Polymorphs with biocidal activity

Abstract

The present disclosure relates to polymorphic forms of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide useful in controlling pests of the orders Hemiptera, Thysanoptera, Lepidoptera, and the like, methods of making such polymorphic forms, intermediates used in such methods, biocidal compositions comprising such polymorphic forms, and methods of using such biocidal compositions against such pests.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 USC § 119(e) to U.S. Provisional Application No. 63 / 228,910, filed August 3, 2021, and U.S. Provisional Application No. 63 / 368,548, filed July 15, 2022, the entire disclosures of which are incorporated herein by reference.

[0002] The present disclosure relates to polymorphic forms of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide useful in controlling pests of the orders Hemiptera, Thysanoptera, Lepidoptera, and the like, methods of making such polymorphic forms, intermediates used in such methods, biocidal compositions comprising such polymorphic forms, and methods of using such biocidal compositions against such pests. [Background technology]

[0003] "Many of the most dangerous diseases for humans are transmitted by vector-borne insects" (Rivero et al.). "Historically, malaria, dengue fever, yellow fever, plague, filariasis, louse-borne typhus, trypanomiasis, leishmaniasis, and other vector-borne diseases caused more human disease and death than all other causes combined between the 17th and early 20th centuries" (Gubler). Vector-borne diseases account for approximately 17% of parasitic and infectious diseases worldwide. Malaria alone is responsible for more than 800,000 deaths annually, 85% of which occur in children under the age of 5. There are approximately 50 million to 100 million cases of dengue fever each year. In addition, there are 250,000 to 500,000 cases of dengue hemorrhagic fever each year (Matthews). Vector control plays a major role in the prevention and control of infectious diseases. However, resistance to insecticides (including multiple resistance to insecticides) has arisen in all insect species that are major vectors of human disease (Rivero et al.). In recent years, over 550 arthropod species have developed resistance to at least one pesticide (Whalon et al.). Moreover, examples of insect resistance continue to far exceed the number of examples of herbicide and fungicide resistance (Sparks et al.).

[0004] Each year, insects, plant pathogens, and weeds destroy over 40% of all food production. This loss occurs despite the application of pesticides and the use of a variety of non-chemical controls, such as crop rotation and biological controls. If even some of this food could be salvaged, it would be possible to feed the more than 3 billion undernourished people in the world (Pimental).

[0005] Plant-parasitic nematodes are among the most widespread pests and often the most difficult and costly to control. Losses due to nematodes are estimated to be about 9% (in developed countries) to about 15% (in developing countries). However, in the United States, a study of various crops in 35 states showed that losses due to nematodes could be as high as 25% (Nicol et al.).

[0006] It should be noted that although gastropods (slugs and snails) are considered pests of less economic importance than other arthropods or nematodes, in some regions they can substantially reduce yields, adversely affect crop quality, and transmit human, animal, and plant diseases. Locally, only a few dozen gastropod species are pests, but on a global scale, hundreds of species are important pests. In particular, gastropods affect a wide variety of agricultural and horticultural crops, including arable, pasture, and fiber crops; vegetables; shrubs and fruit trees; medicinal herbs; and ornamental plants (Speiser).

[0007] Termites cause damage to all kinds of private and public structures. Worldwide termite damage amounts to billions of US dollars each year. In 2005, it was estimated that termites cause over US$50 billion in damage worldwide each year (Korb).

[0008] Thus, for many reasons, including those mentioned above, there is a continuing need to develop new pesticides, which is costly (estimated to cost about US$256 million per pesticide in 2010), time-consuming (on average, about 10 years per pesticide), and difficult (CropLife America).

[0009] New pesticides are urgently needed. Certain pests are developing resistance to pesticides currently in use. Hundreds of pest species are resistant to one or more pesticides. The development of resistance to some of the older pesticides, such as DDT, carbamates, and organophosphates, is well known. However, resistance is also developing to some of the newer pesticides.

[0010] Certain pesticides (e.g., insecticides) have been shown to control insect pests by disrupting physiological processes essential to the development, reproduction, or survival of the target pest. These physiological disruptions can occur in a variety of ways, and therefore compounds that act through many different modes of action have been discovered and developed. Pesticides that fall into the insecticide category have a variety of modes of action that can be broadly categorized into different groups based on which physiological process they disrupt. Exemplary modes of action include nerve and muscle, growth and development, respiratory, midgut targets, and insecticides of unknown or nonspecific action (IRAC 2022). Although these are broad classifications, the cause of death of the target pest does not always match the specific mode of action of the insecticide (Matsumura 1985).

[0011] One example is insecticides that affect chordotonal organs. Examples of such insecticides are commercially available and include compounds such as pymetrozine, pyrifluquinazone, and flonicamid, as well as new members recently introduced to the market such as afidopyropen. Although broadly classified as targeting nervous and muscular tissues, chordotonal organ regulators induce a variety of behavioral symptoms (e.g., breakdown in coordination and feeding ability) in target pest species, ultimately leading to death due to starvation and desiccation (Kandasamy et al. 2017, Morita et al. 2007, Maienfisch 2019, Wang et al. 2011, Zhou et al. 2021). Behavioral studies have investigated the behavioral effects of chordotonal organ regulators. For example, Lee and colleagues (Lee et al. 2013) evaluated the effect of pyrifluquinazon on adult Bemisia tabaci and Trialeurodes vaporarium flies and noted a rapid knockdown effect as well as strong toxic symptoms such as convulsions and paralysis. Similar behavioral effects were reported in Drosophila melanogaster, where exposure to chordotonal modifiers strongly inhibited the climbing behavior of treated flies (Nesterov et al. 2015, Wang et al. 2019). Chordodotonal modifiers affect locomotion and contact, and thus mortality due to starvation and desiccation occurs more slowly than other insecticides such as neonicotinoids (He et al. 2010, Maienfisch 2019). However, toxic symptoms are seen soon after exposure and the effects can be diagnosed (Lee et al. 2013, Morita et al. 2007). Therefore, it has been shown that behavioral effects of chordotonal modulators, such as knockdown effects, are changes that lead to increased mortality and can serve as an index of mortality.

[0012] Thus, for many reasons, including those mentioned above, there is a need for new pesticides. One such compound, [ka] N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide, represented by the formula: or a solvate or hydrate thereof (also referred to herein as "Compound 1", also known as N-(4-chloro-2-(pyridin-3-yl)thiazol-5-yl)-N-ethyl-3-(methylsulfonyl)propanamide), is a potent small molecule that exhibits activity against a variety of pests. Compound 1 has been studied for its insecticidal utility. Compounds related to Compound 1 are disclosed in WO 2010 / 139497 A1 and U.S. Pat. No. 8,350,044, which are incorporated herein by reference in their entireties.

[0013] Compound 1 finds use as an agricultural chemical, and it would be advantageous to have a polymorphic form that has improved properties (e.g., improved crystallinity, solubility, reduced hygroscopicity, and / or ease of formulation into commercially viable compositions for field application) while maintaining chemical stability.

[0014] CERTAIN REFERENCES CITED IN THIS DISCLOSURE Busvine, JR (1971). Contact poisons in solid form: residual films of contact insecticides. In A Critical Review of the Techniques for Testing Insecticides (Second Edition ed., pp. 102-128). Commonwealth Agricultural Bureaux. CropLife America,The Cost of New Agrochemical Product Discovery,Development & Registration,and Research & Development predictions for the Future,2010. Drewes,M.,Tietjen,K.,Sparks,T.C.,High-Throughput Screening in Agrochemical Research,Modern Methods in Crop Protection Research,Part I,Methods for the Design and Optimization of New Active Ingredients,Edited by Jeschke,P.,Kramer,W.,Schirmer,U.,and Matthias W.,p.1-20,2012. Gubler,D.,Resurgent Vector-Borne Diseases as a GlobalHealth Problem,Emerging Infectious Diseases,Vol .4,No.3,p.442-450,1998. He,Y.,Chen,L.,Chen,J.,Zhang,J.,Chen,L.,Shen,J.,& Cheng Zhu,Y.(2011).Electrical penetration graph evidence that pymetrozine toxicity to the rice brown planthopper is by inhibition of phloem feeding.Pest Management Science,67(4),483-491. IRAC Insecticide Resistance Action Committee(2022).IRAC Mode of Action Classification Scheme,Version 10.2.39.Retrieved March 2022,fromHttps: / / irac-online.org / mode-of-action / Kandasamy,R.,London,D.,Stam,L.,von Deyn,W.,Zhao,X.,Salgado,V.L.,& Nesterov,A.(2017).Afidopyropen:New and potent modulator of insect transient receptor potential channels.Insect Biochemistry and Molecular Biology,84,32-39. Korb,J.,Termites,Current Biology,Vol.17,No.23,2007. Lee,S.-W.,Song,M.-K.,Ahn,Y.J.,Kim,Y.-J.,Moon,Y.-S.,Koo,H.N.,& Kim,G.H.(2013).Insecticidal Activity and Behavioral Disorders by Pyrifluquinazon to Trialeurodes vaporariorum and Bemisia tabaci.The Korean Journal of Pesticide Science,17(1),33-40 Maienfisch,P.(2019).Selective feeding blockers:pymetrozine,flonicamid,and pyrifluquinazon.In P.Jeschke,M.Witschel,W.Kraemer,& U.Schirmer(Eds.),Modern Crop Protection Compounds(Third Edition ed.,Vol.Volume 3:Insecticides,pp.1501-1526).Wiley-VCH. Matsumura,F.(1985).Modes of action of insecticides.In Toxicology of Insecticides:Second Edition(pp.111-202).Plenum Press. Matthews,G.,Integrated Vector Management:Controlling Vectors of Malaria and Other Insect Vector Borne Diseases,Ch.1,p.1,2011. Morita,M.,Ueda,T.,Yoneda,T.,Koyanagi,T.,&Haga,T.(2007).Flonicamid,a novel insecticide with a rapid inhibitory effect on aphid feeding.Pest Management Science,63,969-973. Nesterov,A.,Spalthoff,C.,Kandasamy,R.,Katana,R.,Rankl,Nancy B.,Andres,M.,Jaehde,P.,Dorsch,John A.,Stam,Lynn F.,Braun,F.-J.,Warren,B.,Salgado,Vincent L.,& Goepfert,Martin C.(2015).TRP Channels in Insect Stretch Receptors as Insecticide Targets.Neuron,86(3),665-671. Nicol,J.,Turner S.,Coyne,L.,den Nijs,L.,Hocksland,L.,Tahna-Maafi,Z.,Current Nematode Threats to World Agriculture,Genomic and Molecular Genetics of Plant-Nematode Interactions,p.21-43,2011. Pimental,D.,Pest Control in World Agriculture,Agricultural Sciences - Vol.,II,2009. Rivero,A.,Vezilier,J.,Weill,M.,Read,A.,Gandon,S.,Insect Control of Vector- Borne Diseases:When Is Insect Resistance a Problem? Public Library of Science Pathogens,Vol .6,No.8,p.1-9,2010. Sparks T.C.,Nauen R.,IRAC:Mode of action classification and insecticide resistance management,Pesticide Biochemistry and Physiology(2014)available online 4 December 2014. Speiser,B.,Molluscicides,Encyclopedia of Pest Management,Ch.219,p.506-508,2002. Stroup,W.W.(2012).Generalized Linear Mixed Models:Modern Concepts,Methods and Applications.CRC Press.555 pp. Wang,H.,Lei,Z.,Mei,Y.,Shuo,L.,& YunLiang,J.(2011).Effect of pymetrozine interferes with feeding behavior of Bemisia tabaci(Homoptera,Aleyrodidae).Chinese Journal of Applied Entomology,48(1),54-59. Wang, L.-X., Niu, C.-D., Salgado, VL, Lelito, K., Stam, L., Jia, Y.-L., Zhang, Y., Gao, C.-F., & Wu, S.-F. (2019). Pymetrozine activates TRPV channels of brown planthopper Nilaparvata lugens. Pesticide Biochemistry and Physiology,153,77-86. Whalon, M., Mota -Sanchez, D., Hollingworth, R., Analysis of Global Pesticide Resistance in Arthropods, Global Pesticide Resistance in Arthropods, Ch. 1, p. 5-33, 2008. Zhou, X., Zhang, Z., Zheng, H., Zhang, Q., Gong, J., Li, C., & Wang, R. (2021). Physiological and Biochemical Responses to Sublethal Concentrations of the Novel Pyropene Insecticide, Afidopyropen, in Whitefly Bemisia tabaci MED(Q Biotype). Agronomy, 11(11).

[0015] Definitions of this Disclosure The examples given in these definitions are generally non-exhaustive and should not be construed as limiting the present disclosure. It should be understood that a substituent should comply with the chemical bonding rules and steric compatibility constraints for the particular molecule to which it is attached. These definitions are used solely for the purposes of this disclosure.

[0016] The phrase "active ingredient" means a substance having activity useful for controlling pests and / or useful for supporting other substances to have better activity in controlling pests, examples of such substances include, but are not limited to, acaricides, algaecides, antifeedants, birdicides, bactericides, bird repellents, chemosterilants, fungicides, herbicide safeners, herbicides, insect attractants, insect repellents, insecticides, mammalian repellents, mating disruptants, molluscicides, nematicides, plant activators, plant growth regulators, rodenticides, synergists, and virucides (see bcpc.org).

[0017] The term "active ingredient group alpha" (hereinafter "AIGA") collectively refers to the following substances: abamectin, abamectin-aminomethyl, abscisic acid, ACC, acephate, acequinocyl, acetamiprid, acetione, acetochlor, acetophenate, acetophos, acetoprole, acibenzolar, acifluorfen, aclonifen, ACN, acrep, acrinathrin, acrolein, acrylonitrile, acinonapyr, acipetax, afidopiropen, afoxolaner, (S)-afoxolaner, and AITC. , alachlor, alanap, alanycarb, albendazole, aldicarb, aldicarb sulfone, aldimorph, aldoxycarb, aldrin, allethrin, d-trans-allethrin, allicin, allidochlor, allosamidin, alloxydim, allyl alcohol, allyl isothiocyanate, alixycarb, arorac, alpha-bromadiolone, alpha-cypermethrin, alpha-endosulfan, alphamethrin, altretamine, aluminum phosphide, aluminum phosphide, amethoctrazine, amethoctidine ... Ametryn, ametryne, amivudine, amicarbazone, amicarthiazole, amidithione, amidochlor, amidoflumet, amidosulfuron, aminocarb, aminocyclopyrachlor, aminopyralid, 4-aminopyridine, aminopyrifen, aminotriazole, amiprophos-methyl, amiprophos, amiprophos-methyl, amisulbrom, amiton, amitraz, amitrole, ammonium sulfamate, amovam, amorphous silica gel, amorphous silicon dioxide, ampropylphos, AMS, anaba Sin, Ancymidol, Anilazine, Anilofos, Anicifluprine, Anisrone, Anthraquinone, Antimony potassium tartrate, Anz, Aphorate, Aramite, Arprocarb, Arsenic trioxide, Asomate, Ashlam, Atidathion, Atraton, Atrazine, Aureofungin, Avermectin B1, AVG, Aviglycin, Azaconazole, Azadirachtin, Azafenidin, Azamethiphos, Azidithion, Azimsulfuron, Azinphos-ethyl, Azinphos-ethyl, Azinphos-methyl, Azinphos-methyl,Aziprotryn, Aziprotryne, Adithiram, Azobenzene, Azocyclotine, Azotoate, Azoxystrobin, Bachmedesh, Barban, Barbanate, Barium Hexafluorosilicate, Barium Polysulfide, Barium Silicofluoride, Barthrin, Basic Copper Carbonate, Basic Copper Chloride, Basic Copper Sulfate, BCPC, Beflubutamid, Beflubutamid-M, Benalaxyl, Benalaxyl-M, Benazolin, Bencarbazone, Benclotiaz, Bendakingubi Bendaqingbingzhi, bendiocarb, benzoxide, benefin, benfluralin, benfuracarb, benfuresate, benmihuangcaoan, benodanil, benomyl, benoxacor, benoxafos, benquinox, benquitrione, bensulfuron, bensulide, bensultap, bentallon, bentazon, bentazone, benthiavalicarb, benthiazole, benthiocarb, bentranil, benzadodec benzadox, benzalkonium chloride, benzamacryl, benzamisole, benzamorph, benzene hexachloride, benzphendizone, benzimine, benzipram, benzobicyclon, benzoepin, benzofenap, benzofluor, benzohydroxamic acid, benzomate, benzophosphate, benzothiadiazole, benzovindiflupyr, benzoximate, benzoylprop, benzpyrimoxan, benzthiazuron, benz benzuocaotong, benzyladenine, benzyl benzoate, berberine, beta-cyfluthrin, beta-cypermethrin, bethoxadin, BHC, gamma-BHC, bialaphos, bicyclopyrone, bifenazate, bifenox, bifenthrin, kappa-bifenthrin, bifujunzhi, bilanafos, binapacryl, binghuanzuo, bingqingxiao, bioallethrin,S-bioallethrin, bioethanomethrin, biopermethrin, bioresmethrin, biphenyl, bipyrazone, bisadyl, bismerthiazole, bismerthiazole-copper, bisphenylmercury methylenedi(x-naphthalene-y-sulphonate), bispyribac, bistrifluron, bisultap, bitertanol, bithionol, bixafen, bixilozone, blasticidin-S, borax, Bordeaux mixture, boric acid, boscalid, BPCMS, BPMC, BPPS, brassinolide, brassinolide-ethyl, brevicomin, Brodifacoum, brofenprox, brofenvalerate, brofuranilide, broflutrinate, bromacil, bromadiolone, alpha-bromadiolone, bromoclofos, bromethalin, bromethrin, bromfenvinphos, bromoacetamide, bromobonyl, bromobutide, bromociclen, bromocyclen, bromo-DDT, bromofenoxime, bromophos, bromometa bromophos, bromophos-ethyl, bromopropylate, bromothalonil, bromoxynil, brompyrazone, bromuconazole, bronopol, bropropdifacoum, BRP, BTH, bucarpolate, bufencarb, buminafos, bupirimate (bupirimate), buprofezin, burgundy mixture, busulfan, busulphan, butacarb, butachlor, butafenacil, butam, butamifos, butane-fipronil, butathiofos, butenachlor, butene-fipronil, butetryn, butidazole, buthiobate, buthiuron, butifos,butocarboxim, butonate, butopyronoxyl, butoxycarboxim, butralin, butrizol, butroxydim, buturon, butylamine, butyrate, butylchlorophos, butylene-fipronil, cacodylic acid, cadusafos, cafenstrole, calciferol, calcium arsenate, calcium chlorate, calcium cyanamide, calcium cyanide, calcium polysulfide, carbinphos, cambendichlor, campheclor, camphor, d-camphor, canthorodifen, captafol, captan, carbam, carbamorph, carbanolate, carbaryl, carbaryl carbaryl, carbasulam, carbathiin, carbathion, carbendazim, carbendazole, carbetamide, carbophenothione, carbofuran, carbon disulfide, carbon tetrachloride, carbonyl sulfide, carbophenothione, carbophos, carbosulfan, carboxazole, carboxide, carboxin, carfentrazone, carpropamid, cartap, carvacrol, carvone, CAVP, CDAA, CDEA, CDEC, cerocidin, CEPC, ceralua, selenox, cetoctaelat, sabadilla, cheshunt mixture mixture), quinalphos, quinalphos-methyl, chinomethionat, chinomethionate, chiralaxyl, chitosan, clobenziazone, chlomethoxyfen, chlor-IPC, chloralose, chloramben, chloramine phosphorus, chloramizole, chloramphenicol, chloraniformethane, chloranil, chloranocryl, chlorantraniliprole, chlorazifop, chlorazine, chlorbencide, chlorbenzuron, chlorbicyclen, chlorbromuron, chlorbufam, chlordane, chlordecone, chlordimeform, chlorenpentrin, chloretazate, chlorethephon, chlorethoxyfos, chloreturon,Chlorfenac, chlorfenapyr, chlorphenazole, chlorphenetole, chlorphenidim, chlorfenprop, chlorfenson, chlorphenesulfide, chlorfenvinphos, chlorfenvinphos-methyl, chlorfluazuron, chlorflurazole, chlorflurecol, chlorflurene, chlorflurenol, chloridazon, chlorimuron, chlorinate, chlormephos, chlormequat, chlormethuron, chlormethoxynil , chlornidine, chlornitrofen, chloroacetic acid, chlorobenzilate, chlorodinitronaphthalenes, chlorophenisone, chloroform, α-chlorohydrin, chloroinconazide, chloromebuform, chloromethiuron, chloroneb, chlorophacinone, chlorophos, chlorophthalim, chloropicrin, chloropon, chloroprallethrin, chloropropylate, chlorothalonil, chlorotoluron, chloroxyphenidim roxifenidim, chloroxuron, chloroxynil, chlorphonium, chlorphoxim, chlorphthalim, chlorprazophos, chlorprocarb, chlorpropham, chlorpyrifos, chlorpyrifos-methyl, chlorquinox, chlorsulfuron, chlorthal, chlorthiamid, chlorthiophos, chlortoluron, chlozolinate olinate), chltosan, cholecalciferol, choline chloride, chromafenozide, cycloheximide, simectakarb, simetacarb, cinerin I, cinerin II, cinerins, cinidon-ethyl, cinmethylin, cinosulfuron, synthofen, siobutide, cisanilide, cismethrin, clasifos, clefoxydim, clenpirin, clenpirin, clethodim, climbazole, cliodinate, clodinafop, cloethocarb, clofenset, clofenotan, clofentezine,Clofenvinphos, clofibric acid, clofop, clomazone, clomeprop, clonitralid, clopindol, cloprop, cloproxyzim, clopyralid, cloquintocet, tocet, cloransulam, closantel, clothianidin, clotrimazole, cloxyfonac, cloxylacon, clozylacon, CMA, CMMP, CMP, CMU, codlelure, cholecalciferol, colophonate, copper acetate, copper acetoarsenite, copper arsenate, copper carbonate (basic), copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper 8-quinolinoleate 8-quinolinolate), copper silicate, copper sulfate, copper sulfate (basic), zinc copper chromate, coumachlor, coumafen, coumaphos, coumafuryl, coumaphos, coumatetralyl, coumethoxystrobin, coumithoate, coumoxystrobin, 4-CPA, 4-CPB, CPMC, CPMF, 4-CPP, CPPC, credazine, cresol, cresylic acid, Crimidine, croconazole, crotamiton, crotoxyfos, crotoxyphos, curfomate, cryolite, cue-lure, kufuraneb, cumileron, cumylron, cuprobam, cuprous oxide, curcumenol, CVMP, cyanamide, cyanatrin, cyanazine, cyanofenphos, cyanogen, cyanophos, cyanthoate, cyantranilp rol, cyanuric acid, cyazofamid, cybutryne, cyclafuramid, cyclanilide, cyclaniliprole, ciclethrin, cycloate, cyclobutrifluram, cycloheximide, cycloplate, cycloprothrin, cyclopyranyl, cyclopyrimorate, cyclosulfamuron, cycloxydim, cicurulon, cyenopyrafen, sietopyrafen, cyflufenamid, cyflumetofe cyfluthrin, beta-cyfluthrin, cyhalodiamide, cyhalofop, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cyhexatin, cymergan, cymiazole, cymoxanil, cyometrinil, cypendazole, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyperquat, cyphenothrin,Cyprazine, cyprazole, cyproconazole, cyprodinil, cyprofanilide, cyprofuram, cypromide, cyprosulfamide, cypirafluon, cyromazine, cythioate, citrex, 1,3-D, 2,4-D, 3,4-DA, dymron, dalapon, daminozide, dayoutong, dazomet, 2,4-DB, 3,4-DB, DBCP, d-camphor, DCB, DCD, DCIP, DCPA (US), DCPA (Japan), DCPTA, DC U, DDD, DDPP, DDT, pp'-DDT, DDVP, 2,4-DEB, debacarb, decaphentin, decamethrin, decarbofuran, DEET, dehydroacetic acid, diquat, delachlor, delnav, deltamethrin, demefion, demefion-O, demefion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methyl sulfone sulphone, demeton-S-methylsulphon, DEP, 2,4-DEP, deparethrin, delis, 2,4-DES, desmedipham, desmetryn, desmetryne, d-fanshiluquebingjuzhi, DFDT, diafenthiuron, dialifol, dialifos, di-allate, diallate, diamidaphos, diamiphene diamiphenethide, dianat, diatomaceous earth, diatomite, diazinon, dibrom, 1,2-dibromoethane, dibutyl phthalate, dibutyl succinate, dicamba, dikapton, dicarbasulf, dicarbosulf, dichlobenil, dichlobentiazox, dichlorobenzo-methyl, dichlophenthion, dichlofluanid, dichloron, dichloralurea, dichlorbenzuron, dichlorphenidim, dichlorflurecol, dichlorflurenol, dichlormate, dichlormid,o-Dichlorobenzene, ortho-dichlorobenzene, p-dichlorobenzene, para-dichlorobenzene, 2,5-dichlorobenzoic acid, 1,2-dichloroethane, dichloromethane, dichlorophen, 3,6-dichloropicolinic acid, 1,2-dichloropropane, 1,3-dichloropropene, dichlorprop, dichlorprop-P, dichlorvos, dichlozolin, dichlozoline, diclobutrazol, diclocymet ocymet, diclofop, diclomedine, dicloran, diclomezotiaz, diclosulam, dicofol, dicophane, dicoumarol, dicresyl, dicrotophos, dicryl, dicoumarol, dicyclanil, dicyclonon, dieldrin, dienochlor, diethamquat, diethathyl, diethion, diethion, diethfencarb, dieth rate, dieton, diethyl pyrocarbonate, diethyl toluamide, difenacoum, difenoconazole, difenopentene, difenoxuron, difenzoquat, difethialone, diflobidazin, diflubenzuron, diflufenican, diflufenicanil, diflufenzopyr, diflumetrim, dikegulac, dilor, dimatif, dimefluazole, dimefluthrin, dimefox, dimefron, dimehypo ypo), dimenoxypyrine, dimepiperate, dimesulfazet, dimethaclon, dimethane, dimethacarb, dimethaclon, dimethachlor, dimethamethrine, dimethenamid, dimethenamid-P, dimethipine, dimethirimol, dimethoate, dimethomorph, dimethrine, dimethylcarbamate, dimethyl disulfide, dimethyl phthalate, dimethylvinphos, dimethilan, dimexano, dimidazon, dimoxystrobin, dimpropyridaz, dimpirate, dymron, ginex,Dingjunezuo, diniconazole, diniconazole-M, R-diniconazole, dinitramine, dinitrophenols, dinobuton, dinocap, dinocap-4, dinocap-6, dinoktone, dinofenate, dinopenton, dinoprop, dinosam, dinoseb, dinosulfone, dinotefuran, dinoterb, dinoterbone, diofenolan, dioxabenzophos, dioxacarb, dioxathione, dioxopyritrione, diphacin, diphacinone, diphenadione, diphenamide, diphenylamine, diphenyl sulfone, diphenyl sulfide, diprogulic acid acid), diproparin, dipropetrine, dipterex, dipimethitron, dipyrithione, diquat, disosultap, disparlure, disgran, disul, disulfiram, disulfoton, ditalimphos, dithianon, dithiofos, dithioether, dithiometon, dithiopyr, dithiuron, diuron, dixanthogen, d-limonene, DMDS, DMPA, DNOC, dodemorph, dodizin, dodine, dofenapine, doguazine, dominicalure, doramectin, 2,4-DP, 3,4-DP, DPC, drazoxolone, DSMA, d-teflumethrin, d-trans-allethrin, d -trans-resmethrin, dufulin, dymron, EBEP, EBP, ebfos, alpha-ecdysone, beta-ecdysone, ecdysterone, eclomezol, EDB, EDC, EDDP, difenphos, eglinazine, emamectin, EMPC, empenthrin, enadenine, endosulfan, alpha-endosulfan, endothal, endothall, endothion, endrin, enestrobin, enilconazole, enoxastrobin, ephirsulfonate, 24-epibrassinolide, EPN, epocholeone,epofenonane, epoxiconazole, eprinomectin, epronaz, epsilon-metofluthrin, epsilon-momfluorotrine, EPTC, iprifenacil, erbon, ergocalciferol, erlujixiancaoan, esafoxolaner, esdeparethrin, esfenvalerate, ESP, esprocarb, etaceracil, etaconazole, etaphos, etem, ethaboxam , ethaclor, ethalfluralin, ethametsurfuron, ethaprochlor, ethephon, ethidimuron, ethiphencarb, ethiolate, ethion, ethiozin, ethiprole, ethirimol, ethoate-methyl, etobenzanide, ethofumesate, ethohexadiol, ethoprop, ethoprophos, ethoxyphene, (3-ethoxypropyl)mercury bromide, ethoxyquin, etho Xysulfuron, ethychlozate, ethylane, ethyl-DDD, ethylene, ethylene dibromide, ethylene dichloride, ethylene oxide, ethyl formate, ethylisin, ethylmercuric acetate, ethylmercuric bromide, ethylmercuric chloride, ethylmercuric 2,3-dihydroxypropyl mercuric phosphate, N-(ethylmercury)-p-toluenesulfonanilide, N-(ethylmercury)-p-toluenesulfonanilide, ethyl pyrophosphate, ethyl thiometone, ethyl trianol ianol), ethyltrianol, ethinofen, ETM, etonipromide, etobenzanide, etofenprox, etoxazole, etridiazole, etrimphos, eugenol, EXD, famoxacarb, famoxadone, famful, d-fanshiluquebingjuzhi, fenac, fenamidone, fenaminosulf, phenaminestrobin, fenamiphos, fenapanil, fenarimol, fenasulam,Fenazaflor, fenazaquin, fenbuconazole, fenbutatin oxide, fenchlorazole, fenchlorphos, fenclofos, fenclorim, fenethacarb, fenetrazole, fenfluthrin, , fenfuram, fenhexamid, phenidim, fenitropan, fenitrothion, fenizon, fenjuntong, fenmezoditiaz, fenobucarb, fenorobo, fenoprop, fenothiocarb, fenoxacrim, fenoxanil, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenoxycarb, fenpiclonil, fenpicoxamid, fenpirithrin, fen ampropathrin, fenpropidin, fenpropimorph, fenpyrazamine, fenpyrazone, fenpyroximate, fenquinotrione, fenridazon, fenthone, fensulfothion, fenteracol, fenthiaprop, fenthion, fenthion-ethyl, fentiaprop, fentin, fentrazamide, fentrifanil, fenuron, fenuron-TCA, fenvalerate valerate, ferbam, ferimzone, ferric phosphate, ferrous sulfate, fipronil, flamprop, flamprop-M, flazasulfuron, flocumafen, flometoquin, flonicamid, florasulam, florpyrauxifen, florylpicoxamide, fluacrypyrim, fluazaindolizine, fluazifop, fluazifop- P, fluazinam, fluazolate, fluazuron, flubendiamide, fluveneteram, flubenzimine, flubrocythrinate, flucarbazone, flucetosulfuron, fluchloralin, fluchloraminopyr, fluchlordinylipol, flucofuron, flucycloxuron, flucythrinate, fludioxonil, fluenethyl, fluenetil, fluensulfone, flufenacet, flufenerim, flufenican,Flufenoxadiazam, Flufenoxuron, Flufenoxystrobin, Flufenprox, Flufenpyr, Flufenzine, Flufiprole, Fluhexafon, Fluindapyr, Flumethrin, Flumetober, Flumetralin, Flumetsulam, Flumethylsulfolim, Flumezin, Flumiclorac, Flumioxazin, Flumipropin, Flumorph, Fluometuron, Fluopicolide, Fluopimomi, Fluopyram, Fluorobenside, Fluoridamide, Fluoroacetamide, Fluoroacetic acid, Fluoroc rolidone, fluoro-DDT, fluorodifen, fluorogesarol, fluoroglycofen, fluoroimide, fluoromide, fluoromidine, fluoronitrofen, fluroxypyr, fluothiuron, fluotrimazole, fluoxapiproline, fluoxastrobin, fluoxythioconazole, flupentiofenox, flupoxam, flupropacil, flupropazine, flupropanate, flupyradifurone, flupyrazophos, flupirimine, flupyrsulfuron, flupyrazophos ruquinconazole, fluralaner, flurazole, flurecol, flurenol, fluridone, flurochloridone, fluromidine, fluroxypyr, flurprimidol, flursuramide, flurtamone, flusilazole, flusulfamide, flutensin, fluthiacet, fluthiamide, flutianil, flutolanil, flutriafol, fluvalinate, tau-fluvalinate, fluxametamide, fluxapyroxad, fluxofenim, forper, folpet, fomesafen , fonofos, foramsulfuron, forchlorfenuron, formaldehyde, formetanate, formothion, formparanate, fosamine, fosetyl, fosmetilan, hospirate, hosthiazate, hosthietan, frontalin, fthalide, fuberidazole, fukaojing, fukaomi, fufenozide, fujunmanzhi, flumi, fumarin, funaihecaoling, fuphenthiourea, furalan, furaxyl, furametrin, furametpyr,Furan tebufenozide, furathiocarb, flucarbanil, fluconazole, fluconazole-cis, fretrin, furfural, furilazole, flumecyclox, furophanate, furyloxyfen, gamma-BHC, gamma-cyhalothrin, gamma-HCH, genit, gibberellic acid, gibberellin A3, gibberellins, griftor, glitor, glucochloralose, glufosinate, glufosinate-P, L-glufosinate, glyodine glyoxime, glyphosate, glyphosine, gossyplure, grandlure, griseofulvin, guanectin, guazatine, halacrinate, haluxifen, halfenprox, halofenozide, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, haloxyfop-R, HCA, HCB, HCH, gamma-HCl, hemel, hempa, HEOD, heptachlor, hepta fulthrin, heptamaloxyloglucan, heptenophos, heptopargyl, herbimycin, herbimycin A, heterophos, hexachlor, hexachloran, hexachloroacetone, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexaflumuron, hexafluoramine, hexaflurate, hexalure, hexamide, hexazinone, hexylthiophos, hexythiazox, HHDN, holosulf, Homobrassinolide, Huanbifucaotong, Huankaiwo, Huanchongjing, Huangcaoling, Huanjunzuo, Hydramethylnon, Hydralgaphen, Slaked lime, Hydrogen cyanamide, Hydrogen cyanide, Hydroprene, S-hydroprene, Hydroxyisoxazole, 4-Hydroxyphenethyl alcohol,8-hydroxyquinoline sulfate, hymexazole, hyquincarb, IAA, IBA, IBP, icaridin, imazalil, imazamethabenz, imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, imibenconazole, imicyaphos, imidacloprid, imidaclothiz, iminoctadine, imiprothrin, Inabenfide, indanofan, indazapyroxamet, indaziflam, indoxacarb, inedin, infusorial earth, impilfluxam, iodobonyl, iodocarb, iodofenphos, iodomethane, iodosulfuron, iofensulfuron, ioxynil, ipazine, IPBC, IPC, ipconazole, ipfencarbazone, ipfentrifluconazole, ipflufenoquin, iprobenfos, Iprodione, iprovalicarb, iprimidam, ipsdienol, ipsenol, IPSP, IPX, isamidophos, isazophos, isobenzane, isocarbamide, isocarbamide, isocarbophos, isosyl, isocycloceram, isodrin, isofenphos, isofenphos-methyl, isofetamide, isoflucipram, isolane, isomethiozine, isonorurone, isopamphos, isopolynate, isoprocarb, isoprosil, isoproparin, isopropazole, isoprothiolane, isoproturon, isopy Razam, isopirimol, isothioate, isotianil, isouron, isovalerion, isoxaben, isoxacarbol, isoxachlorthor, isoxadifen, isoxaflutole, isoxapyrifop, isoxathion, islon, ivermectin, ixoxaben, isopamphos, isopamphos, japonilure, japothrins, jasmolin I, jasmolin II, jasmonic acid, jiahuangchongzong,Jiajizengxiaolin, Jiaxiangjunzhi, Jiecaowan, Jiecaoxi, Jinggangmycin A, Iodofenphos, Juvenile hormone I, Juvenile hormone II, Juvenile hormone III, Kadethrin, Kappa-bifenthrin, Kappa-tefluthrin, Carbutilate, Caletazane, Kasugamycin, Kejunlin, Kereban, Ketospiradox, Diatomaceous earth, Kinetin tin), kinoprene, S-kinoprene, chiralaxyl, kresoxim-methyl, quicaoxy, lactofen, lambda-cyhalothrin, lancotrione, latilure, lead arsenate, lenacil, lepimectin, leptophos, L-glufosinate, lianbenjingzhi, lime sulfur, lindane, lineatin, linuron, lilimphos, litura, lupurua, lotilane, lufenuron, luefuqing kong xanan chongxianan), lvdingjunzhi, lvfumijvzhi, lvxiancaolin, lythidathion, M-74, M-81, MAA, magnesium phosphide, malathion, maldison, maleic hydrazide, malonoven, maltodextrin, MAMA, manam, mancopper, mancozeb, mandestrobin, mandipropamid, maneb, Matrine, magidox, MCA, MCC, MCP, 1-MCP, MCPA, 2,4-MCPA, MCPA-thioethyl, MCPB, 2,4-MCPB, MCPP, mebenil, mecarbam, mecarbinzid, mecarbone, mecoprop, mecoprop-P, medimeform, medinoterb, medlure, mefenacet, mefenoxam, mefenpyr, mefentrifluconazole, mefluidide, megatomoic acid, melissyl alcohol,Melitoxin, MEMC, Menazone, MEP, Mepanipyrim, Meperfluthrin, Mephenate, Mefolan, Mepiquat, Mepitriflufenpyr, Mepronil, Meptyldinocap, dinocap, mercaptodimetur, mercaptophos, mercaptophosthiol, mercaptothione, mercuric chloride, mercuric oxide, mercurous chloride, merphos, merphos oxide, mesoprazine, mesosulfuron, mesotrione, mesulfen, mesulfenphos, mesulfen, metacresol, metaflumizone, metalaxyl, metalaxyl-M, R-methylaxyl, metaldehyde, metam, metamifop, metamitron, metaphos, metarylpicoxamid, metaxone, metazachlor, metazosulfuron, metazoxolone, metacamifen, metoc Nazole, Metepa, Metoflurazon, Methabenzthiazuron, Methacrifos, Methalproparin, Metam, Methamidophos, Methasulfocarb, Methazole, Methfuroxam, Methybenzuron, Methidathion, Methiobencarb, Methiocarb, Methiopyrisulfuron, Methiotepa, Methiozoline, Methiuron, Metoclotophos, Metolcarb, Metometon, Methomyl, Methoprene, S-Methoprene, Metoprothrin, Metoprothrin, Metoquin-butyl, Metothrin, Methothrin, Methochlor, 2-Methoxyethylmercury chloride, Methoxyfenozide, Methophenone, Methyl afolate apholate), methyl bromide, methyl eugenol, methyl iodide, methyl-isofenphos, methyl isothiocyanate, methyl parathion, methylacetophos, methyl chloroform, 1-methylcyclopropene, methyl dithiocarbamic acid, methyldymron, methylene chloride, methylmercaptophos, methylmercaptophos oxide, methylmercaptophos thiol, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, methylneodecanamide, methylnitrophos, methyl triazothion, methiozoline, metiram, metiram zinc, metobenzuron, metobromuron, metofluthrin, epsilon-metofluthrin, metolachlor, S-metolachlor, metolcarb, metomecran, metometuron, metominostrobin, metosulam, metoxadiazone,Metoxuron, metrafenone, metriam, metribuzin, metrifonate, metsulfovax, metsulfuron, methyltetraprole, mevinphos, mexacalvert, miechuwei, mieshuan, miewenjuzhi, milbemectin, milbemycin oxime, milneb, mimanan, mipafox, MIPC, mirex, MITC, mivoriraner, MNAF, modofuranel, Moguchun, molinate, morosultap, momfluorothrin, epsilon-momfluorothrin, monalide, monisouron, monistron, monoamitraz, monochloroacetic acid, monocrotophos, monolinuron, monomehypo, monosulfuram, monosulfuron, monosulfuron-ester, monosultap, monuron, monuron-TCA, morfamquat, moroxydine, mol Photoion, Morzide, Moxidectin, MPMC, MSMA, MTMC, α-multistriatin, Muscarua, Myclobutanil, Myclozolin, Myricyl alcohol, NAA, NAAm, Nabam, Naphthalophos, Naled, Naphthalene, Naphthaleneacetamide, α-naphthaleneacetic acid, Naphthalic anhydride, Naphthalophos, 1-naphthol, Naphthoxyacetic acid, Naphthylacetic acid, Naphthylindan-1,3-diones, Naphthyloxyacetic acid, Naproanilide, Napropamide, Napropamide-M, Naptalam, Natamycin, NB POS, neburea, nebulon, nendrin, neonicotine, nichlorphos, niclofen, niclosamide, nicobifen, two fluproles, nicosulfuron, nicotine, nifluridide, nikkomycins, ningunamycin, ningunamycin, NIP, nipiraclofen, nipiralofen, nitenpyram, nithiazine, nitralin, nitrapyrin, nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene, nitrothal-isopropyl,NNM, noborumid, nonanol, norborumid, norea, norflurazon, nornicotine, norlon, novaluron, noviflumuron, NPA, nuarimol, nuranone, OCH, octachlorodipropyl ether, octhilinone, 2-(octylthio)ethanol, o-dichlorobenzene, ofrace, omethoate, o-phenylphenol, orbencarb, orfralure, orthobencarb, ortho-dichlorobenzene, orthonil, orthosulfamuron, oryctalure, orysastrobin, oryzalin, osthol, osthole, ostramon, obatlon, obex, oxabetrinil, oxadiargyl, oxadiazon, oxadixyl, oxamate, oxamyl, oxapyrazon , oxapyrazone, oxasulfuron, oxathiapiproline, oxaziclomepho, oxazosulfil, oxine-copper, oxine-Cu, oxolinic acid, oxpoconazole, oxycarboxin, oxydemeton-methyl, oxydeprophos, oxydisulfoton, oxyenadenine, oxyfenthiin, oxyfluorfen, oxymatrine, oxytetracycline, oxythioquinox, PAC, paclobutrazol, paichongding, parethrin, PAP, para-dichlorobenzene, parafluron, paraquat, parathion, parathion-methyl, parinol, Paris Green green), PCNB, PCP, PCP-Na, p-dichlorobenzene, PDJ, pebulate, pezinex, pefurazoate, pelargonic acid, penconazole, pencycuron, pendimethalin, penphenate, penflufen, penfluron, penoxalin, penoxsulam, pentachlorophenol, pentachlorophenyl laurate, pentanochlor,Penthiopyrad, pentomethrin, pentoxazone, perbutin, perchlordecone, perfluidone, permethrin, perthane, petoxamid, PHC, fenamacril, fenamacril-ethyl, fenaminosulf, phenazine oxide, fenetacarb, phenisofam, fencaptone, phenmedipham, phenmedipham-ethyl, fenobenzuron, fenothiol, fenothrin, fenproxide, Phenthoate, 8-phenylmercurioxyquinoline, phenylmercuric urea, phenylmercuric acetate, phenylmercuric chloride, phenylmercuric derivative of pyrocatechol, phenylmercuric nitrate, phenylmercuric salicylate, 2-phenylphenol, phorate, fosacetim, phosalone, fosamethine, fosazetim, fosazetine, foscyclotine, phosdifen, fosetyl, phosphorane, phosphorane-methy le, phosglycine, phosmet, phosnichlor, phosphamide, phosphamidon, phosphine, phosphinothricin, phosphocarb, phosphorus, fostebupirim, phostin, phoxim, phoxim-methyl, phthalide, phthalophos, phthalthrin, picarbutrazox, picaridin, picloram, picolinafen, picoxystrobin, pimaricin, pindone, pinoxaden, piperaline, piperazine , piperonyl butoxide, piperonyl cyclone, piperophos, piprotanil, piprotal, pirimetaphos, pirimicarb, piriminil, pirimioxyphos, pirimiphos-ethyl, pirimiphos-methyl, pival, pivaldione, priphenate, PMA, PMP, polybutenes, polycarbamates, polychlorcamphenes, polyethoxyquinolines, polyoxins D, polyoxins, polyoxorim, polyram, polythiaran, potassium arsenite, potassium azide, potassium cyanate, potassium ethylxanthogenate, potassium naphthenate, potassium polysulfide, potassium thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III, pretilachlor, primidophos, primisulfuron, probenazole, prochloraz,Proclonol, procyazin, procymidone, prodiamine, profenofos, profluazole, profluralin, profluthrin, profoxydim, profurite-aminium, proglinadin, prohexadione, prohydrojasmon, promacyl, promecarb, prometon, prometryn, prometryne, promurit, pronitridine, Pronamide, propachlor, propafos, propamidine, propamocarb, propanil, propafos, propaquizafop, propargite, proparthrin, propazine, propetamphos, propham, propiconazole, propizin, propineb, propisochlor, propoxur, propoxycarbazone, propyl isom, propyrisulfuron, propyzamide, proquinazid, prosrel, prosulfarin, prosulfocarb, prosulfocarb, Losulfuron, protidathion, prothiocarb, prothioconazole, prothiofos, protoate, protrifenbute, proxan, primidophos, prinachlor, psoralen, psoralene, pydanon, pyridiflumetofen, piflubumid, pymetrozine, pyracarbollide, pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, pyrafluprole, pyramat, pyrameth Strobin, pyraoxystrobin, pyrapropoyne, pyrasulfotole, pyraziflumide, pyrazolate, pyrazolinate, pyrazone, pyrazophos, pyrazosulfuron, pyrazothion, pyrazoxyfen, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyribambenz-isopropyl, pyribambenz-propyl, pyribencarb, pyribenzoxim, pyributicarb, pyriclor, pyridaben, pyridaclomethyl, pyridafol, pyridalyl, pyridaphenthion, pyridaphenthion, pyridate,Pyridinitrile, pyrifenox, pyrifluquinazon, pyriftalid, pyrimetaphos, pyrimethanil, pirimicarb, pyrimidifen, pyriminobac, pyriminostrobin, pirimiphos-ethyl, pirimiphos-meth, Chil, pyrimisulfan, pyrimitate, pyrinuron, pyriophenone, pyriprole, pyripropanol, pyriproxyfen, pyrisoxazole, pyrithiobac, pyrrolan, pyroquilon, pyroxasulfon, pyroxsulam, pyroxychlor, pyroxiflur, qincaosuan, qingkuling, kwashia, quinacetol, quinalphos, quinalphos-methyl, quinazamide, quinclorac Quinclorac, quinconazole, quinmerac, quinoclamine, quinofumelin, quinomethionate, quinonamide, quinothione, quinotrion, quinoxyfen, quinthiophos, quintozene, quintrione, quizalofop, quizalofop-P, quwenzhi, quyingding, rabenzazole, rafoxanide, R-dinicoconazole, levemid, regron, renofluthrin, renridu renriduron, rescalure, resmethrin, d-trans-resmethrin, rhodetanil, rhodojaponin-III, ribavirin, imisoxafen, rimsulfuron, rizasol, R-metalaxyl, rhodetanil, ronnel, rotenone, riania, sabadilla, saflufenacil, saijunmao, saisentong, salicylanilide, salifluofen, sanguinarine, Santonin, S-bioallethrin, Schradan, Sciriroside, Sevotyramine, Sebutylazine, Secbumetone, Sedaxane, Selamectin, Semiamitraz, Sesamex, Sesamolin, Sesone, Sethoxydim, Sevin, S-Hydroprene, Shuangjiaancaolin, Shuangjianancaolin, Siduron, Sifumijvzhi,Siglure, silafluofen, silatran, silica aerogel, silica gel, silthiofam, silthiopham, silthiophan, silvex, simazine, simeconazole, simeton, simetryn, simetryne, synthofen, S-kinoprene, hydrated lime, SMA, S-methoprene, S-metolachlor, sodium arsenite, sodium azide, sodium chlorate, sodium chloroacetate, sodium cyanide sodium, sodium fluoride, sodium fluoroacetate, sodium hexafluorosilicate, sodium naphthenate, sodium orthophenylphenoxide, sodium pentachlorophenate, sodium pentachlorophenoxide, sodium o-phenylphenoxide, sodium polysulfide, sodium silicofluoride, sodium tetraborate, sodium tetrathiocarbonate, sodium thiocyanate, solan, sofamid, spidoxamat, spinetoram, spinosad, spirobudifen, spirodiclofen, spiromesif phenanthrene, spiropydine, spirotetramat, spiroxamine, stylophos, streptomycin, strychnine, sulcatol, sulcofuron, sulcotrione, sulfurate, sulfathiadiazuron, sulfathiazuron, sulfentrazone, sulfiram, sulfuramide, sulfodiazole, sulfometuron, sulfosate, sulfosulfuron, sulfotep, sulfotepp, sulfoxaflo sulfoxaflor, sulfoxide, sulfoxime, sulfur, sulfuric acid, sulfuryl fluoride, sulglicapin, sulfosate, sulprofos, sultropene, suthiazuron, supermethrin, swep, 2,4,5-T, tartar emetic, tau-fluvalinate, tabron, tazimcal, 2,4,5-TB, 2,3,6-TBA, TBTO, TBZ, TCA, TCBA, TCMTB, TCNB, TDE, tebuconazole, tebufenozide, tebufenpyrad,Tebufloquine, tebupirimfos, tebutam, tebuthiuron, tecloftalam, tecnazene, tecolum, tedion, teflubenzuron, tefluthrin, kappa-tefluthrin, d-teflumethrin, tefuryltrione, tembotrione, temefos, temephos, tepa, TEPP, tepraloxydim, teproloxydim, teralethrin, terbacil, terbucarb, terbuchlor, terbuconazole, terbufos, terbumeton, terbuthylazine, terbutol, terbutrazol, terbutryn, terbutry ne), terraclor, terramycin, terramycin, tetcyclacis, tetflupyrolimet, tetrachlorantraniliprole, tetrachloroethane, tetrachlorvinphos, tetraconazole, tetradifon, tetradisulf, tetrafluron, tetramethrin, tetramethylfluthrin, tetramine, tetranactin, tetraniliprole, tetrapion, tetrasulf, thallium sulfate, thallous sulfate sulfate), thenylchlor, theta-cypermethrin, thiabendazole, thiacloprid, thiadiazine, thiadifluor, thiamethoxam, thiamethuron, thiapronil, thiazafluron, thiazfluron, thiazone, thiazopyr, cyclophos, thithiofen, thidiadimine, thidiazuron, thiencarbazone, thifensulfuron, thifluzamide, thimerosal, thi Thimet, thiobencarb, thiocarboxime, thiochlorfenphim, thiocyanatodinitrobenzenes, thiocyclam, thiodan, thiodemeton, thiodiazole-copper, thiodicarb, thiophanocarb, thiofanox, thiofluoximate, thiohempa, thiomersal, thiometon, thionazine, thiophanate, thiophanate-ethyl,Thiophanate-methyl, thiophos, thioquinox, thiosemicarbazide, thiosultap, thiotepa, thioxamyl, thiram, thuringiensin, thiabendazole, tiadinil, thiaphenacyl, tiaojiean, TIBA, tifatol, tigolaner, thiocarbazil, thioclorim, thioantraniliprole, thioxazaphen, tioximide, TMTD, tirpate ), tolclofos-methyl, tolfenpyrad, tolnifanide, tolprocarb, tolpyralate, tolyfluanid, tolylfluanid, tolylmercuric acetate, tomalin, topramezone, toxaphene, 2,4,5-TP, 2,3,3-TPA, TPN, tralkoxydim, tralocitrin, tralomethrin, tralopyril, d-trans-allethrin, d-trans-resmethrin, transfluthrin, transpermethrin, toretamine, tri- Alate, triacontanol, triadimefon, triadimenol, triallate, triafamone, triazamate, triazbutyl, triaziflam, triazofenamide, triazophos, triazothion, triazoxide, tribasic copper chloride, tribasic copper sulfate, tribenuron, tribufos, tributyltin oxide, tricamba, triclamide, triclophenidin, triclopyr, trichlorfon, trichlormethaphos-3, trichloronat, trichloronate, trichlorotrinitro Benzene, trichlorfon, triclopyr, triclopyricarb, tricresol, tricyclazole, tricyclohexyltin hydroxide, tridemorph, tridiphan, trietazine, triphenmorph, triphenofos, trifloxystrobin, trifloxysulfuron, trifludimoxazine, trifluenfuronate, triflumezopyrim, triflumizole, triflumuron, trifluralin, triflusulfuron, trifop, trifopsim, triforine, trihydroxytriazine, 2,3,5-tri-iodobenzoic acid,2,3,5-triiodobenzoic acid, trimedlure, trimeflor, trimethacarb, trimeturon, trimorfamid, trimorphamide, trinexapac, triphenyltin, triplen, tripropindan, triptolide, tripyrasulfone, tritac, trithialan, triticonazole, tritosulfuron, tuoyelin, tric tyclopyrazoflor, umifoxolaner, uniconazole, uniconazole-P, urvacid, uredepa, valerate, validamycin, validamycin A, valifenalate, baron, vamidothion, vanguard, vaniliprole, verbutin, vernolate, vinclozolin, viniconazole, vitamin D3, warfarin, xiaochongliulin, xinjunan, xiwojunan an), xiwojunzhi, XMC, xylachlor, xylenols, xyloxazine, xylylcarb, xymiazole, yishijing, zaliramide, zeatin, zengxiaoan, zengxiaolin, zeta-cypermethrin, zinc naphthenate, zinc phosphide, zinc thiazole, zinc thiozole, zinc trichlorophenate, zinc trichlorophenoxide, zineb, ziram, zolaprophos, zoocoumarin marin), zoxamide, zuoanjunzhi, zuocaoan, zuojunzhi, zuomihuanglong, 1-MCP, 1-methylcyclopropene, 1-naphthol, 1,2-dichloropropane, 1,3-D, 1,3-dichloropropene, 2iP, 2M-4C, 2M-4CM, 2-methoxymercury chloride, 2-(octylthio)ethanol, 2-phenylphenol, 2,2,3-TPA, 2,3,5-triiodobenzoic acid, 2,3,6-TBA,2,4-D, 2,4-DB, 2,4-DEB, 2,4-DEP, 2,4-DES, 2,4-DP, 2,4-MCPA, 2,4-MCPB, 2,4,5-T, 2,4,5-TB, 2,4,5-TP, 2,5-dichlorobenzoic acid, (3-ethoxypropyl)mercury bromide, 3,4-DA, 3,4-DB, , 3,4-DP, 3,6-dichloropicolinic acid, 4-aminopyridine, 4-CPA, 4-CPB, 4-CPP, 4-hydroxyphenethyl alcohol, 8-hydroxyquinoline sulfate, 8-phenylmercuryoxyquinoline, and 24-epibrassinolide.

[0018] As used in this disclosure, each of the above is an active ingredient. For further information, see the substances listed in the "Compendium of Pesticide Common Names" at https: / / pesticidecompendium.bcpc.org.

[0019] Particularly preferred choices of active ingredients are chlorantraniliprole, cyantraniliprole, hexaflumuron, methomyl, methoxyfenozide, noviflumuron, oxamyl, spinetoram, spinosad, sulfoxaflor, and triflumezopyrim (hereinafter "AIGA-2").

[0020] In addition, another particularly preferred selection of active ingredients is acequinocyl, acetamiprid, acetoprole, avermectin, azinphos-methyl, bifenazate, bifenthrin, carbaryl, carbofuran, chlorfenapyr, chlorfluazuron, chromafenozide, clothianidin, cyfluthrin, cypermethrin, deltamethrin, diafenthiuron, emamectin benzoate, endosulfan, esfenvalerate, ethiprole. The following are listed in the AIGA-3 list: fluacrypyrim, etoxazole, fipronil, flonicamid, fluacrypyrim, gamma-cyhalothrin, halofenozide, indoxacarb, lambda-cyhalothrin, lufenuron, malathion, methomyl, novaluron, permethrin, pyridalyl, pyrimidifen, spirodiclofen, tebufenozide, thiacloprid, thiamethoxam, thiodicarb, tolfenpyrad, and zeta-cypermethrin (hereinafter referred to as "AIGA-3").

[0021] Seed treatments are used alone or in combination to combat or prevent many pests, diseases, nutritional deficiencies, and to promote plant growth. These seed treatments may include fungicides, insecticides, inoculants, plant growth regulators, fertilizers, and fertilizer enhancers. Currently, the following fungicides are available: (R)-flutriafol, (R)-hexaconazole, (S)-flutriafol, (S)-hexaconazole, 10,10'-oxybisphenoxarsine, 2-(thiocyanomethylthio)benzothiazole, 2,2-dibromo-3-nitrilopropionamide, 2,4,5-trichlorophenol, 2,4-dimethylphenol, 2,5-dichlorobenzoic acid methyl ester, 2,6-dichloro-N-((4-(trifluoromethyl)phenyl)methyl-benzamide ... nzamide, 24-epibrassinolide, 2-aliphenol, 2-aminobutane, 2-methoxyethylmercuric acetate, 2-methoxyethylmercuric chloride, 2-phenylphenol, 8-hydroxyquinoline, acibenzolar-S-methyl, aldimorph, amethoctrazine, amisulbrom, ammonium acetate, ammonium carbonate, ampropylphos, anilazine, anthracene oil, asomate, azaconazole, adityram, azoxystrobin, barium polysulfide, benalaxyl, Benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benthiavalicarb isopropyl, benzalkonium chloride, benzamacryl, benzamacryl isobutyl, benzamorph, benzoic acid, benzovindiflupyr, bethoxadin, binapacryl, biphenyl, bis(methylmercury) sulfate, bismerthiazole, bis-trichloromethylsulfone, bitertanol, bithionol, bixafen, Bordeaux mixture, boric acid, boscalid, bromine Conazole, bronopol, bupirimate, buthiobate, calcium carbonate, calcium chloride, calcium cyanamide, calcium hydroxide, calcium phosphate, captafol, captan, carbamorph, carbendazim, carboxin, carpropamid, quinomethionate, clobenziazone, chloraniformethane, chloranil, chlordecone, chlorphenazole, chloroneb, chlorothalonil, chloroxylenol, chlorquinox, clozolinate, cis-propiconazole,Climbazole, copper(1) oxide, copper abietic acid, copper bis(3-phenylsalicylate), copper(II) acetate, copper(II) carbonate, copper(II) chloride, copper(II) hydroxide, copper naphthenate, copper oxychloride, copper sulfate, COS-OGA, cumoxystrobin, cumoxystrobin, cufuraneb, cuprobam, cyazofamid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, cyprofuram, dazomet, DD, debacarb, decafentin, dehydroacetic acid, diammonium ethylenebis(dithiocarbame) ate), dibromochloropropane, diclobenchiazox, dichlorofluanid, dicloron, dichlorophen, diclobutrazol, diclocymet, diclomedine, dicloran, didecyldimethylammonium chloride, diethofencarb, difenoconazole, difenzoquat, difenzoquat methylsulfate, diflumetrim, dimethachlon, dimethirimol, dimethomorph, dimethyldisulfide, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, dinokton, dinopenton, dinosulfone , diphenylamine, dipimethitron, dipyrithione, disodium octaborate tetrahydrate, disodium phosphonate, ditalimphos, dithianone, DNOC, dodemorph, dodemorph acetate, dodine, drazoxolone, edifenphos, enoxastrobin, epoxiconazole, etaconazole, ethem, ethaboxam, ethirimol, ethoxyquin, ethylenebisisothiocyanate sulfide, ethirisin, ethylmercuric bromide, etridiazole, famoxadone, fenamidone, fenaminosulf, fenaminstrobin, fenapanil , fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpicoxamide, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin chloride, fentin hydroxide, ferbam, florylpicoxamide, fluazinam, fluveneteram, flubenzimine, fludioxonil, flufenoxystrobin, flumorph, flupicolide, fluopimomide, furopyram, fluoroimide, fluotrimazole, fluoxapiproline,Fluoxastrobin, Fluquinconazole, Flusilazole, Flusulfamide, Flutianil, Flutolanil, Flutriafol, Fluxapyroxad, Folpet, Formaldehyde, Fosetyl, Fosetyl-aluminum, Fuberidazole, Furalaxyl, Furalaxyl-M, Furamethpyr, Fluconazole, Fluconazole-cis, Furfural, Flumesilox, Furyloxyfen, Gliotoxin, Glutaraldehyde, Gliodin, Griseofulvin, Guazatine, Halacrinate, Hexachlorobenzene, Hexachlorophene , Hexaconazole, Hexylthiophos, Huanjunzuo, Hydrogen peroxide, Hymexazole, Imazalil, Imibenconazole, Iminoctadine, Iminoctadine triacetate, Iminoctadine tris(albesilate), Inedin, Ipconazole, Ipfentrifluconazole, Ipflufenoquin, Iprobenfos, Iprodione, Iprovalicarb, Isobutyric acid, Isofetamide, Isoflucipram, Isopamphos, Isoprothiolane, Isopyrazam, Isotianil, Izopamphos, Kresoxim-methyl, Lime sulfur Combination drugs, mancopper, mancozeb, mandestrobin, mandipropamide, maneb, mebenil, mecarbinzide, mefentrifluconazole, mepanipyrim, mepronil, meptyldinocap, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam-potassium, metam-sodium, metazoxolone, meconazole, metasulfocarb, metofloxam, methylisothiocyanate, methylarsenic sulfide, methylenebisthiocyanate, metiram, metominostrobin, metrafenone, methsulfovax, methyltetraprole, muco Chloric anhydride, myclobutanil, myclozolin, N-(3-chloro-2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)acetamide, nabam, nickel bis(dimethyldithiocarbamate), niclosamide, nitrotar isopropyl, nuarimol, octhilinone, ofrace, orysastrobin, oxadixyl, oxathiapiproline, oxazosulfil, oxine-copper, oxypoconazole fumarate, oxycarboxin, paclobutrazol, paraffin oil (C11-C25) (4a),Paraffin oil (C11-C30) (4c), Paraffin oil (C15-C30) (4b), Parinol, Penconazole, Pencycuron, Penflufen, Pentachlorophenol, Penthiopyrad, Peroxyacetic acid, Phenylmercuric acetate, Phenylmercuric chloride, Phenylmercuric nitrate, Phosdifen, Phthalide, Picarbtrazox, Picoxystrobin, Piperalin, Potassium bicarbonate, Potassium iodide, Potassium phosphonate, Potassium thiocyanate, Probenazole, Prochloraz, Procymidone, Propamidine, Propamocarb, Propamine ... Pamocarb hydrochloride, Propiconazole, Propineb, Propionic acid, Proquinazid, Prothiocarb, Prothioconazole, Pydiflumetofen, Pyracarbollide, Pyraclostrobin, Pyrametstrobin, Pyraoxystrobin, Pyrapropoin, Pyraziflumide, Pyrazophos, Pyribencarb, Pyridaclomethyl, Pyridinitrile, Pyrifenox, Pyrimethanil, Pyrimorph, Pyriophenone, Pyrosoxazole, Pyroquilon, Quinovumelin, Quinoxyfen, Quintozene, Saisenton, Se Daxane, Silthiofam, Simeconazole, Sodium arsenite, Sodium carbonate, Sodium bicarbonate, Sodium hypochlorite, Sodium tetraborate pentahydrate, Spiropydione, Spiroxamine, Sulfuryl fluoride, Sulfur, Tebuconazole, Tebufloquine, Tecloftalam, Tecnazene, Tetraconazole, Thiabendazole, Thithiofen, Thifluzamide, Thiomersal, Thiophanate, Thiophanate-methyl, Thioquinox, Thiram, Tiadinil, Tolclofos-methyl, Tolfenpyrad, Tolprocarb, Tri Fluranid, trans-propiconazole, triadimefon, triadimenol, triamiphos, triazoxide, tributyltin oxide, triclamide, triclopyricarb, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, trioxymethylene, triticonazole, urea, valifenalate, vinclozolin, zaliramide, zinc borate, zinc oxide, zineb, ziram, and zoxamide may be used in conjunction with polymorphic forms A and B, this group of fungicides being hereinafter referred to as "FGK-1."

[0022] Another preferred group of fungicides for use with polymorphic forms A and B of Compound 1 (disclosed herein) in seed treatments are azoxystrobin, benomyl, benzovindiflupyr, bixafen, carbendazim, chlorothalonil, cymoxanil, cyproconazole, diclobenthiazox, difenoconazole, ethaboxam, famoxadone, fenbuconazole, fluopyram, fluindapyr, fludioxonil, folpet, inpirfluxam, ipconazole, ipsulfame ... Fentrifluconazole, isoflucipram, mancozeb, maneb, mefentrifluconazole, meptyldinocap, metalaxyl, and metalaxyl-M (mefenoxam), oxathiapiproline, penflufen, picoxystrobin, prochloraz, proquinazid, prothioconazole, pyraclostrobin, quinoxyfen, sedaxane, thiabendazole, thiram, tricyclazole, and trifloxystrobin; this group of fungicides is hereafter referred to as "FGK-2".

[0023] The following two fungicide molecules are also preferred for use in conjunction with polymorphic forms A and B of Compound 1 (disclosed herein): [ka] (2S,3S)-3-(o-tolyl)butan-2-yl (4-methoxy-3-(propionyloxy)picolinoyl)-L-alaninate (hereinafter "FGK-3"), and [ka] 4-((6-(2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4,5-dihydro-1H-1,2,4-triazol-1-yl)propyl)pyridin-3-yl)oxy)benzonitrile (hereinafter referred to as "FGK-4").

[0024] FGK-3 is described in WO2019173665 as compound number 278, and FGK-4 is described in Example 2 of WO2016187201.

[0025] The term "area" refers to a habitat, breeding ground, plant, seed, soil, material, or environment in which a pest is growing, is capable of growing, or is capable of moving about. For example, an area can be, but is not limited to, the following: an area in which crops, trees, fruits, grains, forage seeds, vines, lawns, and / or ornamental plants are growing; an area in which livestock live; an interior or exterior surface of a building (e.g., where grain is stored); construction materials used in a building (e.g., impregnated wood); and the soil around a building.

[0026] The term "MoA substance" means an active ingredient that has a mechanism of action ("MoA") as outlined in the IRAC MoA Classification v.10.3 available at irac-online.org.

[0027] The phrase "biocidally effective amount" refers to the amount of biocide required to achieve an observable effect on a pest (e.g., necrosis, death, suppression, prevention, elimination, destruction, or otherwise reducing the occurrence and / or activity of a pest in an area). This effect may occur when a pest population is eliminated from an area, a pest is incapacitated in or around an area, and / or a pest is eradicated in or around an area. Of course, a combination of these effects may occur. In general, the pest population, activity, or both are desirably reduced by more than 50 percent, preferably by more than 90 percent, and most preferably by more than 99 percent. Generally, a biocidal effective amount for agricultural purposes is from about 0.0001 grams per hectare to about 5000 grams per hectare, preferably from about 0.0001 grams per hectare to about 500 grams per hectare, and even more preferably from about 0.0001 grams per hectare to about 50 grams per hectare. Summary of the Invention

[0028] In one aspect, the present disclosure provides a compound of formula [ka] The present invention provides one or more crystalline forms of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide represented by the formula:

[0029] In one embodiment, one or more crystalline forms of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide.

[0030] In another embodiment, the one or more crystalline forms of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide are anhydrous and solvent-free crystalline polymorphic forms.

[0031] In another embodiment, the one or more crystalline forms are crystalline polymorphic forms A and B of Compound 1 (referred to herein individually as polymorphic form A and polymorphic form B).

[0032] In a further embodiment, the crystalline polymorphic form A of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 20.3±0.2. In a further embodiment, the crystalline polymorphic form A of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 17.4±0.2 and 20.3±0.2. In a further embodiment, the crystalline polymorphic form A of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 17.4±0.2, 19.9±0.2, and 20.3±0.2. In a further embodiment, the crystalline polymorphic form A of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 17.4±0.2, 19.9±0.2, and 20.3±0.2. In a further embodiment, the crystalline polymorphic Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 17.4±0.2, 18.2±0.2, 19.9±0.2, and 20.3±0.2. In a further embodiment, the crystalline polymorphic Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.7, 19.9±0.2, and 20.3±0.2. In a further embodiment, the crystalline polymorphic form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.7, 19.9±0.2, and 20.3±0.2. In a further embodiment, the crystalline polymorphic form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.7, 19.9±0.2, and 20.3±0.2. In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.7, 18.9±0.2, 19.9±0.2, and 20.3±0.2.In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.0±0.2, 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.7, 18.9±0.2, 19.9±0.2, and 20.3±0.2. In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.0±0.2, 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 17.9±0.2, 18.2±0.2, 18.7±0.7, 18.9±0.2, 19.9±0.2, and 20.3±0.2.

[0033] In a further embodiment, the crystalline polymorphic form A of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 20.3±0.2. In a further embodiment, the crystalline polymorphic form A of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 20.3±0.2 and 24.7±0.2. In a further embodiment, the crystalline polymorphic form A of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 17.4±0.2, 20.3±0.2, and 24.7±0.2. In a further embodiment, the crystalline polymorphic form A of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 17.4±0.2, 20.3±0.2, 24.7±0.2, and 26.6±0.2. In a further embodiment, the crystalline polymorphic Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 17.4±0.2, 19.9±0.2, 20.3±0.2, 24.7±0.2, and 26.6±0.2. In a further embodiment, the crystalline polymorphic Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 17.4±0.2, 19.9±0.2, 20.3±0.2, 24.7±0.2, and 26.6±0.2. In a further embodiment, the crystalline polymorphic form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 17.4±0.2, 18.2±0.2, 19.9±0.2, 20.3±0.2, 24.7±0.2, and 26.6±0.2. In a further embodiment, the crystalline polymorphic form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 17.4±0.2, 18.2±0.2, 19.9±0.2, 20.3±0.2, 24.7±0.2, 26.6±0.2, and 28.1±0.2. In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 17.4±0.2, 18.2±0.2, 19.9±0.2, 20.3±0.2, 24.7±0.2, 25.3±0.2, 26.6±0.2, and 28.1±0.2.In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.2, 19.9±0.2, 20.3±0.2, 24.7±0.2, 25.3±0.2, 26.6±0.2, and 28.1±0.2. In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.2, 19.9±0.2, 20.3±0.2, 24.7±0.2, 25.3±0.2, 26.6±0.2, and 28.1±0.2. In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.2, 19.9±0.2, 20.3±0.2, 24.7±0.2, 25.3±0.2, 26.6±0.2, and 28.1±0.2.

[0034] In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.2, 19.9±0.2, 20.3±0.2, 21.0±0.2, 24.7±0.2, 25.3±0.2, 26.6±0.2, and 28.1±0.2. In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.2, 19.9±0.2, 20.3±0.2, 21.0±0.2, 24.7±0.2, 25.3±0.2, 26.6±0.2, 28.1±0.2, and 28.6±0.2. In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.2, 18.9±0.2, 19.9±0.2, 20.3±0.2, 21.0±0.2, 24.7±0.2, 25.3±0.2, 26.6±0.2, 28.1±0.2, and 28.6±0.2. In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.2, 18.9±0.2, 19.9±0.2, 20.3±0.2, 21.0±0.2, 23.9±0.2, 24.7±0.2, 25.3±0.2, 26.6±0.2, 28.1±0.2, and 28.6±0.2. In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.0±0.2, 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.2, 18.9±0.2, 19.9±0.2, 20.3±0.2, 21.0±0.2, 23.9±0.2, 24.7±0.2, 25.3±0.2, 26.6±0.2, 28.1±0.2, and 28.6±0.2.In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.0±0.2, 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 17.9±0.2, 18.2±0.2, 18.7±0.2, 18.9±0.2, 19.9±0.2, 20.3±0.2, 21.0±0.2, 23.9±0.2, 24.7±0.2, 25.3±0.2, 26.6±0.2, 28.1±0.2, and 28.6±0.2.

[0035] In a further embodiment, the crystalline polymorph Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) essentially identical to those shown in FIG. 1 or FIG.

[0036] In a further embodiment, the crystalline polymorph Form A of Compound 1 has a Differential Scanning Calorimetry (DSC) thermogram comprising an endothermic peak having a peak temperature at about 101.09° C. and a heat of fusion=75.707 J / g or substantially identical to FIG. 4.

[0037] In a further embodiment, the crystalline polymorph Form A of Compound 1 has a molecular weight of about 255 cm -1 , approx. 441cm -1 , approx. 539cm -1 , approx. 778cm -1 , approx. 921cm -1 , approx. 991cm -1 , approx. 1048cm -1 , approx. 1123cm -1 , approx. 1191cm -1 , approx. 1526cm -1 , approx. 1569cm -1 , approx. 1588cm -1 , approx. 1701cm -1 , approx. 2949cm -1 , and about 3053 cm -1 In a further embodiment, the crystalline polymorph Form A of Compound 1 has a low frequency Raman spectrum including peaks at essentially the same wavenumbers as shown in FIG.

[0038] In some embodiments relating to any of the powder X-ray diffraction patterns of crystalline polymorph Form A described herein, the crystalline polymorph Form A has a (DSC) thermogram that includes an endothermic peak having a peak temperature at about 101.09 °C, and / or a peak temperature at about 255 cm -1 , approx. 441cm -1 , approx. 539cm -1 , approx. 778cm -1 , approx. 921cm -1 , approx. 991cm -1 , approx. 1048cm -1 , approx. 1123cm -1 , approx. 1191cm -1 , approx. 1526cm -1 , approx. 1569cm -1 , approx. 1588cm -1 , approx. 1701cm -1 , approx. 2949cm -1 , and about 3053 cm -1 In some embodiments related to any of the X-ray powder diffraction patterns of crystalline polymorph Form A described herein, crystalline polymorph Form A further comprises a DSC thermogram substantially identical to that in Figure 4, and / or a low frequency Raman spectrum comprising peaks at essentially the same wavenumbers as those shown in Figure 6.

[0039] In a further embodiment, the crystalline polymorphic form B of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 15.4±0.2. In a further embodiment, the crystalline polymorphic form B of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2 and 15.4±0.2. In a further embodiment, the crystalline polymorphic form B of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, and 20.2±0.2. In a further embodiment, the crystalline polymorphic form B of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, and 20.2±0.2. In a further embodiment, the crystalline polymorphic form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 17.5±0.2, and 20.2±0.2. In a further embodiment, the crystalline polymorphic form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 17.5±0.2, 18.4±0.2, and 20.2±0.2. In a further embodiment, the crystalline polymorphic form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.5±0.2, 18.4±0.2, and 20.2±0.2. In a further embodiment, the crystalline polymorphic form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.5±0.2, 18.4±0.2, and 20.2±0.2. In a further embodiment, the crystalline polymorph Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.3±0.2, 17.5±0.2, 18.4±0.2, and 20.2±0.2.In a further embodiment, the crystalline polymorphic Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.3±0.2, 17.5±0.2, 18.4±0.2, 19.8±0.2, and 20.2±0.2.

[0040] In a further embodiment, the crystalline polymorphic form B of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 15.4±0.2. In a further embodiment, the crystalline polymorphic form B of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2 and 15.4±0.2. In a further embodiment, the crystalline polymorphic form B of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, and 20.2±0.2. In a further embodiment, the crystalline polymorphic form B of compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 20.2±0.2, and 24.1±0.2. In a further embodiment, the crystalline polymorphic Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 20.2±0.2, and 24.1±0.2. In a further embodiment, the crystalline polymorphic Form A of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 20.2±0.2, 24.1±0.2, and 31.1±0.2. In a further embodiment, the crystalline polymorphic form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 20.2±0.2, 24.1±0.2, 26.1±0.2, and 31.1±0.2. In a further embodiment, the crystalline polymorphic form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 17.5±0.2, 20.2±0.2, 24.1±0.2, 26.1±0.2, and 31.1±0.2. In a further embodiment, the crystalline polymorph Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 17.5±0.2, 20.2±0.2, 24.1±0.2, 26.1±0.2, 26.6±0.2, and 31.1±0.2.In a further embodiment, the crystalline polymorph Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 17.5±0.2, 20.2±0.2, 24.1±0.2, 26.1±0.2, 26.6±0.2, 27.0±0.2, and 31.1±0.2. In a further embodiment, the crystalline polymorphic Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 17.5±0.2, 20.2±0.2, 24.1±0.2, 26.1±0.2, 26.6±0.2, 27.0±0.2, 31.1±0.2, and 33.4±0.2. In a further embodiment, the crystalline polymorph Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 17.5±0.2, 18.5±0.2, 20.2±0.2, 24.1±0.2, 26.1±0.2, 26.6±0.2, 27.0±0.2, 31.1±0.2, and 33.4±0.2. In a further embodiment, the crystalline polymorph Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 17.5±0.2, 18.5±0.2, 20.2±0.2, 21.8±0.2, 24.1±0.2, 26.1±0.2, 26.6±0.2, 27.0±0.2, 31.1±0.2, and 33.4±0.2. In a further embodiment, the crystalline polymorphic Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.5±0.2, 18.5±0.2, 20.2±0.2, 21.8±0.2, 24.1±0.2, 26.1±0.2, 26.6±0.2, 27.0±0.2, 31.1±0.2, and 33.4±0.2.In a further embodiment, the crystalline polymorphic Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.5±0.2, 18.5±0.2, 20.2±0.2, 21.8±0.2, 24.1±0.2, 25.8±0.2, 26.1±0.2, 26.6±0.2, 27.0±0.2, 31.1±0.2, and 33.4±0.2.

[0041] In a further embodiment, the crystalline polymorphic Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.5±0.2, 18.5±0.2, 20.2±0.2, 21.8±0.2, 24.1±0.2, 25.8±0.2, 26.1±0.2, 26.6±0.2, 27.0±0.2, 31.1±0.2, and 33.4±0.2. In a further embodiment, the crystalline polymorphic Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.5±0.2, 18.5±0.2, 20.2±0.2, 20.9±0.2, 21.8±0.2, 24.1±0.2, 25.8±0.2, 26.1±0.2, 26.6±0.2, 27.0±0.2, 31.1±0.2, and 33.4±0.2. In a further embodiment, the crystalline polymorphic Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.5±0.2, 18.5±0.2, 20.2±0.2, 20.9±0.2, 21.8±0.2, 22.9±0.2, 24.1±0.2, 25.8±0.2, 26.1±0.2, 26.6±0.2, 27.0±0.2, 31.1±0.2, and 33.4±0.2. In a further embodiment, the crystalline polymorphic Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.3±0.2, 17.5±0.2, 18.5±0.2, 20.2±0.2, 20.9±0.2, 21.8±0.2, 22.9±0.2, 24.1±0.2, 25.8±0.2, 26.1±0.2, 26.6±0.2, 27.0±0.2, 31.1±0.2, and 33.4±0.2.In a further embodiment, the crystalline polymorphic Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.3±0.2, 17.5±0.2, 18.5±0.2, 19.8±0.2, 20.2±0.2, 20.9±0.2, 21.8±0.2, 22.9±0.2, 24.1±0.2, 25.8±0.2, 26.1±0.2, 26.6±0.2, 27.0±0.2, 31.1±0.2, and 33.4±0.2.

[0042] In a further embodiment, the crystalline polymorph Form B of Compound 1 has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) essentially identical to those shown in FIG.

[0043] In a further embodiment, the crystalline polymorphic Form B of Compound 1 has a Differential Scanning Calorimetry (DSC) thermogram comprising an endothermic peak having a peak temperature at about 105.24° C. and a heat of fusion=92.879 J / g or substantially identical to FIG. 5.

[0044] In a further embodiment, the crystalline polymorphic form B of Compound 1 has a molecular weight of about 266 cm -1 , approx. 446cm -1 , approx. 546cm -1 , approx. 763cm -1 , approx. 987cm -1 , approx. 1044cm -1 , approx. 1137cm -1 , approx. 1187cm -1 , and about 1308 cm -1 , about 1518cm -1 , approx. 1573cm -1 , approx. 1592cm -1 , approx. 1673cm -1 , approx. 2919cm -1 , and about 2937 cm -1 7. In a further embodiment, the crystalline polymorphic Form B of Compound 1 has a low frequency Raman spectrum including one or more peaks at wavenumbers essentially the same as those shown in FIG.

[0045] In some embodiments relating to any of the powder X-ray diffraction patterns of crystalline polymorph Form B described herein, the crystalline polymorph Form B has a (DSC) thermogram that includes an endothermic peak having a peak temperature at about 105.24° C. and / or a peak temperature at about 266 cm -1 , approx. 446cm -1 , approx. 546cm -1 , approx. 763cm -1 , approx. 987cm -1 , approx. 1044cm -1 , approx. 1137cm -1 , approx. 1187cm -1 , and about 1308 cm -1 , about 1518cm -1 , approx. 1573cm -1 , approx. 1592cm -1 , approx. 1673cm -1 , approx. 2919cm -1 , and about 2937 cm -1 In some embodiments related to any of the powder X-ray diffraction patterns of crystalline polymorph Form B described herein, crystalline polymorph Form B further comprises a DSC thermogram substantially identical to that in FIG. 5, and / or a low frequency Raman spectrum comprising peaks at essentially the same wavenumbers as those shown in FIG.

[0046] The disclosure further provides compositions comprising one or more of polymorphic Forms A and B of Compound 1.

[0047] In another aspect, the disclosure provides a method of controlling pests comprising applying to an area a biocidally effective amount of a composition comprising one or more of the polymorphic forms A and B of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide described herein or one or more of the polymorphic forms A and B of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide described herein.

[0048] In some embodiments of this aspect, the pest is selected from the group consisting of ants, aphids, bedbugs, beetles, silverfish, caterpillars, cockroaches, crickets, earwigs, fleas, flies, grasshoppers, grubs, leafhoppers, lice, locusts, maggots, mites, nematodes, planthoppers, psyllids, sawflies, scale insects, silverfish, slugs, snails, spiders, springtails, stink bugs, symphytes, termites, thrips, mites, digger wasps, whiteflies, and wireworms. In some embodiments, the pest is a sap-feeding or chewing pest.

[0049] In some embodiments, the pest is from the order Hemiptera, Thysanoptera, Lepidoptera, and the like.

[0050] In some embodiments of this aspect, the pest is a member of the genus Adelges spp., Aulacaspis spp., Aphrophora spp., Aphis spp., Bemisia spp., Ceroplastes spp., Chionaspis spp., Chrysomphalus spp., Coccus spp., Empoasca spp., Euschistus spp., Lepidosaphes spp., Lagynotomus spp., Lygus spp., Macrosiphum spp., Nephotichis spp., or any of the genus Macrosiphum spp. tettix spp., Nezara spp., Nilaparvata spp., Philaenus spp., Phytocoris spp., Piezodorus spp., Planococcus spp., Pseudococcus spp., Rhopalosiphum spp., Saissetia spp., Therioaphis spp., Toumeyella spp., Toxoptera spp., Trialeurodes spp., Triatoma spp., and Unaspis spp.

[0051] In some embodiments of this aspect, the pest is Acrosternum hilare, Acyrthosiphon pisum, Aleyrodes proletella, Aleurodicus dispersus, Aleurothrixus floccosus, Amrasca biguttula biguttula, Aonidiella aurantii, Aphis fabae, Aphis gossypii, Aphis glycines, Aphis pomi, Aulacorthum solani ... solani, Bactericera cockerelli, Bagrada hilaris, Bemisia argentifolii, Bemisia tabaci, Blissus leucopterus, Boisea trivittata, Brachycorynella asparagi, Brevennia rehi, Brevicoryne brassicae, Cacopsylla pyri, Cacopsylla pyricola, Calocoris norvegicus, Ceroplastes rubens rubens, Cimex hemipterus, Cimex lectularius, Coccus pseudomagnoliarum, Dagbertus fasciatus, Dichelopsfurcatus, Diuraphis noxia, Diaphorina citri, Dysaphis plantaginea, Dysdercus suturellus, Edessa meditabunda, Empoasca vitis, Eriosoma lanigerum, Erythroneura elegantula, Eurygaster maura, Euschistus conspersus, Euschistus heros, Euschistus servus, Halyomorpha halys, Helopeltis antonii, Hyalopterus pruni, Helopeltis theivora, Icerya purchasi, Idioscopus nitidulus, Jacobiasca formosana, Laodelphax striatellus, Lecanium corni, Leptocorisa oratorius, Leptocorisa varicornis, Lygus hesperus hesperus, Maconellicoccus hirsutus, Macrosiphum euphorbiae, Macrosiphum granarium, Macrosiphum rosae, Macrosteles quadrilineatusquadrilineatus, Mahanarva frimbiolata, Megacopta cribraria, Metopolophium dirhodum, Mictis longicornis, Myzus persicae, Nasonovia ribisnigri, Nephotettix cinctipes, Neurocolpus longirostris, Nezara viridula, Nilaparvata lugens, Paracoccus marginatus marginatus, Paratrioza cockerelli, Parlatoria pergandii, Parlatoria ziziphi, Peregrinus maidis, Phylloxera vitifoliae, Physokermes piceae, Phytocoris californicus, Phytocoris relativus, Piezodorus guildinii, Planococcus. Planococcus citri, Planococcus ficus, Poecilocapsus lineatus, Psallus vaccinicola, Pseudacysta perseae, Pseudococcus brevipes, Quadraspidiotus perniciosus, Rhopalosiphum maydismaidis, Rhopalosiphum padi, Saissetia oleae, Scaptocoris castanea, Schizaphis graminum, Sitobion avenae, Sogatella furcifera, Trialeurodes vaporariorum, Trialeurodes abutiloneus, Unaspis yanonensis, and Zulia entrriana.

[0052] In some embodiments of this aspect, the pest is selected from the group consisting of Caliothrips spp., Frankliniella spp., Scirtothrips spp., and Thrips spp.

[0053] In some embodiments of this aspect, the pest is selected from the group consisting of Caliothrips phaseoli, Frankliniella bispinosa, Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella tritici, Frankliniella williamsi, Heliothrips haemorrhoidalis, Rhipiphorothrips cruentatus, Scirtothrips citri, Scirtothrips dorsalis, and the like. dorsalis, Taeniothrips rhopalantennalis, Thrips hawaiiensis, Thrips nigropilosus, Thrips orientalis, Thrips palmi, and Thrips tabaci.

[0054] In some embodiments of this aspect, the pest is a member of the genus Adoxophyes spp., Agrotis spp., Argyrotaenia spp., Cacoecia spp., Caloptilia spp., Chilo spp., Chrysodeixis spp., Colias spp., Crambus spp., Diaphania spp., Diatraea spp., Earias spp., Ephestia spp., Epimecis spp., Feltia spp., Gortyna spp., Helicobacter ... The species is selected from the group consisting of Helicoverpa species, Heliothis species, Indarbela species, Lithocolletis species, Loxagrotis species, Malacosoma species, Nemapogon species, Peridroma species, Phyllonorycter species, Pseudaletia species, Plutella species, Sesamia species, Spodoptera species, Synanthedon species, and Yponomeuta species.

[0055] In some embodiments of this aspect, the pest is Achaea janata, Adoxophyes orana, Agrotis ipsilon, Alabama argillacea, Amorbia cuneana, Amyelois transitella, Anacamptodes defectaria, Anarsia lineatella, Anomis sabulifera, Anticarsia gemmatalis, Archips argyrospila, Archips rosana, Argyrotaenia citrana, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, Argyrotaenia sieboldii, citrana, Autographa gamma, Bonagota cranaodes, Borbo cinnara, Bucculatrix thurberiella, Capua reticulana, Carposina niponensis, Chlumetia transversa, Choristoneura rosaceana, Cnaphalocrocis medinalis, Conopomorpha cramerella, Corcyra cephalonica, Cossus cossus, Cydia caryana, Cydia funebrana, Cydia molesta, Cydia nigricana, Cydia pomonella, Darna didactadiducta, Diaphania nitidalis, Diatraea saccharalis, Diatraea grandiosella, Earias insulana, Earias vittella, Ecdytolopha aurantianum, Elasmopalpus lignosellus, Ephestia cautella, Ephestia elutella, Ephestia kuehniella, Epinotia aporema, Epiphyas postificittana postvittana, Erionota thrax, Estigmene acrea, Eupoecilia ambiguella, Euxoa auxiliaris, Galleria mellonella, Grapholita molesta, Hedylepta indicata, Helicoverpa armigera, Helicoverpa zea, Heliothis virescens, Hellula undalis, Keiferia lycopersicella, Leucinodes orbonaris orbonalis, Leucoptera coffeella, Leucoptera malifoliella, Lobesia botrana, Loxagrotis albicosaalbicosta, Lymantria dispar, Lyonetia clerkella, Mahasena corbetti, Mamestra brassicae, Manduca sexta, Maruca testulalis, Metisa plana, Mythimna unipuncta, Neoleucinodes elegantalis, Nymphula depunctalis, Operophtera brumata, Ostrinia nubilalis, Oxydia bessaria vesulia, Pandemis cerasana, Pandemis heparana, Papilio demodocus, Pectinophora gossypiella, Peridroma saucia, Perileucoptera coffeella, Phthorimaea operculella, Phyllocnistis citrella, Phyllonorycter blancardella, Pieris rapae, Plathypena scabra, Platynota ideusalis idaeusalis, Plodia interpunctella, Plutella xylostella, Polychrosis viteana, Prays endocarpa, Prays oleaoleae, Pseudaletia unipuncta, Pseudoplusia includens, Rachiplusia nu, Scirpophaga incertulas, Sesamia inferens, Sesamia nonagrioides, Setora nitens, Sitotroga cerealella, Sparaganothis pilleriana, Spodoptera exigua, Spodoptera frugiperda, Spodoptera eridaniana eridania, Thecla basilides, Tineola bisselliella, Tineola bisselliella, Trichoplusia ni, Tuta absoluta, Zeuzera coffeae, and Zeuzera pyrina.

[0056] The crystalline polymorphic forms A and B of compound 1 described herein (referred to herein individually as polymorphic form A and polymorphic form B) have been unexpectedly discovered to affect the behavior, neurological function, and muscular function of adult sweet potato whitefly B. tabaci, consistent with insecticides affecting chordotonal organs previously described herein. In direct comparison with a known non-crystalline form of compound 1 (amorphous oil), the crystalline polymorphic forms A and B of compound 1 (referred to herein individually as polymorphic form A and polymorphic form B) surprisingly induce significantly greater knockdown of insects, which has been shown to correlate with mortality in prior studies of previous insecticides affecting chordotonal organs.

[0057] Further embodiments, features, and advantages of the present disclosure will be apparent from the following detailed description and through the practice of the present disclosure. The compounds of the present disclosure may be described as embodiments in any of the clauses listed below. It will be understood that any embodiment described herein may be used in conjunction with any other embodiment described herein to the extent that the embodiments are not mutually exclusive.

[0058] 1. A crystalline form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide.

[0059] 2. The crystalline form of embodiment 1, wherein said crystalline form is a crystalline polymorphic form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide.

[0060] 3. The crystalline polymorph of embodiment 1 or 2, wherein the crystalline form is anhydrous or solvent-free.

[0061] A crystalline polymorphic form A of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide having a powder X-ray diffraction pattern including a peak at a diffraction angle (2θ) of 4.20.3±0.2.

[0062] 5. The crystalline polymorphic form of embodiment 4, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 17.4±0.2 and 20.3±0.2.

[0063] 6. The crystalline polymorphic form of embodiment 4 or 5, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 17.4±0.2, 19.9±0.2, and 20.3±0.2.

[0064] 7. The crystalline polymorphic form of any one of embodiments 4 to 6, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 17.4±0.2, 19.9±0.2, and 20.3±0.2.

[0065] 8. The crystalline polymorphic form of any one of embodiments 4 to 7, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 17.4±0.2, 18.2±0.2, 19.9±0.2, and 20.3±0.2.

[0066] 9. The crystalline polymorphic form of any one of embodiments 4 to 8, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern including peaks at diffraction angles (2θ) of 10.6±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.7, 19.9±0.2, and 20.3±0.2.

[0067] 10. The crystalline polymorphic form of any one of embodiments 4 to 9, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.7, 19.9±0.2, and 20.3±0.2.

[0068] 11. The crystalline polymorphic form of any one of embodiments 4 to 10, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern including peaks at diffraction angles (2θ) of 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.7, 19.9±0.2, and 20.3±0.2.

[0069] 12. The crystalline polymorphic form of any one of embodiments 4 to 11, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.7, 18.9±0.2, 19.9±0.2, and 20.3±0.2.

[0070] 13. The crystalline polymorphic form of any one of embodiments 4 to 12, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 10.0±0.2, 10.1±0.2, 10.6±0.2, 16.0±0.2, 17.4±0.2, 18.2±0.2, 18.7±0.7, 18.9±0.2, 19.9±0.2, and 20.3±0.2.

[0071] 14. The crystalline polymorphic form of any one of embodiments 4 to 13, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern including one or more peaks essentially identical to those shown in Figures 1 and 2.

[0072] 15. The crystalline polymorphic form of any one of embodiments 4-14, wherein the crystalline polymorphic form has a DSC thermogram comprising an endothermic peak having a peak temperature at about 101.09° C.

[0073] 16. The crystalline polymorphic form of any one of embodiments 4-15, having a DSC thermogram substantially identical to FIG.

[0074] 17.About 255cm -1 , approx. 441cm -1 , approx. 539cm -1 , approx. 778cm -1 , approx. 921cm -1 , approx. 991cm -1 , approx. 1048cm -1 , approx. 1123cm -1 , approx. 1191cm -1 , approx. 1526cm -1 , approx. 1569cm -1 , approx. 1588cm -1 , approx. 1701cm -1 , approx. 2949cm -1 , and about 3053 cm -1 17. The crystalline polymorphic form according to any one of embodiments 4 to 16, having a Raman spectrum comprising one or more peaks at wavenumbers of

[0075] 18. The crystalline polymorphic form of any one of embodiments 4-17 having a low frequency Raman spectrum including peaks at wavenumbers essentially identical to those shown in FIG.

[0076] A crystalline polymorphic form B of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide having a powder X-ray diffraction pattern including peaks at diffraction angles (2θ) of 19.15.4±0.2.

[0077] 20. The crystalline polymorphic form of embodiment 19, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2 and 15.4±0.2.

[0078] 21. The crystalline polymorphic form of embodiment 19 or 20, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, and 20.2±0.2.

[0079] 22. The crystalline polymorphic form of any one of embodiments 19 to 21, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, and 20.2±0.2.

[0080] 23. The crystalline polymorphic form of any one of embodiments 19 to 22, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 17.5±0.2, and 20.2±0.2.

[0081] 24. The crystalline polymorphic form of any one of embodiments 19 to 23, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern including peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.7±0.2, 17.5±0.2, 18.4±0.2, and 20.2±0.2.

[0082] 25. The crystalline polymorphic form of any one of embodiments 19 to 24, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.5±0.2, 18.4±0.2, and 20.2±0.2.

[0083] 26. The crystalline polymorphic form of any one of embodiments 19 to 25, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.5±0.2, 18.4±0.2, and 20.2±0.2.

[0084] 27. The crystalline polymorphic form of any one of embodiments 19 to 26, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.3±0.2, 17.5±0.2, 18.4±0.2, and 20.2±0.2.

[0085] 28. The crystalline polymorphic form of any one of embodiments 19 to 27, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.3±0.2, 17.5±0.2, 18.4±0.2, 19.8±0.2, and 20.2±0.2.

[0086] 29. The crystalline polymorphic form of any one of embodiments 19-28, wherein the crystalline polymorphic form has an X-ray powder diffraction pattern comprising one or more peaks essentially identical to those shown in FIG. 3.

[0087] 30. The crystalline polymorphic form of any one of embodiments 19-29, wherein the crystalline polymorphic form has a DSC thermogram comprising an endothermic peak having a peak temperature at about 105.24° C.

[0088] 31. The crystalline polymorphic form of any one of embodiments 19-30, having a DSC thermogram substantially identical to FIG.

[0089] 32. Approximately 266cm -1 , approx. 446cm -1 , approx. 546cm -1 , approx. 763cm -1 , approx. 987cm -1 , approx. 1044cm -1 , approx. 1137cm -1 , approx. 1187cm -1 and about 1308 cm -1 , about 1518cm -1 , approx. 1573cm -1 , approx. 1592cm -1 , approx. 1673cm -1 , approx. 2919cm -1 , and 2937 cm -1 32. The crystalline polymorphic form according to any one of embodiments 19 to 31, having a Raman spectrum comprising one or more peaks at wavenumbers of

[0090] 33. The crystalline polymorphic form of any one of embodiments 19-32 having a low frequency Raman spectrum including peaks at wavenumbers essentially identical to those shown in FIG.

[0091] 34. A composition comprising the crystalline form according to embodiment 1, or the crystalline polymorphic form according to any one of embodiments 2-33.

[0092] 35. A method for controlling pests, comprising applying to an area a biocidally effective amount of the crystalline form described in embodiment 1, the crystalline polymorphic form described in any one of embodiments 2-23, or the composition described in embodiment 34. [Brief description of the drawings]

[0093] [Figure 1] FIG. 1 shows the powder X-ray diffraction pattern of the crystalline form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (neat and anhydrous) polymorphic Form A prepared in Example 1. [Diagram 2] FIG. 2 shows the powder X-ray diffraction pattern of the crystalline form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (neat and anhydrous) polymorphic Form A prepared in Example 2. [Diagram 3] FIG. 1 shows the powder X-ray diffraction pattern of the crystalline form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (neat and anhydrous) polymorphic form B prepared in Example 5. [Figure 4] 1 shows a differential scanning calorimetry (DSC) thermogram of the crystalline form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (neat and anhydrous) polymorphic Form A. [Diagram 5] 1 shows a differential scanning calorimetry (DSC) thermogram of the crystalline form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (neat and anhydrous) polymorphic form B. [Figure 6] FIG. 1 shows the Raman spectrum of the crystalline form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (neat and anhydrous) polymorphic Form A. [Figure 7] FIG. 1 shows the Raman spectrum of the crystalline form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (neat and anhydrous) polymorphic form B. [Figure 8] 1 is a graph showing the control treatment of the knockdown experiment in which the percentage of B. tabaci above the 2 cm line in the acetone solvent blank control vials was recorded over time. [Figure 9]FIG. 1 shows the results of a knockdown experiment in which adult whiteflies, B. tabaci, were placed into vials pre-treated with 25 g / ha of Compound 1 polymorphic form B, or Compound 1 non-crystalline amorphous oil, from an acetone solvent, respectively, and the percentage of B. tabaci adults above the 2 cm line in the polymorph B vials (●) or non-crystalline amorphous oil vials (black squares) was recorded. [Figure 10] FIG. 1 shows the results of a knockdown experiment in which adult whiteflies, B. tabaci, were placed into vials pre-treated with 2.5 g / ha of Compound 1 polymorphic form B, or Compound 1 non-crystalline amorphous oil, from an acetone solvent, respectively, and the percentage of B. tabaci adults above the 2 cm line in the polymorph B vials (●) or non-crystalline amorphous oil vials (black squares) was recorded. [Figure 11] 1 is a graph showing the control treatment of the knockdown experiment, in which the percentage of B. tabaci adults above the 2 cm line in the hexane solvent blank control vials was recorded over time. [Figure 12] FIG. 13 shows the results of a knockdown experiment in which adult whiteflies, B. tabaci, were placed from a hexane antisolvent suspension into vials pretreated with 25 g / ha of Compound 1 polymorph A, Compound 1 polymorph B, or Compound 1, non-crystalline amorphous oil, respectively, and the percentage of B. tabaci adults above the 2 cm line in the Polymorph A vials (black diamonds), Polymorph B vials (●), or non-crystalline amorphous oil vials (black squares) was recorded over time. [Figure 13] FIG. 13 shows the results of a knockdown experiment in which adult whiteflies, B. tabaci, were placed from a hexane antisolvent suspension into vials pretreated with 2.5 g / ha of Compound 1 polymorph A, Compound 1 polymorph B, or Compound 1 non-crystalline amorphous oil, respectively, and the percentage of B. tabaci adults above the 2 cm line in the Polymorph A vials (black diamonds), Polymorph B vials (●), or non-crystalline amorphous oil vials (black squares) was recorded over time. [Figure 14]FIG. 13 shows the results of a knockdown experiment in which adult whiteflies, B. tabaci, were placed from a hexane antisolvent suspension into vials pretreated with 0.25 g / ha of Compound 1 polymorph A, Compound 1 polymorph B, or Compound 1 non-crystalline amorphous oil, respectively, and the percentage of B. tabaci adults above the 2 cm line in the Polymorph A vials (black diamonds), Polymorph B vials (●), or non-crystalline amorphous oil vials (black squares) was recorded over time. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0094] Before the present disclosure is further described, it is to be understood that the present disclosure is not limited to particular embodiments described, and as such, may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.

[0095] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this disclosure belongs. All patents, applications, published applications, and other publications mentioned herein are incorporated by reference in their entirety. If the definitions set forth in this section are contrary to or otherwise inconsistent with the definitions set forth in the patents, applications, or other publications incorporated herein by reference, the definitions set forth in this section shall take precedence over the definitions incorporated herein by reference.

[0096] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. It is further noted that the claims may be drafted to exclude optional elements. As such, this statement is intended to serve as a prelude to using exclusive terminology, such as "solely," "only," and the like in connection with the recitation of claim elements, or to using a "negative" limitation.

[0097] Polymorphic forms of Compound 1 and methods of preparing Compound 1 are detailed below. In some embodiments, amorphous forms of Compound 1 may be prepared according to the methods disclosed and described in WO 2010 / 139497 A1 and U.S. Patent No. 8,350,044, which are incorporated herein by reference in their entireties.

[0098] A unique physical form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide polymorphic Form A has been prepared according to the methods described herein. The powder X-ray diffraction (PXRD) pattern of polymorphic Form A is shown in FIG. 1 and the corresponding tabular data is provided in Table 1.

[0099] [Table 1]

[0100] In some embodiments, the crystalline polymorphic Form A of Compound 1 is 10.2±0.2, 10.6±0.2, 13.2±0.2, 16.0±0.2, 16.7±0.2, 17.5±0.2, 17.9±0.2, 18.2±0.2, 18.7±0.2, 19.0±0.2, 20.0±0.2, 20.4±0.2, 21.1±0.2, 21.2±0.2, 21.4±0.2, 21.6±0.2, 21.8±0.2, 22.4±0.2, 22.8±0.2, 22.8±0.2, 22.4±0.2, 22.2±0.2, 22.4 ... and has an X-ray powder diffraction pattern including one or more peaks at diffraction angles (2θ) of 0.7±0.2, 22.8±0.2, 23.1±0.2, 24.0±0.2, 24.7±0.2, 25.3±0.2, 25.7±0.2, 26.7±0.2, 28.2±0.2, 28.7±0.2, 32.2±0.2, and 33.0±0.2. In some embodiments, the crystalline polymorphic Form A of Compound 1 is 10.2±0.1, 10.6±0.1, 13.2±0.1, 16.0±0.1, 16.7±0.1, 17.5±0.1, 17.9±0.1, 18.2±0.1, 18.7±0.1, 19.0±0.1, 20.0±0.1, 20.4±0.1, 21.1±0.1, 21.2±0.1, 21.4±0.1, 21.6±0.1, 21.8±0.1, 22.4±0.1, 22.8 ... The crystalline polymorphic Form A of Compound 1 has an X-ray powder diffraction pattern that includes one or more peaks at diffraction angles (2θ) of 0.7±0.1, 22.8±0.1, 23.1±0.1, 24.0±0.1, 24.7±0.1, 25.3±0.1, 25.7±0.1, 26.7±0.1, 28.2±0.1, 28.7±0.1, 32.2±0.1, and 33.0±0.1. In some embodiments, the crystalline polymorphic Form A of Compound 1 has an X-ray powder diffraction pattern that includes a combination of two or more peaks at the diffraction angles (2θ) shown in the above embodiments. It will be understood that the diffraction angles (2θ) shown in Table 1 are within experimental error of the values ​​shown above and referred to in this disclosure.

[0101] In some embodiments, the same physical form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (polymorphic form A) shown in FIG. 1 and Table 1 has been prepared according to the methods described herein, and this material may be prepared in higher purity using recrystallization techniques as described herein (e.g., using seed crystals of polymorphic form A, multiple crystallization / recrystallization methods, and the like). Those skilled in the art will appreciate that the use of such techniques to provide higher purity crystalline material may result in higher resolution in powder X-ray diffraction (PXRD) analysis. The powder X-ray diffraction (PXRD) pattern of polymorphic form A using such techniques to obtain higher purity material, and therefore higher quality powder X-ray diffraction (PXRD) analysis, is shown in FIG. 2, and the corresponding tabular data is shown in Table 2. It will be understood by those skilled in the art that the PXRD data presented in Table 2 is within experimental error of the data presented in Table 1, and that the higher resolution PXRD pattern shown in Figure 2 enhances the ability to discern closely spaced peaks in the PXRD pattern that were previously invisible in the PXRD pattern shown in Figure 1.

[0102] [Table 2]

[0103] In some embodiments, the crystalline polymorphic Form A of Compound 1 is 10.0±0.2, 10.1±0.2, 10.6±0.2, 10.9±0.2, 13.2±0.2, 15.6±0.2, 16.0±0.2, 16.6±0.2, 17.4±0.2, 17.9±0.2, 18.2±0.2, 18.7±0.2, 18.9±0.2, 19.9±0.2, 20.3±0.2, 21.0±0.2, 21.3±0.2, 21.4±0.2, 21.2±0.2, 21.6±0.2, 21.8 ... and has an X-ray powder diffraction pattern including one or more peaks at diffraction angles (2θ) of 0.7±0.2, 21.8±0.2, 22.8±0.2, 23.1±0.2, 23.3±0.2, 23.9±0.2, 24.7±0.2, 25.3±0.2, 25.7±0.2, 26.2±0.2, 26.6±0.2, 28.1±0.2, 28.6±0.2, 28.8±0.2, 32.1±0.2, and 32.9±0.2. In some embodiments, the crystalline polymorphic Form A of Compound 1 is 10.0±0.1, 10.1±0.1, 10.6±0.1, 10.9±0.1, 13.2±0.1, 15.6±0.1, 16.0±0.1, 16.6±0.1, 17.4±0.1, 17.9±0.1, 18.2±0.1, 18.7±0.1, 18.9±0.1, 19.9±0.1, 20.3±0.1, 21.0±0.1, 21.3±0.1, 21.4±0.1, 22.4±0.1, 22.2 ... 0.7±0.1, 21.8±0.1, 22.8±0.1, 23.1±0.1, 23.3±0.1, 23.9±0.1, 24.7±0.1, 25.3±0.1, 25.7±0.1, 26.2±0.1, 26.6±0.1, 28.1±0.1, 28.6±0.1, 28.8±0.1, 32.1±0.1, and 32.9±0.1 diffraction angles (2θ). In some embodiments, the crystalline polymorphic Form A of Compound 1 has an X-ray powder diffraction pattern that includes a combination of two or more peaks at the diffraction angles (2θ) shown in the above embodiments. It will be understood that the diffraction angles (2θ) shown in Table 2 are within experimental error of the values ​​shown above and referred to in this disclosure.

[0104] The DSC thermogram of crystalline polymorphic form A is shown in Figure 4. During the DSC method described in Example 10, polymorphic form A was determined to melt at about 101.09°C with a heat of fusion = 75.707 J / g, as shown in Figure 4.

[0105] The Raman spectrum of crystalline polymorph form A is shown in FIG.

[0106] A unique physical form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (neat and anhydrous) polymorphic form B has been prepared according to the methods described herein. The powder X-ray diffraction (PXRD) pattern of polymorphic form B is shown in FIG. 3 and the corresponding tabular data is shown in Table 3.

[0107] [Table 3]

[0108] [Table 4]

[0109] In some embodiments, the crystalline polymorphic form B of Compound 1 is 7.7±0.2, 10.1±0.2, 10.6±0.2, 12.2±0.2, 12.9±0.2, 14.0±0.2, 15.0±0.2, 15.4±0.2, 16.6±0.2, 16.7±0.2, 17.3±0.2, 17.5±0.2, 17.6±0.2, 17.7±0.2, 17.8±0.2, 17.9 ... .2, 18.1±0.2, 18.5±0.2, 19.8±0.2, 20.2±0.2, 20.9±0.2, 21.3±0.2, 21.6±0.2, 21.8±0.2, 22.9±0.2, 23.2±0.2, 23.7±0.2, 24.1±0.2, 24.9±0.2, 25.4±0.2, 25.0±0.2, 25.2±0.2, 25.0 ... and 39.9±0.2.In some embodiments, the crystalline polymorphic form B of Compound 1 is 7.7±0.1, 10.1±0.1, 10.6±0.1, 12.2±0.1, 12.9±0.1, 14.0±0.1, 15.0±0.1, 15.4±0.1, 16.6±0.1, 16.7±0.1, 17.3±0.1, 17.5±0.1, 17.6±0.1, 17.7±0.1, 17.8±0.1, 17.9±0.1, 18.7±0.1, 18.8±0.1, 18.9 ... .1, 18.1±0.1, 18.5±0.1, 19.8±0.1, 20.2±0.1, 20.9±0.1, 21.3±0.1, 21.6±0.1, 21.8±0.1, 22.9±0.1, 23.2±0.1, 23.7±0.1, 24.1±0.1, 24.9±0.1, 25.4±0.1, 25.5±0.1, 26.7±0.1, 27.4±0.1, 28.7±0.1, 29.7±0.1, 30.4±0.1, 31.2±0.1, 32.0±0.1, 33.0±0.1, 34.0±0.1, 35.0±0.1, 36.0±0.1, 37.0±0.1, 38.0±0.1, 39.0±0.1, 40.0±0.1, 41.0±0.1, 42.0±0.1, 43.0±0.1, 44.0±0.1, 45.0±0.1, 46.0±0.1, 47.0±0.1, 48.0±0.1, 49.0±0.1, 50.0±0.1, 51.0±0.1, 52.0±0.1, 53.0±0.1, 54.0±0.1, 55.0±0.1, 56.0±0.1, 57.0±0.1, 58.0±0.1, 59.0±0.1, 59.0±0.1, 59.0±0 and has an X-ray powder diffraction pattern comprising one or more peaks at diffraction angles (2θ) of 0.8±0.1, 26.1±0.1, 26.6±0.1, 27.0±0.1, 27.3±0.1, 27.8±0.1, 28.1±0.1, 28.4±0.1, 28.7±0.1, 29.3±0.1, 30.3±0.1, 30.7±0.1, 31.1±0.1, 32.3±0.1, 32.8±0.1, 33.4±0.1, 34.2±0.1, 34.4±0.1, 34.8±0.1, 35.5±0.1, 36.6±0.1, 36.9±0.1, 38.4±0.1, 38.8±0.1, and 39.9±0.1. In some embodiments, the crystalline polymorphic form B of compound 1 has an X-ray powder diffraction pattern that includes a combination of two or more peaks at the diffraction angles (2θ) shown in the above embodiments. It will be understood that the diffraction angles (2θ) shown in Table 3 are within experimental error of the values ​​shown above and referred to in this disclosure.

[0110] The DSC thermogram of crystalline polymorphic form A is shown in Figure 5. During the DSC method described in Example 10, polymorphic form A was determined to melt at about 105.24°C with a heat of fusion = 92.879 J / g, as shown in Figure 5.

[0111] The Raman spectrum of crystalline polymorph form A is shown in FIG.

[0112] combination In some embodiments, any one of polymorphic forms A and B of Compound 1 may be used in combination (e.g., in a compositional mixture or in simultaneous or sequential application) with one or more active ingredients.

[0113] In some embodiments, any one or more of polymorphic forms A and B of Compound 1 may be used in combination (e.g., in a compositional mixture or in simultaneous or sequential applications) with one or more active ingredients each having the same, similar, but likely different, mode of action (MoA) as any one or more of polymorphic forms A and B of Compound 1. In some embodiments, any one or more of polymorphic forms A and B of Compound 1 may be used in combination (e.g., in a compositional mixture or in simultaneous or sequential applications) with one or more molecules having acaricidal, algicidal, avicidal, bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal, nematicidal, rodenticidal, and / or virucidal properties.

[0114] In some embodiments, any one or more of polymorphic forms A and B of Compound 1 may be used in combination (e.g., in a compositional mixture or in simultaneous or sequential application) with one or more molecules that are antifeedants, bird repellents, sterilizers, herbicide antidotes, insect attractants, insect repellents, mammalian repellents, mating disruptors, plant activators, plant growth regulators, and / or synergists.

[0115] In some embodiments, any one or more of polymorphic forms A and B of Compound 1 may also be used in combination with one or more biopesticides (e.g., in a compositional mixture or in simultaneous or sequential application).

[0116] In some embodiments, in the biocidal composition, a combination of any one or more of polymorphic forms A and B of Compound 1 with an active ingredient can be used in various weight ratios. For example, in a two-component mixture, the weight ratio of any one or more of polymorphic forms A and B of Compound 1 to the active ingredient can be used in various ratios. However, generally, a weight ratio of about 10:1 to less than about 1:10 is preferred. It may also be preferred to use a mixture of 3, 4, 5, 6, 7, or more components including any one or more of polymorphic forms A and B of Compound 1 and two or more additional active ingredients.

[0117] The weight ratio of any one or more of polymorphic forms A and B of Compound 1 to the active ingredient can also be expressed as X:Y, where X is the number of parts by weight of any one or more of polymorphic forms A and B of Compound 1, and Y is the number of parts by weight of the active ingredient. The numerical range of the number of parts by weight of X is 0 < X ≤ 100, and the number of parts by weight of Y is 0 < Y < 100. By way of non-limiting example, the weight ratio of any one or more of polymorphic forms A and B of Compound 1 to the active ingredient can be 20:1.

[0118] Formulations Pesticides are often not suitable for application in their pure form. Usually, other substances need to be added, whereby the pesticides can be used at the required concentration and in a suitable form, facilitating application, handling, transportation, storage, and maximum pesticidal activity. Thus, pesticides are formulated, for example, as baits, concentrated emulsions, dusts, emulsions, fumigants, gels, granules, microencapsulated agents, seed treatment agents, suspension concentrates, suspoemulsion agents, tablets, water-soluble liquids, water-dispersible granules, or dry flowables, wettable powders, and ultra-low volume solutions.

[0119] Pesticides are most often applied as aqueous suspensions or emulsions prepared from concentrated formulations of such pesticides. Such water-soluble, water-suspendable, or emulsifiable formulations may be solids, commonly known as wettable powders, water-dispersible granules, liquids, commonly known as emulsifiable powders, or aqueous suspensions. Wettable powders may be compressed to form water-dispersible granules and contain a homogenous mixture of pesticide, carrier, and surfactant. The concentration of pesticide is usually about 10% to about 90% by weight. The carrier is usually selected from attapulgite clay, montmorillonite clay, diatomaceous earth, or purified silicates. The active surfactants, which make up about 0.5% to about 10% of the wettable powder, are found among sulfonated lignin, condensed naphthalene sulfonates, naphthalene sulfonates, alkylbenzene sulfonates, alkyl sulfates, and nonionic surfactants, such as ethylene oxide adducts of alkylphenols.

[0120] Emulsifiable concentrates of pesticides contain a liquid, usable concentration of pesticide, for example, about 50 to about 500 grams per liter (g / L), dissolved in a carrier that is a water-miscible solvent or a mixture of a water-immiscible organic solvent and an emulsifier. Useful organic solvents include aromatics, especially xylenes, and petroleum fractions, especially the high-boiling naphthalene and olefinic portions of petroleum, such as heavy aromatic naphtha. Other organic solvents, such as terpene-based solvents, such as rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2-ethoxyethanol, may also be used. Emulsifiers suitable for emulsifiable concentrates are selected from conventional anionic and nonionic surfactants.

[0121] Aqueous suspensions include suspensions of water-insoluble pesticides dispersed in an aqueous carrier at concentrations ranging from about 5% to about 50% by weight. Suspensions are prepared by finely grinding the pesticide and vigorously mixing it into a carrier consisting of water and surfactants. Also, ingredients such as inorganic salts and synthetic or natural gums may be added to increase the density and viscosity of the aqueous carrier. In many cases, it is most effective to simultaneously grind and mix the pesticide by preparing an aqueous mixture and homogenizing it in an apparatus such as a sand mill, ball mill, or piston-type homogenizer. The pesticide in the suspension may be microencapsulated in a plastic polymer.

[0122] An oil dispersion (OD) comprises a suspension of an organic solvent-insoluble pesticide finely dispersed in a mixture of an organic solvent and an emulsifier at a concentration ranging from about 2% to about 50% by weight. One or more pesticides may be dissolved in the organic solvent. Useful organic solvents include aromatics, especially xylenes, and petroleum fractions, especially the high boiling naphthalene and olefinic portions of petroleum, such as heavy aromatic naphtha. Other solvents may include vegetable oils, seed oils, and esters of vegetable and seed oils. Suitable emulsifiers for oil dispersions are selected from conventional anionic and nonionic surfactants. Thickeners or gelling agents are added in the oil dispersion formulation to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets.

[0123] Pesticides can also be applied as granular compositions, which are particularly useful for application to soil. Granular compositions usually contain about 0.5% to about 10% by weight of the pesticide dispersed in a carrier that includes clay or similar material. Such compositions are usually prepared by dissolving the pesticide in a suitable solvent and applying it to a granular carrier that has been preformed to a suitable particle size, ranging from about 0.5 mm to about 3 mm. Such compositions can also be formulated by making a dough or paste of the carrier and molecules, which is then crushed and dried to obtain the desired granule particle size. Another form of granule is the water-emulsifiable granule (EG). It is a formulation consisting of granules that are disintegrated and dissolved in water, and then applied as an oil-in-water emulsion of the conventional active ingredient, dissolved or diluted in an organic solvent. Water-emulsifiable granules contain one or several active ingredients solubilized or diluted in a suitable organic solvent, absorbed in a shell of a water-soluble polymer or some other type of soluble or insoluble matrix.

[0124] Dusts containing the pesticide are prepared by homogeneously mixing the pesticide in powder form with a suitable powdered agricultural carrier (e.g., kaolin clay, ground volcanic rock, etc.). The dust may suitably contain from about 1% to about 10% pesticide. The dust may be applied as a seed dressing or as a foliar spray using a dust blower.

[0125] It is equally practical to apply the pesticide in the form of a solution, for example a spray oil, using a suitable organic solvent, usually petroleum, which is widely used in agricultural chemistry.

[0126] Pesticides can also be applied in the form of aerosol compositions, in which the pesticide is dissolved or dispersed in a carrier that is a pressure-generating propellant mixture, which is packaged in a container that is then dispensed through an atomizing valve.

[0127] Pesticide baits are formed when a pesticide is mixed with food or an attractant or both. When a pest eats the bait, it also ingests the pesticide. Baits can be in the form of granules, gels, flowable powders, liquids, or solids. Baits can be used in the harborage of pests.

[0128] Fumigants are pesticides that have a relatively high vapor pressure and can therefore exist as gases in soil or confined spaces in sufficient concentrations to kill pests. The toxicity of fumigants is proportional to their concentration and exposure time. They are characterized by good diffusion ability and act by penetration into the respiratory system of pests or absorption through the cuticle of pests. Fumigants are applied in airtight rooms or buildings or in special chambers under gas-tight sheets to control pests in stored products.

[0129] Pesticides can be microencapsulated by suspending particles or droplets of the pesticide in various plastic polymers. By varying the chemistry of the polymer or by varying factors in the processing, microcapsules of various sizes, solubility, wall thickness and permeability can be formed. These factors control the rate at which the active ingredient therein is released, which in turn affects the residual performance, rate of action and odor of the product. Microcapsules may be formulated as suspension concentrates or water-dispersible granules.

[0130] Oil concentrates are made by dissolving the pesticide in a solvent that holds it in solution, and the oil solution of the pesticide usually knocks down and kills pests more quickly than other formulations, both because the solvent itself has biocidal properties and because it dissolves the waxy coating of the cuticle, increasing the rate of uptake of the pesticide. Other advantages of oil concentrates include better storage stability, better crevices penetration, and better adhesion to greasy surfaces.

[0131] Another embodiment is an oil-in-water emulsion comprising oil droplets, each having a lamellar liquid crystalline coating and dispersed in an aqueous phase, each oil droplet comprising at least one agriculturally active molecule and individually coated with a mono- or oligolamellar comprising: (1) at least one non-ionic lipophilic surfactant, (2) at least one non-ionic hydrophilic surfactant, and (3) at least one ionic surfactant, the droplets having an average particle size of less than 800 nanometers.

[0132] Other formulation ingredients In general, when any one or more of the polymorphic forms A and B of Compound 1 are used in a formulation, such formulation may also contain other ingredients. These ingredients include, but are not limited to, wetting agents, spreading agents, adhesives, penetrating agents, buffers, sequestering agents, drift reducing agents, compatibilizers, antifoaming agents, detergents, and emulsifiers (this is a non-exhaustive and non-mutually exclusive list). Some ingredients are described below.

[0133] Wetting agents are substances that, when added to a liquid, increase the spreading or penetrating power of the liquid by reducing the interfacial tension between the liquid and the surface it spreads on. Wetting agents are used in agrochemical formulations for two main functions: to increase the rate at which powders are wetted with water during processing and manufacturing to make soluble liquid concentrates or suspension concentrates, and to reduce the wetting time of wettable powders and improve the penetration of water into water-dispersible granules when the product is mixed with water in the spray tank. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations are sodium lauryl sulfate, sodium dioctyl sulfosuccinate, alkylphenol ethoxylates, and fatty alcohol ethoxylates.

[0134] Dispersants are substances that adsorb to the surface of particles, help keep them dispersed, and prevent them from re-agglomerating. Dispersants are added to pesticide formulations to facilitate dispersion and suspension during manufacturing and to ensure that particles redisperse in water in the spray tank. Dispersants are widely used in wettable powders, suspension concentrates, and water-dispersible granules. Surfactants used as dispersants have the ability to strongly adsorb to the particle surface and provide a charge barrier or steric barrier against particle re-agglomeration. The most commonly used surfactants are anionic, nonionic, or a mixture of the two. In wettable powder formulations, the most common dispersant is sodium lignosulfonate. In suspension concentrates, very good adsorption and stabilization are obtained by using polyelectrolytes (e.g., sodium naphthalene sulfonate formaldehyde condensates). Tristyrylphenol ethoxylate phosphate esters are also used. Nonionic materials (e.g., alkylaryl ethylene oxide condensates, and EO-PO block copolymers) may also be combined with anionic materials as dispersants in suspension concentrates. In recent years, a new class of very high molecular weight polymeric surfactants has been developed as dispersants. They have a very long hydrophobic "backbone" and many ethylene oxide chains that form the "teeth" of the surfactant "comb". These high molecular weight polymers can provide very good long-term stability for suspension concentrates because the hydrophobic backbone has many anchoring points on the particle surface.

[0135] Examples of dispersants used in agrochemical formulations are sodium lignosulfonate, sodium naphthalenesulfonate formaldehyde condensates, tristyrylphenol ethoxylate phosphate esters, fatty alcohol ethoxylates, alkyl ethoxylates, EO-PO block copolymers, and graft copolymers.

[0136] An emulsifier is a substance that stabilizes the suspension of droplets of one liquid phase in another. Without the emulsifier, the two liquids would separate into two immiscible liquid phases. The most commonly used emulsifier blends include an alkylphenol or aliphatic alcohol having 12 or more ethylene oxide units and the calcium salt of oil-soluble dodecylbenzenesulfonic acid. A hydrophilic-lipophilic balance ("HLB") value in the range of about 8 to about 18 will usually result in a good stable emulsion. Emulsion stability can sometimes be improved by adding a small amount of an EO-PO block copolymer surfactant.

[0137] Solubilizers are surfactants that form micelles in water at concentrations above the critical micelle concentration. The micelles can then dissolve or solubilize water-insoluble substances inside the hydrophobic portion of the micelle. The types of surfactants commonly used for solubilization are nonionic substances, sorbitan monooleate, sorbitan monooleate ethoxylate, and methyl oleate ester.

[0138] Surfactants are sometimes used alone or with other additives such as mineral or vegetable oils that are added as adjuvants to spray tank mixtures to improve the biological performance of pesticides on their targets. The type of surfactant used for bioenhancement generally depends on the nature and mechanism of action of the pesticide. However, they are often non-ionic materials such as alkyl ethoxylates, linear fatty alcohol ethoxylates, and fatty amine ethoxylates.

[0139] Carriers or diluents in agricultural formulations are substances added to pesticides to obtain a product of the required strength. Carriers are usually substances with high absorption capacity, whereas diluents are usually substances with low absorption capacity.

[0140] Carriers and diluents are used in dusts, wettable powders, granules, and water dispersible granule formulations.

[0141] Organic solvents are primarily used in the formulation of emulsifiable concentrates, oil-in-water emulsions, suspoemulsions, oil dispersions and microformulations, and less frequently in granular formulations. Mixtures of solvents may also be used. The first main group of solvents are aliphatic paraffinic oils, such as kerosene or refined paraffin. The second main group (and the most common) are aromatic solvents, such as xylene, and C9 and C10 solvents. 10 These include the higher molecular weight fractions of aromatic solvents. Chlorinated hydrocarbons are useful as co-solvents to prevent the crystallization of pesticides when the formulation is emulsified in water. Alcohols are sometimes used as co-solvents to increase solvent power. Other solvents may include vegetable oils, seed oils, and esters of vegetable and seed oils.

[0142] Thickening or gelling agents are primarily used in the formulation of suspension concentrates, oil dispersions, emulsions, and suspoemulsions to change the rheology, i.e., flow properties, of liquids and to prevent separation and settling of dispersed particles or droplets. Thickening, gelling, and anti-settling agents are generally divided into two categories: water-insoluble particulates and water-soluble polymers. Clays and silicas can be used to make suspension concentrate and oil dispersion formulations. Examples of these types of materials include, but are not limited to, montmorillonite, bentonite, magnesium aluminum silicate, and attapulgite. Water-soluble polysaccharides in aqueous suspension concentrates have been used as thickening and gelling agents for many years, and the most commonly used types of polysaccharides are natural extracts of seeds and seaweeds, or synthetic derivatives of cellulose. Examples of these types of materials include, but are not limited to, guar gum, locust bean gum, carrageenan, alginates, methylcellulose, sodium carboxymethylcellulose (SCMC), and hydroxyethylcellulose (HEC). Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol, and polyethylene oxide. Another good anti-settling agent is xanthan gum.

[0143] Microorganisms can cause spoilage of formulated products. Therefore, preservatives are used to eliminate or reduce their effects. Examples of such agents include, but are not limited to, propionic acid and its sodium salt, sorbic acid and its sodium or potassium salt, benzoic acid and its sodium salt, p-hydroxybenzoic acid sodium salt, methyl p-hydroxybenzoate, and 1,2-benzisothiazolin-3-one (BIT).

[0144] The presence of surfactants often causes foaming of water-based formulations during mixing operations during manufacture and application through spray tanks. Antifoaming agents are often added during the manufacturing stage or before filling into bottles to reduce foaming tendency. In general, there are two types of antifoaming agents: silicone and non-silicone antifoaming agents. Silicones are usually aqueous emulsions of dimethylpolysiloxanes, and non-silicone antifoaming agents are water-insoluble oils such as octanol and nonanol, or silica. In either case, the function of the antifoaming agent is to displace the surfactant from the air-water interface.

[0145] "Environmentally friendly" agents (e.g., adjuvants, surfactants, solvents) can reduce the total environmental footprint of crop protection formulations. Environmentally friendly agents are biodegradable and generally derived from natural and / or sustainable sources, such as from plant and animal sources. Specific examples are vegetable oils, seed oils, and their esters.

[0146] application Any one or more of the polymorphic forms A and B of Compound 1 may be applied to any area. Particular areas to which such molecules may be applied include areas where alfalfa, almonds, apples, barley, beans, canola, corn, cotton, cauliflower (crucifer), flowers, forage species (ryegrass, sudangrass, tall fescue, longgrass, and clover), fruits, lettuce, oats, oilseed crops, oranges, peanuts, pears, peppers, potatoes, rice, sorghum, soybeans, strawberries, sugarcane, sugar beets, sunflowers, tobacco, tomatoes, wheat (e.g., hard red winter wheat, soft red winter wheat, white winter wheat, hard red spring wheat, and durum spring wheat), and other valuable crops are grown or the seeds of which will be planted.

[0147] Any one or more of the polymorphic forms A and B of compound 1 may also be applied to areas where plants, such as crops, are grown and where there are low levels (even non-existent) of pests that may commercially damage such plants. By applying such molecules to such areas, the plants grown in such areas can benefit. Such benefits include, but are not limited to, helping plants develop better root systems, helping plants better tolerate high-stress growing conditions, improving plant health, improving plant yields (e.g., increased biomass and / or increased content of active ingredients), improving plant vigor (e.g., improved plant growth and / or greener leaves), improving plant quality (e.g., increased content or composition of certain ingredients), and improving plant resistance to abiotic and / or biotic stresses.

[0148] Any one or more of polymorphic forms A and B of Compound 1 may be applied along with ammonium sulfate in growing various plants to provide additional benefits.

[0149] Any one or more of polymorphic forms A and B of Compound 1 may be applied onto, within, or around a plant that has been genetically modified to express a unique trait, such as, for example, Bacillus thuringiensis (e.g., Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Abl / Cry35Abl), other insecticidal toxins, or expressing herbicide resistance or having "stacked" foreign genes expressing insecticidal toxins, herbicide resistance, nutritional enhancement, or any other beneficial trait.

[0150] Any one or more of the polymorphic forms A and B of Compound 1 may be applied to the foliage and / or fruit parts of a plant to control pests, such polymorphs of Compound 1 coming into direct contact with the pests or the pests ingesting such polymorphs of Compound 1 when feeding on the plant or while uptake of sap or other nutrients from the plant.

[0151] Any one or more of the polymorphic forms A and B of Compound 1 may also be applied to the soil and, when so applied, may control root and stem feeding pests. The roots may take up such molecules and transport them to the plant foliage, thereby controlling above ground chewing pests and sap feeding pests.

[0152] Systemic movement of pesticides in plants can be used to control pests in one part of a plant by applying (e.g., spraying an area) any one or more of polymorphic forms A and B of Compound 1 to another part of the plant. For example, control of foliage-feeding insects can be achieved by drip irrigation or furrow application, or by treating the soil, for example, with a pre- or post-plant soil drench, or by treating the seeds of the plant before planting.

[0153] Any one or more of the polymorphic forms A and B of compound 1 can be used with bait.Generally, for bait, the bait is placed in the ground, where, for example, termites can come into contact with the bait and / or be attracted to the bait.The bait can also be applied to the surface (horizontal, vertical, or inclined surface) of a building, where, for example, ants, termites, cockroaches, and flies can come into contact with the bait and / or be attracted to the bait.

[0154] Any one or more of polymorphic forms A and B of Compound 1 may be enclosed within a capsule or disposed on the surface of the capsule. The size of the capsule may range from nanometer size (diameter of about 100-900 nanometers) to micrometer size (diameter of about 10-900 microns).

[0155] Any one or more of polymorphic forms A and B of Compound 1 may be applied to pest eggs. Because some pest eggs have a unique ability to resist certain pesticides, it may be desirable to apply such molecules repeatedly to control newly emerged larvae.

[0156] Any one or more of the polymorphic forms A and B of Compound 1 may be applied as a seed treatment. The seed treatment may be applied to all types of seeds, including seeds from which plants genetically modified to express unique traits will germinate. Representative examples include those expressing proteins with toxicity to invertebrate pests, such as Bacillus thuringiensis or other insecticidal toxins, those expressing herbicide resistance, such as "Roundup Ready" seeds, or those with "stacked" foreign genes expressing insecticidal toxicity, herbicide resistance, nutritional enhancement, drought tolerance, or any other beneficial trait. Furthermore, such seed treatment with any one or more of the polymorphic forms A and B of Compound 1 may further enhance the plant's ability to better tolerate stressful growing conditions. The result is healthier and more vigorous plants, which may translate into higher yields at harvest. In general, amounts of about 1 gram to about 500 grams of such polymorphs per 100,000 seeds are expected to provide good benefit, amounts of about 10 grams to about 100 grams per 100,000 seeds are expected to provide better benefit, and amounts of about 25 grams to about 75 grams per 100,000 seeds are expected to provide even better benefit. Any one or more of polymorphic forms A and B of Compound 1 may be applied in conjunction with one or more active ingredients in soil amendments.

[0157] Any one or more of the polymorphic forms A and B of compound 1 may be used in the veterinary sector or in the field of non-human animal husbandry to control endo- and ectoparasites. Such molecules may be applied by oral administration, for example in the form of tablets, capsules, drinks, and granules, by dermal application, for example in the form of immersion, spray, injection, spot-on, and dusting, and by parenteral administration, for example in the form of injection.

[0158] Any one or more of the polymorphic forms A and B of compound 1 may also be advantageously used in livestock breeding, such as cattle, chickens, geese, goats, pigs, sheep, and turkeys. They may also be advantageously used in pets, such as horses, dogs, and cats. Particular pests to be controlled may be flies, fleas, and ticks that are a nuisance to such animals. A suitable formulation is administered orally to the animal with drinking water or feed. Suitable doses and formulations vary according to species.

[0159] Any one or more of the polymorphic forms A and B of Compound 1 may also be used to control parasites, particularly intestinal parasites, in animals as listed above. Any one or more of the polymorphic forms A and B of Compound 1 may also be utilized in methods of treatment for non-human health care, including, but not limited to, oral administration in the form of tablets, capsules, drinks, and granules, as well as transdermal application.

[0160] Polymorphic forms A and B of compound 1 can also be applied to invasive pests. Pests from all over the world are moving to new environments (for them) and become new invasive species in these new environments after moving. Such polymorphs can also be used on these new invasive species to control them in these new environments. EXAMPLES

[0161] Certain aspects of the embodiments of the present disclosure are further described and exemplified in the examples and preparations provided below, with it being understood that the scope of the present disclosure is in no way limited by the scope of the following examples.

[0162] Example 1 Synthesis of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (Compound 1) and its isolation as Form A [ka] Step 1: Preparation of tert-butyl (2-(ethylamino)-2-oxoethyl)carbamate (S1) A 1 L round bottom was charged with 70% ethylamine in water (347 mL, 4360 mmol, 3 eq.) and methyl (tert-butoxycarbonyl)glycinate (255 ml, 1453 mmol) was added in small portions to maintain the temperature below 35° C. The reaction was stirred at room temperature and monitored by NMR using CDCl3. Excess ethylamine and water were removed by atmospheric distillation. The mixture was cooled and cyclopentyl methyl ether (CPME) (400 mL) was added. Atmospheric distillation was continued to azeotrope out residual water (pot temperature: 115° C., overhead temperature: 95° C.). Approximately 260 mL of CPME was distilled overhead. The mixture was cooled to room temperature and CPME (140 mL) was added to the bottom. This solution was used in the next step without further manipulation. 1 H NMR(400MHz,Chloroform-d)δ 3.77(d,J=5.9Hz,2H),3.37-3.26(m,2H),1.46(s,9H),1.15(t,J=7.3Hz,3H).

[0163] Step 2: Preparation of 2-amino-N-ethylacetamide hydrochloride (S2) A 5 L jacketed reactor was charged with 6N HCl in isopropanol (1055 mL, 6.3 mol, 4 equiv.) and CPME (1055 mL) and the jacket was set to 30° C. tert-Butyl (2-ethylamino)-2-oxoethyl)carbamate (estimated 320 g, 1582 mmol) as a solution in CMPE from the previous reaction was added via peristaltic pump over 30 min. The reaction was stirred at 30° C. for 6 h and cooled to 25° C. with stirring overnight. The reaction was monitored by NMR in DMSO. The reaction formed a very viscous slurry. The slurry was diluted with CPME (650 mL) and the solid was isolated by filtration through a coarse glass frit and washed with CPME (300 mL). The wet cake was then washed with 1 cake volume of hexane to remove CPME and dried. This material was dried in a vacuum oven at 45° C. to give 2-amino-N-ethylacetamide hydrochloride (S2) (184.11 g, 1315 mmol, 83% yield) as a fluffy white solid. 1 H NMR(400MHz,DMSO-d6)δ 3.49(s,2H),3.14(qd,J=7.3,5.4Hz,2H),1.05(t,J=7.3Hz,3H).

[0164] Step 3: Preparation of N-ethyl-2-(pyridin-3-yl)-1,3-thiazol-5-amine dihydrochloride (S3) A 125 mL three-necked flat-bottom flask equipped with a reflux condenser and thermocouple was charged with 2-amino-N-ethylacetamide hydrochloride (4.99 g, 36.0 mmol, 1.25 equiv.) and anhydrous acetonitrile (48 mL) to give a white slurry. The reactor was inerted with nitrogen. Anhydrous triethylamine (99%, 5.60 mL, 39.7 mol, 1.38 equiv.) was added and the mixture was stirred for 1 h to give a thick white slurry. Nicotinaldehyde (98%, 2.70 mL, 28.8 mmol, 1.0 equiv.) was added to give a less viscous slurry. Solid sulfur powder (1.20 g, 37.4 mmol, 1.30 equiv.) was added. The mixture was stirred at 79° C. and gradually became a dark red-orange solution. The reaction was monitored by HPLC for disappearance of nicotinaldehyde, which took about 5 hours, and then cooled to 50° C. Phosphorus oxychloride (POCl3, 99%, 6.70 mL, 77.8 mmol, 2.50 equiv.) was added dropwise to the reaction mixture while maintaining the pot temperature below 60° C. The dark brown low viscosity slurry / oil was stirred at 50° C. for 7 hours during which a yellow slurry formed (monitored by HPLC). The orange-yellow slurry was cooled to 15° C. and toluene (20 mL) was added. The mixture was filtered and washed with toluene (3×10 mL). The wet yellow cake was dried under vacuum at 40° C. for 16 hours to give N-ethyl-2-(pyridin-3-yl)-1,3-thiazol-5-amine dihydrochloride (S3) as a yellow solid (5.14 g) with a purity of 92% by weight as determined by 1H NMR assay, indicating a yield of 57.8% over the two steps. 1 H NMR(400MHz,DMSO-d6)δ 9.07(d,J=2.1Hz,1H),8.71(dd,J=5.6,1.3Hz,1H),8.66(ddd,J=8.3,2.2,1.3Hz,1H),7.97(ddd,J= 8.3,5.5,0.7Hz,1H),7.54-7.19(m,1H),7.02(s,1H),3.15(q,J=7.2Hz,2H),1.21(t,J=7.2Hz,3H). 13C NMR(101MHz,DMSO)δ 155.15,140.81,139.39,139.16,136.62,133.13,127.52,120.35,41.56,13.89.ESIMS m / z 206[(M+H-2HCl)+].

[0165] Step 4: Preparation of 4-chloro-N-ethyl-2-(pyridin-3-yl)thiazol-5-amine dihydrochloride (S4) A 1 L round bottom flask was charged with N-ethyl-2-(pyridin-3-yl)-1,3-thiazol-5-amine dihydrochloride (30 g, 108 mmol) and water (360 mL) and the resulting orange / red solution was cooled to about 5° C. in an ice bath. N-chlorosuccinimide (14.4 g, 108 mmol, 1 equiv.) was added in small portions while maintaining the temperature below 7° C. The resulting brown solution was stirred at 5° C. for 40 min and monitored by HPLC. The reaction was poured into 20% potassium carbonate solution, forming a gummy red solid and the product was extracted with ethyl acetate. The organic layer was washed with 10% sodium thiosulfate followed by 20% potassium carbonate. The organic layer was dried over sodium sulfate, filtered and concentrated to give 4-chloro-N-ethyl-2-(pyridin-3-yl)-1,3-triazol-5-amine (S4) (27 g, 104%) as a red oil, which was carried on to step 6 without further purification. 1 H NMR(300MHz,CDCl3)δ 8.96(dd,J=2.4,0.8Hz,1H),8.54(dd,J=4.8,1.6Hz,1H),8.07(ddd,J=8.1,2.4,1.6Hz,1H),7.3 1(ddd,J=8.1,4.8,0.9Hz,1H),4.02(s,1H),3.27(qd,J=7.2,5.8Hz,2H),1.34(t,J=7.2Hz,3H).

[0166] Step 5: Preparation of 3-(methylsulfonyl)propanoyl chloride (S6) A 500 mL three-necked round bottom flask equipped with a nitrogen inlet, reflux condenser, vent to a 1N NaOH based scrubber, and stir bar was charged with 3-(methylsulfonyl)propanoic acid (50 g, 329 mmol) and toluene (299 mL) to give a heterogeneous solution. To this was added thionyl chloride (1.5 equiv.) and the solution was heated to an internal temperature of 70-75° C. The reaction was stirred at this temperature while being monitored by NMR. The reaction was cooled to room temperature at which point significant solid formation was observed. To the slurry was added 250 mL of heptane and the mixture was stirred for 10 min. The solid was isolated by filtration and washed with heptane (90% yield). 1 H NMR(500MHz,CDCl3)δ 3.51 - 3.46(m,2H),3.43-3.38(m,2H),3.00(s,1H);13C NMR(126MHz,CDCl3)δ 171.8,49.5,41.6,39.3.

[0167] Step 6: Preparation of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (Compound 1) as Form A Acetonitrile (300 mL) was added to a L round bottom flask containing crude 4-chloro-N-ethyl-2-(pyridin-3-yl)-1,3-thiazol-5-amine (27 g) to give a red solution. 3-(Methylsulfonyl)propanoyl chloride (27.6 g, 162 mmol, 1.5 equiv) was added in portions over 5 min and the reaction was monitored by HPLC until >98% conversion was achieved. During the course of the reaction, the HCl salt of the product formed as a yellow / brown solid. The solid was isolated by filtration and then neutralized with 20% potassium carbonate and extracted with ethyl acetate. The organic layer was dried over sodium sulfate, filtered and concentrated to give 52.3 g of a crude oil. The crude material was crystallized from isopropanol-heptane to give compound 1 (35.2 g, 80%) as a crystalline solid. 1H NMR(300MHz,Chloroform-d)δ 9.17-9.06(m,1H),8.74(dd,J=4.9,1.6Hz,1H),8.22(ddd,J=8.0,2.4,1.6Hz,1H),7.45(ddd,J=8.0,4.9 ,0.9Hz,1H),3.79(q,J=7.2Hz,2H),3.43(s,2H),2.96(s,3H),2.80(t,J=7.1Hz,2H),1.34-1.15(m,3H); 13 C NMR(75MHz,CDCl3)δ 169.43,163.02,152.15,147.29,138.62,133.37,131.86,128.41,123.92,50.21,45.26,41.75,27.29,12.82;HRMS-ESI(m / z)[M+H]+C 14 H 16 Calculated for ClN3O3S2: 373.0322; found: 374.0397. This crystalline solid was analyzed by PXRD according to Example 8, as shown in Figure 1, and assigned the designation Form A.

[0168] Example 2 Synthesis of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (Compound 1) and its recrystallization as Form A [ka] Step 1: Preparation of tert-butyl (2-(ethylamino)-2-oxoethyl)carbamate (S1) A 3 L jacketed reactor equipped with a temperature logger, mechanical stirrer, and low / high flow nitrogen setup was charged with an aqueous solution of ethylamine (70%) (599 mL, 7.53 mol). The reactor was set at 23° C. (internal temperature=22° C.). Methyl (tert-butoxycarbonyl) glycinate (500 g, 2510 mmol) was added slowly to the stirred solution using a peristaltic pump while maintaining an internal temperature below 35° C. The reaction was stirred overnight at 23° C. (internal temperature). In-process control ( 1H NMR showed complete conversion of starting material to product tert-butyl (2-(ethylamino)-2-oxoethyl)carbamate (S1). The reactor was set up with a short path distillation head and the reaction vessel was heated to 127° C. (internal temperature approx. 115° C., distillation head temperature varied from 70-85° C.). The receiver flask was cooled in an ice bath and approx. 240 mL of ethylamine / water / MeOH was removed. The reaction was cooled to an internal temperature of 60° C. and approx. 350 mL of CPME was added followed by two distillations to remove residual ethylamine (bath temperature set at 117° C., internal temperature approx. 98° C., distillation head temperature approx. 80° C.). Upon distillation completion (determined by a drop in head temperature indicating a lack of distillate), the reaction vessel was set to 23° C. (internal temperature=22° C.) and stirred overnight. The product, tert-butyl (2-(ethylamino)-2-oxoethyl)carbamate, was used in the next step without further purification.

[0169] Step 2: Preparation of 2-amino-N-ethylacetamide hydrochloride (S2) HCl (6M in isopropyl alcohol) (1.67 L, 10.0 mol) was charged to a 5 L jacketed reactor equipped with a nitrogen inlet, peristaltic pump, mechanical stirrer, and exhaust through a base scrubber (alligator trap with 10% NaOH solution). The amide from step 1 was added dropwise from the 3 L jacketed reactor to the 5 L jacketed reactor using the peristaltic pump. After the addition was complete, 400 mL of CPME was added to the 3 L reactor to wash the reactor, and the CPME solution was peristaltic pumped into the 5 L reactor. The reaction was stirred overnight, during which time a white precipitate formed. The contents of the reactor were filtered to provide approximately 100 g of 2-amino-N-ethylacetamide hydrochloride (S2), which was set aside for drying. The filtrate was concentrated to 1.3 L (approximately 50% volume) followed by the addition of 600 mL of CPME and 100 mL of isopropyl alcohol to induce further precipitation of S2. The mixture was stirred for 60 min. The resulting slurry was filtered and the solid was combined with the solid obtained initially and dried overnight in a vacuum oven (50° C., less than 500 mmHg) to give 2-amino-N-ethylacetamide hydrochloride as a white solid (300.5 g, 2168 mmol, 86% yield): 1 H NMR(400MHz,DMSO-d6)δ 3.49(s,2H),3.14(qd,J=7.2,5.4Hz,2H),1.05(t,J=7.2Hz,3H).ESIMS m / z 103[(M+H) + ].

[0170] Step 3: Preparation of N-ethyl-2-(pyridin-3-yl)-1,3-triazol-5-amine dihydrochloride (S3) 2-Amino-N-ethylacetamide hydrochloride (S2) (238 g, 1.72 mol) and anhydrous acetonitrile (2.00 L) were added to a 5 L jacketed reactor equipped with a reflux condenser (dry ice), mechanical stirrer, N2 inlet, and thermocouple to give a white slurry. The reactor was inerted with nitrogen. Anhydrous triethylamine (264 ml, 1.89 mmol) was added and the mixture was stirred for 1 h to give a thick white slurry. Nicotinaldehyde (131 ml, 1.37 mol) was added to give a less viscous slurry. Sulfur (57.2 g, 1.78 mol) was then added. The jacket temperature was set to 72° C. (internal temperature=70° C.) and gradually (within 30 min) a dark red-orange solution was obtained and a precipitate formed. The reaction was monitored by HPLC for the disappearance of nicotinaldehyde, which took approximately 5 hours when heated at 72° C., then cooled to room temperature and stirred overnight. The heterogeneous reaction was reheated to an internal temperature of 50° C. (where it again became a dark red / brown clear solution). To the reaction at an internal temperature of 50° C., phosphoryl trichloride (321 ml, 3431 mmol) was added dropwise such that the internal temperature did not exceed 65.5° C. The reaction was monitored by HPLC until the thioamide intermediate was consumed (which took 6 hours). The jacket temperature was reduced to 20° C. (internal temperature=20° C.) and the solids were isolated by filtration and washed with acetonitrile. The reactor was washed with 100 mL acetonitrile. The filtrate was removed and quenched. The solids were further washed with 300 mL DCM. The damp yellow / green cake was dried under vacuum for 16 hours (40° C., <50 mmHg) to give N-ethyl-2-(pyridin-3-yl)-1,3-triazol-5-amine dihydrochloride as a green solid (200 g, 703 mmol, 51% yield): 1H NMR(400MHz,CDCl3)δ 8.98(dd,J=2.3,0.9Hz,1H),8.53(dd,J=4.8,1.6Hz,1H),8.07(ddd,J=8.0,2.3,1.6Hz,1H),7.31(ddd ,J=8.0,4.8,0.9Hz,1H),6.98(s,1H),3.95(s,1H),3.24(q,J=7.2Hz,2H),1.31(t,J=7.2Hz,3H).ESIMS m / z 206[(M+H) + ].

[0171] Step 4: Preparation of 4-chloro-N-ethyl-2-(pyridin-3-yl)thiazol-5-amine dihydrochloride (S4) A 5 L reactor equipped with a mechanical stirrer, N2 inlet, and temperature probe was charged with N-ethyl-2-(pyridin-3-yl)-1,3-thiazol-5-amine dihydrochloride (210 g, 755 mmol) and water (630 mL), followed by ethyl acetate (2.10 L). To this stirred dark red solution was added a solution of potassium carbonate (209 g, 1.51 mol) in water (209 mL) dropwise over 10 min with a peristaltic pump. Upon completion, the jacket temperature was set to 45° C. (internal temperature=44° C.) and the reaction was stirred for 2 h. The reaction was then transferred to a separatory funnel and the bottom aqueous layer was removed. This aqueous layer was a light clear orange color. This aqueous layer was discarded (HPLC showed no desired product). The organic layer was poured into an Erlenmeyer flask equipped with a magnetic stirrer and containing MgSO4 (210 g). The flask was stirred for 3 hours until the water level of the organic solution was less than 0.5 wt. % as measured by Karl Fischer titration. The mixture was filtered and the inorganic solids were washed with EtOAc (100 mL). The filtrate was poured back into the 5 L reactor and cooled to an internal temperature of 0° C. during which time the dark orange solution became heterogeneous. To this heterogeneous slurry was added 1-chloropyrrolidine-2,5-dione (101 g, 755 mmol) as a solid, maintaining the internal temperature below 12° C. After the addition was complete, the reaction became heterogeneous and was monitored by HPLC. 10 minutes after the addition was complete, the reaction was determined to be complete by HPLC. 4M HCl in dioxane (566 mL, 2.27 mol) was then added dropwise over 90 minutes with a peristaltic pump. The jacket temperature was set to 23° C. (internal temperature=22° C.) and the reaction was stirred at room temperature overnight. After stirring overnight, the heterogeneous slurry was filtered to give a yellow / brown solid which was dried in a vacuum oven (30° C., <50 mmHg) to give 4-chloro-N-ethyl-2-(pyridin-3-yl)thiazol-5-amine dihydrochloride (S4) as a yellow / brown solid (195 g, 629 mmol, 83% yield): 1H NMR(400MHz,DMSO-d6)δ 9.05(d,J=2.2Hz,1H),8.66(dd,J=5.3,1.4Hz,1H),8.45(dt,J=8.4,1.8Hz,1H), 7.78(dd,J=8.2,5.2Hz,1H),3.19(q,J=7.2Hz,2H),1.23(t,J=7.1Hz,3H).ESIMS m / z 240[(M+H) + ].

[0172] Step 5: Preparation of 3-(methylsulfonyl)propanoyl chloride (S6) 3-(Methylsulfonyl)propanoic acid (S5) (101 g, 663 mmol, purchased from Orchev) was charged to a 1 L jacketed reactor followed by acetonitrile (304 g) and then stirred to dissolve the acid. Thionyl chloride (83.7 g, 697 mmol) was added dropwise over 5 minutes. The solution was held at 25° C. for 3 hours to convert the acid (S5) to the acid chloride, 3-(methylsulfonyl)propanoyl chloride (S6). The acid chloride product was used in the next step without further purification.

[0173] Step 6: Preparation of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (Compound 1) To a separate 5 L reactor was charged 4-chloro-N-ethyl-2-(pyridin-3-yl)thiazol-5-amine dihydrochloride (164 g, 84 wt% purity, 442 mmol, 1.0 equiv.) followed by MeCN (415 g, 22.9 equiv.) and potassium carbonate (156 g, 1.11 mol). The orange slurry was stirred and then the acid chloride solution was transferred from the 1 L reactor. The solution of 3-(methylsulfonyl)propanoyl chloride prepared in step 5 was transferred via peristaltic pump over 15 min and an exotherm of +3° C. was observed. The reaction was stirred at room temperature overnight.

[0174] After stirring overnight, the slurry was cooled to an internal temperature of 8° C., and then water (554 g) was transferred to the 5 L reactor via a peristaltic pump over 3 hours. After the solids had dissolved, stirring was stopped and the biphasic mixture was allowed to separate. The lower aqueous phase was discarded, and the organic phase was then concentrated on a rotary evaporator at 50° C. to give N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (compound 1) as a crude brown oil.

[0175] Step 7: Isolation of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (Compound 1) The oil from step 6 was dissolved in 1-butanol (497 g) and the solution was recharged to a 1 L reactor. The reactor was warmed to 30° C. and seeded with N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (Compound 1, Form A) (8.18 g, 21.9 mmol). The slurry was held at 30° C. for 8 hours and then cooled to 18° C. for 12 hours. The slurry was held at 18° C. for 4 hours and then cooled to 10° C. for 8 hours. The slurry was filtered and the wet cake was washed with heptane. The wet cake was dried in an oven at 50° C. and less than 50 mmHg. In this example, uncontrolled heating was performed in the oven, which resulted in some of the wet cake melting. The resulting solid (150 g, 90%) was used in the next step without further purification.

[0176] Step 8: Recrystallization of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (Compound 1) as Form A N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (150 g, 401 mmol) from step 7 was charged into a 1 L reactor followed by MeOH (176 g). The reactor was filled with nitrogen and stirring was started. The contents were heated to 55° C. to dissolve the solids into solution. The dark brown solution was cooled to 25° C. and seeded with N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (Compound 1, Form A) (1.50 g, 4.01 mmol). The slurry was held for 5 hours, after which water (253 g) was added to the reactor via a peristaltic pump over 3 hours. The slurry was held at 25° C. overnight. The next day, the slurry was cooled to an internal temperature of 4° C. over 4 hours and then filtered. The wet cake was washed with 10% MeOH in water (100 g) and then dried in a vacuum oven at 55° C. to give Compound 1 (92.15 g, 61%, 99.3% wt. purity) as a crystalline solid. The solid was analyzed by PXRD according to Example 8, as shown in FIG. 2, and assigned the designation Form A. 1 H NMR(400MHz,CDCl3)δ 9.12(d,J=2.3Hz,1H),8.77-8.71(m,1H),8.22(dt,J=8.1,2.0Hz,1H),7.45(dd,J=8.1,4.8Hz,1H), 3.79(q,J=7.2Hz,2H),3.43(s,2H),2.96(s,3H),2.80(t,J=7.1Hz,2H),1.23(t,J=7.2Hz,3H).ESIMS m / z 374[(M+H) + ].

[0177] Example 3 Crystallization of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (Compound 1) as Form A from 1,4-dioxane In a 1-dram vial, 25.2 mg of Compound 1 Form A prepared in Example 2 was dissolved in 500 μL of 1,4-dioxane. The vial was covered with aluminum foil with a pinhole and the solvent was allowed to evaporate by placing the vial in a fume hood for 3 days to give a crystalline solid. The sample was analyzed by PXRD according to Example 9 and assigned the designation Form A.

[0178] Example 4 Alternative Crystallization of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (Compound 1) as Form A from MeOH In a 1-dram vial, 24.9 mg of Compound 1 Form A prepared in Example 2 was dissolved in 1 mL of MeOH. The vial was covered with aluminum foil with a pinhole and placed in a fume hood to allow the solvent to evaporate for 3 days to give a crystalline solid. The sample was analyzed by PXRD according to Example 9 and assigned the designation Form A.

[0179] Example 5 Crystallization of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (Compound 1) as Form B from acetonitrile In a 1-dram vial, 24.6 mg of Compound 1 Form A prepared in Example 2 was dissolved in 500 μL of acetonitrile. The vial was covered with aluminum foil with a pinhole and placed in a fume hood to allow the solvent to evaporate for 3 days to give a crystalline solid. The sample was analyzed by PXRD according to Example 9 as shown in FIG. 3 and assigned the designation Form B.

[0180] Example 6 Alternative crystallization of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (compound 1) as form B from EtOH In a 1-dram vial, 25.2 mg of Compound 1 Form A prepared in Example 2 was dissolved in 2 mL of EtOH. The vial was covered with aluminum foil with a pinhole and placed in a fume hood to allow the solvent to evaporate for 3 days to give a crystalline solid. The sample was analyzed by PXRD according to Example 9 and assigned the designation Form B.

[0181] Example 7 Evaporative crystallization solvent screening of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide (compound 1) Compound 1 Form A prepared in Example 2 was dissolved in various solvents and subjected to evaporative crystallization procedures according to the same general procedures described in Examples 3 to 6. The results are summarized in Table 4, and the PXRD patterns were confirmed according to Example 9.

[0182] [Table 5]

[0183] Example 8 Powder X-ray diffraction (PXRD) of crystalline polymorphic forms A and B of compound 1 The samples were analyzed using a Rigaku Miniflex II Benchtop X-ray diffractometer. The X-ray source is a Cu Normal Focus tube operated at 30 kV and 15 mA. Further operating parameters are listed in the table below.

[0184] [Table 6]

[0185] Powder samples were prepared by placing at least 20 mg in a glass sample holder and using light finger pressure to keep the sample surface flat and level with the reference plane of the sample holder. The glass holder was placed on an aluminum support. Each sample was analyzed from 3 to 40° 2θ using a continuous scan of 5° 2θ per minute with an effective step size of 0.02° 2θ. High resolution samples were analyzed using a continuous scan of 0.2° 2θ per minute and an effective step size of 0.01° 2θ.

[0186] Example 9 Alternative Powder X-ray Diffraction (PXRD) of Crystalline Polymorphic Forms A and B of Compound 1 The samples were analyzed using a Rigaku Smart-Lab X-ray diffraction system configured for reflection BraggBrentano geometry using a linear source X-ray beam. The X-ray source was a Cu Long Fine Focus tube operated at 40 kV and 44 ma. The source gave the sample an incident beam profile that varied from a thin line at high angles to a wide rectangle at low angles. Beam-tuning slits were used on the linear X-ray source such that the maximum beam size was less than 10 mm along and perpendicular to the line. The Bragg-Brentano geometry is a parafocusing geometry controlled by passive divergence and receiving slits, with the sample itself acting as the focusing component of the optical system. The intrinsic resolution of the Bragg-Brentano geometry is governed in part by the radius of the diffractometer and the width of the receiving slit used. Typically, the Rigaku Smart-Lab was operated such that the peak width was less than 0.1° 2θ. The axial divergence of the X-ray beam was controlled by a 5.0 degree Soller slit in both the incident and diffracted beam paths. Powder samples were prepared in a low background Si holder and light finger pressure was used to keep the sample surface flat and level with the reference plane of the sample holder. Each sample was analyzed from 2 to 40° 2θ using a continuous scan of 6° 2θ per minute with an effective step size of 0.02° 2θ.

[0187] Example 10: Differential Scanning Calorimetry (DSC) of Polymorphic Forms A and B of Compound 1 DSC analysis was performed using a TA Instruments Q2500 DSC. Calibration and validation with indium was completed prior to measuring the samples. Approximately 3-5 mg of sample of polymorphic form A or B was loaded into a sealed aluminum pan under air. In the TA Q2500 DSC, the sample was heated from 0°C to 120°C at a rate of 10°C / min. The resulting thermograms were analyzed using TRIOS software to calculate the melting points and heats of solution. The results are shown in Figure 4 (polymorphic form A) and Figure 5 (polymorphic form B).

[0188] Example 11: Low-frequency Raman spectra of polymorphic forms A and B of Compound 1 Raman spectra were obtained using a Kaiser RXN2 spectrometer equipped with a 785 nm Invictus laser (15 mW). Spectra were collected using a parallel beam probe with Kaiser cosmic ray suppression and a collection time of 4 minutes per spectrum. The results are shown in Figure 6 (polymorph A) and Figure 7 (polymorph B).

[0189] Example 12: Air milling of Polymorph A and Polymorph B materials Compound 1 polymorph A sample and Compound 1 polymorph B sample were separately air milled in a Jet Mill to particle sizes of d(0.5)<6 μm and d(0.9)<15 μm. Powder X-ray diffraction (PXRD) was performed on the samples before and after the air milling process. The PXRD data indicates that the polymorphic form of the samples was not changed by the milling process. After milling, the PXRD data indicated that the milled Compound 1 polymorph A was consistent with the PXRD data of Compound 1 polymorph A described herein. After milling, the PXRD data indicated that the milled Compound 1 polymorph B was consistent with the PXRD data of Compound 1 polymorph B described herein.

[0190] Example 13: Comparison of crystalline Compound 1 Polymorph A and Compound 1 Polymorph B with non-crystalline compound (amorphous oil) in a direct sweet potato whitefly B. tabaci adult knockdown test In this study, the effect of Compound 1 on the behavior of sweet potato whitefly B. tabaci adults was evaluated. In general, various forms of Compound 1 (either polymorphic form A of the present invention, polymorphic form B of the present invention, or the amorphous compound, amorphous oil) were applied to the inside of glass vials, and B. tabaci adults were transferred into the treated vials and exposed to Compound 1 by contact with the treated glass surface. To quantify the knockdown effect as previously reported (Lee et.al. 2013), a line was scored 2 cm above the bottom of the treated vials, and the number of B. tabaci above the 2 cm line was recorded after the first 3 hours of initial exposure. The knockdown whiteflies were not killed immediately, but mock field trials and field trials on treated plants have shown that this effect leads to mortality due to starvation and desiccation.

[0191] This study characterized the effects of Compound 1 Polymorph A and Compound 1 Polymorph B on the behavior of adult B. tabaci whiteflies using a common treated glass vial bioassay to expose the test insects by direct contact (Busvine 1971), and compared these effects in a head-to-head comparison with amorphous Compound 1. Test compounds were dissolved in acetone (Example 11A) or suspended in a volatile antisolvent (hexane) (Example 11B) and then coated evenly onto the inside of a glass vial using a laboratory roller.

[0192] Example 13A: Acetone Experiments In this experiment, two forms of Compound 1 (polymorphic form B and amorphous oil) were evaluated for their effect on B. tabaci behavior. Three application rates (25 g / ha, 2.5 g / ha, and 0.25 g / ha) were evaluated for each form of Compound 1, in addition to a solvent blank control. Each treatment and control was replicated three times. Compound 1 samples were dissolved in acetone and coated onto the inside of 11-dram screw-top glass vials (Fisherbrand 03-339-21N) (Fisher Scientific, Hampton, NH). Each vial had internal dimensions of 2.5 x 9 cm, resulting in a treatment area of ​​75.6 cm. 2 To process the vials, a stock solution of each sample was first prepared by dissolving 1 mg of Compound 1 sample (either polymorphic form B or amorphous oil) in 2 ml of acetone. The stock solutions were stirred using a laboratory vortex mixer to thoroughly mix the solution. 151 μL of each stock solution was added to 11.85 mL of acetone to obtain a 25 g / ha rate (0.25 μg / m 2Treatment solutions of 0.25 g / ha were made. The 25 g / ha treatment solution was serially diluted 10-fold twice to produce treatment solutions at 2.5 g / ha and 0.25 g / ha rates. 3 mL of each treatment solution was transferred to an 11-dram vial, which was placed on a laboratory tube roller and rolled at room temperature until the acetone had completely evaporated leaving a coating of Compound 1 on the inside of the vial. A solvent blank vial was treated with 3 mL of acetone. After treatment, the vials were left open in a fume hood overnight at room temperature in preparation for testing the next day. Mixed B. tabaci whitefly adults (Middle East Asian Minor 1 (MEAM1) biotype) were collected from a susceptible colony maintained at Corteva Agriscience (Indianapolis, IN). Adult B. tabaci were anesthetized with CO2 and introduced into each of the treated vials at approximately 66.5, 32-102 (mean, min-max) and their behavior was recorded. To assess B. tabaci behavior, a line was scored 2 cm above the bottom of the vial and the number of individuals above this line was recorded at 15, 30, 45, 60, 90, 120, 150, and 180 min after introduction. After completion of the experiment, the insects were inactivated by freezing at -30°C for 72 hours, after which the total number of insects in each vial was recorded. The percentage of B. tabaci above 2 cm was calculated for each percentage and used to graph the effect of compound 1 on whiteflies over time.

[0193] statistical analysis For each trial and rate, the proportion of insects above the 2 cm line was analysed with a generalised linear mixed model (GLMM) for repeated measures with binomial response and logit link function (Stroup, 2012). Using a generalised linear model with a binomial distribution for the response instead of a linear model with a normal distribution (ANOVA) allows accurate use of distribution assumptions and the actual sample size (number of insects) used in the experiment.

[0194] The model included treatment, time point, and the interaction treatment × time point as fixed effects, and replicates (experimental units) as a random effect. Correlations between repeated measures were modeled with a compound symmetric covariance matrix.

[0195] Generalized linear mixed models were estimated using the residual pseudo-likelihood method, and means of treatment proportions were compared using Tukey's test (α = 0.05) (Stroup 2012). Statistical analyses were performed with SAS Proc GLIMMIX (SAS Software, version 9.4, SAS Institute Inc., Cary, NC).

[0196] result In the solvent blank control, approximately 20-30% of the insects were above the 2 cm line at any one time (34.1% ± 2.18, mean ± SEM) (Figure 8). At the highest rate, 25 g / ha, there was a significant effect of Compound 1 exposure over time, demonstrating a decrease in the number of insects above the 2 cm line over time as exposure to Compound 1 began to adversely affect insect behavior (Figure 9, Table 5). However, there was no significant effect of treatment and no interaction between treatment and time point, indicating no difference in the effects of Polymorph B and amorphous oil at the 25 g / ha rate (Table 5). At the intermediate rate, 2.5 g / ha, there was a significant difference between the effects of Polymorph B and amorphous oil, with fewer insects exposed to Polymorph B above the 2 cm line because their behavior was affected compared to insects exposed to amorphous oil at the same rate (Figure 10, Table 6). At the 2.5 g / ha rate, there was no effect of time or an interaction between treatment and time (Table 6). Finally, at the lowest rate of 0.25 g / ha, no significant effect was observed in any of the model effects, indicating that at this rate there was no difference in the effects of polymorph B and amorphous oil (Table 7).

[0197] [Table 7]

[0198] [Table 8]

[0199] [Table 9]

[0200] Example 13B: Hexane Experiments In this experiment, three forms of Compound 1 (polymorph A, polymorph B, and non-crystalline amorphous oil) were evaluated for their effect on B. tabaci behavior, polymorph A, polymorph B, and amorphous oil. Samples of polymorph A and polymorph B were finely ground as described in Example 12. The experimental design of the hexane experiment (e.g., rates (25, 2.5, and 0.25 g / ha), replicates (three replicates per treatment), and preparation of treatment suspensions) were similar to the process described in Example 13A. However, hexane was used instead of acetone. Compound 1 does not readily dissolve in hexane, so hexane was used as an anti-solvent to suspend particles of each polymorphic form of Compound 1 and the non-crystalline amorphous oil of Compound 1 in order to coat the inner surface of a glass vial while retaining the polymorphic structure. Since Compound 1 does not readily dissolve in hexane, the stock suspensions were mixed using a laboratory vortex mixer for 30 seconds to disperse the particles as uniformly as possible in each vial, followed by agitation in an ultrasonic bath for 5 minutes (Branson 2800, Branson Ultrasonics Corp., Danbury, CT). After sonication, the samples were mixed again using the vortex mixer, and immediately thereafter 151 μl of each stock suspension was transferred to 11.85 mL of hexane and diluted at a rate of 25 g / ha (0.25 μg / cm 2Treatment suspensions of 25 g / ha were made. The 25 g / ha treatment suspension was serially diluted 10-fold twice to produce treatment suspensions at 2.5 g / ha and 0.25 g / ha rates. 3 mL of each treatment suspension was transferred to an 11-dram vial, and the vial was placed on a laboratory tube roller and rolled at room temperature until the hexane had completely evaporated leaving a uniform coating of Compound 1 particles on the inside of the vial. A solvent blank vial was treated with 3 mL of hexane. After treatment, the vials were stored and loaded with approximately 117.4, ranging from 47 to 219 (average, min-max) B. tabaci adults and assessed as described in the acetone experiment.

[0201] statistical analysis For each trial and rate, the proportion of insects above the 2 cm line was analysed with a generalised linear mixed model (GLMM) for repeated measures with binomial response and logit link function (Stroup, 2012). Using a generalised linear model with a binomial distribution for the response instead of a linear model with a normal distribution (ANOVA) allows accurate use of distribution assumptions and the actual sample size (number of insects) used in the experiment.

[0202] The model included treatment, time point, and the interaction treatment × time point as fixed effects, and replicates (experimental units) as a random effect. Correlations between repeated measures were modeled with a compound symmetric covariance matrix.

[0203] Generalized linear mixed models were estimated using the residual pseudo-likelihood method, and means of treatment proportions were compared using Tukey's test (α = 0.05) (Stroup 2012). Statistical analyses were performed with SAS Proc GLIMMIX (SAS Software, version 9.4, SAS Institute Inc., Cary, NC).

[0204] result In the solvent blank control, approximately 30-50% of the insects were always above the 2 cm line (42.1% ± 3.31, mean ± SEM) (Figure 11). As in the acetone experiment, at the highest rate (25 g / ha), A significant effect of Compound 1 exposure over time was seen for both polymorphic forms and amorphous oil, demonstrating a decrease in the number of insects above the 2 cm line over time as the insecticide begins to adversely affect insect behavior (Figure 12, Table 8). However, no significant effect of treatment was seen, indicating that there was no difference in the effects of Polymorph A, B, and amorphous oil at this rate (Table 8). At the intermediate rate of 2.5 g / ha, a significant effect of treatment was seen, with whiteflies exposed to either Polymorph A or Polymorph B being significantly affected when compared directly to amorphous oil (Figure 13, Table 9). In addition, at the 2.5 g / ha rate, a significant effect of Compound 1 exposure over time was seen, which was highly pronounced for both Polymorph A and Polymorph B treatments (Figure 13, Table 9). Finally, at the 2.5 g / ha rate, a significant treatment x time interaction was found, indicating that there were differences in how insects responded to each treatment over time as evidenced by the difference in the shape of the response curves over time between the Polymorph A and Polymorph B treatments compared to amorphous oil (Figure 13, Table 9). At the lowest rate (0.25 g / ha), results were similar to those observed at the 2.5 g / ha rate. At 0.25 g / ha, significant effects of treatment, time, and the interaction between treatment and time were found (Figure 14, Table 10). Similar to the 2.5 g / ha rate, insects exposed to the Polymorph A and Polymorph B treatments at the 0.25 g / ha rate were adversely affected compared to insects exposed to amorphous oil at the 0.25 g / ha rate (Figure 14, Table 10).

[0205] [Table 10]

[0206] [Table 11]

[0207] [Table 12]

Claims

1. A crystalline form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide, which may be a crystalline polymorphic form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide.

2. 10. The crystalline form of claim 1, wherein the crystalline form is anhydrous or solvent-free.

3. 1. A crystalline polymorphic form of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide having an X-ray powder diffraction pattern including peaks at diffraction angles (2θ) of 20.3±0.2, wherein the crystalline polymorphic form may have an X-ray powder diffraction pattern including peaks at diffraction angles (2θ) of 17.4±0.2, 19.9±0.2, 10.6±0.2, 18.2±0.2, 18.7±0.7, 16.0±0.2, 10.1±0.2, 18.9±0.2, 10.0±0.2, or any combination thereof.

4. 4. The crystalline polymorphic form of claim 3, wherein said crystalline polymorphic form has an X-ray powder diffraction pattern comprising one or more peaks essentially identical to those shown in Figures 1 and 2.

5. 4. The crystalline polymorphic form of claim 3, wherein the crystalline polymorphic form has a DSC thermogram comprising an endothermic peak having a peak temperature at about 101.09°C, or has a DSC thermogram substantially identical to Figure 4.

6. Approximately 255cm －１ , approx. 441cm －１ , approx. 539cm －１ , about 778cm －１ , approx. 921cm －１ , approx. 991cm －１ , approx. 1048cm －１ , approx. 1123cm －１ , approx. 1191cm －１ , approx. 1526cm －１ , approx. 1569cm －１ , approx. 1588cm －１ , about 1701cm －１ , approx. 2949cm －１ , and approximately 3053 cm －１ 4. The crystalline polymorphic form of claim 3 having a Raman spectrum comprising one or more peaks at wavenumbers of

7. 4. The crystalline polymorphic form of claim 3 having a low frequency Raman spectrum containing peaks at wavenumbers essentially identical to those shown in FIG.

8. crystalline polymorphic Form B of N-[4-chloro-2-(pyridin-3-yl)-1,3-thiazol-5-yl]-N-ethyl-3-(methylsulfonyl)propanamide, having an X-ray powder diffraction pattern including a peak at a diffraction angle (2θ) of 15.4±0.2, and optionally having an X-ray powder diffraction pattern including peaks at diffraction angles (2θ) of 7.7±0.2, 15.0±0.2, 16.6±0.2, 16.7±0.2, 17.3±0.2, 17.5±0.2, 18.4±0.2, 19.8±0.2, and 20.2±0.2, or any combination thereof.

9. 10. The crystalline polymorphic form of claim 8, wherein said crystalline polymorphic form has an X-ray powder diffraction pattern comprising one or more peaks essentially identical to those shown in Figure 3.

10. 9. The crystalline polymorphic form of claim 8, wherein the crystalline polymorphic form has a DSC thermogram comprising an endothermic peak having a peak temperature at about 105.24°C, or has a DSC thermogram substantially identical to Figure 5.

11. Approximately 266cm －１ , approx. 446cm －１ , approx. 546cm －１ , approx. 763cm －１ , approx. 987cm －１ , approx. 1044cm －１ , approx. 1137cm －１ , approx. 1187cm －１ and approximately 1,308 cm －１ , approx. 1518cm －１ , approx. 1573cm －１ , approx. 1592cm －１ , approx. 1673cm －１ , approx. 2919cm －１ , and 2937 cm －１ 9. The crystalline polymorphic form of claim 8 having a Raman spectrum comprising one or more peaks at wavenumbers of

12. 9. The crystalline polymorphic form of claim 8, having a low frequency Raman spectrum comprising peaks at essentially the same wavenumbers as those shown in FIG.

13. 10. A composition comprising the crystalline form of claim 1, or the crystalline polymorphic form of claim 3 or 8.

14. A method of controlling pests comprising applying to an area the crystalline form of claim 1, the crystalline polymorphic form of claim 3 or 8.

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