MXPA99004442A - Bicyclic amine derivatives - Google Patents

Abstract

The present invention concerns bicyclic amine derivatives of formula (I) wherein R 1 is an optionally substituted 5-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 eight carbon atoms, and wherein two substituents may join to form a fused ring;R 2 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, dithiocarboxyl or XR 3 (where X represents oxygen or a group NR 4), provided that when R 2 is alkenyl, aralkenyl or alkynyl said group does not have an unsaturated carbon atom bonding directly to the ring nitrogen of formula (I);R 3 and R 4 are, independently, hydrogen, alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, heterocyclylalkyl, alkoxycarbonyl or carboxylic acyl;alkyl moieties of R 2, R 3 and R 4 comprise from 1 to 15 carbon atoms, and are 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 an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom;to processes for preparing them, to insecticidal compositions comprising them and to methods of using them to combat and control insect pests.

Description

AMINE BICICLIC DERIVATIVES.

Field of Invention This invention relates to novel bicyclic amines, to processes for preparing them, to insecticidal compositions thereof and to methods of using same to combat and control insect pests.

Description of the invention.

The invention provides a phosphorus compound wherein R1 is a substituted 5-member heterocyclic ring system which contains from 1 to 3 heteroatoms selected individually from nitrogen, or igene and sulfur atoms, and at least one non-saturation (double link) between the atoms REF .: 30126 adjacent to the ring, wherein the substituents, if present, are selected from halogen atoms, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, alkylthio and aminoalkyl groups, any of the groups containing more than eight carbon atoms, and wherein two substituents can be joined to form a molten ring; R 2 represents hydrogen or cyano or a group selected from alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulphonic, arenesulphonyl, alkenyloxycarbonyl, aralkylcarbonyl, aryloxycarbonyl or heterocyclic, carbamyl , carboxyloxy or XR3 (where X represents oxygen or a group NR4), with the proviso that when R2 is alkenyl, aralkenyl or alkynyl said group will not have an unsaturated carbon atom attached directly to the nitrogen ring of formula ( I); R3 and R4 are, independently, hydrogen, alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, heterocarboxylic or carboxylic acyl; alkyl portions of R2, R3 and R4 comprise from 1 to 15 carbon atoms, and are optionally substituted with one or more substituents selected from, halogen, cyano, carboxyl, carboxylic acyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro groups , amino, acylamino, imidate and phthophonate; Aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, alkynyl, alkoxycarbonyl, alkanesul fonyl, arenesulphonyl, canyloxycarbonyl, aralkoxycarbonyl, aryloxycarbonyl, heterocyclealkyl, carbamyl, dithiocarboxyl groups of R2, R3 and R4 comprise from 1 to 15 atoms carbon, and are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl, acyl carboxylic, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, haloalkyl, alkyl, amino, acylamino, imidate and phosphonate groups; or an acid addition salt, quaternary ammonium salt or N-oxide derivative of the same.

It will be appreciated that the bicyclic amine compounds of formula (I) are capable of existing in more than one isomeric form since the R1 and CN groups can be positioned in either exo or endo ratios, and the present invention encompasses within this scope at the same time exo and endo forms and mixtures thereof in all proportions and also in any additional isomeric variant as a consequence of cis and t rans substitution forms of chiral centers present in either R1 or R2.

Examples of 5-membered ring systems represented by R1 include those based on pyrrole, pyrazole, imidazole, 1,2,3- and 1,2,4-triazoles, furan, thiophene, oxazole, isoxazole, thiazole, isothiazole, 1, 2,3- and 1, 3, 4 -oxadia zol is, and 1,2,3- and 1, 3, -thiadiazoles, and partially reduced forms of these containing a double bond, or as those based on oxatiolo rings, dioxolo, and dithiole that contain a double bond.

When two substituents together in R1 form a ring, the resulting ring system is, for example, indole, benzofuran, benzoxazole, benzothiophene or benzylimide zol.

Halogen includes fluorine, chlorine, bromine or iodine.

The alkyl portions preferably contain from 1 to 6, more preferably from 1 to 4, carbon atoms. These can be in the form of linear or branched chains, for example methyl, ethyl, n-1 or iso-propyl, r ^, sec-, i or tert-butyl.

Haloalkyl is preferably Ci-6 haloalkyl, especially f luoroalkyl (for example t riforomethyl, 2, 2, 2-t r i f luoroe t i lo or 2,2-di f luoroetyl) or chloroalkyl. For R2, haloalkyl is preferably C2-6 haloalkyl wherein it is not halogen in the α-carbon (for example 2, 2, 2 - 1 r i f luor oe t i 1 or 2, 2 -di f luoroe t il o).

The alkenyl and alkynyl portions as substituents of R1 preferably contain from 2 to 6, more preferably from 2 to 4, carbon atoms. These may be in the straight or branched chain form, and, appropriately, the alkenyl portions may be of either (E) - or (Z _) - configuration. Examples are vinyl, allyl and propargyl.

Aryl includes naphthyl but is preferably phenol.

Heteroaryl includes 5 and 6 membered aromatic rings containing one, two, three or four heteroatoms selected from the list comprising oxygen, sulfur and nitrogen and may 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, tiazolyl, oxadiazolyl, oxadia zol i lo, tiadia zol i lo, quinolinyl, and soquinol ini it, cinolinyl, quinazolinyl, quinoxalinyl, indolinyl, isoindolinyl, benzofuranyl, benzothienyl and benzimidazolinyl.

The heterocyclyl portion of heterocyclylalkyl is a ring containing one or two heteroatoms selected from the list comprising oxygen, sulfur and nitrogen. Examples are piperidine, piperazine, pyrrolidine, tetrahydrofuran, morpholino, thietane, pyridine or thiazole.

The alkylenedioxy group is a substituent for a ring and is especially alkylenedioxy Ci-. Alkylene dioxy groups are optionally substituted with halogen (especially fluoride) and are, for example, methylenedioxy (OCH 0) or difluoromethylenedioxy (OCF 20).

Suitable acid addition salts include those with an inorganic acid such as hydrochloric, hydrobromic, sulfuric, nitric and phosphoric acids, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic and italic acids, or sulfonic acids such as methane, benzene and toluene acids Other examples of organic carboxylic acids include halo acids such as trifluoroacetic acid.

In a particular aspect, the present invention provides a compound of for (I), wherein R 1 is an optically substituted 5-membered ring system containing from 1 to 3 heteroatoms individually selected from nitrogen, oxygen and sulfur atoms, and at least one non-saturation (double bond) between the adjacent atoms in the ring, wherein the substituents, if present, are selected from groups of halogen atoms, alkyl (especially C? -4 alquiloalkyl, C2-4 alkenyl), alkynyl especially C2_4 alkynyl), alkoxy and C4-4 alkoxy specifically), haloalkyl (especially C1-4 haloalkyl), haloalkenyl (especially C2_4 haloalkenyl), alkylthio (especially C1-4 alkylthio), and amino alkyl (especially mono- or di- (C 1-4 alkyl) ainino, such as mono- or di- (C? -3) alkyl amino), any of these groups contain more than eight carbon atoms, and wherein two substituents may join pa to form a molten ring; R 2 represents hydrogen or cyano or a group selected from alkyl (especially C 1 -4 alkyl), aryl (especially phenyl), heteroaryl (especially pyridinyl or pyrimidinyl), aralkyl (specifically aryl (C 1-4) alkyl, such as phenyl ( C1-) alkylo), heteroarylalkyl (speci cmen e have eroa ri lo (C? - allo lo, such as pi ri di ni 1 or (C 1-) al qui 1 oo pi r imidini lo (C? N alkyl), alkenyl (especially C3_4 alkenyl), aralkenyl (especially aryl (C3.4) alkenyl), such as phenyl (C3-4) alkenyl), alkynyl (especially C3_4 alkynyl) alkoxycarbonyl (especially C1-4 alkoxycarbonyl), canosul phonyl (especially C5-4 alkyl sulphonyl), arenesulfonyl (especially phenyl sulphonyl) , alkenyloxycarbonyl (especially C 3-4 alkenyloxycarbonyl), for loxicone rbonium (especially phenyl (C 1-6) alkoxycarbonyl), aryloxycarbonyl (especially phenoxycarbonyl), heterocyclylalkyl (especially heterocyclic (C 1-4) alkyl, such as piper i dini (C 1-4) alkyl), carbamyl (H 2 NC (0)), di-oxycarboxy or XR 3 (where X represents oxygen or a group NR 4) with the proviso that when R 2 is alkenyl, aralkenyl or alkynyl, said group will not have an unsaturated carbon atom attached directly to the nitrogen ring of formula (I); R3 and R4 are, independently, hydrogen, alkyl (especially C? _4 alkyl), aryl (especially phenyl), heteroaryl (especially pyridinyl or pyrimidinyl), aralkyl (especially aryl (C1-4) alkyl, such as (Cx-4) alkyl o), heteroarylalkyl (especially (C1-4) -alkyl) alkyl, such as pyridinyl (C1-) alkyl or pyrimidinyl (C? 4) alkyl), alkenyl (especially C2.4 alkenyl), aralkenyl (especially aryl (C2.4) alkenyl, such as phenyl (C2-4) alkenyl), alkynyl (especially C2-4 alkynyl), heterocyclylalkyl (especially tercyclic) ilo (C 1-4) alkyl, such as piperidinyl (C? -) alkyl), alkoxycarbonyl (especially C 1-4 alkoxycarbonyl) or acyl carboxylic acid (especially alkylchloroxyC 1-4 alkyl); alkyl portions of R2, R3 and R4 comprising from 1 to 15 carbon atoms, and are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl (HOC (O)), carboxylic acyl (especially alkylaminocarbonyloxy) groups 4), carbamyl (H2NC (0)), alkoxycarbonyl (especially C 1-4 alkoxycarbonyl), alkoxy (especially C 1-4 alkoxy), alkylenedioxy (especially C 1-4 alkylenedioxy), hydroxy, nitro, amino, acylamino (especially at 1 qui 1 ca rbon i lami no C? -4) , imidate (Ci-4 alkyl [C (O) NHC (O)]) and phosphonate (OP (OH) 2); portions of aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, arenesulphonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclic alkyl, carbamyl, di tiocarboxyl of R 2, R 3 and R 4 comprising from 1 to 15 atoms of carbon, and are optionally substituted with one or more substituents selected from, halogen, cyano, carboxyl (HOC (O)), carboxylic acyl groups (especially alky1 ca rboni 1 C1-4 oxy), carbamyl (H2NC (0) ), alkoxycarbonyl (especially C 1 alkoxycarbonyl), alkoxy (especially C 1-4 alkoxy), alkylenedioxy (especially C 1-4 alkylenedioxy), hydroxy, nitro, haloalkyl (especially C 1-4 haloalkyl), alkyl (especially C 1-4 alkyl) , amino, acylamino (especially C 1-4 alkylcarbonylamino), imidate (C 1-4 alkyl [C (O) NHC (O)]) and phosphonate (0P0H) 2); or an acid addition salt, quaternary ammonium salt or N-oxide derivative thereof.

In another aspect, the present invention provides a compound of formula (I), wherein R 1 represents an optionally substituted 5-membered heterocyclic ring system containing from 1 to 3 heteroatoms individually selected from nitrogen, oxygen and sulfur atoms, and at least a non-saturation (double bond) between the adjacent atoms in the ring, wherein the substituents, if present, are selected from halogen atoms, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, alkylthio and amino alkyl groups , any of these groups containing above six carbon atoms, and R2 representing hydrogen or cyano or a selected group of alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, a canosulfonyl, arenesulfonyl, alkanoyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclic alkyl, carbamyl or di ti oca rboxi lo, dic The groups comprise 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, 1-alkylenedioxy, hydroxy, nitro, haloalkyl, alkyl, amino, acylamino, imidate and phosphonate; and acid addition salts and salts of quaternary ammonium and derivatives of N-oxides thereof.

In still another aspect, the present invention provides a compound of formula (I) wherein R 2 is hydrogen, C 4 alkyl (substituted, but not on the a-carbon, with halogen (especially fluoride)), C 1-4 alkyl (optionally substituted with cyano), C3-4 alkenyl, C3-4 haloalkenyl, C3_4 alkynyl or (C1-4) phenyl alkyl (wherein the phenyl ring is optionally substituted with halogen, C1-4 alkyl, C1-4 haloalkyl, C1-6 alkoxy 4 or cyano), with the proviso that when R2 is a substituted or unsubstituted alkenyl, or an alkynyl group, said group will not have an unsaturated carbon atom directly attached to the nitrogen ring of formula (I).

In a further aspect, the present invention provides a compound of formula (I) wherein R 1 is pyrrole, pyrazole, imidazole, 1, 2, 4-ria zol, furan, thiophene, oxazole, isoxazole, thiazole or isothiazole all optionally substituted with one or more of halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, mono (C 1-) a 1 qui lamino or di (C? 4) alkylamino; R represents hydrogen, C2_alkyl (substituted, but not on the α-carbon, with halogen (especially fluoride)), C ?4 alkyl (optionally substituted with cyano), C3-4 alkenyl, C3-4 haloalkenyl, C3_4 alkynyl or phenyl (C 1-4) alkyl (wherein the phenyl ring is optionally substituted with halogen, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, C 1-4 haloalkoxy or cyano), with the proviso that when R 2 is a substituted or unsubstituted alkenyl, or an alkynyl group, said group will not have an unsaturated carbon atom directly attached to the nitrogen ring of formula (I).

In a further aspect, the present invention provides a compound of formula (I) wherein R2 is C1- alkyl (optionally substituted with cyano, C02 (C1-4 alkyl) or phenyl (itself optionally substituted with halogen, alkyl C? 4, C 1-4 alkoxy, C 1-4 haloalkyl or C 1-4 haloalkoxy), C 2-4 haloalkyl (the α-carbon being unsubstituted), C 3 alkenyl or C 3-4 alkynyl; with the proviso that when R "is alkenyl or alkynyl, said group will not have an unsubstituted carbon atoms attached directly to the nitrogen ring of formula (I).

In yet a further aspect, the present invention provides a compound of formula (I) wherein R 1 is a pyrrole, thiophene or isoxazole ring optionally substituted with one or more of halogen, C 1-4 alkyl or C 1-4 haloalkyl; and R 2 is hydrogen, C 1-4 alkyl, fluorine or C 2-4 alkyls (the α-carbon being unsubstituted, with one FH 2 CH 2 C, F 2 HCH 2 C or F 3 CH 2 C), C 3-4 alkenyl (such as allyl) or C 3-4 alkynyl (such as propargyl), with the proviso that when R2 is a substituted or unsubstituted alkenyl, or an alkynyl group, said group will not have an unsaturated carbon atoms attached directly to the nitrogen ring of formula (I).

The specific compounds of formula (I) according to the invention include those listed in the following Table I in which the groups represented by R1 and R 'are given for each compound, together with the melting point (° C) or an indication of the physical state of the compound.

TABLE I Compound R1 Rz Point of No. Fusion Tiof en-3-il Methyl Acetyl Tiof en-2-il Met ilo Acei te 3 2-methylpyrrol-3-ylmethyl 4 5-methylpyrrol-2-ylmethyl 5-chlorothiophen-3-ylmethyl 6 thiazol-2-yl 2,2-difluoroethyl 5-chlorothiazol-2-yl 2,2,2 - t ri f luoretyl 5-trif 1 or omet i 1-Methyl pyrazol-3-yl 9 2-methyloxazol-4-yl Allyl 3-methylsiloxazol-5-benzyl-yl 11 l -methylimidazol-4-yl chlorobenzyl 1-methyl-l, 2,4- Methyl triazol-3-yl 13 2-chloro-l, 3,4- Propargyl thiadiazol-5-yl 14 Thiazolin-2-yl Methyl Compound R 1 R2 N point. Fusion 5-chlorothiazol-2-yl H 16 5 -chlorot-yiazol-2-yl-2,4-chlorobenzyl-2-methylthiazol-4-yl-propyl-3-methylphenyl-4,4-yl luor obu t- 3-enyl 19 5-chlorothiophen-2-yl H 20 5-bromothiof en-3-yl Methyl 21 4, 5-dichlorof ur-2 -i 1 2 -f luor oet ilo 22 4-ethoxif ur- 2-yl Methyl 23 2-dimethylamino-Allyl thiazol-4-yl 24 3-trif 1 uorome i 1-Methyl and soxa zol-3-yl 5-methyl thiophen-2-yl 2,2- di f luoroet yl 26 3-methoxy-l, 2,4- 4-triazol-5-yl 1 for obenci 1 or 27 3-trif 1 uorome i 1-Methyl pyrazol-4-yl 28 Isothiazol-4-yl 2,2,2 - trifluoroethyl Compound R1 R2 Point of No. Fusion 29 5-chlorothiazol-2-yl-2, 2-difluoroeth yl, 2, 5-dichlorot, iofen-Methyl, 2-yl, 5-bromothiazol-2-yl, methyl, 32-5-bromothiazol-2-yl, H, 4, 5- dichlorothiazole-Methyl 2-yl-5-methoxy-thiazole-2-ylmethyl-2-methyl-thia-zol-4-yl-2-cyanoethyl-2-methyl-yl-thiaminot-yl-methyl-4-yl, - 4 -i 1 Methyl 38 3-met il isothiazol-5-Methyl-il-3-chloropi-rol-4-l-methyl-lime-1, 3 -di tiac i 1 open t -methyl-in--i 1 41 3 -me ti 1 i soxa zo 1 - 5- Methyl Oil il 42 1 -me ti lpi r rol -2 - i 1 Benzyl Oil 43 Benzoxa zol -2 -i 1 Methyl Oil 44 2 -cl orot i a zol - 5- i 1 Methyl Compound R1 R2 Score of No. Fu s i on 45 2-chlorothiazol-5-yl 2,2,2- trif luoret ilo 46 2-chlorothiazol-5-yl 2,2- di f luoroetyl 47 2 -cl orot ia zol- 5-i 1 Propargyl 48 2 -chlorotia zol-5-yl allyl 49 2-chlorothiazol-5-yl H 50 3-chloroisothiazol-5-methyl il 51 3-chloroisothiazol-5-2,2,2-yl t rif luoroeil or 52 3 -chloroi sotia zol-5-2,2-yl-di-luoroet-yl-3-chloroisothiazol-5-propargyl-il-3-chloroisothiazol-5-allyl-3-chloro-1-ylthia-5-H-56 3 -methyl isothiazol-5-methyl-1 Compound R1 R2 No-Fusion Point 57 3-methylisothiazol-5,2,2,2-yl trifluoroethyl 58 3-methyl-isothiazol-5-2,2-yl-di-luoroheyl-59 3 -methyl-1-yl-5-propargyl il 60 3-met i 1 i sot ia zol-5-allyl 61 3-met i 1 i t ia zol -5- H il 62 2 -me ti 1 tia zol -5 -i 1 methyl 63 2-methylthiazole -5-yl 2,2,2-trifluoroet yl or 64 2-methylthiazol-5-yl 2,2-di f luoroeti lo 65 2 -me ti 1 yl-5 -i-1 propargyl 66 2 -me ti 1 thiazol-5-yl allyl 67 2-met il thia zol-5-yl H The preparation of the compounds of formula can be carried out by the use of one or more of the synthetic techniques described below and further illustrated in the Examples.

The compounds of formula (I) can be prepared from the compound of formula (II) by treatment with an appropriate base, such as potassium carbonate, in the presence of a compound of formula R2L, where L is an appropriate starting group such as a halide, triflate or mesylate.

Alternatively, the compounds of formula (I) can be prepared from the compounds of formula (II) by reductive amination with an aldehyde (R5CHO; wherein R5CH2 = R2) in the presence of an appropriate reducing agent such as formic acid.

The compounds of formula (II) can be prepared by demethylating a compound of formula (III), by, for example, treating themselves with a chloroform ester (such as vinyl chloroformate) to produce a carbamate, and subjecting the product to it forms an acid hydrolysis.

The compounds of formula (III) can be prepared by treatment of 3-cyano-8-methyl-8-azabicyclo [3.2.1] octane (IV) with an appropriate base, such as lithium diisopropylamide (LDA), and reacting the product thus formed with a halide R1Hal, wherein Hal is a halogen atom. 3-Cyano-8-methyl-8-azabicyclo [3.2.1] octane (IV) can be prepared by tropinone treatment (V) with tosylmethyl isocyanide in the presence of an appropriate base, such as a potassium ethoxide. Alternatively, 3-ci ano-8-methyl ti-8-azabicyclo [3.2.1] octane (IV) can be prepared by treating tropine (XIII) with thionyl chloride to give 3-chloro-8-met i 1 -8 to zabicyclo [3.2.1] octane (XII) and reacting (XII) with cyanide as described in J. Am. Chem. Soc., (1958) 80, 4677.

The compounds of formula (I) can also be prepared by treatment of compound of formula (VI) with an appropriate base, such as lithium diisopropylamide (LDA), and reacting the product thus formed with a Hal halide, wherein Hal is a halogen atom.

The compounds of formula (VI) can be prepared by treatment of 3-cyano-8-azabicyclo [3.2.1] octane (VII) with an appropriate base, such as potassium carbonate, in the presence of a halide R2L ', in where L 'is a starting group (especially halogen). 3-cyano-8-azabicyclo [3.2.1] octane (VII) can be prepared by demethylating 3-cyano-8-methyl-1 -8-a-zabicyclo [3.2.1] octane (IV) by, for example, treating themselves with a chloroformate ester (such as vinyl chloroformate) to produce a carbamate, and subjecting the thus formed product to an acid hydrolysis.

As a further alternative, the compounds of formula (VI) can be prepared by treating the compounds of formula (VIII) with a tosylmethyl isocyanide in the presence of an appropriate base, such as potassium ethoxide.

The compounds of formula (VIII) can be prepared by Robinson's tropionone synthesis, see, for reference, J. Chem. Soc., (1917) 111, 762. Alternatively, compounds of formula (VIII) can be prepared by reacting a cyclohepta- 2,6-dienone (XI) with an amine, R2NH2, as described in, for example, Tetrahedron, (1973), 155, Bull. Chem. Chem. Soc. Jpn. , (1971) 44, 1708 or Org. Chem., (1971) 36, 1718.

Alternatively, the compounds of formula (I) can be prepared by treatment of a compound of formula (IX) with an acetonitrile of formula (X) in the presence of an appropriate base, for example sodium hydride. A similar process is described in J. Med. Chem. (1975) 18, 496.

In additional aspects, the present invention provides processes for preparing compounds of formula (I), as described above, and the intermediates of formula (II) and (III).

In a further aspect, the invention provides a method for combating insects and such pests from the site by application to the site or pests an effective insecticidal amount of an insecticidal composition comprising a compound of formula (I) or an acid addition salt, salt of quaternary ammonium or N-oxide derivative thereof.

The compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Homoptera and Coleoptera (including Diabrotica, this is corn rootworm) and also other invertebrate pests, for example, pests. of acariñas. The insect and acarine pests that can be combated and controlled by the use of the compounds of the invention include those pests associated with agriculture (whose terms include the growth of crops for food and fiber products), horticulture and livestock breeding, forestry, the storage of products of vegetable origin, such as fruits, grains and wood, and also those pests associated with the transmission of diseases of man and animals. Examples of acarine insect and pest species that can be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Dysdercus fasciatus (capsid), Musca domestica (housefly), Pieris brassicae (white butterfly), Plutella xylostella (black diamond night butterfly, Phaedon cochleariae (mustard beetle), Aonidiella spp. (scale insects), Trialeurodes spp. (white fly), Bermisa tabaci (white fly), Blattella germanica (cockroach), Periplaneta americana (cockroach), Ba t ta orientalis (cockroach), Spodoptera 1 i 11 ora 1 i s (worm of the cotton leaf), Heliothis virescens (cocoon of the tobacco worm), Chortiocetes te rmini fera (cricket), Diabrotica spp. (root worm), Agrot i s spp. (cutworm), Chilo partellus (cornfield stem borer), Nilaparvata lugens (plant flea), Nephotettix cincticeps (leaf flea), Panonychus ulmi (European red mite), Panonychus citri (red citrus mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phy 11 cop t oleivora route (citric mold acrid), Polyphagotarsonemus la tus (broad acarid) and Brevipalpus spp. (acarids). Additional examples include insects that adversely affect the health of the public or animals.

In order to apply the compounds of formula (I) to the place of nematodes, insects or acarids, or to the plant susceptible to being attacked by nematodes, insects or acarids, the compounds are usually formulated in a composition that includes in addition to the compound of formula (I) an appropriate inert diluent or a carrier material, and, optionally, a surface active agent. The amount of the composition generally applied for the control of nematode pests gives a range of active ingredient from 0.01 to 10 kg per hectare, preferably from 0.1 to 6 kg per hectare.

Thus in a further aspect, the present invention provides an effective insecticidal, acaricidal or nematicidal amount of a compound of formula (I) and an appropriate carrier or diluent of the same.

The compositions can be applied to the soil, plants or seed, to the place of the pests, or to the habitat of the pests, in the form of dusting powders, wettable powders, granules (of fast or slow release), concentrated in emulsions or suspensions, liquid solutions, emulsions, revival seeds, mist or smoke formulations or liberated control compositions, such as microencapsulated granules or suspensions.

Dusting powders are formulated by mixing an active ingredient with one or more diluents and / or finely divided solid carriers, for example natural clay, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, diatomine, limestone, diatomaceous earths, calcium phosphates, carbonates of calcium and magnesium, sulfur, lime, fluorides, talc, and other solid organic and inorganic carriers.

The granules are formed by either absorbing the active ingredient in a porous granular material such as pumice stone, attapulgite clay, Fuller earth, diatomite, diatomaceous earth, ground corn cobs, and the like, or in hard core materials such as sands, silicates, mineral carbonates, sulfates, phosphates, or the like. Agents that are commonly used to aid in the impregnation, ligation or coating of solid carriers, include aliphatic or aromatic petroleum solvents, alcohols, polyvinyl acetates, polyvinyl alcohols, ethers, ketones, esters, dextrins, sugars and vegetable oils, with the active ingredient. Other additives may also include, such as emulsifying agents, wetting agents or dispersing agents.

The roencapsulated formulations (suspensions of CS microcapsules) or other controlled release formulations can 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 for use as soaks, irrigation additives or dispersions, 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 (wetting agents). active surface). Compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of an emulsifiable concentrate concentrate (EC) or a concentrated suspension (SC) containing a high proportion of the active ingredient (s). An EC is a homogeneous liquid composition, usually containing the active ingredient dissolved in a substantially non-volatile organic solvent. A 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 dispersion for the area to be treated.

Suitable liquid solvents for ECs include methyl ketones, methyl isobutyl ketones, cyanohexanone, xylenes, toluene, chlorobenzene, paraffins, kerosene, white oil, alcohols, (eg, butanol), metha Ina to eno, trimeebenzene , trichloride, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THFA).

The 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, a quaternary ammonium compound, for example, ammonium bromide ce ti 11 rimeti lo. Suitable agents of the anionic type include, for example, soaps, salts or aliphatic monoesters or sulfuric acid, for example lauryl sodium sulfate, salts or aromatic sulphonated compounds, for example, sodium, sodium, calcium, or sodium bisphosphonates. or ammonia lignosulfonate, or butylnane sulfonate, and a mixture of the sodium salts of diisopropyl sulfonate and tri-sodium sulfonate. Suitable agents of the nonionic 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 nonionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of 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 being diluted with water to form aqueous preparations which remain homogeneous for a sufficient time to allow them to be applied by conventional dispersion 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 on the purpose for which they will be used.

The compounds of formula (I) can also be formulated as powders (dry seed treatment DS or water dispersible powders WS) or liquids (flowable concentrate FS, liquid seed treatment LS, or suspension my croencapsulated CS) for use in the treatment of seeds.

In use, the compositions are applied to insect pests, to the place of pests, to the habitat of pests, or to the growth of plants exposed to infestation by pests, by any of the known means to apply pesticidal compositions, by example, by sprinkling, dispersing, or incorporating granules.

The compound of formula (I) may be only the active ingredient of the compositions or it may be mixed with one or more additional active ingredients such as insecticides, synergists, herbicides, fungicides or plant growth regulators where appropriate. Additional active ingredients suitable for inclusion in a mixture with a compound of formula (I) can be compounds that are of broad spectrum activity of the compositions of the invention or increase this persistence in the location of the pest. These can have a synergy with the activity of the compound of formula (I) or complement the activity for example by increasing the speed of the effect or expiration of the repellency.

Mixtures of these additional components of this type can help overcome or prevent the increase in resistance to individual components. The particular additional active ingredient includes depending on 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, fenvalerate, deltamethrin, cyhalothrin in particular 1 ambda -cyanot r in, bifentrin, f enpropa rin, cyfluthrin, tefrluthrin, pyrethroids safe for fish eg etofenprox, natural pyrethrin, tetramethrin, s -bi oalet Rhen, fenfluthrin, praletrin and 5-benzyl-1 -3-furylmet i 1 - (EJ- (1R, 3S) -2,2-dimethyl-3- (2-oxothiolan-3-ylidenemethyl) -cyclopropanecarboxylate; b) Organophosphates such as profenofos, sulprofos, me ti lpa ra on, az infos-me ti 1, demeton-s-methyl, heptenophos, thiometon, fenamiphos, onocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, cl oropi rifos, fosalona, terbufos, f ens ul fot i on, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion or diazinon; c) Carbamates (including aryl carbamates) such as pyrimicarbo, cloetocarb, carbofuran, f ur a t iocarbo, e t iofencarbo, aldicarbo, thiofurox, carbosulfan, bendiocarbo, phenobucarb, propoxur or oxamyl; d) Benzoyl ureas such as triflumuron, or chlorofluazuron; e) Organic tin compounds such as cyhexatin, fenbutatin oxide, azocyclotin; f) Macrolides such as avermectins or mybebicins, for example such as abamectin, iver ectin, and milbemycin; g) Hormones and pheromones; h) Compounds or ganoclorurs such as benzene hexachloride, DDT, chlordane or dieldrin; i) Amidines, such as cl orodime form or amitraz; j) Fumigant agents k) Imidacloprid; 1) thorny.

In addition to the major chemical classes of insecticides listed above, other insecticides that have particular objectives can be used in the mixture if they are appropriate for the intended utility of the mixture. To illustrate selective insecticides for particular crops, for example, specific stemboreous insecticides for use in rice such as cartap or buprofezin can be used. Alternative insecticides specific to species / stages of insects, in particular for example ovoids such as chlorophyllin, f lubenzimine, hexitiazox and tetradifon, molticides such as dicofol or propargite, acaricides such as br omopr opy to, c lor obenci la to, or growth regulators such as Hydrame Ir on, cyromazine, methoprene, chlorofor ur a zuron and di f 1 uben zu rum can be included in the compositions.

Examples of suitable synergistic compounds for use in the compositions include piperonyl, butoxide, sesamax, safroxan and dodecyl imide zol.

Appropriate herbicides, fungicides and plant growth regulators to be included in the compositions will depend on the intended purpose and the effect required.

An example of a herbicide selected for rice that may 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 bla sti cidin-S The range of the compound of formula (I) for the other active ingredient in the composition will depend on a number of factors including the type of objective, the effect required for the mixture etc. However in general, the ingredient Additional active of the composition will be applied around a range to which it is usually employed, or at a slightly lower range if synergism occurs.

The invention is illustrated by the following Examples. Examples 1-5 illustrate the preparation of a range of compounds of formula (I). Examples 6-13 illustrate compositions suitable for the application of the compounds of formula (I) according to the invention. The following ingredients are referred to by their Registered Trade Marks and have the composition as shown in the document.

The selected NMR data are presented in the Examples. For NMR data, no effort has been made to list all absorption. The following abbreviations are used entirely in the following: ppm = parts per million m = multiple s = singlet brs = broad singlet dd = doublet.

Example 1.

This Example illustrates the preparation of 3- (thiophen-3-yl) -3-cyano-8-methyl-8-a-zabicyclo [3.2.1] octane (Compound No. 1 of Table I).

Sodium hydride (0.367 g of a dispersion in 50% oil) was added in portions to a stirred mixture of meso-2,5-bis (chloromethyl) -1-benzylpi rolino [prepared by washing the hydrochloride of meso-2, 5-bis (chlorometyl) -1-benzylpirol idine (1.0 g) in dichloromethane with 2M sodium hydroxide solution and brine, dried (MgSO4) and evaporated under reduced pressure] and 3- (cyanomethyl). 1) t-iofen (0.46 ml) in N, N-dimethylformamide (15 ml) at 0 ° C under nitrogen. After 4 hours, the mixture was allowed to warm to room temperature and left overnight. The mixture was then cooled to 0 ° C, water was added dropwise and the resulting mixture was extracted with ethyl acetate (x3). The combined extracts were washed with water (x4) and brine, dried (gS04) and evaporated under reduced pressure. Chroma tope [Si02, hexane: tert-butyl methyl ether (100: 0) to (90:10)] is chrooted to give 3- (thiophen-3-yl) -3-cyano-8-methyl-8-azabicyclo [ 3.2.1] octane (0.40 g). XH NMR (270MHz) in CDC13: d 7.5-7.1 (8H, both isomers, m), 3.54 and 3.57 (2H, both isomers 2xs), 3.31 (2H, both isomers, m), 2.78 (2H, one isomer, dd ), 2.4-2.0 (4H an isomer and 6H another isomer, m), and 1.41 and 1.28 (2H, both isomers, m) ppm.

Example 2 This Example illustrates the preparation of 3- (thiophen-2-yl) -3-cyano-8-methyl-8-a-zabicyclo [3.2.1] octane (Compound No. 2 of the Table I).

Sodium hydride (0.367 g of a dispersion in 50% oil) was added in portions to a stirred mixture of meso-2,5-bis (chloromethyl) -1-benzylpyrrolidine [prepared by washing the meso-2, 5- hydrochloride bis (chloromethyl) -1-benzylpyrrolidine (1.0 g) in dichloromethane with 2M sodium hydroxide solution and brine, dried (MgSO 4) and evaporated under reduced pressure] and 2 - (cyanomethyl) thiophene (0.46 ml) in N, N-dimethylformamide (15 ml) at 0 ° C under nitrogen. After 4 hours, the mixture was allowed to warm to room temperature and left overnight. The mixture was then cooled to 0 ° C, water was added dropwise and the resulting mixture was extracted with ethyl acetate (x3). The combined extracts were washed with water (x4) and brine, dried (MgSO4) and evaporated under reduced pressure. Tog ra fi o [Si02, hexane: tert-butyl methyl ether (100: 0) to (90:10)] is given to give 3- (thiophen-2-yl) -3-cyano-8-methyl-8- azabicyclo [3.2.1] octane (0.425 g). XH NMR (270MHz) in CDC13: d 7.5-7.2 (6H an isomer and 7H another isomer, m), 7.13 (ÍH an isomer, m), 7.05-6.95 (ÍH, both isomers, m), 3.59 (2H, both isomers, 2xs), 3.31 (2H, both isomers, m), 2.81 (2H, one isomer, dd), 2.4-1.95 (6H, both isomers) and 1.50 (2H, one isomer, dd) ppm.

Example 3 This Example illustrates the preparation of exo-3- (3-met i 1 isoxazol-5-yl) -endo-3-cyano-8-methyl-8-azabicyclo [3.2.1] octane (Compound No. 41 of the Table I).

The rt-but potassium oxide (22.4 g) was added in portions to a stirred mixture of tropinone (11.58 g) and tosylmethyl isocyanide (21.2 g) in dimethoxyethane (240 ml) and ethanol (8 ml) at 0 ° C under nitrogen in a range to maintain the temperature between 0 ° C and 10 ° C. The mixture was then allowed to warm to room temperature and stirred for an additional 4 hours. After remaining at room temperature for 3 days, the mixture was filtered and the solid residue was washed with dimethoxyethane. The filtrate was evaporated under reduced pressure and cured to tog [SiO2; I gave the ring: me t anol (90:10)] to give the exo-3-cia o-8 -me t i 1 - 8 -a z abi cycle [3.2.1] oc taño (9.1 g).

Exo-3-cyano-8-methyl-8-azabicyclo [3.2.1] octane (0.50 g? In tetrahydrofuran (5 ml) was added dropwise to a stirred solution of lithium diisopropy-lamide [made by adding n- lithium butyl (8.33 ml of a 1.6M solution in hexane) to dii sopropi sheet (1346 g) enb tetrahydrofuran (20 ml) at -70 ° C under nitrogen and then stirring at -40 ° C for 30 minutes] to -70 C for 5 minutes After 1.5 hours, 1, 1-dichloroethane (1.29 g) in tetrahydrofuran (5 ml) was slowly added in. After 15 minutes the mixture was allowed to warm to room temperature and then stirred After 5 hours, water (1 ml) was added followed by ethyl acetate (150 ml), the mixture was dried (MgSO 4), evaporated under reduced pressure and chrome-free [SiO 2, di chloromethane: t anol (90:10)] to give the exo-3- (1-chlorovinyl) -endo-3-cyano-8-methyl-8-azabicyclo [3.2.1] octane (0.41 g).

Tert-bu potassium oxide (0.95 g) was added to a stirred solution of exo-3- (l-chlorovinyl) -endo-3-cyano-8-met i-8-a-zabicyclo [3.2.1] octane ( 0.90 g) in tet ahydrofuran (20 ml) at room temperature. After 4 hours the mixture was evaporated under reduced pressure and the residue was absorbed in neutral alumina which was then washed with ethyl acetate to give exo-3-ethynyl-endo-3-cyano-8-methyl-8-azabicyclo [ 3.2.1] octane (0.50 g).

Nitroethane (0.203 g) and trimethylamine (0.045 g) in toluene (5 ml) were added slowly to a solution of exo-3-ethynyl-endo-3-cyano-8-methyl-8-azabicyclo [3.2.1] octane ( 0.40 g) and phenyl isocyanate (0.61 g) in toluene (10 ml) at room temperature. The mixture was heated to 100 ° C for 2 hours and then allowed to cool to room temperature and filtered. The filtrate was evaporated under reduced pressure and chromatographed [SiO2; di chloroform: me tanol (92.5: 7.5)] to give the e_x_o- 3- (3-methyl-1-iso-zol-5-yl) -endo-3-cyano-8-methyl-8-azabicyclo [3.2. 1] octane (0.125 g). H NMR (270MHz) in CDC13: d 6.12 (HH, s), 3.30 (2H, m), 2.34 (3H, s), 2.28 (3H, s) and 2.45-2.10 (8H, m) ppm.

Example 4 This Example illustrates the preparation of 3- (1-methylpyrrol-2-yl) -3-cyano-8-benzyl-8-azabicyclo [3.2.1] octane (Compound No. 42 of Table I).

The hydrochloride of meso-2,5-bis (chloromethyl) -1-benzylpyrrolidine (1.0 g) is dissolved in dichloromethane and the mixture is washed with 2M sodium hydroxide solution. the aqueous layer is separated, extracted with dichloromethane and the combined organic phases are washed with brine, dried (MgSO.sub.4) and evaporated under reduced pressure. The residue is dissolved in N, N-dimethylformamide (15 ml) and the solution is cooled to 0 ° C. Add 2-cyanomethyl-1-methyl-1-methyl (0.49 g) followed by the portionwise addition of sodium hydride (0.734 g of a 50% oil dispersion). After 5 hours at 0 ° C the mixture is allowed to warm to room temperature and is left overnight. The mixture is then cooled to 0 ° C and water is added dropwise carefully and the mixture is extracted with ethyl acetate (x3). The combined extracts are washed with water (x4) and brine, dried (MgSO4), evaporated under reduced pressure and chroma tography [Si02]; hexane: tert-butyl methyl ether (100: 0) to (80:20)] to give 3 - (1-methyl-1-diol-2-yl) -3-cyano-8-benzyl-8-azabicyclo [ 3.2.1] octane (0.098 g) as a 1: 1 mixture of exo and endo isomers. XH NMR (270MHz) in CDC13: d 7.51 (ΔI, both isomers, m), 7.4-7.2 (4H, both isomers, m), 6.59 (ΔI, both isomers, m), 6.04 (2H, both isomers, m) , 3.89 and 3.88 (3H, both isomers, 2xs), 3.54 (2H, both isomers, brs), 3.33 (2H, both isomers, m), 2.89 (2H, one isomer, dd), 2.4-1.9 (6H, both isomers, m) and 1.49 (2H, one isomer, dd) ppm.

Example 5 This Example illustrates the preparation of exo-3- (benzoxazol-2-yl) -endo-3-cyano-8-methyl-8-a abicyclo [3.2.1] octane (Compound No. 43 of Table I).

Bi s (t r ime t i 1 i i 1 i) lithium amide was added (6.5 ml of a 1M solution in tetrahydrofuran) dropwise to a stirred solution of exo-3-cyano-8-methyl-8-azabicyclo [3.2.1] octane (0.50 g) and 2-chlorobenzoxa zola (0.516 g) in tetrahydrofuran (5 ml) at room temperature. After 3 hours water was added and the mixture was extracted with ethyl acetate (x3). The combined extracts were washed with water and brine, dried (MgSO) and evaporated under reduced pressure to give exo-3- (benzoxazol-2-yl) -endo-3-cyano-8-met i-8- azabicyclo [3.2.1] octane (0.78 g) pf 143-147 ° C. XH NMR (270MHz) in CDC13: d 7.72 (HH, m), 7.54 (HH, m), 7.38 (2H, m), 3.39 (2H, m), 2.66 (2H, dd), 2.38 (3H, s) and 2.45-2.3 (6H, m) ppm.

Example 6 This Example illustrates a concentrated emulsion which is readily convertible by diluting with water in an appropriate liquid preparation for dispersion purposes. The concentrate has the following composition:% by weight Compound No. 1 25.5 SYNPERONIC NP13 2.5 Calcium dodecylbenzenesulfonate 2.5 AROMASOL H 70.

Example 7 This Example illustrates a wettable powder composition that is readily convertible by diluting with water in an appropriate liquid preparation for dispersion purposes. The wettable powder has the following composition: % by weight Compound No. 13 25.0 Silica 25.0 Sodium lignosulfonate 5.0 Sodium lauryl sulfate 2.0 Kaolinite 43.0 Example 8.

This Example illustrates a voreable spray powder that can be applied directly to plants or other surfaces and comprises 1% by weight of Compound No. 25 and 99% by weight talc.

Example 9 This Example illustrates a concentrated liquid formulation suitable for application by ultra-low volume techniques after blends with paraffinic diluents. % by weight Compound No. 29 90.0 SOLVESSO 200 10.0 Example 10 This Example illustrates a concentrated capsule suspension that is rapidly convertible by diluting with water to form a preparation suitable for application as an aqueous dispersion. % by weight Compound No. 43 10.0 Solvent to l-alkylbenzene (for example AROMASOL H) 5.0 Di- i sic acid of toluene 3.0 Ethylenedi amine 2.0 Polyvinyl alcohol 2.0 Bentonite 1.5 Polysaccharide (for example KELTROL) 0.1 Water 76.4 Example 11 A granular formulation of fast use % by weight Compound No. 4 0.5 SOLVESSO 200 0.2 Nonylphenol ethoxylate (for example, Synperonic NP8) 0.1 Calcium carbonate granules (0.3-0.7 mm 99.2 Example 12 A concentrated aqueous suspension % by weight Composed to No. 8 5.0 Kaolinite 15.0 Sodium lignosulfonate 3.0 Noni 1 phenoletoxy lato (for example Synperonic NP 8) 1.5 Propylene glycol 10.0 Bentonite 2.0 Polysaccharide (for example Keltrol) 0.1 Bactericide (for example Proxel; Proxel is a registered trademark 0.1 Water 63.3 Example 13 This Example illustrates a granular formulation dispersible in water:% by weight Compound 'No. 20 Silica Sodium lignosulfonate 10 Dioc tyl sulphosuccinate sodium Sodium acetate 10 Monomer powder 1 liter 65 Example 14 This Example illustrates the insecticidal properties of the compounds of formula (I). The activity of the compounds of formula (I) is determined using a variety of pests. The pests were treated with a liquid composition containing 500 parts per million (ppm) by weight of the compound unless otherwise stated. The compositions were made by dissolving the compound in acetone and ethanol (50:50), mixing and diluting the solutions with water containing 0.05% by weight of a wetting agent sold under the trademark "SYNPERONIC" NP8 until the liquid composition contained the required concentration of the compound. "SYNPERONIC" is a registered trademark.

The test procedure adopted with each pest was basically the same and comprises supporting a number of the pests in a medium that was usually a substrate, a host plant or a food product in which the pests ate, and treating either or both. both the medium and the pests with the compositions. The mortality of the pests was then evaluated at periods usually ranging from two to five days after treatment.

The results of the tests against the peach aphid (Myzus persicae) are presented below. The results indicated a mortality gradient (outcome) designated A, B or C, where C indicated less than 40% mortality, B indicated 40-79% mortality and A indicated 80-100% mortality; "-" indicated that either the compound was not tested or a non-significant result was obtained. In this test, Chinese cabbage leaves were infested with aphids, the infested leaves were dispersed with the test composition, and the mortality was evaluated after 3 days. Compound No. 1 gave a gradient of A.

Chemical Formulas Referred to in the Description It is hereby stated that in relation to this date, the best method known by the applicant to carry out said invention is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (10)

Claims

1. A compound of formula (I) characterized in that R1 is an optionally substituted 5-membered heterocyclic ring system containing from 1 to 3 heteroatoms individually selected from nitrogen, oxygen and sulfur atoms, and at least one non-saturation (double bond) between the atoms adjacent to the ring, wherein the substituents, if present, are selected from halogen atoms, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, alkylthio and ammonium alkyl groups, any of the groups containing more than eight carbon atoms, and where two substituents can be joined to form a molten ring; R "represents hydrogen or cyano or a group selected from alkyl, aryl, heteroaryl, aralkyo, heteroarylalkyl, alkynyl aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, arenesulfonyl, alkenyloxycarbonyl, aralkylcarbonyl, aryloxycarbonyl heterocyclylalkyl, carbamyl, di tiocarboxyl or XR3 (where X represents oxygen or a group NR4), with the proviso that when R2 is alkenyl, aralkenyl or alkynyl said group will not have an unsaturated carbon atom directly attached to the nitrogen ring of formula (I); R3 and R4 are, independently, hydrogen, alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, het erocyclic alkyl, alkoxycarbonyl or acyl carboxylic, alkyl portions of R2, R3 and R4 comprise from 1 to 15 carbon atoms, and are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl, carboxylic acyl, carbamyl, alkoxycarbonyl groups or, alkoxy, alkylenedioxy, hydroxy, nitro, amino, acylamino, imidate and phosphonate; Aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, alkynyl, alkoxycarbonyl, a canosulphonyl, arenesulphonyl, alkanoyloxycarbonyl, aralkoxycarbonyl, aryloxycarbonyl, glycoalkyl, carbamyl, dihydrogen peroxide fractions of R2, R3 and R4 comprise from 1 to 15 carbon atoms, and are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl, carboxylic acyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, haloalkyl, alkyl, amino, acylamino groups , imidate and phosphonate; or an acid addition salt, salt of quaternary ammonium or N-oxide derivative of the same.

2. The compound according to claim 1, characterized in that R1 represents an optionally substituted 5-membered ring system based on: pyrrole, pyrazole, imidazole, 1,2,3- or 1, 2, 4 - 1 r ia zol, furan , thiophene, oxazole, isoxazole, thiazole, isothiazole, 1,2,3- or 1, 3, 4 -oxadia zol, or 1,2,3- or 1,3,4-thiadiazole, or a partially reduced form of one of the previous ones containing a double bond; or an oxathiol or dithiol ring containing a double bond.

3. The compound of formula (I) as claimed in claim 1 or 2, characterized in that R "is hydrogen, C2-4 alkyl (substituted but not on the α-carbon, with halogen), C ?4 alkyl (optionally substituted with cyano), C3-4 alkenyl, C3-4 haloalkenyl, C3-4 alkynyl or phenyl (C4-4) alkyi (wherein the phenyl ring is optionally substituted with halogen, C1-4alkyl, haloalkyl C4-4, alkoxy C) ? 4, C 1-4 haloalkoxy or cyano), with the proviso that when R 2 is a substituted or unsubstituted alkenyl, or an alkynyl group such a group will not have an unsaturated carbon atom bonded directly to the nitrogen ring of the formula (I)

4. The compound of formula (I) as claimed in claim 1, 2 or 3, characterized in that R1 is pyrrole, pyrazole, imidazole, 1, 2, 4 - 1 riaz ol, furan, thiophene, oxazole, isoxazole, thiazole or isothiazole all optionally substituted with one or more of halogen, Cj-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, mono (Ci-4) to 1 qui 1 amino or di (C 4 -4) alkylamino.

5. The compound of formula (I) as claimed in claim 1, characterized in that R1 is a pyrrole, thiophene or isoxazole ring optionally substituted with one or more of halogen, C1- alkyl. or haloalkyl C? -4; and R2 is hydrogen, C? _4 alkyl, C2_4 fluoroalkyl (not substituted on the a-carbon), C3-4 alkenyl or C3-4 alkynyl), with the proviso that when R2 is a substituted or unsubstituted alkenyl, or a Alkynyl group such group will not have an unsaturated carbon atom linked directly to the nitrogen ring of formula (I).

6. An intermediate compound of formula (II) III characterized in that R * is as defined in claim 1.

7. An insecticidal, acaricidal or nematicidal composition, characterized in that it comprises an effective insecticidal, acaricidal or nematicidal amount of a compound of formula (I) as claimed in claim 1 and an appropriate carrier or diluent thereof.

8. A method of combating and controlling pests of insects, ruffs or nematodes in the place, characterized in that it comprises treating the pests or the place of the pests with an effective amount of a compound according to claim 1 or a composition in accordance with the claim 7; with the condition that the place is not a human or animal body.

9. The method according to claim 8, characterized in that the pests are insect pests of growing plants.

10. A method for preparing a compound of formula (I), characterized in that it comprises: (a) reacting a compound of formula (IX): with a co-formula (X): R -CH2-CN (X) in the presence of a base; (b) reacting a compound of formula (VI) with a compound of formula R Hal, wherein Hal is halogen, in the presence of a base; or, (c) reacting a compound of formula (II i or H 0 with a compound of the formula R'L, wherein L is an appropriate starting group, in the presence of a base. Summary of the Invention The present invention concerns bicyclic amine derivatives of formula (I) wherein R1 is an optionally substituted 5-membered heterocyclic ring system containing from 1 to 3 heteroatoms individually selected from nitrogen, oxygen and sulfur atoms, and at least one non-saturation (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 these groups containing more than eight carbon atoms, and wherein two substituents can be joined to form a fused ring; R * represents hydrogen or cyano or a group selected from alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulphonyl, arenesulphomethyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aploxycarbonyl, heterocyclylalkyl, carbamyl, tcarboxy or XR3 (where X represents oxygen or a group NR4), with the proviso that when R2 is alkene, aralkenyl or alkynyl, said group does not have an unsaturated carbon atom directly linked to the nitrogen ring of formula (I ); R3 and R4 are, independently, hydrogen, alkyl, aryl, heteroaryl, aralkyl, heteroaryl, alkenyl, aralkenyl, alkynyl, I have sprayed 1 to 1 carbonyl or acyl carboxylic acid; Alkyl portions of R2, R3 and R4 comprise from 1 to 15 carbon atoms, and are optionally substituted with one or more subsites and are selected from, halogen, cyano, carboxyl, carboxylic acyl, carbamyl, a1 groups coxi ca rboni 1, alkoxy, alkylenodioxy, hydroxy, nitro, amino, acylamino, imidate and phthophonate; Aryl, heteroaryl, aralkyl, heteroaryl, alkyl, alkenyl, alkynyl, coxycarbonyl, alkanesulphyl, fonrosyl, alkyloxycarbonyl, aralkoxycarbonyl, aryloxycarbonyl, 1, carbamyl, dithiocarboxyl of R2, R3 and R4 comprise from 1 to 15 carbon atoms, and are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl, carboxylic acyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy groups , hydroxy, nitro, haloalkyl, alkyl, amino, acylamino, imidate and phosphonate; or an acid addition salt, quaternary ammonium salt or N-oxide derivative thereof; to processes for preparing them, for insecticidal compositions comprising them and to methods for using them to combat and control insect pests.