JP2022158274A - Solvate - Google Patents

Abstract

To provide a crystal of a solvate of pyridaben, particularly a toluene solvate, and a method for producing the same.SOLUTION: The present invention discloses a crystal of a toluene solvate of pyridaben. In powder X-ray diffraction with Cu-Kα rays, the crystal has peaks at diffraction angles: 2θ=(7.7°±0.2, 8.8°±0.2, 10.5°±0.2, 10.9°±0.2, 11.4°±0.2, 11.9°±0.2, 12.9°±0.2, 13.6°±0.2, 14.2°±0.2, 14.7°±0.2, 15.6°±0.2, 16.1°±0.2, 17.3°±0.2, 17.7°±0.2, 18.4°±0.2, 19.0°±0.2, 19.9°±0.2, 20.4°±0.2, 21.0°±0.2, 22.7°±0.2, 23.2°±0.2, 23.6°±0.2, 24.1°±0.2, 24.9°±0.2, 25.8°±0.2, 27.2°±0.2, 28.8°±0.2, 29.2°±0.2, 31.6°±0.2, 32.2°±0.2, 41.0°±0.2). There is also provided a method for producing the same.SELECTED DRAWING: Figure 1

Description

The present invention relates to a solvate of pyridaben and a process for preparing the solvate.

Pyridaben included in the present invention is already known to be useful as a pest control agent (see, for example, Patent Documents 1 and 2). The pest control agent in the present invention is used in the agricultural and horticultural fields or in the livestock and hygiene fields (internal or external parasite control agents for mammals or birds as livestock and pets, sanitary pests for household and business use, unpleasant pests pest control agent for harmful arthropods).

JP-A-60-004173 JP-A-61-097270

An object of the present invention is to provide a novel solvate of pyridaben and a process for its preparation.

As a result of intensive studies, the present inventors have found crystals of a novel solvate of pyridaben, particularly toluene solvate, and a method for producing the same.

That is, the present invention relates to the following [1] to [4].

[1]
In powder X-ray diffraction using Cu—Kα rays, the diffraction angle 2θ=(7.7°±0.2, 8.8°±0.2, 10.5°±0.2, 10.9°±0. 2, 11.4°±0.2, 11.9°±0.2, 12.9°±0.2, 13.6°±0.2, 14.2°±0.2, 14.7 °±0.2, 15.6°±0.2, 16.1°±0.2, 17.3°±0.2, 17.7°±0.2, 18.4°±0.2 , 19.0°±0.2, 19.9°±0.2, 20.4°±0.2, 21.0°±0.2, 22.7°±0.2, 23.2° ±0.2, 23.6°±0.2, 24.1°±0.2, 24.9°±0.2, 25.8°±0.2, 27.2°±0.2, 28.8° ± 0.2, 29.2° ± 0.2, 31.6° ± 0.2, 32.2° ± 0.2, 41.0° ± 0.2), Crystals of toluene solute of pyridaben.

[2]
In powder X-ray diffraction using Cu—Kα rays, the diffraction angle 2θ=(7.7°±0.1, 8.8°±0.1, 10.5°±0.1, 10.9°±0. 1, 11.4°±0.1, 11.9°±0.1, 12.9°±0.1, 13.6°±0.1, 14.2°±0.1, 14.7 °±0.1, 15.6°±0.1, 16.1°±0.1, 17.3°±0.1, 17.7°±0.1, 18.4°±0.1 , 19.0°±0.1, 19.9°±0.1, 20.4°±0.1, 21.0°±0.1, 22.7°±0.1, 23.2° ±0.1, 23.6°±0.1, 24.1°±0.1, 24.9°±0.1, 25.8°±0.1, 27.2°±0.1, 28.8° ± 0.1, 29.2° ± 0.1, 31.6° ± 0.1, 32.2° ± 0.1, 41.0° ± 0.1), Crystals of toluene solute of pyridaben.

[3]
A suspension composition containing the crystals of the toluene solute of pyridaben according to [1] or [2] above and a dispersion medium.

[4]
The suspension composition according to [3] above, which contains water as a surfactant and a dispersion medium.

According to the present invention, it is possible to control the crystals of pyridaben solvates, particularly toluene solvates.

Powder X-ray diffraction chart of crystals of pyridaben Differential scanning calorimetry chart of crystals of pyridaben Powder X-ray diffraction chart of pyridaben toluene hydrate crystals Differential scanning calorimetry chart of pyridaben toluene hydrate crystals

Pyridaben (CAS Reg. No.: 96489-71-3) included in the present invention is 2-tert-butyl-5-[(4-tert-butylbenzyl)thio]-4-chloropyridazine-3 ( 2H)-one (2-tert-butyl-5-[(4-tert-butylbenzyl)thio]-4-chloropyridazin-3(2H)-one) represented by the following structural formula.

Among solvates of pyridaben, the powder X-ray diffraction peaks are shown in Table 1 as characteristics of crystals of toluene solvate of pyridaben.

[Table 1]
―――――――――――――――――――――――――――――――――――――――
Characteristic powder X-ray diffraction peaks――――――――――――――――――――――――――――――――――――――――
2-theta: 7.7°, 8.8°, 10.5°, 10.9°, 11.4°, 11.9°, 12.9°, 13.6°, 14.2°, 14.7 °, 15.6°, 16.1°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.4°, 21.0°, 22.7 °, 23.2°, 23.6°, 24.1°, 24.9°, 25.8°, 27.2°, 28.8°, 29.2°, 31.6°, 32.2° °, 41.0 °
―――――――――――――――――――――――――――――――――――――――
In addition, the error of the powder X-ray diffraction peak is usually ±0.2, and in some cases ±0.1. Therefore, the peak value of the toluene sodate of pyridaben in consideration of the error is usually 2θ = 7.7. °±0.2, 8.8°±0.2, 10.5°±0.2, 10.9°±0.2, 11.4°±0.2, 11.9°±0.2 , 12.9°±0.2, 13.6°±0.2, 14.2°±0.2, 14.7°±0.2, 15.6°±0.2, 16.1° ±0.2, 17.3°±0.2, 17.7°±0.2, 18.4°±0.2, 19.0°±0.2, 19.9°±0.2, 20.4°±0.2, 21.0°±0.2, 22.7°±0.2, 23.2°±0.2, 23.6°±0.2, 24.1°± 0.2, 24.9°±0.2, 25.8°±0.2, 27.2°±0.2, 28.8°±0.2, 29.2°±0.2, 31 .6° ± 0.2, 32.2° ± 0.2, 41.0° ± 0.2 and optionally 2θ = 7.7° ± 0.1, 8.8° ± 0.1, 10.5°±0.1, 10.9°±0.1, 11.4°±0.1, 11.9°±0.1, 12.9°±0.1, 13.6°± 0.1, 14.2°±0.1, 14.7°±0.1, 15.6°±0.1, 16.1°±0.1, 17.3°±0.1, 17 .7°±0.1, 18.4°±0.1, 19.0°±0.1, 19.9°±0.1, 20.4°±0.1, 21.0°±0 .1, 22.7°±0.1, 23.2°±0.1, 23.6°±0.1, 24.1°±0.1, 24.9°±0.1, 25. 8°±0.1, 27.2°±0.1, 28.8°±0.1, 29.2°±0.1, 31.6°±0.1, 32.2°±0. 1, 41.0° ± 0.1.

The measurement conditions for the powder X-ray diffraction peaks shown in Table 1 are as follows.
[Powder X-ray diffraction]
Model name: MiniFlex 600 (manufactured by Rigaku)
Measurement method: reflection method X-ray: Cu-Kα
Voltage: 40kV
Current: 15mA
Scan speed: 10.0°/min Scan interval: 0.01°
Scan range: 2θ = 3 to 50°
Crystals of toluene solvates among solvates of pyridaben can be produced by the following method. Pyridaben is dissolved in a mixed solvent containing toluene by heating, and the resulting solution is gradually cooled to crystallize to obtain crystals of toluene solute of pyridaben.

The solvent to be used together with toluene may be any solvent as long as it is inert to pyridaben. Aromatic hydrocarbon solvents such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, nitrobenzene, and tetrahydronaphthalene can be used, and these solvents can be used alone or in combination of two or more. can. Among these solvents, heptane, xylene and toluene are preferred.

The ratio of the mixed solvent to be used is usually 0.1 to 3 parts by mass, preferably 0.1 to 1 part by mass, of the solvent per 1 part by mass of toluene.

The amount of the mixed solvent used is usually 0.5 to 50 parts by mass, preferably 1 to 30 parts by mass, per 1 part by mass of pyridaben. Of these, the amount of toluene used is usually 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass, per 1 part by mass of pyridaben.

The temperature for dissolving pyridaben in the mixed solvent is usually 30 to 100°C, preferably 30 to 80°C.

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

The temperature of the solution when the precipitated toluene salt crystals are taken out is usually -30 to 50°C, preferably -20 to 30°C.

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

Crystals of toluene sodate of pyridaben can be produced by the following method. Crystals of toluene solute of pyridaben are obtained by suspending crystals of pyridaben in toluene and then stirring the suspension.

The amount of toluene used is usually 0.5 to 50 parts by mass, preferably 1 to 30 parts by mass, per 1 part by mass of pyridaben.

The temperature at which the suspension is stirred is usually -30 to 50°C, preferably -20 to 30°C.

The time for stirring the suspension is usually 0.1 to 100 hours, preferably 1 to 50 hours.

The temperature of the solution when the precipitated toluene salt crystals are taken out is usually -30 to 50°C, preferably -20 to 30°C.

In addition to pyridaben solvates, one or more other known pesticides such as herbicides, insecticides, acaricides, nematicides, antiviral agents, plant growth regulators, fungicides, synergists, Agents, attractants, repellents, etc., may also be contained, in which case a more excellent control effect may be exhibited. Among known pesticides, particularly preferred are fungicides, bactericides, nematicides, acaricides and insecticides. Specific examples of common names thereof are as follows, but are not necessarily limited to these.

Fungicides: acibenzolar-S-methyl, acypetacs, aldimorph, allyl alcohol, ametoctradin, aminopyrifen, amisulbrom, amobam, ampropylfos, anilazine, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M (benalaxyl-M), benodanil, benomyl, benquinox, bentaluron, benthiavalicarb-isopropyl, benthiazole, benzamacril, benzamorf, benzovindiflupyr, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, bordeaux mixture, boscalid, bromconazole, bupirimate, buthiobate, butylamine, calcium polysulfide, captafol, captan, carbamorph ( carbamorph, carbendazim, carboxin, carpropamid, carvone, cheshunt mixture, chinomethionat, clobenzazone hiazone), chloraniformmethane, chloranil, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlorquinox, clozolinate, climbazole, copper acetate, copper carbonate, basic, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper sulfate, copper sulfate, basic, copper zinc chromate, coumoxystrobin, cresol, cufraneb, cuprobam, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil ), cyprofuram, dazomet, debacarb, decafentin, dehydroacetic acid, dichlobentiazox, dichlofluanid, dichlone ), dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomezine, dicloran, diethofe diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton ), dinocap, dinocap-4, dinocap-6, dinocton, dinosulfon, dinoterbone, diphenylamine, dipymetitrone , dipyrithione, disulfiram, ditalimfos, dithianon, DNOC, dodemorph, dodine, drazoxolon, edifenphos, enestrobin, enoxastrobin, epoxiconazole, ethaboxam, etaconazole, etem, ethirimol, ethoxyquin, etridiazole, famoxadone (famoxadone), fenamidone, fenaminosulf, fenaminstrobin, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin, fenpropimorph ( fenpropimorph, fenpyrazamine, fentin, ferbam, ferimzone, florylpicoxamid, fluazinam, flubeneteram, fludioxonil, flufenoxist flufenoxystrobin, fluindapyr, flumetover, flumorph, fluopicolide, fluopimomide, fluopyram, fluoroimide, fluotrimazole, fluoxapi proline (fluoxapiprolin), fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutianil, flutriafol, fluxapirox fluxapyroxad, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, fluconazole-cis, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexaconazole (hexaconazole), hexylthiofos, 8-hydroxyquinoline sulfate ate), hymexazol, imazalil, imibenconazole, iminoctadine-albesilate, iminoctadine-triacetate, inpyrfluxam, iodocarb ( iodocarb), ipconazole, ipfentrifluconazole, ipflufenoquin, iprobenfos, iprodione, iprovalicarb, isofetamide, isoflucypram , isotianil, isoprothiolane, isopyrazam, isovaledione, kasugamycin, kresoxim-methyl, laminarin, mancopper, mancozeb , mandestrobin, mandipropamid, maneb, mebenil, mecarbinzid, mefentrifluconazole, mepanipyrim, mepronil, meptyl dinocap, metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyltetraprole (methyltetraprole), metiram, metominostrobin, metrafenone, metsulfovax, milneb (milneb), myclobutanil, myclozolin, nabam, naftifine, natamycin, nickel bis (dimethyldithiocarbamate), nitrostyrene, nitrotal-isopropyl nitrothal-isopropyl), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxine copper, okispoco oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, penthiopyrad, orthophenyl 2-phenylphenol, phosdiphen, phthalide, picarbutrazox, picoxystrobin, piperalin, polycarbamate, polyoxins, polyoxins - D (polyoxorim), potassium azide, potassium hydrogen carbonate, probenazole, prochloraz, procymidone, propamocarb hydrochloride, propiconazole ), propineb, proquinazid, prothiocarb, pyrazophos, pyriben pyribencarb, pyrifenox, pyrimethanil, pyriminostrobin, pyroquilon, prothiocarb, prothioconazole, pydiflumetofen, pyracarbolid, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrapropoyne, pyraziflumid, pyridaclomethyl, pyridinitril, pyriophenone pyriofenone, pyrisoxazole, pyroxychlor, pyroxyfur, quinacetol-sulfate, quinazamid, quinconazole, quinoxyfen, quinofumelin, quintozene quintozene, rabenzazole, salicylanilide, sedaxane, silthiofam, simeconazole, sodium hydrogen carbonate, sodium hypochlorite, spiroxamine (spiroxamine), sulfur, tebuconazole, tebufloquin, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thidifluor ( thiadifluor), thicyofen
, thifluzamide, thiochlorfenphim, thiophanate, thiophanate-methyl, thiram, tiadinil, tioxymid, tolclofos-methyl ), tolprocarb, tolylfluanid, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tributyltin tributyltin oxide, trichlamide, triclopyricarb, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, tritico triticonazole, validamycin, valifenalate, vinclozolin, zarilamid, zinc naphthenate, zinc sulfate, zineb, ziram ), zoxamide, shiitake mycelium extract, shiitake fruiting body extract.

Insecticides: abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, acynonapyr, afidopyropen, afoxolaner, alanycarb, aldicarb ( aldicarb, allethrin, alpha-cypermethrin, alpha-endosulfan, amidoflumet, amitraz, azamethifos, azinphos-ethyl ), azinphos-methyl, azocyclotin, bacillus thuringiensis, bendiocarb, benfluthrin, benfuracarb, bensultap, benzoximate ( benzoximate, benzpyrimoxan, beta-cyfluthrin, beta-cypermethrin, bifenazate, bifenthrin, bioallethrin, bioresmethrin , bistrifluron, broflanilide, bromopropylate, buprofezin, butocarbboxim, carbaryl, carbofuran, carbosulfan, cartap (cartap), chinomethionat, chlorantraniliprole, chlorethoxyfos, chlorfe napyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorobezilate, chloroprallethrin, chlorpyrifos, chlorpyrifos -methyl), chromafenozide, clofentezine, clothianidin, cyanophos, cyantraniliprole, cyclaniliprole, cycloprothrin, cyenopyrafen cyenopyrafen, cyetpyrafen, cyflumetofen, cyfluthrin, cyhalodiamide, cyhalothrin, cyhexatine, cypermethrin, cyphenothrin, cyproflanilide , cyromazine, deltamethrin, diacloden, diafenthiuron, diazinon, dichlorvos, dichloromezotiaz, dicofol, dienochlor ), diflovidazin, diflubenzuron, dimefluthrin, dimethoate, dimethylvinphos, dimpropyridaz, dinotefuran, diofenolan, disulfoton, day DNOC, dT-80-phthalthuri d-tetramethrin, emamectin-benzoate, empenthrin, endosulfan, EPN, epsilon-metofluthrin, epsilon-momfluorothrin, esfenvalerate, ethiofencarb, ethiprole, etofenprox, etoxazole, etrimfos, febantel, fenazaquin, fenbutatin oxide), fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyroximate, fenthion, fenvalerate, fipronil ), flometoquin, flonicamid, fluacrypyrim, fluazuron, flubendiamide, flucycloxuron, flucythrinate, flufenerim, flufenoc flufenoxuron, flufenprox, flufiprole, fluhexafon, flumethrin, flupentiofenox, flupyradifurone, flupyrimin, fluralaner ), fluvalinate, fluxametamide, phonophos, formetanate, formothion, furathiocarb, gamma-cyhalothrin, halfenprox, halofenozide, heptafluthrin, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, imiprothrin, indoxacarb, indoxacarb-MP, isocycloseram, isofenphos ), isoprocarb, isoxathion, kappa-bifenthrin, kappa-tefluthrin, lambda-cyhalothrin, lepimectin, lufenuron, malathion (malathion), meperfluthrin, metaflumizone, metalcarb, metaldehyde, methacrifos, methamidophos, methidathion, methomyl, methoprene, methoxychlor methoxychlor, methoxyfenozide, methyl bromide, metofluthrin, milbemectin, momfluorothrin, monocrotophos, muscalure, nicofluprole, nitenpyram, novaluron, noviflumuron, omega omethoate, oxazosulfyl, oxydemeton-methyl, oxydeprofos, parathion, parathion-methyl, pentachlorophenol, permethrin, phenothrin, phenthoate, folate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos -methyl), Praziquantel, profenofos, profluthrin, propaphos, propargite, prothiofos, protrifenbute, pyflubumide, pymetrozine ), pyraclofos, pyrafluprole, pyrethrins, pyridaben, pyridalyl, pyrifluquinazon, pyrimidifen, pyriprole, pyriproxyfen , resmethrin, rotenone, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spiropidion, spirotetramat ), spyromesifen, sulfotep, sulfoxaflor, sulprofos, tau-fluvalinate (ta u-fluvalinate), tebfenozide, tebufenpyrad, teflubenzuron, tefluthorin, terbufos, tetrachlorantraniliprole, tetrachlorvinphos, tetramethrin ( tetramethrin, tetramethylfluthrin, tetraniliprole, thiacloprid, thiamethoxam, thiocyclam, thiodicarb, thiofanox, thiometon, tolfenpyrad, tralomethrin, transfluthrin, triazamate, triazuron, trichlorfon, triflumezopyrim, triflumuron, tyclopyrazoflor ), vamidothion, zeta-cypermethrin.

Next, a suspension composition containing a solvate of pyridaben (hereinafter referred to as the present composition) will be described in detail.

The present composition can use water or an organic liquid in which crystals of the solvate of pyridaben are difficult to dissolve as its 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 oil, aliphatic hydrocarbons such as normal paraffin, isoparaffin and naphthene, aromatic hydrocarbons and aliphatics such as kerosene Mixtures of hydrocarbons, oils such as soybean, linseed, rapeseed, coconut, cottonseed and castor oils may be mentioned.

The content of crystals of the pyridaben solvate is generally 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, per 100 parts by mass of the composition of the present invention.

The composition can optionally contain a surfactant. These surfactants include (A), (B), (C), (D) and (E) below.

(A) nonionic surfactant:
(A-1) Polyethylene glycol-type surfactants: for example, polyoxyethylene alkyl (eg C _8-18 ) ether, ethylene oxide adduct of alkylnaphthol, polyoxyethylene (mono- or di)alkyl (eg C _8-12 ) ) phenyl ether, formalin condensate of polyoxyethylene (mono or di)alkyl (for example C _8-12 ) phenyl ether, polyoxyethylene (mono, di or tri)phenylphenyl 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, polyoxyethylene Polymers of (mono, di or tri)styryl phenyl ethers, polyoxyethylene polyoxypropylene (mono, di or tri) styryl phenyl ethers, polyoxyethylene polyoxypropylene block polymers, alkyl (eg C _8-18 ) polyoxyethylenes Polyoxypropylene block polymer ethers, alkyl (eg C _8-12 ) phenyl polyoxyethylene polyoxypropylene block polymer ethers, polyoxyethylene bisphenyl ethers, polyoxyethylene resin acid esters, polyoxyethylene fatty acids (eg C _8-18 ) monoesters, polyoxyethylene fatty acid (eg C _8-18 ) diesters, polyoxyethylene sorbitan (mono, di or tri) fatty acid (eg C _8-18 ) esters, glycerol fatty acid ester ethylene oxide adducts, castor oil ethylene oxide adducts, hydrogenated castor oil ethylene oxide adducts, alkyl (eg C _8-18 ) amine ethylene oxide adducts and fatty acid (eg C _8-18 ) amide ethylene oxide adducts and the like.

(A-2) Polyhydric alcohol surfactants: for example, glycerol fatty acid esters, polyglycerol fatty acid esters, pentaerythritol fatty acid esters, sorbitol fatty acid (eg C _8-18 ) esters, sorbitan (mono-, di- or tri) fatty acids ( For example, C _8-18 ) esters, sucrose fatty acid esters, polyhydric alcohol alkyl ethers, alkyl glycosides, alkyl polyglycosides and fatty acid alkanolamides.

(A-3) Acetylene-based surfactants: for example, acetylene glycol, acetylene alcohol, ethylene oxide adducts of acetylene glycol, ethylene oxide adducts of acetylene alcohol, and the like.

(B) an anionic surfactant:
(B-1) Carboxylic acid-type surfactants: for example, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, maleic acid, or co-polymers of maleic anhydride and olefins (e.g., isobutylene, diisobutylene, etc.) Polymers, copolymers of acrylic acid and itaconic acid, copolymers of methacrylic acid and itaconic acid, copolymers of maleic acid or maleic anhydride and styrene, copolymers of acrylic acid and methacrylic acid, acrylic acid and acrylic acid methyl ester, copolymers of acrylic acid and vinyl acetate, copolymers of acrylic acid and maleic acid or maleic anhydride, polyoxyethylene alkyl (for example C _8-18 ) ether acetic acid, Carboxylic acids such as N-methyl-fatty acid (eg C _8-18 ) sarcosinates, resin acids and fatty acids (eg C _8-18 ), and salts of these carboxylic acids.

(B-2) Sulfuric acid ester type surfactants: for example, alkyl (eg C _8-18 ) sulfates, polyoxyethylene alkyl (eg C _8-18 ) ether sulfates, polyoxyethylene (mono- or di)alkyl ( For example C _8-12 )phenyl ether sulfates, polymeric sulfates of polyoxyethylene (mono or di)alkyl (eg C _8-12 )phenyl ethers, polyoxyethylene (mono, di or tri)phenylphenyl ether sulfates , polyoxyethylene (mono, di or tri) benzylphenyl ether sulfate, polyoxyethylene (mono, di or tri) styrylphenyl ether sulfate, polyoxyethylene (mono, di or tri) styrylphenyl ether sulfuric acid Esters, sulfates of polyoxyethylene polyoxypropylene block polymers, sulfates such as sulfated oils, sulfated fatty acid esters, sulfated fatty acids and sulfated olefins, and salts of these sulfates.

(B-3) Sulfonic acid-type surfactants: For example, formalin of paraffin (eg C _8-22 ) sulfonic acid, alkyl (eg C _8-12 ) benzene sulfonic acid, alkyl (eg C _8-12 ) benzene sulfonic acid Condensates, formalin condensates of cresol sulfonic acid, α-olefin (eg C _8-16 ) sulfonic acids, dialkyl (eg C _8-12 ) sulfosuccinic acids, lignin sulfonic acids, polyoxyethylene (mono- or di)alkyl (eg C _8-12 ) phenyl ether sulfonic acid, polyoxyethylene alkyl (eg C _8-18 ) ether sulfosuccinic acid half ester, naphthalene sulfonic acid, (mono or di) alkyl (eg C _1-6 ) naphthalene sulfonic acid, naphthalene sulfone Formalin condensates of acids, formalin condensates of (mono or di)alkyl (eg C _1-6 ) naphthalene sulfonic acids, formalin condensates of creosote oil sulfonic acids, alkyl (eg C _8-12 ) diphenyl ether disulfonic acids, Igepon Sulfonic acids such as T (trade name), polystyrenesulfonic acid and copolymers of styrenesulfonic acid and methacrylic acid, and salts of these sulfonic acids.

(B-4) Phosphate ester type surfactants: for example, alkyl (eg C _8-12 ) phosphate esters, polyoxyethylene alkyl (eg C _8-18 ) ether phosphate esters, polyoxyethylene (mono- or di)alkyl ( For example C _8-12 )phenyl ether phosphates, polymeric phosphate esters of polyoxyethylene (mono-, di- or tri)alkyl (eg C _8-12 )phenyl ethers, polyoxyethylene (mono-, di- or tri)phenyl phenyl ethers Phosphate esters, polyoxyethylene (mono, di or tri) benzylphenyl ether phosphates, polyoxyethylene (mono, di or tri) styrylphenyl ether phosphates, polymers of polyoxyethylene (mono, di or tri) styrylphenyl ether phosphates phosphate esters of polyoxyethylene polyoxypropylene block polymers, phosphate esters such as phosphatidylcholine, phosphatidylethanolimine and condensed phosphoric acid (eg, tripolyphosphoric acid), and salts of these phosphate esters.

Counter ions of the salts in (B-1) to (B-4) above include alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.), ammonium and various amines (e.g., alkyl amines, cycloalkylamines, alkanolamines, etc.).

(C) cationic surfactant:
For example, alkylamines, alkyl quaternary ammonium salts, ethylene oxide adducts of alkylamines, ethylene oxide adducts of alkyl quaternary ammonium salts, and the like.

(D) amphoteric surfactant:
(D-1) Betaine-type surfactants: for example, alkyl (eg C _8-18 ) dimethylamino acetate betaine, acyl (eg C _8-18 ) aminopropyl dimethylamino acetate betaine, alkyl (eg C _8-18 ) hydroxy sulfobetaine and 2-alkyl (eg C _8-18 )-N-carboxymethyl-N-hydroxyethylimidazolinium betaines (D-2) Amino acid-type surfactants: such as alkyl (eg C _8-18 ) aminopropionic acid, alkyl (eg C _8-18 )aminodipropionic acid and N-acyl (eg C _8-18 )-N′-carboxyethyl-N′-hydroxyethylethylenediamine.

(D-3) Amine oxide type surfactants: Examples include alkyl (eg C _8-18 ) dimethylamine oxide and acyl (eg C _8-18 ) aminopropyl dimethylamine oxide.

(E) Other surfactants:
(E-1) Silicone surfactant: for example, polyoxyethylene/methylpolysiloxane copolymer, polyoxypropylene/methylpolysiloxane copolymer and poly(oxyethylene/oxypropylene)/methylpolysiloxane copolymer etc.

(E-2) Fluorinated surfactant: for example, perfluoroalkenylbenzenesulfonate, perfluoroalkylsulfonate, perfluoroalkylcarboxylate, perfluoroalkenylpolyoxyethylene ether, perfluoroalkylpolyoxyethylene ether and perfluoroalkyltrimethylammonium salts.

These surfactants can be used singly or in combination of two or more, and the ratio in the case of mixing can also be freely selected. The content of the surfactant in the present composition can be appropriately selected, but is preferably in the range of 0.1 to 20 parts by mass per 100 parts by mass of the present composition.

The composition may further contain various adjuvants. The adjuvants that can be used include thickeners, organic solvents, antifreeze agents, antifoaming agents, antibacterial and antifungal agents, coloring agents, and the like, and include the following.

The thickening agent is not particularly limited, and organic and inorganic natural products, synthetic products and semi-synthetic products can be used. Water-soluble polymer compounds such as pyrrolidone, polyacrylic acid, sodium polyacrylate and polyacrylamide, cellulose derivatives such as methylcellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose, montmorillonite, saponite, hectorite, bentonite, laponite and smectite clay minerals such as synthetic smectite. One or two or more of these thickeners may be mixed, and the mixing ratio can be freely selected. These thickeners may be added as they are, or may be added after previously being dispersed in water. Also, the content in the composition of the present invention can be freely selected.

Examples of organic solvents 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, xylene, alkylbenzene, phenylxylylethane and alkylnaphthalene; aliphatic hydrocarbons such as machine oil, normal paraffin, isoparaffin and naphthene; aromatic hydrocarbons such as kerosene and aliphatic hydrocarbons Mixtures of hydrogen, oils such as soybean, linseed, rapeseed, coconut, cottonseed and castor oils.

Examples of antifreezing agents that can be used include ethylene glycol, diethylene glycol, propylene glycol, and glycerin. Propylene glycol and glycerin are preferred. Also, the content in the composition of the present invention can be freely selected.

Furthermore, antifoaming agents such as silicone emulsions, antibacterial and antifungal agents, coloring agents, and the like may be blended.

The method for producing the present composition is not particularly limited, but it can be obtained by adding each of the above components to a dispersion medium and mixing them with a stirrer. In addition, if necessary, the solvate crystals of pyridaben, the surfactant and other auxiliary agents may be finely pulverized by a dry or wet pulverizer, either singly or in combination.

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

The present composition can be used, for example, as an undiluted solution or by diluting it with water about 50 to 5,000 times, and spraying it on crops, trees, or the soil where they grow using a sprayer or the like, or by using a helicopter from the air, and applying the undiluted solution. Alternatively, it can be applied by a method of diluting with water about 2 to 100 times and spraying.

The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these. Powder X-ray diffraction, differential scanning calorimetry (DSC measurement) and toluene determination by gas chromatography in the examples were carried out under the following measurement conditions.
[Powder X-ray diffraction]
Model name: MiniFlex 600 (manufactured by Rigaku)
Measurement method: reflection method X-ray: Cu-Kα
Voltage: 40kV
Current: 15mA
Scan speed: 10.0°/min Scan interval: 0.01°
Scan range: 2θ = 3 to 50°
[DSC measurement] (measured in a nitrogen atmosphere)
Model name: Suggestive scanning calorimeter DSC1 manufactured by METTLER TOLEDO
Comparative substance: None Sample pan: Aluminum Sampling rate: 1 second Heating rate: 10°C/min [toluene determination method by gas chromatography]
Column: HP-INNOWAX 3.0m, 0.32mm ID, 0.25μm
Temperature program: 50°C (10 minutes) -10°C/min -250°C (10 minutes)
Vaporization chamber temperature: 200°C (split 1:30)
Detector: FID (300°C)
Carrier gas: helium (linear velocity control: 30 cm)
Implantation amount: 5 μL
(procedure)
About 1.0 g of a toluene standard was accurately weighed into a 100 mL volumetric flask and adjusted to 100 mL with N,N-dimethylformamide. A toluene standard solution was prepared by placing 2 mL of the prepared liquid in a 50 mL volumetric flask and adjusting the total volume to 50 mL with N,N-dimethylformamide. Put 5 mL, 10 mL, and 20 mL of toluene standard solution in each 50 mL volumetric flask, and add 5 mL of internal standard solution (about 0.5 g of 1,4-dimethoxybenzene dissolved in 500 mL of N,N-dimethylformamide) to each volumetric flask. Then, each was adjusted to a total volume of 50 mL with N,N-dimethylformamide to prepare calibration curve solutions L1, L2, and L3 of toluene. Each calibration curve solution was analyzed by gas chromatography, and a calibration curve of toluene weight/area ratio was created from the area ratio of toluene and internal standard substance.

About 0.05 to 0.2 g of pyridaben crystals or pyridaben toluene sodate crystals obtained in each example was accurately weighed into a 50 mL volumetric flask, and 5 mL of the internal standard solution was accurately added. -Dimethylformamide was added to make the total volume 50 mL. The liquid after preparation was analyzed by gas chromatography, and toluene contained in the crystal was quantified from the amount of toluene collected and the area ratio of toluene/internal standard substance.

[Example 1]: Method for producing crystals of toluene solute of pyridaben Part 1
Step 1: Method for producing crystals of pyridaben To 3.0 g of crystals of pyridaben produced according to the method described in Example 1 of JP-A-61-097270, 0.75 g of toluene and 6.75 g of n-heptane were added. The mixed solution was added and heated to 70°C. After confirming the dissolution of pyridaben crystals, the mixture was cooled to 20° C. for 15 minutes. Crystals precipitated after cooling were separated by filtration. The obtained crystals were dried under reduced pressure under conditions of 30° C. and 4 kPa using a rotary evaporator to obtain 2.6 g of white crystals of pyridaben. As a result of quantifying toluene in the crystals by an internal standard method using gas chromatography, it was confirmed that the obtained crystals did not contain toluene and were not a solvate.

As a result of measuring the powder X-ray diffraction of the obtained crystals of pyridaben, the diffraction pattern shown in FIG. 1 was shown. Also, characteristic peak values are described below.

2θ: 6.1°, 9.1°, 12.7°, 15.1°, 16.3°, 17.7°, 18.7°, 19.9°, 21.4°, 22.3 °, 24.9°, 22.7°, 26.5°, 27.9°, 29.4°, 31.0°, 39.0°, 41.3°
The obtained pyridaben crystals were subjected to DSC measurement, and the peak pattern shown in FIG. 2 was shown.

Step 2: Method for producing crystals of toluene solute of pyridaben To 5.0 g of pyridaben crystals obtained in step 1, a mixed solution of 4.50 g of toluene and 0.56 g of heptane was added and heated to 65°C. After confirming the dissolution of pyridaben crystals, the mixture was cooled to 20° C. for 15 minutes. Crystals precipitated after cooling were separated by filtration. The obtained crystals were dried under reduced pressure under conditions of 30° C. and 4 kPa using a rotary evaporator to obtain 4.1 g of white crystals of pyridaben. As a result of quantifying toluene in the crystals by the internal standard method in gas chromatography, it was found to be a toluene hydrate having a pyridaben/toluene ratio of 2/1 (molar ratio).

As a result of measuring the powder X-ray diffraction of the obtained crystals of the toluene solute of pyridaben, the diffraction pattern shown in FIG. 2 was shown. Also, characteristic peak values are described below.

2-theta: 7.7°, 8.8°, 10.5°, 10.9°, 11.4°, 11.9°, 12.9°, 13.6°, 14.2°, 14.7 °, 15.6°, 16.1°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.4°, 21.0°, 22.7 °, 23.2°, 23.6°, 24.1°, 24.9°, 25.8°, 27.2°, 28.8°, 29.2°, 31.6°, 32.2° °, 41.0°.

The DSC measurement of the obtained pyridaben toluene solute crystals showed the peak pattern shown in FIG.

[Example 2] Method for producing crystals of toluene solute of pyridaben Part 2
2.0 g of toluene was added to 2.0 g of pyridaben crystals obtained in step 1 of Example 1, and the mixture was stirred at room temperature for 1 hour. After stirring, the slurry was filtered, and the obtained crystals were dried under reduced pressure at 30° C. and 4 kPa using a rotary evaporator to obtain 1.8 g of white crystals of pyridaben.

As a result of measuring the powder X-ray diffraction of the obtained crystals, the peak value coincided with the crystals of the pyridaben toluene solute obtained in the step 2 of Production Example 1. Characteristic peak values are described below. From this, it was found that crystals of toluene sodate of pyridaben were obtained in this step.

2-theta: 7.7°, 8.8°, 10.5°, 10.9°, 11.4°, 11.9°, 12.9°, 13.6°, 14.2°, 14.7 °, 15.6°, 16.1°, 17.3°, 17.7°, 18.4°, 19.0°, 19.9°, 20.4°, 21.0°, 22.7 °, 23.2°, 23.6°, 24.1°, 24.9°, 25.8°, 27.2°, 28.8°, 29.2°, 31.6°, 32.2° °, 41.0 °
[Reference example 1]
2.0 g of the toluene sodate crystals of pyridaben obtained in Example 2 were dried under reduced pressure at 60° C. and 1 kPa or less in a rotary evaporator for 1 hour. Powder X-ray diffraction of 1.8 g of pyridaben crystals obtained after drying under reduced pressure was measured. Characteristic peak values are described below. Thus, it was found that crystals of pyridaben were obtained in this step.

2θ: 6.1°, 9.1°, 12.7°, 15.1°, 16.3°, 17.7°, 18.7°, 19.9°, 21.4°, 22.3 °, 24.9°, 22.7°, 26.5°, 27.9°, 29.4°, 31.0°, 39.0°, 41.3°

According to the present invention, it is possible to produce crystals of solvates of pyridaben, in particular toluenes.

Claims (4)

In powder X-ray diffraction using Cu—Kα rays, the diffraction angle 2θ=(7.7°±0.2, 8.8°±0.2, 10.5°±0.2, 10.9°±0. 2, 11.4°±0.2, 11.9°±0.2, 12.9°±0.2, 13.6°±0.2, 14.2°±0.2, 14.7 °±0.2, 15.6°±0.2, 16.1°±0.2, 17.3°±0.2, 17.7°±0.2, 18.4°±0.2 , 19.0°±0.2, 19.9°±0.2, 20.4°±0.2, 21.0°±0.2, 22.7°±0.2, 23.2° ±0.2, 23.6°±0.2, 24.1°±0.2, 24.9°±0.2, 25.8°±0.2, 27.2°±0.2, 28.8° ± 0.2, 29.2° ± 0.2, 31.6° ± 0.2, 32.2° ± 0.2, 41.0° ± 0.2), Crystals of toluene solute of pyridaben. In powder X-ray diffraction using Cu—Kα rays, the diffraction angle 2θ=(7.7°±0.1, 8.8°±0.1, 10.5°±0.1, 10.9°±0. 1, 11.4°±0.1, 11.9°±0.1, 12.9°±0.1, 13.6°±0.1, 14.2°±0.1, 14.7 °±0.1, 15.6°±0.1, 16.1°±0.1, 17.3°±0.1, 17.7°±0.1, 18.4°±0.1 , 19.0°±0.1, 19.9°±0.1, 20.4°±0.1, 21.0°±0.1, 22.7°±0.1, 23.2° ±0.1, 23.6°±0.1, 24.1°±0.1, 24.9°±0.1, 25.8°±0.1, 27.2°±0.1, 28.8° ± 0.1, 29.2° ± 0.1, 31.6° ± 0.1, 32.2° ± 0.1, 41.0° ± 0.1), Crystals of toluene solute of pyridaben. A suspension composition containing the crystals of the toluene salt according to claim 1 or 2 and a dispersion medium. 4. The suspension composition according to claim 3, which contains water as a surfactant and a dispersion medium.

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