WO2013050317A1

WO2013050317A1 - Polymorphs of an isoxazoline derivative

Info

Publication number: WO2013050317A1
Application number: PCT/EP2012/069325
Authority: WO
Inventors: Neil George; John Hone; Ian Kevin Jones; Rhea Brent
Original assignee: Syngenta Limited
Priority date: 2011-10-03
Filing date: 2012-10-01
Publication date: 2013-04-11

Abstract

The present invention relates to solid forms of certain benzamide isoxazoline insecticides, processes for their preparation, compositions comprising the solid forms and methods of their use as insecticides, acaricides, nematicides or molluscicides.

Description

POLYMORPHS OF AN ISOXAZOLINE DERIVATIVE

This invention relates to solid forms of certain benzamide isoxazoline insecticides, to processes for their preparation, compositions comprising the solid forms and methods of their use as insecticides, acaricides, nematicides or molluscicides.

WO 2009/080250 discloses that certain isoxazoline compounds have insecticidal activity. In particular, a compound of formula I is disclosed:

(I)

This compound is also described in WO2011/104089, WO2011/104088 and

WO2011/104087, including as specific stereo-isomers, together with its use as a pesticide, in particular an insecticide, nematicide, molluscicide and acaricide, and pesticidal compositions containing it.

New solid forms of this compound, their compositions and methods of their preparation and use have now been discovered.

Accordingly, the present invention relates to novel crystalline forms of an isoxazoline insecticide of formula I:

(I) The compound of formula I exists in two different geometric isomeric forms as well as two different optical isomeric forms. It will be appreciated that this leads to four isomers of the compound of formula I, which are shown below: the two cis compounds are designated as compounds la (S) and (R) and the two trans compounds as compounds lb (S) and (R).

la(R) lb(R)

The compound of formula I may be provided as a mixture with the alternative stereoisomer as a racemic mixture, or as an enantiomerically enriched mixture, e.g. in which the proportion of the compound of formula I compared to the total amount of the compound of formula I and the alternative stereoisomer is greater than 50%, e.g. at least 60%, 70%, 80%), 90%), 95%o or at least 99%>. The compound of formula I may also be provided as a mixture with the trans sulfoxide isomer, e.g. in which the proportion of the compound of formula I compared to the total amount of the compound of formula I and the trans isomer is greater than 50%, e.g. at least 60%, 70%, 80%, 90%, 95% or at least 99%.

In one aspect of the invention, there is provided a crystalline polymorph of the compound of formula la (i.e. the compound of formula I in the cis configuration), designated Form 1 , which is characterised by the unit cell parameters of its single crystal as shown in Table 1. This polymorph Form 1 is formed from either the R configuration of the compound of formula la or the S configuration. The polymorph was obtained using the method of Example la.

TABLE 1

In the table, a, b, c = Length of the edges of the unit cell; α, β , γ = Angles of the unit cell; and Z = molecules per cell.

Thus, in one aspect of the present invention, the crystalline polymorph of the invention designated Form 1 has the following lattice parameters: a=5.28(5), b=10.87(5), c=18.70(5), a = 90.00, β = 96.29(5), γ = 90.00 and volume = 1066.7(5) A³.

In another aspect of the invention, the polymorph of the compound of formula la designated Form 1 is characterised by a powder X-ray diffraction pattern expressed in terms of 2Θ angles, wherein the powder X-ray diffraction pattern comprises at least three 2Θ angle values (in degrees) selected from the group comprising 4.74 ± 0.2, 16.98 ± 0.2, 18.90 ± 0.2, 23.54 ± 0.2 and 29.94 ± 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2Θ angle values. These 2Θ angle values are derived from a powder X- ray diffraction pattern that has been calculated using data from the single crystal of the polymorph of the compound of formula la obtained using the method of Example la. The values are generated using a wavelength of 1.54056A with a 2Θ step size of 0.02°. In another aspect, the polymorph of the compound of formula la designated Form 1 has a melting point of 198°C ± 5°C. This melting point is obtained using Differential Scanning Calorimetry (DSC) with a heating rate of 10°C/minute.

In a further aspect, there is provided a polymorph of the compound of formula la that is a racemate of the R and S forms. This polymorph, designated Form 2, is characterized by a powder X-ray diffraction pattern expressed in terms of 2Θ angles, wherein the powder X- ray diffraction pattern comprises at least three 2Θ angle values (in degrees) selected from the group comprising 12.27 ± 0.2, 16.48 ± 0.2, 18.78 ± 0.2, 20.48 ± 0.2 and 20.95 ± 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2Θ angle values. These 2Θ angle values are derived from a powder X-ray diffraction pattern of polymorph Form 2 obtained using the method of Example lb. The values are measured using a wavelength of 1.54056A with a 2Θ step size of 0.02°.

In a another aspect of the invention, the polymorph of the compound of formula la designated Form 2 has a melting point of 198°C ± 5°C. This melting point is obtained using Differential Scanning Calorimetry (DSC) with a heating rate of 10°C/minute.

In a further aspect, the present invention provides a further crystalline form of the compound of formula la, designated Form 3. This polymorph is anhydrous and metastable. This polymorph is characterised by the unit cell parameters of its single crystal as shown in Table 2 and is formed from either the R configuration of the compound of formula la or the S configuration. This polymorph was obtained using the method of Example la.

TABLE 2

In another aspect of the invention, the polymorph of the compound of formula la designated Form 3 is characterised by a powder X-ray diffraction pattern expressed in terms of 2Θ angles, wherein the powder X-ray diffraction pattern comprises at least three 2Θ angle values (in degrees) selected from the group comprising 3.80 ± 0.2, 4.82 ± 0.2, 5.62 ± 0.2, 6.61 ± 0.2, 9.63 ± 0.2, 11.28 ± 0.2 and 13.23 ± 0.2. More preferably, the powder X-ray diffraction pattern comprises all of these 2Θ angle values. These 2Θ angle values are derived from a powder X-ray diffraction pattern that has been calculated using data from the single crystal of the polymorph of the compound of formula la obtained using the method of Example la. The values are generated using a wavelength of 1.54056A with a 2Θ step size of 0.02°.

In another aspect, the polymorph of the compound of formula la designated Form 3 has a melting point of 185°C ± 5°C. This melting point is obtained using Differential Scanning Calorimetry (DSC) with a heating rate of 10°C/minute.

In the context of the present invention, a polymorph is a particular crystal form of a chemical compound that can exist in more than one crystal form in the solid state. A crystal form of a compound contains the constituent molecules arranged in orderly repeating patterns extending in all three spatial dimensions (in contrast, an amorphous solid form has no long-range order in the position of molecules). Different polymorphs of a compound have different arrangements of atoms and or molecules in their crystal structure. When the compound is a biologically active compound, such as an insecticide, the difference in crystal structures can lead to different polymorphs having differing chemical, physical and biological properties. Properties which may be affected include crystal shape, density, hardness, colour, chemical stability, melting point, hydroscopicity, suspensibility, dissolution rate and biological availability. As such, a specific polymorph may have properties which make it more advantageous in a particular use relative to another polymorph of the same compound: in particular, the physical, chemical and biological properties listed above can have a significant effect on the development of production methods and formulations and the quality and efficacy of plant treatment agents, such as insecticides. It is noted that predicting whether the solid state of a compound may be present as more than one polymorph is not possible and nor is it possible to predict the properties of any of these crystal forms. In particular, in the context of the present invention, it has been found that the compound of formula la can exist as a stable polymorph designated Form 1 when present in either the S or the R configuration or as a stable polymorph designated Form 2 when present in a racemic form. Both the Form 1 and Form 2 polymorphs are advantageous due to their stability which decreases the amount of crystallization occurring in formulations of the compound of formula I. Such crystallization is detrimental because it leads to thickening and potentially solidification of the formulation which can lead to blockages in application equipment e.g. in spray nozzles in agricultural application machinery.

The present invention also relates to methods for the preparation of the polymorphs of the invention either directly (i.e. not starting with other solid forms of the compound of formula la) or by conversion of other solid forms of the compound of formula la.

Thus, in one aspect of the invention, there is provided a method for preparing a crystalline polymorph of the compound of formula la designated Form 1 comprising i) providing a compound of formula Ia(S) or (R) which is completely dissolved in a solvent in which the compounds of formula la is sufficiently soluble to allow a solution of 0.5 to 10% w/v of the compound of formula la to be formed and then evaporating the solvent rapidly and then ii) adding a solvent which is suitable for forming a flowable slurry and maintaining the slurry at 25°C for 24 hours with stirring. Suitable solvents for step i) include, but are not limited to, acetonitrile, methyl ethyl ketone, methanol or a mixture of any of these solvents with water. Suitable solvents for step ii) include, but are not limited to, acetonitrile, methanol and mixtures of these solvents with water.

In a further aspect there is provided a method for preparing the crystalline polymorph designated Form 1 comprising mixing a compound of formula Ia(S) or Ia(R) in any form, crystalline or otherwise, with a solvent which is suitable for forming a flowable slurry, adding seed crystals of polymorph Form 1 to the slurry and maintaining the slurry whilst the compound of formula Ia(S) or Ia(R) converts to polymorph Form 1. Suitable solvents include, but are not limited to, acetonitrile, methanol and mixtures of these solvents with water.

In a further aspect, there is provided a method for preparing the crystalline polymorph designated Form 2 comprising i) providing a racemic mixture of the compound of formula la and a solvent in which the compounds of formula la is sufficiently soluble to allow a solution of 0.5 to 10% w/v of the compound of formula la to be formed ii) mixing the compound of formula la and the solvent such that at least some of the compound of formula la is present as a solid at 40°C and then iii) subjecting the mixture so formed to temperature cycling for at least three days, the temperature being cycled between about room temperature and 40°C every 4 hours with stirring. Suitable solvents include, but are not limted to acetonitrile, methanol and mixtures of these solvents with water.

Assaying the solid phase for the presence of crystals may be carried out by conventional methods known in the art. For example, it is convenient and routine to use powder X-ray diffraction techniques. Other techniques which may be used include differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA) and Raman or Infra-red spectroscopy, NMR, gas chromatography or HPLC. Single crystal X-ray diffraction is especially useful in identifying crystal structures.

The polymorphs of the invention may be readily incorporated into insecticidal compositions by conventional means. Accordingly, in a further aspect, the invention provides an insecticidal composition comprising a polymorph of the invention as defined above and an agriculturally acceptable carrier or diluent.

It has been determined that compounds of formula la in which the chiral centre exists in the S configuration are more biologically active than compounds of formula la in which the chiral centre exists in the R configuration. Thus, whilst it is possible for the

compositions of the invention to contain a mixture of the S and R configurations in any ratio, e.g. in a molar ratio of 1 :99 to 99: 1, the compositions of the invention may also comprise a racemic mixture of the compound of formula la in the S and R configurations or, preferably, be enantiomerically enriched for the compound of formula la in the S configuration.

Preferably, when the composition comprises an enantiomerically enriched mixture the compound of formula la in the S configuration, the proportion of the S configuration compared to the total amount of both enantiomers is for example greater than 50mol%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or at least 99mol% of the combined amount of compound of formula I in the R and S configuration. It is noted that, where the composition of the invention comprises a racemic mixture of the S and R configurations or is enantiomerically enriched for the compound of formula la in the S configuration, the composition may be made up of i) cis S polymorph Form 1 and cis R polymorph Form 1 or ii) racemic polymorph Form 2 or iii) a mixture thereof.

Thus, in one embodiment, the composition of the invention comprises i) a crystalline polymorph of the compound of formula la designated Form 1, ii) a crystalline polymorph of the compound of formula la designated Form 2 or iii) a mixture thereof.

In another embodiment, the composition further comprises at least one form of the compound of formula la which differs from Form 1 and Form 2, for example, Form 3 or an amorphous form or a mixture of Form 3 and the amorphous form. In a more preferred embodiment, the composition comprises less than about 20mol%, preferably less than about 10mol% and most preferably less than about 5mol%, of the at least one form of the compound of formula la which differs from Form 1 and Form 2.

In another embodiment, the composition of the invention further comprises, in addition to the compound of formula la, the compound of formula lb. In a more preferred embodiment, the composition comprises less than about 25mol% of the compound of formula lb and more preferably less than about 20mol% of the compound of formula lb.

Compositions comprising compounds of formula I are preferably enriched for compounds of formula I in the S configuration and preferably enriched for compounds of formula I in the cis configuration. Preferably said compositions are simultaneously enriched for compounds of formula I in the S configuration and cis configuration.

Compositions comprising compounds of formula I may contain at least 70mol% of compounds Ia(S) and Ib(S) compared to the total amount of Ia(S), Ib(S), Ia(R) and Ib(R). In some cases said compositions contain at least 80mol%, at least 90mol%, or even at least 95mol% of compounds Ia(S) and Ib(S) compared to the total amount of Ia(S), Ib(S), Ia(R) and Ib(R). Compositions comprising compounds of formula I may contain at least 70mol% of compounds Ia(S) and Ia(R) compared to the total amount of Ia(S), Ib(S), Ia(R) and Ib(R). In some cases said compositions contain at least 80mol%, at least 90mol%, or even at least 95mol% of compounds Ia(S) and Ia(R) compared to the total amount of Ia(S), Ib(S), Ia(R) and Ib(R).

Compositions comprising compounds of formula I may contain at least 90mol% of compounds Ia(S) and Ib(S) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R) and at least 60mol% of compounds Ia(S) and Ia(R) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R).

Compositions comprising compounds of formula I may contain at least 90mol% of compounds Ia(S) and Ib(S) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R) and at least 70mol% of compounds Ia(S) and Ia(R) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R).

Compositions comprising compounds of formula I may contain at least 90mol% of compounds Ia(S) and Ib(S) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R) and at least 80mol% of compounds Ia(S) and Ia(R) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R).

Compositions comprising compounds of formula I may contain at least 90mol% of compounds Ia(S) and Ib(S) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R) and at least 90mol% of compounds Ia(S) and Ia(R) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R).

Compositions comprising compounds of formula I may contain at least 95mol% of compounds Ia(S) and Ib(S) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R) and at least 60mol% of compounds Ia(S) and Ia(R) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R).

Compositions comprising compounds of formula I may contain at least 95mol% of compounds Ia(S) and Ib(S) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R) and at least 70mol% of compounds Ia(S) and Ia(R) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R).

Compositions comprising compounds of formula I may contain at least 95mol% of compounds Ia(S) and Ib(S) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R) and at least 80mol% of compounds Ia(S) and Ia(R) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R).

Compositions comprising compounds of formula I may contain at least 95mol% of compounds Ia(S) and Ib(S) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R) and at least 90mol% of compounds Ia(S) and Ia(R) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R).

Compositions comprising compounds of formula I may contain at least 95mol% of compounds Ia(S) and Ib(S) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R) and at least 95mol% of compounds Ia(S) and Ia(R) compared to the total amount of compounds Ia(S), Ib(S), Ia(R) and Ib(R).

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera,

Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests. The pests which may be combated and controlled by the polymorphs and compositions of the invention include those pests associated with agriculture (which term includes the growing of crops for food and fiber products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).

Examples of pest species which may be controlled by the polymorphs and

compositions of the invention (preferably wherein the compound of formula I is

simultaneously enriched for S and cis as defined above) include: coleopterans, for example, Callosobruchus chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna

vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Monochamus alternatus, Lissorhoptrus oryzophilus, Lyctus bruneus, Aulacophora femoralis; lepidopterans, for example, Lymantria dispar, Malacosoma neustria), Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis),

Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella,

Agrotisfucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens, Phyllocnistis citrella; hemipterans, for example, Nephotettix cincticeps, Nilaparvata lugens,

Pseudococcus comstocki, Unaspis yanonensis, Myzus persicas, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nezara spp., Trialeurodes vaporariorm, Psylla spp.; thysanopterans, for example, Thrips palmi, Franklinella occidental;

orthopterans, for example, Blatella germanica, Periplaneta americana, Gryllotalpa

Africana, Locusta migratoria migratoriodes; isopterans, for example, Reticulitermes speratus, Coptotermes formosanus; dipterans, for example, Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles sinensis, Culex tritaeniorhynchus, Liriomyza trifolii; acari, for example, Tetranychus cinnabarinus, Tetranychus urticae, Panonychus citri, Aculops pelekassi, Tarsonemus spp. ; nematodes, for example, Meloidogyne incognita, Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides besseyi, Heterodera glycines, Pratylenchus spp.. Examples of further pest species which may be controlled by the polymorphs and compositions of the invention (preferably wherein the compound of formula I is

simultaneously enriched for S and cis as defined above) include: from the order of the Anoplura (Phthiraptera), for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.; from the class of the Arachnida, for example, Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae,

Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici; from the class of the Bivalva, for example, Dreissena spp.; from the order of the Chilopoda, for example, Geophilus spp., Scutigera spp.; from the order of the Coleoptera, for example, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp.,

Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp.,

Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna

consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus

surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleariae,

Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.; from the order of the Collembola, for example, Onychiurus armatus; from the order of the Dermaptera, for example, Forficula auricularia; from the order of the Diplopoda, for example, Blaniulus guttulatus; from the order of the Diptera, for example, Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia spp., Tipula paludosa,

Wohlfahrtia spp.; from the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.; from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius

vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana,

Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti; ft may be furthermore possible to control protozoa, such as Eimeria; from the order of the Heteroptera, for example, Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlbergella singularis,

Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.; from the order of the Homoptera, for example, Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui,

Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp.,

Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp.,

Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii; from the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Mono- morium pharaonis, Vespa spp.; from the order of the Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber; from the order of the Isoptera, for example, Reticulitermes spp., Odontotermes spp.; from the order of the

Lepidoptera, for example, Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp., Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella, Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mods repanda, Mythimna separata, Oria spp., Oulema oryzae, Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp.; from the order of the Orthoptera, for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria; from the order of the Siphonaptera, for example,

Ceratophyllus spp., Xenopsylla cheopis. From the order of the Symphyla, for example, Scutigerella immaculata; from the order of the Thysanoptera, for example, Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.; from the order of the Thysanura, for example, Lepisma saccharina. The phytoparasitic nematodes include, for example, Anguina spp., Aphelenchoides spp.,

Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp.,

Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipenetrans, Xiphinema spp.

In particular, the compositions and polymorphs of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used to control the following pest spcies:

Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp.

(capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp.

(stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa

decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta_ migratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms),

Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite),

Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite),

Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), the Kalotermitidae (for example Neotermes spp.), the

Pvhinotermitidae (for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis) and the Termitidae (for example Globitermes sulfureus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh's ant),

Damalinia spp. and Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp.

(lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabditis elegans_ (vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug). The polymorphs and compositions of the invention of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used to control animal housing pests including: Ants, Bedbugs (adult), Bees, Beetles, Boxelder Bugs, Carpenter Bees, Carpet Beetles, Centipedes, Cigarette, Beetles, Clover Mites, Cockroaches, Confused Flour Beetle, Crickets, Earwigs, Firebrats, Fleas, Flies, Lesser Grain Borers, Millipedes, Mosquitoes, Red Flour Beetles, Rice Weevils, Saw- toothed Grain Beetles, Silverfish, Sowbugs, Spiders, Termites, Ticks, Wasps, Cockroaches, Crickets, Flies, Litter Beetles (such as Darkling, Hide, and Carrion), Mosquitoes, Pillbugs, Scorpions, Spiders, Spider Mites (Twospotted, Spruce), Ticks. The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used to control ornamental pests including: Ants (Including Imported fire ants), Armyworms, Azalea caterpillars, Aphids, Bagworms, Black vine weevils (adult), Boxelder bugs,

Budworms, California oakworms, Cankerworms, Cockroaches, Crickets, Cutworms, Eastern tent caterpillars, Elm leaf beetles, European sawflies, Fall webworms, Flea beetles, Forest tent caterpillars, Gypsy moth larvae, Japanese beetles (adults), June beetles (adults), Lace bugs, Leaf- feeding caterpillars, Leafhoppers, Leafminers (adults), Leaf rollers, Leaf skeletonizers, Midges, Mosquitoes, Oleander moth larvae, Pillbugs, Pine sawflies, Pine shoot beetles, Pinetip moths, Plant bugs, Root weevils, Sawflies, Scale insects (crawlers), Spiders, Spittlebugs, Striped beetles, Striped oakworms, Thrips, Tip moths, Tussock moth larvae, Wasps, Broadmites, Brown softscales, California redscales (crawlers), Clover mites, Mealybugs, Pineneedlescales (crawlers), Spider mites, Whiteflies

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used to control turf pests including: Ants (Including Imported fire ants, Armyworms, Centipedes, Crickets, Cutworms, Earwigs, Fleas (adult), Grasshoppers, Japanese beetles (adult), Millipedes, Mites, Mosquitoes (adult), Pillbugs, Sod webworms, Sow bugs, Ticks (including species which transmit Lyme disease), Bluegrass billbugs (adult), Black turfgrass ataenius (adult), Chiggers, Fleas (adult), Grubs (suppression), Hyperodes weevils (adult), Mole crickets (nymphs and young adults), Mole Crickets (mature adults), Chinch Bugs.

The invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a polymorph or composition of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) to a pest, a locus of pest, preferably a plant, or to a plant susceptible to attack by a pest. The polymorphs and compositions of the invention are preferably used against insects, acarines or nematodes.

The term "plant" as used herein includes seedlings, bushes and trees.

Plants are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD- inhibitors) by conventional methods of breeding or by genetic engineering. An example of a plant that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of plants that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names

PvOundupReady® and LibertyLink®. Plants are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plants are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes

(resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate. Traits include those that increase plant defences against insects, arachnids, nematodes and slugs and snails by virtue of toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CrylA(Al), CrylA(b), CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and also combinations thereof). Traits also include those that plant defences against fungi, bacteria and viruses by systemic acquired resistance (SA ), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.

Plants or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate. Plants are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavor). Plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods, and parts thereof, may be treated by the

polymorphs and compositions of the invention. Plant cultivars are understood as meaning plants having novel properties ("traits") which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- or genotypes. Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive "synergistic" effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected. The preferred transgenic plants or plant cultivars (obtained by genetic engineering) which are to be treated according to the invention include all plants which, by virtue of the genetic modification, received genetic material which imparts particularly advantageous, useful traits to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further examples of such traits are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, sugar beet, tomatoes, peas and other vegetable varieties, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton, tobacco and oilseed rape.

In particular, the polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used for pest control on various plants, including soybean (e.g. 10-70g/ha), corn (e.g. 10- 70g/ha), sugarcane (e.g. 20-200g/ha), alfalfa (e.g. 10-70g/ha), brassicas (e.g. 10-50g/ha), oilseed rape (e.g. canola) (e.g. 20-70g/ha), potatoes (including sweet potatoes) (e.g. 10- 70g/ha), cotton (e.g. 10-70g/ha), rice (e.g. 10-70g/ha), coffee (e.g. 30-150g/ha), citrus (e.g. 60-200g/ha), almonds (e.g. 40-180g/ha), fruiting vegetables (e.g. tomatoes, pepper, chili, eggplant, cucumber, squash etc.) (e.g. 10-80g/ha), tea (e.g. 20-150g/ha), bulb vegetables (e.g. onion, leek etc.) (e.g. 30-90g/ha), grapes (e.g. 30-180g/ha), pome fruit (e.g. apples, pears etc.) (e.g. 30-180g/ha), and stone fruit (e.g. pears, plums etc.) (e.g. 30-180g/ha). In addition, the compound of formula I per se, may be used for pest control on the various plants listed above.

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on soybean to control, for example, Elasmopalpus lignosellus (Dl), Diloboderus abderus (D2), Diabrotica speciosa (D3), Sternechus subsignatus (D4), Formicidae (D5), Agrotis ypsilon (D6), Julus ssp. (D7), Anticarsia gemmatalis (D8), Megascelis ssp. (D9), Procornitermes ssp. (D10), Gryllotalpidae (Dl 1), Nezara viridula (D12), Piezodorus spp. (D13), Acrosternum spp. (D14), Neomegalotomus spp. (D15), Cerotoma trifurcata (D16), Popillia japonica (D17), Edessa spp. (D18), Liogenys fuscus (D19), Euchistus hews (D20), stalk borer (D21), Scaptocoris castanea (D22), phyllophaga spp. (D23), Pseudoplusia includens (D24), Spodoptera spp. (D25), Bemisia tabaci (D26), Agriotes spp. (D27). The polymorphs and compositions of the invention are preferably used on soybean to control Diloboderus abderus, Diabrotica speciosa, Nezara viridula, Piezodorus spp., Acrosternum spp., Cerotoma trifurcata, Popillia japonica, Euchistus her os, phyllophaga spp., Agriotes spp..

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on corn to control, for example, Euchistus heros (D28), Dichelops furcatus (D29), Diloboderus abderus (D30), Elasmopalpus lignosellus (D31), Spodoptera frugiperda (D32), Nezara viridula (D33), Cerotoma trifurcata ponica (D34), Popillia japonica (D35), Agrotis ypsilon (D36), Diabrotica speciosa (D37), Heteroptera (D38), Procornitermes ssp. (D39), Scaptocoris castanea (D40), Formicidae (D41), Julus ssp. (D42), Dalbulus maidis (D43), Diabrotica virgifera (D44), Mods latipes (D45), Bemisia tabaci (D46), heliothis spp. (D47), Tetranychus spp. (D48), thrips spp. (D49), phyllophaga spp. (D50), scaptocoris spp. (D51), Liogenys fuscus (D52), Spodoptera spp. (D53), Ostrinia spp. (D54), Sesamia spp. (D55), Agriotes spp. (D56). The compositions and polymorphs of the invention are preferably used on corn to control Euchistus heros, Dichelops furcatus, Diloboderus abderus, Nezara viridula, Cerotoma trifurcata, Popillia japonica, Diabrotica speciosa, Diabrotica virgifera, Tetranychus spp., thrips spp., phyllophaga spp., scaptocoris spp., Agriotes spp..

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on sugar cane to control, for example, Sphenophorus spp. (D57), termites (D58), Mahanarva spp. (D59). The compositions and polymorphs of the invention are preferably used on sugar cane to control termites, Mahanarva spp..

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on alfalfa to control, for example, Hyper a brunneipennis (D60), Hyper a postica (D61), Colias eurytheme (D62), Collops spp. (D63), Empoasca solana (D64), Epitrix (D65), Geocoris spp. (D66), Lygus hesperus (D67), Lygus lineolaris (D68), Spissistilus spp. (D69), Spodoptera spp. (D70), Trichoplusia ni (D71). The compositions and polymorphs of the invention are preferably used on alfalfa to control Hypera brunneipennis, Hypera postica, Empoasca solana, Epitrix, Lygus hesperus, Lygus lineolaris, Trichoplusia ni.

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on brassicas to control, for example, Plutella xylostella (D72), Pieris spp. (D73), Mamestra spp. (D74), Plusia spp. (D75), Trichoplusia ni (D76), Phyllotreta spp. (D77), Spodoptera spp. (D78), Empoasca solana (D79), thrips spp. (D80), Spodoptera spp. (D81), Delia spp. (D82). The compositions and polymorphs of the invention are preferably used on brassicas to control Plutella xylostella Pieris spp. , Plusia spp. , Trichoplusia ni, Phyllotreta spp., thrips spp.. The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on oil seed rape, e.g. canola, to control, for example, Meligethes sp. (D83),

Ceutorhynchus napi (D84), Psylloides sp. (D85). The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on potatoes, including sweet potatoes, to control, for example, Empoasca sp. (D86), Leptinotarsa sp. (D87), Diabrotica speciosa (D88), Phthorimaea sp. (D89), Paratrioza sp. (D90), Maladera matrida (D91), Agriotes sp. (D92). The compositions and polymorphs of the invention are preferably used on potatoes, including sweet potatoes, to control Empoasca sp, Leptinotarsa sp, Diabrotica speciosa, Phthorimaea sp, Paratrioza sp, Agriotes sp.

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on cotton to control, for example, Anthonomus grandis (D93), Pectinophora sp. (D94), heliothis sp. (D95), Spodoptera sp. (D96), Tetranychus sp. (D97), Empoasca sp. (D98), thrips sp. (D99), Bemisia tabaci (D100), Lygus sp. (D101), phyllophaga sp. (D102), Scaptocoris sp. (D103). The compositions and polymorphs of the invention are preferably used on cotton to control Anthonomus grandis, Tetranychus sp, Empoasca sp, thrips sp, Lygus sp, phyllophaga sp, Scaptocoris sp.

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on rice to control, for example, Leptocorisa sp. (D104), Cnaphalocrosis sp. (D105), Chilo sp. (D106), Scirpophaga sp. (D107), Lissorhoptrus sp. (D108), Oebalus pugnax. (D109). The compositions and polymorphs of the invention are preferably used on rice to control Leptocorisa sp, Lissorhoptrus sp, Oebalus pugnax. The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on coffee to control, for example, Hypothenemus Hampei (DUO), Perileucoptera Coffeella (Dl 11), Tetranychus sp. (Dl 12). The compositions and polymorphs of the invention are preferably used on coffee to control Hypothenemus Hampei, Perileucoptera Coffeella.

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on citrus to control, for example, Panonychus citri (Dl 13), Phyllocoptruta oleivora (Dl 14), Brevipalpus sp. (Dl 15), Diaphorina citri (Dl 16), Scirtothrips sp. (Dl 17), thrips sp. (D118), Unaspis sp. (D119), Ceratitis capitata (D120), Phyllocnistis sp. (D121). The compositions and polymorphs of the invention are preferably used on citrus to control Panonychus citri, Phyllocoptruta oleivora, Brevipalpus sp, Diaphorina citri, Scirtothrips sp, thrips sp, Phyllocnistis sp.

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on almonds to control, for example, Amyelois transitella (D122), Tetranychus sp.

(D123).

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on fruiting vegetable, including tomatoes, pepper, chili, eggplant, cucumber, squash etc, to control thrips sp. (D124), Tetranychus sp. (D125), Polyphagotarsonemus sp. (D126),

Aculops sp. (D127), Empoasca sp. (D128), Spodoptera sp. (D129), heliothis sp. (D130), Tuta absoluta (D131), Liriomyza sp. (D132), Bemisia tabaci (D133), Trialeurodes sp. (D134), Paratrioza sp. (D135), Frankliniella occidentalis (D136), Frankliniella sp. (D137),

Anthonomus sp. (D138), Phyllotreta sp. (D139), Amrasca sp. (Dl 40), Epilachna sp. (D141), Halyomorpha sp. (D142), Scirtothrips sp. (D143), Leucinodes sp. (D144), Neoleucinodes sp. (D145). The compositions and polymorphs of the invention are preferably used on fruiting vegetable, including tomatoes, pepper, chili, eggplant, cucumber, squash etc, to control, for example, thrips sp, Tetranychus sp, Polyphagotarsonemus sp, Aculops sp, Empoasca sp, Spodoptera sp, heliothis sp, Tuta absoluta, Liriomyza sp, Paratrioza sp, Frankliniella occidentalis, Frankliniella sp, Amrasca sp, Scirtothrips sp, Leucinodes sp, Neoleucinodes sp.

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on tea to control, for example, Pseudaulacaspis sp. (D146), Empoasca sp. (D147), Scirtothrips sp. (D148), Caloptilia theivora (D149). The compositions and polymorphs of the invention are prefrerably used on tea to control Empoasca sp, Scirtothrips sp. The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on bulb vegetables, including onion, leek etc to control, for example, thrips sp. (D150), Spodoptera sp. (D183), heliothis sp. (D151). The compositions and polymorphs of the invention are preferably used on bulb vegetables, including onion, leek etc to control thrips sp.

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on grapes to control, for example, Empoasca sp. (D152), Lobesia sp. (D153),

Frankliniella sp. (D154), thrips sp. (D155), Tetranychus sp. (D156), Rhipiphorothrips Cruentatus (D157), Eotetranychus Willamettei (D158), Erythroneura Elegantula (D159), Scaphoides sp. (D161). The compositions and polymorphs of the invention are preferably used on grapes to control Frankliniella sp, thrips sp, Tetranychus sp, Rhipiphorothrips Cruentatus, Scaphoides sp.

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on pome fruit, including apples, pairs etc, to control, for example, Cacopsylla sp.

(D162), Psylla sp. (D163), Panonychus ulmi (D164), Cydia pomonella (D165). The compositions and polymorphs of the invention are preferably used on pome fruit, including apples, pears etc, to control Cacopsylla sp, Psylla sp, Panonychus ulmi. The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on stone fruit to control, for example, Grapholita molesta (D166), Scirtothrips sp. (D167), thrips sp. (D168), FranklinieUa sp. (D169), Tetranychus sp. (D170). The compositions and polymorphs of the invention are preferably used on stone fruit to control Scirtothrips sp, thrips sp, FranklinieUa sp, Tetranychus sp.

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on ornamental garden plants (e.g. flowers, shrubs, broad-leaved trees or evergreens), e.g. to control aphids (D171), whitefly (D172), scales (D173), meelybug (D174), beetles (D175) and caterpillars (D176).

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on garden plants (e.g. flowers, shrubs, broad-leaved trees or evergreens), on indoor plants (e.g. flowers and shrubs) and on indoor pest e.g. to control aphids (D177), whitefly (D178), scales (D179), meelybug (D180), beetles (D181) and caterpillars (D182). In addition, the compound of formula I per se, may be used for pest control on the various plants listed above to control one or more plant diseases Dl to D183.

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on transgenic plants (including cultivars) obtained by genetic engineering methods and/or by conventional methods. These are understood as meaning plants having novel properties ("traits") which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive "synergistic") effects.

Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.

The preferred transgenic plants or plant cultivars which are to be treated according to the invention include all plants which, by virtue of the genetic modification, received genetic material which imparts particularly advantageous, useful traits to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products.

Further and particularly emphasized examples of such traits are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain

herbicidally active compounds.

Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soybean, potatoes, sugar beet, tomatoes, peas and other vegetable varieties, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes).

The polymorphs and compositions of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) may be used on transgenic plants that are capable of producing one or more pesticidal proteins which confer upon the transgenic plant tolerance or resistance to harmful pests, e.g. insect pests, nematode pests and the like. Such pesticidal proteins include, without limitation, Cry proteins from Bacillus thuringiensis CrylAb, CrylAc, CrylF, Cry2Ab, Cry2Ae, Cry3A, Cry3Bb, or Cry9C; engineered proteins such as modified Cry3A ( US Patent 7,030,295) or CrylA.105; or vegetative insecticidal proteins such as Vipl, Vip2 or Vip3. A full list of Bt Cry proteins and VIPs useful in the invention can be found on the worldwide web at Bacillus

thuringiensis Toxin Nomenclature Database maintained by the University of Sussex {see also, Crickmore et al. (1998) Microbiol. Mol. Biol. Rev. 62:807-813). Other pesticidal proteins useful in the invention include proteins of bacteria colonizing nematodes, e.g.

Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG- CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels;

juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. Further examples of such pesticidal proteins or transgenic plants capable of synthesizing such proteins are disclosed, e.g., in EP- A 374753, WO 93/007278, WO 95/34656, EP-A 427529, EP-A 451878, WO 03/18810 and WO 03/52073. The methods for producing such transgenic plants are generally known to the person skilled in the art and some of which are commercially available such as Agrisure®CB (PI) (corn producing Cryl Ab), Agrisure®RW (P2) (corn producing mCry3A), Agrisure® Viptera (P3) (corn hybrids producing Vip3Aa); Agrisure300GT (P4) (corn hybrids producing Cryl Ab and mCry3A); YieldGard® (P5) (corn hybrids producing the Cryl Ab protein), YieldGard® Plus (P6) (corn hybrids producing Cryl Ab and Cry3Bbl), Genuity®

SmartStax® (P7) (corn hybrids with Cryl A.105, Cry2Ab2, CrylF, Cry34/35, Cry3Bb) ; Herculex® I (P8) (corn hybrids producing CrylFa) and Herculex®RW (P9) (corn hybrids producing Cry34Abl, Cry35Abl and the enzyme Phosphinothricin-N-Acetyltransferase [PAT]) ; NuCOTN®33B (P10) (cotton cultivars producing Cryl Ac), Bollgard®I (PI 1) (cotton cultivars producing Cryl Ac), Bollgard®II (PI 2) (cotton cultivars producing Cryl Ac and Cry2Ab2) and VIPCOT® (PI 3) (cotton cultivars producing a Vip3Aa). Soybean Cyst Nematode resistance soybean (SCN® - Syngenta (P 14)) and soybean with Aphid resistant trait (AMT® (PI 5)) are also of interest.

Further examples of such transgenic crops are: 1. Bill Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.

Sauveur, France, registration number C/FR/96/05/10 (P16). Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer {Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylA(b) toxin. Btl 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

2. Btl76 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.

Sauveur, France, registration number C/FR/96/05/10 (P17). Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer {Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CryIA(b) toxin. Btl 76 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR 96/05/10 (P18). Maize which has been rendered insect-resistant by transgenic expression of a modified CrylllA toxin. This toxin is

Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, fil l 50 Brussels, Belgium, registration number C/DE/02/9 (PI 9). MON 863 expresses a CrylllB(bl) toxin and has resistance to certain Coleoptera insects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/ES/96/02. (P20)

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-l 160 Brussels, Belgium, registration number C/NL/00/10. (P21) Genetically modified maize for the expression of the protein CrylF for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium. 7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03 (P22). Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from

Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer. Further examples of transgenic plants, and of very high interest, are those carrying traits conferring resistance to 2.4D (e.g. Enlist®) (e.g. WO 2011066384) (P23), glyphosate (e.g. Roundup Ready® (P24), Roundup Ready 2 Yield® (P25)), sulfonylurea (e.g. STS®) (P26), glufosinate (e.g. Liberty Link® (P27), Ignite® (P28)), Dicamba (P29) (Monsanto), HPPD tolerance (P30) (e.g. isoxaflutole herbicide) (Bayer CropScience, Syngenta). Double or triple stacks of any of the traits described here are also of interest, including glyphosate and sulfonyl-urea tolerance ((e.g. Optimum GAT®) (P31), plants stacked with STS® and Roundup Ready® (P32) or plants stacked with STS® and Roundup Ready 2 Yield® (P33)), dicamba and glyphosate tolerance (P34) (Monsanto). Of particular interest are soybean plants carrying trains conferring resistance to 2.4D (e.g. Enlist®), glyphosate (e.g. Roundup Ready®, Roundup Ready 2 Yield®), sulfonylurea (e.g. STS®), glufosinate (e.g. Liberty Link®, Ignite®), Dicamba (Monsanto) HPPD tolerance (e.g. isoxaflutole herbicide) (Bayer CropScience, Syngenta). Double or triple stack in soybean plants of any of the traits described here are also of interest, including glyphosate and sulfonyl-urea tolerance (e.g. Optimum GAT®, plants stacked with STS® and Roundup Ready® or Roundup Ready 2 Yield®), dicamba and glyphosate tolerance (Monsanto).

Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fur Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

Examples of cotton transgenic events include MON 531 / 757 / 1076 (Bollgard I ® - Monsanto), MON1445 (Roundup ready cotton ®- Monsanto), MON531 x MON1445 (Bollgard I + RR ®- Monsanto), MON15985 (Genuity Bollgard II cotton ®- Monsanto), MON88913 (Genuity RR FLEX cotton ®- Monsanto), MON15985 x MON1445 (Genuity Bollgard II + RR FELX cotton ®- Monsanto), MON15983 x MON88913 (Genuity Bollgard II + RR FLEX cotton ® - Monsanto), MON15985 (FibreMax Bollgard II Cotton ® - Monsanto), LL25 (FibreMax LL cotton ® - BCS Stoneville), GHB614 (FibreMax GlyTol cotton ®- BCS Stoneville), LL25 x MON15985 (FibreMax LL Bollgard II cotton ® - BCS Stoneville / Monsanto), GHB614 x LL25 (FibreMax LL GlyTol cotton ® - BCS Stoneville), GHB614 x LL25 x MON15985 (FibreMax RR GlyTol Bollgard II cotton ® - BCS

Stoneville), MON88913 x MON15985 (FibreMax LL GlyTol Bollgard II cotton ® - Monsanto), MON88913 (FibreMax RR Flex cotton ® - Monsanto), GHB119 + T304-40 (Twinlink ® - BCS Stoneville), GHB119 + T304-40 x LL25 x GHB614 (Twinlink LL GT ® - BCS Stoneville), 3006-210-23 x 281-24-236 (PhytoGen Widestrike Insect Protection ® - Dow), 3006-210-23 x 281-24-236 x MON88913 (PhytoGen Widestrike Insect Protection + RR FLEX - ® Dow / Monsanto), 3006-210-23 x 281-24-236 x MON1445 ((PhytoGen Widestrike Insect Protection + RR ® - Dow / Monsanto), MON1445 (PhytoGen Roundup Ready ® - Monsanto), MON88913 (PhytoGen Roundup Ready FLEX ® - Monsanto),

COT102 x COT67B (Vipcot ® - Syngenta), COT102 x COT67B x MON88913 (Vipcot RR FLEX ® - Syngenta / Monsanto), 281-24-236 (Dow), 3006-210-23 (Dow), COT 102 (Syngenta), COT67B (Syngenta), T304-40 (BCS Stoneville). Examples of Soy transgenic events include MON87701 x MON89788 (Genuity

Roundup ready 2 Yield soybeans® - Monsanto), MON89788 (Roundup Ready2Yield®, RR2Y® - Monsanto), MON87708 (Monsanto), 40-3-2 (Roundup Ready®, RR1® - Monsanto), MON87701 (Monsanto), DAS-68416 (Enlist Weed Control System® - Dow), DP356043 (Optimum GAT® - Pioneer), A5547-127 (LibertyLink soybean® - Bayercropscience), A2704-12 (Bayercropscience), GU262 (Bayercropscience), W62 W98 (Bayercropscience), CRV127 (Cultivance® - BASF / EMBRAPA), SYHT0H2

(WO2012/082548).

Examples of Maize transgenic events include T25 (LibertyLink®, LL® - Bayerscropscience), DHT-1 (Dow), TC1507 (Herculex I® - Dow), DAS59122-7 (Herculex RW® - Dow), TC1507 + DAS59122-7 - Herculex Xtra® - Dow), TC1507 x DAS-59122-7 x NK603 (Herculex Xtra + RR® - Dow), TC1507 x DAS-59122- x MON88017 x

MON89034 (Genuity Smartstax corn®, Genuity Smartstax RIB complete® - Monsanto / Dow), MON89034 x NK603 (Genuity VT double PRO® - Monsanto), MON89034 + MON88017 (Genuity VT Triple PRO® - Monsanto), NK603 (Roundup Ready 2®, RR2® - Monsanto), MON810 (YieldGard BT®, Yieldgard cornborer® - Monsanto), MON810 x NK603 (YieldGard cornborer RR Corn 2® - Monasnto), MON810 x MON863 (YieldGard Plus® - Monsanto), MON863 x MON810 x NK603 (YieldGard Plus + RR Corn2® /

YieldGard RR Maize® - Monsanto), MON863 x NK603 (YieldGard Rotworm + RR Corn 2® - Monsanto), MON863 (YieldBard RW® - Monsanto), MON89034 (YieldGard RW® - Monsanto), MON88017 (YieldGard VT RW® - Monsanto), MON810 + MON88017 (YieldGard VT Triple® - Monsanto), MON88017 + MON89034 (YieldGard VT Triple Pro® - Monsanto), Btl 1 + MIR604 + GA21 (Agrisure 3000® - Syngenta), Btl 1 + TC1507 + MIR604 + 5307 + GA21 (Syngenta), Btl 1 + TC1507 + MIR604 + DAS59122 + GA21 (Agrisure 3122® - Syngenta), BT11 (Agrisure CB® - Syngenta), GA21 - (Agrisure GT® - Syngenta), MIR604 (Agrisure RW® - Syngenta), Btl 1 + MIR162 (Agrisure TL VIP® - Syngenta), BT11 + MIR162 + GA21 (Agrisure Viptra 3110® - Syngenta), BT11 + MIR162 + MIR604 (Agrisure TM 3100® - Syngenta), Event3272 + BT 11 + MIR604 + GA21

(Syngenta), BT11 + MIR1692 + MIR604 + GA21 (Agrisure Viptera 3111® - Syngenta), BT11 + MIR 162 + TCI 507 + GA21 (Agrisure Viptera 3220® - Syngenta), BT11 + MIR162 + TCI 507 + MIR604 + 5307 + GA21 (Agrisure Viptera 3222® - Syngenta), MIR162 (Syngenta), BT11 + GA21 + MIR162 + MIR604 + 5307 (Syngenta), 5307 (Syngenta).

In addition, the compound of formula I per se, may be used on transgenic plants, in particular, those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest, as well as the specific transgenic events listed above. In order to apply a polymorph or composition of the invention as an insecticide, acaricide, nematicide or molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, the polymorph or composition of the invention as described above may be used in straight form but is usually formulated so that it further comprises a suitable inert diluent or carrier and, optionally, a wetting, dispersing and/or emulsifying agent or a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). Examples of such formulations are given on pages 35 to 39 of WO2011/104089 and below. It is preferred that all such formulated compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of the compound of formula I. In this context and when used below, the 'compound of formula Γ means the total amount of all forms of the compound of formula I i.e. both the R and S forms of each of compounds of formula la and lb, whether present in specific polymorphic form or not. The formulated composition is generally used for the control of pests such that a compound of formula I is applied at a rate of from O. lg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare. The compound of formula I per se may also be applied as described here.

When used in a seed dressing, the compound of formula I is used at a rate of 0.000 lg to lOg (for example O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.

It is preferred that the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20%> agriculturally acceptable surfactant and 10 to 99.99%) solid or liquid formulation inerts and adjuvant(s). Concentrated forms of compositions generally contain in between about 2 and 80%>, preferably between about 5 and 70%> by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations. Compositions of the compound of formula I with other active ingredients may, for example, be provided as a formulated product or may be mixed in a spray tank.

The formulated compositions may be employed in any conventional form, for example in the form of a twin pack, an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants. The type of compositions used in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula I. In particular, the formulated compositions are chosen from a number of formulation types, including dustable powders (DP), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), dispersible

concentrates (DC), suspension concentrates (SC), aerosols, fogging/smoke formulations and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged.

Dustable powders (DP) may be prepared by mixing the compound of formula I with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

Wettable powders (WP) may be prepared by mixing the compound of formula I with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of the compound of formula I and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing the compound of formula I (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing the compound of formula I (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulfates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent). Dispersible Concentrates (DC) may be prepared by dissolving the compound of formula I in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallization in a spray tank).

Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of the compound of formula I. SCs may be prepared by ball or bead milling the solid compound of formula I in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, the compound of formula I may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product. Aerosol formulations comprise the compound of formula I and a suitable propellant

(for example /? -butane). The compound of formula I may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurized, hand-actuated spray pumps. The compound of formula I may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.

A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of the compound of formula I). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of the compound of formula I).

The compound of formula I may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), or a water dispersible powder for slurry treatment (WS). The preparations of DS and WS compositions are very similar to those of, respectively, DP and WP compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).

Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.

Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulfate), salts of sulfonated aromatic compounds (for example sodium dodecylbenzenesulfonate, calcium

dodecylbenzenesulfonate, butylnaphthalene sulfonate and mixtures of sodium di- z^'sopropyl- and tri-z^'sopropyl-naphthalene sulfonates), ether sulfates, alcohol ether sulfates (for example sodium laureth-3-sulfate), ether carboxylates (for example sodium laureth-3- carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide

(predominately di-esters), for example the reaction between lauryl alcohol and

tetraphosphoric acid; additionally these products may be ethoxylated), sulfosuccinamates, paraffin or olefine sulfonates, taurates and lignosulfonates.

Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.

Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins. Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

The compound of formula I and the compositions of the invention can be used for preventative, protectant and eradicant treatments and can be applied in a number of ways.

The compound of formula I and the compositions of the invention may be applied by any of the known means of applying pesticidal compounds. For example, they may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapor or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.

The compound of formula I may also be injected into plants or trees or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, WPs and WGs , are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of the compound of formula I (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used. The compound of formula I can also be used in combination with other active ingredients, e.g. other herbicides, and/or insecticides, and/or acaricides, and/or nematocides, and/or moUuscicides, and/or fungicides, and/or plant growth regulators, which can give rise to synergistic effects, e.g. the control observed from the combination is greater than the expected control according to the Colby formula. Examples for such combinations with fungicides are described in are given in WO2011/104088 and examples of such combinations with insecticides are given in WO2011/104087. In particular, the present invention also relates to a composition of the invention which comprises at least one further insecticide in addition to the compound of formula I and to compositions which comprise at least one further fungicide.

In particular, the present invention provides a composition of the invention which further comprises an insecticide (where "Tx" means a composition or polymorph of the invention, in particular those compositions described above that are simultaneously enriched for the S and cis configuration and which may result in a synergistic combination with the given active ingredient particularly at the ratios indicated below) which compositions are selected selected from: a) Pyrethroids, wherein suitable combinations include permethrin +Tx, cypermethrin +Tx, fenvalerate +Tx, esfenvalerate +Tx, deltamethrin +Tx, cyhalothrin +Tx (in particular lambda-cyhalothrin +Tx and gamma cyhalothrin +Tx), bifenthrin +Tx, fenpropathrin +Tx, cyfluthrin +Tx, tefluthrin +Tx, fish safe pyrethroids +Tx (for example ethofenprox +Tx), natural pyrethrin +Tx, tetramethrin +Tx, S-bioallethrin +Tx, fenfluthrin +Tx, prallethrin +Tx or

5 -benzyl-3 -furylmethyl-(E)-( 1 R,3 S)-2,2-dimethyl- 3 -(2-oxothio lan-3 -ylidenemethyl) cyclopropane carboxylate +Tx; b) Organophosphates, wherein suitable combinations include profenofos +Tx, sulprofos +Tx, acephate +Tx, methyl parathion +Tx, azinphos-methyl +Tx, demeton-s-methyl +Tx, heptenophos +Tx, thiometon +Tx, fenamiphos +Tx, monocrotophos +Tx, profenofos +Tx, triazophos +Tx, methamidophos +Tx, dimethoate +Tx,

phosphamidon +Tx, malathion +Tx, chlorpyrifos +Tx, phosalone +Tx, terbufos +Tx, fensulfothion +Tx, fonofos +Tx, phorate +Tx, phoxim +Tx, pirimiphos-methyl +Tx, pirimiphos-ethyl +Tx, fenitrothion +Tx, fosthiazate +Tx or diazinon +Tx;

Carbamates (including aryl carbamates), wherein suitable combinations include pirimicarb +Tx, triazamate +Tx, cloethocarb +Tx, carbofuran +Tx, furathiocarb +Tx, ethiofencarb +Tx, aldicarb +Tx, thioiurox +Tx, carbosulfan +Tx, bendiocarb +Tx, fenobucarb +Tx, propoxur +Tx, methomyl +Tx or oxamyl +Tx;

Benzoyl ureas, wherein suitable combinations include diflubenzuron +Tx, triflumuron +Tx, hexaflumuron +Tx, flufenoxuron +Tx, lufeneron +Tx or chlorfluazuron +Tx;

Organic tin compounds, wherein suitable combinations include cyhexatin +Tx, fenbutatin oxide +Tx or azocyclotin +Tx;

Pyrazoles, wherein suitable combinations include tebufenpyrad +Tx and

fenpyroximate +Tx;

Macrolides, such as avermectins or milbemycins, wherein suitable combinations include for example abamectin +Tx, emamectin benzoate +Tx, ivermectin +Tx, milbemycin +Tx, spinosad +Tx, azadirachtin +Tx or spinetoram +Tx;

Hormones or pheromones;

Organochlorine compounds, wherein suitable combinations include endosulfan +Tx (in particular alpha-endosulfan +Tx), benzene hexachloride +Tx, DDT +Tx, chlordane +Tx or dieldrin +Tx;

Amidines, wherein suitable combinations include chlordimeform +Tx or amitraz +Tx;

Fumigant agents, wherein suitable combinations include chloropicrin +Tx, dichloropropane +Tx, methyl bromide +Tx or metam +Tx; Neonicotinoid compounds, wherein suitable combinations include imidacloprid +Tx, thiacloprid +Tx, acetamiprid +Tx, nitenpyram +Tx, dinotefuran +Tx, thiamethoxam +Tx, clothianidin +Tx or nithiazine +Tx;

Diacylhydrazines, wherein suitable combinations include tebufenozide +Tx, chromafenozide +Tx or methoxyfenozide +Tx;

Diphenyl ethers, wherein suitable combinations include diofenolan +Tx or pyriproxifen +Tx; combinations of Indoxacarb +Tx; combinations of Chlorfenapyr +Tx; combinations of Pymetrozine +Tx or flonicamid +Tx; combinations of pirotetramat +Tx, spirodiclofen +Tx or spiromesifen +Tx;

Diamides, wherein suitable combinations include flubendiamide +Tx,

chlorantraniliprole(Rynaxypyr®) +Tx or cyantraniliprole +Tx; combinations of Sulfoxaflor +Tx; combinations of Metaflumizone +Tx; combinations of Fipronil +Tx and Ethiprole +Tx; combinations of yrifluqinazon +Tx; combinations of buprofezin +Tx; or combinations of 4-[(6-Chloro-pyridin-3-ylmethyl)-(2,2-difluoro-ethyl)-amino]-5H- furan-2-one +Tx.

In a preferred embodiment, the further insecticide is selected from: pymetrozine; an organophosphate selected from the group consisting of sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate and diazinon; a pyrethroid selected from the group consisting of permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin, lambda-cyhalothrin, gamma- cyhalothrin, bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, ethofenprox, natural pyrethrin, tetramethrin, S-bioallethrin, fenfluthrin, prallethrin and

5 -benzyl-3 -furylmethyl-(E)-( 1 R,3 S)-2,2-dimethyl- 3 -(2-oxothio lan-3 -ylidenemethyl)cy clopropane carboxylate; a macrolide selected from the group consisting of abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad, azadirachtin and spinetoram; a diamide selected from the group consisting of flubendiamide, chlorantraniliprole (Rynaxypyr®) and cyantraniliprole; a neonicotinoid compound selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, nithiazine and flonicamid; spirotetramat, spirodiclofen and spiromesifen; and sulfoxaflor, lufeneron, diafenthiuron, and fipronil. In a particularly preferred embodiment, the compound of formula I is simultaneously enriched for S and cis as defined above and the insecticide is selected from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda cyhalothrin, pymetrozine, spirotetramat, thiamethoxam, clothianidin, imidacloprid, chlorantraniliprole, flonicamid, sulfoxaflor, lufeneron, diafenthiuron, flubendiamide, tefluthrin, and fipronil. Even more preferably the insecticide is selected from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda cyhalothrin, pymetrozine, spirotetramat, thiamethoxam, clothianidin, imidacloprid and flonicamid. Such combinations can give rise to synergistic effects at the ratios mentioned below.

In another embodiment the the compound of formula I is simultaneously enriched for S and cis as defined above and the insecticide is selected from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda cyhalothrin, pymetrozine, spirotetramat, thiamethoxam, clothianidin, imidacloprid and chlorantraniliprole. Such combinations can give rise to synergistic effects at the ratios mentioned below.

In another embodiment the the compound of formula I is simultaneously enriched for S and cis as defined above and the insecticide is selected from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda cyhalothrin, pymetrozine, spirotetramat, and thiamethoxam. Such combinations can give rise to synergistic effects at the ratios mentioned below.

The active ingredients combinations described above comprising a polymorph or composition of the invention and an insecticide as described above are preferably combined in a mixing ratio of from 100: 1 to 1 :6000, especially from 50: 1 to 1 :50, more especially in a ratio of from 20 : 1 to 1 :20, even more especially from 10: 1 to 1 : 10, very especially from 5 : 1 to 1 :5, special preference being given to a ratio of from 2: 1 to 1 :2, and a ratio of from 4: 1 to 2: 1 being likewise preferred, above all in a ratio of 1 : 1, or 5: 1, or 5:2, or 5:3, or 5:4, or 4: 1, or 4:2, or 4:3, or 3: 1, or 3:2, or 2: 1, or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 : 150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 : 1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. The present invention also provides a composition of the invention which further comprises a fungicide (where "Tx" means a composition or polymorph of the invention, in particular those compositions described above that are simultaneously enriched for the S and cis configuration, and which may result in a synergistic combination with the given active ingredient, particularly at the ratios indicated below) which compositions are selected selected from:

a) a composition comprising a strobilurin fungicide including those selected from the group consisting of: Azoxystrobin +Tx, Dimoxystrobin+Tx, Enestrobin+Tx,

Fluoxastrobin+Tx, Kresoxim-methyl+Tx, Metominostrobin+Tx, Orysastrobin+Tx, Picoxystrobin+Tx, Pyraclostrobin+Tx and Trifloxystrobin+Tx; b) a composition comprising an azole fungicide including those selected from the group consisting of: Azaconazole+Tx, Bromuconazole+Tx, Cyproconazole+Tx,

Difenoconazole+Tx, Diniconazole+Tx, Diniconazole-M+Tx, Epoxiconazole+Tx, Fenbuconazole+Tx, Fluquinconazole+Tx, Flusilazole+Tx, Flutriafol+Tx,

Hexaconazole+Tx, Imazalil+Tx, Imibenconazole+Tx, Ipconazole+Tx,

Metconazole+Tx, Myclobutanil+Tx, Oxpoconazole+Tx, Pefurazoate+Tx,

Penconazole+Tx, Prochloraz+Tx, Propiconazole+Tx, Prothioconazole+Tx,

Simeconazole+Tx, Tebuconazole+Tx, Tetraconazole+Tx, Triadimefon+Tx,

Triadimenol+Tx, Triflumizole+Tx, Triticonazole+Tx, Diclobutrazol+Tx,

Etaconazole+Tx, Furconazole+Tx, Furconazole-cis+Tx, Thiabendazole+Tx and Quinconazole+Tx; c) a composition comprising a phenyl pyrrole fungicide including those selected from the group consisting of: Fenpiclonil+Tx and Fludioxonil+Tx; d) a composition comprising an anilino-pyrimidine fungicide including those selected from the group consisting of: Cyprodinil+Tx, Mepanipyrim+Tx and Pyrimethanil+Tx; e) a composition comprising a morpholine fungicide including those selected from the group consisting of: Aldimorph+Tx, Dodemorph+Tx, Fenpropimorph+Tx,

Tridemorph+Tx, Fenpropidin+Tx and Spiroxamine+Tx; f) a composition comprising a carboxamide fungicide including those selected from the group consisting of: Isopyrazam+Tx, Sedaxane+Tx, Bixafen+Tx, Penthiopyrad+Tx, Fluxapyroxad+Tx, Boscalid+Tx, Penflufen+Tx, Fluopyram+Tx, a compound of formula II+Tx

a composition comprising a compound of formula III+Tx

and a composition comprising a compound of formula IV+Tx

g) a composition comprising a carboxylic acid amide fungicide including those selected from the group consisting of: Mandipropamid+Tx, Benthiavalicarb+Tx and

Dimethomorph+Tx; composition comprising Chlorothalonil+Tx, Fluazinam+Tx, Dithianon+Tx,

Metrafenone+Tx, Tricyclazole+Tx, Mefenoxam+Tx, Metalaxyl+Tx, Acibenzolar+Tx, Mancozeb+Tx, Ametoctradine+Tx and Cyflufenamid+Tx. In a preferred embodiment, the compound of formula I is simultaneously enriched for S and cis as defined above and the fungicide is selected from the group consisting of Azoxystrobin, Isopyrazam, Chlorothalonil, Cyproconazole, Difenoconazole,

Mandipropamid, Mefenoxam, Metalaxyl, Sedaxane, Acibenzolar (including Acibenzolar-S- methyl), Fludioxonil, Cyprodinil, Penconazole, Propiconazole, Mancozeb, Prothioconazole, Pyraclostrobin, Boscalid, Bixafen, Fluopyram, Penthiopyrad, Thiabendazole, Fluazinam, Fenpropidin, Cyclufenamid, Tebuconaozle, Trifoxystrobin, Fluxapyroxad, Penflufen, Fluoxastrobin, Kresoxim-methyl, Benthiavalicarb, Dimethomorph, a compound of formula II, a compound of formula III and a compound of formula IV. Such combinations can give rise to synergistic effects at the ratios mentioned below.

In a particularly preferred embodiment, the compound of formula I is simultaneously enriched for S and cis as defined above and the fungicide is selected from the group consisting of Azoxystrobin, Isopyrazam, Chlorothalonil, Cyproconazole, Difenoconazole, Mandipropamid, Mefenoxam, Metalaxyl, Sedaxane, Acibenzolar (including Acibenzolar-S- methyl), Fludioxonil, Cyprodinil, Penconazole, Propiconazole, Mancozeb, Prothioconazole, Pyraclostrobin, Boscalid, Bixafen, Fluopyram, Penthiopyrad, Thiabendazole, a compound of formula III and a compound of formula IV. Such combinations can give rise to synergistic effects at the ratios mentioned below.

In an even more preferred embodiment, the compound of formula I is simultaneously enriched for S and cis as defined above and the fungicide is selected from the group consisting of Azoxystrobin, Isopyrazam, Chlorothalonil, Cyproconazole, Difenoconazole, Mandipropamid, Mefenoxam, Metalaxyl, Sedaxane, Acibenzolar (including Acibenzolar-S- methyl), Fludioxonil, Thiabendazole, a compound of formula III and a compound of formula IV and, most preferably, the fungicide is selected from the group consisting of Azoxystrobin, Isopyrazam, Chlorothalonil, Cyproconazole, Difenoconazole, Mandipropamid, Mefenoxam, a compound of formula III and a compound of formula IV. Such combinations can give rise to synergistic effects at the ratios mentioned below.

The active ingredients combinations described above comprising a polymorph or composition of the invention and a fungicide as described above are preferably combined in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20 : 1 to 1 :20, even more especially from 10:1 to 1:10, very especially from 5 : 1 to 1:5, special preference being given to a ratio of from 2: 1 to 1 :2, and a ratio of from 4: 1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750.

Compositions comprising a compound of formula I and abamectin may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to abamectin by weight in the composition is preferably 1 :0.05 to 1:1. Examples of ratios falling within this range include 1:0.1, 1 :0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9. Where used for soil application the ratio of compound of formula I to abamectin may be up to 1 : 1.3, additional examples include 1:1.15, 1 : 1.2, 1 : 1.25. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and chlorpyrifos may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to chlorpyrifos by weight in the composition is preferably 1:1 to 1:10. Examples of ratios falling within this range include 1:2, 1:3, 1:4, 1:5, 1 :6, 1 :7, 1 :8, 1 :9. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and cyantraniliprole may be used to control one or more of plant diseases selected from Dl to D 183 as described above, wherein the ratio of the compound of formula I to cyantraniliprole by weight in the composition is preferably 1 :0.2 to 1 :4. Examples of ratios falling within this range include 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest. Compositions comprising a compound of formula I and emamectin (preferably emamectin benzoate) may be used to control one or more of plant diseases selected from Dl to D 183 as described above, wherein the ratio of the compound of formula I to emamectin by weight in the composition is preferably 1 : 0.05 to 1 : 1. Examples of ratios falling within this range include 1 :0.1, 1 :0.2, 1 :0.3, 1 :0.4, 1 :0.5, 1 :0.6, 1 :0.7, 1 :0.8, 1 :0.9. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest. Compositions comprising a compound of formula I and lambda cyhalothrin may be used to control one or more of plant diseases selected from Dl to D 183 as described above, wherein the ratio of the compound of formula I to lambda cyhalothrin by weight in the composition is preferably 1 :0.1 to 1 :2. Examples of rates falling within this range include 1 :0.2, 1 :0.4, 1 :0.6, 1 :0.8, 1 : 1, 1 : 1.2, 1 : 1.4, 1 : 1.6, 1 :1.8. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and pymetrozine may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to pymetrozine by weight in the composition is preferably 1 : 1 to 1 :6. Examples of rates falling within this range include 1 :2, 1 :3, 1 :4, 1 :5. Where used for soil application the ratio of compound of formula I to pymetrozine may be up to 1 : 10, additional examples include 1 :7, 1 :8, 1 :9. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and spirotetramat may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to spirotetramat by weight in the composition is preferably 1 :0.5 to 1 :4. Examples of rates falling within this range include 1 :1, 1 : 1.5, 1 :2, 1 :2.5, 1 :3, 1 :3.5. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest. Compositions comprising a compound of formula I and thiamethoxam may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to thiamethoxam by weight in the composition is preferably 1 : 0.5 to 1 :6. Examples of rates falling within this range include 1 : 1, 1 :2, 1 :3, 1 :4 and 1 :5. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and clothianidin may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to clothianidin by weight in the composition is preferably 1 : 0.5 to 1 :6. Examples of rates falling within this range include 1 : 1, 1 :2, 1 :3, 1 :4 and 1 :5. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and imidacloprid may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to imidacloprid by weight in the composition is preferably 1 : 0.5 to 1 :6. Examples of rates falling within this range include 1 : 1, 1 :2, 1 :3, 1 :4 and 1 :5. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and chlorantraniliprole may be used to control one or more of plant diseases selected from Dl to D 183 as described above, wherein the ratio of the compound of formula I to chlorantraniliprole by weight in the composition is preferably 1 :0.2 to 1 :4. Examples of ratios falling within this range include 1 :0.5, 1 : 1, 1 : 1.5, 1 :2, 1 :2.5, 1 :3, 1 :3.5. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest. Compositions comprising a compound of formula I and sulfoxaflor may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to sulfoxaflor by weight in the composition is preferably 1 : 0.5 to 1 :6. Examples of rates falling within this range include 1 : 1, 1 :2, 1 :3, 1 :4 and 1 :5. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and azoxystrobin may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to azoxystrobin by weight in the composition is preferably 1 : 1.5 to 1 : 10. Examples of ratios falling within this range include 1 :2, 1 :3, 1 :4, 1 :5, 1 :6, 1 :7, 1 :8, 1 :9. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and isopyrazam may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to isopyrazam by weight in the composition is preferably 1 : 1 to 1 :3. Examples of ratios falling within this range include 1 : 1.5, 1 :2, 1 :2.5. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and chlorothalonil may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to chlorothalonil by weight in the composition is preferably 1 :5 to 1 :50. Examples of ratios falling within this range include 1 : 10, 1 : 15, 1 :20, 1 :25, 1 :30, 1 :35, 1 :40, 1 :45. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and cyproconazole may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to cyproconazole by weight in the composition is preferably 1 : 1 to 1 :5. Examples of ratios falling within this range include 1 : 1.5, 1 :2, 1 :2.5, 1 :3, 1 :3.5, 1 :4, 1 :4.5. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and difenoconazole may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to difenoconazole by weight in the composition is preferably 1 :0.3 to 1 :5. Examples of ratios falling within this range include 1 :0.5, 1 :0.7, 1 :0.9, 1 : 1, 1 : 1.2, 1 : 1.4. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest. Compositions comprising a compound of formula I and mandipropamid may be used to control one or more of plant diseases selected from Dl to D 183 as described above, wherein the ratio of the compound of formula I to mandipropamid by weight in the composition is preferably 1 : 1 to 1 : 15. Examples of ratios falling within this range include 1 :2, 1 :4, 1 :6, 1 :8, 1 : 10, 1 : 12, 1 : 14. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and mefenoxam may be used to control one or more of plant diseases selected from Dl to D183 as described above, wherein the ratio of the compound of formula I to mefenoxam by weight in the composition is preferably 1 :0.3 to 1 :8. Examples of ratios falling within this range include 1 : 1, 1 :2, 1 :3, 1 :4, 1 :5, 1 :6, 1 :7. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and a compound of formula II

may be used to control one or more of plant diseases selected from Dl to D 183 as described above, wherein the ratio of the compound of formula I to the compound of formula II by weight in the composition is preferably 1 :0.3 to 1 :8. Examples of ratios falling within this range include 1 : 1, 1 :2, 1 :3, 1 :4, 1 :5, 1 :6, 1 :7. These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Compositions comprising a compound of formula I and a compound of formula III

may be used to control one or more of plant diseases selected from Dl to D 183 as described above, wherein the ratio of the compound of formula I to the compound of formula III by weight in the composition is preferably 1 :0.3 to 1 :8. Examples of ratios falling within this range include 1 : 1, 1 :2, 1 :3, 1 :4, 1 :5, 1 :6, 1 :7. . These compositions may also be used on transgenic plants, in particular those described above, in particular PI to P34. Transgenic soybean, e.g. P23 to P34, is of particular interest.

Abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda cyhalothrin, pymetrozine, spirotetramat, thiamethoxam, clothianidin, imidacloprid, chlorantraniliprole, azoxystrobin, isopyrazam, chlorothalonil, cyproconazole, difenoconaozle, mandipropamid and mefenoxam are well known pesticides and are described for example in The Pesticide Manual - A World Compendium; Fifteenth Edition; Editor: C. D. S. Tomlin; The British Crop Protection Council. The compound of formula II is known from WO 2007/048556, the compound of formula III is known from WO 2010/000612. It is known e.g. from WO2011/104088 and WO2011/104087, that combinations of compounds of formula I and these active ingredients gives rise to synergistic control, as defined by the Colby formula.

Abamectin , chlorpyrifos, cyantraniliprole, emamectin, lambda cyhalothrin, pymetrozine, spirotetramat, thiamethoxam, clothianidin, imidacloprid, chlorantraniliprole, azoxystrobin, isopyrazam, chlorothalonil, cyproconazole, difenoconaozle, mandipropamid, mefenoxam, the compound of formula II and the compound of formula III are preferably applied in combination with the compound of formula I at a rate corresponding to the ratios indicated above.

The compositions and polymorphs of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) are also useful in the field of animal health, e.g. they may be used against parasitic invertebrate pests, more preferably against parasitic invertebrate pests in or on an animal. Examples of pests include nematodes, trematodes, cestodes, flies, mites, tricks, lice, fleas, true bugs and maggots. The animal may be a non-human animal, e.g. an animal associated with agriculture, e.g. a cow, a pig, a sheep, a goat, a horse, or a donkey, or a companion animal, e.g. a dog or a cat. In a further aspect the invention provides a composition or polymorph of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) for use in a method of therapeutic treatment. In a further aspect the invention relates to a method of controlling parasitic invertebrate pests in or on an animal comprising administering a pesticidally effective amount of a composition or polymorph of the invention. The administration may be for example oral administration, parenteral administration or external administration, e.g. to the surface of the animal body. In a further aspect the invention relates to a composition or polymorph of the invention for controlling parasitic invertebrate pests in or on an animal. In a further aspect the invention relates to use of a composition or polymorph of the invention in the manufacture of a medicament for controlling parasitic invertebrate pests in or on an animal

In a further aspect, the invention provides a pharmaceutical composition comprising a composition or polymorph of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) and a pharmaceutically suitable excipient. The compositions and polymorphs of the invention may be used alone or in combination with one or more other biologically active ingredients. When used in

combination with other active ingredients, the compositions of the invention are preferably selected from (where "Tx" means a composition or polymorph of the invention, in particular those compositions described above that are simultaneously enriched for the S and cis configuration, and which may result in a synergistic combination with the given active ingredient, particularly at the ratios indicated below) imidacloprid + Tx, enrofloxacin + Tx, praziquantel + Tx, pyrantel embonate + Tx, febantel + Tx, penethamate + Tx, moloxicam + Tx, cefalexin + Tx, kanamycin + Tx, pimobendan + Tx, clenbuterol + Tx, fipronil + Tx, ivermectin + Tx, omeprazole + Tx, tiamulin + Tx, benazepril + Tx, milbemycin + Tx, cyromazine + Tx, thiamethoxam + Tx, pyriprole + Tx, deltamethrin + Tx, cefquinome + Tx, florfenicol + Tx, buserelin + Tx, cefovecin + Tx, tulathromycin + Tx, ceftiour + Tx, selamectin + Tx, carprofen + Tx, metaflumizone + Tx, moxidectin + Tx, methoprene (including S-methoprene) + Tx, clorsulon + Tx, pyrantel + Tx, amitraz + Tx, triclabendazole + Tx, avermectin + Tx, abamectin + Tx, emamectin + Tx, eprinomectin + Tx, doramectin + Tx, selamectin + Tx, nemadectin + Tx, albendazole + Tx, cambendazole + Tx, fenbendazole + Tx, flubendazole + Tx, mebendazole + Tx, oxfendazole + Tx, oxibendazole + Tx, parbendazole + Tx, tetramisole + Tx, levamisole + Tx, pyrantel pamoate + Tx, oxantel + Tx, morantel + Tx, triclabendazole + Tx, epsiprantel + Tx, fipronil + Tx, lufenuron + Tx, ecdysone + Tx or tebufenozide + Tx; more preferably enrofloxacin + Tx, praziquantel + Tx, pyrantel embonate + Tx, febantel + Tx, penethamate + Tx, moloxicam + Tx, cefalexin + Tx, kanamycin + Tx, pimobendan + Tx, clenbuterol + Tx, omeprazole + Tx, tiamulin + Tx, benazepril + Tx, pyriprole + Tx, cefquinome + Tx, florfenicol + Tx, buserelin + Tx, cefovecin + Tx, tulathromycin + Tx, ceftiour + Tx, selamectin + Tx, carprofen + Tx, moxidectin + Tx, clorsulon + Tx or pyrantel + Tx.

Examples of ratios include 100: 1 to 1 :6000, 50: 1 to 1 :50, 20: 1 to 1 :20, even more especially from 10: 1 to 1 : 10, 5: 1 to 1 :5, 2: 1 to 1 :2, 4: 1 to 2: 1, 1 : 1, or 5: 1, or 5:2, or 5:3, or 5:4, or 4: 1, or 4:2, or 4:3, or 3: 1, or 3:2, or 2: 1, or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 : 150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 : 1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.

Of particular note is a combination where the additional active ingredient has a different site of action from the compound of formula I. In certain instances, a combination with at least one other parasitic invertebrate pest control active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a combination product of the invention may comprise a pesticidally effective amount of a compound of formula I and pesticidally effective amount of at least one additional parasitic invertebrate pest control active ingredient having a similar spectrum of control but a different site of action.

One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding non salt forms, salts share the biological utility of the non salt forms.

The compositions and polymorphs of the invention may be suitable for combating parasitic invertebrate pests that infest companion animals and pets (e.g., dogs, cats, pet birds and aquarium fish), research and experimental animals (e.g., hamsters, guinea pigs, rats and mice), as well as animals raised for/in zoos, wild habitats and/or circuses.

In an embodiment of this invention, the animal is preferably a vertebrate, and more preferably a mammal, avian or fish. In a particular embodiment, the animal subject is a mammal (including great apes, such as humans). Other mammalian subjects include primates (e.g., monkeys), bovine (e.g., cattle or dairy cows), porcine (e.g., hogs or pigs), ovine (e.g., goats or sheep), equine (e.g., horses), canine (e.g., dogs), feline (e.g., house cats), camels, deer, donkeys, buffalos, antelopes, rabbits, and rodents (e.g., guinea pigs, squirrels, rats, mice, gerbils, and hamsters). Avians include Anatidae (swans, ducks and geese), Columbidae (e.g., doves and pigeons), Phasianidae (e.g., partridges, grouse and turkeys), Thesienidae (e.g., domestic chickens), Psittacines (e.g., parakeets, macaws, and parrots), game birds, and ratites (e.g., ostriches). Birds treated or protected by the compositions and polymorphs of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) can be associated with either commercial or noncommercial aviculture. These include Anatidae, such as swans, geese, and ducks, Columbidae, such as doves and domestic pigeons, Phasianidae, such as partridge, grouse and turkeys, Thesienidae, such as domestic chickens, and Psittacines, such as parakeets, macaws and parrots raised for the pet or collector market, among others.

For purposes of the present invention, the term "fish" is understood to include without limitation, the Teleosti grouping of fish, i.e., teleosts. Both the Salmoniformes order (which includes the Salmonidae family) and the Perciformes order (which includes the Centrarchidae family) are contained within the Teleosti grouping. Examples of potential fish recipients include the Salmonidae, Serranidae, Sparidae, Cichlidae, and Centrarchidae, among others.

Other animals are also contemplated to benefit from the inventive methods, including marsupials (such as kangaroos), reptiles (such as farmed turtles), and other economically important domestic animals for which the inventive methods are safe and effective in treating or preventing parasite infection or infestation.

Examples of parasitic invertebrate pests controlled by administering a pesticidally effective amount of the compositions and polymorphs of the invention to an animal to be protected include ectoparasites (arthropods, acarines, etc.) and endoparasites (helminths, e.g., nematodes, trematodes, cestodes, acanthocephalans, etc. and protozoae, such as coccidia).

The disease or group of diseases described generally as helminthiasis is due to infection of an animal host with parasitic worms known as helminths. The term 'helminths' is meant to include nematodes, trematodes, cestodes and acanthocephalans. Helminthiasis is a prevalent and serious economic problem with domesticated animals such as swine, sheep, horses, cattle, goats, dogs, cats and poultry.

Among the helminths, the group of worms described as nematodes causes widespread and at times serious infection in various species of animals. Nematodes that are contemplated to be treated by the compositions and polymorphs of the invention (preferably wherein the compound of formula I is simultaneously enriched for S and cis as defined above) include, without limitation, the following genera:

Acanthocheilonema, Aelurostrongylus, Ancylostoma, Angiostrongylus, Ascaridia, Ascaris, Brugia, Bunostomum, Capillaria, Chabertia, Cooperia, Crenosoma, Dictyocaulus,

Dioctophyme, Dipetalonema, Diphyllobothrium, Dirofilaria, Dracunculus, Enterobius, Filaroides, Haemonchus, Heterakis, Lagochilascaris, Loa, Mansonella, Muellerius, Necator, Nematodirus, Oesophagostomum, Ostertagia, Oxyuris, Parafilaria, Parascaris,

Physaloptera, Protostrongylus, Setaria, Spirocerca, Stephanofilaria, Strongy hides,

Strongylus, Thelazia, Toxascaris, Toxocara, Trichinella, Trichonema, Trichostrongylus, Trichuris, Uncinaria and Wuchereria. Of the above, the most common genera of nematodes infecting the animals referred to above are Haemonchus, Trichostrongylus, Ostertagia, Nematodirus, Cooperia, Ascaris, Bunostomum, Oesophagostomum, Chabertia, Trichuris, Strongylus, Trichonema, Dictyocaulus, Capillaria, Heterakis, Toxocara, Ascaridia, Oxyuris, Ancylostoma, Uncinaria, Toxascaris and Parascaris. Certain of these, such as Nematodirus, Cooperia and Oesophagostomum attack primarily the intestinal tract while others, such as Haemonchus and Ostertagia, are more prevalent in the stomach while others such as

Dictyocaulus are found in the lungs. Still other parasites may be located in other tissues such as the heart and blood vessels, subcutaneous and lymphatic tissue and the like.

Trematodes that are contemplated to be treated by the invention and by the inventive methods include, without limitation, the following genera: Alaria, Fasciola, Nanophyetus, Opisthorchis, Paragonimus and Schistosoma.

Cestodes that are contemplated to be treated by the invention and by the inventive methods include, without limitation, the following genera: Diphyllobothrium, Diplydium, Spirometra and Taenia. The most common genera of parasites of the gastrointestinal tract of humans are

Ancylostoma, Necator, Ascaris, Strongy hides, Trichinella, Capillaria, Trichuris and

Enterobius. Other medically important genera of parasites which are found in the blood or other tissues and organs outside the gastrointestinal tract are the filarial worms such as Wuchereria, Brugia, Onchocerca and Loa, as well as Dracunculus and extra intestinal stages of the intestinal worms Strongyloides and Trichinella.

Numerous other helminth genera and species are known to the art, and are also contemplated to be treated by the compositions and polymorphs of the invention. These are enumerated in great detail in Textbook of Veterinary Clinical Parasitology, Volume 1, Helminths, E. J. L. Soulsby, F. A. Davis Co., Philadelphia, Pa.; Helminths, Arthropods and Protozoa, (6^thEdition of Monnig's Veterinary Helminthology and Entomology), E. J. L. Soulsby, Williams and Wilkins Co., Baltimore, Md.

The compositions and polymorphs of the invention may be effective against a number of animal ectoparasites (e.g., arthropod ectoparasites of mammals and birds in particular insects such as flies (stinging and licking), parasitic fly larvae, lice, hair lice, bird lice, fleas and the like; or acarids, such as ticks, for examples hard ticks or soft ticks, or mites, such as scab mites, harvest mites, bird mites and the like).

Insect and acarine pests include, e.g., biting insects such as flies and mosquitoes, mites, ticks, lice, fleas, true bugs, parasitic maggots, and the like. Adult flies include, e.g., the horn fly or Haematobia irritans, the horse fly or

Tabanus spp., the stable fly or Stomoxys calcitrans, the black fly or Simulium spp., the deer fly or Chrysops spp., the louse fly or Melophagus ovinus, and the tsetse fly or Glossina spp. Parasitic fly maggots include, e.g., the bot fly {Oestrus ovis and Cuterebra spp.), the blow fly or Phaenicia spp., the screwworm or Cochliomyia hominivorax, the cattle grub or

Hypoderma spp., the fleeceworm and the Gastrophilus of horses. Mosquitoes include, for example, Culex spp., Anopheles spp. and Aedes spp.

Mites include Mesostigmalphatalpha spp. e.g., mesostigmatids such as the chicken mite, Dermalphanyssus galphallinalphae; itch or scab mites such as Sarcoptidae spp. for example, Salpharcoptes scalphabiei; mange mites such as Psoroptidae spp. including Chorioptes bovis and Psoroptes ovis; chiggers e.g., Trombiculidae spp. for example the North American chigger, Trombiculalpha alphalfreddugesi. Ticks include, e.g., soft-bodied ticks including Argasidae spp. for example Argalphas spp. and Ornithodoros spp.; hard-bodied ticks including Ixodidae spp., for example

Rhipicephalphalus sanguineus, Dermacentor variabilis, Dermacentor andersoni,

Amblyomma americanum, Ixodes scapularis and other Rhipicephalus spp. (including the former Boophilus genera).

Lice include, e.g., sucking lice, e.g., Menopon spp.

and Bovicola spp.; biting lice, e.g., Haematopinus spp., Linognathus spp. and Solenopotes spp.

Fleas include, e.g., Ctenocephalides spp., such as dog flea (Ctenocephalides canis) and cat flea {Ctenocephalides felis); Xenopsylla spp. such as oriental rat flea (Xenopsylla cheopis); and Pulex spp. such as human flea (Pulex irritans).

True bugs include, e.g., Cimicidae or e.g., the common bed bug (Cimex lectularius); Triatominae spp. including triatomid bugs also known as kissing bugs; for example

Rhodnius prolixus and Triatoma spp.

Generally, flies, fleas, lice, mosquitoes, gnats, mites, ticks and helminths cause tremendous losses to the livestock and companion animal sectors. Arthropod parasites also are a nuisance to humans and can vector disease-causing organisms in humans and animals.

Numerous other parasitic invertebrate pests are known to the art, and are also contemplated to be treated by the compositions and polymorphs of the invention. These are enumerated in great detail in Medical and Veterinary Entomology, D. S. Kettle, John Wiley AND Sons, New York and Toronto; Control of Arthropod Pests of Livestock: A Review of Technology, R. O. Drummand, J. E. George, and S. E. Kunz, CRC Press, Boca Raton, Fla.

The compositions and polymorphs of the invention may also be effective against ectoparasites, e.g. insects such as flies (stinging and licking), parasitic fly larvae, lice, hair lice, bird lice, fleas and the like; or acarids, such as ticks, for examples hard ticks or soft ticks, or mites, such as scab mites, harvest mites, bird mites and the like. These include e.g. flies such as Haematobia (Lyperosia) irritans (horn fly), Simulium spp. (blackfly), Glossina spp. (tsetse flies), Hydrotaea irritans (head fly), Musca autumnalis (face fly), Musca domestica (house fly), Morellia simplex (sweat fly), Tabanus spp. (horse fly), Hypoderma bovis, Hypoderma lineatum, Lucilia sericata, Lucilia cuprina (green blowfly), Calliphora spp. (blowfly), Protophormia spp., Oestrus ovis (nasal botfly), Culicoides spp. (midges), Hippobosca equine, Gastrophilus intestinalis, Gastrophilus haemorrhoidalis and

Gastrophilus nasalis; lice such as Bovicola (Damalinia) bovis, Bovicola equi, Haematopinus asini, Felicola subrostratus, Heterodoxus spiniger, Lignonathus setosus and Trichodectes canis; keds such as Melophagus ovinus; and mites such as Psoroptes spp., Sarcoptes scabei, Chorioptes bovis, Demodex equi, Cheyletiella spp., Notoedres cati, Trombicula spp. and Otodectes cyanotis (ear mites).

Treatments of the invention are by conventional means such as by enteral administration in the form of, for example, tablets, capsules, drinks, drenching preparations, granulates, pastes, boli, feed-through procedures, or suppositories; or by parenteral administration, such as, for example, by injection (including intramuscular, subcutaneous, intravenous, intraperitoneal) or implants; or by nasal administration; or by dermal application in the form of, for example, bathing or dipping, spraying, pouring-on and spotting-on, washing, dusting, and with the aid of active-compound-comprising shaped articles such as collars, ear tags, tail tags, limb bands, halters, marking devices and the like.

When compositions and polymorphs of the invention are applied in combination with an additional biologically active ingredient, they may be administered separately e.g. as separate compositions. In this case, the biologically active ingredients may be administered simultaneously or sequentially. Alternatively, the biologically active ingredients may be components of one composition.

The compositions and polymorphs of the invention may be administered in a controlled release form, for example in subcutaneous or orally adminstered slow release formulations.

Typically a parasiticidal composition according to the present invention comprises a composition or polymorph of the invention, optionally in combination with an additional biologically active ingredient, or N-oxides or salts thereof, with one or more pharmaceutically or veterinarily acceptable carriers comprising excipients and auxiliaries selected with regard to the intended route of administration (e.g., oral or parenteral administration such as injection) and in accordance with standard practice. In addition, a suitable carrier is selected on the basis of compatibility with the one or more active ingredients in the composition, including such considerations as stability relative to pH and moisture content. Therefore of note are compositions and polymorphs of the invention for protecting an animal from an invertebrate parasitic pest comprising a parasitically effective amount of a composition or polymorph of the invention, optionally in combination with an additional biologically active ingredient and at least one carrier.

For parenteral administration including intravenous, intramuscular and subcutaneous injection, the compositions and polymorphs of the invention can be formulated in suspension, solution or emulsion in oily or aqueous vehicles, and may contain adjuncts such as suspending, stabilizing and/or dispersing agents.

The compositions and polymorphs of the invention may also be formulated for bolus injection or continuous infusion. Pharmaceutical compositions for injection include aqueous solutions of water-soluble forms of active ingredients (e.g., a salt of an active compound), preferably in physiologically compatible buffers containing other excipients or auxiliaries as are known in the art of pharmaceutical formulation. Additionally, suspensions of the active compounds may be prepared in a lipophilic vehicle. Suitable lipophilic vehicles include fatty oils such as sesame oil, synthetic fatty acid esters such as ethyl oleate and triglycerides, or materials such as liposomes.

Aqueous injection suspensions may contain substances that increase the viscosity of the suspension, such as sodium carboxymethyl cellulose, sorbitol, or dextran. Formulations for injection may be presented in unit dosage form, e.g., in ampoules or in multi-dose containers. Alternatively, the active ingredient may be in powder form for constitution with a suitable vehicle, e.g., sterile, pyrogen- free water, before use.

In addition to the formulations described above, the compositions and polymorphs of the invention may also be formulated as a depot preparation. Such long acting formulations may be administered by implantation (for example, subcutaneously or intramuscularly) or by intramuscular or subcutaneous injection.

The compositions and polymorphs of the invention may be formulated for this route of administration with suitable polymeric or hydrophobic materials (for instance, in an emulsion with a pharmacologically acceptable oil), with ion exchange resins, or as a sparingly soluble derivative such as, without limitation, a sparingly soluble salt.

For administration by inhalation, the compositions and polymorphs of the invention can be delivered in the form of an aerosol spray using a pressurized pack or a nebulizer and a suitable propellant, e.g., without limitation, dichlorodifluoromethane,

trichlorofluoromethane, dichlorotetrafluoro ethane or carbon dioxide. In the case of a pressurized aerosol, the dosage unit may be controlled by providing a valve to deliver a metered amount. Capsules and cartridges of, for example, gelatin for use in an inhaler or insufflator may be formulated containing a powder mix of the compound and a suitable powder base such as lactose or starch.

The compositions and polymorphs of the invention may have favourable

pharmacokinetic and pharmacodynamic properties providing systemic availability from oral administration and ingestion. Therefore after ingestion by the animal to be protected, parasiticidally effective concentrations of a composition or polymorph of the invention in the bloodstream may protect the treated animal from blood-sucking pests such as fleas, ticks and lice. Therefore of note is a composition for protecting an animal from an invertebrate parasite pest in a form for oral administration (i.e. comprising, in addition to a parasiticidally effective amount of a composition or polymorph of the invention, one or more carriers selected from binders and fillers suitable for oral administration and feed concentrate carriers).

For oral administration in the form of solutions (the most readily available form for absorption), emulsions, suspensions, pastes, gels, capsules, tablets, boluses, powders, granules, rumen-retention and feed/water/lick blocks, the compositions and polymorphs of the invention can be formulated with binders/fillers known in the art to be suitable for oral administration compositions, such as sugars and sugar derivatives (e.g., lactose, sucrose, mannitol, sorbitol), starch (e.g., maize starch, wheat starch, rice starch, potato starch), cellulose and derivatives (e.g., methylcellulose, carboxymethylcellulose,

ethylhydroxycellulose), protein derivatives (e.g., zein, gelatin), and synthetic polymers (e.g., polyvinyl alcohol, polyvinylpyrrolidone). If desired, lubricants (e.g., magnesium stearate), disintegrating agents (e.g., cross-linked polyvinylpyrrolidinone, agar, alginic acid) and dyes or pigments can be added. Pastes and gels often also contain adhesives (e.g., acacia, alginic acid, bentonite, cellulose, xanthan gum, colloidal magnesium aluminum silicate) to aid in keeping the composition in contact with the oral cavity and not being easily ejected. In one embodiment a composition of the present invention is formulated into a chewable and/or edible product (e.g., a chewable treat or edible tablet). Such a product would ideally have a taste, texture and/or aroma favored by the animal to be protected so as to facilitate oral administration of the compositions and polymorphs of the invention. If the parasiticidal compositions are in the form of feed concentrates, the carrier is typically selected from high-performance feed, feed cereals or protein concentrates. Such feed concentrate-containing compositions can, in addition to the parasiticidal active ingredients, comprise additives promoting animal health or growth, improving quality of meat from animals for slaughter or otherwise useful to animal husbandry. These additives can include, for example, vitamins, antibiotics, chemotherapeutics, bacteriostats, fungistats, coccidiostats and hormones.

The rate of application required for effective parasitic invertebrate pest control (e.g. "pesticidally effective amount") will depend on such factors as the species of parasitic invertebrate pest to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. One skilled in the art can easily determine the pesticidally effective amount necessary for the desired level of parasitic invertebrate pest control. In general for veterinary use, the compositions and polymorphs of the invention are administered in a pesticidally effective amount to an animal, particularly a homeothermic animal, to be protected from parasitic invertebrate pests. A pesticidally effective amount is the amount of active ingredient needed to achieve an observable effect diminishing the occurrence or activity of the target parasitic invertebrate pest. One skilled in the art will appreciate that the pesticidally effective dose can vary for the various compounds and compositions useful for the method of the present invention, the desired pesticidal effect and duration, the target parasitic invertebrate pest species, the animal to be protected, the mode of application and the like, and the amount needed to achieve a particular result can be determined through simple experimentation. For oral or parenteral administration to animals, a dose of the compositions of the present invention administered at suitable intervals typically ranges from about 0.01 mg/kg to about 100 mg/kg, and preferably from about 0.01 mg/kg to about 30 mg/kg of animal body weight. Suitable intervals for the administration of the compositions of the present invention to animals range from about daily to about yearly. Of note are administration intervals ranging from about weekly to about once every 6 months. Of particular note are monthly adminstration intervals (i.e.

administering the compounds to the animal once every month). Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention.

For the avoidance of doubt, where a literary reference, patent application, or patent, is cited within the text of this application, the entire text of said citation is herein incorporated by reference.

EXAMPLES

1. Preparation of Polymorphs

la Preparation of Form 1 and Form 3

The compound of formula Ia(R) was produced using the methods described in WO 2009/080250 and WO 2011/104089. 14mg of this compound in 450μ1 of a mixture of 10% water and 90% methanol was placed in a stream of dry nitrogen at 40°C until all the solvent was removed. A mixture of polymorphs was generated.

Analysis on polymorph Form 3 was carried out directed from this mixture.

In order to isolate polymorph Form 1, acetonitrile was added to the polymorph mixture to form a flowable slurry which was held at 25°C for 24 hours with stirring.

Analysis using PXRD and DSC confirmed the presence of the specific polymorphs.

lb. Preparation of Form 2

The compound of formula la (racemic mixture) was produced using the methods described in WO 2009/080250. 2g of this compound in 10ml of methanol was subjected to temperature cycling. For the first 1.5 days, the temperature was cycled between room temperature and 40°C every 4 hours with stirring. Stirring was then increased and the upper temperature increased to 50°C and the cycling continued for a further 2 days.

Analysis using PXRD and DSC confirmed the presence of the specific polymorph.

2. Analysis of polymorphs

After preparation by the methods detailed above, the samples were subject to analysis by single crystal X-ray diffraction and/or powder X-ray diffraction. The parameters of the unit cell for polymorph Form 1 and Form 3 are shown in Tables 1 and 2, respectively. The measured 2Θ values of peak positions of the powder X-ray diffraction pattern of the polymorph of Form 2 are shown in Table 3 below. In addition, it was possible to calculate the expected powder X-ray diffraction pattern from the single crystals of the polymorphs of Form 1 and Form 3 - this data is also shown in Table 3 below. The 2Θ values are generated or calculated using a wavelength of 1.54056Ά with a 2Θ step size of 0.02°.

TABLE 3

The polymorphs were further analysed by DSC. The melting points of Form 1, Form 2 and Form 3 are 198°C ± 5°C, 198°C ± 5°C and 185°C ± 5°C, respectively.

Although the invention has been described with reference to preferred embodiments and examples thereof, the scope of the present invention is not limited only to those described embodiments. As will be apparent to persons skilled in the art, modifications and adaptations to the above-described invention can be made without departing from the spirit and scope of the invention, which is defined and circumscribed by the appended claims. All publications cited herein are hereby incorporated by reference in their entirety for all purposes to the same extent as if each individual publication were specifically and individually indicated to be so incorporated by reference.

Claims

1. A crystalline polymorph of compound la which has the following lattice parameters: a=5.28(5), b=10.87(5), c=18.70(5), a = 90.00, β = 96.29(5), γ = 90.00 and volume = 1066.7(5)9 A³

2. The polymorph according to claim 1 wherein the polymorph is characterised by a powder X-ray diffraction pattern expressed in terms of 2Θ angles, wherein the powder X-ray diffraction pattern comprises at least three 2Θ angle values selected from the group comprising 4.74 ± 0.2, 16.98 ± 0.2, 18.90 ± 0.2, 23.54 ± 0.2 and 29.94 ± 0.2.

3. The polymorph according to claim 1 or claim 2, which has a melting point of 198°C ± 5°C.

4. A polymorph of compound la, which is characterized by a powder X-ray diffraction pattern expression in terms of 2Θ angles, wherein the powder X-ray diffraction pattern comprises at least three 2Θ angle values selected from the group comprising 12.27 ± 0.2, 16.48 ± 0.2, 18.78 ± 0.2, 20.48 ± 0.2 and 20.95 ± 0.2.

5. The polymorph according to claim 4, which has a melting point of 198°C ± 5°C.

6. An insecticidal composition comprising a polymorph as claimed in any one of claims 1 to 5 and an agriculturally acceptable carrier or diluent.

7. The insecticidal composition of claim 6 which comprises at least 90mol% of the

compound of formula la in the S configuration compared to the total amount of both the S and R enantiomer of the compound of formula la.

8. The insecticidal composition of claim 6 or claim 7 which comprises i) a crystalline polymorph of the compound of formula la as claimed in any one of claims 1 to 3, ii) a crystalline polymorph of the compound of formula la as claimed in claim 4 or claim 5 or iii) a mixture thereof.

9. The composition of any one of claim 6 to 8, which further comprises the compound of formula lb.

10. The composition of claim 9, wherein the composition comprises less than about 20% by weight of the compound of formula lb.

11. The composition of any one of claims 6 to 10 which comprises a further insecticide.

12. A method of combating and controlling insects, acarines, nematodes or molluscs, which comprises applying an insecticidally, acaricidally, nematicidally or

molluscicidally effective amount of a composition as claimed in any one of claims 6 to 11 to a pest, a locus of pest or to a plant susceptible to attack by a pest.

13. A mixture of a compound of formula I

and abamectin wherein the ratio of the compound of formula I to abamectin by weight in the composition is 1 :0.05 to 1 : 1 ; or

a mixture of a compound of formula I and chlorpyrifos , wherein the ratio of the compound of formula I to chlorpyrifos by weight in the composition is 1 : 1 to 1 : 10; or a mixture of formula I and cyantraniliprole, wherein the ratio of the compound of formula I to cyantraniliprole by weight in the composition is 1 :0.2 to 1 :4; or a mixture of a compound of formula I and emamectin (preferably emamectin benzoate), wherein the ratio of the compound of formula I to emamectin by weight in the composition is 1 :0.05 to 1 : 1; or a mixture of a compound of formula I and lambda cyhalothrin, wherein the ratio of the compound of formula I to lambda cyhalothrin by weight in the composition is 1 :0.1 to 1 :2; or

a mixture of a compound of formula I and pymetrozine, wherein the ratio of the compound of formula I to pymetrozine by weight in the composition is 1 : 1 to 1 :6; or a mixture of a compound of formula I and spirotetramat, wherein the ratio of the compound of formula I to spirotetramat by weight in the composition is 1 :0.5 to 1 :4; or a mixture of a compound of formula I and thiamethoxam, wherein the ratio of the compound of formula I to thiamethoxam by weight in the composition is 1 : 0.5 to 1 :6; or

a mixture of a compound of formula I and, wherein the ratio of the compound of formula I to clothianidin by weight in the composition is 1 : 0.5 to 1 :6; or

a mixture of a compound of formula I and imidacloprid, wherein the ratio of the compound of formula I to imidacloprid by weight in the composition is 1 : 0.5 to 1 :6; or a mixture of a compound of formula I and chlorantraniliprole, wherein the ratio of the compound of formula I to chlorantraniliprole by weight in the composition is 1 :0.2 to 1 :4; or

a mixture of a compound of formula I and sulfoxaflor, wherein the ratio of the compound of formula I to sulfoxaflor by weight in the composition is 1 : 0.5 to 1 :6; or a mixture of a compound of formula I and azoxystrobin, wherein the ratio of the compound of formula I to azoxystrobin by weight in the composition is 1 : 1.5 to 1 : 10; or

a mixture of a compound of formula I and isopyrazam, wherein the ratio of the compound of formula I to isopyrazam by weight in the composition is 1 : 1 to 1 :3; or a mixture of a compound of formula I and chlorothalonil wherein the ratio of the compound of formula I to chlorothalonil by weight in the composition is 1 :5 to 1 :50; or a mixture of a compound of formula I and cyproconazole, wherein the ratio of the compound of formula I to cyproconazole by weight in the composition is 1 : 1 to 1 :5; or a mixture of a compound of formula I and difenoconazole, wherein the ratio of the compound of formula I to difenoconazole by weight in the composition is 1 : 0.3 to 1 :5; or a mixture of a compound of formula I and mandipropamid, wherein the ratio of the compound of formula I to mandipropamid by weight in the composition is 1 : 1 to 1 : 15; or

a mixture of a compound of formula I and mefenoxam, wherein the ratio of the compound of formula I to mefenoxam by weight in the composition is preferably 1 :0.3 to 1 :8; or

a mixture of a compound of formula I and a compound of formula II

wherein the ratio of the compound of formula I to the compound of formula II by weight in the composition is 1 :0.3 to 1 :8; or

a mixture of a compound of formula I and a compound of formula III

wherein the ratio of the compound of formula I to the compound of formula III by weight in the composition is 1 :0.3 to 1 :8.