CRYSTAL OF 3-(DIFLUOROMETHYL)-1-METHYL-N-(1,1,3-TRIMETHYL-2,3-DIHYDRO-1H-INDEN-4-YL)-1H-PYRAZOLE-4-CARBOXAMIDE

3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, which is selected from at least one of a group consisting of a Ra1 type crystal form, a Ra2 type crystal form, and a Ra3 type crystal form, each of the crystal form has a diffraction peaks described in the Description in a powder x-ray diffraction due to Cu-Kα radiation.

TECHNICAL FIELD

The present invention relates to a novel crystal of 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide having a plant disease controlling efficacy.

BACKGROUND ART

Hitherto, it has been reported that 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide (hereinafter, referred to as “Compound A”) is a crystal having a melting point of 131 to 134° C., and showing a control efficacy against plant diseases (see Patent Literature 1).Patent Literature 1: WO 92/12970 pamphlet

DISCLOSURE OF INVENTION

Technical Problem

An object of the present invention is to provide a novel crystal which has different physical properties than those of a publicly known crystal described in the Patent Literature 1 (hereinafter, the crystal is referred to as “Ra4 type crystal form”) and also shows more excellent control efficacy against plant diseases.

Technical Solution

The present inventors have found out three kinds of novel crystals of the Compound A (“Ra1 type crystal form”, “Ra2 type crystal form”, and “Ra3 type crystal form”), each having an excellent control efficacy against plant diseases.

That, the present invention provides the following embodiments.

[1] A crystal of 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, which is selected from at least one of a group consisting of

a Ra2 type crystal form which in a powder x-ray diffraction due to Cu-Kα radiation, has a diffraction peaks 2θ of 4.3±0.2°, 8.5±0.2°, 10.8±0.2°, 11.4±0.2°, 12.4±0.2°, 12.8±0.2°, 15.1±0.2°, 16.1±0.2°, 16.8±0.2°, and 19.1±0.2°, and

a Ra3 type crystal form which in a powder x-ray diffraction due to Cu-Kα radiation, has a diffraction peaks 2θ of 3.6±0.2°, 7.1±0.2°, 7.4±0.2°, 9.6±0.2°, 11.9±0.2°, 12.5±0.2°, 12.9±0.2°, 14.3±0.2°, 15.7±0.2°, and 17.9±0.2°.

[2] The crystal of 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide according to [1], which is a Ra1 type crystal form which in a powder x-ray diffraction due to Cu-Kα radiation, has a diffraction peaks 2θ of 7.1±0.2°, 8.6±0.2°, 8.9±0.2°, 9.1±0.2°, 13.3±0.2°, 14.0±0.2°, 14.3±0.2°, 14.8±0.2°, 16.0±0.2°, 16.4±0.2°, 20.3±0.2°, and 20.6±0.2°.
[3] The crystal of 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide according to [1], which is a Ra2 type crystal form which in a powder x-ray diffraction due to Cu-Kα radiation, has a diffraction peaks 2θ of 4.3±0.2°, 8.5±0.2°, 10.8±0.2°, 11.4±0.2°, 12.4±0.2°, 12.8±0.2°, 15.1±0.2°, 16.1±0.2°, 16.8±0.2°, and 19.1±0.2°.
[4] The crystal of 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide according to [1], which is a Ra3 type crystal form which in a powder x-ray diffraction due to Cu-Kα radiation, has a diffraction peaks 2θ of 3.6±0.2°, 7.1±0.2°, 7.4±0.2°, 9.6±0.2°, 11.9±0.2°, 12.5±0.2°, 12.9±0.2°, 14.3±0.2°, 15.7±0.2°, and 17.9±0.2°.
[5] A composition for controlling a plant disease comprising one or more crystals according to any one of [1] to [4].
[6] A method for controlling a plant disease which comprises applying an effective amount of one or more crystals according to any one of [1] to [4] to a plant or a soil where the plant grows.
[7] Use of one or more crystal according to any one of [1] to [4] for controlling a plant disease.
[8] A composition which comprises one or more ingredients selected from the group consisting of the following Groups (a), (b), (c) and (d), as well as one or more crystals according to any one of [1] to [4]:

Group (a): a group consisting of insecticidal ingredients, miticidal ingredients, and nematicidal ingredients;

Group (c): plant growth modulating ingredients; and

[9] A seed or vegetative reproductive organ carrying an effective amount of one or more crystal according to any one of [1] to [4] or an effective amount of the composition according to [7].

Effect of Invention

The present invention provides three kinds of novel crystals of the compound A showing a control efficacy against plant diseases (that is, a Ra1 type crystal form, a Ra2 type crystal form, and a Ra3 type crystal form). These crystals can show superior control efficacy against plant diseases compared to a publicly known Ra4 type crystal form.

MODE FOR CARRYING OUT THE INVENTION

The present invention relates to novel crystals of the compound A (that is, the Ra1 type crystal form, the Ra2 type crystal form, and the Ra3 type crystal form). The 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide is a compound encompassing two kinds of enantiomers such as R form and S form, and the compound A is a mixture composed of each equivalent amount of thereof, that is, a racemate. Also, the crystal in which each equal amount of the R form and the S form are arranged with a regularity in a crystal lattice represents a crystal of the present invention, which makes depending on the process condition, the Ra1 type crystal form, the Ra2 type crystal form, or the Ra3 type crystal form, respectively.

The Ra4 type crystal form has a melting point of about 131 to 134° C., and in a powder x-ray diffraction due to Cu-Kα radiation, has a diffraction peak values 2θ (°) of 5.8±0.2, 7.2±0.2, 8.6±0.2, 13.8±0.2, 16.3±0.2, 16.7±0.2, 17.4±0.2, 17.7±0.2, 19.4±0.2, 19.8±0.2, and 20.7±0.2.

The Ra1 type crystal form, the Ra2 type crystal form, and the Ra3 type crystal form has the following physical property respectively.

The Ra1 type crystal form is a crystal which has a melting point of about 134 to 136° C., and in a powder x-ray diffraction due to Cu-Kα radiation, has a diffraction peak values 2θ (°) of 7.1±0.2, 8.6±0.2, 8.9±0.2, 9.1±0.2, 13.3±0.2, 14.0±0.2, 14.3±0.2, 14.8±0.2, 16.0±0.2, 16.4±0.2, 20.3±0.2, and 20.6±0.2.

The Ra1 type crystal form can be prepared according to the below-mentioned process.

The required amount (for example, about 200 mg) of the Ra2 type crystal form is heated at about 130° C. for a certain time (about 2 hours) in an appropriate container (for example, 20 mL sample bottle) to obtain the Ra1 type crystal form.

The Ra2 type crystal form is a crystal which has a melting point of about 124 to 126° C., and in a powder x-ray diffraction due to Cu-Kα radiation, has a diffraction peak values 2θ (°) of 4.3±0.2, 8.5±0.2, 10.8±0.2, 11.4±0.2, 12.4±0.2, 12.8±0.2, 15.1±0.2, 16.1±0.2, 16.8±0.2, and 19.1±0.2.

The Ra2 type crystal form can be prepared according to the below-mentioned process.

The required amount (for example, about 30 mg) of the compound A is dissolved in an appropriate amount (about 80 μL) of organic solvents (for example, methanol) at about 60° C. to adjust the solution to be a certain amount of a dissolution concentration (about 375 mg/mL). After the solution is cooled to room temperature, a laser is irradiated to the solution under a certain condition, and the solution is allowed to stand at about 20° C. to obtain the Ra2 type crystal form.

The laser irradiation condition may include below, and should not be limited thereto.

number of pulse: 125 pulses/10 seconds

Examples of the organic solvents include alcohol solvents, and include preferably an alkyl solvents containing 1 to 3 carbon atoms. Specific examples thereof include methanol, ethanol, propanol, and isopropanol, and preferably methanol.

The amounts of the organic solvent include an amount that achieves a dissolution concentration of about 200 mg/mL to about 1000 mg/mL of the compound A as opposed to the organic solvents to be used at dissolving. The dissolution concentration of the compound A include preferably about 300 mg/L to about 500 mg/mL, and for example, about 375 mg/mL.

The Ra3 type crystal form is a crystal which has a melting point of about 129 to 131° C., and in a powder x-ray diffraction due to Cu-Kα radiation, has a diffraction peak values 2θ (°) of 3.6±0.2, 7.1±0.2, 7.4±0.2, 9.6±0.2, 11.9±0.2, 12.5±0.2, 12.9±0.2, 14.3±0.2, 15.7±0.2, and 17.9±0.2.

The Ra3 type crystal form can be prepared according to the below-mentioned process.

To the required amount (for example, about 100 mg) of the Ra1 type crystal form prepared above, an appropriate amount (for example, about 1 mL) of organic solvent is added, and the resulting suspension was heated s to about 60° C., and then allowed to stir for a certain time (about 2 days) under a certain condition (about 1000 rpm), and thereafter, the solvents were removed to obtain the Ra3 type crystal form.

Examples of the organic solvents include ether solvents, and preferably dialkyl ether solvents containing 1 to 3 carbon atoms. Specific examples thereof include dimethyl ether, diethyl ether, dipropyl ether, and diisopropyl ether, and preferably diisopropyl ether.

The amount of the organic solvent is within a range of 5 to 10 parts by weight, and preferably 6 to 8 parts by weight, as opposed to 1 part by weight of the used Ra1 type crystal form.

The one or more crystals selected from the group consisting of the Ra1 type crystal form, the Ra2 type crystal form and the Ra3 type crystal form may be mixed or combined with one or more kinds of ingredients selected from a group consisting of the following Group (a), Group (b), Group (c), and Group (d) (hereinafter, referred to as Present ingredient).

The above-mentioned mixing or combining represents a use of one or more crystals selected from the group consisting of the Ra1 type crystal form, the Ra2 type crystal form, and the Ra3 type crystal form, and the Present ingredient at the same time, separately or at certain intervals.

When one or more crystals selected from the group consisting of the Ra1 type crystal form, the Ra2 type crystal form, and the Ra3 type crystal form, and the present ingredient are used at the same time, the one or more crystals selected from the group consisting of the Ra1 type crystal form, the Ra2 type crystal form, and the Ra3 type crystal form and the present ingredient may be contained in separate formulations respectively or may be contained in the same one formulation.

One aspect of the present invention is a composition comprising one or more ingredients selected from a group consisting of the following Group (a), Group (b), Group (c), and Group (d) as well as one or more crystals selected from the group consisting of the Ra1 type crystal form, the Ra2 type crystal form, and the Ra3 type crystal form (hereinafter, the composition is referred to as “Present composition” or “Composition of the present invention”).

Group (a) is a group consisting of

These ingredients are classified as a class based on the action mechanism of IRAC.

Group (b) is a group consisting of

Nucleic acid synthesis inhibitors (for example, Phenylamide fungicides, or Acylamino acid fungicides), cell division and cytoskeleton inhibitors (for example, MBC fungicides), Respiratory inhibitors (for example, QoI fungicides or Qil fungicides), Amino acid synthesis and protein synthesis inhibitors (for example, anilinopyridine fungicides), Signal transduction inhibitors, Lipid synthesis and membrane synthesis inhibitors, sterol biosynthesis inhibitors (for example, DMI fungicides such as triazole), cell wall synthesis inhibitors, Melanin synthesis inhibitors, Plant defense inducers, Other action point contact active fungicides, Microbial fungicides, and the other fungicidal ingredients. These are classified as a class based on the action mechanism of FRAC.

Group (c) is a plant growth modulating ingredient group (including Mycorrhizal fungi, and Root nodule bacteria).

Group (d) is a repellent ingredient group consisting of a bird repellent ingredient and an insect repellent ingredient.

Examples of the combination of one or more crystals selected from the group consisting of the Ra1 type crystal form, the Ra2 type crystal form, and the Ra3 type crystal form and the Present ingredient are described below. For example, alanycarb+SX represents a combination of alanycarb and SX.

The symbol of “SX” represents the Ra1 type crystal form, the Ra2 type crystal form, or the Ra3 type crystal form (hereinafter, referred to a “Present crystal or Present crystal form”, or “Crystal of the present invention” or “Crystal form of the present invention”). Also, all of the below-mentioned present active component are known ingredients, and are commercially available or may be produced by the known method. If the present ingredient is a microorganism, it is available from the International Depositary Authority. The numerical number in bracket represents a CAS RN (Register Trademark).

Combination of the Present ingredient of the above Group (a) and the Present crystal:

Combination of the Present ingredient of the above Group (b) and the Present crystal:

Combination of the Present ingredient of the above Group (c) and the Present crystal:

Combination of the Present ingredient of the above Group (d) and the Present crystal:

The present crystal may be mixed or combined with chemical fertilizers (for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, or ammonium chloride).

The Present crystal or the present composition can control plant diseases caused by plant pathogenic microorganisms such as fungi, Oomycete, Phytomyxea, and bacteria. Examples of the fungi include Ascomycota, Basidiomycota, Blastocladiomycota, Chytridiomycota, Mucoromycota, and Olpidiomycota. Specific examples of the plant diseases include the followings. The scientific name of plant pathogenic microorganism which causes each disease is shown in parentheses.

Rape Seed Diseases:

Diseases of Gourd Family:

Various Crops Diseases:

Green Pepper Disease:

Fruit Trees Diseases:

white root rot (Rosellinia necatrix), and violet root rot (Helicobasidium mompa);

Postharvest Disease of Fruits (for Example, Apple and Pear):

Seed diseases or diseases in the early stages of the growth of various plants caused byAspergillusspp.,Penicilliumspp.,Fusariumspp.,Gibberellaspp.,Tricodermaspp.,Thielaviopsisspp.,Rhizopusspp.,Mucorspp.,Corticiumspp.,Phomaspp.,Rhizoctoniaspp. orDiplodiaspp., and the like;

Diseases Caused by Bacteria:

bacterial seedling blight of rice (Burkholderia plantarii), bacterial spot of cucumber (Pseudomonas syringaepv.Lachrymans), bacterial wilt of eggplant (Ralstonia solanacearum), canker of citrus (Xanthomonas citri), bacterial soft rot of Chinese cabbage (Erwinia carotovora), scab of potato (Streptomyces scabiei), Goss's wilt of corn (Clavibacter michiganensis), Pierce's disease of grapes, olive and peach (Xylella fastidiosa), and crown gall of Rosaceae plants such as apple, peach, cherries (Agrobacterium tumefaciens).

The method for controlling plant diseases of the present invention is conducted by applying an effective amount of the Present crystal or the present composition to a plant or soil. Examples of the application method include foliar application, soil application, and seed application.

The Present crystal or the present composition is usually used by mixing it with inert carrier(s) such as solid carrier(s) and liquid carrier(s), and as needed, adding thereto surfactant(s), the other auxiliary agent(s) for formulation so as to be formulated into a solid formulation, and an aqueous suspension formulation. These formulations usually comprise 0.0001 to 99% by weight ratio of the Present crystal or the present composition.

Examples of the other auxiliary agent(s) for formulation include a thickening agent, an antifoam agent, a preservative agent, an antifreezing agent, and the others.

When the present composition comprises a thickening agent, the total amounts thereof is usually within a range of 0.1 to 5% by weight as opposed to 100% by weight of the present composition.

When the present composition comprises an antifoam agent, the total amounts thereof is usually within a range of 0.05 to 0.5% by weight as opposed to 100% by weight of the present composition.

When the present composition comprises a preservative agent, the total amounts thereof is usually within a range of 0.01 to 3% by weight as opposed to 100% by weight of the present composition.

Examples of the antifreezing agent include Water-soluble glycols (such as ethylene glycol, and propylene glycol).

When the present composition comprises an antifreezing agent, the total amounts thereof is usually within a range of 1 to 20% by weight as opposed to 100% by weight of the present composition.

In the present invention, the plant encompasses whole plant and specific part(s) of the plant. Examples of the specific part of the plant include stem and leaf, flower, ear, fruit, tree stem, branch, crown, seed, vegetative reproductive organ, and seedling.

A vegetative reproduction organ means a part of plant such as root, stem, and leaf which has a growth capability even when said part is separated from the plant body and placed into soil. Examples of the vegetative reproduction organ include tuberous root, creeping root, bulb, corm or solid bulb, tuber, rhizome, stolon, rhizophore, cane cuttings, propagule, and vine cutting. Stolon is also referred to as “runner”, and propagule is also referred to as “propagulum” and categorized into broad bud and bulbil. Vine cutting means a shoot (collective term of leaf and stem) of sweet potato, glutinous yam, or the like. Bulb, corm or solid bulb, tuber, rhizome, cane cuttings, rhizophore, and tuberous root are also collectively referred to as “bulb”. For example, cultivation of potato starts with planting a tuber into soil, and the tuber to be used is generally referred to as “seed potato”.

The application dose of the present crystal or the present composition may be varied depending on a climate condition, a formulation form, an application period, an application method, an application site, plant diseases to be controlled, plant to be applied, and the others. In the cases of foliar application or soil application, the application dose thereof is within a range of usually 1 to 500 g per 1,000 m2. In the cases of seed application, the application dose of the present crystal or the present composition is within a range of 0.001 to 100 g per 1 Kg of seeds. In the cases where the present crystal or the present composition is formulated into an emulsifiable concentrate, a wettable powder, a flowable agent etc., these formulations are used by diluting them with water so as to make the active component's concentration 0.01 to 10,000 ppm, while the dust formulation or the granular formulation, etc., is usually applied as itself without diluting them.

Examples of the seed application (or seed treatments) include an application of the present crystal or the present composition to seeds, and specific examples thereof include spraying treatment in which a suspension of the present crystal or the present composition is sprayed onto seed surface or vegetative reproductive organ surface in the form of mist; smearing treatment in which the present crystal or the present composition is coated seeds surface or vegetative reproductive organ surface; a soaking treatment in which the seeds are soaked into the solution of the present crystal or the present composition for a certain time; and a method for coating the seeds or the vegetative reproductive organ with a carrier containing the present crystal or the present composition (film coating treatment, pellet coating treatment). In particular, examples of the above-mentioned vegetative reproductive organ include “seed potato”.

When the present composition is applied to seeds or vegetative reproductive organ, the present composition may be also applied to seeds or vegetative reproductive organ as a single formulation, or the present composition may be applied to seeds or vegetative reproductive organ as a divided plural of formulations by a plurality of times. Examples of the method in which the present composition is applied as a divided plural of formulations by a plurality of times include, for example, a method in which the formulations comprising as an active component the present crystal only are applied, and seeds or vegetative reproductive organ are air dried, followed by applying the formulations comprising the present ingredient: and a method in which the formulations comprising as an active component the present crystal and the present ingredients are applied, and seeds or vegetative reproductive organ are air dried, followed by applying the formulations comprising the present ingredients other than the already-applied present ingredients, are included.

As used herein, seeds or vegetative reproductive organs carrying the present crystal or the present composition means seeds or vegetative reproductive organs in the state where the present crystal or the present composition is adhered to a surface of the seeds or the vegetative reproductive organ. The above-described seeds or vegetative reproductive organs carrying the present crystal or the present composition may be adhered by any other materials that are different from the present crystal or the present composition before or after being adhered the present crystal or the present composition to the seeds or vegetative reproductive organs.

Also, when the present composition is adhered in a form of layer(s) to a surface of seeds or vegetative reproductive organ, the layer(s) is/are composed of one layer or a multiple layers. Also, when multiple layers are formed, each of the layer may be composed of a layer comprising one or more active ingredients, or a combination of a layer comprising one or more active ingredients and a layer not comprising an active ingredient.

Seeds or vegetative reproductive organs carrying the present compound or the Composition A can be obtained, for example, by applying the formulations comprising the present compound or the Composition A by the above-described application method to seeds or vegetative reproductive organs.

The present crystal or the present composition may be used as an agent for controlling plant diseases in agricultural lands such as fields, paddy fields, turfs, and orchards. Examples of the plants include the followings.

The above-mentioned plants include also genetically modified crops.

EXAMPLES

Hereinafter, the present invention is explained in more detail by indicating Preparation examples, Reference preparation examples, Formulation examples, and Test examples, however, the present invention should not be limited to these examples.

Here in the working examples, “%” and “part” represents “weight %” and “weight part” unless otherwise indicated.

Also for the prepared present crystal form, various physical properties were measured using a device (with measurement conditions) as shown below.

Powder XRD

Measured temperature: Room temperature

Measured temperature:Room temperature

Measured temperature:Room temperature

Fourier Transform Infrared Spectroscopy (FT-IR)

Measurement method: Diamond ATR method

Microscopic Raman Spectroscopy

Optical Microscope

A preparation example of the present crystal is described.

Preparation Example 1

The compound A 30 mg was dissolved in methanol at 60° C. so as to adjust it to be 375 mg/mL. After the resulting solution was cooled to room temperature, the mixture was irradiated with laser under the below-mentioned condition, and it was then allowed to stand at 20° C. to obtain the Ra2 type crystal form.

The laser irradiation condition was described below.

Number of pulse: 125 pulse/10 seconds

Preparation Example 2

The Ra2 type crystal form 200 mg which was obtained in the preparation example 1 was weighted in a 20 mL volume sample bottle, and it was heated at 130° C. for 2 hours to obtain the Ra1 type crystal form.

Preparation Example 3

To the Ra1 type crystal form 100 mg obtained in the preparation example 2, diisopropyl ether 1 mL was added, and the resulting suspension was heated to 60° C., and stirred at 1,000 rpm for 2 days, and the solvents were removed to obtain the Ra3 type crystal form.

Reference Preparation Example 1

With respect to the preparation of the Ra4 type crystal form, the compound A was dissolved in toluene and then was recrystallized according to the process described in WO 92/12970 (Patent Literature 1) to prepare the Ra4 type crystal form.

The physical properties of the present crystal(s) are indicated below.

Ra1 Type Crystal Form

With respect to the characteristic diffraction peak(s) in the powder x-ray diffraction pattern as shown inFIG.1, the diffraction peak value(s) as a diffraction angle (2θ±0.2°) is indicated in Table 1, which are not limited thereto.

Ra2 Type Crystal Form

With respect to the characteristic diffraction peak(s) in the powder x-ray diffraction pattern as shown inFIG.2, the diffraction peak value(s) as a diffraction angle (2θ±0.2°) is indicated in Table 2, which are not limited thereto.

Ra3 Type Crystal Form

With respect to the characteristic diffraction peak(s) in the powder x-ray diffraction pattern as shown inFIG.3, the diffraction peak value(s) as a diffraction angle (2θ±0.2°) is indicated in Table 3, which are not limited thereto.

In order to compare with the Ra1 type crystal form, the Ra2 type crystal form, and the Ra3 type crystal form of the present invention, each kind of spectral value of the Ra4 type crystal form is shown below.

Ra4 Type Crystal Form

XRD Characteristic Peak

With respect to the characteristic diffraction peak(s) in the powder x-ray diffraction pattern as shown inFIG.4, the diffraction peak value(s) as a diffraction angle (2θ±0.2°) is indicated in Table 4, which are not limited thereto.

The crystallographic data of the single crystal of the present crystal is indicated in Table 5 below.

The control efficacy of the present crystal against plant diseases was measured by the Test Examples below.

Test Example 1

Each of 5 parts of the Ra1 type crystal form, or the Ra4 type crystal form as comparison control, 35 parts of a mixture of white carbon and ammonium polyoxyethylene alkyl ether sulfate (weight ratio is 1:1) and 60 parts of water were mixed, and the mixture was then finely-ground by a wet grinding method to obtain a formulation. Water was then added to the formulation so as to be 2 ppm as the concentration of the Ra1 type crystal form or the Ra4 type crystal form to obtain a diluted solution respectively.

Each of plastic pots was filled with soil and thereto soybean (cv; Kurosengoku) seeds were sown and the soybeans were grown in a greenhouse for 15 days. Thereafter, an aqueous suspension of spores of soybean rust fungus (Phakopsora pachyrhizi) was spraying-inoculated. After the inoculation, the soybeans were placed under a dark and wet condition at 23° C. for 1 night and were further cultivated in a greenhouse for 3 days, and the above-mentioned diluted solutions were sprayed to foliar parts so as to adhere adequately on the leaves of the above-mentioned soybean. After spraying the diluted solutions, the plants were air-dried and were placed under a dark and wet condition at only night, and after 7 days of the spraying, the lesion area was observed (lesion area in treated group).

Whereas, in the untreated group, the similar procedures to those of the treated group except that the Ra1 type crystal form or the Ra4 type crystal form were not applied, were carried out and the lesion area of soybean rust disease in the untreated group was observed (lesion area in untreated group).

From each of the lesion area in the treated group or the untreated group respectively, the efficacy in the treated group was calculated by the following “Equation 1”.

The test results are indicated in Table 6.

Efficacy (%)=[1−(lesion area in the treated group/lesion area in the untreated group)]×100  [Equation 1]

It was found that the Ra1 type crystal form showed higher efficacy compared to the Ra4 type crystal form.

Test Example 2

Each of 5 parts of the Ra2 type crystal form, the Ra3 type crystal form, the Ra4 type crystal form as comparison control, 35 parts of a mixture of white carbon and ammonium polyoxyethylene alkyl ether sulfate (weight ratio is 1:1) and 60 parts of water were mixed, and the mixture was then finely-ground by a wet grinding method to obtain a formulation. Water was then added to the formulation so as to be 50 ppm as the concentration of the Ra2 type crystal form, the Ra3 type crystal form, or the Ra4 type crystal form to obtain a diluted solution respectively.

Each of plastic pots was filled with soil and thereto rice plant (cv; Hinohikari) seeds were sown and the rice plants were grown in a greenhouse for 17 days. The above-mentioned diluted solutions were sprayed to foliar parts so as to adhere adequately on the leaves of the above-mentioned rice plants. After spraying the diluted solutions, the plants were air-dried and were cultivated outdoor for 8 days. Thereafter, the rice plants treated with the above-mentioned spraying and the rice plants infected with blast fungus (Pyricularia oryzae) were placed for 11 days while contacting each other, and the lesion area of the treated rice plants was observed (lesion area in treated group).

Whereas, in the untreated group, the similar procedures to those of the treated group except that the Ra2 type crystal form, the Ra3 type crystal form, or the Ra4 type crystal form were not applied, were carried out and the lesion area of rice blast disease in the untreated group was observed (lesion area in untreated group).

From each of the lesion area in the treated group or the untreated group respectively, the efficacy in the treated group was calculated by the above “Equation 1”.

The test results are indicated in Table 7.

It was found that the Ra2 type crystal form and the Ra3 type crystal form showed higher efficacy compared to the Ra4 type crystal form.

INDUSTRIAL APPLICABILITY

The present crystals (the Ra1 type crystal form, the Ra2 type crystal form, and the Ra3 type crystal form) show an excellent control efficacy against plant diseases.