.0 0.5 2.0 Ί 000 1.0 0.5 1.0 . 2.5 2,000 0 0.5 1.0 1.5 4,000 3.0 3.0 2.5 8.5 8,000 3.5 3.0 3.0 9.5 B 500 1.0 1.0 1.5 3.5 1,000 1.5 2.0 1.5 5.0 2,000 1.5 ’,o 1.0 3.5 4,000 2.5 1.0 1.5 5.0 8,000 2.0 1.0 1.0 4.0 C 500 1.0 1.0 1.0 3.0 1,000 2.0 1.0 1.0 4.0 2,000 2.0 2.0 1.0 5.0 4,000 2.0 2.0 1.0 5.0 8,000 2.0 2.0 1.5 5.5

Table 7 Compound Concentration (ppm) Agrostis Cynosurus Dactylys Total 1 500 0 0 0 0 1,000 0 0.5 0 0.5 2,000 1.0 1.0 1.0 3.0 4,000 ’,o ’,o 1.0 3.0 8,000 1.0 . i,o 1.0 3.0 2 500 0.5 0 0.5 1.0 1,000 1.0 1.0 1.0 3.0

continuation of table 7

Compound Concentration (ppm) Agrostis Cynosurus Dactylys Total 2 2,000 1.0 1.0 1.0 3.0 4,000 2.0 1.0 2.0 5.0 8,000 4.0 2.0 3.0 9.0 11 500 0 1.0 0 1.0 1,000 0 0.5 0.5 1.0 2,000 1.0 1.,0 1.0 3.0 4,000 1.0 1.0 1.0 3.0 8,000 1.0 1.0 0 2.0 D 500 0 0 0 0 1,000 0 0 0 0 2,000 1.0 1.0 1.0 3.0 4,000 1.0 1.0 1.0 3.0 8,000 1.0 1.0 1.0 3.0 B 500 0 0 0 0 1,000 0 0.5 0 0.5 2,000 0 0.5 0 0.5 4,000 1.0 1.0 1.0 3.0 8,000 1.0 2.0 1.0 4.0 C 500 0 0 0 0 1,000 0 0 0 0 2,000 0 0 0 0 4,000 1.0 1.0 1.0 3.0 8,000 2.0 1.5 1.0 4.5

Discussion of results:

a) The results in Table 6 show that compounds No. 1, 2 and 11 according to the invention have a higher retarding effect on grass plants than standard compounds B, C and D at all concentrations.

b) The results in Table 7 show that all compounds have some phytotoxic effect at a concentration of 2000 ppm (2 kg/ha) and higher. Phytotoxic symptoms are drying and death of leaf tips. The level of phytotoxic effect was similar for all compounds except for compound No. 11 which showed a stronger effect at 4000 and 8000 ppm (4 and 8 kg/ha).

When interpreting these phytotoxic effects, it should be noted that the experiment was conducted on young, sensitive plants, where the phytotoxic effect is more pronounced than in mature turf. The preferred dosage in practical use is about 2 kg/ha for compounds 1, 2 and 11, so many of the doses used in the experiment represent overdoses.

Example 12

The retarding effect of most of the compounds specifically mentioned in the foregoing description was tested in experiments that were not carried out in parallel. The following test method was used.

Three species of grass suitable for ornamental lawns, Agrostis tenuis, Cynosurus cristatus and Dactylis glomerata, are used as grass plants. The grasses are grown in a greenhouse in the environment defined in Example 11. The grass plants are placed in pots made of fibrous material containing peat-sand compost. Spraying with the test compounds is carried out using compositions with a concentration of 1,000 to 4,000 ppm (1 to 4 kg/ha), 14 days after sowing. The test compounds are mixed with 1 ml of a mixture containing 95% cyclohexanone, 3.33% Synperonic NPE 1,800 and 1.67% Tween 85 and the mixture is diluted to 20 ml with distilled water before use. The volume of the applied composition is chosen so as to correspond to 1,000 liters of composition per hectare. After 10 days from spraying, stunting of the grasses is visually observed. The effect is evaluated on a scale of 0 to 5, where grade 0 corresponds to control plants and grades 1, 2, 3, 4 and 5 indicate increasing retarding effect. For each grass species, the experiments are carried out a total of twice and the average values are calculated. The results are shown in Table 8.

Table 8 ^of

Compound No. Retardation effect Compound No. Retardation effect 1 5 27 0 2 3 28 0 3 5 29 5 4 1 30 1 5 2 31 4 6 1 32 1 7 untested 33 untested 8 4 34 0 9 2 35 4 10 3 36 2 11 3 37 1' 12 1 38 3 13 3 39 3 14 2 40 1 15 1 41 0 16 4 42 0 17 4 43 0 18 3 44 0 19 2 45 1 20 3 46 1 21 4 47 1 22 3 48 0 23 2 49 0 24 3 50 3 25 1 51 5 26 0 52 1

The results show that the compounds according to the invention generally have a good retarding effect. Those compounds whose effect corresponds to a level of 0 to 1 at the tested concentrations are only effective at higher concentrations.

Example 13

The protective fungicidal effect of the six compounds listed before Example 11 against rust (Puccinia recondita on wheat) and powdery mildew (Erysiphe graminis hordei on barley and Erysiphe graminis tritici on wheat) is tested in a parallel experiment.

The comparison experiment is carried out as follows:

Wheat and barley plants are grown in John Innes potting compost (No. 1 or Seed as appropriate) in 4 cm diameter mini-pots. A layer of fine sand is placed at the bottom of the pots to facilitate uptake of the test compound by the roots.

The test compounds are prepared into a powder by ball milling with aqueous Dispersol T or by dissolving in acetone/ethanol and diluting the resulting solution to the desired concentration just before use. The suspensions or solutions are sprayed onto the leaves or applied to the roots of the plant through the soil. In spray experiments, Tween 20 is added to the applied suspensions or solutions (to give a final concentration of 0.1%). In the case of Puccinia recondita, the test compound is applied to the soil or leaves 1 or 2 days before inoculation of the plant with the disease. In experiments with Erysiphe graminis, the plants are inoculated 24 hours before treatment. After inoculation, the plants are placed in a suitable environment that allows the infection to develop and then incubated until the disease can be assessed. The period between inoculation and assessment varies from 4 to 14 days, depending on the disease and the environment.

Disease suppression is characterized by the following stages:

= no disease 3 = 0 to 5% = 6 to 25% = 26 to 60% = more than 60%.

In experiments, the concentration of the test compound is systematically reduced to determine the so-called breakpoint. The breakpoint is defined as the concentration at which the efficacy of the compound falls below the disease suppression level of 2.

The results of the experiment are shown in Table 9.

Table 9

Compound Erysiphe graminis bordei Erysiphe graminis tritici Puccinia recondita spray root dressing spray root dressing spray root dressing

A . >10 0.5 to 1 >10 0.5 >25 >25 B >10 10 >10 5 to 10 >25 >25 C 0.5 1 to 5 1 1 to 5 >25 >25 11 <0.1 0.1 to 0.5 <0.1 1 to 5 1 to 5 5 1 < 0.1 <0.1 <0.1 <0.1 1 to 5 1 2 0.1 <0.1 0.1 <0.1 10 to 25 0.5

Notes on Table 9:

a) Where an absolute value is given, this value means the lowest concentration of active ingredient in ppm at which disease suppression level 2 was achieved.

b) Where a > is placed before the number, the compound was effective in the preliminary testing (i.e., the 100 ppm or 50 ppm tests in the case of the retest) but was not effective at any of the concentrations tested in the subsequent testing (i.e., the above-mentioned testing).

c) Where a < sign precedes the number, the compound still provided a disease suppression level of at least 2 even at the lowest concentration tested.

d) Where a range is given (e.g. 5 to 25), a lower concentration will achieve a grade lower than 2 (but not grade 0), while a higher concentration will achieve a grade higher than 2. The breakpoint must lie between these two values.

e) The symbol indicates that the compound is ineffective against the test organism in a preliminary test (i.e. at a concentration of 100 ppm).

The results show that standard compounds A, B and C are substantially weaker fungicides than compounds 1, 2 and 11 according to the invention.

Example 14

Using the technique described in Example 13, the breakpoints of the protective fungicidal activity of the compounds of the invention against the cereal rust Puccinia recondita on wheat and against the grass powdery mildew Erysyphe graminis hordei on barley and Erysyphe graminis tritici on wheat were determined. The experiments were not carried out in parallel. The results, which are shown in Table 10, show that the compounds of the invention have good fungicidal activity against rust and powdery mildew on cereals.

Table 10.

Compound Erysiphe graminis hordei Erysiphe graminis tritici Puccinia recondita spray root dressing spray root dressing spray root dressing 1 0.05 to 0.1 0.05 0.05 to 0.1 0.05 1 to 5 1 .to 5 · 2 0,’ <0.1 0.1 <0.1 1 to 5 5 3 5 0.5 to 1 5 1 to 5 10 0.5 4 5 1 15 1 >50 25 5 0.25 1.0 to 0.5 0.1 to 0.5 0.1 1 to 5 1 to 5 6 0.5 to 1 0.5 to 1 5 1 to 5 100 5 to 25 7 _meters 5 to 25 5 to 25 5 to 25 5 to 25 50 50 8 0.5 0.5 <0.1 0.5 50 1 to 5 9 0.1 to 0.5 0.05 0.05 0.1 to 0.5 25 5 to 25 10 5 0.5 0.05 0.5 25 0.5 to 1 11 0.05 to 0.1 0.01 0.01 0.01 0.5 0.5 to 1 12 >25 0.05 1 0.1 to 0.5 >50 5 to 25 13 1 to 5 1 to 5 0.5 1 >50 5 14 5 1 to 5 1 to 5 1 to 5 >50 >50 15 1 0.1 to 0.5 0.1 1 to 5 5 < 1 16 0.05 0.5 0.1 1 to 5 1 1 17 1 to 5 0.1 to 0.5 0.5 0.1 >25 1 18 1 to 5 1 to 5 0.5 to 1 0.1 to 0.5 50 5 to 50 19 0.5 to 1 1 to 5 1 to 5 5 to 25 50 5 to 50 20 0.5 0.1 to 0.5 0.5 to 1 0.1 to 0.5 > 50 5 to 10 21 0.05 to 0.1 0.05 0.05 to 0.1 0.05 1 to 5 1 to 5 22 0.5 to 1 1 to 5 0.5 1 to 5 >50 10 to 50 23 0.5 to 1 >5 1 >5 5 to 10 10 to 50 24 0.1 to 0.5 <1 1 <1 <5 <5 25 1 to 5 <1 5 <1 >50 10 to 50 26 >50 >50 >50 >50 >100 >100 27 1 to 5 >50 1 to 5 >50 >100 >100 28 0.1 to 0.5 >5 >5 >5 50 > 50 29 0.1 <0.5 <0.5 <0.5 1 to 5 < 1 30 0.05 <0.5 0.5 <0.5 100 100 31 1 <1 <1 <1 10 <5

continuation of table 10

Compound Erysiphe graminis hordei Erysiphe graminis tritici Puccinia recondita spray root dressing spray root dressing spray root dressing 32 5 0.5 >5 <0.5 >50 10 to 50 33 <0.5 <0.5 0.5 1 5 to 10 1 to 5 34 1 to 5 0.5 to 1 <0.5 0.5 50 to 100 10 35 <0.5 <0.5 <0.5 1 to 5 1 1 to 5 36 <0.5 1 to 5 <0.5 >5 1 1 to 5 37 0.5 to 1 <0.5 1 0.5 10 to 50 <1 38 0.5 to 1 <0.5 >5 0.5 to 1 5 1 39 1 0.5 >5 5 5 1 40 >5 1 to 5 >5 1 to 5 1 10 41 1 to 5 >5 >5 >5 >100 100 42 1 5 <0.5 <0.5 >50 .0 to 50 43 <0.5 >5 <0.5 >5 10 to 50 10 44 <1 5 to 25 >5 5 to 25 <1 5 45 1 to 5 1 to 5 5 to 25 5 to 25 50 to 100 50 to 100 46 0.5 1 to 5 <0.5 >5 50 to 100 50 to 100 47 <0.5 1 to 5 0.5 1 to 5 50 to 100 50 to 100 48 5 >5 >5 >5 >100 >100 49 0.5 to 1 >5 >5 >5 50 to .00 50 to 100 50 1 to 5 1 5 1 50 to 100 5 51 >5 1 to 5 - - 50 10 to 50 52 1 1 to 5 - - 50 1 to 5

Claims (11)

SUBJECT OF THE INVENTION Pungicidal and plant growth regulating agent, characterized in that it contains up to 95% by weight of a compound of the formula (I): Y is = N- or = CH- R 1 is O ₂ alkenyl or benzyl, optionally substituted with halo, trifluoromethyl, nitro, cyano, ^C 1-4 alkyl, alkoxy, ^C _1-4 alkylenedioxy, amino, hydroxy, phenyl or phenoxy and / or optionally substituted phenyl- or alkyl-substituted on the alpha carbon atom, R ₂ is propyl or butyl; R 1 represents hydrogen or acid addition salts thereof and a carrier. 2. A composition according to claim 1, wherein the compound of formula (I) comprises a compound wherein Y is as defined in point 1; is benzyl, optionally ring-substituted by halogen, alkyl, nitro, trifluoromethyl, cyano, ^C, _ ₄ alkoxynebo (C, _ ₄ alkylene) dioxy group or / and optionally to the alpha-carbon atom substituted with one phenyl or C _ ₄ alkyl and R ₂ is as defined in 1, or a salt thereof, 3. A composition according to claim 2, wherein the compound of formula (1) is a compound wherein X is as defined in point 1; is benzyl optionally ring substituted by halo ^»C j_4 alkyl, nitro, trifluoromethyl, cyano, alkoxynebo (C, _ ₄ alkylenedioxy) group and / or optionally substituted on the alpha-carbon atom by one alkyl group and R ₂ has the meaning indicated or a salt thereof. 4. A composition according to claim 3, characterized in that the compound of Formula 1 includes a compound wherein Y represents = N-, R is 2,4-dichlorobenzyl, and R ₂ is t-butyl, or a salt thereof. 5. A composition according to claim 3, characterized TLM that a compound of formula I comprises a compound wherein X is as defined in paragraph 1, R is benzyl, optionally ring-substituted by halogen and R ₂ is as defined in paragraph 1, or salt. 6. A composition according to claim 5, characterized in that a compound of formula I comprises a compound wherein Y represents = N-, R is p-chlorobenzyl, and R ₂ is t-butyl, or a salt thereof. 7. A process for the preparation of a compound of the formula I or a salt thereof according to claim 1, characterized in that the compound of the formula 11 is reduced in a polar solvent at a temperature of 0 to 100 [deg.] C. for 1 to 12 hours. H where X, R 1 and R ₂ are as defined in point 1, or a salt thereof. 8 »method according to claim 7, characterized in that as compounds of formula II for the compound in which Y is as defined in paragraph 1, R is benzyl, optionally ring-substituted by halogen, C, _ ₄ alkyl, nitro , trifluoromethyl, cyano, C _1-4 alkoxy or (C 1-4 alkylene) dioxo and / or optionally substituted on the alpha carbon atom by one phenyl or C _1-4 alkyl group and R ₂ is as defined in point 1, or salts. 9. A process according to claim 8, wherein the compound of formula (11) is one in which Y is as defined in (1), R is benzyl, optionally substituted with halo, alkyl, nitro, trifluoromethyl, , cyano, C _1-4 alkoxy- or (C _1-4 alkylenedioxy) groups and / or optionally substituted on the alpha carbon atom by one alkyl group and R ₂ is as defined in point 1, or a salt thereof. 10. A process according to claim 9 wherein the compound of formula (II) is a compound wherein Y is = N-, R is 2,4-dichloro29 benzyl and Rg is t-butyl, or salts thereof. 11. A process according to claim 8, wherein X is as defined in point 1, Rf is benzyl optionally substituted by ring halogens, and Rg is as defined in point 1, or its salts,. 2. The method of claim 2 wherein X is -N-, Rf is p-chlorobenzyl, and Rg is t-butyl, or salts thereof.