WO2007100165A1

WO2007100165A1 - New crystalline modifications and solvate

Info

Publication number: WO2007100165A1
Application number: PCT/JP2007/054746
Authority: WO
Inventors: Yoshiyuki Kusuoka; Hideaki Suzuki; Norio Tanaka; Shinji Takii; Junichi Kouchi
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2006-03-03
Filing date: 2007-03-05
Publication date: 2007-09-07
Also published as: AR059713A1; AR059714A1; PE20071316A1; UY30186A1; TW200804321A; UY30185A1; PE20071018A1; WO2007100161A1; UY30187A1; WO2007100160A1; TW200808787A; AR059715A1; TW200806660A

Abstract

The present invention relates to novel crystalline modifications and a solvate of the pesticidal compound (I), to a process for the preparation of the same, to pesticidal mixtures and compositions comprising said crystalline modifications and solvate and to their use for combating insect and acarid pests.

Description

DESCRIPTION

New Crystalline Modifications and Solvate

The present invention relates to novel crystalline modifications and a solvate of the pesticidal compound I₁ to a process for the preparation of the same, to pesticidal mixtures and compositions comprising said crystalline modifications and solvate and to their use for combating insect and acarid pests.

Compound I is an active compound for controlling certain insect and acarid pests. "Compound I" in this application is defined as the Z-isomer of the following structure:

Compound I and methods for its preparation have been disclosed in WO 97/40009 as well as in co-pending application JP 2006/009789.

Observations of different crystalline forms or of solvates of compound I have not been described, let alone any characterization of a certain crystalline modification or a solvate or a preparation procedure for obtaining a certain crystalline modification or a solvate.

For the large-scale preparation and formulation of a pesticidal compound it is of crucial importance to know whether different crystalline modifications (also frequently referred to as polymorphs) or solvates of the compound exist, how they can be obtained, and what their characteristic properties are. Crystalline modifications and solvates of one compound may have very different properties, for example with regard to solubility, rate of dissolution, suspension stability, stability during grinding, vapour pressure, optical and mechanical properties, hygroscopicity, crystal size, filtration properties, desiccation, density, melting point, degradation stability, stability against phase transformation into other crystalline modifications, colour, and even chemical reactivity.

Against this background, it has been an object of the present invention to find and characterize novel crystalline modifications and solvates of compound I. A further object has been to find preparation procedures for the novel crystalline modifications and the novel solvate which reproducibly give the crystalline modifications and solvate.

Another object of the invention has been to find preparation procedures which give the novel crystalline modifications and solvate of compound I in high yield.

Yet another object of the invention has been to find preparation procedures which give the novel crystalline modifications and the solvate essentially excluding other crystalline modifications forms or solvates (i.e. in over 80% by weight).

Accordingly, the novel crystalline modifications alpha, beta, delta, and the solvate gamma of compound I, a process for their preparation, pesticidal mixtures and compositions comprising them and their use for combating pests have been found.

Novel crystalline modification alpha

Crystalline modification alpha of compound I in an X-ray powder diffractogram at 25°C, shows at least 4 and preferably all of the following reflexes:

(1) d = 16,04 ± 0,1 A

(2) d = 11 ,39 ± 0,07 A

(3) d = 10,03 ± 0,05 A

(4) d = 8,69 ± 0,05 A (5) d = 8,02 ± 0,05A

In a particularly preferred embodiment, the crystalline modification alpha exhibits a powder X-ray diffraction pattern substantially the same as the pattern shown in Figure 1.

Studies of single crystals of the crystalline modification alpha have shown that the basic crystal structure is triclinic and has the space group P-1. The characteristic data of the crystal structure of the crystalline modification alpha are shown in Table 1.

Table 1 : Crystallographic data of the crystalline modification alpha

a,b,c = Length of the unit cell edges α,β,γ = Angles of the unit cell

The crystalline modification alpha of compound I has typically a melting point in the range from 90 to 105°C, in particular in the range from 95 to 105°C and especially in the range from 103 to 105°C, in essentially pure form of 104,8 to 105°C.

The TG-DTA thermogram of the crystalline modification alpha of compound I contains an endotherm with a minimum at 104, 8⁰C.

The crystalline modification alpha of compound I can, depending on the circumstances (e.g. presence of seed crystals of another crystalline modification; scratches in the measurement vials etc), undergo an endothermic phase transformation at about 95 to 98°C, with an onset at 85 to 9O⁰C and completion at 98°C to 103⁰C. This phase transformation leads to crystalline modification beta.

Novel crystalline modification beta

Crystalline modification beta of compound I in an X-ray powder diffractogram at 25°C, shows at least 4 and preferably all of the following reflexes:

(1) d = 10,60 ± 0,1 A

(2) d = 10,50 ± 0,07 A

(3) d = 10,10 ± 0,05 A (4) d = 8,40 ± 0,05 A

(5) d = 8,30 ± 0,05A

In a particularly preferred embodiment, the crystalline modification beta exhibits a powder X-ray diffraction pattern substantially the same as the pattern shown in Figure 2.

The crystalline modification beta of compound I has typically a melting point in the range from 105 to 112°C, in particular in the range from 18 to 112°C and especially in the range from 110 to 112°C, in essentially pure form of 112 to 112,5°C. The TG-DTA thermogram of the crystalline modification beta of compound I contains an endotherm with a minimum at 112,3°C.

Novel crystalline modification delta

Crystalline modification delta of compound I in an X-ray powder diffractogram at 25°C shows at least the following reflexes:

(1) d = 13,45 ± 0,1 A (2) d = 12,98 ± 0,07 A

(3) d = 9,62 ± 0,05 A

(4) d = 6,49 ± 0,05 A

In a particularly preferred embodiment, the crystalline modification delta exhibits a powder X-ray diffraction pattern substantially the same as the pattern shown in Figure 3.

Studies of single crystals of the crystalline modification delta have shown that the basic crystal structure is monoclinic and has the space group C2/c. The characteristic data of the crystal structure of the crystalline modification delta, are shown in Table 2.

Table 2: Crystallographic data of the crystalline modification delta

a,b,c = Length of the unit cell edges α,β,γ = Angles of the unit cell

The crystalline modification delta of compound I can, depending on the circumstances (e.g. presence of seed crystals of another crystalline modification; scratches in the measurement vials etc), undergo an endothermic phase transformation into crystalline modification beta at around 84 to 86⁰C. It can also, depending on the circumstances, undergo an endothermic phase transformation into crystalline modification alpha at around 94 to 97⁰C. Novel solvate gamma

The solvate gamma of compound I in an X-ray powder diffractogram at 25°C, shows at least all of the following reflexes:

(1) d = 14,35 ± 0,1 A

(2) d = 12,43 ± 0,07 A

(3) d = 7,17 ± 0,05 A

(4) d = 7,08 ± 0,05 A

In a particularly preferred embodiment, the solvate gamma exhibits a powder X-ray diffraction pattern substantially the same as the pattern shown in Figure 4.

Studies of single crystals of the solvate gamma have shown that the basic crystal structure is triclinic and has the space group P-1. The characteristic data of the crystal structure of solvate gamma are shown in Table 3.

Table 3: Crystallographic data of the crystalline modification gamma

a,b,c = Length of the unit cell edges α,β,γ = Angles of the unit cell

The solvate gamma of compound I undergoes an endothermic phase transformation at about 77 to 79°C by detoluenation into crystalline modification beta. It can also, depending on the circumstances, undergo an endothermic phase transformation at about 88 to 9O⁰C by detoluenation into crystalline modification alpha.

Listings of the d-spacings obtained from typical X-ray powder d iff ractog rams of the crystalline modifications alpha, beta, delta and the solvate gamma are given in Table 4: Modification/ alpha beta delta gamma Solvate d [A] 16,04 10,88 13,45 14,35

11,39 10,61 12,98 12,43

10,03 10,46 9,62 8,70

8,69 10,10 9,09 7,17

8,02 8,52 6,73 7,08

7,08 8,40 6,63 6,22

6,20 8,25 6,49 6,03

6,14 8,13 5,98 5,93

5,70 7,51 5,88 5,67

5,62 7,10 5,84 5,44

5,35 6,39 5,37 5,27

5,28 6,31 5,09 5,06

5,24 6,12 4,96 5,03

5,15 5,86 4,93 4,83

5,02 5,79 4,81 4,47

4,87 5,75 4,69 4,38

4,82 5,61 4,49 4,34

4,72 5,11 4,33 4,29

4,63 4,94 4,23 4,21

4,56 4,88 4,19 4,16

4,40 4,81 4,10 4,11

4,36 4,68 4,08 3,96

4,15 4,44 3,98 3,92

4,05 4,20 3,91 3,78

4,01 4,11 3,79 3,65

3,97 3,95 3,69 3,54

3,93 3,88 3,60 3,47

3,87 3,81 3,55 3,40

3,86 3,74 3,48 3,02

3,83 3,64 3,43

3,69 3,53 3,37

3,62 3,48 3,33

3,58 3,42 3,30

3,54 3,32 3,23

3,47 3,26 3,21

3,44 3,25 3,17 d [A] 3,31 . 3,22 3,11

3,19 3,14 3,06

3,16 3,09

3,12 3,07

3,08 2,98

3,00 In another embodiment, the present invention relates to the crystalline modification alpha having a compound I content of at least 92 % by weight, particularly at least 96 % by weight and especially at least 98 % by weight.

This invention also relates to solid (compositions of) compound I comprising the crystalline modification alpha as defined hereinabove and a form of compound I being different from said crystalline modification alpha, e.g. amorphous compound I or compound I of a crystalline modification different from crystalline modification alpha.

Preferably, the solid (compositions of) compound I comprise the crystalline modification alpha in at least 85 % by weight, preferably in at least 90 % by weight, more preferably in at least 95 % by weight, and most preferably in at least 98 % by weight.

The crystalline modification alpha, beta, delta and the solvate gamma can be prepared using a process which comprises the following steps:

step i) preparing a solution of a solid form of compound I being different from the crystalline modification to be obtained in a solvent S; step ii) effecting crystallization of compound I; and step iii) isolating the resulting precipitate.

A detailed description of these steps is as follows:

Step i)

Suitable compound I forms different from the crystalline modification or solvate form to be obtained used in step i) are, for example, selected from amorphous compound I or the other crystalline modifications of compound I such as the beta or delta forms and also mixtures of crystalline modifications of compound I.

The compound I form used as starting material in step i) preferably has a purity of at least 85 % by weight, in particular at least 90 % by weight and especially at least 95 % by weight. "Purity" means the absence of chemical compounds other than compound I.

In case of the crystalline modifications alpha, the solvent S used in step i) is defined as solvent S1 and is selected from any suitable solvent except toluene and alcohols that has the ability to dissolve compound I in such concentrations that highly oversaturated solutions of compound I can be obtained.

A "highly oversaturated solution" defines a solution, wherein the extent of the oversaturation is high, e.g. made by cooling drastically a saturated solution at high temperature

Preferred solvents S1 are polar solvents.

A preferred polar solvent S1 is e.g. acetonitrile.

In case of the crystalline modification beta, the solvent S used in step i) is defined as solvent S2 and is selected from any suitable solvent except toluene and alcohols that has the ability to dissolve compound I in such concentrations that a low oversaturated solution of compound I can be obtained.

A "low oversaturated solution" defines a solution, wherein the extent of the oversaturation is low, e.g. made by cooling gradually a saturated solution at high temperature

Preferred solvents S2 are nonpolar solvents.

A preferred nonpolar solvent is e.g. heptane.

In case of the crystalline modifications delta, the solvent S used in step i) is defined as solvent S3 and is selected from alcohols. Solvent S3 may additionally contain water.

Solvent S3 preferably is selected from: (a) a pure alcohol A1 ,

(b) a mixture of different alcohols A1 , and

(c) a mixture of one or more alcohols A1 with water.

Alcohols A1 according to the present invention are C-i-C-₄-alkanols, i.e. methanol, ethanol, n-propanol, isopropariol, n-butanol, isobutanol, 2-butanol, or tert-butanol.

Particularly preferred alcohols A1 are methanol, ethanol, and isopropanol.

In a preferred embodiment, the solvent S3 used in step i) consists of methanol, ethanol, or isopropanol, preferably methanol. In another embodiment, the solvent S3 used in step i) consists of a mixture of an alcohol A1 as defined hereinabove and water. The proportion of water will preferably not exceed about 25 % by weight, based on the total amount of the solvent S3.

In case of the solvate gamma, the solvent S used in step i) is toluene.

In step i), the compound I form different from the crystalline modification I will usually be incorporated into the solvent S as a solid with mixing at a concentration and temperature where the solvent S is capable of completely dissolving the compound I form.

In a preferred embodiment of the invention, the compound I form is dissolved at an elevated temperature, preferably from 30 to 80⁰C and particularly preferably in the range from 50 to 7O⁰C. The amount of compound I form dissolved in the solvent S depends, of course, on the nature of the solvent S and on the dissolution temperature. The person skilled in the art will be able to determine suitable conditions by standard experiments.

Step ii)

In step ii) of the process of this invention, compound I is then crystallized. Crystallization can be effected in a customary manner, for example by cooling the solution obtained in step i), by adding a solvent which reduces the solubility, or by concentrating the solution, or by a combination of the measures mentioned above.

In a preferred embodiment, step ii) is carried out in the presence of seed crystals of the crystalline modification or solvate to be obtained.

In case of the kinetically favored crystalline modification alpha, crystallization preferably is carried out by crash cooling at a rate of faster than 2O⁰C per minute, preferably faster than 60⁰C per minute, e.g. by putting a solution of compound I in S1 having a temperature of about 40 to 60⁰C into an ice bath. Preferably, seed crystals are added.

To achieve a conversion into the thermodynamically favored crystalline modification beta which is as complete as possible, the crystallization is carried out over a period (duration of crystallization) of at least 1 h, in particular at least 3 h. Cooling of the solution typically is effected at a cooling rate of slower than 5°C per minute, preferably 0.1 to 2°C per minute, preferably starting at an elevated temperature close to the boiling point of the solvent S2. For example, in case where the solvent S consists of heptane, cooling is done starting at 71 ⁰C and at a rate of 1O⁰C per hour. Preferably, seed crystals are added.

In case of the modification delta, the crystallization is carried out over a period (duration of crystallization) of at least 1 h, in particular at least 3 h. Cooling of the solution typically is effected at a cooling rate of 5⁰C to 10⁰C per hour, starting at an elevated temperature close to the boiling point of the solvent S3. For example, in case where the solvent S3 consists of methanol, cooling is done starting at 60 ⁰C and at a rate of 10⁰C per hour.

In case of the solvate gamma, the crystallization is carried out over a period (duration of crystallization) of at least 1 h, in particular at least 3 h. Cooling of the solution typically is effected at a cooling rate of 5°C to 10⁰C per hour, starting at about 70⁰C.

In general, the crystallization is allowed to proceed to a point where at least 60%, preferably at least 70%, in particular at least 90% by weight, for example from 80 to ' 90% by weight, of the compound I employed has crystallized out.

Concentration of the solution is effected by gradually removing the solvent S₁ such as by evaporation in vacuum, either at low temperature or at about 20-25⁰C or at elevated temperature, and/or in the presence of a flow of an inert gas such as nitrogen or argon. The values of "low temperature" and "elevated temperature" depend, of course, on the nature of the solvent S and will be readily determined by the skilled artisan. For example, in case where the solvent S consists of methanol, evaporation is done at 18 to 27⁰C in air or at 4O⁰C to 50°C in a nitrogen flow.

The yield of crystallization may be enhanced by cooling to temperatures lower than 2O⁰C, preferably to a temperature of from 0 to 10⁰C.

In another preferred embodiment, the crystallization is effected by concentrating the solution.

Step iii)

In step iii) of the process of this invention, the crystalline modification or solvate is isolated using customary techniques for separating solid components from liquids, for example by filtration, centrifugation or decanting. In general, the isolated precipitate will be washed, for example with the solvent S used for the crystallization. The washing can be carried out in one or more steps. The washing is typically carried out at temperatures lower than 3O⁰C and in particular lower than 25°C, to keep the loss of the product of value as low as possible. The resulting crystalline compound I can then be dried and subjected to further processing.

The preparation process consisting of steps i) to step iii) can be repeated in order to achieve higher purities of compound I.

The crystalline modifications and the solvate of the present invention are especially suitable for efficiently combating the following pests:

millipedes (Diplopoda) such as Blaniulus or Narceus ssp;

insects (Insecta) such as:

ants, bees, wasps, sawflies (Hymenoptera), e.g. Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis ' geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pheidole megacephala, Pogonomyrmex species such as Pogonomyrmex barbatus and Pogonomyrmex californicus, Dasymutilla occidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile,

beetles (Coleoptera), such as Agrilus sinuatus, Agriotes lineatus, Aghotes obscurus and other Agriotes species, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aracanthus morei, Atomaria linearis, Blapstinus species, Blastophagus piniperda, Blitophaga undata, Bothynoderes punciventris, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus and other Conoderus species, Conorhynchus mendicus, Crioceris asparagi, Cylindrocopturus adspersus, Diabrotica (longicomis) barberi, Diabrotica semi-punctata, Diabrotica speciosa, Diabrotica undecimpunctata, Diabrotica virgifera and other Diabrotica species, Eleodes species, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, lps typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus and other Limonius species, Lissorhoptrus oryzophilus, Listronotus bonariensis, Melanotus communis and other Melanotus species, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Oryzophagus oryzae, Otiorrhynchus ovatus, Oulema oryzae, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga cuyabana and other Phyllophaga species, Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, and other Phyllotreta species, Popillia japonica, Promecops carinicollis, Premnotrypes voraz, Psylliodes species, Sitona lineatus, Sitophilus granaria, Sternechus pinguis, Sternechus subsignatus, and Tanymechus palliatus and other Tanymechus species,

Centipedes (Chilopoda), e.g. Scutigera coleoptrata,

Cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,

Crickets/grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamiis italicus, Chortoicetes terminifera, and Locustana pardalina,

fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,

Flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Agromyza oryzea, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpύs, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Geomyza Tripunctata, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Mayetiola destructor, Mu sea domestica, Muscina stabulans, Oestrus ovis, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phlehotomus argentipes, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Progonya leyoscianii, Psila rosae, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, Tabanus similis, Tetanops myopaeformis, Tipula olerace, and Tipula paludosa,

Heteropterans (Heteroptera), such as Acrostemum hilare, Blissus leucopterus, Cicadellidae such as Empoasca fabae, Chrysomelidae, Cyrtopeltis notatus, Delpahcidae, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nephotettix species, Nezara viridula, Pentatomidae, Piesma quadrata, Solubea insularis and Thyanta perditor,

Aphids and other homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis glycines, Aphis gossypii, Aphis grossulariae, Aphis pomi, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes (Myzus) persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ήbis-nigή, Nilaparvata lugens, Pemphigus bursarius, Pemphigus populivenae, and other Pemphigus species, Perkinsiella sacchaheida, Phorodon humuli, Psyllidae such as Psylla mali, Psylla pin and other Psylla species, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurahtiiand, and Viteus vitifolii,

Lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum and other Agrotis species, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, OhIIo suppresalis and other Chilo species, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cnaphlocrocis medinalis, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Euxoa species, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, HeIIuIa undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Lerodea eufala, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Momphidae, Orgyia pseudotsυgata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta,Sesamia nonagrioides and other Sesamia species, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis,

lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus,

orthopterans (Orthoptera), such as Acrididae, Acheta domestica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus,

silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica,

termites (Isoptera), such as Calotermes flavicollis, Coptotermes ssp., Dalbulus maidis, Heterotermes aureus, Leucotermes flavipes, Macrotermes gilvus, Reticulitermes ssp., Termes natalensis, Coptotermes formosanus,

thrips (Thysanoptera), such as Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici and other Frankliniella species, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips simplex, and Thrips tabaci, ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclυs, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus gallinae,

true bugs (Hemiptera), e.g. Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius prolixus, and Arilus critatus,

Arachnoidea, such as arachnids (Acarina), for example of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Latrodectus mactans, Loxosceles reclusa, Ornithodorus moubata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae species such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae species such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae species such as Brevipalpus phoenicis; Tetranychidae species such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and Oligonychus pratensis,

Earwigs (Dermaptera), e.g. forficula auricularia;

Moreover, the crystalline modifications and the solvate of the present invention are especially useful for the control of crop pests, in particular of the Homoptera, Coleoptera, Lepidoptera and Acarina orders.

For use according to the present invention, the crystalline modifications and the solvate of the present invention can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.

The formulations are prepared in a known manner (see e.g. for review US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961 , Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001 , 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active compound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired surfactants (e.g. adjuvans, emulsifiers, dispersing agents), preservatives, antifoaming agents, anti-freezing agents, for seed treatment formulations also optionally colorants and/or binders and/or gelling agents.

Examples of suitable solvents are water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.

Examples of suitable carriers are ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example highly disperse silica, silicates).

Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N- methylpyrrolidone or water.

Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.

Suitable preservatives are for example Dichlorophen und enzylalkoholhemiformal.

Seed Treatment formulations may additionally comprise binders and optionally colorants.

Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are block copolymers EO/PO surfactants but also polyvinylalcoholsl, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol^®, Polymin^®), polyethers, polyurethans, polyvinylacetate, tylose and copolymers derived from these polymers.

Optionally, also colorants can be included in the formulation.

Examples of a gelling agent is carrageen (Satiagel^®).

Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.

Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound(s). In this case, the active compound(s) are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).

For seed treatment purposes, the respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.

The crystalline modifications and the solvate of the present invention can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are ' intended to ensure in each case the finest possible distribution of the active compound(s) according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1% per weight.

The active compound(s) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives. The following are examples of formulations: 1. Products for dilution with water for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.

A) Water-soluble concentrates (SL, LS)

10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolves upon dilution with water, whereby a formulation with 10 % (w/w) of active compound(s) is obtained.

B) Dispersible concentrates (DC)

20 parts by weight of the active compound(s) are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compound(s) is obtained.

C) Emulsifiable concentrates (EC)

15 parts by weight of the active compound(s) are dissolved in 80 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion, whereby a formulation with 15% (w/w) of active compound(s) is obtained.

D) Emulsions (EW, EO, ES)

25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.

F) Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water- soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound(s), whereby a formulation with 50% (w/w) of active compound(s) is obtained.

G) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s), whereby a formulation with 75% (w/w) of active compound(s) is obtained.

H) Gel-Formulation (GF) (for seed treatment purposes only)

In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent/ wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.

2. Products to be applied undiluted for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted.

I) Dustable powders (DP, DS)

5 parts by weight of the active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound(s)

J) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compound(s) is ground finely and associated with 95.5 parts by weight of carriers, whereby a formulation with 0.5% (w/w) of active compound(s) is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use. K) ULV solutions (UL)

10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound(s), which is applied undiluted for foliar use.

Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulation can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds.

In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.

The invention relates in particular to pesticidal compositions in the form of an aqueous suspension concentrate (SC). Such suspension concentrates comprise ^■ the crystalline modifications or solvate in a finely divided particulate form, where the particles of the crystalline modifications or solvates are suspended in an aqueous medium. The size of the active compound particles, i.e. the size which. is not exceeded by 90% by weight of the active compound particles, is typically below 30 μm, in particular below 20 μm. Advantageously, at least 40% by weight and in particular at least 60% by weight of the particles in the SCs according to the invention have diameters below 2 μm.

In addition to the active compound, suspension concentrates typically comprise surfactants, and also, if appropriate, antifoam agents, thickeners, antifreeze agents, stabilizers (biocides), agents for adjusting the pH and anticaking agents.

In such SCs, the amount of active compound, i.e. the total amount of the crystalline modifications or the solvate of the present invention and, if appropriate, further active compounds is usually in the range from 10 to 70% by weight, in particular in the range from 20 to 50% by weight, based on the total weight of the suspension concentrate.

Preferred surfactants are anionic and nonionic surfactants. The amount of surfactants will generally be from 0.5 to 20% by weight, in particular from 1 to 15% by weight and particularly preferably from 1 to 10% by weight, based on the total weight of the SCs according to the invention. Preferably, the surfactants comprise at least one anionic surfactant and at least one nonionic surfactant, the ratio of anionic to nonionic surfactant typically being in the range from 10:1 to 1:10.

Examples of anionic surfactants include alkylaryl sulfonates, phenyl sulfonates, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, alkylaryl ether sulfates, alkyl polyglycol ether phosphates, polyaryl phenyl ether phosphates, alkyl sulfosuccinates, olefin sulfonates, paraffin sulfonates, petroleum sulfonates, taurides, sarcosides, fatty acids, alkylnaphthalenesulfonic acids, naphthalenesulfonic acids, lignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenolsulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, alkyl phosphates, alkylaryl phosphates, for example tristyryl phosphates, and also polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers (for example

Sokalan^® CP9, BASF), including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above. Preferred anionic surfactants are those which carry at least one sulfonate group, and in particular their alkali metal and their ammonium salts. '

Examples of nonionic surfactants comprise alkylphenol alkoxylates, alcohol alkoxylates, fatty amine alkoxylates, polyoxyethylene glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates, fatty acid polyglycol esters, isotridecyl alcohol, fatty amides, methylcellulose, fatty acid esters, alkyl polyglycosides, glycerol fatty acid esters, polyethylene glycol, polypropylene glycol, polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers (polyethylene oxide/polypropylene oxide block copolymers) and mixtures thereof. Preferred nonionic surfactants are fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, lanolin ethoxylates, fatty acid polyglycol esters and ethylene oxide/ propylene oxide block copolymers and mixtures thereof.

In particular, the SGs according to the invention comprise at least one surfactant which improves wetting of the plant parts by the aqueous application form (wetting agent) and at least one surfactant which stabilizes the dispersion of the active compound particles in the SC (dispersant). The amount of wetting agent is typically in the range from 0.5 to 10% by weight, in particular from 0.5 to 5% by weight and especially from 0.5 to 3% by weight, based on the total weight of the SC. The amount of dispersant is typically from 0.5 to 10% by weight and in particular from 0.5 to 5% by weight, based on the total weight of the SC.

Preferred wetting agents are of anionic or nonionic nature and selected, for example, from naphthalenesulfonic acids including their alkali metal, alkaline earth metal, ammonium and amine salts, furthermore fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates and fatty acid polyglycol esters.

Preferred dispersants are of anionic or nonionic nature and selected, for example, from polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers, alkylaryl phosphates, for example tristyryl phosphates, Iignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenolsulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers (for example Sokalan^® CP9, BASF), including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above.

Viscosity-modifying additives (thickeners) suitable for the SCs according to the invention are in particular compounds which bestow upon the formulation pseudoplastic flow properties, i.e. high viscosity in the resting state and low viscosity in the agitated state. Suitable are, in principle, all compounds used for this purpose in suspension concentrates. Mention may be made, for example, of inorganic substances, such as bentonites or attapulgites (for example Attaclay^® from Engelhardt), and organic substances, such as polysaccharides and heteropolysaccharides, such as xanthan gum such as sold under the trademarks Kelzan^® from Kelco, Rhodopol^® 23 from Rhone Poulenc or Veegum^® from RT. Vanderbilt, and preference is given to using xanthan gum. Frequently, the amount of viscosity-modifying additives is from 0.1 to 5% by weight, based on the total weight of the SC.

Antifoam agents suitable for the SCs according to the invention are, for example, silicone emulsions known for this purpose (Silikon^® SRE, from Wacker, or Rhodorsil^®from Rhodia), long-chain alcohols, fatty acids, defoamers of the type of aqueous wax dispersions, solid defoamers (so-called Compounds), organofluorine compounds and mixtures thereof. The amount of antifoam agent is typically from 0.1 to 1 % by weight, based on the total weight of the SC.

Bactericides may be added for stabilizing the suspension concentrates according to the invention. Suitable bactericides are those based on isothiazolones, for example Proxel^® from ICI or Acticide^® RS from Thor Chemie or Kathon^® MK from Rohm & Haas. The amount of bactericides is typically from 0.05 to 0.5% by weight, based on the total weight of the SC.

Suitable antifreeze agents are liquid polyols, for example ethylene glycol, propylene glycol or glycerol. The amount of antifreeze agents is generally from 1 to 20% by weight, in particular from 5 to 10% by weight, based on the total weight of the suspension concentrate.

If appropriate, the SCs according to the invention may comprise buffers for regulating the pH. Examples of buffers are alkali metal salts of weak inorganic or organic acids, such as, for example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.

The invention relates in particular to pesticidal or parasiticidal compositions in the form of water-dispersible granules (WG) or a water dispersible powder (WP). Such formulations comprise the crystalline modification I in a finely divided particulate form, where the particles of the crystalline modification I are homogenized in a solid or powder form. The size of the active compound particles, i.e. the size which is not exceeded by 90% by weight of the active compound particles, is typically below 30 μm, in particular below 20 μm. Advantageously, at least 40% by weight and in particular at least 60% by weight of the particles in the WGs or WPs according to the invention have diameters below 5 μm.

In addition to the active compound, water-dispersible powders and water dispersible granules typically comprise surfactants, and also, if appropriate, antifoam agents, fillers, binders, and anticaking agents.

In such WGs and WPs, the amount of active compound, i.e. the total amount of the crystalline modification I and, if appropriate, further active compounds is usually in the range from 10 to 90% by weight, in particular in the range from 20 to 75% by weight, based on the total weight of the WG/WP.

In particular, the WGs or WPs according to the invention comprise at least one surfactant which improves wetting of the formulation by the aqueous application form (wetting agent) and at least one surfactant which allows dispersion of the active compound particles in aqueous dilutions. The amount of wetting agent is typically in the range from 0.5 to 10% by weight, in particular from 0.5 to 5% by weight and especially from 0.5 to 3% by weight, based on the total weight of the WGΛΛ/P. The amount of dispersant is typically from 0.5 to 10% by weight and in particular from 2.0 to 8% by weight, based on the total weight of the WG/WP.

Fillers, binders, or additional dispersing aids suitable for the WGs and WPs according to the invention typically make up the remainer of the formulation. These typically are for example kaolin or attapulgite clay, fumed or precipitated silica, diatomateous earth, ammonium sulphate, or calcium silicate.

The crystalline modifications and the solvate of the present invention are effective through both contact and ingestion.

According to a preferred embodiment of the invention, the crystalline modifications and the solvate of the present invention are employed via soil application.

Compositions of this invention may also contain other active ingredients, for example other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.

The following list of pesticidal or parasiticidal compounds which can be used together with the crystalline modifications and the solvate of the present invention according to the invention is intended to illustrate the possible combinations, but not to impose any limitation:

A.1. Organo(thio)phosphates: acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos- methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion;

A.2. Carbamates: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate;

A.3. Pyrethroids: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-, yfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta- cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, permethrin, phenothrin, prallethrin, resmethrin, RU 15525, silafluofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin, ZXI 8901;

A.4. Juvenile hormone mimics: hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;

A.5. Nicotinic receptor agonists/antagonists compounds: acetamiprid, bensultap, cartap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nicotine, spinosad (allosteric agonist), thiacloprid, thiocyclam, thiosultap-sodium, and AKD1022.

A.6. GABA gated chloride channel antagonist compounds: chlordane, endosulfan, gamma-HCH (lindane); acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, vaniliprole, the phenylpyrazole compound of formula r¹

A.7. Chloride channel activators: abamectin, emamectin benzoate, milbemectin, lepimectin; A.8. METI I compounds: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim, rotenone;

A.9. METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;

A.10. Uncouplers of oxidative phosphorylation: chlorfenapyr, DNOC;

A.11. Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fenbutatin oxide, propargite, tetradifon;

A.12. Moulting disruptors: cyromazine, chromafenozide, halofenozide, methoxyfenozide, tebufenozide;

A.13. Synergists: piperonyl butoxide, tribufos;

A.14. Sodium channel blocker compounds: indoxacarb, metaflumizone;

A.15. Fumigants: methyl bromide, chloropicrin sulfuryl fluoride;

A.16. Selective feeding blockers: crylotie, pymetrozine, flonicamid;

A.17. Mite growth inhibitors: clofentezine, hexythiazox, etoxazole;

A.18. Chitin synthesis inhibitors: buprofezin, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;

A.19. Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;

A.20. octapaminergic agonsits: amitraz;

A.21. ryanodine receptor modulators: flubendiamide;

A.22. Various: aluminium phosphide, amidoflumet, benclothiaz, benzoximate, bifenazate, borax, bromopropylate, cyanide, cyenopyrafen, cyflumetofen, chinomethionate, dicofol, fluoroacetate, phosphine, pyridalyl, pyrifluquinazon, sulfur, tartar emetic; A.23. N-R'-2,2-dihalo-1-R"cyclo-propanecarboxamide-2-(2,6-dichloro- αqα -tri- fluoro-p-tolyl)hydrazone or N-R'-2,2-di(R'")propionamide-2-(2,6-dichloro- qqα - trifluoro-p-tolyl)-hydrazone, wherein R' is methyl or ethyl, halo is chloro or bromo, R" is hydrogen or methyl and R'" is methyl or ethyl;

A.24. Anthranilamides: chloranthraniliprole, the compound of formula r²

A.25. Malononitrile compounds: CF₃(CH2)₂C(CN)2CH₂(CF₂)₃CF₂H, CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₅CF₂H, CF₃(CH₂)₂C(CN)₂(CH₂)₂C(CF₃)₂F_I

CF₃(CH2)2C(CN)2(CH2)2(CF2)3CF_3J CF₂H(CF₂)SCH₂C(CN)₂CH₂(CF₂)SCF₂H₁ CF₃(CHZ)₂C(CN)₂CH₂(CF₂)SCF₃, CF₃(CF₂)2CH₂C(CN)₂CH₂(CF₂)₃CF₂H, CF₃CF₂CH₂C(CN)₂CH₂(CF₂)SCF₂H, 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2- (3,3,4,4,4-pentafluorobutyl)-malonodinitrile, and CF₂HCF₂CF₂CF₂CH₂C(CN) ₂CH₂CH₂CF₂CF₃;

A.26. Microbial disruptors: Bacillus thuringiensis subsp. Israelensi, Bacillus sphaericus, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;

The commercially available compounds of the group A may be found in The Pesticide Manual, 13^th Edition, British Crop Protection Council (2003) among other publications.

Thioamides of formula r¹ and their preparation have been described in WO

98/28279.

Lepimectin is known from Agro Project, PJB Publications Ltd, November 2004.

Benclothiaz and its preparation have been described in EP-A1 454621.

Methidathion and Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Acetoprole and its preparation have been described in WO 98/28277. Metaflumizone and its preparation have been described in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p.237-243 and in US 4822779.

Pyrafluprole and its preparation have been described in JP 2002193709 and in WO 01/00614. Pyriprole and its preparation have been described in WO 98/45274 and in US 6335357. Amidoflumet and its preparation have been described in US 6221890 and in JP 21010907. Flufenerim and its preparation have been described in WO 03/007717 and in WO 03/007718. AKD 1022 and its preparation have been described in US 6300348. Chloranthraniliprole has been described in WO 01/70671 , WO 03/015519 and WO 05/118552. Anthranilamide derivatives of formula r² have been described in WO 01/70671 , WO 04/067528 and WO 05/118552. Cyflumetofen and its preparation have been described in WO 04/080180. The aminoquinazolinone compound pyrifluquinazon has been described in EP A 109 7932. The malononitrile compounds CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₃CF₂H, CF₃(CHZ)₂C(CN)₂CH₂(CF₂)_SCF₂H₁ CF₃(CH₂)₂C(CN)₂(CH₂)2C(CF₃)2F_I CF₃(CH2)2C(CN)₂(CH₂)₂(CF₂)₃CF_3I CF₂H(CF₂)_SCH₂C(CN)₂CH₂(CF₂)_SCF₂H, CF₃(CH₂)2C(CN)₂CH₂(CF₂)₃CF_3I CFs(CF₂)₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H, CF₃CF₂CH₂C(CN)₂CH₂(CF₂)_SCF₂H, 2- (2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,4_!4,4-pentafluorobutyl)-malonodinitrile, and CF₂HCF₂CF₂CF₂CH₂C(CN) ₂CH₂CH₂CF₂CF₃ have been described in WO 05/63694.

The crystalline modifications and the solvate of the present invention and the one or more compound(s) of groups A.1 - A.26 are usually applied in a weight ratio of from 500:1 to 1 :100, preferably from 20:1 to 1 :50, in particular from 5:1 to 1 :20.

Depending on the desired effect, the application rates of the compounds or mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 1500 g/ha, in particular from 50 to 750 g/ha.

The crystalline modifications and the solvate of the present invention, the mixtures and the compositions according to the invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the crystalline modifications and the solvate of the present invention or the mixtures or the compositions according to the invention.

"Locus" means a plant, seed, soil, area, material. or environment in which a pest is growing or may grow.

In general, "pesticidally effective amount" means the amount of crystalline modifications or the solvate of the present invention, the mixtures and the compositions according to the invention needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various mixtures / compositions used in the invention. A pesticidally effective amount of the mixtures / compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

The crystalline modifications and the solvate of the present invention, the mixtures and the compositions according to the invention can also be employed for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting a plant, or soil or water in which the plant is growing.

In the context of the present invention, the term plant refers to an entire plant, a part of the plant or the propagation material of the plant, that is, the seed or the seedling.

Plants which can be treated with the crystalline modifications and the solvate of the present invention, the mixtures and the compositions according to the invention include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures.

Some of the inventive mixtures and compositions have systemic action and can therefore be used for the protection of the plant shoot against foliar pests as well as for the treatment of the seed and roots against soil pests. The term seed treatment comprises all suitable seed treatment techniques known in the art, such as, but not limited to, seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping, and seed pelleting.

The present invention also comprises seeds coated with or containing crystalline modifications and the solvate of the present invention or the mixtures or the compositions according to the invention.

The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds. Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

In addition, the crystalline modifications and the solvate of the present invention, the mixtures and the compositions according to the invention may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides or nematicides owing to breeding, mutation and/or genetic engineering methods.

For example, the crystalline modifications and the solvate of the present invention, the mixtures and the compositions according to the invention can be employed in transgenic crops which are resistant to herbicides from the group consisting of the sulfonylureas (EP-A-0257993, U.S. Pat. No. 5,013,659), imidazolinones (see for example US 6222100, WO0182685, WO0026390, WO9741218, WO9802526, WO9802527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073), glufosinate-type (see for example EP-A-0242236, EP-A- 242246) or glyphosate-type (see for example WO 92/00377) or in plants resistant towards herbicides selected from the group of cyclohexadienone/aryloxyphenoxypropionic acid herbicides (US 5,162,602 , US 5,290,696 , US 5,498,544 , US 5,428,001 , US 6,069,298 , US 6,268,550 , US 6,146,867 , US 6,222,099 , US 6,414,222) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A-0142924, EP-A-0193259).

Furthermore, the crystalline modifications and the solvate of the present invention, the mixtures and the compositions according to the invention can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated, for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972).

The seed treatment application of the crystalline modifications and the solvate of the present invention, the mixtures and the compositions according to the invention is carried out by spraying or dusting the seeds before sowing of the plants and before emergence of the plants.

In the treatment of seeds the corresponding formulations are applied by treating the seeds with an effective amount of the crystalline modifications and the solvate of the present invention, the mixtures or the compositions according to the invention. Herein, the application rates of the crystalline modifications and the solvate are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 2.5 kg per 100 kg of seed. For specific crops such as lettuce and onions the rates can be higher.

The mixtures and the compositions according to the invention are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part) and through trophallaxis and transfer.

For use in spray compositions, the content of the active ingredient(s) is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.

For use in treating crop plants, the rate of application of the active ingredient(s) may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.

The figure and examples below serve to illustrate the invention and are not to be understood as limiting it.

Figure 1: X-ray powder diffractogram of modification alpha Figure 2: X-ray powder diffractogram of modification beta Figure 3: X-ray powder diffractogram of modification delta Figure 4: X-ray powder diffractogram of solvate gamma

Analysis: The picture of the X-ray powder diffractogram displayed in the figures were taken using a MXP18VAHF diffractometer (manufacturer: Bruker AXS) in reflection geometry in the range from 2Θ = 2°- 60° with increments of 0.02° using Cu-Ka radiation at 25°C. The 2Θ values found were used to calculate the stated interplanar spacing d. In Figure 1 , the intensity of the peaks (y-axis: linear intensity in counts) is plotted versus the 2Θ angle (x-axis in degrees 2Θ).

Melting points indicated herein refer to values determined on a Mettler hot stage microscope and represent equilibrium melting points.

TG-DTA was performed on a TG 8120(Rigaku). Crystals taken from the mother liquor were blotted dry on filter paper and place in crimped but vented aluminum sample pans for the TG-DTA experiment. The sample size in each case was 4 to 6 mg. The temperature range was typically 2O⁰C to 300⁰C at a heating rate of 5°C/min. The samples were purged with a stream of air flowing at 70 mL/min for the TG-DTA experiment.

Preparation examples

All preparation examples 1 to 4 below were conducted with two samples of solid compound I as starting material which were obtained according to the following procedure:

Preparation of solid compound I:

Step 1) 0.4g of 2-phenyl-4-cyanomethylthiazol and 0.52g of 1 -(2-methyl-4- trifluoromethylthiazol-5-carbonyl)pyrazole were dissolved in 10ml of THF(tetrahydrofuran), and 0.49g of potassium tert.-butoxide was added at 0⁰C. The temperature was raised to 20 to 25°C, and the solution was stirred overnight.The solvent was removed in vacuo, the product was acidified by diluted hydrochloric acid and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate, the solvent was removed in vacuo to give {2-(2-phenylthiazol-4-yl)- 3-(2-methyl-4-trifluoromethylthiazol-5-yl)-.3-hydroxy}acrylonitrile. Step 2) 2.77g of {2-(2-phenylthiazol-4-yl)-3-(2-methyl-4-trifluoromethylthiazol-

5-yl)-3-hydroxy}acrylonitrile was dissolved in 30ml of dioxane, and heated to 80⁰C after addition of 1.07g of potassium carbonate. After adding 0.94g of pivaloylchloride, it was stirred with heating at the same temperature for 1 hour. Then the mixture was cooled to 20 to 25°C and stirred for 12 hours, the solvent was removed in vacuo, and the mixture was extracted by adding water and ethyl acetate. After being extracted with ethyl acetate from the water layer, the combined organic layer was washed with aqueous sodium chloride, dried over anhydrous sodium sulfate, and the solvent was removed in vacuo. Then 7Og of heptane was added and heated to 5O⁰C, slowly cooled to 20 to 25⁰C and stirred for 0.5 hours. A precipitated solid was removed by filtration, the solvent of the mother liquor was removed in vacuo to obtain 1.5g of a mixture. 3.Og of acetonitrile was added and cooled to 0⁰C, then precipitated crystals were obtained by filtration. The crystals was washed with 1.0ml of acetonitrile being cooled to 0°C to obtain 0.63g of compound I.

Example 1 :

1g of compound I was suspended in 3g of acetonitrile and then dissolved completely by heating to 50 °C with stirring. After the stirring was stopped, the solution was cooled drastically to under 10 ⁰C by an ice bath, the precipitation occurred soon after adding a seed crystal of crystalline modification alpha with stirring. The stirring was continued for 10 minutes with ice cooling, and the precipitated crystal was obtained by filtration. The material obtained has the X-ray powder diffractogram shown in figure 1 with the reflexes as listed above, m.p.: - 104.8⁰C.

Example 2:

1g of compound I was suspended in 7g of heptane and then dissolved completely by heating to 71 ⁰C with stirring. After cooling it to 60 ⁰C in 80 minutes, and the precipitation of the crystal was observed by eye after adding a seed crystal of crystalline modification beta. The solution was cooled overnight to 20 ⁰C, and the crystal was obtained by filtration. The material obtained has the X-ray powder diffractogram shown in figure 2 with the reflexes as listed above, m.p.: 112- 112.3 ⁰C.

Example 3:

1g of compound I was suspended in 5g of methanol and then dissolved completely by heating to 60 ⁰C with stirring. After cooling it to 15 ⁰C with continuous stirring, crystals of crystalline modification delta were obtained by filtration. The material obtained has the X-ray powder diffractogram shown in figure 3 with the reflexes as listed above.

Example 4:

1g of compound I was suspended in 3g of toluene and then dissolved completely by heating to 70⁰C with stirring. After cooling it to 5⁰C with continuous stirring, the crystals of the solvate gamma precipitated. The material obtained has the X-ray powder diffractogram shown in figure 4 with the reflexes as listed above.

Formulation examples

Formulation Example 1

1. Preparation of ground slurry

2.0 parts of Sorpol 3353 (trade name of mixture of polyoxyethylene- polyoxypropylene block copolymer and polyoxyethylenestyrylphenylether manufactured by Toho Chemical Ind.) , 10 parts of propylene glycol and 0.1 part of RHODORSIL ANTIFOAM 432 (trade name of silicone defoamer manufactured by Rodia Inc.) were dissolved in 22.8 parts of water. 20.1 parts of crystalline modification beta was dispersed therein. Then the dispersion was subjected to wet milling with a sand-grinder (AIMEX Co., Ltd.) using glass beads (0.8 to 1.2 mm in diameter) to obtain 55 parts of ground slurry.

2. Preparation of dispersion medium

0.3 part of VEEGUM GRANULES (trade name of smectite clay mineral ^■ manufactured by R.T.VANDERBILT Corp.), 0.1 part of KELZAN ASX (trade name of xanthan gum manufactured by Kelco Industrial Biopolymers Co.) and 0.1 part of PROXEL GXL (trade name of 1 ,2-benzisothiazol-3(2H)-one manufactured by Avecia Ltd.) were dispersed in 44.5 parts of water in the order named to obtain 45 parts of dispersion medium.

3. Preparation of aqueous suspended pesticide composition

55 parts of the above-mentioned ground slurry and 45 parts of the above- mentioned dispersion medium were mixed to obtain 100 parts of homogeneous aqueous suspended pesticide composition.

Formulation Example 2

1. Preparation of ground slurry

2.5 parts of Vanillex N (trade name of sodium lignosulfonate manufactured by Nippon Paper Chemicals Co., Ltd.), 2.5 parts of Newpol PE78 (trade name of polyoxyethylenepolyoxypropylene block copolymer manufactured by Sanyo Chemical Ind., Ltd.), 10 parts of propylene glycol and 0.1 part of RHODORSIL ANTIFOAM 432 were dissolved in 21.8 parts of water. 20.1 parts of crystalline modification beta was dispersed therein. Then the dispersion was subjected to wet milling with a sand-grinder using glass beads (0.8 to 1.2 mm in diameter) to obtain 55 parts of ground slurry.

2. Preparation of dispersion medium 0.3 part of VEEGUM GRANULES, 0.1 part of KELZAN ASX and 0.1 part of PROXEL GXL were dispersed in 44.5 parts of water in the order named to obtain 45 parts of dispersion medium.

3. Preparation of aqueous suspended pesticide composition 55 parts of the above-mentioned ground slurry and 45 parts of the above- mentioned dispersion medium were mixed to obtain 100 parts of homogeneous aqueous suspended pesticide composition.

Comparative Example 1

1. Preparation of ground slurry

2.0 parts of Sorpol 3353, 10 parts of propylene glycol and 0.1 part of RHODORSIL ANTIFOAM 432 were dissolved in 22.8 parts of water. 20.1 parts of crystalline modification alpha was dispersed therein. Then the dispersion was subjected to wet milling with a sand-grinder using glass beads (0.8 to 1.2 mm in diameter) to obtain 55 parts of ground slurry.

2. Preparation of dispersion medium

0.3 part ofVEEGUM GRANULES, 0.1 part of KELZAN ASX and 0.1 part of PROXEL GXL were dispersed in 44.5 parts of water in the order named to obtain 45 parts of dispersion medium.

3. Preparation of aqueous suspended pesticide composition

Test Example

Particle sizes of crystalline modification beta in the aqueous suspended pesticide composition obtained in Formulation Examples 1 and 2, and in Comparative

Example 1 were measured. Further, after they had been put into vials (volume 30 ml) respectively and stored in a thermostatic chamber at 4O⁰C for 1 , 2 and 3 months, the particle sizes were measured. Table 5 shows the result.

Method of measurement of the particle size Volume median diameter (μm) of the particles were measured with a laser diffraction technique particle size analyzer LS-13320 (Beckman Coulter Corp.).

Table 5 Volume Median Diameter of Particles (μm)

Example Initial 4O⁰C for 1 month 4O⁰C for 2months 4O⁰C for 3months

Formulation

Example 1 1.1 1.3 1.4 1.4

Formulation

Example 2 1.0 1.1 1.1 1.2

Comparative 1.0 5.6 7.3 8.3

Example 1 ^~

Thus, it was found that the particle size of the Formulation Example 1 and 2 (crystalline modification beta) changes very little over time whereas the particle size of Comparative Example 1 (crystalline modification alpha) increased significantly.

The pesticidal activity of the formulations obtained according to Formulation Example 1 , Formulation Example 2 and Comparative Example 1 was compared according to the following procedure:

lnsecticidal test against Japanese mealybug (first and second stage larva)

In a styrol cup with a lid hole at the center (7.5cm-diameter of lid, 4cm height), water was added, and a filter paper was set so as to suck up the water. On the filter paper, a leaf disk made by a leaf of kidney bean was put. On the leaf disk, 10 Japanese mealybug larva were inoculated thereon, the test sample (2.5 mg/cm²) was sprayed uniformly by using a rotary sprinkler (NZ-3 available from Mizuho chemical Co., Ltd., tradename). A 5% formulation of the compound I of the present invention was diluted with water. After 4 days and 8 days mortality of the insects was calculated by an equation below. Mortality (%)=[number of insect killed/(number of insect killed+number of living insect)]*100

In these tests, the SC formulation of the crystalline modification beta proofed to have higher insecticidal activity.

Claims

Claims:

1. A crystalline modification alpha of compound

having an X-ray powder diffractogram showing, at 25⁰C, at least 4 of the following reflexes:

(1) d = 16,04 ± 0,1 A

(2) d = 11 ,39 ± 0,07 A

(3) d = 10,03 ± 0,05 A (4) d = 8,69 ± 0,05 A

(5) d = 8,02 ± 0,05A.

2. The crystalline modification alpha according to claim 1 having a melting point in the range of from 103 to 105⁰C.

3. A crystalline modification beta of compound I as defined in claim 1, which has an X-ray powder diffractogram showing, at 25°C, at least 4 of the following reflexes:

(1) d = 10,60 ± 0,1 A

(2) d = 10,50 ± 0,07 A

(3) d = 10,10 ± 0,05 A

(4) d = 8,40 ± 0,05 A

(5) d = 8,30 ± 0,05A.

4. The crystalline modification beta according to claim 3 having a melting point in the range of from 110 to 112°C.

5. The crystalline modification alpha according to claim 1 undergoing a phase transformation at 95 to 98⁰C into the crystalline modification beta of compound I as defined in claim 3 or 4.

6. A crystalline modification delta of compound I as defined in claim 1 which has an X-ray powder diffractogram showing, at 25°C, at least the following reflexes:

(1) d = 13,45 ± 0,1 A

(2) d = 12,98 ± 0,07 A

(3) d = 9,62 ± 0,05 A

(4) d = 6,49 ± 0,05 A

7. The crystalline modification delta according to claim 6 undergoing a phase transformation at 84 to 86°C into the crystalline modification beta of compound I as defined in claim 3 or 4.

8. The crystalline modification delta according to claim 6 undergoing a phase transformation at 94 to 97⁰C into the crystalline modification alpha of compound I as defined in claim 1 , 2 or 5.

9. A toluene solvate gamma of compound I as defined in claim 1 which has an X-ray powder diffractogram showing, at 25⁰C, at least the following reflexes:

(1) d = 14,35 ± 0,1 A

(2) d = 12,43 ± 0,07 A

(3) d = 7,17 ± 0,05 A

(4) d = 7,08 ± 0,05 A.

10. The solvate gamma according to claim 9 undergoing a phase transformation at 77 to 79⁰C by detoluenation into the crystalline modification beta of compound I as defined in claim 3 or 4.

11. The solvate gamma according to claim 9 undergoing a phase transformation at 88 to 9O⁰C by detoluenation into the crystalline modification alpha of compound I as defined in claim 1 , 2 or 5.

12. The crystalline modifications alpha, beta, delta and the solvate gamma according to any one of claims 1 to 11 having a compound I content of at least 98% by weight.

13. Solid compound I comprising the crystalline modification alpha as defined in claim 1 , 2 or 5, the crystalline modification beta as defined in claim 3 or 4, the crystalline modification delta as defined in any one of claims 6 to 8 or the solvate gamma as defined in any one of claims 9 to 11 and a form of compound I being different from the crystalline modification alpha, beta, delta or the solvate gamma.

14. Solid compound I according to claim 13 comprising the crystalline modification alpha, beta, delta or the solvate gamma in at least 85% by weight.

15. A process for preparing the crystalline modification alpha as defined in claim 1 , 2 or 5, comprising the steps of: step i) preparing a highly concentrated solution of a solid form of compound I being different from the crystalline modification alpha in a solvent S1 selected from any solvent except toluene and alcohols; step ii) effecting crystallization of compound I; and . step iii) isolating the resulting precipitate.

16. The process according to claim 15, wherein the solvent S1 is acetonitrile.

17. The process according to claim 15 or 16, wherein the crystallization is effected by crash cooling.

18. A process for preparing the crystalline modification beta as defined in claim 3 or 4, comprising the steps of: step i) preparing a low concentrated solution of a solid form of compound I being different from the crystalline modification beta in a solvent S2 selected from any solvent except toluene and alcohols; step ii) effecting crystallization of compound I; and step iii) isolating the resulting precipitate.

19. The process according to claim 18, wherein the solvent S2 is heptane.

20. A process for preparing the crystalline modification delta as defined in any one of claims 6 to 8, comprising the steps of: step i) preparing a solution of a solid form of compound I being different from the crystalline modification delta in a solvent S3 selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, and tert- butanol; step ii) effecting crystallization of compound I; and step iii) isolating the resulting precipitate.

21. The process according to claim 20, wherein the solvent S3 is methanol.

22. A process for preparing the toluene solvate gamma as defined in any one of claims 9 to 11 , comprising the steps of: step i) preparing a solution of a solid form of compound I being different from the solvate gamma in toluene; step ii) effecting crystallization of compound I; and step iii) isolating the resulting precipitate.

23. A synergistic pesticidal mixture comprising, as active components, crystalline modification alpha as defined in claim 1 , 2 or 5, the crystalline modification beta as defined in claim 3 or 4, the crystalline modification delta as defined in any one of claims 6 to 8 or the solvate gamma as defined in any one of claims 9 to 11 and one or more pesticidal compounds.

24. A pesticidal composition, comprising the crystalline modification alpha as defined in claim 1 , 2 or 5, the crystalline modification beta as defined in claim 3 or 4, the crystalline modification delta as defined in any one of claims 6 to 8 or the solvate gamma as defined in any one of claims 9 to 11 and pesticidally acceptable carriers and/or auxiliaries.

25. The composition according to claim 24 in the form of an aqueous suspension concentrate.

26. The composition according to claim 24 in the form of water-dispersible granules.

27. The composition according to claim 24 in the form of a water-dispersible powder.

28. Use of the crystalline modification alpha as defined in claim 1 , 2 or 5, the crystalline modification beta as defined in claim 3 or 4, the crystalline modification delta as defined in any one of claims 6 to 8 or the solvate gamma as defined in any one of claims 9 to 11 or of the composition as defined in any of claims 25 to 27 for controlling pests.

29. A method for controlling pests which comprises contacting the pests or their food supply, habitat, breeding grounds or their locus with a pesticidally effective amount of the crystalline modification alpha as defined in claim 1 , 2 or 5, the crystalline modification beta as defined in claim 3 or 4, the crystalline modification delta as defined in any one of claims 6 to 8 or the solvate gamma as defined in any one of claims 9 to 11 or of the composition as defined in any of claims 25 to 27.

30. A method for protecting a plant from infestation and attack by pests which comprises applying to the foliage or stem of said plant a pesticidally effective amount of the crystalline modification alpha as defined in claim 1 , 2 or 5, the crystalline modification beta as defined in claim 3 or 4, the crystalline modification delta as defined in any one of claims 6 to 8 or the solvate gamma as defined in any one of claims 9 to 11 or of the composition as defined in any of claims 25 to 27.

31. A method as claimed in claims 29 or 30, wherein the crystalline modification alpha as defined in claim 1 , 2 or 5, the crystalline modification beta as defined in claim 3 or 4, the crystalline modification delta as defined in any one of claims 6 to 8 or the solvate gamma as defined in any one of claims 9 to 11 or the composition as defined in any of claims 25 to 27 are applied in an amount of from 5 g/ha to 2000 g/ha.

32. A method of the protection of seed comprising contacting the seeds with the crystalline modification alpha as defined in claim 1 , 2 or 5, the crystalline modification beta as defined in claim 3 or 4, the crystalline modification delta as defined in any one of claims 6 to 8 or the solvate gamma as defined in any one of claims 9 to 11 or the composition as defined in any of claims 25 to 27 in pesticidally effective amounts.

33. A method as claimed in claim 32 wherein the crystalline modification alpha as defined in claim 1 , 2 or 5, the crystalline modification beta as defined in claim 3 or 4, the crystalline modification delta as defined in any one of claims 6 to 8 or the solvate gamma as defined in any one of claims 9 to 11 or the composition as defined in any of claims 25 to 27 is applied in an amount of from 0.1 g to 10 kg per 100 kg of seeds.

34. Seed comprising the crystalline modification alpha as defined in claim 1 , 2 or 5, the crystalline modification beta as defined in claim 3 or 4, the crystalline modification delta as defined in any one of claims 6 to 8 or the solvate gamma as defined in any one of claims 9 to 11 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.