Pesticide

The present invention relates to a fungicide containing new valinamide derivatives.

The new agents have excellent pest control activity. They are used in particular as fungicides, primarily in the field of plant protection.

Certain amino acid amides are already known, for example, from European Patent No. 236,874. The use of these compounds in pest control agents, however, has not been described.

In addition, fungicidal amino acid derivatives are known from European Patent No. 398 027. The above compounds are defined in this general description by formula 1, within which the compounds of formula 1 are theoretically included. However, the above description does not describe or provide data for specific compounds of formula 1 in which R1 is isopropyl or Il-Rz -butyl, i.e. the active compound of the agent according to the present invention. Accordingly, the group of compounds of formula I in which R1 has the above two meanings is completely new.

It has been surprisingly found that the fungicidal activity of this particular, selected group of compounds exceeds so far the action of the compounds described in the description No. 398 072 that it was absolutely unpredictable on the basis of previous data. The results of the experimental studies given below confirm that the compounds proposed in the present invention are not only new but have unexpected properties.

The agent according to the invention contains as active substance new valinamide derivatives of the general formula (I) in which R1 is an isopropyl or II-butyl radical and R² is chlorine, methyl, ethyl or methoxy, in combination with diluents and / or surfactants.

The compounds of formula I contain two chiral centers and may therefore be present in different mixtures of enantiomers and diastereomers, which can optionally be separated in known manner. Agents containing both pure enantiomers and diastereomers as well as mixtures thereof are included in the invention.

Below, for simplicity, compounds of Formula 1 are discussed continuously, although this applies to both pure compounds and mixtures with different proportions of isomers, enantiomers and diastereomers.

A method for preparing the above valinamide derivatives of general formula I is described in Patent No. 165 204.

Preference is given to agents containing a valinamide derivative of formula 1, in which the basic amino acid of formula 4 is isopropyloxycarbonyl-L-valine or t-butoxycarbonyl-Lvaline, and the portion derived from phenethylethylamine of formula 5, wherein R² is a chlorine atom,

167 The methyl, ethyl or methoxy group is either racemic or has the R (+) configuration at the asymmetric center.

The new compositions containing the active substances of the formula I have a strong anti-fungal effect and can be used in practice to control undesirable harmful fungi, especially for use as fungicides for plant protection.

Fungicides in the field of plant protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes.

For example, but not limiting, some pathogens of fungal diseases that fall under the following terms:

Pythium types, such as, for example, Pythium ultimum; Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Peronospora species, such as, for example Peronospora pisi or P. brassicae, Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; Podosphaera species, such as, for example, Podosphaera leucotricha; Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidial form: Drechsler, Syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechsler, Syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

Good tolerance of active substances by plants in the concentrations necessary to combat plant diseases allows treatment of aerial parts of plants, planting and seeding material and soil.

With particularly good effect, new preventive active ingredients can be used to control Phytophthora on tomatoes or Plasmopara on vine.

Depending on their physical and / or chemical properties, the active substances can be converted into known preparations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, small capsules in polymeric substances and in seed coatings, as well as preparations ULV for nebular spraying of cold and heat. These preparations are prepared in a known manner, for example by mixing active substances with diluents, i.e. liquid solvents, pressurized liquefied gases and / or solid carriers, optionally with the addition of surfactants such as emulsifiers and / or dispersants and / or foaming agents. When using water as the diluent, organic solvents can, for example, also be used as auxiliary solvents.

As liquid solvents, aromatic compounds such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenb, chloroethylene methylmethylene chloride, hydrocarbons are generally considered

167 Aliphatic, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents such as dimethylformamide and dimethyl sulfoxide and water. Liquefied gaseous diluents or carriers are liquids that are gases at normal temperature and pressure, e.g. aerosol forming gases such as halohydrocarbons and butane, propane, nitrogen and carbon dioxide.

For example, solid rock powders such as kaolins, aluminum oxides, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic mineral powders such as high-dispersion silicic acid, alumina and silicates are used as solid carriers. As solid carriers are considered for granules e.g. crushed and fractionated natural minerals such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn on the cob and tobacco stalks. As emulsifying and / or foaming agents, e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene ethers of fatty alcohols, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. As dispersants, for example, lignin sulphite lye and methyl cellulose are used.

The preparations may use adhesion promoters such as carboxymethyl cellulose, natural and synthetic polymers, powdered, granular or in latex form, such as acacia, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalin and lecithin, and synthetic phospholipids. Mineral and vegetable oils are mentioned as further additives.

Dyes, such as inorganic pigments, e.g. iron oxide, titanium oxide, ferrocyanine blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes, as well as trace elements such as iron, manganese, boron, copper, cobalt salts can be added to the preparations. molybdenum and zinc.

The formulations generally contain 0.1-95% by weight of active compound, preferably 0.5-90%.

New active substances may be present in the preparation in a mixture with other known active substances, such as fungicides, insecticides, acaricides and herbicides, and in the mixture with fertilizers and plant growth regulators.

The active substances can be used as such, in the form of preparations or of the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusting agents and granules. The agents are applied in a known manner, e.g. by watering, spraying, spraying, scattering, dusting, foaming, coating, etc. The active substances can also be applied by the Ultra-Low-Volume method, or the active substance preparation or the active substance itself can be injected into the soil. You can also treat plant seed.

When treating parts of plants, the concentration of the active substance in the use forms can vary widely. Generally, this concentration is 1-0.0001% by weight, preferably 0.5-0.001% by weight.

For the treatment of seeds, the active substance is generally used in an amount of 0.001-50 g per kg of seed, preferably 0.01-10 g.

For soil treatment, an active substance concentration of 0.00001-0.1% by weight, preferably 0.0001-0.02% at the site of application is used.

The following examples will explain in more detail the method for producing the active ingredient of the agent according to the invention.

Example I. Compound of formula 2 (code number 1).

To 4.67 g (0.023 mol) of isopropoxycarbonyl-L-valine dissolved in 50 ml of CH2O2 is introduced at -20 ° C 2.3 g (0.023 mol) of N-methylpiperidine. Then 3.2 g (0.23 mole) of chloroformic acid isobutyl ester are quickly added dropwise at -20 ° C, stirred at the same temperature for 10 minutes, cooled to -60 ° C and brought to 3.5 g (0.023 mol) 4-methoxy-1-phenylethylamine, keeping the temperature below -15 ° C. After 2 hours, keeping the mixture at -15 ° C, stirring for 15 hours at room temperature, filtering the precipitate, washing with CH 2 Cl₂, concentrated, the residue is taken up in water, extracted twice with ethyl acetate, the combined phases in ethyl acetate are washed with NaHCO 3 solution and water, dried and concentrated. 4.64 g (60% of theory) of N- / isopropoxycarbonyl / -L-valine 4-methoxyphenylethylamide is obtained with a melting point of 167 ° C.

Analogously to Example 1, the compounds of formula 1 are obtained in the table.

Table 1 Compounds of formula 1

<td>Relationship Code No.</td><td>R1</td><td>R²</td><td>Melting point ° C</td><td>Amino acid used</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>

<td> 2</td><td>-CH (CH) and</td><td>Cl</td><td> 176</td><td>isopropoxycarbonyl-L-valine</td>

<td> 3</td><td>-CH (CH₃)2</td><td>CH3</td><td> 160</td><td>isopropoxycarbonyl-L-valine</td>

<td> 4</td><td>-CH (CH3) 2</td><td>Cl</td><td> 170</td><td>isopropoxycarbonyl-L-valine (R +) amide</td>

<td> 5</td><td>formula 3</td><td>Cl</td><td> 166</td><td>11 rz.butolasylkarbonylo-L-valine</td>

<td> 6</td><td>formula 3</td><td>CH3</td><td> 143</td><td>II-n. butoxycarbonyl-L-valine</td>

<td> 7</td><td>formula 3</td><td>-OCH3</td><td> 153</td><td>Π-rz.butoksykaΓbonylo-L-valine</td>

<td> 8</td><td>formula 3</td><td>Cl</td><td> 168</td><td>II-zz.butoxykazbonyl-L-valine (R +) amide</td>

<td> 9</td><td>CH (CH3) 2</td><td>-c₂h₅</td><td> 121-122</td><td>isopropoxycarbonyl-L-valine</td>

<td> 10</td><td>formula 3</td><td>C2H5</td><td> 111-112</td><td>Π-rz.butoksylkazbonylorLrwalina</td>

<td> 11</td><td>CH (CH3) 2</td><td>-C₂hs</td><td> 154-156</td><td>isopzopyloxykazbonylor Lvaline (R +) amide</td>

<td> 12</td><td>formula 3</td><td>C2H5</td><td> 140-142</td><td>n-n-butoxycarbonyl-L-valine (R +) amide</td>

<td> 13</td><td>-CH (CH₃)and</td><td>CH3</td><td> 177-179</td><td>isopropoxycarbonyl-L-valine (R +) amide</td>

<td> 14</td><td>formula 3</td><td>CH3</td><td> 169-171</td><td>Butyroxy-carbonyl-L-valine (R +) amide</td>

<td> 15</td><td>-CH (CH₃)2</td><td>-OCH3</td><td> 183-185</td><td>isopropoxycarbonyl-L-valine (R +) amide</td>

<td> 16</td><td>formula 3</td><td>-OCH3</td><td> 178-180</td><td>T-butoxycarbonyl-L-valine (R +) amide</td>

<td> 17</td><td>-CH (CH₃)and</td><td>Cl</td><td> 162</td><td>izopropyloksykazbonylo-D Lrwalina</td>

<td> 18</td><td>-CH (CHa) 2</td><td>Cl</td><td> 168</td><td>isopropyloxycarbonyl-D ^ valine (R +) amide</td>

<td> 19</td><td>CH (CH3) 2</td><td>CH3</td><td> 140</td><td>izopropyloksykazbonylorD_&gt;Lrwalina</td>

<td> 20</td><td>CH (CH3) 2</td><td>-och₃</td><td> 138</td><td>izopropyloksykazbonylorD, L-valine</td>

<td> 21</td><td>-CH (CH 3) 3</td><td>CH₂CH3</td><td> 130</td><td>isopropyloxycarbonyl-D, L-valine</td>

<td> 22</td><td>-CH (CH3)</td><td>CH3</td><td> 147</td><td>isopropyloxycarbonyl-DL-valine (R +) amide</td>

The following examples explain in more detail the use of the agent according to the invention.

Example I I. Testing of Phytophthora (tomatoes) - preventive action.

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To obtain a preferred preparation of active substance, 1 part by weight of active substance is mixed with the stated amount of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test the preventive effect, young plants are sprayed to the reflux with an active substance preparation. After the spray dries, the plants are infected with an aqueous spore suspension of Phytophthora infastans. Plants are kept in an incubation cabin with 100% relative humidity and a temperature of about 20 ° C. An assessment of the results is carried out 3 days after infection.

Table 2 below shows the fungicidal activity of compounds with code numbers 1-20 and 22 compared to the activity of compounds of formulas 6-8, known from European Patent No. 398 072. The results presented clearly show the unexpectedly much higher activity of the agents according to the invention compared to to known means.

167 500

Table 2

Test for Phytophthora (tomatoes) - preventive action

Activity level in%

Name of active substance Compound code number for untreated control samples or formula at 2.5 ppm active substance concentration

Compounds known from EP-OS-398 072:

<td>Racemic L-valine amide</td><td>formula 6</td><td></td><td> 54</td>

<td>Racemic L-valine amide</td><td>formula 7</td><td></td><td> 12</td>

<td>Racemic L-valine amide</td><td colspan="2">formula 8 Compounds used in the compositions according to the invention:</td><td> 25</td>

<td>Racemic L-valine amide</td><td>code number</td><td> 1</td><td> 77</td>

<td>Racemic L-valine amide</td><td></td><td> 2</td><td> 85</td>

<td>Racemic L-valine amide</td><td></td><td> 3</td><td> 92</td>

<td>R (+) - L-valine amide</td><td></td><td> 4</td><td> 97</td>

<td>Racemic L-valine amide</td><td></td><td> 5</td><td> 94</td>

<td>Racemic L-valine amide</td><td></td><td> 6</td><td> 85</td>

<td>Racemic L-valine amide</td><td></td><td> 7</td><td> 86</td>

<td>R (+) - L-valine amide</td><td></td><td> 8</td><td> 95</td>

<td>Racemic L-valine amide</td><td></td><td> 9</td><td> 91</td>

<td>Racemic L-valine amide</td><td></td><td> 10</td><td> 94</td>

<td>R (+) - L-valine amide</td><td></td><td> 11</td><td> 98</td>

<td>R (+) - L-valine amide</td><td></td><td> 12</td><td> 92</td>

<td>R (+) - L-valine amide</td><td></td><td> 13</td><td> 88</td>

<td>R (+) - L-valine aniid</td><td></td><td> 14</td><td> 96</td>

<td>R (+) ^^ mid L-valine</td><td></td><td> 15</td><td> 86</td>

<td>R (+) - L-valine amide</td><td></td><td> 16</td><td> 93</td>

<td>Racemic amide D, L-valine</td><td></td><td> 17</td><td> 89</td>

<td>R (+) - amide D, L-valine</td><td></td><td> 18</td><td> 95</td>

<td>Racemic amide D, L-valine</td><td></td><td> 20</td><td> 71</td>

<td>Racemic amide D, L-valine</td><td></td><td> 19</td><td> 78</td>

<td>R (+) - amide D, L-valine</td><td></td><td> 22</td><td> 93</td>

Example III. Plasmopar (grapevine) testing - preventive action.

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

In order to obtain a preferred preparation of the active substance, 1 part by weight of the active substance is mixed with the indicated amount of solvent and emulsifier and the dilution concentrate with water to the desired concentration.

To test for prevention, young plants are sprayed with the preparation of the active substance for reflux. After spray drying, the plants are infected with an aqueous spore suspension of Plasmopara viti cola and then stored for 1 day in a humid chamber at 20-22 ° C and 100 ° relative air humidity. Then the plants are kept for 5 days in a greenhouse at 22 ° C and about 80% humidity. It is then moistened and kept for 1 day in a moist chamber. Seven days after infection, the results are evaluated.

Compounds with code numbers 1-16 exhibit excellent fungicidal activity in this test, as shown in Table 3

167 500

Table 3

Plasmopar test (vine) - preventive action

<td>Name of active substance</td><td>Relationship Code No.</td><td>Activity level in% relative to untreated control samples at 5 ppm active substance concentration</td>

<td> 1</td><td> 2</td><td> 3</td>

<td>Racemic L-valine amide</td><td>code number 1</td><td> 89</td>

<td>Racemic L-valine amide</td><td> 2</td><td> 96</td>

<td>Racemic L-valine amide</td><td> 3</td><td> 100</td>

<td>R (+) -amide of L-valine</td><td> 4</td><td> 100</td>

<td>Racemic L-valine amide</td><td> 5</td><td> 100</td>

<td>Racemic L-valine amide</td><td> 6</td><td> 100</td>

<td>Racemic L-valine amide</td><td> 7</td><td> 100</td>

<td>R (+) -amide of L-valine</td><td> 8</td><td> 100</td>

<td>Racemic L-valine amide</td><td> 9</td><td> 99</td>

<td>Racemic L-valine amide</td><td> 10</td><td> 96</td>

<td>R (+) - L-valine amide</td><td> 11</td><td> 97</td>

<td>R (+) - L-valine amide</td><td> 12</td><td> 98</td>

<td>R (+) - L-valine amide</td><td> 14</td><td> 91</td>

<td>R (+) -amide of L-valine</td><td> 15</td><td> 89</td>

<td>R (+) - L-valine amide</td><td> 16</td><td> 96</td>

Example IV Testing Pyrenophora teres (barley) - preventive action.

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

In order to obtain a suitable preparation of the active substance, 1 part by weight of the active substance is mixed with the amount of solvent and emulsifier given, after which the concentrate is diluted with water to the desired concentration.

To test for prevention, the young plants are sprayed with the preparation of the active substance. After the spray dries, the plants are sprayed with an aqueous spore suspension of Pyrenophora teres.

Plants are kept in an incubation cabin with 100% relative humidity and 20 ° C for 48 hours.

The plants are then placed in a greenhouse at a temperature of about 20 ° C and in air with a relative humidity of about 80%.

days after vaccination, results are evaluated. Table 4 below shows the active substances used, their concentration and activity compared to the activity of the compounds known from European Patent No. 398072. The results presented clearly show the unexpectedly much higher activity of the agents according to the invention compared to known agents.

Table 4

Pyrenphora teres (barley) test for preventive action

Concentration Activity level in%

Active compound compound code number for untreated controls

<td>Name of active substance</td><td colspan="2">or formula in the spray liquid ppm</td>

<td>R (+) -amide of L-valine</td><td>Compound known from EP 398 072: model 9 250</td><td> 0</td>

<td>Racemic L-valine amide</td><td>Compounds used in the compositions according to the invention: code no. 19 250</td><td> 70</td>

<td>R (+) -amide of L-valine</td><td> 18 250</td><td> 61</td>

EXAMPLE. Cochliobolus (barley) testing - preventive action. Solvent: 100 parts by weight of dimethylformamide.

167 500

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether.

In order to obtain a suitable preparation of the active substance, 1 part by weight of the active substance is mixed with the amount of solvent and emulsifier given, after which the concentrate is diluted with water to the desired concentration.

To test for prevention, the young plants are sprayed with the preparation of the active substance. After spray drying, the plants are sprayed with an aqueous spore suspension of Cochliobolus sativus.

Plants are kept in an incubation cabin with 100% relative humidity and 20 ° C for 48 hours.

The plants are then placed in a greenhouse at a temperature of about 20 ° C and in air with a relative humidity of about 80%.

days after vaccination, results are evaluated. Table 5 below shows the active substances used, their concentration and activity compared to the activity of the compounds known from European patent specification No. 398072. The results presented clearly demonstrate the unexpectedly much higher activity of the agents according to the invention compared to known agents.

Table 5

Test for Cochliobolus sativus (barley) - preventive action

Concentration Activity level in%

Active compound compound code number for untreated controls

Name of active substance or formula for spraying ppm

R (+) -amide of L-valine

Racemic L-valine amide

Compound known from EP 398 072:

model 9 250 0

The compound used in the composition according to the invention:

code no. 19 250 85

H3k .CH₃CH

R¹-O-CO-NH-CH-CO-NH-CH ^^ ~ R² * Chh₃

Formula 1

H₃C ^ / CH₃ ch₃ O © o₃

CH-OC-NH-CH-C-NH-CH ^ yoCH

CH₃ ,

Formula 2 ^^c2^h5

CH

CH₃Formula 3

H3 &lt;&lt; / CH₃CH

R¹-0-C0-NH-CH-C00H

AND

Formula 4

H2N-CH - ^ - R²

ch₃

Formula 5

H3C.CH3 ch₃ and&gt; CH-CHo-OC-NH-CH-O-NH-CH

chb ¹¹ II I ^LM3 oo ch₃

<img file="PL167500B1_D0001.tif" />

cl

Model 6 ru ^Η© -^CH3 CH3 CH

CFB-COC-NH-CH-C-NH-CH-f

I II li I

CH₃ 0

OH CH₃

Formula 7

H₃C ch₃ch₃ © h ³ ch₃-C-OC-NH-CH ~ C-NH-CH / ~ Vch₃ch₃ oo ch₃

Formula 8

H₃C_x .ch₃CH₃ CH

C K3-COC-NH-C HC-NH-C Η-ΓΛ- Cl ³ I II II 1 ^ =⁷

CH3 OO CH3

Formula 9

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