OXADIAZOLINE COMPOUND OR SALTS THEREOF, AGRICULTURAL AND HORTICULTURAL BACTERICIDE CONTAINING SAID COMPOUND, AND METHOD FOR USING SAME

Abstract

In production of crops of agriculture and horticulture or the like, damage caused by diseases is still large, and, due to factors such as occurrence of resistant diseases to existing drugs, development of new agrohorticultural fungicides is desired.

General formula (I)

##STR00001##

As a result of intensive research to develop novel fungicides, the present inventors found that the compound represented by the general formula (I) of the present invention or a salt thereof is useful as an agrohorticultural fungicide to complete the present invention.

Claims

1-6. (canceled)

7. A compound represented by the general formula (I) or salts thereof: ##STR00199## wherein: L is either of the following structural formula L.sup.1, L.sup.2, or L.sup.3: ##STR00200## Q is: (a1) a (C.sub.1-C.sub.6)alkyl group; (a2) a (C.sub.2-C.sub.6)alkenyl group; (a3) a (C.sub.2-C.sub.6)alkynyl group; (a4) a (C.sub.3-C.sub.6)cycloalkyl group; (a5) a (C.sub.1-C.sub.6)alkoxy group; (a6) a halo(C.sub.1-C.sub.6)alkyl group; (a7) a halo(C.sub.2-C.sub.6)alkenyl group; (a8) a halo(C.sub.2-C.sub.6)alkynyl group; (a9) a halo(C.sub.3-C.sub.6)cycloalkyl group; (a10) a halo(C.sub.1-C.sub.6)alkoxy group; (a11) a (C.sub.1-C.sub.6)alkylthio group; (a12) a (C.sub.1-C.sub.6)alkylsulfinyl group; (a13) a (C.sub.1-C.sub.6)alkylsulfonyl group; (a14) a halo(C.sub.1-C.sub.6)alkylthio group; (a15) a halo(C.sub.1-C.sub.6)alkylsulfinyl group; (a16) a halo(C.sub.1-C.sub.6)alkylsulfonyl group; (a17) an R.sup.3(R.sup.4)N group; (a18) an aryl group; (a19) a substituted aryl group having on the ring one to eight substituents each independently selected from the group consisting of a halogen atom, cyano group, nitro group, (C.sub.1-C.sub.6)alkyl group, (C.sub.1-C.sub.6)alkoxy group, (C.sub.3-C.sub.6)cycloalkyl group, halo(C.sub.1-C.sub.6)alkyl group, halo(C.sub.1-C.sub.6)alkoxy group, halo(C.sub.3-C.sub.6)cycloalkyl group, (C.sub.1-C.sub.6)alkylthio group, (C.sub.1-C.sub.6)alkylsulfinyl group, (C.sub.1-C.sub.6)alkylsulfonyl group, halo(C.sub.1-C.sub.6)alkylthio group, halo(C.sub.1-C.sub.6)alkylsulfinyl group, halo(C.sub.1-C.sub.6)alkylsulfonyl group, R.sup.3(R.sup.4)N group, (C.sub.1-C.sub.6)alkoxycarbonyl group, and R.sup.3(R.sup.4)N carbonyl group; (a20) a 5- to 6-membered hetero ring or 8- to 10-membered fused hetero ring; or (a21) a substituted 5- to 6-membered hetero ring or substituted 8- to 10-membered fused hetero ring having on the ring one to three substituents each independently selected from the group consisting of a halogen atom, cyano group, nitro group, (C.sub.1-C.sub.6)alkyl group, (C.sub.1-C.sub.6)alkoxy group, (C.sub.3-C.sub.6)cycloalkyl group, halo(C.sub.1-C.sub.6)alkyl group, halo(C.sub.1-C.sub.6)alkoxy group, halo(C.sub.3-C.sub.6)cycloalkyl group, (C.sub.1-C.sub.6)alkylthio group, (C.sub.1-C.sub.6)alkylsulfinyl group, (C.sub.1-C.sub.6)alkylsulfonyl group, halo(C.sub.1-C.sub.6)alkylthio group, halo(C.sub.1-C.sub.6)alkylsulfinyl group, halo(C.sub.1-C.sub.6)alkylsulfonyl group, R.sup.3(R.sup.4)N group, (C.sub.1-C.sub.6)alkylthio(C.sub.1-C.sub.6)alkyl group, phenyl group, halogen substituted phenoxy group, (C.sub.1-C.sub.6)alkoxycarbonyl group, and R.sup.3(R.sup.4)N carbonyl group; R.sup.1 and R.sup.2 are each independently: (b1) a hydrogen atom; (b2) a halogen atom; (b3) a (C.sub.1-C.sub.6)alkyl group; (b4) a halo(C.sub.1-C.sub.6)alkyl group; or (b5) a (C.sub.1-C.sub.6)alkoxy group; or R.sup.1 and R.sup.2 form a cyclopropane ring with a carbon atom to which they bond; R.sup.3 and R.sup.4 are each independently: (c1) a hydrogen atom; (c2) a (C.sub.1-C.sub.6)alkyl group; (c3) a (C.sub.2-C.sub.6)alkenyl group; (c4) a (C.sub.2-C.sub.6)alkynyl group; (c5) a (C.sub.3-C.sub.6)cycloalkyl group; (c6) a (C.sub.1-C.sub.6)alkoxy group; (c7) a halo(C.sub.1-C.sub.6)alkyl group; (c8) a (C.sub.1-C.sub.6)alkylthio group; (c9) a (C.sub.1-C.sub.6)alkylsulfinyl group; (c10) a (C.sub.1-C.sub.6)alkylsulfonyl group; (c11) a (C.sub.3-C.sub.6)cycloalkylsulfonyl group; (c12) a phenylsulfonyl group; (c13) a (C.sub.3-C.sub.6)cycloalkyl(C.sub.1-C.sub.6)alkyl group; (c14) a (C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6)alkylcarbonyl group; (c15) a (C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6)alkyl group; (c16) a di(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6)alkyl group; (c17) a cyano(C.sub.1-C.sub.6)alkyl group; (c18) a (C.sub.1-C.sub.6)alkylthio(C.sub.1-C.sub.6)alkyl group; (c19) a di((C.sub.1-C.sub.6)alkyl)amino(C.sub.1-C.sub.6)alkyl group; (c20) a (C.sub.1-C.sub.6)alkylcarbonyl group; (c21) a halo(C.sub.1-C.sub.6)alkylcarbonyl group; (c22) a (C.sub.3-C.sub.6)cycloalkylcarbonyl group; (c23) a benzoyl group; (c24) a mono((C.sub.1-C.sub.6)alkyl)aminocarbonyl group; (c25) a di((C.sub.1-C.sub.6)alkyl)aminocarbonyl group; (c26) a phenylaminocarbonyl group; (c27) a (C.sub.1-C.sub.6)alkoxycarbonyl(C.sub.1-C.sub.6)alkyl group; (c28) a phenylcarbony group; (c29) a (C.sub.1-C.sub.6)alkoxyiminomethylenyl group; (c30) a tetrahydropyran-4-ylcarbonyl group; (c31) a benzyl group; (c32) a phenyl group; (c33) a halosubstituted phenyl group; (c34) a formyl group; or (c35) a pyrimidinyl group; and R.sup.5 is: (d1) a hydrogen atom; (d2) a (C.sub.1-C.sub.6)alkyl group; (d3) a (C.sub.1-C.sub.6)alkylcarbonyl group; (d4) a (C.sub.1-C.sub.6)alkoxycarbonyl group; or (d5) a (C.sub.1-C.sub.6)alkyl(C.sub.1-C.sub.6)alkyl group.

8. The compound of claim 7 or salts thereof, wherein: Q is: (a1) a (C.sub.1-C.sub.6)alkyl group; (a11) a (C.sub.1-C.sub.6)alkylthio group; (a12) a (C.sub.1-C.sub.6)alkylsulfinyl group; (a13) a (C.sub.1-C.sub.6)alkylsulfonyl group; (a17) an R.sup.3(R.sup.4)N group; or (a21) a substituted 5- to 6-membered hetero ring or substituted 8- to 10-membered fused hetero ring having on the ring one to three substituents each independently selected from the group consisting of a halogen atom, cyano group, nitro group, (C.sub.1-C.sub.6)alkyl group, (C.sub.1-C.sub.6)alkoxy group, (C.sub.3-C.sub.6)cycloalkyl group, halo(C.sub.1-C.sub.6)alkyl group, halo(C.sub.1-C.sub.6)alkoxy group, halo(C.sub.3-C.sub.6)cycloalkyl group, (C.sub.1-C.sub.6)alkylthio group, (C.sub.1-C.sub.6)alkylsulfinyl group, (C.sub.1-C.sub.6)alkylsulfonyl group, halo(C.sub.1-C.sub.6)alkylthio group, halo(C.sub.1-C.sub.6)alkylsulfinyl group, halo(C.sub.1-C.sub.6)alkylsulfonyl group, R.sup.3(R.sup.4)N group, (C.sub.1-C.sub.6)alkylthio(C.sub.1-C.sub.6)alkyl group, phenyl group, halogen substituted phenoxy group, (C.sub.1-C.sub.6)alkoxycarbonyl group, and R.sup.3(R.sup.4)N carbonyl group; R.sup.1 and R.sup.2 are each independently: (b1) a hydrogen atom; (b3) a (C.sub.1-C.sub.6)alkyl group; or (b5) a (C.sub.1-C.sub.6)alkoxy group; R.sup.3 and R.sup.4 are each independently: (c1) a hydrogen atom; (c2) a (C.sub.1-C.sub.6)alkyl group; (c3) a (C.sub.2-C.sub.6)alkenyl group; (c4) a (C.sub.2-C.sub.6)alkynyl group; (c5) a (C.sub.3-C.sub.6)cycloalkyl group; (c6) a (C.sub.1-C.sub.6)alkoxy group; (c10) a (C.sub.1-C.sub.6)alkylsulfonyl group; (c11) a (C.sub.3-C.sub.6)cycloalkylsulfonyl group; (c12) a phenylsulfonyl group; (c13) a (C.sub.3-C.sub.6)cycloalkyl(C.sub.1-C.sub.6)alkyl group; (c14) a (C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6)alkylcarbonyl group; (c16) a di(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6)alkyl group; (c17) a cyano(C.sub.1-C.sub.6)alkyl group; (c20) a (C.sub.1-C.sub.6)alkylcarbonyl group; (c21) a halo(C.sub.1-C.sub.6)alkylcarbonyl group; (c22) a (C.sub.3-C.sub.6)cycloalkylcarbonyl group; (c23) a benzoyl group; (c24) a mono((C.sub.1-C.sub.6)alkyl)aminocarbonyl group; (c26) a phenylaminocarbonyl group; (c27) a (C.sub.1-C.sub.6)alkoxycarbonyl(C.sub.1-C.sub.6)alkyl group; (c29) a (C.sub.1-C.sub.6)alkoxyiminomethylenyl group; (c30) a tetrahydropyran-4-ylcarbonyl group; (c33) a halosubstituted phenyl group; (c34) a formyl group; or (c35) a pyrimidinyl group; and R.sup.5 is: (d1) a hydrogen atom; or (d2) a (C.sub.1-C.sub.6)alkyl group.

9. The compound of claim 7 or salts thereof, wherein: Q is: (a13) a (C.sub.1-C.sub.6)alkylsulfonyl group; (a17) an R.sup.3(R.sup.4)N group; or (a21) a substituted 5- to 6-membered hetero ring or substituted 8- to 10-membered fused hetero ring having on the ring one to three substituents each independently selected from the group consisting of a halogen atom, cyano group, nitro group, (C.sub.1-C.sub.6)alkyl group, (C.sub.1-C.sub.6)alkoxy group, (C.sub.3-C.sub.6)cycloalkyl group, halo(C.sub.1-C.sub.6)alkyl group, halo(C.sub.1-C.sub.6)alkoxy group, halo(C.sub.3-C.sub.6)cycloalkyl group, (C.sub.1-C.sub.6)alkylthio group, (C.sub.1-C.sub.6)alkylsulfinyl group, (C.sub.1-C.sub.6)alkylsulfonyl group, halo(C.sub.1-C.sub.6)alkylthio group, halo(C.sub.1-C.sub.6)alkylsulfinyl group, halo(C.sub.1-C.sub.6)alkylsulfonyl group, R.sup.3(R.sup.4)N group, (C.sub.1-C.sub.6)alkylthio(C.sub.1-C.sub.6)alkyl group, phenyl group, halogen substituted phenoxy group, (C.sub.1-C.sub.6)alkoxycarbonyl group, and R.sup.3(R.sup.4)N carbonyl group; R.sup.3 and R.sup.4 are each independently: (c1) a hydrogen atom; (c2) a (C.sub.1-C.sub.6)alkyl group; (c10) a (C.sub.1-C.sub.6)alkylsulfonyl group; (c14) a (C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6)alkylcarbonyl group; (c20) a (C.sub.1-C.sub.6)alkylcarbonyl group; (c22) a (C.sub.3-C.sub.6)cycloalkylcarbonyl group; (c23) a benzoyl group; (c24) a mono((C.sub.1-C.sub.6)alkyl)aminocarbonyl group; (c30) a tetrahydropyran-4-ylcarbonyl group; (c34) a formyl group; or (c35) a pyrimidinyl group; and R.sup.5 is: (d1) a hydrogen atom.

10. A fungicide comprising an active ingredient selected from the compound of claim 7 or salts thereof.

11. A method of controlling plant disease, comprising the administration of an effective amount of the fungicide of claim 10 to a plant or soil in need thereof.

12. A use of the compound of claim 7 or salts thereof as a fungicide.

Description

EXAMPLES

Example 1

Production of N-cyclopropyl-5-[5-(trifluoromethyl)-4,5-dihydro-1,2,4-oxadiazol-3-yl]thiophene-2-carboxamide (Compound No. 2-5)

[0105] ##STR00197##

[0106] N-cyclopropyl-5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiophene-2-carboxamide (0.30 g, 0.90 mmol) was dissolved in methanol (5 mL), cooled to 0° C., sodium borohydride (0.0075 g, 0.20 mmol) was added and stirred at room temperature for 1.3 hours. Thereafter, acetone (1 mL) was added, and the mixture was stirred at room temperature for one hour, added with silica gel, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the title compound (0.23 g, 0.67 mmol).

Yield: 75%

[0107] Physical property: Melting point 237-240° C.

Reference Example 1

Production of N-cyclopropyl-5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiophene-2-carboxamide

[0108] ##STR00198##

[0109] 5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiophene-2-carboxylic acid (0.20 g, 0.76 mmol) prepared by the method described in WO2011/088181 pamphlet was dissolved in chloroform (7 mL), and cyclopropylamine (0.056 g, 0.99 mmol), triethylamine (0.23 g, 2.3 mmol), propylphosphonic acid anhydride (cyclic trimer) (50% ethyl acetate solution, about 1.7 mol/L) (0.97 g, 1.5 mmol) were added at room temperature and stirred for 3.5 hours. Thereafter, water was added and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate and concentrated under reduced pressure. The residue was washed with a mixture solvent of hexane and ethyl acetate to obtain the title compound (0.20 g, 0.67 mmol).

Yield: 88%

[0110] Physical property: Melting point 179-180° C.

[0111] Formulation examples are recited but the present invention is not limited thereto. In the formulation examples, the term “parts” denotes “parts by weight”.

Formulation Example 1

[0112]

TABLE-US-00004 Present inventive compound represented by the general formula (I) 10 parts Xylene 70 parts N-methylpyrrolidone 10 parts Mixture of polyoxyethylene nonylphenyl ether and 10 parts calcium alkylbenzenesulfonate

[0113] An emulsifiable concentrate was prepared by uniformly mixing and dissolving the above ingredients.

Formulation Example 2

[0114]

TABLE-US-00005 Present inventive compound represented by the general formula (I)  3 parts Clay powder 82 parts Diatomaceous earth powder 15 parts

[0115] A dust was prepared by mixing uniformly and grinding the above ingredients.

Formulation Example 3

[0116]

TABLE-US-00006 Present inventive compound represented by the general formula (I)  5 parts Mixed powder of bentonite and clay 90 parts Calcium lignin sulfonate  5 parts

[0117] Granules were prepared by mixing the above ingredients uniformly together with a suitable amount of water, and kneading the resulting mixture, followed by granulation and drying.

Formulation Example 4

[0118]

TABLE-US-00007 Present inventive compound represented by the general formula (I) 20 parts Mixture of Kaolin and synthetic high-dispersion silicic acid 75 parts Mixture of polyoxyethylene nonylphenyl ether and  5 parts calcium alkylbenzenesulfonate

[0119] A wettable powder was prepared by mixing uniformly and grinding the above ingredients.

Test Example 1. Fungicidal Efficacy Test for Soybean Rust

[0120] A chemical agent prepared according to Formulation Examples 1 to 4 containing the present inventive compound represented by the general formula (I) as an active ingredient was diluted with water to a predetermined concentration. Soybeans (cultivar: Enrei, 2-leaf stage) grown in pots of 6 cm in diameter were foliage sprayed at a rate of 10 ml per pot. After air-drying the solution, the spore suspension prepared from spores obtained from soybean leaves infected with soybean rust (Phakopsora pachyrhizi) was spray-inoculated, kept at 20° C. humidified conditions for 24 hours, and then transferred to a greenhouse to be left about 10 days.

[0121] For evaluation, various diseased area ratios were assessed to calculate the control value from the following formula I.

(Formula I)

[00001]$\begin{array}{cc}\mathrm{Control}\mathrm{value}\left(\%\right)=\frac{\begin{array}{c}\mathrm{Average}\mathrm{lesion}\mathrm{area}\mathrm{ratio}\mathrm{in}\mathrm{untreated}\\ \mathrm{plot}-\mathrm{Average}\mathrm{lesion}\mathrm{area}\mathrm{ratio}\mathrm{in}\mathrm{treated}\mathrm{plot}\end{array}}{\mathrm{Average}\mathrm{lesion}\mathrm{area}\mathrm{ratio}\mathrm{in}\mathrm{untreated}\mathrm{plot}}\times 100& \left[\mathrm{Math}1\right]\end{array}$

Assessment Criteria

[0122] 0: Control value 9% or lower

[0123] 1: Control value 10-19%

[0124] 2: Control value 20-29%

[0125] 3: Control value 30-39%

[0126] 4: Control value 40-49%

[0127] 5: Control value 50-59%

[0128] 6: Control value 60-69%

[0129] 7: Control value 70-79%

[0130] 8: Control value 80-89%

[0131] 9: Control value 90-99%

[0132] 10: Control value 100%

[0133] As the result of the above mentioned test, of the present inventive compounds represented by the general formula (I), the following compounds showed, at the treatment concentration of 50 ppm, an effect with a control value of 8 or higher: 1-1, 1-11, 1-14, 1-16, 1-20, 1-23, 1-25, 1-31, 1-32, 1-33, 1-35, 1-36, 1-37, 1-38, 1-40, 1-41, 1-42, 1-43, 1-44, 1-45, 1-46, 1-49, 2-1, 2-5, 2-8, 2-23, 3-1, 3-17, 3-43, 3-44, 3-54, 3-60, 3-64, 3-67, 3-68, 3-69, 3-89 and 3-97.

INDUSTRIAL APPLICABILITY

[0134] The present inventive compound represented by the general formula (I) or salts thereof has a remarkable effect as an agrohorticultural fungicide. The present invention hence can contribute to development of agrochemical-related industries, agriculture and fields related thereto.