EP0971893A1

EP0971893A1 - Cyano substituted cycloalkanes

Info

Publication number: EP0971893A1
Application number: EP98910859A
Authority: EP
Inventors: David Philip John Pearson; Christopher John Urch; Roger Salmon; John Finney; Mark Adrian Huggett
Original assignee: Zeneca Ltd
Current assignee: Syngenta Ltd
Priority date: 1997-04-01
Filing date: 1998-03-05
Publication date: 2000-01-19
Also published as: AR012114A1; KR20010005811A; ZA982408B; GB9706574D0; AU6508598A; WO1998043957A1; JP2002504092A

Abstract

A compound of formula (I); wherein R1 is Ar-(CH¿2?)n- where n is zero or one and Ar is an optionally substituted phenyl or an optionally substituted 5- or 6-membered heterocyclic ring system containing from 1 to 3 heteroatoms independently selected from nitrogen, oxygen and sulfur atoms, and at least one unsaturation (double bond) between adjacent atoms in the ring, wherein the substituents, if present, are selected from halogen atoms, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, haloalkoxy, alkylthio and alkyl amino groups, said groups having up to six carbon atoms; wherein R?2 and R3¿ and independently hydrogen or a group selected from alkyl, aryl, heteroaryl, aralkyl, formyl, alkylcarbonyl, arylcarbonyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl or dithiocarboxyl groups; alkyl moieties of R?2 and R3¿ comprise from 1 to 15 carbon atoms, and are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl, carboxylic acyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, amino, acylamino, imidate and phosphonato groups; aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl and dithiocarboxyl moieties of R?2 and R3¿ are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl, carboxylic acyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, haloalkyl, alkyl, amino, acylamino, imidate and phosphonato groups; or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom; compositions comprising a compound of formula (I) and a carrier or diluent; and a method of combating insect, acarine or nematode pests using a compound or composition as defined hereinbefore.

Description

CYANO SUBSTITUTED CYCLOALKANES This invention relates to novel cyano-substituted cycloalkanes, to processes for their preparation, to insecticidal compositions comprising them and to their use in combating insect and like pests.

Tetracyanocyclopentadiene salts are disclosed as rocket propellants and dyes

(US 3536694). A l-cyano-3-amino-4-oxo-cyclopentane derivative has also been dislcosed

(Tetrahedron 33 463 (1977)).

The present invention provides a compound of formula (I)

( I ) wherein R¹ is Ar-(CH₂)_n- where n is zero or one and Ar is an optionally substituted phenyl or an optionally substituted 5- or 6-membered heterocyclic ring system containing from 1 to 3 heteroatoms independently selected from nitrogen, oxygen and sulfur atoms, and at least one unsaturation (double bond) between adjacent atoms in the ring, wherein the substituents, if present, are selected from halogen atoms, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, haloalkoxy, alkylthio and alkyl amino groups, said groups having up to six carbon atoms; wherein R² and R³ are independently hydrogen or a group selected from alkyl, aryl, heteroaryl, aralkyl, formyl, alkylcarbonyl, arylcarbonyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl or dithiocarboxyl groups; alkyl moieties of R² and R³ comprise from 1 to 15 carbon atoms, and are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl, carboxylic acyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, amino, acylamino, imidate and phosphonato groups; aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl and dithiocarboxyl moieties of R² and R³ are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl, carboxylic acyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, haloalkyl, alkyl, amino, acylamino, imidate and phosphonato groups; or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom.

Throughout this description, compounds are named according to the IUPAC system, with a ring atom numbering as shown below.

It will be appreciated that the compounds of formula (I) have chiral centres at ring positions 1 and 3 and are therefore capable of existing in four isomeric forms (comprising two pairs of diastereoisomers) which can be designated as (1R,3R), (1R,3S), (1S,3S) and (1S,3R). The present invention embraces all isomeric forms individually and mixtures (including racemic mixtures) thereof in all proportions.

Examples of 5- and 6-membered heterocyclic ring systems represented by Ar include those based on pyridine, pyrazine, pyridazine, pyrimidine, pyrrole, pyrazole, imidazole, 1,2,3- and 1,2,4-triazoles, furan, thiophene, oxazole, isoxazole, thiazole. isothiazole, 1,2,3- and 1,3,4-oxadiazoles, 1,2,3- and 1,3,4-thiadiazoles and such rings fused to a benzene ring and partially reduced forms of the foregoing rings containing at least one double bond derived from these, as well as those based on oxathiole, dioxole, and dithiole rings containing one double bond. Preferably Ar represents a halo-substituted phenyl, pyridyl, or diazinyl group.

Halogen includes fluorine, chlorine, bromine and iodine.

Alkyl moieties of R² and R³ and substituents of Ar preferably contain from 1 to 6, more preferably from 1 to 4, carbon atoms. They can be in the form of straight or branched chains (for example methyl, ethyl, n- or i-propyl, or n-, s-, i- or t-butyl). Haloalkyl is preferably C,„₆ haloalkyl, especially fluoroalkyl (for example trifluoromethyl, 2,2,2-trifluoroethyl or 2,2-difluoroethyl). Alkenyl and alkynyl moieties of R² and R³ and substituents of Ar preferably contain from 2 to 6, more preferably from 2 to 4, carbon atoms. They can be in the form of straight or branched chains, and, where appropriate, the alkenyl moieties can be of either (E)- or (Z)-confιguration. Examples are vinyl, allyl and propargyl. Aryl includes naphthyl but is preferably phenyl.

Heteroaryl includes 5- and 6-membered aromatic rings containing one, two, three or four heteroatoms selected from the list comprising oxygen, sulphur and nitrogen and can be fused to benzenoid ring systems. Examples of heteroaryl are pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl (1,2,3-, 1,2,4- and 1,3,5-), furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (1,2,3- and 1,2,4-), tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, indolinyl, isoindolinyl, benzofuranyl, benzothienyl and benzimidazolinyl.

The heterocyclyl part of heterocyclylalkyl is a ring containing one or two heteroatoms selected from the list comprising oxygen, sulphur and nitrogen. Examples are piperidine, piperazine, pyrrolidine, tetrahydro furan, morpholine, thietane, pyridine or thiazole. The alkylenedioxy group is a substituent for a ring and is especially C_M alkylenedioxy. Alkylenedioxy groups are optionally substituted with halogen (especially fluorine) and are, for example, methylenedioxy (OCH₂0) or difluoromethylenedioxy (OCF₂0). Suitable acid addition salts include salts of a compound of formula (I) with an inorganic acid such as hydrochloric, hydrobromic, sulfuric, nitric or phosphoric acid, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic or phthalic acid, or a sulphonic acid such as methane, benzene or toluene sulphonic acid. Other examples of organic carboxylic acids include haloacids such as trifluoroacetic acid. In one particular aspect the invention provides a compound of formula (I) wherein R' is Ar-(CH₂)_n- where n is zero or one and Ar is an optionally substituted phenyl or an optionally substituted 5- or 6-membered heterocyclic ring system containing from 1 to 3 heteroatoms independently selected from nitrogen, oxygen and sulfur atoms, and at least one unsaturation (double bond) between adjacent atoms in the ring, wherein the substituents, if present, are selected from halogen atoms (especially fluorine, chlorine or bromine), alkyl (especially C_M alkyl), alkenyl (especially C₂.₄ alkenyl), alkynyl (especially C^ alkynyl), alkoxy (especially C_M alkoxy), haloalkyl (especially C_M haloalkyl), haloalkenyl (especially C₂.₄ haloalkenyl), haloalkoxy (especially C haloalkoxy), alkylthio (especially C,_₄ alkylthio), and alkylamino (especially mono- or di-(C,.₄ alkyl)amino, such as mono- or di- (C,_₃ alkyl)amino) groups, wherein R² and R³ are independently hydrogen or a group selected from alkyl (especially C alkyl), aryl (especially phenyl), heteroaryl (especially pyridinyl or pyrimidinyl), aralkyl (especially aryl(C )alkyl, such as phenyl(C_M)alkyl), heteroarylalkyl (especially heteroaryl(C_M)alkyl, such as pyridinyl(C_M)alkyl or pyrimidinyl(C,_.4)alkyl), alkenyl (especially C₃.₄ alkenyl), aralkenyl (especially aryl(C_3^,)alkenyl, such as phenyl(C_3.4) alkenyl), alkynyl (especially C₃.₄ alkynyl), formyl, alkylcarbonyl, arylcarbonyl (especially phenylcarbonyl), alkoxycarbonyl (especially C alkoxycarbonyl), alkanesulfonyl (especially C,„₄ alkylsulfonyl), phenylsulfonyl, alkenyloxycarbonyl (especially C₃. alkenyloxycarbonyl), aralkyloxycarbonyl (especially phenyl(C,.₄)alkoxycarbonyl), aryloxycarbonyl (especially phenoxycarbonyl), heterocyclylalkyl (especially heterocyclyl(C,.₄)alkyl, such as piperidinyl(C,_.4)alkyl), carbamyl (H₂NC(0)) or dithiocarboxyl groups; alkyl moieties of R² and R³ comprise from 1 to 15 carbon atoms (especially 1 to 8 carbon atoms) and are optionally substituted with one or more substituents selected from halogen (especially fluorine or chlorine), cyano, carboxyl(HOC(0)), carboxylic acyl (especially C_M alkylcarbonyloxy), formyl, carbamyl (H₂NC(0)), alkoxycarbonyl (especially C alkoxycarbonyl), alkoxy (especially C,_₄ alkoxy), alkylenedioxy (especially C alkylenedioxy), hydroxy, nitro, amino, acylamino (especially C_M alkylcarbonylamino), imidate (C alkyl [C(O)NHC(O)]) and phosphonato (OP(OH)₂) groups; aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl and dithiocarboxyl moieties of R² and R^J are optionally substituted with one or more substituents selected from halogen (especially fluorine, chlorine or bromine), cyano, carboxyl(HOC(0)), carboxylic acyl (especially C_M alkylcarbonyloxy), formyl, carbamyl (H₂NC(0)), alkoxycarbonyl (especially C_M alkoxycarbonyl), alkoxy (especially C_M alkoxy), alkylenedioxy (especially C alkylenedioxy). hydroxy, nitro, haloalkyl (especially C_M haloalkyl), alkyl (especially C alkyl), amino, acylamino (especially C,.₄ alkylcarbonylamino), imidate (C alkyl [C(0)NHC(0)]) and phosphonato (OP(OH)₂) groups; or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom.

In another aspect the invention provides compounds of formula (I) wherein R' represents a group Ar-(CH₂)_n- where n is zero or one and Ar represents an optionally substituted phenyl or 5- or 6-membered heterocyclic ring system containing from 1 to 3 heteroatoms individually selected from nitrogen, oxygen and sulfur atoms, and at least one unsaturation (double bond) between adjacent atoms in the ring, wherein the substituents, if present, are selected from halogen atoms, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, alkylthio and alkyl amino groups, any of which groups contain up to six carbon atoms, wherein R² and R³ each individually represents hydrogen or cyano or a group selected from alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, arenesulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl or dithiocarboxyl groups, said groups comprising from 1 to 15 carbon atoms, said groups being optionally substituted with one or more substituents selected from halogen, cyano, carboxyl, carboxylic acyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, haloalkyl, alkyl, amino. acylamino, imidate and phosphonato groups; or R² and R³ together with the adjacent nitrogen atom represent a nitrogen containing heterocyclic group which may contain a further heteroatom selected from oxygen, sulfur and nitrogen: and acid addition salts and quaternary ammonium salts and N-oxides derived therefrom.

Preferred compounds of formula (I) are those wherein n is zero and Ar is a pyridyl or diazinyl group which is optionally substituted with halogen (such as chlorine or bromine).

In yet another aspect the invention provides a compound of formula (I) wherein R¹ is Ar-(CH₂)_n- where n is zero or one and Ar is a 5- or 6-membered aromatic heterocyclic ring system containing from 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, and optionally fused to a benzene ring, the system being optionally substituted by halogen (especially fluorine, chlorine or bromine), haloalkoxy (especially trifluoromethoxy) or haloalkyl (especially trifluoromethyl).

In a further aspect the invention provides a compound of formula (I) wherein R² and R³ are independently hydrogen; alkyl comprising from 1 to 15 carbon atoms (especially 1 to 8 carbon atoms, more especially 1 to 4 carbon atoms) optionally substituted with halogen (especially fluorine) or alkoxy (especially methoxy); phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alkoxy (especially ethoxy); alkenyl (especially allyl); formyl; alkoxycarbonyl (especially t-butyloxycarbonyl); or alkenyloxycarbonyl (especially vinyloxycarbonyl). In a still further aspect the invention provides a compound of formula (I) wherein R¹ is a group Ar-(CH₂)_n- where n is zero or one and Ar is a 5- or 6-membered aromatic heterocyclic ring system containing from 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, and optionally fused to a benzene ring, the system being optionally substituted by halogen (especially fluorine, chlorine or bromine), haloalkoxy (especially trifluoromethoxy) or haloalkyl (especially trifluoromethyl); wherein R² and R³ are independently hydrogen; alkyl comprising from 1 to 15 carbon atoms (especially 1 to 8 carbon atoms, more especially 1 to 4 carbon atoms) optionally substituted with halogen (especially fluorine) or alkoxy (especially methoxy); phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alkoxy (especially ethoxy); alkenyl (especially allyl); formyl; alkoxycarbonyl (especially t- butyloxycarbonyl); or alkenyloxycarbonyl (especially vinyloxycarbonyl).

In an additional aspect the invention provides a compound of formula (I) wherein R¹ is Ar-(CH₂)_n- where n is zero or one and Ar is a 6-membered aromatic heterocyclic ring system containing from 1 to 3 nitrogen atoms, optionally substituted by halogen atoms (especially chlorine or bromine).

In another aspect the invention provides a compound of formula (I) wherein R² and R³ are independently hydrogen; alkyl (especially C alkyl) optionally substituted with halogen (especially fluorine) or alkoxy (especially methoxy) groups; phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alkoxy (especially ethoxy); formyl; alkoxycarbonyl (especially t-butyloxycarbonyl); or alkenyloxycarbonyl (especially vinyloxycarbonyl).

In yet another additional aspect the invention provides a compound of formula (I) wherein R¹ is Ar-(CH₂)_n- where n is zero or one and Ar is a 6-membered aromatic heterocyclic ring system containing from 1 to 3 nitrogen atoms, optionally substituted by halogen atoms (especially chlorine or bromine); wherein R² and R³ are independently hydrogen; alkyl (especially C_M alkyl) optionally substituted with halogen (especially fluorine) or alkoxy (especially methoxy); phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alkoxy (especially ethoxy); formyl; alkoxycarbonyl (especially t-butyloxycarbonyl); or alkenyloxycarbonyl (especially vinyloxycarbonyl).

Specific compounds according to the invention include those set out in Table I below where the values of R¹, R² and R³ are given for each compound.

TABLE I

Table II shows selected mass spectroscopy data or selected NMR data (with CDC1₃ as the solvent - no attempt is made to list every resonance in all cases), for compounds of Table I. Selected data are also presented in some of the Examples. The following abbreviations are used throughout this description: mp = melting point (uncorrected) ppm = parts per million s = singlet t = triplet d = doublet q = quartet dd = double doublet dt = double triplet tt - triple triplet MH+ = Protonated molecular ion m = multiplet M+ = Molecular ion

TABLE II

Compounds of formula (I) can be prepared as described below. Throughout Schemes 1 and 2, R¹, R² and R³ are as defined above; R⁴ is hydrogen, optionally substituted alkyl or optionally substituted aryl; X and X¹ are, independently, leaving groups (such as halogen or alkyl sulphonate); and R is optionally substituted alkyl (for example t-butyl), optionally substituted alkenyl or optionally substituted aralkyl (for example benzyl).

Base R'X

Scheme 1

Methods for preparing a compound of formula (I) are shown in Scheme 1. This scheme also shows a method for preparing a compound of formula (7) (that is, a compound of formula (I) wherein R³ is hydrogen). Conjugate addition of cyanide to cyclopentenone (2) can be carried out by a variety of methods, for example in P Perlmutter, Tetrahedron Organic Chemistry Series Vol. 9, Conjugate Addition Reactions in Organic Synthesis, pl76 and references therein, Pergamon 1992. The reductive amination of (3) is readily carried out for example with reducing agents such as cyanoborohydrides (for example R O Hutchins et al, J. Org. Chem., 46, 3571, (1981)) and references therein) or formic acid and its amine salts (for example E Staple et al, J. Org. Chem., 14, 559, (1949)). Protection of an amine compound of formula (4) by reaction with a chloro formate ester, for example t-butyl chloro formate, in the presence of a suitable base provides a carbamate compound of formula (5). Substitution on the carbon bearing the nitrile group to give a compound of formula (6) may be effected using a suitable base such as lithium diisopropylamide, lithium hexamethyldisilazide or sodamide in a suitable solvent such as diethyl ether, tetrahydrofuran (THF) or dimethoxy ethane at a variety of temperatures usually between -100 °C and 30 °C and adding an aryl, heteroaryl, benzyl or similar substrate suitably substituted with a leaving group, for example halide. Removal of the carbamate residue in a compound of formula (6) may be effected by a variety of methods well known to those skilled in the art and the amine compound of formula (7) can then be converted to a compound of formula (I) either by direct reaction with an alkylating agent, such as an alkyl halide, or by reductive coupling with a carbonyl compound using methods analogous to those described for the preparation of (4). The order of the stages of the above route may be altered, for instance reductive amination of a compound of formula (3) with a secondary amine can yield a compound of formula (8) directly which may then be substituted adjacent to the nitrile group as described above (for example using lithium diisopropylamide, lithium hexamethyldisilazide or sodamide as a base) to produce a compound of formula (I).

Q, Y = Br, OTf Conjugate Addition

Scheme 2

Further methods of preparing a compound of formula (I) are shown in Scheme 2. A suitably 3-substituted cyclopentenone compound of formula (9), containing a group such as halogen, alkylsulphonate or a trisubstituted tin residue, may be reacted with a substrate containing a trisubstituted tin residue, a trifluoromethanesulphonate (OTf) or bromide residue, provided that only one component of the reaction contains tin, in a Stille-type coupling using a metal catalyst (for example Palladium) to give a cyclopentenone compound of formula (10). This may then be further transformed by conjugate addition of cyanide, as described above, to produce a cyanocyclopentanone compound of formula (1 1) which on reductive amination, as above, provides the a compound of formula (I). Alternatively, a ketone compound of formula (11) may be reacted with a suitable hydro xylamine to give an oxime compound of formula (12) which may be reduced to give a primary amine compound of formula (13) for further elaboration, by methods well known to those skilled in the art, into a compound of formula (I). The preparation of specific compounds of formula (I) according to the invention is exemplified by the preparative details set out in the Examples below. Other compounds of the invention may be prepared by similar procedures to those illustrated using the appropriate reactants. In these processes the compounds of formula (I) as defined hereinabove are prepared by reacting the corresponding 3-cyanocyclopentylamine of formula (I) where R¹ is replaced by hydrogen with a compound of formula R'-X in the presence of a base, where R¹ is as defined hereinabove and X is a leaving group, for example a halogen.

Many of the 3-cyanocyclopentylamines of formula (I) where R' is replaced by hydrogen have not been described previously and therefore in a further aspect the invention provides such compounds useful as intermediates in the preparation of the compounds of formula (I) as defined hereinabove.

In another aspect the present invention provides processes for preparing the compounds of formula (I).

In a still further aspect the invention provides a method of combating and controlling insect, acarine or nematode pests at a locus which comprises treating the pests or the locus of the pests with an insecticidally, acaricidally or nematocidally effective amount of a composition comprising a compound of formula (I) or an acid addition salt thereof.

The compounds of formula (I) and acid addition salts thereof can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Homoptera and Coleoptera (including Diabrotica i.e. corn rootworms) and also other invertebrate pests, for example, acarine pests. The insect and acarine pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, forestry, the storage of products of vegetable origin, such as fruit, grain and timber, and also those pests associated with the transmission of diseases of man and animals. Examples of insect and acarine pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossvpii (aphid), Aphis fabae (aphid), Aedes aegvpti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Dysdercus fasciatus (capsid), Musca domestica (housefly), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Phaedon cochleariae (mustard beetle), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Agrotis spp. (cutworms), Chilo partellus (maize stem borer), Nilaparvata lugens (planthopper), Nephotettix cincticeps (leafhopper), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllcoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite) and Brevipalpus spp. (mites). Further examples include insects which adversely affect the health of the public or of animals. In order to apply the compounds of formula (I) to the locus of the nematode, insect or acarid pest, or to a plant susceptible to attack by the nematode, insect or acarid pest, the compound is usually formulated into a composition which includes in addition to a compound of formula (I) a suitable inert diluent or carrier material, and, optionally, a surface active agent. The amount of composition generally applied for the control of nematode pests gives a rate of active ingredient from 0.01 to 10 kg per hectare, preferably from 0.1 to 6 kg per hectare.

Thus in another aspect the present invention provides an insecticidal, acaricidal or nematicidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor. The compositions can be applied to the soil, plant or seed, to the locus of the pests, or to the habitat of the pests, in the form of dusting powders, wettable powders, granules (slow or fast release), emulsifiable concentrates, suspension concentrates, liquid solutions, emulsions, seed dressings, fogging/smoke formulations or controlled release compositions, such as microencapsulated granules or suspensions. Dusting powders are formulated by mixing the active ingredient with one or more finely divided solid carriers and/or diluents, for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers. Granules are formed either by absorbing the active ingredient in a porous granular material for example pumice, attapulgite clays, fuller's earth, kieselguhr. diatomaceous earths, ground corn cobs, and the like, or by adsorbing the active ingredient on to hard core materials such as sands, silicates, mineral carbonates, sulphates, phosphates, or the like. Agents which are commonly used to aid absorption or adsorption include aliphatic and aromatic petroleum solvents, alcohols, polyvinyl acetates, polyvinyl alcohols, ethers, ketones, esters, dextrins, sugars and vegetable oils. Other additives may also be included in granules, such as emulsifying agents, wetting agents or dispersing agents.

Microencapsulated formulations (microcapsule suspensions CS) or other controlled release formulations may also be used, particularly for slow release over a period of time and for seed treatment. Alternatively the compositions may be in the form of liquid preparations to be used as dips, irrigation additives or sprays, which are generally aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents (surface active agents). The compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of an emulsifiable concentrate (EC) or a suspension concentrate (SC) containing a high proportion of the active ingredient or ingredients. An EC is a homogeneous liquid composition, usually containing the active ingredient dissolved in a substantially non-volatile organic solvent. An SC is a fine particle size dispersion of solid active ingredient in water. In use, the concentrates are diluted in water and applied by means of a spray to the area to be treated. Suitable liquid solvents for ECs include methyl ketones, methyl isobutyl ketone, cyclohexanone, xylenes, toluene, chlorobenzene, paraffins, kerosene, white oil, alcohols, (for example, butanol), methylnaphthalene, trimethylbenzene, trichloroethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THF A).

Wetting agents, dispersing agents and emulsifying agents may be of the cationic, anionic or non-ionic type. Suitable agents of the cationic type include, for example, quaternary ammonium compounds, for example cetyltrimethyl ammonium bromide. Suitable agents of the anionic type include, for example, soaps, salts of aliphatic monoesters of sulphuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, or butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl- and tri i sopropy lnaphthalene sulphonates. Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octyl phenol, nonyl phenol and octyl cresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins.

These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may contain 10-85% by weight of the active ingredient or ingredients. When diluted to form aqueous preparations such preparations may contain varying amounts of the active ingredient depending upon the purpose for which they are to be used.

The compounds of formula (I) may also be formulated as powders (dry seed treatment DS or water dispersible powder WS) or liquids (flowable concentrate FS, liquid seed treatment LS, or microcapsule suspension CS) for use in seed treatments.

In use the compositions are applied to the insect pests, to the locus of the pests, to the habitat of the pests, or to growing plants liable to infestation by the pests, by any of the known means of applying pesticidal compositions, for example, by dusting, spraying or incorporation of granules. The compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as insecticides, synergists, herbicides, fungicides or plant growth regulators where appropriate. Suitable additional active ingredients for inclusion in admixture with a compound of formula (I) may be compounds which will broaden the spectrum of activity of the compositions of the invention or increase their persistence in the location of the pest. They may synergise the activity of the compound of formula (I) or complement the activity for example by increasing the speed of effect or overcoming repellency. Additionally multi-component mixtures of this type may help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient included will depend upon the intended utility of the mixture and the type of complementary action required. Examples of suitable insecticides include the following: a) Pyrethroids such as permethrin, esfenvalerate, deltamethrin, cyhalothrin in particular lambda-cyhalothrin, biphenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids for example ethofenprox, natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin and 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl-3-(2-oxothiolan- 3-ylidenemethyl) cyclopropane carboxy late; b) Organophosphates such as profenofos, sulprofos, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenophos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chloropyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pyrimiphos-methyl, pyrimiphos-ethyl, fenitrothion or diazinon; c) Carbamates (including aryl carbamates) such as pirimicarb, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur or oxamyl; d) Benzoyl ureas such as triflumuron, or chlorfluazuron; e) Organic tin compounds such as cyhexatin, fenbutatin oxide, azocyclotin; f) Macrolides such as avermectins or milbemycins, for example such as abamectin, ivermectin, and milbemycin; g) Hormones and pheromones; h) Organochlorine compounds such as benzene hexachloride, DDT, chlordane or dieldrin; i) Amidines, such as chlordimeform or amitraz; j) Fumigant agents; k) Imidacloprid; 1) Spinosad.

In addition to the major chemical classes of insecticide listed above, other insecticides having particular targets may be employed in the mixture if appropriate for the intended utility of the mixture. For instance selective insecticides for particular crops, for example stemborer specific insecticides for use in rice such as cartap or buprofezin can be employed. Alternatively insecticides specific for particular insect species/stages for example ovo-larvicides such as chlofentezine, flubenzimine, hexythiazox and tetradifon, motilicides such as dicofol or propargite, acaricides such as bromopropylate, chlorobenzilate, or growth regulators such as hydramethylron, cyromazine, methoprene, chlorofluazuron and diflubenzuron may also be included in the compositions.

Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamax, safroxan and dodecyl imidazole.

Suitable herbicides, fungicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.

An example of a rice selective herbicide which can be included is propanil, an example of a plant growth regulator for use in cotton is "Pix", and examples of fungicides for use in rice include blasticides such as blasticidin-S. The ratio of the compound of formula (I) to the other active ingredient in the composition will depend upon a number of factors including type of target, effect required from the mixture etc. However in general, the additional active ingredient of the composition will be applied at about the rate at which it is usually employed, or at a slightly lower rate if synergism occurs.

The invention is illustrated by the following Examples. The following ingredients are referred to by their Registered Trade Marks and have the composition as shown below.

EXAMPLE 1 This Example illustrates the preparation of 3-cyanocyclopentanone. 2-Cyclopenten-l-one (lg, 0.012mol) was stirred in THF (50ml) at ambient temperature and N-(2-hydroxyethyl)piperazine-N'-ethane-2-sulphonic acid (2.86g, 0.012mol) added in one portion followed by water (25ml). Sodium cyanide (1.2g, 0.024mol) was added portionwise to the stirred solution. After stirring for 3.5h the mixture was poured into water (50ml) and extracted with ethyl acetate (3x25ml). The combined organic fractions were washed with brine (50ml), dried (magnesium sulphate) and evaporated under reduced pressure giving the product as a pale yellow oil (1.15g, 88%).

Η NMR CDC1₃): δ 3.22(m,lH), 2.19-2.70(m,6H)ppm. M+ = 109.

EXAMPLE 2

This Example illustrates the preparation of N-benzyl-3-cyano-cyclopentylamine.

Benzylamine (1.57g, 14.68mmol) was stirred in methanol (20ml) at room temperature and a solution of 3-cyanocyclopentanone (0.80g, 7.34mmol) in methanol (10ml) added dropwise. The solution was stirred for 80min and a solution of sodium cyanoborohydride (0.37g, 5.87mmol) in methanol (10ml) was added dropwise. Stirring was continued and after 18 hours the mixture was acidified to ~pH2 by addition of concentrated hydrochloric acid before being concentrated under reduced pressure. The residue was partitioned between 2M hydrochloric acid (40ml) and diethyl ether (15ml) and the aqueous phase further extracted with diethyl ether (2x10ml). The aqueous layer was basified to pH 10-11 by addition of solid potassium hydroxide and extracted with diethyl ether (4x15ml). These latter extracts were combined, washed with brine, dried using potassium carbonate/magnesium sulphate and evaporated under reduced pressure leaving a yellow oil (2.03g). Residual benzylamine was removed at 50°C and 0.4mm of mercury (53.3Nιτf²) leaving the product as a pale brown oil (1.6g). EXAMPLE 3

This Example illustrates the preparation of N-benzyl-N-t-butyloxycarbonyl-3- cyanocyclopentylamine.

N-Benzyl-3-cyanocyclopentylamine (1.6g, 8mmol) was stirred in dichloromethane (15ml) at room temperature and di-t-butyl dicarbonate (1.92g, 8.8mmol) in dichloromethane (10ml) added dropwise. After 3.5 hours the solvent was removed under reduced pressure leaving a brown oil (3.05g). The product was purified by filtration chromatography on silica using 5% then 10% ethyl acetate in hexane giving the product as a mixture of diastereoisomers (1.335g).

MH+ = 301. EXAMPLE 4 This Example illustrates the preparation of N-benzyl-N-t-butyloxycarbonyl-3-(5- bromopyrid-3-yl)-3-cyanocyclopentylamine.

Lithium bis(trimethylsilyl)amide (4.58ml of a 1M solution in THF, 4.58mmol) was stirred under nitrogen and cooled to 5°C and N-benzyl-N-t-butyloxycarbonyl-3- cyanocyclopentylamine (550mg, 1.83mmol) in THF (5ml) added dropwise. The reaction mixture was allowed to warm to 15°C and 3,5-dibromopyridine (477mg, 2.01mmol) in THF (5ml) added dropwise and the reaction mixture allowed to warm to room temperature. The reaction mixture was stirred for 5 hours and allowed to stand overnight. The mixture was carefully poured into water (20ml) and extracted with ethyl acetate (4x20ml). The combined organic extracts were dried with potassium carbonate/magnesium sulphate and the solvent removed under reduced pressure leaving a brown oil (820mg). The product was purified by filtration chromatography on silica using a gradient elution of 5% to 20% ethyl acetate in hexane giving the desired product as a mixture of diastereoisomers (130mg). EXAMPLE 5

This Example illustrates the preparation of N-benzyl-3-(5-bromopyrid-3-yl)-3- cyanocyclopentylamine (Compound No.5).

N-Benzyl-N-t-butyloxycarbonyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine (120mgs, 0.263mmol) was stirred in dichloromethane (2ml) and trifluoroacetic acid (1ml) added dropwise. The solution was stirred at room temperature for 5h and the solvents removed under reduced pressure. The residue was treated with toluene (92ml) which was evaporated leaving a pale brown solid (134mg). The material was partitioned between dichloromethane (20ml) and saturated sodium bicarbonate (20ml). The organic layer was separated and the aqueous phase extracted with further dichloromethane (2x20ml). The combined organic fractions were dried using potassium carbonate/magnesium sulphate and the solvent removed under reduced pressure leaving a yellow oil (75mg). This was purified by filtration chromatography on silica using a gradient in dichloromethane of 1 to 4% of a 10% solution of aqueous ammonia in methanol giving the desired product as a mixture of diastereoisomers (55mg). EXAMPLE 6 This Example illustrates the preparation of N-benzyl-N-methyl-3-(5-bromopyrid-3- yl)-3-cyanocyclopentylamine (Compound No.17).

N-Benzyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine (24mg, 0.067mmol) was stirred in acetonitrile (2ml) at room temperature, 37% aqueous formaldehyde (0.06ml, 0.674mmol) added followed by sodium cyanoborohydride (8.5mg, 0.135mmol). The mixture was stirred overnight, concentrated under reduced pressure and partitioned between 2M caustic soda (10ml) and dichloromethane (10ml), the aqueous layer was further extracted with dichloromethane (3x10ml) and the combined organic phase dried using potassium carbonate/magnesium sulphate and the solvent removed under reduced pressure leaving a colourless oil (25mg). This was purified by filtration chromatography on silica using a gradient in dichloromethane of 0.5% to 2% of a 10% solution of aqueous ammonia in methanol. This gave the desired product as a mixture of diastereoisomers (colourless oil, 20mg). EXAMPLE 7

This Example illustrates the preparation of N,N-dimethyl-3-cyanocyclopentylamine. Dimethylamine hydrochloride (46.45g, 0.57mmol) was stirred in methanol (250ml) at room temperature and a solution of 3-cyanocyclopentanone (6.25g, 0.057mmol) in methanol (50ml) was added dropwise. After 55 minutes a solution of sodium cyanoborohydride (2.87g, 0.046mmol) in methanol (25ml) was added dropwise. Stirring was continued and after 4 hours the mixture was concentrated under reduced pressure. The residue was dissolved in 2M sodium hydroxide (200ml) and extracted with diethyl ether (3x100ml). The combined organic extracts were washed with brine, dried using potassium carbonate/magnesium sulphate and evaporated under reduced pressure to leave an orange oil (4.05g). This was dissolved in ethyl acetate (50ml) and extracted with 2M hydrochloric acid (1x50ml, lxl 0ml). The combined acid extracts were basified to pH 10-1 1 by the addition of solid potassium hydroxide and extracted with diethyl ether (3x50ml). The organic extracts were combined, dried using potassium carbonate/magnesium sulphate and evaporated under reduced pressure to leave the product as a mixture of diastereoisomers (yellow oil, 3.35g). M+ = 138. EXAMPLE 8 This Example illustrates the preparation of N,N-dimethyl-3-(5-bromopyrid-3-yl)-3- cyanocyclopentylamine (Compound No.14).

N,N-Dimethyl-3-cyanocyclopentylamine (0.52g, 3.77mmol) and 3,5- dibromopyridine (0.983g, 4.15mmol) were stirred together in dry THF (1 Oml) under nitrogen and cooled to 0°C. Lithium bis(trimethylsilyl)amide (5.65ml of a 1M solution in THF, 5.65mmol) was added dropwise at a rate of 2.7ml per hour using a syringe pump. The reaction mixture was stirred for 30 minutes then further lithium bis(trimethylsilyl)amide (2.83ml, 2.83mmol) was added similarly. Stirring was continued at low temperature for 1.5 hours then the mixture was carefully poured into water (30ml) and extracted (3x30ml of ethyl acetate). The combined organic extracts were dried using potassium carbonate/ magnesium sulphate and evaporated under reduced pressure leaving a brown oil (1.30g). Residual 3,5-dibromopyridine and N,N-dimethyl-3-cyanocyclopentylamine were partially removed at 100°C and 0.6mm of mercury (80Nm^"2) and the product (brown oil, 0.96g) was further purified by filtration chromatography on silica using a gradient in dichloromethane of 1% to 3% of a 10% solution of aqueous ammonia in methanol giving a yellow gum (21 Omg). Residual N,N-dimethyl-3-cyanocyclopentylamine was removed at 100°C and 0.3mm of mercury (40Nm^"2) to give the product as a mixture of diastereoisomers (160mg).

EXAMPLE 9 This Example illustrates the preparation of N-methyl-N-t-butyloxycarbonyl-3-(5- bromopyrid-3-yl)-3-cyanocyclopentylamine (Compound No.22).

Sodium amide (109mg, 2.79mmol) was suspended in THF (2ml) and stirred under nitrogen at room temperature. N-methyl-N-t-butyloxycarbonyl-3-cyanocyclopentylamine (0.50g, 2.23mmol) in THF (2ml) was added dropwise. The reaction mixture was stirred a further 30 minutes then cooled to 0°C, whereupon 3,5-dibromopyridine (58 lmg, 2.45mmol) in THF (2ml) was added dropwise. Stirring was continued at low temperature for 1.5 hours and then at room temperature overnight. The reaction mixture was carefully poured into water (30ml) and extracted (3x30ml of ethyl acetate). The combined extracts were dried using potassium carbonate/magnesium sulphate and evaporated under reduced pressure leaving a brown semi-solid (81 Omg). The product was purified by filtration chromatography on silica using a gradient elution of 5% to 15% ethyl acetate in hexane giving the desired product as a mixture of diastereoisomers (205mg).

EXAMPLE 10 This Example illustrates the preparation of N-methyl-3-(5-bromopyrid-3-yl)-3- cyanocyclopentylamine (Compound No.2).

N-Methyl-N-t-butyloxycarbonyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine (185mg, 0.49mmol) was stirred in dichloromethane (3ml) and trifluoroacetic acid (1.9ml) was added dropwise. The solution was stirred at room temperature for 2 hours and then allowed to stand overnight. The solvents were removed under reduced pressure and the residue was partitioned between saturated sodium bicarbonate (15ml) and dichloromethane (15ml). The organic layer was separated and the aqueous phase extracted with further dichloromethane (2x15ml). The combined organic fractions were dried using potassium carbonate/magnesium sulphate and the solvent removed under reduced pressure leaving a yellow oil (135mg) which was purified by preparative thin layer chromatography on silica using a 10% solution in dichloromethane of a 10% solution of aqueous ammonia in methanol to give the desired product as a mixture of diastereoisomers (70mg).

EXAMPLE 1 1 This Example illustrates the preparation of N-methyl-N-vinyloxycarbonyl-3-(5- bromopyrid-3-yl)-3 -cyanocyclopentylamine (Compound No.23). N,N-Dimethyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine (1 15mg, 0.39mmol) was stirred in 1 ,2-dichloroethane under nitrogen at reflux. Vinylchloro formate (125mg, 1.17mmol) was added dropwise and the reaction mixture was held at reflux for 5 hours and then allowed to stand overnight at room temperature. The reaction mixture was concentrated under reduced pressure leaving a brown gum (150mg). The product was purified by filtration chromatography on silica using 20% ethyl acetate in hexane giving the desired product as a mixture of diastereoisomers (75mg).

EXAMPLE 12 This Example illustrates the preparation of N-methyl-N-formyl-3-(5-bromopyrid-3- yl)-3 -cyanocyclopentylamine (Compound No.16). N-Methyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine(l lOmg, 0.39mmol) was stirred in methyl formate (2ml) for 2 hours and allowed to stand overnight. The reaction mixture was concentrated under reduced pressure to give a yellow oil (120mg). The reaction was incomplete and therefore the oil was stirred with methyl formate (2ml) for a further 6 hours and allowed to stand overnight. More methyl formate (3 ml) was added and the mixture was stirred a further 6 hours and then allowed to stand overnight. Stirring was continued for a further 6 hours and the mixture was allowed to stand overnight. Further methyl formate (2ml) was added and the reaction mixture was allowed to stand for 7 days and was then concentrated under reduced pressure to give a yellow oil (130mg). The product was purified by filtration chromatography on silica using dichloromethane followed by a 2% solution in dichloromethane of a 10% solution of aqueous ammonia in methanol giving the desired product as a mixture of diastereoisomers (95mg).

EXAMPLE 13 This Example illustrates the preparation of N-methyl-N-(2,2-difluoroethyl)-3-(5- bromopyrid-3-yl)-3-cyanocyclopentylamine (Compound No.18).

N-Methyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine (lOOmg, 0.36mmol) and 2-bromo- 1 , 1 -difluoroethane (79mg, 0.54mmol) were stirred together in dimethylformamide (DMF) (3ml) at room temperature. Potassium carbonate (75mg, 0.54mmol) was added in one portion, followed by potassium iodide (15mg, 0.09mmol) and then the reaction mixture was heated to 50°C. After 24 hours more 2-bromo- 1,1 -difluoroethane (79mg, 0.54mmol) was added in DMF (1ml) followed by potassium carbonate (75mg, 0.54mmol). The reaction mixture was held at 50°C for 24 hours then more 2-bromo-l , 1 -difluoroethane (79mg,

0.54mmol) was added in DMF (1ml). After 3 days at 50°C, the reaction mixture was allowed to cool and was then diluted with dichloromethane, filtered to remove inorganics and evaporated under reduced pressure to give a yellow gum (1 lOmg). The reaction was incomplete, therefore the mixture was stirred with 2-bromo- 1,1 -difluoroethane (522mg, 3.60mmol) in DMF (3ml) and potassium carbonate (75mg, 0.54mmol) was added in one portion, followed by potassium iodide (60mg, 0.36mmol). The reaction mixture was heated to 50°C, held at temperature overnight and then more 2-bromo- 1 ,1 -difluoroethane (522mg, 3.60mmol) in DMF (3ml) was added followed by potassium carbonate (75mg, 0.54mmol). After a further 3 days, the reaction mixture was allowed to cool and was then filtered to remove inorganics, washed through with DMF and concentrated under reduced pressure to give a yellow oil (31 Omg). The oil was purified by preparative thin layer chromatography on silica using a 10% solution in dichloromethane of a 10% solution of aqueous ammonia in methanol giving the desired product as a mixture of diastereoisomers (65mg).

EXAMPLE 14 This Example illustrates the preparation of N-mefhyl-N-(4-efhoxybenzyl)-3-(5- bromopyrid-3-yl)-3 -cyanocyclopentylamine (Compound No.24).

N-Methyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine (160mg, 0.57mmol) was stirred in methanol (2ml) at room temperature and 4-ethoxybenzaldehyde (171mg, 1.14mmol) in methanol (2ml) was added dropwise. After 90 minutes sodium cyanoborohydride (36mg, 0.57mmol) was added in one portion. After stirring at room temperature for 24 hours, a further addition of sodium cyanoborohydride (36mg, 0.57mmol) was made and after a further 24 hours 4-ethoxybenzaldehyde (86mg, 0.57mmol) in methanol (lml) was added dropwise followed by a further addition of sodium cyanoborohydride (36mg, 0.57mmol). The reaction mixture was stirred at room temperature for a further 24 hours before sodium cyanoborohydride (36mg, 0.57mmol) was added and after a further 24 hours 4-ethoxybenzaldehyde (86mg, 0.57mmol) in methanol (lml) was added dropwise followed by sodium cyanoborohydride (36mg, 0.57mmol). After 4 days the reaction mixture was concentrated under reduced pressure and the residue partitioned between 2M sodium hydroxide (5ml) and diethyl ether (5ml) and the aqueous phase further extracted with diethyl ether (2x5ml). The combined organic extracts were washed with water (lxl 0ml), dried with potassium carbonate/magnesium sulphate and concentrated under reduced pressure to give a yellow oil (460mg). This was dissolved in dichloromethane (10ml) and extracted with 2M hydrochloric acid (3x5ml). The combined acid extracts were basified to pH 10-1 1 by the addition of solid potassium hydroxide and extracted with dichloromethane (4 10ml). The organic extracts were combined, dried using potassium carbonate/magnesium sulphate and evaporated under reduced pressure leaving the product as a colourless oil (140mg). The oil was purified by preparative thin layer chromatography on silica using a 10% solution in dichloromethane of a 10% solution of aqueous ammonia in methanol giving the desired product as a mixture of diastereoisomers (120mg). NMR data is also provided for the intermediate N-allyl-N-t-butyloxycarbonyl-3- cyanocyclopentylamine, 'H NMR (CDC1₃): δ 5.80(m,lH), 5.12(m,2H), 3J8(d,2H), 1.80- 4.50(m,8H), 1.47(s,9H)ppm.

EXAMPLE 15

This Example illustrates an emulsifiable concentrate composition which is readily convertible by dilution with water into a liquid preparation suitable for spraying purposes. The concentrate has the following composition:

% Weight Compound No. 1 25.5

SYNPERONIC NP 13 2.5

Calcium dodecylbenzenenesulphonate 2.5

AROMASOL H 70

EXAMPLE 16

This Example illustrates a wettable powder composition which is readily convertible by dilution with water into a liquid preparation suitable for spraying purposes. The wettable powder has the following composition:

% Weight Compound No. 1 25.0

Silica 25.0

Sodium lignosulphonate 5.0

Sodium lauryl sulphate 2.0

Kaolinite 43.0

EXAMPLE 17

This Example illustrates a dusting powder which may be applied directly to plants or ^• other surfaces and comprises 1% by weight of Compound No. 1 and 99% by weight of talc. EXAMPLE 18 This Example illustrates a concentrated liquid formulation suitable for application by ultra low volume techniques after mixing with paraffinic diluents.

% Weight Compound No. 1 90.0

SOLVESSO 200 10.0

EXAMPLE 19

This Example illustrates a capsule suspension concentrate which is readily convertible by dilution with water to form a preparation suitable for application as an aqueous spray.

% Weight Compound No. 1 10.0

Alkylbenzene solvent (for example AROMASOL H) 5.0

Toluene di-isocyanate 3.0

Ethylenediamine 2.0

Polyvinyl alcohol 2.0

Bentonite 1.5

Polysaccharide (for example KELTROL) 0.1

Water 76.4

EXAMPLE 20

A ready for use granular formulation:

% Weight

Compound No. 1 0.5

SOLVESSO 200 0.2

Nonylphenol ethoxylate (for example Synperonic NP8) 0.1

Calcium carbonate granules (0.3-0.7mm) 99.2 EXAMPLE 21 An aqueous suspension concentrate:

% Weight

Compound No. 1 5.0

Kaolinite 15.0

Sodium lignosulphonate 3.0

Nonylphenolethoxylate (for example Synperonic NP8) 1.5

Propylene glycol 10.0

Bentonite 2.0

Polysaccharide (for example KELTROL) 0.1

Bactericide (for example Proxel; 0.1 Proxel is a registered Trade Mark)

Water 63.3

EXAMPLE 22 This Example illustrates a water dispersible granule formulation.

% Weight

Compound No. 1 5

Silica 5

Sodium lignosulphate 10

Sodium dioctylsulphosuccinate 5

Sodium acetate 10

Montmorillonite powder 65

EXAMPLE 23 This Example illustrates the insecticidal properties of compounds of formula (I). The activities of individual compounds of formula (I) were determined using a variety of pests. The pests were treated with a liquid composition containing 500 parts per million (ppm) by weight of a compound unless otherwise stated. Each composition was made by dissolving the compound in acetone and ethanol (50:50) mixture and diluting the solution with water containing 0.05% by weight of a wetting agent sold under the trade name "SYNPERONIC" NP8 until the liquid composition contained the required concentration of the compound. "SYNPERONIC" is a Registered Trade Mark.

The test procedure adopted with regard to each pest was basically the same and comprised supporting a number of the pests on a medium which was usually a substrate, a host plant or a foodstuff on which the pests feed, and treating either or both the medium and the pests with a composition. The mortality of the pests was then assessed at periods usually varying from two to five days after the treatment.

The results of the tests against peach aphid (Myzus persicae) are presented below. The results indicate a grading of mortality (score) designated as A, B or C wherein C indicates less than 40% mortality, B indicates 40-79% mortality and A indicates 80-100% mortality. In this test Chinese cabbage leaves were infested with aphids, the infested leaves were sprayed with the test composition, and the mortality assessed after 3 days.

Compound Nos.2, 3, 5, 9, 14, 16, 17, 18, 23, 24, 25, 39 and 52 each gave a mortality score of A whilst Compound No.82 gave a score of B. In addition, in a similar test against red spider mites (Tetranychus urticae) Compound

Nos.9 and 88 each gave a mortality score of B.

Claims

1. A compound of formula (I)

( I ) wherein R' is Ar-(CH₂)_n- where n is zero or one and Ar is an optionally substituted phenyl or an optionally substituted 5- or 6-membered heterocyclic ring system containing from 1 to 3 heteroatoms independently selected from nitrogen, oxygen and sulfur atoms, and at least one unsaturation (double bond) between adjacent atoms in the ring, wherein the substituents, if present, are selected from halogen atoms, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, haloalkoxy, alkylthio and alkyl amino groups, said groups having up to six carbon atoms; wherein R² and R³ are independently hydrogen or a group selected from alkyl, aryl, heteroaryl, aralkyl, formyl, alkylcarbonyl, arylcarbonyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, phenylsulfonyl. alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl or dithiocarboxyl groups; alkyl moieties of R² and R³ comprise from 1 to 15 carbon atoms, and are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl, carboxylic acyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, amino, acylamino, imidate and phosphonato groups; aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl and dithiocarboxyl moieties of R² and R³ are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl, carboxylic acyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, haloalkyl, alkyl, amino, acylamino, imidate and phosphonato groups; or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom.

2. A compound of formula (I) as claimed in claim 1 wherein R¹ is Ar-(CH₂)_n- where n is zero or one and Ar is a 5- or 6-membered aromatic heterocyclic ring system containing from 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, and optionally fused to a benzene ring, the system being optionally substituted by halogen, haloalkoxy or haloalkyl.

3. A compound of formula (I) as claimed in claim 1 or 2 wherein R² and R³ are independently hydrogen; alkyl comprising from 1 to 15 carbon atoms, optionally substituted with halogen or alkoxy; phenylalkyl optionally substituted with halogen or alkoxy; alkenyl; formyl; alkoxycarbonyl; or alkenyloxycarbonyl.

4. A compound of formula (I) as claimed in claim 1, 2 or 3 wherein R' is Ar-(CH₂)_╧Ç- where n is zero or one and Ar is a 6-membered aromatic heterocyclic ring system containing from 1 to 3 nitrogen atoms, optionally substituted by halogen atoms; wherein R² and R³ are independently hydrogen; alkyl optionally substituted with halogen or alkoxy; phenylalkyl optionally substituted with halogen or alkoxy; formyl; alkoxycarbonyl; or alkenyloxycarbonyl.

5. An intermediate compound of formula (I) wherein R¹ is hydrogen and R² and R³ are as claimed in claim 1.

6. A process for preparing a compound of formula (I) as claimed in claim 1 which comprises either

(a) reacting a 3 -cyanocyclopentylamine of formula (8):

(8) with a compound of formula R'-X, where X is a leaving group, in the presence of a base, or

(b) reacting a 3-cyanocyclopentylamine of formula (7):

(7) with an alkylating agent of formula R³-X', where X¹ is a leaving group, or

(c) reductively coupling a 3-cyanocyclopentylamine of formula (7) with a carbonyl compound of formula R³CHO, or

(d) when R³ is hydrogen, decarboxylating a compound of formula (6):

(6) or (e) substituting the amine group of a compound of formula (13):

(13) or (f) reductively aminating a compound of formula (11):

7. An insecticidal, acaricidal or nematicidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of formula (I) as claimed in claim 1 and a suitable carrier or diluent therefor.

8. A method of combating and controlling insect, acarine or nematode pests at a locus which comprises treating the pests or the locus of the pests with an insecticidally, acaricidally or nematocidally effective amount of a composition according to claim 7.

9. A method according to claim 8 where the locus is a growing plant and the pests are pests of plants.