JP2020023443A - Crystal of ortho-substituted haloalkylsulfonanilide compound and production method therefor - Google Patents

Abstract

To provide a crystal of an ortho-substituted haloalkylsulfonanilide compound and a production method therefor.SOLUTION: The ortho-substituted haloalkylsulfonanilide compound, which is a compound having useful activity as a herbicide and represented by the formula (1), wherein R represents isobutyl oxycarbonyl or a hydrogen atom, has a novel crystal.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a crystal which can be obtained by an ortho-substituted haloalkylsulfonanilide compound represented by the following formula (1) which is a compound having a herbicidal activity useful as a herbicide, a method for producing the same, and a suspension composition containing the crystal About things.

  Ortho-substituted haloalkylsulfonanilide compound represented by the following formula (1) [hereinafter, abbreviated as “compound (1)” when R represents isobutyloxycarbonyl, and “compound (2)” when R represents a hydrogen atom. ] Is known (for example, Patent Document 1).

International Publication No. 2010/026989

  In general, it is still impossible to predict physical properties such as the melting point and water solubility of compound crystals.

  An object of the present invention is to provide novel crystals of compound (1) and compound (2) and a method for producing the same. Another object of the present invention is to provide a suspension composition containing the crystals and having improved storage stability.

  The present inventors have conducted intensive studies and have found that compound (1) and compound (2) each have novel crystals. That is, the present invention relates to the following [1] to [6].

[1]
Equation (1):

[Wherein R represents isobutyloxycarbonyl], among the possible crystals of the ortho-substituted haloalkylsulfonanilide compound represented by the formula: 2θ = 6.36, 7.92; Crystals having peaks at 12.70, 15.48, 16.53, 17.42, 18.82 and 20.48.

[2]
Equation (1):

Among the possible crystals of the ortho-substituted haloalkylsulfoneanilide compound represented by the formula: wherein R represents a hydrogen atom, 2θ = 6.75, 7.89, 10 in powder X-ray diffraction by Cu-Kα ray 0.07, 10.71, 11.49, 12.16, 13.30, 13.54, 17.63, 18.09, 18.59, 19.69, 20.44 and 23.34. crystal.

[3]
A suspension composition comprising the crystal according to the above [1] and a dispersion medium.

[4]
The suspension composition according to the above [3], further comprising a surfactant, wherein the dispersion medium is water.

[5]
A suspension composition comprising the crystal according to [2] and a dispersion medium.

[6]
The suspension composition according to the above [5], further comprising a surfactant, wherein the dispersion medium is water.

  According to the present invention, various crystals of compound (1) and compound (2) can be obtained with good reproducibility.

Powder X-ray diffraction chart of compound (1) crystal DSC chart of compound (1) crystal Powder X-ray diffraction chart of compound (2) crystal DSC chart of compound (2) crystal

  The compound (1) in the present invention is 1- [2- (N-isobutyloxycarbonyl-N-trifluoromethanesulfonyl) aminobenzyl] -3,3-dimethyl-azetidin-2-one, and its structural formula is shown below. Shown in

[In the formula, R represents isobutyloxycarbonyl. ]
The powder X-ray diffraction peak is shown below as a characteristic of the compound (1) crystal.
2θ = 6.36, 7.92, 12.70, 15.48, 16.53, 17.42, 18.82, 20.48.

  In addition, since the error of the powder X-ray diffraction peak can be usually ± 0.2 and possibly ± 0.1, the peak value of the crystal of the compound (1) considering the error is usually 2θ = 6.36 ±. 0.2, 7.92 ± 0.2, 12.70 ± 0.2, 15.48 ± 0.2, 16.53 ± 0.2, 17.42 ± 0.2, 18.82 ± 0. 2, 20.48 ± 0.2, and in some cases 2θ = 6.36 ± 0.1, 7.92 ± 0.1, 12.70 ± 0.1, 15.48 ± 0.1, 16. 53 ± 0.1, 17.42 ± 0.1, 18.82 ± 0.1, and 20.48 ± 0.1.

The measurement conditions of the powder X-ray diffraction peak shown above are as follows.
[Powder X-ray diffraction]
Model name: X'PERT-PRO MPD (Spectris Inc.)
Measurement method: transmission method X-ray: Cu-Kα
Voltage: 45kV
Current: 40mA
Sampling interval: 0.01671 deg
Data range: 2θ = 4 to 40 deg
The crystals of the compound (1) have a melting point of 40 to 42 ° C., and an endothermic peak in a lower temperature range than the melting point is not observed in the differential thermal analysis.

  The crystal of compound (1) can be produced by the following method. The compound (1) is dissolved by heating the compound (1) in a solvent and gradually cooling the resulting solution to crystallize, or by distilling the solvent from the obtained solution to crystallize the compound (1). ) Is obtained. The solvent to be used may be any solvent which is inert to the compound (1), for example, diethyl ether, methyl-t-butyl ether, tetrahydrofuran, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether Ethers such as ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether and 1,4-dioxane; Ter solvents, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 2-methyl-2-propanol, Methyl cellosolve, ethyl cellosolve, i-propyl cello Alcohols such as rub, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclohexanol, benzyl alcohol, pentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, Aliphatic hydrocarbon solvents such as decane, aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, nitrobenzene and tetrahydronaphthalene, acetonitrile and propio Nitrile solvents such as nitrile, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, Halogenated hydrocarbon solvents such as 1,2-trichloroethane, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethylimidazolidinone, N, N , N ', N'-tetramethylurea and other urea-based solvents, dimethylsulfoxide, sulfolane and other sulfur-containing polar solvents, pyridine, 2-picoline, 3-picoline, 4-picoline, 5-ethyl-2-picoline and the like , A ketone-based solvent such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, water and the like, and these solvents can be used alone or in combination of two or more. Among these solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents or nitrile solvents are preferred, and heptane, xylene, toluene or acetonitrile is more preferred.

  The amount of the solvent to be used is generally 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight, per 1 part by weight of compound (1).

  The temperature at which the compound (1) is dissolved in the solvent is usually 30 to 150 ° C, preferably 30 to 100 ° C.

  The cooling rate is usually 0.1 to 40 ° C./hour, preferably 1 to 30 ° C./hour, and can be changed to any cooling rate within the above range as needed.

  The temperature of the solution when removing the precipitated crystals is usually -30 to 50C, preferably -20 to 30C.

  The time required for crystallization is generally 0.1 to 100 hours, preferably 1 to 50 hours.

  When the solvent is distilled off, the solvent can be distilled off by heating the solvent to a temperature not lower than the boiling point of the solvent under atmospheric pressure. Further, by adjusting the degree of reduced pressure in the container, the solvent can be distilled off at an arbitrary temperature up to the boiling point of the solvent under reduced pressure.

  The compound (2) in the present invention is 1- [2- (N-trifluoromethanesulfonyl) aminobenzyl] -3,3-dimethylazetidin-2-one, and its structural formula is shown below.

[Wherein, R represents a hydrogen atom. ]
The powder X-ray diffraction peak is shown below as a feature of the crystal of compound (2).

  2θ = 6.75, 7.89, 10.07, 10.71, 11.49, 12.16, 13.30, 13.54, 17.63, 18.09, 18.59, 19.69, 20.44, 23.34.

  In addition, since the error of the powder X-ray diffraction peak can be usually ± 0.2 and possibly ± 0.1, the peak value of the crystal of the compound (2) considering the error is usually 2θ = 6.75 ±. 0.2, 7.89 ± 0.2, 10.07 ± 0.2, 10.71 ± 0.2, 11.49 ± 0.2, 12.16 ± 0.2, 13.30 ± 0. 2, 13.54 ± 0.2, 17.63 ± 0.2, 18.09 ± 0.2, 18.59 ± 0.2, 19.69 ± 0.2, 20.44 ± 0.2, 23.34 ± 0.2, 2θ = 6.75 ± 0.1, 7.89 ± 0.1, 10.07 ± 0.1, 10.71 ± 0.1, 11.49 ± 0.1, 12.16 ± 0.1, 13.30 ± 0.1, 13.54 ± 0.1, 17.63 ± 0.1, 18.09 ± 0.1, 18.59 ± 0. 1, 19.69 ± 0.1, 20.44 0.1,23.34 is ± 0.1.

The measurement conditions of the powder X-ray diffraction peak shown above are as follows.
[Powder X-ray diffraction]
Model name: X'PERT-PRO MPD (Spectris Inc.)
Measurement method: transmission method X-ray: Cu-Kα
Voltage: 45kV
Current: 40mA
Sampling interval: 0.01671 deg
Data range: 2θ = 4 to 40 deg
The crystal of the compound (2) has a melting point of 114 to 116 ° C., and does not show an endothermic peak in a region lower than the melting point in the differential thermal analysis.

  The crystal of compound (2) can be produced by the following method. The compound (2) is dissolved by heating the compound (2) in a solvent and gradually cooling the resulting solution to crystallize, or by distilling the solvent from the obtained solution to crystallize the compound (2). ) Is obtained. The solvent to be used may be any solvent which is inert to the compound (2), for example, diethyl ether, methyl-t-butyl ether, tetrahydrofuran, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether Ethers such as ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether and 1,4-dioxane; Ter-based solvents, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 2-methyl-2-propanol, Methyl cellosolve, ethyl cellosolve, i-propyl cello Alcohols such as rub, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclohexanol and benzyl alcohol, pentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, Aliphatic hydrocarbon solvents such as decane, aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, nitrobenzene and tetrahydronaphthalene, acetonitrile and propio Nitrile solvents such as nitrile, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, Halogenated hydrocarbon solvents such as 1,2-trichloroethane, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethylimidazolidinone, N, N , N ', N'-tetramethylurea and other urea-based solvents, dimethylsulfoxide, sulfolane and other sulfur-containing polar solvents, pyridine, 2-picoline, 3-picoline, 4-picoline, 5-ethyl-2-picoline and the like , A ketone-based solvent such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, water and the like, and these solvents can be used alone or in combination of two or more. Among these solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents or nitrile solvents are preferred, and heptane, xylene, toluene or acetonitrile is more preferred.

  The amount of the solvent to be used is generally 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight, per 1 part by weight of compound (2).

  The temperature at which compound (2) is dissolved in a solvent is usually 30 to 150 ° C, preferably 30 to 100 ° C.

  The cooling rate is usually 0.1 to 40 ° C./hour, preferably 1 to 30 ° C./hour, and can be changed to any cooling rate within the above range as needed.

  The temperature of the solution when removing the precipitated crystals is usually -30 to 50C, preferably -20 to 30C.

  The time required for crystallization is generally 0.1 to 100 hours, preferably 1 to 50 hours.

  When the solvent is distilled off, the solvent can be distilled off by heating the solvent to a temperature not lower than the boiling point of the solvent under atmospheric pressure. Further, by adjusting the degree of reduced pressure in the container, the solvent can be distilled off at an arbitrary temperature up to the boiling point of the solvent under reduced pressure.

  Next, the suspension composition containing the compound (1) or compound (2) crystals of the present invention (hereinafter, referred to as the present composition) will be described in detail.

  In the composition of the present invention, water or an organic liquid in which crystals of the compound (1) or the compound (2) are hardly dissolved can be used as the dispersion medium. Examples of the organic liquid include alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and isopropanol, ethers such as butyl cellosolve, ketones such as cyclohexanone, esters such as γ-butyrolactone, N-methylpyrrolidone and N-octyl. Acid amides such as pyrrolidone; aromatic hydrocarbons such as xylene, alkylbenzene, phenylxylylethane and alkylnaphthalene; machine oils; aliphatic hydrocarbons such as normal paraffin, isoparaffin and naphthene; aromatic hydrocarbons such as kerosene and aliphatic. Fatty oils such as mixtures of hydrocarbons, soybean oil, linseed oil, rapeseed oil, coconut oil, cottonseed oil and castor oil.

  The content of the crystal of the compound (1) or the compound (2) is usually 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the composition of the present invention.

  In the suspension composition containing the compound (1) or compound (2) crystals, the growth of suspended particles of the compound (1) or compound (2) over time is suppressed.

  In addition to the compound (1) or the compound (2), one or more other known pesticides such as herbicides, insecticides, acaricides, nematicides, antiviral agents, plant growth regulators, and bactericidal agents. Agents, synergists, attractants, repellents and the like may be contained, and in this case, a more excellent controlling effect may be exhibited. Particularly preferred among the known pesticides are fungicides, bactericides, nematicides, acaricides and insecticides. Specific examples of the common names are as follows, but are not necessarily limited thereto.

Herbicides: TCBA (2,3,6-TBA), TCBA salts and esters (2,3,6-TBA-salts and esters), 2,4-D (2,4-D), 2,4- DB (2,4-DB), 2,4-DB salts and esters, 2,4-PA (2,4-PA), 2,4-PA salts And esters (2,4-PA-salts and esters), acetochlor (acetochlor), acifluorfen (acifluorfen), acronifen (aclonifen), alachlor (alachlor), alloxydim (alloxydim), alloxydim-sodium (alloxydim-sodium) ), Ametryn (ametryn), amicarbazone, amidosulfuron, aminocyclopirachlor, aminocyclopyrachlor-salts and esters (aminocyclopirachlor-salts and esters), aminopyralid, aminopyralid Salts and esters (aminopyrali d-salts and esters), amiprophos-methyl, amitrol, amitrol, anilofos, aslam, asuram, atrazine, azafenidin, azafenidurin, azimsulfuron, beflubutamide beflubutamid), benazolin-ethyl, bencarbazone, benfluralin, benefin, benfuresate, bensulfuron-methyl, bensulfuron-methyl, benzulide, bentazone, bentazone bentazone-salts, bentazone sodium (bentazone-sodium), benthiocarb (benthiocarb), benzfendizone (benzfendizone), benzobicyclon (benzobicyclon), benzofenap (benzofenap), bialaphos (bialaphos), bialaphos sodium (bialaphos- sodium) , Bicyclopyrone, bifenox, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromobutide, bromofenoxim, bromoxynil, bromoxynil Salts and esters (bromoxynil-salts and esters), butachlor (butachlor), butafenacyl (butafenacil), butamifos (butamifos), butenachlor (butenachlor), butralin (butralin), butroxydim (butroxydim), butyrate (butylate), cafenstrole (cafenstrole) ), Carbetamide, carfentrazone-ethyl, chloromethoxyfen, chlomethoxynil, chloramben, chloramben salts and es (Chloramben-salts and esters), chloransulam-methyl, chlorflurenol-methyl, chloridazon, chloridazon, chlorimuron-ethyl, chlorobromuron , Chlorotoluron, chloroxuron, chlorphtalim, chlorpropham, chloroIPC (chlorpropham), chlorsulfuron, chlorthal-dimethyl, TCTP (chlorthal-dimethyl) ), Chlorthiamid, sinidon-ethyl, cinmethrin (cinmethylin), cinosulfuron (cinosulfuron), clethodim (clethodim), clodinafop (clodinafop), clodinafop-propargyl (clodinafop-propargyl), clomazone (clomazone) Clomeprop, Clopyralid, Clopyralid-salts and esters, CNP (CNP), Cumyluron, Cyanazine, Cyanazin, Cycloate, Cyclopyrimorate , Cyclosulfamuron, cycloxydim, cycloxydim, cyhalofop-butyl, dalapon, dazomet, desmedipham, desmethrin (desmetryn), dicamba , Dicamba-salts and esters, dichlobenil, dichlorprop, dichlorprop-P, dichlorprop-P, dichlorprop-P-salts and esters), dichlorprop-salts and este rs), dicloofop, diclofop-methyl, dicloslam, difenzoquat, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium , Dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-p, dimethenapine, dimethipin, dinitroamine, dinosebdi, terosebdi, rbose Diphenamid, diquqt, dithiopyl, diuron, DNOC (DNOC), DSMA (DSMA), dimron (dymron), endothal, EPTC (EPTC), esprocarb (esprocarb) , Ethal Fluralin (ethalfluralin), ethametsulfuron-methyl (ethametsulfuron-methyl), ethofumesate (ethofumesate), ethoxysulfuron (ethoxysulfuron), etobenzanide (etobenzanid), fenoxaprop (fenoxaprop), fenoxaprop-ethyl, fenoxaprop-ethyl Sulfone (fenoxasulfone), fenquinotrione (fenquionotrion), fentrazamide (fentrazamide), flamprop (flamprop), flazasulfuron (flazasulfuron), florasulam (florasulam), florpyrauxifen, florpyrauxifen benzyl ( florpyrauxifen-benzyl, fluazifop, fluazifop-butyl, fluazolate, fluazolate, flucarbazone-sodium, flucetosulfuron, fluchloraril (Flucloralin), flufenacet (flufenacet), flufenpyl-ethyl (flufenpyl-ethyl), flumetetsulam (flumetsulam), flumiclorac-pentyl (flumiclorac-pentyl), flumioxazin (flumioxazin), fluometuron, fluometuron Phenethyl (fluoroglycofen-ethyl), flupoxam (flupoxam), flupirsulfuron (flupyrsulfuron), flurenol (flurenol), fluridone (fluridone), flurochloridone (flurochloridone), fluroxypyr (fluroxypyr), ester of fluroxypyr-sr Flufluprimidol, Flutamone, Fluthiacet-methyl, Fomesafen, Fomesafen, Foramsulfuron, Fosamine, Glufosinate, Glufosinate Glyphosate (glyphosate-ammonium), glyphosate (glyphosate), glyphosate ammonium (glyphosate-ammonium), glyphosate-isopropylamine (glyphosate-iso-propylammonium), glyphosate potassium (glyphosate-potassium), glyphosate sodium (glyphosate-sodium) (Glyphosate-trimesium), halauxifen, halauxifen-salts and esters, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop haloxyfop), haloxyfop-methyl (haloxyfop-methyl), hexazinone (hexazinone), imazamethabenz-methyl (imazamethabenz-methyl), imazamox (imazamox), imazapic (imazapic), imazapyr (imazapyr), imazaquin (imazaquin), Imazethapyr, imazosulfuron, imanosulfuron, indanofan, indaziflam, indaziflam, iodosulfuron-methyl-sodium, ioxynil octanoate, salts and esters of ioxynil ), Ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, carbutilate, lactofen, lancotrione Lancotrione-sodium salt, lenacil, linuron, maleic hydrazide, MCPA (MCPA), MCPA salts and esters, MCPB MCPB), CPB salts and esters (MCPB-salts and esters), mecoprop (MCPP), P-mecoprop (MCP-P), P-mecoprop salts and esters (mecoprop-P-salts and esters), mecoprop Salts and esters (mecoprop-salts and esters), mefenacet (mefenacet), mefluidide (mefluidide), mesosulfuron-methyl (mesosulfuron-methyl), mesotrione (mesotrione), metatam (metam), metamifop (metamifop), metamitron (metamitron), Metazachlor (metazachlor), metazosulfuron (metazosulfuron), metabenzthiazuron (methabenzthiazuron), methiozolin (methiozolin), methyl azide (methyl azide), methyl bromide (methyl bromide), methyl dimron (methyl dymron), methyl iodide ( methyl iodide), metobenzuron (metobenzuron), metolachlor (metolachlor) ), S-metolachlor-S, metosuram, metoxuron, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, monosulfuron , Monosulfuron-methyl, MSMA (MSMA), naproanilide (naproanilide), napropamide (napropamide), naptalam (naptalam), naptalam sodium (naptalam-sodium), nebulon, nicosulfuron, Norflurazon, oleic acid, orbencarb, orthosulfamuron, oryzalin, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxasulfuron Oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendimethalin, penoxsulam, pentanochlor, pentanochlor, pentoxazone, petoxoxamid Phenmedipham-ethyl, picloram, picloram-salts and esters, picolinafen, picoxafen, pinoxaden, piperophos, pretilachlor, pretilachlor Misulfuron-methyl, prodiamine, profluazol, profludim, profoxydim, prometon, promethrin, prometryn, propachlor, propanil anil), propaquizafop, propazin, propham, propham, propisochlor, propoxycarbazone-sodium, propyrisulfuron, propyzamide, propyzamide Prosulfocarb, prosulfuron, pyraclonil, pyraflufeneth


(Pyraflufen-ethyl), pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen (pyrazoxyfen), pyribenzoxim, pyributicarbi (pyributicarbi) (Pyridafol), pyridate, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac-sodium, pyroxasulfone, pyroxyslam ( pyroxsulam), quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, P quizalofop-P, quizalofop-P pP-ethyl, P quizalofop-P-tefuryl, quizalofop-tefuryl, rimsulfuron, rimsulfuron, saflufenacil, sethoxydim, siduron , Simazine, Simetrin, Sulcotrione, Sulfentrazone, Sulfometuron-methyl, Sulfometuron-methyl, Sulfosulfuron, Tebutam, Tebuthiuron ), Tefuryltrione, tebotrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbumeton, terbuthylazine, terbutryn, terbutryn, tetrapion / flupropanate thenylchlor), chiaza Luron (thiazafluron), thiazopyr (thiazopyr), thidiadimine (thidiazimin), thidiazuron (thidiazuron), thiencarbazonemethyl (thiencarbazone-methyl), thifensulfuron-methyl, thifenenacil, tiafenacil, tolpyralate , Topramezon, tolalkoxydim, tralkoxydim, triafamone, trilatelate, triasulfuron, triaziflam, triaziflam, tribenuron-methyl, triclopyr, triclopyr Of salts and esters (triclopyr-salts and esters), tridiphane, trietazine, trifloxysulfuron, trifludimoxadin, trifluralin, trifluralin Flusulfuron-methyl, tritosulfuron, OK-701 (test name).
Fungicides: acibenzolar-S-methyl, acipetaxs, aldimorph, allyl alcohol, amethoctrazine, amisolambrom, amisombromam Amphopylfos, anilazine, azaconazole, azithiram, azoxystrobin, barium polysulfide (barium valenyl, valenalyl benzyl, valenyl benzyl, valenyl benzyl) Benodanil, benomyl, benquinox, bentaluron, bentavalicalcarb-isopropyl, benthiazole, benziamzl, benzomazole, benzomazr, benzomazr, benzomazole, benzomazole Benzovindiflupyr, binapacacryl, biphenyl, bitertanol, bitafenol, bixafen, blasticidin-S, bordeaux liquid, and bordeaux liquid ), Bromoconazole, bupirimate, butiobate, butyamine, butylamine, calcium polysulphide, captaptan, captaphorb, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafol, captafolp, captafol, captafolp, captafol, captafolp, captafolp, captafol, captafol, captafol, captafol, captafol, captafol, captafol) Carbendazim, carboxin, carpropamide, carvone, cheshunt mixture, quinomethionate, chlorobenzizone, clobenthiazion, clobenciazone. iformethane, chloranil, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlorquinox, chlorquinox, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, clozolin, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorozinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorquinox, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol, chlorzinol), (Copper acetate), basic copper carbonate (basic), copper hydroxide (copper hydroxide), copper naphthenate, copper oleate, basic copper chloride (cop) chloride, copper sulfate, basic copper sulfate, basic, copper zinc chromate, cresol, crefurane, couprobazo, muprobazo, mupro, amizo, mupro, amizo, mupro, amizo, mupro, amizo, mupro, amo, mupro, amo, mupro, amo, mupro, amo, fupro, amo, fupro, amo, fupro, amo, amo, m, a, m , Cyclafuramide, cycloheximide, cyflufenamide, cymoxanil, cypendazole, cyprodazole, cyproconidol, cyproconazole, cyproconazole, cyproconidol, cyproconazole, cyproconazole (Dazomet), debacarb, decafentin, dehydroacetate, dichlofluanid, dichlone, dichlozendiclochlorin, dichlorophenochloride Diclobutrazol, diclocymet, diclomethine, dichloran, diethofencarb, diphenoconazole, difirimetime, diflumetrime , Dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4, dinocap-4. (Dinocap-6), dinocton, dinosulfone, dinoterbone, diphenylamine, dipymetitrone, dipyrimethionone, dipyrimethionone, dipyrimethionone, dipyrimethionone, dipyrimethionone, dipyrimethionone, dipyrimethionone, dipyrimethionone, dipyrimethione, dipyrithium, dipyrimethione, dipyrithium, dipyrithium, dipyrithium, dipyrithium, dipyrithion, dipyrithium, dipyrithium, dipyrithium, dipyrithion, dipyrithium, dipyrithium, dipyrithion, dipyrithium, dipyrithium, dipyrithion, dipyrithium). itianon, DNOC, dodemorph, dodine, drazoxolon, edifenphos, enestrobin (enestrobin), epoxyconazole, epoxiconasol, epoxiconasol (Etaconazole), ethem, etirimol, ethoxyquin, ethodiizole, etradiazole, famoxadone, fenamidone, fenamifenafenalpenafenafenalpenafenafnil, fenamidofenafnil (Fenarimol), fenbuconazole, fenfuram, fenhexamide, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropifin, fenpropionil (Fenpropimorph), fenpyrazamine, fentin, fenbam, ferbam, ferimzone, fluazinam, fludioxonil, flufenoxtrobin, flufenoxtrobin lumetover, flumorphol, fluopicolide, fluopyram, fluoimide, fluotriauzol, fluoxazol, fluoxazol, flunaxol, fluoxazol Flusulfamide,
Flutolanil, Flutianil, Flutriafol, Fluxapyroxad, Folpet, Folpet, Fosetyl-aluminium, Fthalidez, Fthalidez, Fthalidez, Fthalidez Furalaxyl, furamepyr, furcarbanil, furconazole, fluconazole-cis, furmecyclox, glyphanate, glyphanate, glyphanate, glyphanate, glyphanate, glyphanate, glyphanate, glyphanate, glyphanate, glyphanate, glyphanate, glyphanate, glyphanate, glyphanate, glyphanate and glyphanate. Ofulvin (griseofulvin), guazatine (guazatinine), halacrinate (halacrinate), hexachlorobenzene (hexachlorobenzene), hexaconazole (hexaconazole), hexylthiophos (hexylthioxol, hexylthioxyl, oxyquinoline, oxyquinoline) Imazalil, imibenconazole, iminoctadine-albesilate, iminoctadine-triacetate, iodocarb, iodocarb, iodocarb (Ipconazole), iprobenfos, iprodione, iprovalicarb, iprovaliccarb, isofetamide, isotianil, isopiani, isoprotiopylanis, isoprotiova, isoprotizan, isoprotiosyl, isoprotiosyl, isoprotiosyl, isoprotiosyl, isoprothiopia , Kresoxim-methyl, laminarin, mancopper, mancozeb, mandestrobin, mandipropamide, mandipropamide aneb), mebenil, mecarbinzid, mepanipirim, mepronil, mepronil, metalaxyl, metalaxyl-M (metasol, metazol, metazol) (Metconazole), metasulfocarb (methasulfocarb), methofloxam (methfuroxam), metiram (metiram), metominostrobin (methinostrobin), metrafenone (metrafenone), metsulfobu ne (metuxulfne) nil), myclozolin, nabam, naftifine, natamycin, organic nickel (nickel bis (dimethylethylthiocarbamate)), nitrostyrene (nitropropyl-nitropropyl-nitro-pyrro-nitro-pyrro-nitrosyl-nitro-nitro-pyrroline) (Nuarimol), octinoline, offurase, orysastrobin, oxadixyl, oxathiapiprolin, oxyquinoline copper, oxyquinoline oxapoxol copoxol oconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentochlorophenol, pentochlorophenol 2-phenylphenol, phosdiphen, phthalide, picarbutrazox, picoxystrobin, piperalin, polycarbam te), polyoxins (polyoxins), polyoxin-D (polyoxorim), potassium azide (potassium azide), potassium hydrogencarbonate (potassium hydrogen carbonate), probenazole (probenzale), prochlorazole, prochlorazole, prochlorazole propamocarb hydrochloride, propiconazole, propineb, propinezide, proquinazide, prothiocarb, prozicarb, pyrazifluzophilo piramizopromipirophilo, pyrazifluzrophilid (Pyribencarb-methyl), pyrifenox (pyrifenoxil), pyrimethanil (pyrimethanoil), pyriminostrobin (pyriminostrobin), pyroquilon (pyroquiquilon), prothiocarb (prothiothiol, prothioconazole, prothioconazole, prothioconazole). ), Pyracarbolide, pyraclostrobin, pyridinitrile, pyriophenone, pyrisoxazole, pyroxychloryl, pyroxychlorylpyroxychlor (pyroxychlor) ), Quinacetol-sulfate (quinacetol-sulfate), quinazamide (quinazamid), quinconazole (quinconazole), quinoxyfen (quinoxenfen), quintozene (quintozenesil), rabenzadizalizane, rabenzadazole, rabenzadazole silthiofam), simeconazole, sodium hydrogencarbonate, sodium hypochlorite, spiroxamine, sulcona, sulcona, sulcona, and sulcona ole), tebufloquin, tecloftalam, tecnazene, tecolam, tetraconazole, thiabendazole, thiazifluor, thiazifluor, thiazifluor, thiazifluor, thiazifluor, thiazifluor, thiazifluor. ), Thiochlorfenfhim, thiophanate, thiophanate-methyl, thiuram, thiram, thiazinyl, thioximid, tolclofos-methyl. s-methyl, tolprocarb, tolylfluanid, triadimefon, triadimenol, triadimenol, triamiphos, triarimol, triazol, triazol, triazol, triazol, triazol, triazol, triazol, triazol, triazol, triazol, triazol, triazol, triazol, triazol, triazol) , Tributyltin oxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizoline , Triticonazole, validamycin, valifenalate, vinclozolin, zarilamid, zincnaphthenate, zinc sulfate, zinc naphthenate, zinc sulfate Ziram, zoxamide, shiitake mushroom mycelium extract, shiitake mushroom body extract, quinofumelin, quinofumelin, mefentrifluconazole, ipfentrifluconazole, ipfentrizophilus , Fenpicoxamide, isoflucypram, fluindapyr, flupyxam, inpyrfluxam, aminopyrifen, OAF-211 (test name-303F, test name -N) 180 (test name), etc.

  Nematicides: cadusafos, dichlofenthion, etoprophos, fenamiphos, fluensulfone, phosthiazium, phosthiazite, phosthiazite, phosthiazemite , Isazofos, methyl bromide, methyl isothiocyanate, oxamyl, sodium azidide, thioxazafen lysine, thioxazafen lysine Such as uazaindolizine) and fluopyram (fluopyram).

Nematicides: aldoxycarb, aldusacarb, cadusafos, davy cp (DBCP), diclofenthion (dichlofenthion), dsp (DSP), etoprophos (ethoprophos), fenamiphos, fensulfothion, fluensulfothion Sulfone (fluensulfone), fostiazate (fosthiazate), fosthietane (fosthietan), imiciaphos (imicyafos), isamidophos (isamidofos), isazofos (isazofos), oxamyl (oxamyl) and thionazin (thionazin).
Acaricides: acequinocyl, acrinathrin, asinonapyr, acynonapyr, amidoflumet, amitraz, amitraz, azocyclotin, azocyclotin, BCI-033 (test name), benzoximate, Bifenazate, bromopropylate, chinomethionat, chlorobenzilate, clofenthedine, clofentezine, cyenopyrafen, cyflumetofen, cyhexatine, dicofol , Dienochlor, diflovidazin, denuocy (DNOC), etoxazole, fenazaquin, fenbutatin oxide, fenbutatin oxide fenothiocarb), fenpropathrin, fenpyroximate, fluacrypyrim, halfenprox, halfenprox, hexthiazox, hexythiazox, milbemectin, propargite, piflubide Pyridaben, pyrimidifen, S-1870 (test name), spirodiclofen, spiromesifen (spyromesifen), CL900167 (test name), tebufenpyrad (tebufenpyrad), and the like.

  Insecticides: abamectin (abamectin), acephate (acephate), acetamipirid (acetamipirid), afidopyropen (afidopyropen), afoxolaner (afoxolaner), alanicarb (alanycarb), aldicarb (aldicarb), azazinephos (allethrin), azamephos (allethrin) -Ethyl (azinphos-ethyl), azinphos-methyl, bacillus thuringiensis, bendiocarb (bendiocarb), benfluthrin (benfluthrin), benflacarb (benfuracarb), bensultap (bensultap), benzpyrimoxane ( benzpyrimoxan, bifenthrin, bioallethrin, bioresmethrin, bistrifluron, broflanilide, buprofezin, butoxycarbome butocarboxim), carbaryl, carbofuran, carbosulfan, cartap, cartap, chlorantraniliprole, chlorethxyfos, chlorfenapyr, chlorfenapyr (Chlorfenvinphos), chlorfluazuron (chlorfluazuron), chlormephos (chlormephos), chloroprallethrin (chloroprallethrin), chlorpyrifos (chlorpyrifos), chlorpyrifos-methyl (chlorpyrifos-methyl), chromafenozide (chromafenozide), clothianidin (clothianidin), cyanide cyanophos, cyanantraniliprole, cyclaniliprole, cycloprothrin, cyflumetofen, cyflumetrin, beta-cyfluthrin ta-cyfluthrin), cyhalodiamide (cyhalodiamide), cyhalothrin (cyhalothrin), lambda-cyhalothrin (lambda-cyhalothrin), cypermethrin (cypermethrin), alpha-cypermethrin (alpha-cypermethrin), beta-cypermethrin (beta-cypermethrin), Zeta-cypermethrin, cyphenothrin, cyromazine, deltamethrin, diamethden, diacloden, diafenthiuron, diazinon, dichlororomezotiaz ), Dichlorvos, diflubenzuron, dimefluthrin, dimefluthrin, dimethylvinphos, dinotefuran, dinotefuran, diofenolan, disulfoton, dimethoate, emethoate Mectin benzoate (emamectin-benzoate), empenthrin (empenthrin), endosulfan (endosulfan), alpha-endosulfan (alpha-endosulfan), EPN (EPN), esfenvalerate (esfenvalerate), ethiofencarb (ethiofencarb), ethiprole, Etofenprox, etofenfos, etrimfos, fenitrothion, fenobucarb, phenoxycarb, fenoxycarb, fenpropathrin, fenthion, fenvalerate, fipronil , Flonicamid (flonicamid), fluazuron (fluazuron), flubendiamide (flubendiamide), flucycloxuron (flucycloxuron), flucitrinate (flucythrinate), flufenerim (flufenerim), Flufenoxuron, flufenprox, flumethrin, flumethrin, fluralaner, fluvalinate, fluvalinate, tau-fluvalinate, tau-fluvalinate, fluxametamide, fonophos, folphomethate formetanate, formothion, furathiocarb, flufiprole, fluhexafon, flupyradifurone, flupyradifurin, flupyrimin, flometoquin, and the like.

  Insecticides (continued): gamma-cyhalothrin, halofenozide, heptafluthrin, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, imiprothrin , Isofenphos, indoxacarb, indoxacarb-MP, indoxacarb-MP, isoprocarb, isoxathion, kappa-bifenthrin, kappa-tefluthrin ), Lepimectin, lufenuron, malathion, malapion, meperfluthrin, metaflumizone, metaflumizone, metalaldehyde, metaldehyde, methamidophos, methidathion, meta Methacrifos, metalcarb, metalcarb, methomyl, methoprene, methoxychlor, methoxyfenozide, methoxyfenozide, methyl bromide, epsilon-methoffluthrin, metofluthrin , Momfluorothrin, epsilon-momfluorothrin, epsilon-momfluorothrin, monocrotophos, muscalure, nitenpyram, nitenpyram, novaluron, noviflumuron, ometoate (ome) Oxamyl, oxydemeton-methyl, oxydeprofos, parathion, parathion-methyl, pentachlorophe nol (PCP)), permethrin, phenothrin, phentoate, phoxim, pholate, phosalone, phosmet, phosmet, phosphamidon, pirimicarb , Pirimiphos-methyl, profenofos, profluthrin, prothiofos, propaphos, protrifenbute, pymetrozine, pyraclofos, pyreclofos pyrethrins), pyridalyl, pyrifluquinazone (pyrifluquinazon), pyriprole (pyriprole), pyrafluprole (pyrafluprole), pyriproxyfen (pyriproxyfen), resmethrin (resmethrin), rotenone, SI-0405 (test name), Sulprofos, silafluofen, spinetoram, spinosad, spiromesifen, spiromesifen, spiropidion, spirotetramat, sulfoxaflor, sulfoteflor SYJ-159 (test name), tebufenozide (tebfenozide), teflubenzuron (teflubenzuron), tefluthrin (tefluthorin), terbufos (terbufos), tetrachlorovinphos (tetrachlorvinphos), tetramethrin (tetramethrin), d-T-80-phthalthrin ( d-tetramethrin), tetramethylfluthrin, tetraniliprole, thiacloprid, thiocyclam, thiodicarb, thiomethoxam, thiofano Thiofanox, thiometon, tolfenpyrad, tralomethrin, transfluthrin, transfluthrin, triazamate, trichlorfon, triazuron, triflumezopyrim, triflumezopyrim (Triflumuron), tyclopyrazoflor, and vamidothion.

  In the composition of the present invention, a surfactant can be added as necessary. Examples of such surfactants include the following (A), (B), (C), (D) and (E).

(A) Nonionic surfactant:
(A-1) Polyethylene glycol type surfactant: for example, polyoxyethylene alkyl (for example, _C8-18 ) ether, an ethylene oxide adduct of alkyl naphthol, polyoxyethylene (mono or di) alkyl (for example, _C8-12 ) ) Phenyl ether, formalin condensate of polyoxyethylene (mono or di) alkyl (e.g. _C8-12 ) phenyl ether, polyoxyethylene (mono, di or tri) phenyl phenyl ether, polyoxyethylene (mono, di or tri) ) Benzyl phenyl ether, polyoxypropylene (mono, di or tri) benzyl phenyl ether, polyoxyethylene (mono, di or tri) styryl phenyl ether, polyoxypropylene (mono, di or tri) styryl phenyl ether, polyoxy Ethylene (mono-, di- or tri-) styryl phenyl ether polymer, polyoxyethylene polyoxypropylene (mono-, di- or tri-) styryl phenyl ether, polyoxyethylene polyoxypropylene block polymers, alkyl (e.g., C _{8 to 18)} polyoxy Ethylene polyoxypropylene block polymer ether, alkyl (e.g., _C8-12 ) phenyl polyoxyethylene polyoxypropylene block polymer ether, polyoxyethylene bisphenyl ether, polyoxyethylene resin acid ester, polyoxyethylene fatty acid (e.g., _{C8-12) 18)} monoesters, polyoxyethylene fatty acid (e.g. _{C 8 to 18)} diesters, polyoxyethylene sorbitan (mono-, di- or tri) fatty acid (e.g. _{C 8 to 18)} Ester, glycerol fatty acid ester ethylene oxide adduct, castor oil ethylene oxide adduct, hydrogenated castor oil ethylene oxide adduct, alkyl (e.g., C _{8 to 18)} amine ethylene oxide adduct and a fatty acid (e.g. C _{8 to 18)} amide ethylene oxide Additives etc.

(A-2) Polyhydric alcohol type surfactant: For example, glycerol fatty acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid (for example, C _8-18 ) ester, sorbitan (mono, di or tri) fatty acid ( For example, _C8-18 ) esters, sucrose fatty acid esters, polyhydric alcohol alkyl ethers, alkyl glycosides, alkyl polyglycosides, and fatty acid alkanolamides.

  (A-3) Acetylene-based surfactant: For example, acetylene glycol, acetylene alcohol, an ethylene oxide adduct of acetylene glycol, an ethylene oxide adduct of acetylene alcohol, and the like.

(B) anionic surfactant:
(B-1) Carboxylic acid type surfactant: For example, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, maleic acid or maleic anhydride and an olefin (for example, isobutylene and diisobutylene etc.) Polymer, copolymer of acrylic acid and itaconic acid, copolymer of methacrylic acid and itaconic acid, copolymer of maleic acid or maleic anhydride and styrene, copolymer of acrylic acid and methacrylic acid, acrylic acid Copolymer of acrylic acid and methyl ester, copolymer of acrylic acid and vinyl acetate, copolymer of acrylic acid and maleic acid or maleic anhydride, polyoxyethylene alkyl (e.g., _C8-18 ) ether acetic acid, methyl N-- fatty acids (e.g., _{C 8 to 18)} sarcosinates, resin acids and fatty acids (e.g., _{C 8 to 18),} such as Carboxylic acid, and salts thereof carboxylic acid.

(B-2) sulfate surfactants: for example, alkyl (e.g. C8～18) sulfates, polyoxyethylene alkyl (for example _{C 8 to 18)} ether sulfuric acid ester, polyoxyethylene (mono or di) alkyl (e.g. C _8-12 phenyl ether sulfate, polyoxyethylene (mono or di) alkyl (eg, C _8-12 ) phenyl ether polymer sulfate, polyoxyethylene (mono, di or tri) phenyl phenyl ether sulfate, Polyoxyethylene (mono, di or tri) benzyl phenyl ether sulfate, polyoxyethylene (mono, di or tri) styryl phenyl ether sulfate, polymer sulfate of polyoxyethylene (mono, di or tri) styryl phenyl ether , Sulfate esters of polyoxyethylene polyoxypropylene block polymers, sulfated oils, fatty acid ester sulfuric, sulfate ester such as sulfated fatty acids and sulfated olefins, and salts thereof sulfate.

(B-3) Sulfonic acid type surfactant: For example, formalin of paraffin (for example, _C8-22 ) sulfonic acid, alkyl (for example, _C8-12 ) benzenesulfonic acid, and alkyl (for example, _C8-12 ) benzenesulfonic acid. Condensates, formalin condensates of cresol sulfonic acid, α-olefins (eg, C _8-16 ) sulfonic acids, dialkyl (eg, C _8-12 ) sulfosuccinic acids, ligninsulfonic acids, polyoxyethylene (mono or di) alkyls (eg, _C8-12 ) phenyl ether sulfonic acid, polyoxyethylene alkyl (e.g., _C8-18 ) ether sulfosuccinic acid half ester, naphthalenesulfonic acid, (mono or di) alkyl (e.g., _C1-6 ) naphthalenesulfonic acid, naphthalenesulfonic acid Formalin condensate of acid, (mono or ) Alkyl (e.g. _{C 1 to 6)} formalin condensates of naphthalenesulfonic acid formalin condensate of creosote oil sulfonic acid, alkyl (e.g., _{C 8 to 12)} ether disulfonic acid, Igepon T (trade name), and polystyrene sulfonic acid Sulfonic acids, such as copolymers of styrenesulfonic acid and methacrylic acid, and salts of those sulfonic acids.

(B-4) Phosphate-type surfactant: For example, alkyl (e.g., _C8-12 ) phosphate, polyoxyethylene alkyl (e.g., _C8-18 ) ether phosphate, polyoxyethylene (mono or di) alkyl ( For example, _C8-12 ) phenyl ether phosphate, polyoxyethylene (mono, di or tri) alkyl (e.g., _C8-12 ) phenyl ether polymer phosphate, polyoxyethylene (mono, di or tri) phenyl phenyl ether Phosphoric acid ester, polyoxyethylene (mono, di or tri) benzyl phenyl ether phosphate, polyoxyethylene (mono, di or tri) styryl phenyl ether phosphate, polyoxyethylene (mono, di or tri) styryl phenyl ether polymer Phosphate esthetic And phosphoric esters of polyoxyethylene polyoxypropylene block polymers, phosphatidylcholine, phosphatidylethanolimine, phosphoric esters such as condensed phosphoric acid (eg, tripolyphosphoric acid, etc.), and salts of these phosphoric esters.

  As the counter ion of the salt in the above (B-1) to (B-4), alkali metals (such as lithium, sodium and potassium), alkaline earth metals (such as calcium and magnesium), ammonium and various amines (for example, alkyl Amines, cycloalkylamines and alkanolamines).

(C) Cationic surfactant:
For example, alkyl amines, alkyl quaternary ammonium salts, ethylene oxide adducts of alkyl amines, and ethylene oxide adducts of alkyl quaternary ammonium salts.

(D) amphoteric surfactant:
(D-1) Betaine type surfactant: for example, alkyl (for example, _C8-18 ) dimethylaminoacetate betaine, acyl (for example, _C8-18 ) aminopropyldimethylaminoacetate betaine, alkyl (for example, _C8-18 ) hydroxy Examples include sulfobetaine and 2-alkyl (e.g., _C8-18 ) -N-carboxymethyl-N-hydroxyethylimidazolinium betaine. (D-2) Amino acid type surfactant: for example, alkyl (e.g., _C8-18) ) Aminopropionic acid, alkyl (e.g., _C8-18 ) _{aminodipropionic} acid, and N-acyl (e.g., _C8-18 ) -N'-carboxyethyl-N'-hydroxyethylethylenediamine.

(D-3) Amine oxide type surfactant: For example, alkyl (for example, C _8-18 ) dimethylamine oxide and acyl (for example, C _8-18 ) aminopropyldimethylamine oxide, etc.

(E) Other surfactants:
(E-1) Silicon surfactant: For example, polyoxyethylene / methylpolysiloxane copolymer, polyoxypropylene / methylpolysiloxane copolymer and poly (oxyethylene / oxypropylene) / methylpolysiloxane copolymer And the like.

  (E-2) Fluorinated surfactant: For example, perfluoroalkenylbenzenesulfonate, perfluoroalkylsulfonate, perfluoroalkylcarboxylate, perfluoroalkenylpolyoxyethylene ether, perfluoroalkylpolyoxyethyleneether And perfluoroalkyltrimethylammonium salts.

  These surfactants can be used alone or as a mixture of two or more kinds, and the ratio when they are mixed can be freely selected. The content of the surfactant in the composition of the present invention can be appropriately selected, but is preferably in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the composition of the present invention.

  The composition of the present invention may further contain various auxiliary agents. Examples of the auxiliary agent that can be used include a thickener, an organic solvent, an antifreezing agent, an antifoaming agent, a fungicide / antifungal agent, a coloring agent, and the like.

  The thickener is not particularly limited, and organic and inorganic natural products, synthetic products and semi-synthetic products can be used. For example, heteropolysaccharides such as xanthan gum (xanthan gum), welan gum and ramzan gum, polyvinyl alcohol, polyvinyl alcohol Water-soluble polymer compounds such as pyrrolidone, polyacrylic acid, sodium polyacrylate and polyacrylamide, cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, montmorillonite, saponite, hectorite, bentonite, laponite And smectite-based clay minerals such as synthetic smectite. These thickeners may be used alone or in combination of two or more, and the mixing ratio can be freely selected. These thickeners may be added as they are, or may be added in advance dispersed in water. In addition, the content in the composition of the present invention can be freely selected.

  Examples of the organic solvent include alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and isopropanol, ethers such as butyl cellosolve, ketones such as cyclohexanone, esters such as γ-butyrolactone, N-methylpyrrolidone and N-octylpyrrolidone. Aromatic hydrocarbons such as acid amides such as xylene, alkylbenzene, phenylxylylethane and alkylnaphthalene, machine oils, aliphatic hydrocarbons such as normal paraffin, isoparaffin and naphthene, and aromatic hydrocarbons such as kerosene and aliphatic hydrocarbons Mixtures of hydrogen, oils and fats such as soybean oil, linseed oil, rapeseed oil, coconut oil, cottonseed oil and castor oil.

  As the antifreezing agent, for example, ethylene glycol, diethylene glycol, propylene glycol, glycerin and the like can be used. Preferred are propylene glycol and glycerin. In addition, the content in the composition of the present invention can be freely selected.

  Further, an antifoaming agent such as a silicone emulsion, a fungicide / antifungal agent, and a coloring agent may be added.

  The method for producing the composition of the present invention is not particularly limited, but is obtained by adding each of the above-mentioned components to a dispersion medium and mixing with a stirrer. Further, if necessary, the pesticidal active ingredient, the surfactant and the other auxiliary may be used alone or as a mixture and finely pulverized by a dry or wet pulverizer.

  Dry pulverization can be performed by a hammer mill, pin mill, jet mill, ball mill, roll mill, or the like. Fine pulverization by wet pulverization can be performed by a wet pulverizer such as an in-line mill or a bead mill.

  The composition of the present invention is, for example, diluted about 50 to 5000 times with a stock solution or water, and sprayed onto a crop or a tree or a soil where it grows using a sprayer or the like, using a helicopter or the like from the air, It can be applied by a method of spraying after diluting it about 2 to 100 times with a stock solution or water.

  Hereinafter, the present invention will be described in more detail by specifically describing production examples of crystals of the compound of the present invention as examples, but the present invention is not limited thereto.

  In addition, various measurement conditions are as follows.

[X-ray powder diffraction measurement conditions]
Model name: X'PERT-PRO MPD (Spectris Inc.)
Measurement method: transmission method X-ray: Cu-Kα
Voltage: 45 kV
Current: 40 mA
Sampling interval: 0.01671 deg
Data range: 2θ = 4 to 40 deg
[Differential thermal analysis measurement conditions]
Apparatus: DSC-60 (manufactured by Shimadzu Corporation)
Temperature rise: 20 ° C-(10 ° C / min)-500 ° C
Atmosphere: Nitrogen control: Al2O3
Container: SUS sampling: 1 sec
[Production Example 1]: Production of crystals of 1- [2- (N-isobutyloxycarbonyl-N-trifluoromethanesulfonyl) aminobenzyl] -3,3-dimethyl-azetidin-2-one [compound (1)] 1-1: Synthesis of 2- (trifluoromethanesulfonylamino) benzonitrile Part 1
After adding 45 g of toluene to 8.99 g of 2- (trifluoromethanesulfonylamino) benzamide, 6.76 g of phosphoryl chloride was added dropwise while stirring at 90 ° C. After the addition was completed, the reaction solution was stirred at 90 ° C. for 5 hours. After completion of the reaction, the reaction mixture was cooled to 50 ° C., 45 g of water was added, and the organic layer was separated. The obtained organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. The solvent of the obtained solution was distilled off under reduced pressure to obtain 7.25 g of the desired product as a white solid.
Melting point: 78-81 ° C
Step 1-2: Synthesis of 2- (trifluoromethanesulfonylamino) benzonitrile Part 2
After adding 1.3 g of toluene to 0.27 g of 2- (trifluoromethanesulfonylamino) benzamide, 0.18 g of thionyl chloride was added dropwise under reflux with heating. After completion of the dropwise addition, the reaction solution was stirred for 4 hours while heating under reflux. After completion of the reaction, the reaction mixture was added dropwise to 2.0 g of water, and the organic layer was separated. The obtained organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. The solvent of the obtained solution was distilled off under reduced pressure to obtain 0.18 g of the desired product as a white solid.

Step 1-3: Synthesis of 2- (trifluoromethanesulfonylamino) benzonitrile Part 3
After adding 2.0 g of dichloromethane and 0.01 g of N, N-dimethyl-4-aminopyridine to 0.13 g of 2-aminobenzamide, 0.3 g of trifluoromethanesulfonic anhydride was added dropwise with stirring at room temperature. After completion of the dropwise addition, the reaction solution was stirred at the same temperature for 17 hours. After completion of the reaction, 5 g of water and 5 g of ethyl acetate were added to the reaction mixture, and the organic layer was separated. The obtained organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. The solvent of the obtained solution was distilled off under reduced pressure to obtain 0.13 g of the desired product as a white solid.

Step 2: Synthesis of 2- (trifluoromethanesulfonylamino) benzylamine sulfate In a solution of 1.0 g of 2- (trifluoromethanesulfonylamino) benzonitrile in 10 g of methanol, 0.41 g of concentrated sulfuric acid and 5% by mass palladium carbon (N. 0.10 g) (STD type, about 50% water content, manufactured by E-Chemcat Co.). After the addition was completed, the reaction mixture was stirred at room temperature under a hydrogen atmosphere for 7 hours. After completion of the reaction, the reaction mixture was filtered through celite to remove palladium carbon. The solvent of the obtained solution was distilled off under reduced pressure to obtain 1.40 g of the desired product as a white solid.

Step 3: Synthesis of 1- [2- (N-trifluoromethanesulfonyl) aminobenzyl] -3,3-dimethylazetidin-2-one [compound (2)] 2- (trifluoromethanesulfonylamino) benzylamine sulfate To 1.40 g, 7.0 g of toluene and 8.0 g of water were added, and while stirring at room temperature, 2.24 g of a 30% by mass aqueous sodium hydroxide solution was added. After the addition was completed, 0.68 g of 3-chloropivaloyl chloride was added to the reaction mixture at 40 ° C, and the mixture was stirred at the same temperature for 3 hours. After completion of the stirring, 1.07 g of a 30% by mass aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was stirred at 70 ° C. for 3 hours. After the completion of the reaction, the reaction mixture was cooled to 60 ° C., and 1.25 g of 35% by mass hydrochloric acid was added, and the aqueous layer was separated. The obtained organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. The obtained solution was cooled to 0 ° C. to form a slurry, and the mixture was further stirred at the same temperature for 2 hours. The obtained slurry was filtered and dried under reduced pressure to obtain 1.35 g of crude crystals of the target product.

Step 4: Synthesis of 1- [2- (N-isobutyloxycarbonyl-N-trifluoromethanesulfonyl) aminobenzyl] -3,3-dimethyl-azetidin-2-one [compound (1)] 1- [2- ( 6.75 g of toluene and 0.33 g of potassium carbonate were added to 1.35 g of crude crystals of [N-trifluoromethanesulfonyl) aminobenzyl] -3,3-dimethylazetidin-2-one. After the addition was completed, 0.66 g of isobutyl chloroformate was added while stirring the reaction mixture at 90 ° C., and the mixture was stirred at the same temperature for 2 hours. After completion of the reaction, the reaction mixture was cooled to 60 ° C., the reaction was stopped by adding water, and then the organic layer was separated. The obtained organic layer was washed with water, dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 1.73 g of crude crystals of the target product.

Step 5: Preparation of crystals of 1- [2- (N-isobutyloxycarbonyl-N-trifluoromethanesulfonyl) aminobenzyl] -3,3-dimethyl-azetidin-2-one 1- [2- (N-isobutyloxy To 1.73 g of crude crystals of carbonyl-N-trifluoromethanesulfonyl) aminobenzyl] -3,3-dimethyl-azetidin-2-one, 5.19 g of n-heptane and 0.173 g of dichloromethane were added. To dissolve the crystals. The mixed solution was cooled to 20 ° C., and while stirring, 5 mg of a seed crystal of the target substance (using the crude crystal of the target substance obtained in Step 4) was added, and stirring was continued at the same temperature. After visually confirming the precipitation of, it was cooled to 0 ° C at a rate of 10 ° C per hour. After the obtained slurry was stirred at 0 ° C. for 3 hours, it was filtered and dried under reduced pressure to obtain 1.38 g of the target crystal.

  As a result of measuring the powder X-ray diffraction of the obtained crystal, the diffraction pattern of FIG. 1 was shown.

  In addition, as a result of a DSC measurement of the obtained crystal, a peak pattern shown in FIG. 2 was shown.

[Production Example 2]: Production of Crystal of 1- [2- (N-trifluoromethanesulfonyl) aminobenzyl] -3,3-dimethylazetidin-2-one [Compound (2)] In Step 3 of Synthesis Example 1, 5.40 g of toluene was added to 1.35 g of the obtained crude crystals of 1- [2- (N-trifluoromethanesulfonyl) aminobenzyl] -3,3-dimethylazetidin-2-one, and the mixture was stirred at 60 ° C. To dissolve. The mixed solution was cooled to 0 ° C. at a rate of 12 ° C. in one hour. After the slurry obtained after cooling was stirred at 0 ° C. for 2 hours, it was filtered and dried under reduced pressure to obtain 1.22 g of the desired crystal.

  As a result of measuring the powder X-ray diffraction of the obtained crystal, the diffraction pattern shown in FIG. 3 was shown.

In addition, DSC measurement of the obtained crystal showed a peak pattern in FIG.
[Reference example]
Reference Example 1: Synthesis of 2- (trifluoromethanesulfonylamino) benzamide Part 1
To a solution of 10 g of 2-aminobenzamide in 100 g of toluene was added dropwise 10.4 g of trifluoromethanesulfonic anhydride over 1 hour under ice cooling. After completion of the dropwise addition, the reaction mixture was stirred for 1 hour, and then 40 g of water and 40 g of ethyl acetate were added. After the addition was completed, the temperature of the reaction mixture was raised to 50 ° C., and then the organic layer was separated. The obtained organic layer was washed with diluted hydrochloric acid and water in that order, and dried over anhydrous sodium sulfate. From the resulting solution, 40 g of ethyl acetate and 50 g of toluene were distilled off under reduced pressure, and the mixture was cooled to 0 ° C. The slurry obtained after cooling was stirred at 0 ° C. for 30 minutes, and then filtered and dried under reduced pressure to obtain 8.83 g of the desired product as a white solid.

Melting point: 155-156 ° C
Reference Example 2: Synthesis of 2- (trifluoromethanesulfinylamino) benzamide To 1.64 g of sodium trifluoromethanesulfinate, 12 g of toluene, 6 g of dichloromethane and 0.12 g of N, N-dimethylformamide were added. After the addition was completed, the reaction mixture was cooled to 0 ° C., and 1.43 g of thionyl chloride was added dropwise. After completion of the dropwise addition, the reaction mixture was stirred at 0 ° C. for 2 hours, and then a mixed solution of 1.36 g of 2-aminobenzamide in 3 g of toluene and 1.5 g of dichloromethane was added dropwise, followed by stirring for 15 minutes. Subsequently, a solution of 1.82 g of N, N-dimethylaniline in 15 g of dichloromethane was added dropwise over 2 hours. After stirring this reaction solution at 0 ° C. for 1 hour, it was added dropwise to 20 g of a 10% by mass aqueous sodium hydroxide solution. 5.21 g of concentrated hydrochloric acid was added to the separated aqueous layer at 0 ° C., and the obtained slurry was filtered and dried under reduced pressure to obtain 1.84 g of the desired product as a white solid.

Melting point: 148-149 ° C
Reference Example 3: Synthesis of 2- (trifluoromethanesulfonylamino) benzamide Part 2
To a solution of 1.84 g of 2- (trifluoromethanesulfinylamino) benzamide in 15 g of toluene, 2.48 g of 30% by mass aqueous hydrogen peroxide, 0.24 g of sodium tungstate dihydrate and 0.25 g of tetrabutylammonium hydrogen sulfate are added. did. After the addition was completed, the reaction mixture was stirred at 50 ° C. for 7 hours. After the completion of the reaction, the reaction mixture was cooled to 25 ° C., 50 g of a 5% by mass aqueous sodium bisulfite solution and 50 g of ethyl acetate were added, and the mixture was stirred for 15 minutes, and then the organic layer was separated. The obtained organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. The solvent of the obtained solution was distilled off under reduced pressure to obtain 1.89 g of the desired product as a pale yellow solid.

Reference Example 4: Synthesis of 2- (trifluoromethanesulfonylamino) benzonitrile Part 4
To a solution of 11.8 g of 2-aminobenzonitrile in 118 g of toluene, 14.1 g of trifluoromethanesulfonic anhydride was added dropwise over 1 hour under ice cooling. After the addition was completed, the reaction mixture was stirred at the same temperature for 1 hour. After completion of the stirring, 35 g of water was added to the reaction mixture, and the organic layer was separated. The obtained organic layer was extracted twice with 20 g of a 10% by mass aqueous sodium hydroxide solution, and 13 g of 35% by mass hydrochloric acid and 59 g of toluene were added to the aqueous solution obtained, and the organic layer was separated. The obtained organic layer was washed with water and saturated saline in this order, and dried over anhydrous magnesium sulfate. The solvent of the obtained solution was distilled off under reduced pressure to obtain 9.92 g of the desired product as a white solid.

According to the present invention, it is possible to produce crystals of compound (1) and compound (2).

Claims (6)

Equation (1):

[Wherein R represents isobutyloxycarbonyl], among the possible crystals of the ortho-substituted haloalkylsulfonanilide compound represented by the formula: 2θ = 6.36, 7.92; Crystals having peaks at 12.70, 15.48, 16.53, 17.42, 18.82 and 20.48. Equation (1):

Among the possible crystals of the ortho-substituted haloalkylsulfonanilide compound represented by the formula: wherein R represents a hydrogen atom, 2θ = 6.75, 7.89, 10 in powder X-ray diffraction by Cu-Kα ray 0.07, 10.71, 11.49, 12.16, 13.30, 13.54, 17.63, 18.09, 18.59, 19.69, 20.44 and 23.34. crystal.   A suspension composition comprising the crystal according to claim 1 and a dispersion medium.   The suspension composition according to claim 3, further comprising a surfactant, wherein the dispersion medium is water.   A suspension composition comprising the crystal according to claim 2 and a dispersion medium.   The suspension composition according to claim 5, further comprising a surfactant, wherein the dispersion medium is water.