Haloalkylsulfonanilide compound or crystal thereof, agricultural and horticultural herbicide containing compound or crystal, methods for using these, and methods for producing these

Abstract

The present invention addresses the problem of providing a novel compound or a crystal thereof that can be used as an active ingredient of a herbicide having both high safety to crops and excellent herbicidal activity against weeds, for resolving a food crisis associated with an increase in the world population expected in the near future.　The problem is solved by a compound represented by formula (1) or a crystal thereof, and an agricultural and horticultural herbicide containing the same, and a method for using the same.

Description

Haloalkyl sulfonanilide compounds or their crystals, and horticultural herbicides containing said compounds or crystals, as well as methods for using and manufacturing them.

[0001] The present invention relates to novel haloalkylsulfonanilide compounds, crystals of said haloalkylsulfonanilide compounds, herbicides for agricultural and horticultural use containing said compounds or their crystals, and methods for using them. The present invention also relates to methods for using and producing haloalkylsulfonanilide compounds or their crystals.

[0002] In recent years, the use of flowable pesticide formulations has been increasing in agricultural and horticultural settings. Flowable pesticide formulations were developed to improve the exposure of workers to pesticides caused by dust during the preparation of spray solutions for wettable powder formulations, which are typically in powder form. They also allow for the liquid formulation of active ingredients of pesticides that are poorly soluble in water and organic solvents. Because flowable pesticide formulations can primarily use water as a solvent, they have fewer problems associated with organic solvents, such as toxicity and irritation to humans and animals, environmental impact, unpleasant odors, and flammability. For these reasons, there is a growing demand for novel active ingredients in pesticides to be available in crystalline form, which allows for the preparation of flowable pesticide formulations.

[0003] Patent Document 1 describes that haloalkylsulfon anilide compounds have herbicidal activity.

[0004] International Publication No. 2008 / 059948 Brochure

[0005] Edited by the Research Committee on Pesticide Formulation and Application Methods of the Pesticide Society of Japan, "Guide to Pesticide Formulations," Japan Plant Protection Association, October 30, 1997, pp. 35-42.

[0006] To resolve the food crisis expected in the near future due to the increase in the world's population, a stable food supply is essential. A stable food supply requires economically and efficiently eliminating or controlling weeds that hinder cultivation and harvesting, making the development of new herbicides and plant growth regulators increasingly important. At the same time, herbicides are required to be highly safe for humans and animals, and to minimize environmental impact. To meet these societal demands, the present invention aims to provide a compound, or crystal thereof, that can be used as an active ingredient in a herbicide, allowing for the preparation of multiple formulations, including flowable pesticide formulations ("flowable formulations").

[0007] The inventors diligently conducted research to develop novel active ingredients for herbicides and discovered that certain compounds among haloalkylsulfon anilide compounds have the potential to form crystals. Further investigations led to the completion of the present invention.

[0008] That is, the present invention relates to at least the following inventions: [1] A compound represented by formula (1) or a salt thereof; [2] Formula (1): Crystals of the compound represented by [1]; [3] Type 1 crystals of the compound described in [1], with a melting point of 86 to 100°C as measured by differential scanning calorimetry (DSC); [4] Crystals having diffraction peaks at diffraction angles (2θ) of 6.14°±0.2°, 8.69°±0.2°, 12.5°±0.2°, 13.94°±0.2°, 17.27°±0.2°, 17.69°±0.2°, 19.77°±0.2°, 20.75°±0.2°, 21.34°±0.2° and 26.16°±0.2° in powder X-ray diffraction spectra, or crystals having diffraction peaks at diffraction angles (2θ) of 6.34°±0.2°, 8.92°±0.2°, 12.70°±0.2°, 14.18°±0.2° and 25.86°±0.2° in powder X-ray diffraction spectra; Crystals having diffraction peaks at diffraction angles (2θ) of 6.42°±0.2°, 9.04°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 25.96°±0.2° in powder X-ray diffraction spectra; crystals having diffraction peaks at diffraction angles (2θ) of 6.40°±0.2°, 9.00°±0.2°, 12.76°±0.2°, 14.26°±0.2°, and 25.92°±0.2° in powder X-ray diffraction spectra; crystals having diffraction peaks at diffraction angles (2θ) of 6.38°±0.2°, 9.00°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 25.94°±0.2° in powder X-ray diffraction spectra; A crystal having diffraction peaks at diffraction angles (2θ) of 6.42°±0.2°, 9.10°±0.2°, 12.78°±0.2°, 14.26°±0.2°, and 25.96°±0.2° in a powder X-ray diffraction spectrum; a crystal having diffraction peaks at diffraction angles (2θ) of 6.38°±0.2°, 8.96°±0.2°, 12.74°±0.2°, 14.20°±0.2°, and 25.96°±0.2° in a powder X-ray diffraction spectrum; or a crystal having diffraction peaks at diffraction angles (2θ) of 6.40°±0.2°, 9.06°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 26.02°±0.2° in a powder X-ray diffraction spectrum, which is a type 1 crystal of the compound described in [1];[5] In the powder X-ray diffraction spectrum, it is a crystal having at least diffraction peaks at diffraction angles (2θ) of 6.14° ± 0.2° to 6.34° ± 0.2°, 8.69° ± 0.2° to 8.92° ± 0.2°, 12.5° ± 0.2° to 12.70° ± 0.2°, 13.94° ± 0.2° to 14.18° ± 0.2°, and 25.86° ± 0.2° to 26.16° ± 0.2°, the type 1 crystal described in [1]; [6] In the infrared absorption spectrum, the wave numbers are 1767 ± 4 cm; －１ , 1694 ± 4 cm －１ , 1407 ± 4 cm －１ , 1269 ± 4 cm －１ , 1200 ± 4 cm －１ , 1126 ± 4 cm －１ , 980 ± 4 cm －１ , 756 ± 4 cm －１ , 610 ± 4 cm －１ , 584 ± 4 cm －１ having peaks at the positions of, the type 1 crystal of the compound described in [1]; [7] Formula (1): A method for producing a crystal of a compound represented by, comprising precipitating a crystal by recrystallizing the compound represented by formula (1) using ethyl acetate and heptane, or precipitating a crystal by recrystallizing the compound represented by formula (1) using a good solvent and / or a poor solvent, a method for producing the type 1 crystal according to any one of [3] to [6]; [8] An agricultural and horticultural herbicide characterized by containing as an active ingredient the compound described in [1] or the crystal according to any one of [2] to [6]; [9] The agricultural and horticultural herbicide according to [8], which is a flowable formulation;

[10] A method for using an agricultural and horticultural herbicide, characterized by treating an effective amount of the agricultural and horticultural herbicide according to [8] on weeds, soil, paddy fields or cultivation carriers;

[11] A method for using an agricultural and horticultural herbicide, characterized by treating an effective amount of the agricultural and horticultural herbicide according to [9] on weeds, soil, paddy fields or cultivation carriers;

[12] A method for controlling weeds, characterized by treating an effective amount of the agricultural and horticultural herbicide according to [8] on weeds, soil, paddy fields or cultivation carriers;

[13] A method for controlling weeds, characterized by treating an effective amount of the agricultural and horticultural herbicide according to [9] on weeds, soil, paddy fields or cultivation carriers.

[0009] Examples of salts of the compound represented by formula (1) of the present invention include the following salts: • Inorganic acid salts such as hydrochloride, sulfate, nitrate, and phosphate; • Organic acid salts such as acetate, fumarate, maleate, oxalate, methanesulfonate, benzenesulfonate, and p-toluenesulfonate; • Salts with inorganic or organic bases such as sodium ions, potassium ions, calcium ions, and trimethylammonium.

[0010] The present invention provides a novel haloalkylsulfonanilide compound, its salt, or its crystals, which has excellent efficacy as an agricultural and horticultural herbicide. The compound, its salt, or its crystals of the present invention make it possible to prepare or efficiently prepare an agricultural chemical formulation containing the compound of formula (1) as an active ingredient. Furthermore, according to the present invention, it is possible to prepare or efficiently prepare a flowable formulation containing the compound of formula (1) as an active ingredient. The compound of formula (1) of the present invention also has the effect of maintaining at least the same level of herbicidal activity when prepared as a flowable formulation as when prepared as at least one of the other major formulations, such as emulsion, granules, or wettable powder. The compound of the present invention (the compound of formula (1) of the present invention) also exhibits herbicidal effects against tuberous weeds such as arrowhead and sedge.

[0011] Non-patent document 1 states that one of the advantageous conditions for a raw material that can be made into a flowable formulation is that it is solid at room temperature and usually has a melting point of 60°C or higher. The melting point of the compound of formula (1) of the present invention is 91°C, which is above 60°C.

[0012] This graph shows the differential scanning calorimetry (DSC) results of the type 1 crystal of the compound represented by formula (1) of the present invention, manufactured in Manufacturing Example 1. This graph shows the powder X-ray diffraction spectrum of the type 1 crystal of the compound represented by formula (1) of the present invention, manufactured in Manufacturing Example 1. This is another graph showing the powder X-ray diffraction spectrum of the type 1 crystal of the compound represented by formula (1) of the present invention, manufactured in Manufacturing Example 1. This graph shows the IR spectrum of the type 1 crystal of the compound represented by formula (1) of the present invention, manufactured in Manufacturing Example 1. This graph shows the powder X-ray diffraction spectrum of the type 1 crystal of the compound represented by formula (1) of the present invention, manufactured in Manufacturing Example 2. This graph shows the powder X-ray diffraction spectrum of the type 1 crystal of the compound represented by formula (1) of the present invention, manufactured in Manufacturing Example 3. This graph shows the powder X-ray diffraction spectrum of the type 1 crystal of the compound represented by formula (1) of the present invention, manufactured in Manufacturing Example 4. This graph shows the powder X-ray diffraction spectrum of the type 1 crystal of the compound represented by formula (1) of the present invention, manufactured in Manufacturing Example 5. This graph shows the powder X-ray diffraction spectrum of a type 1 crystal of the compound represented by formula (1) of the present invention, produced in Production Example 6. This graph shows the powder X-ray diffraction spectrum of a type 1 crystal of the compound represented by formula (1) of the present invention, produced in Production Example 7.

[0013] Definitions In this specification, unless otherwise specified, a crystal means a solid formed by the regular three-dimensional arrangement of constituent atoms, ions, molecules, etc., and is not an amorphous solid that does not have a regular internal structure. In this specification, "compound represented by formula (1) of the present invention," "compound of formula (1) of the present invention," and "compound of the present invention" all refer to a compound having the structure of formula (1) above, and may also be used as a general term for its crystals and other forms (amorphous, etc.). The compound represented by formula (1) of the present invention may exist as a crystal at room temperature. Therefore, the compound can be prepared into multiple formulations, including flowable formulations. Crystals of the compound represented by formula (1) of the present invention The crystals of the compound represented by formula (1) of the present invention may exist in two or more crystal forms. The crystals of the present invention also include all those substantially consisting of each crystal form, those consisting only of each crystal form, and mixtures containing multiple different crystal forms in any proportion. The following ratios are examples of the proportion of each crystal in a mixture containing crystals of multiple different crystalline forms: • Type 1 crystals: crystals other than Type 1 crystals = 0.01:0.99 to 0.99:0.01 Here, "Type 1 crystals" refer to crystals of the compound represented by formula (1) of the present invention, which are specified by the following physical properties: • Type 1 crystals (1) Shown as having a melting point of 86 to 100°C in differential scanning calorimetry (DSC), or (2) In the powder X-ray diffraction spectrum, diffraction peaks are present at diffraction angles (2θ) of 6.14°±0.2°, 8.69°±0.2°, 12.5°±0.2°, 13.94°±0.2°, 17.27°±0.2°, 17.69°±0.2°, 19.77°±0.2°, 20.75°±0.2°, 21.34°±0.2° and 26.16°±0.2°, or in the powder X-ray diffraction spectrum, Diffraction peaks are present at diffraction angles (2θ) 6.34°±0.2°, 8.92°±0.2°, 12.70°±0.2°, 14.18°±0.2°, and 25.86°±0.2°, or in the powder X-ray diffraction spectrum, diffraction peaks are present at diffraction angles (2θ) 6.42°±0.2°, 9.04°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 25.96°±0.2°;In the powder X-ray diffraction spectrum, diffraction peaks are present at diffraction angles (2θ) 6.40°±0.2°, 9.00°±0.2°, 12.76°±0.2°, 14.26°±0.2°, and 25.92°±0.2°; In the powder X-ray diffraction spectrum, diffraction peaks are present at diffraction angles (2θ) 6.38°±0.2°, 9.00°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 25.94°±0.2°; In the powder X-ray diffraction spectrum, diffraction peaks are present at diffraction angles (2θ) 6.42°±0.2°, 9.10°±0.2°, 12.78°±0.2°, 14.26°±0.2°, and 25.96°±0.2°; In the powder X-ray diffraction spectrum, diffraction peaks are present at diffraction angles (2θ) 6.38°±0.2°, 8.96°±0.2°, 12.74°±0.2°, 14.20°±0.2°, and 25.96°±0.2°; or in the powder X-ray diffraction spectrum, diffraction peaks are present at diffraction angles (2θ) 6.40°±0.2°, 9.06°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 26.02°±0.2°, or (3) Having diffraction peaks at diffraction angles (2θ) 6.14°±0.2° to 6.34°±0.2°, 8.69°±0.2° to 8.92°±0.2°, 12.5°±0.2° to 12.70°±0.2°, 13.94°±0.2° to 14.18°±0.2°, and 25.86°±0.2° to 26.16°±0.2° in the powder X-ray diffraction spectrum, and / or (4) Having a wavenumber of 1767±4 cm in the infrared absorption spectrum; －１ , 1694±4cm －１ , 1407±4cm －１ , 1269±4cm －１ , 1200±4cm －１ , 1126±4cm －１ , 980±4cm －１ 756±4cm －１ , 610±4cm －１ , 584±4cm －１ It has a peak at this position.

[0014] The propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate crystals, represented by formula (1) of the present invention, can be produced by, for example, the following production methods, but the methods for producing the crystals of the present invention are not limited to these.

[0015] Method for producing crystals of the compound represented by formula (1) of the present invention - 1. Crystals of the compound represented by formula (1) of the present invention can be produced, for example, by recrystallizing the compound represented by formula (1) of the present invention using ethyl acetate and heptane.

[0016] The amount of ethyl acetate used in this manufacturing method can be appropriately selected from the range of 0.1 L to 5 L per mole of the compound represented by formula (1) of the present invention. The amount of heptane used in this manufacturing method can be appropriately selected from the range of 0.1 L to 5 L per mole of the compound represented by formula (1) of the present invention.

[0017] In this manufacturing method, the recrystallization temperature should typically be in the range of 10°C to 80°C, and the recrystallization time should be appropriately selected from the range of 1 hour to 48 hours.

[0018] The method for producing the type 1 crystal of the present invention is not limited, and the crystal may be obtained, for example, by precipitating the amorphous compound represented by formula (1) as a crystal using ethyl acetate and heptane. The amount of ethyl acetate and heptane used during recrystallization (as a ratio to the amount of the compound represented by formula (1) of the present invention) may be selected from the above-mentioned range of amounts. Furthermore, the ratio of the amount of ethyl acetate and heptane used is not limited as long as it is a ratio that produces the type 1 crystal of the present invention. Ethyl acetate and heptane may each be added in two or more separate additions. The recrystallization temperature may be selected from the range of 10°C to 80°C, and the recrystallization time may be selected from the range of 1 hour to 48 hours. In the production of the type 1 crystal of the present invention, it is preferable to include the steps of adding ethyl acetate and heptane to the compound of formula (1), raising the internal temperature (for example to about 60°C), and lowering the internal temperature (for example to about 20°C). Although not bound by theory, it is presumed that different crystals can be obtained by adjusting the temperature at which ethyl acetate and heptane are added to the amorphous compound of formula (1).

[0019] Method for producing crystals of the compound represented by formula (1) of the present invention - 2 Crystals of the compound represented by formula (1) of the present invention may be obtained, for example, by dissolving or suspending the compound represented by formula (1) of the present invention in a good solvent and / or a poor solvent, heating to 30°C to 50°C, allowing it to cool, and then cooling to 0°C to 10°C to precipitate the crystals. The amount of good solvent used in this production method can be appropriately selected from the range of 0.1 L to 5 L per mole of the compound represented by formula (1) of the present invention. The amount of poor solvent used in this production method can be appropriately selected from the range of 0.1 L to 5 L per mole of the compound represented by formula (1) of the present invention. Furthermore, the ratio of the amount of good solvent to the amount of poor solvent used is not particularly limited as long as it is a ratio that produces type 1 crystals of the present invention, but a volume ratio (good solvent:poor solvent) of 1:0.1 to 1:10 is exemplified, 1:0.5 to 1:5 is preferred, and 1:1 to 1:3 is more preferred. In this invention, the numerical range specified by the notation "and" is a numerical range specified that includes the numbers written to the left and right of "and" as the lower limit and upper limit, respectively. In this invention, the numerical range specified by the notation "~" is a numerical range specified that includes the numbers written to the left and right of "~" as the lower limit and upper limit, respectively. ●Good solvents Examples of good solvents include at least one selected from the group consisting of amides, alcohols, ethers, esters, carboxylic acids, ketones, sulfoxides, nitriles, halogenated hydrocarbons, and aromatic hydrocarbons. Good solvents may be used alone or as a mixture of two or more of these. Examples of amides include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone. Of these, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide are preferred. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 2,2Examples include 2-trifluoroethanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, etc. Of these, methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, and 2,2,2-trifluoroethanol are preferred. Examples of ethers include linear ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tert-butyl methyl ether, and cyclopentyl methyl ether; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; etc. Of these, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane is preferred. Examples of esters include ethyl acetate, propyl acetate, and isopropyl acetate. Ethyl acetate, propyl acetate, and isopropyl acetate are all preferred. Examples of carboxylic acids include acetic acid. Acetic acid is preferred. Examples of ketones include acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone. Examples of sulfoxides include dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Examples of nitriles include acetonitrile. Acetonitrile is preferred. Examples of halogenated hydrocarbons include methylene chloride, chloroform, dichloroethane, and carbon tetrachloride. Of these, methylene chloride, chloroform, and dichloroethane are preferred. Examples of aromatic hydrocarbons include aromatic hydrocarbons such as benzene, toluene, xylene (e.g., o-xylene), tetrahydronaphthalene, and nitrobenzene; halogenated hydrocarbons such as chlorobenzene, fluorobenzene, dichlorobenzene, and benzotrifluoride; and so on. Of these, toluene, o-xylene, chlorobenzene, fluorobenzene, and benzotrifluoride are preferred. ●Poor solvents Examples of poor solvents include at least one selected from the group consisting of aliphatic hydrocarbons, diols, and water. Examples of aliphatic hydrocarbons include linear aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane, and decane; cyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, and cycloheptane; etc. Examples of diols include ethylene glycol and 1,2-propanediol. Of these poor solvents, water is preferred. Furthermore, of the above aliphatic hydrocarbons, heptane, isooctane, and cyclohexane are preferred. Furthermore, of the above diols, ethylene glycol and 1,Any 2-propanediol is preferred. These poor solvents may be used individually or in combination of two or more of them. ● Combination of good solvents and poor solvents The crystals of the compound represented by formula (1) of the present invention may be produced by combining one or more good solvents with one or more poor solvents. Such combinations are not limited, but the following combinations are examples: • Combinations of one or more of the following good solvents with water: N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, methanol, ethanol, 2-propanol, 2,2,2-trifluoroethanol, tert-butyl methyl ether, tetrahydrofuran, 1,4-dioxane, ethyl acetate, propyl acetate, isopropyl acetate, methyl isobutyl ketone, methyl ethyl ketone, acetone, dimethyl sulfoxide, acetonitrile, chloroform, toluene, fluorobenzene, 1-propanol, chlorobenzene, and benzotrifluoride; • Combinations of one or more of the following good solvents with heptane: N,N-dimethylformamide, toluene, propyl acetate, 1,4-dioxane, isopropyl acetate, 2-propanol, acetonitrile, methyl ethyl ketone, ethanol, ethyl acetate, 2,2,2-trifluoroethanol, tetrahydrofuran, methanol, acetone, tert-butyl methyl ether, dimethyl sulfoxide, fluorobenzene, chloroform, methyl isobutyl ketone, and benzotrifluoride; cyclopentyl methyl ether in combination with one or more of the following poor solvents: ethylene glycol, 1,2-propanediol, isooctane, cyclohexane, heptane, and water; 2-methyltetrahydrofuran in combination with one or more of the following poor solvents: ethylene glycol, 1,2-propanediol, cyclohexane, heptane, water, and isooctane; ・A combination of dichloroethane and one or more of the following poor solvents: ethylene glycol, 1,2-propanediol, cyclohexane, heptane, water, and isooctane; ・A combination of methylene chloride and one or more of the following poor solvents: ethylene glycol, cyclohexane, heptane, water, 1,2-propanediol, and isooctane; ・A combination of o-xylene and one or more of the following poor solvents: ethylene glycol, 1,2-propanediol, isooctane, cyclohexane, heptane, and water; ・A combination of chlorobenzene and one or more of the following poor solvents: ethylene glycol, isooctane, cyclohexane, heptane, and 1,2-propanediol; ・A combination of benzotrifluoride and one or more of the following poor solvents: 1,2-propanediol, isooctane, cyclohexane, and ethylene glycol; and ・A combination of acetic acid and one or more of the following poor solvents: cyclohexane, isooctane, and heptane.,

[0020] The compound represented by the formula (1) of the present invention can be produced, for example, by the following production method, but the production method of the compound is not limited thereto.

[0021] Production method of the compound of formula (1) of the present invention The compound represented by the formula (1) of the present invention can be produced from the compound represented by the formula (2) by the following step [a].

[0022] {In the formula, L represents a leaving group such as a halogen such as chlorine, bromine, iodine, or an (C １ -C ４ ) alkoxy group.}

[0023] The compound represented by the formula (2) described in Patent Document 1 of the manufacturing method of the engineering [a] can be reacted with the compound represented by the general formula (3) in the presence of a base and an inert solvent to produce the compound represented by the formula (1) of the present invention.

[0024] Examples of the base that can be used in this reaction include nitrogen-containing organic bases such as triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]-7-undecene, and pyridine; inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and metallic sodium; organic bases such as sodium acetate and potassium acetate; and alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide. The amount used is usually in the range of 0.5 to 10 times the molar amount of the compound represented by the formula (2).

[0025] The inert solvent that can be used in this reaction may be any that does not significantly inhibit the progress of this reaction. Examples include chain or cyclic ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, and halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitriles such as acetonitrile; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, water, etc. These inert solvents can be used alone or in combination of two or more. The amount used may be appropriately selected from the range of usually 0.1 L to 100 L per 1 mol of the compound represented by the formula (2).

[0026] In this reaction, a phase transfer catalyst can also be used for the purpose of promoting the reaction. Examples of the phase transfer catalyst that can be used include quaternary ammonium salts such as tetra-n-butylammonium bromide and benzyltriethylammonium bromide; crown ethers such as 18-crown-6, etc.

[0027] Since this reaction is equimolar, equimolar amounts of each compound should be used, although an excess of one of the compounds can also be used. The reaction temperature in this reaction can usually be anywhere from -20°C to the boiling point of the solvent used, and the reaction time varies depending on the scale of the reaction, the reaction temperature, etc., and is not constant, but can usually be appropriately selected within the range of a few minutes to 48 hours. After the reaction is complete, the target product can be isolated from the reaction system containing the target product by conventional methods, and the target product can be produced by purification by recrystallization, column chromatography, etc., if necessary.

[0028] The conditions for measuring the physical properties of the compound represented by formula (1) of the present invention are not limited. In this specification, powder X-ray diffraction of the compound represented by formula (1) of the present invention was measured under the following conditions: Instrument name: Mini Flex (Rigaku Corporation) X-ray: Cu-Kα (40kV, 15mA) Scanning range: 5 to 90° Sampling width: 0.01° Scanning speed: 5° / min Or, Instrument name: Ultima IV (Rigaku Corporation) X-ray: Cu-Kα (40kV, 40mA) Scanning range: 5 to 45° Sampling width: 0.02° Scanning speed: 10° / min Powder X-ray diffraction of the compound represented by formula (1) of the present invention may be measured under either of the above conditions. In this specification, differential scanning calorimetry (DSC) was measured under the following conditions: Instrument name: DSC Q20 Sample cell: SUS gold plated Temperature range: 50°C to 250°C (heating: 3°C / min)

[0029] In this specification, Fourier transform infrared spectroscopy (FT-IR) was measured under the following conditions: Instrument name: Nicolet iS20 (Thermo Fisher Scientific) Measurement method: ATR method Number of integrations: 16 Resolution: 4 cm －１ The physical properties characterizing the crystal of the present invention are not limited to powder X-ray diffraction or DSC, but also include IR spectroscopy and the like.

[0030] The useful plants in which the compounds or crystals of the present invention can be used are not particularly limited, but examples include: cereals (rice, barley, wheat, rye, oats, corn, sorghum, etc.), legumes (soybeans, adzuki beans, broad beans, peas, kidney beans, peanuts, etc.), fruit trees and fruits (apples, citrus fruits, pears, grapes, peaches, plums, cherries, walnuts, chestnuts, almonds, bananas, etc.), leafy and fruiting vegetables (cabbage, tomatoes, spinach, broccoli, lettuce, onions, leeks (chives, scallions), bell peppers, eggplants, strawberries, peppers, okra, chives, etc.), root vegetables (carrots, potatoes, sweet potatoes, taro, radishes, turnips, lotus roots, burdock, garlic, etc.). Examples of plants include shallots, processing crops (cotton, hemp, beets, hops, sugarcane, sugar beets, olives, rubber, coffee, tobacco, tea, sunflowers, etc.), gourds (pumpkins, cucumbers, watermelons, cantaloupes, melons, etc.), pasture grasses (orchardgrass, timothy, clover, alfalfa, etc.), turfgrasses (Korean grass, bentgrass, etc.), ornamental crops such as lavender, rosemary, thyme, parsley, pepper, ginger, etc.), flowers (chrysanthemums, roses, carnations, orchids, tulips, lilies, etc.), garden trees (ginkgo, cherry trees, Japanese laurel, etc.), and forest trees (fir trees, spruce trees, pine trees, cypress, cedar, hinoki, eucalyptus, etc.).

[0031] The above-mentioned "useful plants" also include plants that have been given resistance to 4-HPPD inhibitors such as isoxaflutol, ALS inhibitors such as imazetapyr and thifensulfuron-methyl, EPSP synthase inhibitors such as glyphosate, glutamine synthase inhibitors such as glufosinate, acetyl-CoA carboxylase inhibitors such as cethoxydim, and herbicides such as bromoxynil, dicamba, and 2,4-D through classical breeding methods, genetic modification technology, or gene editing technology.

[0032] Examples of "plants" that have been given resistance through classical breeding methods include rapeseed, wheat, sunflower, and rice that are resistant to imidazolinone-based ALS inhibitor herbicides such as imazetapyr. The rice is already sold under the trade name Clearfield (registered trademark). Similarly, there are soybeans that have been given resistance to sulfonylurea-based ALS inhibitor herbicides such as thifensulfuron-methyl through classical breeding methods, and are already sold under the trade name STS soybeans. Similarly, SR corn is an example of a plant that has been given resistance to acetyl-CoA carboxylase inhibitors such as trione oxime and aryloxyphenoxypropionic acid herbicides through classical breeding methods. Furthermore, plants that have been conferred resistance to acetyl-CoA carboxylase inhibitors are described in the Proceedings of the National Academy of Sciences of the United States of America (Proc. Natl. Acad. Sci. USA), Vol. 87, pp. 7175-7179 (1990), among other publications. Furthermore, mutant acetyl-CoA carboxylase resistant to acetyl-CoA carboxylase inhibitors has been reported in Weed Science, Vol. 53, pp. 728-746 (2005), etc. By introducing such mutant acetyl-CoA carboxylase genes into plants using genetic engineering technology, or by introducing mutations related to resistance conferral into plant acetyl-CoA carboxylase, it is possible to create plants resistant to acetyl-CoA carboxylase inhibitors. In addition, chimeric plasty technology (Gura T. 1999. Repairing the Genome's Spelling Mistakes. Science 285: By introducing nucleic acids with base substitution mutations, such as those represented in 316-318, into plant cells and introducing site-directed amino acid substitution mutations into plant acetyl-CoA carboxylase genes, ALS genes, etc., it is possible to create plants resistant to acetyl-CoA carboxylase inhibitors, ALS inhibitors, etc.Furthermore, as an example of conferring herbicide resistance to crops using gene editing technology, a method called the CRISPR / Cas9 method, which uses the CRISPR locus and Cas9 nuclease, has been reported in Nature Biotechnology, Vol. 31, pp. 688-691 (2013), and the compound represented by formula (1) of the present invention or its crystals can also be used on these plants. The compound represented by formula (1) of the present invention or its crystals does not harm these useful plants.

[0033] The weeds that can be controlled by the compounds or crystals thereof of the present invention include dicotyledonous weeds such as sweet potato (Ipomoea), Lindernia, Conyza, Sesbania, Abutilon, Matricaria, Rorippa, Urtica, Bacopa, Lamium, Xanthium, Sinapis, Rotala, Aeschynomene, Veronica, Papaver, Bidens, Chenopodium, Tripleurospermum, Trifolium, and Portulaca Examples include Portulaca, Viola, Oenanthe, Eclipta, Galeopsis, Ludwigia, Datura, Solanum, Capsella, Cirsium, Sonchus, Galinsoga, Stellaria, Senecio, Ammannia, Amaranthus, Ambrosia, Bassia, Lepidium, Polygonum, Galium, Centaurea, and Artemisia.

[0034] The genera of monocotyledonous weeds include Leptochloa, Phleum, Poa, Bolboschoenus, Festuca, Elymus, Setaria, Eleusine, Sagittaria, Typha, Agropyron, Ischaemum, Cyperus, Avena, Bromus, Panicum, Cynodon, Monochoria, and Polygonum. Examples include Alisma, Leersia, Alopecurus, Paspalum, Commelina, Fimbristylis, Lolium, Urochloa, Agrostis, Eleocharis, Echinochloa, Potamogeton, Eriocaulon, Scirpus, Schoenoplectus, Ottelia, Digitaria, and Sorghum.

[0035] Other specific examples of weeds include Spirogyra, Amaranthus retroflexus, Amaranthus viridis, Setaria faberi, Leersia japonica, Leptochloa chinensis, Lindernia angustifolia, Lindernia procumbens, Dopatrium junceum, Ipomoea hederacea, Lindernia dubia, Sida spinosa, Heteranthera limosa, Polygonum pensylvanicum, Sesbania exaltata, Geranium carolinense, and Chenopodium ambrosioides), Conyza bonariensis, Setaria italica, Amaranthus powellii, Polygonum cuspidatum, Abutilon theophrasti, Matricaria perforata, Polygonum longisetum, Veronica polita, Echinochloa crus-galli, Amaranthus lividus, Solanum nigrum, Schoenoplectus juncoides (Roxb.) Palla, Bromus catharticus, Murdannia keisak, Bolboschoenus fluviatilis, Scirpus maritimus), Bromus tectorum, Sagittaria pygmaea Miq, Rumexobtusifolius), Leersia oryzoides (L.) Sw., Setaria viridis, Cassia obtusifolia, Gratiola japonica, Conyza sumatrensis, Veronica persica, Spirodela polyrhiza, Xanthium canadens, Coreopsis lanceolata, Panicum dichotomiflorum, Asclepias syriaca, Euphorbia maculata, Plantago asiatica, Rudbeckia laciniata, Amaranthus palmeri), oat (Avena sativa), cocklebur (Xanthium strumarium), wild oat (Avena sterilis), goosegrass (Eleusine indica), arrowhead (Sagittaria trifolia), Dutch geranium (Erodium cicutarium), Dutch chickweed (Cerastium glomeratum), white daisy (Matricaria matricarioides), chamomile (Matricaria chamomilla), black vetch (Vicia angustifolia), black tea flea (Bromus secalinus), wild oat (Avena fatua), variegated grass (Rotala indica Koehne), dock (Rumex japonicus), Japanese barnyard grass (Paspalum distichum), foxglove (Bromus remotiflorus), yellow nutgrass (Cyperus esculentus), Galium kinuta, Setaria glauca, Pueraria lobata, Eleocharis kuroguwai Ohwi, SagittariaTrifolia Caerulea, Ambrosia trifida, Hydrollaria verticillata, Bolboschoenus maritimus (L.) Palla, Chrysanthemum segetum, Cyperus iria, Monochoria vaginalis, Echinochloa colona, ​​Alisma plantago-aquatica, Oryza sativa, Polygonum lapathifolium, Eleusine coracana, Schoenoplectus nipponicus, Cyperus malaccensis, Agropyron repens, Sorghum vulgare, Silky bentgrass (Apera) Spica-venti), Chenopodium album, White clover (Trifolium repens), White-flowered jalapeño (Datura stramonium), Horsetail (Equisetum arvense), Annual bluegrass (Poa annua), Brown tea fern (Bromus japonicus), Japanese bellflower (Alopecurus aequalis), Portulaca oleracea, Tall goldenrod (Solidago altissima), Sorghum halepense, Brassica juncea, Common dandelion (Taraxacum officinale), Common morning glory (Convolvulus arvensis), Water dropwort (Oenanthe javanica), Buckwheat vine (Polygonum convolvulus), Echinochloa Oryzicola Vasing, Taiwanese leopard plant (Ischaemum rugosum), Taiwanese sedge (Schoenoplectus wallichii), Veronicaarvensis), Cyperus difformis L., Amaranthus rudis, Timothy (Phleum pratense), Ludwigia prostrata Roxburgh, Commelina communis, Panicum texanum, Euphorbia helioscopia, Festuca parvigluma, Rumex crispus, Capsella bursa-pastoris, Euphorbia pseudochamaesyce, Brachiaria plantaginea, Lolium multiflorum, Cirsium japonicum, Alopecurus myosuroides, Sinapis arvensis), Senecio vulgaris, Galinsoga ciliata, Amaranthus tricolor, Stellaria media, Cyperus papyrus, Cyperus rotundus, Amaranthus spinosus, Polygonum persicaria, Senecio cannabifolius, Fimbristlylis littoralis, Cyperus flaccidus, Papaver rhoeas, Helianthus annuus, Lamium purpureum, Schoenoplectiella mucronata, Kyllinga gracillima, Ammannia multiflora), Erigeron canadensis, Potamogeton distinctus A. Benn, Amaranthustuberculatus), field pansy (Viola arvensis), Fuji thistle (Cirsium purpuratum), ragweed (Ambrosia artemisiifolia), bulrush (Schoenoplectus tabernaemontani), flabby grass (Veronica hederaefolia), black grass (Alopecurus myosuroides), Florida beggarweed (Desmodium tortuosum), broadleaf plantain (Plantago lanceolata), broom cypress (Kochia scoparia), laurel (Lolium rigidum), narrow-leaved loosestrife (Ammannia coccinea), slender ryegrass (Lolium perenne), firefly grass (Scirpus juncoides Roxburgh), henbit (Lamium amplexicaule), moss (Najas graminea), long-leaved blue amaranth (Amaranthus hybridus), and eleven-leaf quince (Eleocharis acicularis) L.), Portulaca grandiflora, Ipomoea lacunosa, Ipomoea purpurea, Ipomoea hederacea var integriuscula, Commelina bengharensis, Monochoria korsakowii, Cyperus serotinus Rottboel, Elatine triandra Schk, Digitaria ciliaris, Digitaria sanguinalis, Sorghum bicolor, Galium aparine, Artemisia princeps, Viola tricolor, Raphanus raphanistrum, Myosotis arvensis), AlismaExamples include canaliculatum. The compound, crystalline or amorphous form represented by formula (1) of the present invention inhibits the growth of these weeds.

[0036] The compound or crystals thereof of the present invention can be formulated into a form convenient for use in accordance with conventional methods for agricultural chemical formulations. That is, the compound or crystals thereof of the present invention can be dissolved, separated, suspended, mixed, impregnated, adsorbed, or attached to a suitable inert carrier, or together with an auxiliary agent in an appropriate proportion as needed, and then formulated into an appropriate dosage form, such as a suspension, emulsion, liquid, wettable powder, wettable granule, granule, powder, tablet, pack, etc., for use. The compound or crystals thereof of the present invention can be used in herbicides of various dosage forms as described above, and can be particularly suitably used in flowable formulations.

[0037] The composition of the present invention (agricultural and horticultural herbicide) is a composition containing the compound of the present invention or its crystals. The composition of the present invention (agricultural and horticultural herbicide) may contain the crystals of the compound of the present invention or other forms of the compound substantially alone (for example, 80% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more), or it may contain both the crystals and other forms of the compound of the present invention together. The type of crystal of the present invention contained in the agricultural and horticultural herbicide of the present invention is not limited, and any of the crystals may be included alone or as a mixture of two or more types of crystals. Among the agricultural and horticultural herbicides of the present invention, herbicides containing type 1 crystals of the compound of formula (1) are preferred. Furthermore, the agricultural and horticultural herbicides of the present invention also include herbicides containing other crystalline forms of the compound of formula (1) along with type 1 crystals. Crystals other than type 1 crystals of the compound of formula (1) may be present in trace amounts of 5% by weight or less relative to the amount of type 1 crystals. The proportion of crystals of the compound of formula (1) contained in the herbicide for agricultural and horticultural use of the present invention is not limited, and the herbicide for agricultural and horticultural use of the present invention may contain any type of crystal of the present invention in any proportion. When the herbicide for agricultural and horticultural use of the present invention contains two or more types of crystals of the present invention, the following proportions are exemplified as the proportion of the crystals: Type 1 crystal: crystals other than Type 1 crystal = 0.01:0.99 to 0.99:0.01 The herbicide for agricultural and horticultural use of the present invention may also contain in combination an amorphous form of the compound of formula (1) and crystals of the same compound. In addition to the active ingredient, the herbicide for agricultural and horticultural use of the present invention may contain, as necessary, additives commonly used in pesticide formulations or herbicides. Examples of such additives include liquid carriers, surfactants, dispersants, wetting agents, thickeners, colorants, spreading agents, adjuvants, antifreeze agents, and decomposition inhibitors. Other additives such as preservatives and plant fragments may also be used as necessary. These additives may be used individually or in combination of two or more types. The following are examples of typical additives in flowable formulations, but the additives are not limited to these.

[0038] Water can be cited as a liquid carrier.

[0039] Examples of surfactants used as dispersants, wetting agents, spreading agents, and adhering agents include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene resin acid esters, polyoxyethylene fatty acid diesters, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene dialkylphenyl ethers, polyoxyethylene alkylphenyl ether formalin condensates, polyoxyethylene polyoxypropylene block copolymers, polystyrene polyoxyethylene block polymers, alkylpolyoxyethylene polypropylene block copolymer ethers, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene fatty acid bisphenyl ethers, polyalkylene benzylphenyl ethers, polyoxyalkylene styrylphenyl ethers, acetylenediol, polyoxyalkylene-added acetylenediol, polyoxyethylene ether-type silicones, and ester-type silicones. , fluorinated surfactants, nonionic surfactants such as polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styrylphenyl ether sulfates, alkylbenzene sulfonates, alkylaryl sulfonates, lignin sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, alkylnaphthalene sulfonates, salts of formalin condensates of naphthalene sulfonic acid, salts of formalin condensates of alkylnaphthalene sulfonic acid, fatty acid salts, polycarboxylates, polyacrylates, N-methyl fatty acid sarcosinates, resin salts, anionic surfactants such as polyoxyethylene alkyl ether phosphates and polyoxyethylene alkylphenyl ether phosphates, cationic surfactants such as alkylamine salts such as laurylamine hydrochloride, stearylamine hydrochloride, oleylamine hydrochloride, stearylamine acetate, stearylaminopropylamine acetate, alkyltrimethylammonium chloride, and alkyldimethylbenzalkonium chloride,Examples include amphoteric surfactants such as amino acid-type or betaine-type surfactants. These surfactants may be used individually or in combination of two or more types.

[0040] Examples of thickening agents include xanthan gum, guar gum, tung gum, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymers, acrylic polymers, starch compounds, water-soluble polymers such as polysaccharides, high-purity bentonite, and inorganic fine powders such as fumed silica (white carbon).

[0041] Examples of colorants include inorganic pigments such as iron oxide, titanium dioxide, and Prussian blue, as well as organic dyes such as alizarin dyes, azo dyes, and metal phthalocyanine dyes.

[0042] Examples of antifreeze agents include ethylene glycol, diethylene glycol, propylene glycol, and polyhydric alcohols such as glycerin.

[0043] Examples of decomposition inhibitors include desiccants such as zeolite, quicklime, and magnesium oxide; antioxidants such as phenol compounds, amine compounds, sulfur compounds, and phosphoric acid compounds; and ultraviolet absorbers such as salicylic acid compounds and benzophenone compounds.

[0044] Examples of preservatives include potassium sorbate and 1,2-benzothiazolin-3-one. Furthermore, functional spreading agents, activity enhancers such as metabolic degradation inhibitors like piperonyl butoxide, antifreezes such as propylene glycol, antioxidants such as BHT, UV absorbers, and other auxiliary agents may be used as needed.

[0045] The proportion of the active ingredient compound can be adjusted as needed, and can be appropriately selected from the range of 0.01 to 80 parts by weight in 100 parts by weight of the herbicide for agricultural and horticultural use of the present invention. For example, in the case of a flowable formulation, 0.01 to 60 parts by weight relative to the total weight of the herbicide for agricultural and horticultural use is appropriate.

[0046] The amount of the compound or its crystals used in the present invention varies depending on various factors, such as the purpose, target weed, crop growth status, weed emergence tendency, weather, environmental conditions, formulation, application method, application location, and application timing. However, the amount of the active ingredient compound can be appropriately selected from the range of 0.001 g to 10 kg, preferably 0.01 g to 1 kg per 10 ares, depending on the purpose.

[0047] The herbicide for agricultural and horticultural use containing the compound or crystals thereof as an active ingredient can be used to control various weeds by applying an effective amount directly to the stems and leaves of the weeds, either as is or after appropriate dilution or suspension with water, etc. In addition, it can also be used by treating the soil or cultivation carrier, such as by immersing seeds in the chemical, coating seeds with powder, or treating with Calper, as well as by mixing into the entire soil layer, applying in furrows, mixing into bedding soil, treating cell seedlings, treating planting holes, treating around the base of plants, top dressing, treating rice boxes, or applying to the water surface.

[0048] Methods for treating the seeds of useful plants include, for example, immersing the seeds in a liquid or solid formulation (either diluted or undiluted) to allow the agent to penetrate; mixing a solid or liquid formulation with the seeds, coating them with a powder to adhere to the surface; coating the seeds with an adhesive carrier such as a resin or polymer; and spraying the formulation near the seeds at the same time as planting. The "seeds" treated in this manner refer to the early-stage plant body used for the propagation of useful plants, and include, for example, seeds, bulbs, tubers, seed potatoes, buds, bulbils, or plant bodies used for vegetative propagation by cuttings.

[0049] When implementing the method of use of the present invention, the "soil" or "cultivation support" for plants refers to a support for cultivating crops, particularly a support for root growth. The material is not particularly limited, but any material on which useful plants can grow is acceptable, and may be so-called soil, seedling mats, water, etc. Specific materials may include, for example, sand, pumice, vermiculite, diatomaceous earth, agar, gel-like substances, polymer substances, rock wool, glass wool, wood chips, bark, etc.

[0050] Regarding the application method to rice seedling trays, the formulation may vary depending on the application timing, such as application at sowing, greening, or transplanting, but it is acceptable to apply it in powder, wettable granule, or granular form. It can also be applied by mixing it with the growing medium, such as mixing the growing medium with the powder, wettable granule, or granules, for example, mixing it with the seedbed soil, the covering soil, or mixing it into the entire growing medium. Alternatively, the growing medium and the various formulations can be applied in alternating layers.

[0051] For application to paddy fields, solid formulations such as jumbo formulations, pack formulations, granules, and wettable granules, as well as liquid formulations such as flowables and emulsions, are usually scattered onto flooded paddy fields. In addition, at the time of rice planting, a suitable formulation can be applied directly or mixed with fertilizer and scattered or injected into the soil. Furthermore, by using liquid formulations such as emulsions and flowables at the water inflow points into the paddy field, such as water inlets and irrigation systems, application can be carried out in conjunction with the water supply, saving labor. When using spraying equipment, any commonly used equipment is acceptable, including Pankle sprayers, manned helicopters, radio-controlled helicopters, radio-controlled boats, drones, one-shot sprayers, power (manual or automatic) sprayers, carry-type power sprayers, backpack-type power sprayers, and manual sprayers.

[0052] The compound or crystals thereof of the present invention can also be used in combination with other herbicides, plant growth regulators, phytotoxicity reducers (safeners), soil conditioners, fertilizers, etc., for the purpose of expanding the range of weeds to be controlled, the optimal control period, or reducing the amount of chemicals used.

[0053] The following are representative examples of the present invention, but the present invention is not limited to these.

[0054] Manufacturing Example 1: Production of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate crystals (Part 1) To a 14 L acetonitrile solution (550 g, 1.5 mol) of N-(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)-1,1,1-trifluoromethanesulfonamide, sodium bicarbonate (240 g, 2.9 mol) was added at room temperature, and then propyl chloroformate (368 g, 3.0 mol) was added dropwise at room temperature. The mixture was then stirred at 80°C for 3 hours. After cooling to an internal temperature of 30°C, the insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain a white solid (390 g) of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate. To the white solid (390 g), heptane (1050 mL) and ethyl acetate (300 mL) were added, and the mixture was heated to an internal temperature of 60°C. After cooling to an internal temperature of 20°C, the precipitated solid was filtered and dried under reduced pressure to obtain type 1 crystals (356 g, 0.79 mol) of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate. Yield: 53% Properties: １ H-NMR (CDCl ３): δ 7.49 (dd, 2H), 7.39–7.35 (m, 1H), 7.21 (d, 1H), 4.85 (d, 1H), 4.53 (d, 1H), 4.25 (t, 2H), 3.21 (t, 2H), 1.87 (t, 2H), 1.71–1.65 (m, 2H), 1.42 (s, 6H), 0.89 (t, 3H) Differential scanning calorimetry: The results are shown in Figure 1-1. Powder X-ray diffraction (Figure 1-2): Scanning range: 5-90°, Sampling width: 0.01°, Scanning speed: 5° / min, Diffraction angle (2θ): 6.14°±0.2°, 8.69°±0.2°, 12.5°±0.2°, 13.94°±0.2°, 17.27°±0.2°, 17.69°±0.2°, 19.77°±0.2°, 20.75°±0.2°, 21.34°±0.2°, 26.16°±0.2°. The measurement conditions were as follows: Instrument name: Mini Flex (Rigaku Corporation) X-ray: Cu-Kα (40kV, 15mA) Scanning range: 5-90° Sampling width: 0.01° Scanning speed: 5° / min Powder X-ray diffraction (Figure 1-3): Diffraction angle (2θ) 6.34°±0.2°, 8.92°±0.2°, 12.70°±0.2°, 14.18°±0.2°, 25.86°±0.2°. The measurement conditions were as follows: Instrument name: Ultima IV (Rigaku Corporation) X-ray: Cu-Kα (40kV, 40mA) Scanning range: 5-45° Sampling width: 0.02° Scanning speed: 10° / min Peak position in infrared absorption spectrum (Figure 1-4): Wavenumber 1767±4cm －１ , 1694±4cm －１ , 1407±4cm －１ , 1269±4cm －１ , 1200±4cm －１ , 1126±4cm －１ , 980±4cm －１ 756±4cm －１ , 610±4cm －１ , 584±4cm －１ .

[0055] Manufacturing Example 2 Production of crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate (Part 2) White solid (5 mg) of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate was dissolved in tert-butyl methyl ether (100 μL), then heated at 40°C for 1 hour, allowed to cool to room temperature, and then cooled to 5°C to obtain type 1 crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate. Powder X-ray diffraction: The results are shown in Figure 2. The diffraction angles (2θ) were 6.42°±0.2°, 9.04°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 25.96°±0.2°. The measurement conditions were as follows: Instrument name: Ultima IV (Rigaku Corporation) X-ray: Cu-Kα (40kV, 40mA) Scanning range: 5-45° Sampling width: 0.02° Scanning speed: 10° / min Similar powder X-ray diffraction results to those in Figure 2 were obtained when the following solvents or combinations of solvents were used instead of tert-butyl methyl ether: N,N-dimethylacetamide, methanol, ethanol, 2-propanol, 2,2,2-trifluoroethanol, dimethyl sulfoxide, cyclopentyl methyl ether, 2-methyltetrahydrofuran, 1,4-dioxane, ethyl acetate, propyl acetate, isopropyl acetate, acetic acid, methyl ethyl ketone, dimethyl sulfoxide, acetonitrile, dichloroethane, chloroform, methylene chloride, toluene, o-xylene, chlorobenzene, fluorobenzene, heptane, isooctane, cyclohexane, ethylene glycol, 1,2-propanediol, water, N-methylpyrrolidone:water (1:1), N-methylpyrrolidone:water (1:3), N,N-dimethylformamide:water (1:1), N,N-dimethylformamide:water (1:3), N,N-dimethylacetamide:water (1:1), N,N-dimethylacetamide:water (1:3), methanol:water (1:1), methanol:water (1:3), ethanol:water (1:1), ethanol:water (1:3), 2-propanol:water (1:1), 2-propanol:water (1:3), tert-butanol:water (1:1), tert-butanol:water (1:3), 2,2,2-trifluoroethanol:water (1:3), tert-butylmethyl ether:water (1:1), tert-butylmethyl ether:water (1:3), tetrahydrofuran:water (1:1), 1,4-dioxane:water (1:1), 1,4 -Dioxane:Water (1:3), Ethyl acetate:Water (1:1), Ethyl acetate:Water (1:3), Propyl acetate:Water (1:1), Propyl acetate:Water (1:3), Isopropyl acetate:Water (1:1), Isopropyl acetate:Water (1:3), Methyl isobutyl ketone:Water (1:1), Methyl ethyl ketone:Water (1:1), Methyl ethyl ketone:Water (1:3), Acetone:Water (1:1), Dimethyl sulfoxide:Water (1:1), Dimethyl sulfoxide:Water (1:3), Acetonitrile:Water (1:1), Acetonitrile:Water (1:3), Chloroform:Water (1:3), Toluene : Water (1:1), Fluorobenzene: Water (1:1), N,N-Dimethylacetamide: Heptane (1:1), N,N-Dimethylformamide: Heptane (1:1), Toluene: Heptane (1:1), Propyl acetate: Heptane (1:1), 1,4-Dioxane: Heptane (1:1), Isopropyl acetate: Heptane (1:1), 2-Propanol: Heptane (1:1), Acetonitrile: Heptane (1:1), Methyl ethyl ketone: Heptane (1:1), Ethanol: Heptane (1:1), Ethyl acetate: Heptane (1:1), 2,2,2-Trifluoroethanol Methanol:heptane (1:1), tetrahydrofuran:heptane (1:1), methanol:heptane (1:1), acetone:heptane (1:1), tert-butylmethyl ether:heptane (1:1), dimethyl sulfoxide:heptane (1:3), N,N-dimethylformamide:heptane (1:3), propyl acetate:heptane (1:3), isopropyl acetate:heptane (1:3), fluorobenzene:heptane (1:3), acetonitrile:heptane (1:3), methyl ethyl ketone:heptane (1:3), ethyl acetate:heptane (1:3), 2,2,2-Trifluoroethanol:Heptane (1:3), Methanol:Heptane (1:3), Chloroform:Heptane (1:3), Acetone:Heptane (1:3), Tert-Butyl Methyl Ether:Heptane (1:3), Tert-Butyl Methyl Ether:Heptane (1:5), 1-Propanol:Water (1:1), Cyclopentyl Methyl Ether:Ethylene Glycol (1:1), Cyclopentyl Methyl Ether:1,2-Propanediol (1:1), Cyclopentyl Methyl Ether:Iso Octane (1:1), cyclopentyl methyl ether: cyclohexane (1:1), cyclopentyl methyl ether: heptane (1:1), cyclopentyl methyl ether: water (1:1), 2-methyltetrahydrofuran: ethylene glycol (1:1), 2-methyltetrahydrofuran: 1,2-propanediol (1:1), 2-methyltetrahydrofuran: cyclohexane (1:1), 2-methyltetrahydrofuran: heptane (1:1), 2-methyltetrahydrofuran: water (1: 1) Acetic acid: cyclohexane (1:1), dichloroethane: ethylene glycol (1:1), dichloroethane: 1,2-propanediol (1:1), dichloroethane: cyclohexane (1:1), methylene chloride: ethylene glycol (1:1), methylene chloride: cyclohexane (1:1), methylene chloride: heptane (1:1), methylene chloride: water (1:1), o-xylene: ethylene glycol (1:1), o-xylene: 1,2-propanediol (1:1), o-xylene: isopropyl alcohol Tan (1:1), o-xylene:cyclohexane (1:1), o-xylene:heptane (1:1), o-xylene:water (1:1), chlorobenzene:ethylene glycol (1:1), chlorobenzene:isooctane (1:1), chlorobenzene:cyclohexane (1:1), chlorobenzene:heptane (1:1), benzotrifluoride:1,2-propanediol (1:1), benzotrifluoride:isooctane (1:1), or benzotrifluoride:cyclohexane (1:1).

[0056] Manufacturing Example 3 Production of crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate (Part 3) White solid (5 mg) of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate was dissolved in 2-propanol:heptane (1:3) (50 μL:150 μL), then heated at 40°C for 1 hour, allowed to cool to room temperature, and then cooled to 5°C to obtain type 1 crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate. Powder X-ray diffraction: The results are shown in Figure 3. The diffraction angles (2θ) were 6.40°±0.2°, 9.00°±0.2°, 12.76°±0.2°, 14.26°±0.2°, and 25.92°±0.2°. The measurement conditions were as follows: Instrument name: Ultima IV (Rigaku Corporation) X-ray: Cu-Kα (40kV, 40mA) Scanning range: 5-45° Sampling width: 0.02° Scanning speed: 10° / min Similar powder X-ray diffraction results to those shown in Figure 3 were obtained when using benzotrifluoride, tetrahydrofuran:water (1:3), 2-methyltetrahydrofuran:isooctane (1:1), methyl isobutyl ketone:water (1:3), methyl isobutyl ketone:heptane (1:1), acetone:water (1:3), dichloroethane:heptane (1:1), dichloroethane:water (1:1), methylene chloride:1,2-propanediol (1:1), methylene chloride:isooctane (1:1), chlorobenzene:water (1:1), benzotrifluoride:ethylene glycol (1:1), and benzotrifluoride:water (1:1) instead of 2-propanol:heptane (1:3).

[0057] Manufacturing Example 4 Production of crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate (Part 4) White solid (5 mg) of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate was dissolved in 1,4-dioxane:heptane (1:3) (10 μL:30 μL), then heated at 40°C for 1 hour, allowed to cool to room temperature, and then cooled to 5°C to obtain type 1 crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate. Powder X-ray diffraction: The results are shown in Figure 4. The diffraction angles (2θ) were 6.38°±0.2°, 9.00°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 25.94°±0.2°. The measurement conditions were as follows: Instrument name: Ultima IV (Rigaku Corporation) X-ray: Cu-Kα (40kV, 40mA) Scanning range: 5-45° Sampling width: 0.02° Scanning speed: 10° / min Similar powder X-ray diffraction results to those in Figure 4 were obtained when tetrahydrofuran:heptane (1:3), toluene:water (1:3), or dimethyl sulfoxide:heptane (1:1) were used instead of 1,4-dioxane:heptane (1:3).

[0058] Manufacturing Example 5 Production of crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate (Part 5) White solid (5 mg) of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate was dissolved in fluorobenzene:heptane (1:1) (10 μL:10 μL), then heated at 40°C for 1 hour, allowed to cool to room temperature, and then cooled to 5°C to obtain type 1 crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate. Powder X-ray diffraction: The results are shown in Figure 5. The diffraction angles (2θ) were 6.42°±0.2°, 9.10°±0.2°, 12.78°±0.2°, 14.26°±0.2°, and 25.96°±0.2°. The measurement conditions were as follows: Instrument name: Ultima IV (Rigaku Corporation) X-ray: Cu-Kα (40kV, 40mA) Scanning range: 5-45° Sampling width: 0.02° Scanning speed: 10° / min Similar powder X-ray diffraction results to those in Figure 5 were obtained when chloroform:heptane (1:1) or chloroform:water (1:1) was used instead of fluorobenzene:heptane (1:1).

[0059] Manufacturing Example 6 Production of crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate (Part 6) To a white solid (5 mg) of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate, toluene:heptane (1:3) (25 μL:75 μL) was added and dissolved. The mixture was then heated at 40°C for 1 hour, allowed to cool to room temperature, and then cooled to 5°C to obtain type 1 crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate. Powder X-ray diffraction: The results are shown in Figure 6. The diffraction angles (2θ) were 6.38°±0.2°, 8.96°±0.2°, 12.74°±0.2°, 14.20°±0.2°, and 25.96°±0.2°. The measurement conditions were as follows: Instrument name: Ultima IV (Rigaku Corporation) X-ray: Cu-Kα (40kV, 40mA) Scanning range: 5-45° Sampling width: 0.02° Scanning speed: 10° / min Similar powder X-ray diffraction results to those in Figure 6 were obtained when ethanol:heptane (1:3) or dichloroethane:isooctane (1:1) was used instead of toluene:heptane (1:3).

[0060] Manufacturing Example 7 Production of crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate (Part 7) A white solid (5 mg) of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate was dissolved in methyl isobutyl ketone:heptane (1:3) (10 μL:30 μL), then heated at 40°C for 1 hour, allowed to cool to room temperature, and then cooled to 5°C to obtain type 1 crystals of propyl(2-((6,6-dimethyl-2-oxo-1,3-oxadinan-3-yl)methyl)phenyl)((trifluoromethyl)sulfonyl)carbamate. Powder X-ray diffraction: The results are shown in Figure 7. The diffraction angles (2θ) were 6.40°±0.2°, 9.06°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 26.02°±0.2°. The measurement conditions were as follows: Instrument name: Ultima IV (Rigaku Corporation) X-ray: Cu-Kα (40kV, 40mA) Scanning range: 5-45° Sampling width: 0.02° Scanning speed: 10° / min Similar powder X-ray diffraction results to those in Figure 7 were obtained when tetrahydrofuran, methyl isobutyl ketone, acetone, acetic acid: isooctane (1:1), acetic acid: heptane (1:1), fluorobenzene: water (1:3), chlorobenzene: 1,2-propanediol (1:1), or benzotrifluoride: heptane (1:1) was used instead of methyl isobutyl ketone: heptane (1:3).

[0061] Examples of flowable formulations containing the crystals of the present invention are shown below, but the present invention is not limited to these examples. In the formulation examples, "parts" refers to parts by weight. Formulations of the compounds of the present invention in forms other than crystals can be similarly formulated and their herbicidal activity can be evaluated.

[0062] Formulation Examples Formulation Example 1. 87.67 parts water was mixed with 0.50 parts of a mixture of dialkyl sulfosuccinate salt, propylene glycol, and water, 0.75 parts of a mixture of alkylnaphthalene sulfonate sodium formalin condensate and sodium sulfate, 5.00 parts of propylene glycol, 0.50 parts of amorphous silica, and 0.10 parts of a mixture of 1,2-benzisothiazolin-3-one, dipropylene glycol, and water. The mixture was stirred, and then 3.88 parts of the crystals of the present invention were added and finely ground using a wet grinder. 0.10 parts of xanthan gum and 1.50 parts of bentonite were added to the pulverized material and mixed uniformly to obtain a flowable formulation of the crystals of the present invention. The flowable formulation of the crystals of the present invention was dispersed and suspended in a medium mainly consisting of water. In contrast, the amorphous compound of formula (1) does not suspend sufficiently in a water-based medium. Therefore, the usefulness of the crystals of the present invention in formulation was demonstrated. Formulation Example 2. Mix and dissolve 10 parts of the compound, 54 parts of xylene, 28 parts of N,N-dimethylformamide, and 8 parts or more of a polyoxyethylene phenylphenol derivative alkylallyl sulfonate xylene-containing product uniformly to form an emulsion.

[0063] Test Example 1. Herbicidal effect test on paddy field weeds after germination (post) 75 cm ２ Fill a plastic pot with soil (sandy clay loam), sow seeds of barnyard grass and bulrush (Scirpus juncoides), which are rice paddy weeds, and place the seeds in 75 cm of soil. ３ After covering with soil, the plants were flooded to a depth of 5 cm and grown in a greenhouse. When the test plants were in the one-leaf stage, a predetermined effective amount (100 g / ha as active ingredient) of the agent (flowable formulation of Formulation Example 1) containing the crystal of the present invention (type 1 crystal of compound (1)) as the active ingredient was diluted with water and dropped onto the water surface. The plants were then grown in a greenhouse, and the herbicidal effect was investigated 21 days after treatment for Barnyard grass and 28 days after treatment for Scirpus juncoides. The herbicidal effect was evaluated according to the following criteria, compared to the untreated area. The results are shown in Table 1. Criteria for determining herbicidal effectiveness (degree of growth inhibition) and phytotoxicity: 5...100% herbicidal effectiveness, phytotoxicity 4...90% to 99% herbicidal effectiveness, phytotoxicity 3...70% to 89% herbicidal effectiveness, phytotoxicity 2...40% to 69% herbicidal effectiveness, phytotoxicity 1...1% to 39% herbicidal effectiveness, phytotoxicity 0...0% herbicidal effectiveness, phytotoxicity

[0064] Test Example 2. Herbicide efficacy test against *Eleocharis kuroguwai* (75 cm) ２ Plastic pots were filled with soil (sandy clay loam) and flooded to a depth of 5 cm, and tubers of the paddy field weed, *Eleocharis kuroguwai*, were transplanted. The day after transplanting, a predetermined effective amount (100 g / ha of active ingredient) of the agent containing the crystal of the present invention (type 1 crystal of compound (1)) prepared according to Formulation Example 1 was diluted with water and dropped onto the water surface. The plants were then grown in a greenhouse, and the herbicidal effect was investigated 28 days after treatment. The herbicidal effect was evaluated according to the criteria of Test Example 1, compared to the untreated area. The results are shown in Table 1.

[0065] Test Example 3. Phytotoxicity Test on Transplanted Rice (75 cm) ２ A plastic pot was filled with soil (sandy clay loam), flooded to a depth of 5 cm, and two rice plants (variety: Nipponbare) at the two-leaf stage were transplanted at a transplanting depth of 2 cm. On the day of transplanting, a predetermined effective amount (100 g / ha as active ingredient) of the drug containing the crystal of the present invention (type 1 crystal of compound (1)) prepared according to Formulation Example 1 was diluted with water and dropped onto the water surface. The plants were then grown in a greenhouse, and phytotoxicity was investigated 28 days after treatment. The phytotoxicity was evaluated according to the criteria of Test Example 1, in comparison to the untreated plants. The results are shown in Table 1.

[0066]

[0067] Test Example 4. Herbicide Residual Effect Test against Barnyard Grass The residual herbicide effect of the compound of the present invention was compared with that of compounds with similar structures listed in Table 2 below, using a herbicide residual effect test against Barnyard Grass to investigate the effect of the compound of the present invention. 200 cm ２A Wagner pot was filled with soil (sandy clay loam) and flooded with water to a depth of 5 cm. A drug containing the crystal of the present invention (type 1 crystal of compound (1)) as the active ingredient (flowable formulation of Formulation Example 1) and a drug prepared according to Formulation Example 2, containing compound 1 (compound number 1-51) disclosed in Patent Document 1 as the active ingredient, were diluted with water and dropped onto the water surface to a predetermined effective amount (100 g / ha of active ingredient). Fourteen days after treatment, barnyard grass seeds, a paddy weed, were sown and grown in a greenhouse. Twenty-two days after sowing, the herbicidal effect was investigated and evaluated in comparison to the untreated area. The results are shown in Table 2. The compound of the present invention showed a residual herbicidal effect superior to that of the comparative compound.

[0068] Test Example 5. Herbicidal Efficacy Test on Barnyard Grass (Echinochloa crus-galli) after Germination (post-emergence) The herbicidal effect of the compound of the present invention was compared with that of compounds with similar structures listed in Table 3 below, by conducting a herbicidal effect test on Barnyard Grass, and the effect of the compound of the present invention was investigated. 100 cm ２ Fill the Wagner pots with soil (sandy clay loam), sow barnyard grass seeds (a paddy field weed), and cover with 100 cm of soil. ３ After covering with soil, the plants were flooded to a depth of 5 cm and grown in a greenhouse. When the test plants reached the three-leaf stage, a drug containing the crystal of the present invention (type 1 crystal of compound (1)) as the active ingredient (flowable formulation of Formulation Example 1) and a drug prepared according to Formulation Example 2, containing one compound (compound number 1-26) disclosed in Patent Document 1 as the active ingredient, were diluted with water and dropped onto the water surface to a predetermined effective amount. The plants were then grown in a greenhouse, and the herbicidal effect was investigated 27 days after treatment and evaluated compared to the untreated area. The results are shown in Table 3. The compound of the present invention showed a superior herbicidal effect compared to the comparative compound.

[0069] Test Example 6. Herbicide Residual Effect Test against Scirpus juncoides The residual herbicide effect of the compound of the present invention and two compounds with similar structures listed in Table 4 below was compared using a herbicide residual effect test against Scirpus juncoides to investigate the effect of the compound of the present invention. 200 cm ２A Wagner pot was filled with soil (sandy clay loam) and flooded with water to a depth of 5 cm. A drug containing the crystal of the present invention (type 1 crystal of compound (1)) as the active ingredient (flowable formulation of Formulation Example 1) and a drug prepared according to Formulation Example 2, containing two compounds (compound numbers 1-47 and 50) disclosed in Patent Document 1 as comparative compounds as active ingredients, were diluted with water and dropped onto the water surface to a predetermined effective amount (100 g / ha of active ingredient). Fourteen days after treatment, seeds of the paddy field weed *Scirpus juncoides* were sown and grown in a greenhouse. Twenty-two days after sowing, the herbicidal effect was investigated and evaluated in comparison to the untreated area. The results are shown in Table 4. The compound of the present invention showed a residual herbicidal effect superior to all of the comparative compounds.

[0070] The results from Test Examples 1 to 6 clearly show that the crystals of the present invention are capable of being formulated into a flowable form while maintaining herbicidal activity. Obtaining crystals that can be formulated into a flowable form while maintaining herbicidal activity is difficult even considering prior art. In other words, the present invention exhibits exceptionally remarkable effects that cannot be predicted from prior art. The activity of the compound or crystals of the present invention can be confirmed in various formulations by a test method similar to at least one of Test Examples 1 to 6, a test method similar to those known in the art, or a test method that appropriately modifies these test methods.

[0071] The compound or crystal thereof of the present invention can be used as an active ingredient in agricultural and horticultural herbicides.

Claims

A compound represented by formula (1). Equation (1): A crystal of the compound represented by the formula. 　 A type 1 crystal of the compound according to claim 1, with a melting point of 86 to 100°C as measured by differential scanning calorimetry (DSC). 　 Crystals having diffraction peaks at diffraction angles (2θ) of 6.14°±0.2°, 8.69°±0.2°, 12.5°±0.2°, 13.94°±0.2°, 17.27°±0.2°, 17.69°±0.2°, 19.77°±0.2°, 20.75°±0.2°, 21.34°±0.2°, and 26.16°±0.2° in powder X-ray diffraction spectra, or Crystals exhibiting diffraction peaks at diffraction angles (2θ) of 6.34°±0.2°, 8.92°±0.2°, 12.70°±0.2°, 14.18°±0.2°, and 25.86°±0.2° in powder X-ray diffraction spectra; Crystals exhibiting diffraction peaks at diffraction angles (2θ) of 6.42°±0.2°, 9.04°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 25.96°±0.2° in their powder X-ray diffraction spectra; Crystals exhibiting diffraction peaks at diffraction angles (2θ) of 6.40°±0.2°, 9.00°±0.2°, 12.76°±0.2°, 14.26°±0.2°, and 25.92°±0.2° in powder X-ray diffraction spectra; Crystals exhibiting diffraction peaks at diffraction angles (2θ) of 6.38°±0.2°, 9.00°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 25.94°±0.2° in powder X-ray diffraction spectra; Crystals exhibiting diffraction peaks at diffraction angles (2θ) of 6.42°±0.2°, 9.10°±0.2°, 12.78°±0.2°, 14.26°±0.2°, and 25.96°±0.2° in powder X-ray diffraction spectra; Crystals having diffraction peaks at diffraction angles (2θ) of 6.38°±0.2°, 8.96°±0.2°, 12.74°±0.2°, 14.20°±0.2°, and 25.96°±0.2° in their powder X-ray diffraction spectra; or In the powder X-ray diffraction spectrum, the crystal has diffraction peaks at diffraction angles (2θ) of 6.40°±0.2°, 9.06°±0.2°, 12.74°±0.2°, 14.24°±0.2°, and 26.02°±0.2°. A type 1 crystal of the compound according to claim 1. 　 The type 1 crystal according to claim 1, wherein the crystal has diffraction peaks at diffraction angles (2θ) of 6.14°±0.2° to 6.34°±0.2°, 8.69°±0.2° to 8.92°±0.2°, 12.5°±0.2° to 12.70°±0.2°, 13.94°±0.2° to 14.18°±0.2°, and 25.86°±0.2° to 26.16°±0.2° in its powder X-ray diffraction spectrum. 　 In the infrared absorption spectrum, the wavenumbers are 1767 ± 4 cm －１ , 1694 ± 4 cm －１ , 1407 ± 4 cm －１ , 1269 ± 4 cm －１ , 1200 ± 4 cm －１ , 1126 ± 4 cm －１ , 980 ± 4 cm －１ , 756 ± 4 cm －１ , 610 ± 4 cm －１ , 584 ± 4 cm －１ The type 1 crystal of the compound according to claim 1, having peaks at the positions of Equation (1): A method for producing crystals of a compound represented by the following: The compound represented by formula (1) is precipitated as crystals by recrystallization using ethyl acetate and heptane, or To precipitate crystals of the compound represented by formula (1) by recrystallization using a good solvent and / or a poor solvent. A method for producing type 1 crystals according to any one of claims 3 to 6, characterized by including the following: 　 A herbicide for agricultural and horticultural use, characterized by containing the compound described in claim 1 or the crystal described in any of claims 2 to 6 as an active ingredient. 　 The herbicide for agricultural and horticultural use according to claim 8, which is a flowable formulation. 　 A method for using an agricultural and horticultural herbicide, characterized by applying an effective amount of the agricultural and horticultural herbicide described in claim 8 to weeds, soil, paddy fields, or cultivation carriers. 　 A method for using an agricultural and horticultural herbicide, characterized by applying an effective amount of the agricultural and horticultural herbicide described in claim 9 to weeds, soil, paddy fields, or cultivation carriers. 　 A method for controlling weeds, characterized by applying an effective amount of the agricultural and horticultural herbicide described in claim 8 to weeds, soil, paddy fields, or cultivation carriers. 　 A method for controlling weeds, characterized by applying an effective amount of the agricultural and horticultural herbicide described in claim 9 to weeds, soil, paddy fields, or cultivation carriers.

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