Fungicidal N-bicycloalkyl and N-tricycloalkyl pyrazole-4-(thio)carboxamide derivatives

Abstract

The present invention relates to fungicidal N-bicycloalkyl and N-tricycloalkyl pyrazole-4-(thio)carboxamide derivatives of formula (I), wherein T represents O or S; n represents 0 or 1; and B represents where the bond marked by * is attached to the (CZ2Z3)n-N amide moiety, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions. ##STR00001##

Claims

1. A compound of formula (I) ##STR00021## wherein T represents O or S; n represents 1; B represents ##STR00022##  where the bond marked by * is attached to the (CZ.sup.2Z.sup.3).sub.n—N amide moiety; m represents 0 or 1; p represents 0, 1, 2 or 3; providing that m+p is equal to 1 to 3; t represents 1 or 2; u represents 1, 2, 3 or 4; Q.sup.1 represents a direct bond, CZ.sup.7Z.sup.8, O, S, SO, SO.sub.2, NZ.sup.11, —C(═V)—, —C(═NZ.sup.12)—, a non-substituted C.sub.1-C.sub.8-alkylidene or a substituted C.sub.1-C.sub.8-alkylidene substituted by up to 10 atoms or groups that can be the same or different and that can be selected in the list consisting of halogen atoms, cyano, C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C.sub.1-C.sub.8-alkoxy, C.sub.1-C.sub.8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, C.sub.1-C.sub.8-alkoxycarbonyl, C.sub.1-C.sub.8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different, C.sub.1-C.sub.8-alkylaminocarbonyl and di-C.sub.1-C.sub.8-alkylaminocarbonyl; providing that when Q.sup.1 is not a direct bond then t+u is equal to 2 to 4; or when Q.sup.1 is a direct bond then u is equal to 3 or 4; or when t is equal to 2 then [Q.sup.1].sub.2 is not a peroxide group; Q.sup.2 represents CZ.sup.9Z.sup.10 or —CH═CH—; V represents O or S; Z.sup.1 represents a hydrogen atom; a formyl group; a substituted or non-substituted C.sub.1-C.sub.8-alkyl; a non-substituted C.sub.3-C.sub.7-cycloalkyl or a C.sub.3-C.sub.7-cycloalkyl substituted by up to 10 atoms or groups that can be the same or different and that can be selected in the list consisting of halogen atoms, cyano, C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, C.sub.1-C.sub.8-alkoxy, C.sub.1-C.sub.8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, C.sub.1-C.sub.8-alkoxycarbonyl, C.sub.1-C.sub.8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different, C.sub.1-C.sub.8-alkylaminocarbonyl and di-C.sub.1-C.sub.8-alkylaminocarbonyl; provided that—when Z.sup.1 represents a hydrogen atom, n represents 0, T represents O and B represents a optionally mono alkyl-substituted, saturated or partially unsaturated, decahydronaphthalenyl group, octahydro-1H-inden-4-yl group or octahydro-1H-inden-5-yl group then R.sup.1 and R.sup.3 are not simultaneously a methyl group when R.sup.2 is a fluorine atom; Z.sup.2 and Z.sup.3 independently represent a hydrogen atom; a halogen atom; cyano; substituted or non-substituted C.sub.1-C.sub.8-alkyl; C.sub.1-C.sub.8-halogenoalkyl having 1 to 5 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkoxy; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfanyl; or substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbonyl; or Z.sup.2 and Z.sup.3 are a C.sub.2-C.sub.5-alkylene group that can be substituted by up to four C.sub.1-C.sub.8-alkyl groups; Z.sup.4, Z.sup.5, Z.sup.6, Z.sup.7, Z.sup.9 or Z.sup.10 independently represent a hydrogen atom; a halogen atom; cyano; substituted or non-substituted C.sub.1-C.sub.8-alkyl; C.sub.1-C.sub.8-halogenoalkyl having 1 to 5 halogen atoms; substituted or non-substituted C.sub.1-C.sub.8-alkoxy; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfanyl; substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbonyl; or benzyl group; Z.sup.11 represents a hydrogen atom; a substituted or non-substituted C.sub.1-C.sub.8-alkyl; a C.sub.1-C.sub.8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C.sub.2-C.sub.8-alkenyl; C.sub.2-C.sub.8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C.sub.3-C.sub.8-alkynyl; C.sub.3-C.sub.8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl; C.sub.3-C.sub.7-halogeno-cycloalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl-C.sub.1-C.sub.8-alkyl; formyl; substituted or non-substituted C.sub.1-C.sub.8-alkylcarbonyl; C.sub.1-C.sub.8-halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C.sub.1-C.sub.8-alkoxycarbonyl; C.sub.1-C.sub.8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C.sub.1-C.sub.8-alkylsulfonyl; C.sub.1-C.sub.8-halogenoalkylsulfonyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted benzyl; or substituted or non-substituted phenylsulfonyl; Z.sup.12 represents a hydrogen atom, a substituted or non-substituted C.sub.1-C.sub.8-alkyl; C.sub.1-C.sub.8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C.sub.1-C.sub.8-alkoxy; C.sub.1-C.sub.8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C.sub.3-C.sub.7-cycloalkyl; C.sub.3-C.sub.7-halogeno-cycloalkyl comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted C.sub.3-C.sub.7-cycloalkoxy; C.sub.3-C.sub.7-halogenocycloalkoxy comprising up to 9 halogen atoms that can be the same or different; substituted or non-substituted benzyl; substituted or non-substituted phenyl; substituted or non-substituted benzyloxy; or substituted or non-substituted phenoxy; R.sup.1, R.sup.2 and R.sup.3 independently represents a hydrogen atom; halogen atom; non-substituted C.sub.1-C.sub.8-alkyl or C.sub.1-C.sub.8-halogenoalkyl having 1 to 9 halogen atoms; wherein not more than one of R.sup.1, R.sup.2 and R.sup.3 is hydrogen Provided that the compound is not: 5-chloro-N,1,3-trimethyl-N-(tricycle[3.3.1.13,7]dec-1-ylmethyl)-1H-pyrazole-4-carboxamide; N-(adamantan-1-ylmethyl)-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, or 5-benzyl-1,3-dimethyl-1H-pyrazole-4-carboxylic acid (adamantan-1-ylmethyl)-amide N-(adamantan-1-ylmethyl)-5-chloro-1-(4-fluorobenzyl)-3-methyl- 1H-pyrazole-4-carboxamide; 1-benzyl-N-[1-(bicyclo[2.2.1]hept-2-yl)ethyl]-5-chloro-3-methyl-1H-pyrazole-4-carboxamide; N-(adamantan-1-ylmethyl)-1-benzyl-5-chloro-3-methyl-1H-pyrazole-4-carboxamide; N-(adamantan-1-ylmethyl)-5-chloro-3-methyl-1-(4-methylbenzyl)- 1H-pyrazole -4-carboxamide; N-(adamantan-l-ylmethyl)-5-chloro-N,1,3-trimethyl-1H-pyrazole-4-carboxamide; N-[1-(adamantan-1-yl)ethyl]-1-benzyl-5-chloro-3-methyl-1 H-pyrazole-4-carboxamide; N-[1-(bicyclo[2.2.1]hept-2-yl)ethyl]-1-ethyl-3-methyl-1H-pyrazole-4-carboxamide; or N-[1-(bicyclo[2.2.1]hept-2-yl)ethyl]-5-chloro-3-methyl-1-(4-methylbenzyl)-1H-pyrazole-4-carboxamide, as well as its salts, N-oxides, metal complexes, metalloid complexes and optically active isomers.

2. A compound according to claim 1 wherein R.sup.1 represents a non-substituted C.sub.1-C.sub.5-alkyl, or C.sub.1-C.sub.5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different; R.sup.2 represents a hydrogen atom, or a halogen atom; and R.sup.3 represents a non-substituted C.sub.1-C.sub.5-alkyl.

3. A compound according to claim 1 wherein R.sup.1 represents C.sub.1-C.sub.5-alkyl or C.sub.1-C.sub.5-halogenoalkyl comprising up to 3 halogen atoms that can be the same or different; R.sup.2 represents a hydrogen atom, a chlorine atom, or a fluorine atom; and R.sup.3 represents a methyl.

4. A compound according to claim 1 wherein T represents O.

5. A compound according to claim 1 wherein B represents B.sup.1; Q.sup.1 represents a direct bond; u is equal to 3 or 4; and m+p is equal to 2 or 3.

6. A compound according to claim 1 wherein B represents a substituted or non-substituted decahydronaphthalenyl group, a substituted or non-substituted octahydro-1H-indenyl group, or a substituted or non-substituted octahydropentalenyl group.

7. A compound according to claim 1 wherein B represents B.sup.1; Q.sup.1 represents a methylene group, or an oxygen atom; t is equal to 1; and u is equal to 1 or 2.

8. A compound according to claim 1 wherein B represents a substituted or non-substituted bicyclo[2.2.1]heptyl group, a substituted or non-substituted bicyclo[2.2.1]hept-2-enyl group, a substituted or non-substituted 7-oxabicyclo[2.2.1]heptyl group, a substituted or non-substituted 7-oxabicyclo[2.2.1]hept-2-enyl group, a substituted or non-substituted bicyclo[2.2.2]octyl group, or a substituted or non-substituted bicyclo[3.1.1]heptyl group.

9. A compound according claim 1 wherein B represents B.sup.2.

10. A compound according to claim 1 wherein Q.sup.1 represents a direct bond, an oxygen atom, a substituted or non-substituted methylene group, or a substituted or non-substituted C.sub.1-C.sub.5-alkylidene group.

11. A compound according to claim 1 wherein Q.sup.2 represents a methylene group, or a —CH═CH— group.

12. A compound according to claim 1 wherein V represents O.

13. A compound according to claim 1 wherein Z.sup.1 represents a hydrogen atom, a substituted or non-substituted C.sub.1-C.sub.8-alkyl, or a substituted or non-substituted cyclopropyl.

14. A compound according claim 1 wherein Z.sup.2, Z.sup.3, Z.sup.4, Z.sup.5, Z.sup.6, Z.sup.7, Z.sup.8, Z.sup.9 or Z.sup.10 independently represent a hydrogen atom, or a substituted or non-substituted C.sub.1-C.sub.8-alkyl.

15. A compound according to claim 1 wherein Z.sup.11 represents C.sub.1-C.sub.8-alkyl, substituted or non-substituted benzyl, or a tert-butyloxycarbonyl protecting group.

16. A compound according to claim 1 wherein Z.sup.12 represents C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-alkoxy, substituted or non-substituted benzyl, substituted or non-substituted benzyloxy.

17. A fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) according to claim 1 and an agriculturally acceptable support, carrier or filler.

18. A method for controlling phytopathogenic fungi of crops, characterized in that an agronomically effective and substantially non-phytotoxic quantity of a compound according to claim 1 is applied to the soil where plants grow or are capable of growing, to the leaves and/or the fruit of plants or to the seeds of plants.

19. A method for controlling phytopathogenic fungi of crops, characterized in that an agronomically effective and substantially non-phytotoxic quantity of a fungicide composition according to claim 17 is applied to the soil where plants grow or are capable of growing, to the leaves and/or the fruit of plants or to the seeds of plants.

Description

PREPARATION EXAMPLE 1

Preparation of N-[1-(adamantan-1-yl)ethyl]-N-cyclopropyl-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (Compound 103)

Step 1: Preparation of N-[1-(adamantan-1-yl)ethyl]cyclopropanamine hydrochloride

(1) To a solution of 640 mg (11.2 mmol) of cyclopropylamine in 10 mL of methanol is added 1 g of 3 Å molecular sieves followed by a slow addition of 673 mg (11.2 mmol) of acetic acid and 1 g (5.6 mmol) of 1-(adamantan-1-yl)ethanone. The reaction mixture is stirred for 5 hours at reflux. The reaction mixture is then cooled to 0° C. and 528 mg (8.4 mmol) of sodium cyanoborohydride are slowly added. The reaction mixture is further stirred for 2 hours at reflux then left overnight at ambient temperature. The reaction mixture is filtered over a cake of diatomaceous earth and the cake is washed twice by 50 mL of methanol.

(2) The combined methanolic extracts are concentrated under vacuum. The residue is dissolved in 50 mL of ethyl acetate and the organic solution is washed twice by 100 mL of a 1N solution of sodium hydroxide followed by water and dried over magnesium sulfate. Vacuum concentration gives a yellow oil which is dissolved in 5 mL of diethyl ether. Addition of 2 mL of a 4 N solution of HCl in dioxan and filtration, yields 702 mg (57% yield) of the hydrochloride salt of N-[1-(adamantan-1-yl)ethyl]cyclopropanamine as a white solid (M+H=256). log P=5.82 (for the free base).

Step 2: Preparation of N-[1-(adamantan-1-yl)ethyl]-N-cyclopropyl-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide

(3) At ambient temperature, a solution of 114 mg (0.645 mmol) of 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carbonyl chloride in 2 mL of acetonitrile is added dropwise to a solution of 150 mg (0.586 mmol) of N-[1-(adamantan-1-yl)ethyl]cyclopropanamine and 178 mg (1.76 mmol) of triethylamine in 2 ml of acetonitrile. The reaction mixture is stirred for 16 hrs at ambient temperature. 25 mL of water are then added to the reaction mixture and extracted twice by 25 mL of ethyl acetate. The combined organic layers are washed by brine, dried over magnesium sulfate and concentrated. Column chromatography on silica gel (heptaneethyl acetate 7030) yields 146 mg (69% yield) of N-[1-(adamantan-1-yl)ethyl]-N-cyclopropyl-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (M+H=360).

GENERAL PREPARATION EXAMPLE 2

Thionation of Amide of Formula (I) on Chemspeed™ Apparatus

(4) In a 13 ml Chemspeed™ vial is weighted 0.27 mmol of phosphorous pentasulfide (P.sub.2S.sub.5). 3 mL of a 0.18 molar solution of the amide (I) (0.54 mmol) in dioxane is added and the mixture is heated at reflux for two hours. The temperature is then cooled to 80° C. and 2.5 mL of water are added. The mixture is heated at 80° C. for one more hour. 2 mL of water are then added and the reaction mixture is extracted twice by 4 mL of dichloromethane. The organic phase is deposited on a basic alumina cartridge (2 g) and eluted twice by 8 mL of dichloromethane. The solvents are removed and the crude thioamide derivative is analyzed by LCMS and NMR. Insufficiently pure compounds are further purified by preparative LCMS.

EXAMPLE A

In Vivo Preventive Test on Sphaerotheca fuliginea (Cucumber)

(5) Solvent: 49 parts by weight of N,N-dimethylformamide

(6) Emulsifier: 1 part by weight of alkylarylpolyglycolether

(7) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(8) To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. Then the plants are placed in a greenhouse at approximately 23° C. and a relative atmospheric humidity of approximately 70%.

(9) The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(10) Under these conditions, high (at least 80%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table A:

(11) TABLE-US-00003 TABLE A Example Efficacy 14 98 18 83 25 88 71 100 72 93 77 100 78 95 82 93 83 90 93 100 94 100 95 95 96 95 97 100 98 93 103 96 104 96 105 100

EXAMPLE B

In Vivo Preventive Test on Sphaerotheca fuliginea (Powdery Mildew on Cucurbits)

(12) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO and then diluted with water to obtain the desired active material concentration.

(13) Gherkin plants (“Vert petit de Paris” variety), sown in starter cups on a 50/50 peat soil-pozzolana substrate and grown at 24° C. are treated at the Z11 cotyledon stage by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(14) After 24 hours, the plants are contaminated by spraying the cotyledons with an aqueous suspension of Sphaerotheca fuliginea spores (100 000 spores per mL). The spores are collected from infected plants. The contaminated gherkin plants are incubated at about 20° C. and at 70-80% relative humidity.

(15) Grading (90 of efficacy) is carried out 12 days after the contamination, in comparison with the control plants.

(16) Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table B:

(17) TABLE-US-00004 TABLE B Example Efficacy 5 98 6 100 7 100 10 100 11 100 12 98 13 80 19 100 20 100 22 100 23 83 25 100 29 95 30 100 31 100 32 100 33 94 38 93 50 90 59 100 62 100 63 100 64 89 65 100 66 100 67 100 68 98 69 100 70 98 87 79 99 100 100 100 101 100 102 100

EXAMPLE C

In Vivo Preventive Test on Alternaria solani (Tomato)

(18) Solvent: 49 parts by weight of N,N-dimethylformamide

(19) Emulsifier: 1 part by weight of alkylarylpolyglycolether

(20) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(21) To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Alternaria solani. The plants remain for one day in an incubation cabinet at approximately 22° C. and a relative atmospheric humidity of 100%. Then the plants are placed in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of 96%.

(22) The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.

(23) Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table C:

(24) TABLE-US-00005 TABLE C Example Efficacy 14 100 15 89 17 94 18 80 21 90 22 100 23 80 25 100 28 70 34 95 35 80 36 95 37 95 38 95 71 100 72 100 77 95 78 100 79 94 80 100 81 100 82 90 83 95 84 95 88 100 89 95 93 95 94 100 95 100 96 100 97 95 98 95 103 100 104 95 105 95 106 100 107 95

EXAMPLE D

In Vivo Preventive Test on Alternaria brassicae (Leaf Spot on Radish)

(25) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(26) Radish plants (“Pernod Clair” variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 17° C., are treated at the cotyledon stage by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(27) After 24 hours, the plants are contaminated by spraying the cotyledons with an aqueous suspension of Alternaria brassicae spores (50 000 spores per mL). The spores are collected from a 15-day-old culture.

(28) The contaminated radish plants are incubated at 20° C. and at 100% relative humidity.

(29) Grading (% of efficacy) is carried out 6 days after the contamination, in comparison with the control plants.

(30) Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table D:

(31) TABLE-US-00006 TABLE D Example Efficacy 2 70 3 90 4 100 5 100 6 100 7 80 10 100 11 100 19 100 22 93 31 100 32 100 49 96 50 80 65 100 66 96 67 97 69 96 70 91 90 90 91 96 92 96 101 92 102 92

(32) Under these conditions, excellent (at least 90%) to total protection is observed at a dose of 100 ppm of active ingredient with the following compounds from table D2:

(33) TABLE-US-00007 TABLE D2 Example Efficacy 8 100 9 100 60 100 61 92

EXAMPLE E

In Vivo Preventive Test on Pyrenophora teres (Barley)

(34) Solvent: 49 parts by weight of N,N-dimethylformamide

(35) Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(36) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(37) To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Pyrenophora teres.

(38) The plants remain for 48 hours in an incubation cabinet at 22° C. and a relative atmospheric humidity of 100%. Then the plants are placed in a greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80%.

(39) The test is evaluated 7-9 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.

(40) Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table E:

(41) TABLE-US-00008 TABLE E Example Efficacy 14 100 15 100 16 100 17 95 18 95 21 100 22 100 23 100 24 95 25 95 28 95 34 70 36 100 37 100 38 100 71 100 72 100 77 100 78 100 79 100 80 100 81 100 82 95 83 100 84 100 93 100 94 100 95 100 96 100 97 100 98 100 103 100 104 95 105 100 106 90 107 80

EXAMPLE F

In Vivo Preventive Test on Pyrenophora teres (Barley)

(42) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(43) Barley plants (“Plaisant” variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 22° C., are treated at the 1 leaf stage (10 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(44) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Pyrenophora teres spores (12 000 spores per mL). The spores are collected from a 12-day-old culture. The contaminated barley plants are incubated for 48 hours at 20° C. and at 100% relative humidity, and then for 12 days at 20° C. at 70-80% relative humidity.

(45) Grading (% of efficacy) is carried out 14 days after the contamination, in comparison with the control plants.

(46) Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table F:

(47) TABLE-US-00009 TABLE F Example Efficacy 4 100 5 97 6 100 7 100 10 93 11 100 12 100 13 97 19 100 20 97 25 86 31 97 32 97 33 100 38 100 47 88 48 88 49 88 50 88 53 75 58 100 59 100 62 97 63 79 64 71 65 100 66 100 67 98 69 97 70 79 73 100 90 81 91 75 99 100 100 100 101 100 102 100

(48) Under these conditions, good (at least 70%) to total protection is observed at a dose of 100 ppm of active ingredient with the following compounds from table F2:

(49) TABLE-US-00010 TABLE F2 Example Efficacy 8 98 9 75 60 98 61 100

EXAMPLE G

In Vivo Preventive Test on Venturia inaequalis (Apple Scab)

(50) Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of N,N-dimethylacetamide

(51) Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(52) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(53) To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the causal agent of apple scab (Venturia inaequalis) and then remain for 1 day in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of 100%.

(54) The plants are then placed in a greenhouse at approximately 21° C. and a relative atmospheric humidity of approximately 90%.

(55) The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(56) Under these conditions, excellent (at least 95%) to total protection is observed at a dose of 100 ppm of active ingredient with the following compounds from table G:

(57) TABLE-US-00011 TABLE G Example Efficacy 14 99 19 100 71 100 93 100 94 100 97 98 103 100 105 100

EXAMPLE H

In Vivo Preventive Test on Septoria tritici (Wheat)

(58) Solvent: 49 parts by weight of N,N-dimethylacetamide

(59) Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(60) To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(61) To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

(62) After the spray coating has been dried, the plants are sprayed with a spore suspension of Septoria tritici. The plants remain for 48 hours in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of approximately 100% and afterwards for 60 hours at approximately 15° C. in a translucent incubation cabinet at a relative atmospheric humidity of approximately 100%.

(63) The plants are placed in the greenhouse at a temperature of approximately 15° C. and a relative atmospheric humidity of approximately 80%.

(64) The test is evaluated 21 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(65) Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table H:

(66) TABLE-US-00012 TABLE H Example Efficacy 12 100 14 75 19 100 20 100 62 100 69 100 71 100 93 83 94 100 103 100 104 90 105 80

EXAMPLE I

In Vivo Preventive Test on Septoria tritici (Wheat)

(67) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(68) Wheat plants (“Scipion” variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 22° C., are treated at the 1 leaf stage (10 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(69) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of cryopreserved Septoria tritici spores (500 000 spores per mL). The contaminated wheat plants are incubated for 72 hours at 18° C. and at 100% relative humidity, and then for 21 days at 90% relative humidity.

(70) Grading (% of efficacy) is carried out 24 days after the contamination, in comparison with the control plants.

(71) Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table I:

(72) TABLE-US-00013 TABLE I Example Efficacy 1 80 3 92 5 100 7 97 10 93 11 71 12 100 13 90 19 96 20 96 22 88 25 96 31 96 32 80 33 92 38 96 46 75 47 83 48 83 50 97 53 83 56 83 57 75 62 100 63 97 64 93 65 100 66 100 67 94 68 71 69 97 70 96 85 96 90 92 92 83 101 100 102 75

EXAMPLE J

In Vivo Preventive Test on Blumeria graminis (Barley)

(73) Solvent: 49 parts by weight of N,N-dimethylacetamide

(74) Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(75) To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(76) To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

(77) After the spray coating has been dried, the plants are dusted with spores of Blumeria graminis f.sp. hordei.

(78) The plants are placed in the greenhouse at a temperature of approximately 18° C. and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.

(79) The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(80) Under these conditions, good (at least 75%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table J:

(81) TABLE-US-00014 TABLE J Example Efficacy 12 100 14 90 19 100 20 95 62 100 69 100 71 100 93 100 94 89 104 78

EXAMPLE K

In Vivo Preventive Test on Leptosphaeria nodorum (Wheat)

(82) Solvent: 49 parts by weight of N,N-dimethylacetamide

(83) Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(84) To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(85) To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application. After the spray coating has been dried, the plants are sprayed with a spore suspension of Leptosphaeria nodorum.

(86) The plants remain for 48 hours in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of approximately 100%.

(87) The plants are placed in the greenhouse at a temperature of approximately 22° C. and a relative atmospheric humidity of approximately 80%.

(88) The test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(89) Under these conditions, high (at least 80%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table K:

(90) TABLE-US-00015 TABLE K Example Efficacy 12 93 19 100 20 86 62 100 69 100 71 100 93 100 94 80 104 83

EXAMPLE L

In Vivo Preventive Test on Puccinia triticina (Wheat)

(91) Solvent: 49 parts by weight of N,N-dimethylacetamide

(92) Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(93) To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(94) To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

(95) After the spray coating has been dried, the plants are sprayed with a spore suspension of Puccinia triticina.

(96) The plants remain for 48 hours in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of approximately 100%.

(97) The plants are placed in the greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80%.

(98) The test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(99) Under these conditions, good (at least 75%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table L:

(100) TABLE-US-00016 TABLE L Example Efficacy 12 100 14 83 19 100 20 78 62 100 71 100 93 100

EXAMPLE M

In Vivo Preventive Test on Puccinia recondita (Brown Rust on Wheat)

(101) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(102) Wheat plants (“Scipion” variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 22° C., are treated at the 1 leaf stage (10 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(103) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Puccinia recondite spores (100 000 spores per mL). The spores are collected from an infected plant and are suspended in water containing 2.5 mL/L of Tween 80 at 10%. The contaminated wheat plants are incubated for 24 hours at 20° C. and at 100% relative humidity, and then for 10 days at 20° C. and at 70-80% relative humidity.

(104) Grading (% of efficacy) is carried out 12 days after the contamination, in comparison with the control plants.

(105) Under these conditions, good (at least 75%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table M:

(106) TABLE-US-00017 TABLE M Example Efficacy 1 94 2 98 3 75 4 78 5 100 7 98 10 100 11 94 12 94 19 100 20 81 21 94 22 100 23 81 25 100 31 100 32 98 38 100 48 75 58 98 59 89 62 98 63 81 64 94 65 100 66 94 67 97 68 75 69 81 87 75 99 95 100 90 102 90

EXAMPLE N

In Vivo Preventive Test on Fusarium nivale (Wheat)

(107) Solvent: 49 parts by weight of N,N-dimethylacetamide

(108) Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(109) To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(110) To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.

(111) After the spray coating has been dried, the plants are slightly injured by using a sandblast and afterwards they are sprayed with a conidia suspension of Fusarium nivale (var. majus).

(112) The plants are placed in the greenhouse under a translucent incubation cabinet at a temperature of approximately 10° C. and a relative atmospheric humidity of approximately 100%.

(113) The test is evaluated 5 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(114) Under these conditions, high (at least 85%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table N:

(115) TABLE-US-00018 TABLE N Example Efficacy 12 100 14 88 19 100 20 100 62 100 69 93 71 100 93 100 94 100

EXAMPLE O

In Vivo Protective Test on Botrytis cinerea (Beans)

(116) Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of N,N-dimethylacetamide

(117) Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(118) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(119) To test for preventive activity, young plants are sprayed with the preparation of active compound. After the spray coating has dried on, 2 small pieces of agar covered with growth of Botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened chamber at 20° C. and a relative atmospheric humidity of 100%.

(120) 2 days after the inoculation, the size of the lesions on the leaves is evaluated. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

(121) Under these conditions, excellent (at least 95%) to total protection is observed at a dose of 100 ppm of active ingredient with the following compounds from table O:

(122) TABLE-US-00019 TABLE O Example Efficacy 14 100 71 97 93 100 94 100 97 100 103 99 105 100

EXAMPLE P

In Vivo Preventive Test on Botrytis cinerea (Grey Mould)

(123) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO and then diluted with water to obtain the desired active material concentration.

(124) Gherkin plants (“Vert petit de Paris” variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 24° C. are treated at the Z11 cotyledon stage by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(125) After 24 hours, the plants are contaminated by spraying the cotyledons with an aqueous suspension of cryopreserved Botrytis cinerea spores (50 000 spores per mL). The spores are suspended in a nutrient solution composed of 10 g/L of PDB, 50 g/L of D-Fructose, 2 g/L of NH.sub.4NO.sub.3 and 1 g/L of KH.sub.2PO.sub.4. The contaminated gherkin plants are incubated at 17° C. and at 90% relative humidity.

(126) Grading (% of efficacy) is carried out 4 to 5 days after the contamination, in comparison with the control plants.

(127) Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table P:

(128) TABLE-US-00020 TABLE P Example Efficacy 2 70 3 95 4 80 6 100 12 100 13 100 19 100 20 100 31 100 46 88 47 97 48 83 49 98 50 99 51 95 52 80 53 99 54 85 56 100 57 75 59 100 63 85 65 100 66 99 70 100 73 93 86 70 90 100 91 99 92 100 99 100 100 100 101 98 102 95

EXAMPLE Q

In Vivo Preventive Test on Uromyces appendiculatus (Bean Rust)

(129) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(130) Bean plants (“Saxa” variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 24° C., are treated at the 2 leaf stage (9 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(131) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Uromyces appendiculatus spores (150 000 spores per mL). The spores are collected from infected plants and are suspended in water containing 2.5 mL/L of Tween 80 at 10%. The contaminated bean plants are incubated for 24 hours at 20° C. and at 100% relative humidity, and then for 10 days at 20° C. and at 70-80% relative humidity.

(132) Grading (% of efficacy) is carried out 11 days after the contamination, in comparison with the control plants.

(133) Under these conditions, good (at least 75%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table Q:

(134) TABLE-US-00021 TABLE Q Example Efficacy 1 95 2 98 3 100 5 100 6 77 7 94 10 100 11 100 12 97 13 91 19 100 20 100 21 98 22 100 25 80 31 100 32 89 38 100 46 85 47 83 48 87 59 75 62 100 65 100 66 88 67 87 69 96 70 88 100 100 102 92

EXAMPLE R

In Vivo Preventive Test on Pyricularia oryzae (Rice Blast)

(135) The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.

(136) Rice plants (“Koshihikari” variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 26° C., are treated at the 2 leaf stage (10 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.

(137) After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Pyricularia oryzae spores (40 000 spores per mL). The spores are collected from a 15-day-old culture and are suspended in water containing 2.5 g/L of gelatin. The contaminated rice plants are incubated at 25° C. and at 80% relative humidity.

(138) Grading (% of efficacy) is carried out 6 days after the contamination, in comparison with the control plants.

(139) Under these conditions, good (at least 70%) to excellent (at least 90%) protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table R:

(140) TABLE-US-00022 TABLE R Example Efficacy 2 71 11 92 31 80 68 80