KR20010005811A - Cyano substituted cycloalkanes - Google Patents

Abstract

The present invention provides compounds of formula (1) or acid addition salts, quaternary ammonium salts or N-oxides derived therefrom:

[Formula 1]

[Wherein R ¹ is Ar— (CH ₂ ) _n − (where n is 0 or 1 and Ar is optionally substituted phenyl or contains 1 to 3 heteroatoms each selected from nitrogen, oxygen and sulfur atoms An optionally substituted 5- or 6-membered heterocyclic system containing one or more unsaturated (double bonds) between adjacent atoms in the ring, in which the substituent is a halogen atom, alkyl having up to 6 carbon atoms, al Kenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, haloalkoxy, alkylthio and alkyl amino groups); Wherein R ² and R ³ are each hydrogen or alkyl, aryl, heteroaryl, aralkyl, formyl, alkylcarbonyl, arylcarbonyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, Alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl or dithiocarboxyl groups; The alkyl moiety of R ² and R ³ contains 1 to 15 carbon atoms and includes halogen, cyano, carboxyl, carboxylic arsyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, Optionally substituted with one or more substituents selected from amino, acylamino, imidate and phosphonato groups; Aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbon of R ² and R ³ Neyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl and dithiocarbonyl moieties include halogen, cyano, carboxyl, carboxylic arsyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, Optionally selected from nitro, haloalkyl, alkyl, amino, acylamino, imidate and phosphonato groups with one or more substituents; And a compound comprising the compound of formula (1) and a carrier or diluent; And methods of eradicating insects, mites, nematode pests using the aforementioned compounds or compositions.

Description

Cyano substituted cycloalkanes {CYANO SUBSTITUTED CYCLOALKANES}

The present invention relates to novel cyano-substituted cycloalkanes, methods for their preparation, pesticide compositions comprising them and their use to combat insects and similar pests thereof.

Tetracyanocyclopentadiene salts are disclosed as rocket propellant fuels and dyes (US 3536694). 1-cyano-3-amino-4-oxo-cyclopentane derivatives are also disclosed (tetraheadon 33 463 (1977)).

The present invention provides formula (1) or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom:

[Wherein R ¹ is Ar— (CH ₂ ) _n − (where n is 0 or 1 and Ar is optionally substituted phenyl or contains 1 to 3 heteroatoms each selected from nitrogen, oxygen and sulfur atoms An optionally substituted 5- or 6-membered heterocyclic system containing one or more unsaturated (double bonds) between adjacent atoms in the ring, in which the substituent is a halogen atom, alkyl having up to 6 carbon atoms, al Kenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, haloalkoxy, alkylthio and alkyl amino groups); Wherein R ² and R ³ are each hydrogen or alkyl, aryl, heteroaryl, aralkyl, formyl, alkylcarbonyl, arylcarbonyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, Alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl or dithiocarboxyl groups; The alkyl moiety of R ² and R ³ contains 1 to 15 carbon atoms and includes halogen, cyano, carboxyl, carboxylic arsyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, Optionally substituted with one or more substituents selected from amino, acylamino, imidate and phosphonato groups; Aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbon of R ² and R ³ Neyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl and dithiocarbonyl moieties include halogen, cyano, carboxyl, carboxylic arsyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, Optionally substituted with one or more substituents selected from nitro, haloalkyl, alkyl, amino, acylamino, imidate and phosphonato groups.

The names of compounds throughout this specification are named in the IUPAC nomenclature as they are numbered on the ring atoms as shown below.

The compound of formula (1) has an asymmetric central atom at positions 1 and 3 of the ring, and as a result, (1R, 3R), (1R, 3S), (1S, 3S) and (1S, 3R) There may be four isomeric forms that can be designated (including two pairs of diastereomers). The present invention includes in every part all of the isomeric forms and mixtures thereof (including racemic mixtures).

5- and 6-membered heterocyclic systems represented by Ar include pyridine, pyrazine, pyridazine, pyrimidine, pyrrole, pyrazole, imidazole, 1,2,3- and 1,2,4-thiazole, furan, tee Based on opene, oxazole, isoxazole, thiazole, isothiazole, 1,2,3- and 1,3,4-oxadiazole, 1,2,3- and 1,3,4-thiadiazole Oxathiol, dioxol, containing one double bond as well as partially reduced forms of these rings fused to the benzene ring and the aforementioned rings containing one or more double bonds derived therefrom And those based on dithiol rings. Preferably Ar represents a halo-substituted phenyl, pyridyl, or diazinyl group.

Halogens include fluorine, chlorine, bromine and iodine.

The alkyl portion of R ² and R ³ and the substituents of Ar preferably contain 1 to 6, more preferably 1 to 4 carbon atoms. They may be in the form of straight or branched chains (eg methyl, ethyl, n- or i-propyl, or n-, s-, i- or t-butyl).

Haloalkyl is preferably C _1-6 haloalkyl, in particular fluoroalkyl (eg trifluoromethyl, 2,2,2-trifluoroethyl or 2,2-difluoroethyl).

The alkenyl and alkynyl moieties of R ² and R ³ and the substituents of Ar preferably contain 2 to 6, more preferably 2 to 4 carbon atoms. They may be in the form of straight or branched chains and the akenyl moiety in the appropriate place may be an (E)-or (Z)-configuration. Examples are vinyl, allyl and propargyl.

Aryl includes naphthyl but is preferably phenyl.

Heteroaryls include 5- and 6-membered aromatic rings containing one, two, three or four heteroatoms selected from the list comprising oxygen, sulfur and nitrogen, which can be fused to benzenoid ring systems. Examples of heteroaryl include pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl (1,2,3-, 1,2,4- and 1,3,5-), furyl, thienyl, py Rollyl, pyrazolyl, imidazolyl, triazolyl (1,2,3- and 1,2,4-), tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadia Zolyl, quinolinyl, isoquinolinyl, cinnaolinyl, 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, morpholine, thiethane, pyridine or thiazole.

Alkylenedioxy groups are ring substituents, in particular C _1-4 alkylenedioxy. Alkylenedioxy groups are optionally substituted with halogens (especially fluorine), such as methylenedioxy (OCH ₂ O) or difluoromethylenedioxy (OCF ₂ O).

Suitable acid addition salts are inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid or phosphoric acid, or organic carboxylic acids such as oxalic acid, tartaric acid, lactic acid, butyric acid, toluic acid, hexanoic acid or phthalic acid, or sulfuric acid such as methane, benzene or toluene sulfonic acid. Salts of compounds of formula (1) with phonic acid. Examples of other organic carboxylic acids include halo acids such as trifluoroacetic acid.

In a first particular aspect, the present invention provides a compound of formula (1) or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom, wherein R ¹ in formula (1) is represented by Ar- (CH ₂ ) _n- (where n is 0 or 1, Ar is phenyl optionally substituted or contains 1 to 3 heteroatoms each selected from nitrogen, oxygen and sulfur atoms and at least one unsaturated atom between adjacent atoms in the ring Optionally substituted 5- or 6-membered heteroring system containing a (double bond) wherein, in the presence of a substituent, the substituent is a halogen atom (particularly fluorine, chlorine or bromine), alkyl (particularly C _1-4 alkyl), alkenyl (Particularly C _2-4 alkenyl), alkynyl (particularly C _2-4 alkynyl), alkoxy (particularly C _1-4 alkoxy), haloalkyl (particularly C _1-4 haloalkyl), haloalkenyl (particularly C _2-4 haloalkenyl), haloalkoxy (especially C _1-4 haloalkoxy), alkylthio (especially C _1-4 alkylthio), and alkyl Diamino (especially mono- or di - (C _1-3 alkyl), such as a mono-amino or di - (C _1-4 alkyl) amino) in a selected group), and; Wherein R, R ² and R ³ are each hydrogen or alkyl (especially C _1-4 alkyl), aryl (especially phenyl), heteroaryl (especially pyridinyl or pyrimidinyl), aralkyl (especially phenyl (C _1-4) Aryl (C _1-4 ) alkyl, such as alkyl, heteroarylalkyl (especially heteroaryl (C _1-4 ) alkyl, such as pyridinyl (C _1-4 ) alkyl or pyrimidinyl (C _1-4 ) alkyl) , Alkenyl (particularly C _3-4 alkenyl), aralkenyl (particularly aryl (C _3-4 ) alkenyl such as phenyl (C _3-4 ) alkenyl)), alkynyl (particularly C _3-4 alkynyl ), Formyl, alkylcarbonyl, arylcarbonyl (particularly phenylcarbonyl), alkoxycarbonyl (particularly C _1-4 alkoxycarbonyl), alkanesulfonyl (particularly C _1-4 alkylsulfonyl), phenylsulfonyl , Alkenyloxycarbonyl (particularly C _3-4 alkenyloxycarbonyl), aralkyloxycarbonyl (particularly phenyl (C _1-4 ) alkoxycarbonyl), aryloxycarbonyl (particularly phenoxycarbonyl), hetero cycles reel alkyl (in particular piperidinyl (C _1-4) alkyl and hetero cycles, such as (C _1-4) alkyl), carbamyl (H ₂ NC (O)) or a dithiocarbamic acid group selected from the group; The alkyl moiety of R ² and R ³ contains 1 to 15 carbon atoms (particularly 1 to 8 carbon atoms), halogen (particularly fluorine or chlorine), cyano, carboxyl (HOC (O)), carboxylic arsyl (Particularly C _1-4 alkylcarbonyloxy), formyl, carbamyl (H ₂ NC (O)), alkoxycarbonyl (particularly C _1-4 alkylcarbonyloxy), alkoxy (particularly C _1-4 alkoxy) , Alkylenedioxy (particularly C _1-4 alkylenedioxy), hydroxy, nitro, amino, asylamino (particularly C _1-4 alkylcarbonylamino), imidate (C _1-4 alkyl [C (O) NHC (O)]) and phosphonato (OP (OH) ₂ ) groups optionally substituted with one or more substituents; Aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbon of R ² and R ³ Neyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl and dithiocarbonyl moieties include halogens (especially fluorine, chlorine or bromine), cyano, carboxyl (HOC (O)), carboxylic arsyl (especially C _1-4 Alkylcarbonyloxy), formyl, carbamyl (H ₂ NC (O)), alkoxycarbonyl (especially C _1-4 alkoxycarbonyl), alkoxy (especially C _1-4 alkoxy), alkylenedioxy (especially C _1-4 alkylenedioxy), hydroxy, nitro, haloalkyl (particularly C _1-4 haloalkyl), akyl (particularly C _1-4 alkyl), amino, acylamino (particularly C _1-4 alkylcarbonylamino) , Optionally substituted with one or more substituents selected from the group of imidate (C _1-4 alkyl [C (O) NHC (O)]) and phosphonato (OP (OH) ₂ ).

In another aspect, the present invention provides a compound of formula (1) and acid addition salts and quaternary ammonium salts and N-oxides derived therefrom, wherein R ¹ is Ar- (CH _{2 n-} (where n is 0 or 1, Ar is phenyl optionally substituted or contains 1 to 3 heteroatoms each selected from nitrogen, oxygen and sulfur atoms and at least one unsaturation between adjacent atoms in the ring ( Optionally substituted 5- or 6-membered hetero ring system containing a double bond), wherein in the presence of a substituent the substituent contains a halogen atom, alkyl containing up to 6 carbon atoms, alkenyl, alkynyl, alkoxy, haloalkyl, Selected from haloalkenyl, alkylthio and alkyl amino groups, wherein R ² and R ³ are each hydrogen or cyano or alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alky Neal, Alkoxycarbonyl, Alkanes A group selected from the group consisting of sulfonyl, arerensulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl or dithiocarboxyl, containing 1 to 15 carbon atoms, One or more substituents selected from halogen, cyano, carboxyl, carboxyacyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, haloalkyl, alkyl, amino, asylamino, imidate and phosphonato R ² and R ³ adjacent to a nitrogen atom represent a nitrogen-containing heterocyclic group which may contain a heteroatom selected from oxygen, sulfur and nitrogen.

Preferred compounds of formula (1) are pyridyl or diazinyl groups wherein n is 0 and Ar is optionally substituted with pyridyl or halogen (such as chlorine or bromine).

In another aspect, the present invention provides a compound of formula (I), wherein R ¹ is Ar— (CH ₂ ) _n −, wherein n is 0 or 1, and Ar is halogen (particularly fluorine, chlorine or bromine), haloalkoxy (particularly trifluoro 5- or 6-membered aromatic optionally fused to a benzene ring containing 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, optionally substituted with romethoxy) or haloalkyl (especially trifluoromethyl) Provided are compounds of formula (1) that are heterocyclic systems.

In a further aspect, the invention provides that R ² and R ³ are each hydrogen; Alkyl comprising 1 to 15 carbon atoms (particularly 1 to 8 carbon atoms, more particularly 1 to 4 carbon atoms) optionally substituted with halogen (particularly fluorine) or alkoxy (particularly methoxy); Phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alkoxy (especially ethoxy); Alkenyl (particularly allyl); Formyl; Alkoxycarbonyl (particularly t-butyloxycarbonyl); Or alkenyloxycarbonyl (particularly vinyloxycarbonyl).

In a further aspect, the invention provides that in the formula R ¹ is a group Ar— (CH ₂ ) _n −, where n is 0 or 1, Ar is optionally fused to the benzene ring and halogen (especially fluorine, chlorine or bromine), 5- or 6-membered aromatics containing 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, optionally substituted with haloalkoxy (particularly trifluoromethoxy) or haloalkyl (particularly trifluoromethyl) Hetero ring system; Wherein R ² and R ³ are each hydrogen; Alkyl comprising 1 to 15 carbon atoms (particularly 1 to 8 carbon atoms, more particularly 1 to 4 carbon atoms) optionally substituted with halogen (particularly fluorine) or alkoxy (particularly methoxy); Phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alkoxy (especially ethoxy); Alkenyl (particularly allyl); Formyl; Alkoxycarbonyl (particularly t-butyloxycarbonyl); Or alkenyloxycarbonyl (particularly vinyloxycarbonyl).

In an additional aspect, the invention provides ¹ to ³ , wherein R ¹ is Ar— (CH ₂ ) _n −, where n is 0 or 1 and Ar is optionally substituted with a halogen atom (especially chlorine or bromine) Provided are compounds of formula (1) which are 6-membered aromatic heteroring systems containing two nitrogen atoms.

In another aspect, the present invention provides a compound of formula I, wherein R ² and R ³ are each hydrogen; Alkyl (particularly C _1-4 alkyl) optionally substituted with halogen (particularly fluorine) or alkoxy (particularly methoxy) groups; Phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alkoxy (especially ethoxy); Formyl; Alkoxycarbonyl (particularly t-butyloxycarbonyl); Or alkenyloxycarbonyl (particularly vinyloxycarbonyl).

In another aspect, the invention provides ¹ to ³ , wherein R ¹ is a group Ar- (CH ₂ ) _n- , wherein n is 0 or 1 and Ar is optionally substituted with a halogen atom (especially chlorine or bromine) 6-membered aromatic heteroring system containing 2 nitrogen atoms; Wherein R ² and R ³ are each hydrogen; Alkyl (particularly C _1-4 alkyl) optionally substituted with halogen (particularly fluorine) or alkoxy (particularly methoxy); Phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alkoxy (especially ethoxy); Formyl; Alkoxycarbonyl (particularly t-butyloxycarbonyl); Or alkenyloxycarbonyl (particularly vinyloxycarbonyl).

Certain compounds according to the present invention include compounds as described in Table 1 below, wherein the values of R ¹ , R ² and R ³ are given for each compound.

Table 2 below shows the selected mass spectroscopy data or selected NMR data for the compounds of Table 1 above as CDCl ₃ as solvent-not all resonance hybrids in all cases were listed. In some embodiments the selected data is shown. The following abbreviations are used throughout this specification.

mp = melting point ppm = parts per million s = singlet t = triplet d = doublet q = quarter dd = double doublet dt = double triplet tt = triple triplet MH + = protonated molecular ion m = multiplet M + = molecular ion

Compounds of formula (1) may be prepared as shown below. In Schemes (1) and (2), R ¹ , R ² and R ³ are as previously described; R ⁴ is hydrogen, optionally substituted alkyl or optionally substituted aryl; X and X ¹ are each leaving group (such as halogen or alkyl sulfonate); R is optionally substituted alkyl (eg t-butyl), optionally substituted alkenyl or optionally substituted aralkyl (eg benzyl).

The process for preparing the compound of formula (1) is shown in Scheme (1) above. This scheme also shows a method for preparing a compound of formula (7) (ie, a compound of formula (1) wherein R ³ is hydrogen). Conjugation of cyanide to cyclopentenone (2) can be carried out in various ways, such as in P Perlmutter, Tetrahedron Organic Chemistry Series Vol. 9, Conjugate Addition Reaction in Organic Synthesis, p176 and references therein, pergamon 1992. The reductive amination reaction of (3) is, for example, cyanoborohydride (e.g., J. Org. Chem., 46, 3571, (1981), whose author is RO Hutchins and colleagues) or formic acid and amine salts thereof (e.g. , E. Staple and his colleagues, J. Org. Chem., 14, 559, (1949)). The protection of the amine compound of formula (4) by reaction with a chloroformate ester such as t-butyl chloroformate in the presence of a suitable base gives a carbamate compound of formula (5). Substitutions on carbon comprising nitrile groups for obtaining compounds of formula (6) are usually carried out in suitable solvents such as diethyl ether, tetrahydrofuran (THF) or dimethoxyethane under various temperatures between -100 ° C and 30 ° C. It can be carried out by using a suitable base such as lithium diisopropylamide, lithium hexamethyldisilazide or somide, and adding aryl, heteroaryl, benzyl or similar substances (e.g. halides) suitably substituted with leaving groups. have. Removal of carbamate residues in the compound of formula (6) can be carried out by various techniques already known in the art, after which the amine compound of formula (7) is reacted directly with an alkylating agent such as an alkyl halide. Or by reductive coupling with the carbonyl compound using a similar method as described for the preparation of the compound of formula (4). The order of steps of the procedure may be varied, for example, directly through reductive amination of a compound of formula (3) with a secondary amine to obtain a compound of formula (8) directly, as described above ( For example, lithium diisopropylamide, lithium hexamethyldisyl azide or somamide as base) may be substituted adjacent to the nitrile group to obtain the compound of formula (1).

An additional method of preparing the compound of formula (1) is represented by scheme (2). A suitably 3-substituted cyclopentenone compound of formula (9) containing a group such as halogen, alkylsulfonate or 3-substituted tin residues may be selected from the 3-substituted tin residue, trifluoromethanesulfonate ( OTf) or when reacting with a substance containing bromine residues, only one component of the reaction contains tin, and in stille-type coupling using a metal catalyst (e.g. palladium) A cyclopentenone compound is obtained. Subsequently, the compound may be transformed into a conjugate addition reaction of cyanide as described above to prepare a cyanocyclopentanone compound of Formula (11), followed by reductive amination as described above. Compound is obtained. Alternatively, the primary amine compound of formula (13) for further synthesis into a compound of formula (1) by reacting the ketone compound of formula (11) with a suitable hydroxyamine by methods known in the art It is possible to produce oxime compounds of formula (12) which can be reduced to provide.

The preparation of certain compounds of formula (1) according to the invention is illustrated by the preliminary detailed description set forth in the examples below. Other compounds of the present invention can be prepared by similar procedures as those described using suitable reactants. In the above process, as detailed herein, the compound of formula (1) has the formula 3- corresponding cyanocyclopentylamine of formula (1) in which R ¹ is replaced by hydrogen It is prepared by reaction with a compound of R ¹ -X wherein R ¹ is as described above and X is a leaving group, for example halogen.

Although many of the 3-cyanocyclopentylamines of formula (1) (wherein R ¹ is replaced with hydrogen) have not been previously described, a further aspect of the present invention is a compound of formula (1) as described above. It is to provide such compounds useful as intermediates in the preparation of the compounds.

In another aspect, the present invention provides a method for preparing a compound of formula (1).

In another aspect, the present invention is directed to treating a pest or locus of a pest with a composition comprising a compound of formula (1) or an acid addition salt thereof in an amount effective for pesticidal, aphid, nematicide It provides a method for eradicating and controlling insects, ticks or nematode pests in the place of activity, including.

Compounds of formula (1) and acid addition salts thereof can be used to eradicate and control rampant and invertebrate pests of insect pests such as Lepidoptera, Diptera, Homoptera and Coleoptera (including Diabrotica, ie corn rootworm), such as tick pests. have. Insects and mite pests that can be eradicated and controlled using the compounds of the present invention include agricultural species (the term includes growing crops for food and textile products), horticultural agriculture and livestock, forestry, vegetable species such as fruits. , Pests associated with the storage industry of grain and wood products, and also pests associated with the transmission of diseases of humans and animals. Examples of insect and mite pest species that can be controlled by the compound of formula (1) include: Myzus persicae (Aphid), Aphis gossypii (Aphid), Aphis fabae (Aphid), Aedes aegypti (Mosquito) , Anopheles spp. (Mosquitoes), Culex spp. (Mosquitoes), Dysdercus fasciatus (capsid), Musca donestica (housefly), Pieris brassicae (white butterfly), Plutella xylostella (diamond-like moth), Phaedon cochleariae (mustard stag beetle), Aonidiella spp. (Scale insect), Trialeurodes spp. (White fly), Bemisia tabaci (white fly), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), Spodoptera littoralis (cotton leaf beetle), Heliothis virescens (cigarette seed beetle), Chortiocetes terminifera (grasshopper) , Diabrotica spp. (Root beetle), Agrotis spp. (Root worm), Chilo partellus (corn stem), Nilaparvata lugens (plant flea), Nephotettix cincticeps (leaves flea), Panonychus ulmi (European red tick), Panonychus citri (citrus red tick), Tetranychus urticae Spot spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllcoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (photo mite) and Brevipalpus spp. (mite). Further examples include insects that adversely affect the health of the air or animals.

For the use of the compounds of formula (1) in the locus of nematode, insect or mite pests or in plants suitable for attack by nematode, insect or mite pests, the compounds are usually of formula (1). As well as a suitable inert diluent or carrier material, and optionally a surfactant. The amount of the composition used for control of nematode debris is generally provided at a rate of 0.01 to 10 kg per hectare, preferably 0.1 to 6 kg per hectare of active ingredient.

Thus, in a further aspect, the present invention provides an insecticidal, acaricidal or nematicidal composition comprising an effective amount of a compound of formula (1) and an appropriate carrier or diluent thereof in an insecticidal, acaricidal or nematicidal form.

The composition may be used in soil, plants or seeds, or in locus where pests are present, or in the habitat of pests, wetting agents, wetting powders, fine (slowly or rapidly released), emulsifying concentrates, suspension concentrates, liquid solutions. It may be used in the form of controlled release compositions such as emulsions, seed dressings, fog / fog preparations or microencapsulated granules or suspensions.

Spraying agents can be used to prepare the active ingredients in one or more finely divided soil carriers and / or diluents, such as natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, diatomaceous earth, chalk, diatomaceous earths , Calcium phosphate, calcium and magnesium carbonate, sulfur, lime, flour, talc and other organic and inorganic soil carriers.

Granules absorb the active ingredients into porous granular materials, such as pumice, attapulgite clays, topsoil, diatomaceous earth, diatomaceous earth soil, ground corn, or the like, or the active ingredient in sand, silicates. It is prepared by absorbing into a hard core material such as mineral carbonate, sulfate, phosphate, and the like. Formulations commonly used for auxiliary absorption or absorption include aliphatic and aromatic petroleum solvents, alcohols, polyvinyl acetates, polyvinyl alcohols, ethers, ketones, esters, dextrins, sugars and vegetable oils. Other additives may include granules such as emulsifiers, wetting agents or dispersants.

Microencapsulated preparations (microcapsule suspension CS) or other controlled release preparations can be used, in particular, during slow release or during seed treatment.

Alternatively, the compositions are liquid preparations for use as immersion, irrigation additives or sprays, which are typically aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifiers (surfactants). It may be in the form of. The compositions used in the form of aqueous dispersions or emulsions are generally used in the form of emulsified concentrates (EC) or suspension concentrates (SC) containing a high proportion of active ingredient or components. EC is typically a homogeneous liquid composition containing the active ingredient dissolved in virtually non-volatile organic solvents. SC is a fine particle size dispersion in which the solid active ingredient is dissolved in water. In practice, this concentrate is diluted with water and used as a means of spraying to the area to be treated.

Suitable liquid solvents for EC include methyl ketone, methyl isobutyl ketone, cyclohexanone, xylene, toluene, chlorobenzene, paraffin, kerosene, white oil, alcohols (eg butanol), methylnaphthalene, trimethylbenzene, trichloro Ethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THFA).

Wetting agents, dispersants and emulsifiers may be in cationic, anionic or non-ionic form. Suitable agents in cationic form include, for example, quaternary ammonium compounds such as cetyltrimethyl ammonium bromide. Suitable preparations in anionic form include, for example, salts of aliphatic monoesters of sulfuric acid, such as sodium lauryl sulfate, salts of sulfonated aromatic compounds, such as sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfo Or a mixture of sodium salts of butylnaphthalene sulfonate and diisopropyl- and triisopropylnaphthalene sulfonate. Suitable formulations in non-ionic form include, for example, fatty alcohols such as oleyl alcohol or cetyl alcohol, or condensation products of ethylene oxide such as alkyl phenols such as octyl phenol, nonyl phenol and octyl cresol. Other non-ionic agents include partial esters derived from long chain fatty acids and hexitol anhydrides, condensation products of ethylene oxide with the partial esters, and lecithin.

The concentrate is required to produce an aqueous preparation that is allowed to be preserved for long term storage and that remains homogeneous for a sufficient time so that it can be diluted with water after such storage and used with conventional spray equipment.

The concentrate contains 10 to 85% by weight of the active ingredient or components. When diluted to prepare aqueous preparations, these preparations may contain varying amounts of active ingredients depending on their purpose of use.

The compounds of formula (1) 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 the treatment of seeds. Can be.

In practice, the compositions are prevalent by insect known pests, locus with pests, pest habitat or pests by any known means using a composition that kills pests, such as by spraying, spraying or blending granules. Applied to growing plants.

The compound of formula (1) may be the only active ingredient in the composition, or it may be used in admixture with one or more additional active ingredients, such as insecticides, nematicides, herbicides, fungicides or plant growth regulators, where appropriate. Suitable additional active ingredients for inclusions containing compounds of formula (1) may be compounds which broaden the activity spectrum of the compositions of the invention or increase their persistence in the presence of pests. This may supplement the activity by co-increasing the activity of the compound of formula (1), for example by increasing the effect of rate or overcoming repulsion. In addition, the multicomponent mixture of this type allows to overcome or inhibit the promotion of resistance to the respective components. This particular additional particulate active ingredient included may depend upon the intended use of the mixture and the type of supplementary action required. Examples of suitable pesticides include:

a) Fermedrin, espenvelrate, deltamedrin, sihalodlin in certain lambda-sihalodlins, bipendrin, phenpropadrine, cyfludrine, tefrudrin, fish stable pyredroids such as Etofenprox, natural pyredrin, tetramedrine, s-bioallylin, fenfludrine, praledrin and 5-benzyl-3-furylmethyl- (E)-(1R, 3S) -2,2-dimethyl Pyredoids such as 3- (2-oxothiolane-3-ylidenemethyl) cyclopropane carboxylate;

b) Propenophos, Sulprophos, Methyl Paradione, Azinfos-methyl, Demethone-s-methyl, Heptenophos, Thiomethone, Phenamiphos, Monoclotophos, Propenophos, Triazophos, Meta Midophos, Dimethoate, Phospamidon, Malathion, Chloropyriphos, Posalon, Terbufoss, Pensulfothion, Phonophos, Forrate, Bombide, Pyrimifos-methyl, Pyrimifos-ethyl, Penny Organophosphates such as trothion or diazinone;

c) carbamate (aryl carba) such as pyrimikab, chloretocarb, carbofuran, purathiocarb, thiophencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, phenobucarb, propoxyr or oxamyl Mate);

d) benzoyl urea, such as triflumuron, or chlorfluazuron;

e) organic tin compounds such as hexahexatin, fenbutatin oxide, azocyclotin;

f) macrolides such as avermectin or milbemicin (eg, milbemicin such as avemectin, ivermectin);

g) hormones and pheromones;

h) organochlorine compounds such as benzene hexachloride, DDT, chlordine or dieldrin;

i) amidines, such as chlordimeform or amitraz;

j) Fumigant agent

k) Imidacloprid;

l) Spinosad.

In addition to the pesticides of the main chemical classes described in the above list, other pesticides with specific targets may be used in the mixture if they are suitable for the intended use of the mixture. As an example, selective pesticides for specific grains, such as stemborer specific pesticides for use in rice such as cartab or buprofezin, can be used. Alternatively, certain insecticides for certain insect species / stages, such as ovo-larvicide, dicopol or propazite, such as clofentezin, flubenzimine, hexiaxans and tetradipon Growth regulators such as motilicides, bromopropylates, acaricides such as chlorobenzylate, hydramide, thymarazine, metoprene, chlorofluazuron and diflubenzuron are also described above. It may be included in the composition.

Examples of suitable co-elevating agents for use in the compositions include pyreronyl butoxide, sesamax, saproxane and dodecil imidazole.

Suitable herbicides, fungicides and plant-growth regulators for inclusion in the composition will depend upon the intended goal and the intended effect.

Examples of rice selective herbicides that may be included include propanyl, examples of plant growth regulators for cotton use include Pix, and examples of bactericidal agents for rice use such as blasticidin-S. Blasticides are included. The ratio of the compound of formula (1) to the additional other active ingredient included in the composition can be used at the rate normally used, or can be used at a rather low rate at which synergistic action occurs.

The invention is illustrated by the following examples. The components mentioned by the following registered trademarks have compositions as indicated below.

trademark Composition Synperonic NP8} Synperonic NP13} Nonylphenol-Ethylene Oxide Concentrate Synperonic OP10 Octylphenol-ethylene oxide concentrate Aromasol h Alkylbenzene solvent Solvesso 200 Inert Organic Diluent Keltrol Polysaccharides

Example 1

This example describes the preparation of 3-cyanocyclopentanone.

At room temperature, 2-cyclopenten-l-one (1 g, 0.012 mol) was stirred in THF (50 ml), N- (2-hydroxyethyl) piperazine-N'-ethane-2-sulfonic acid (2.86 g, 0.012 mol) was added in part, followed by water (25 ml). Sodium cyanide (1.2 g, 0.024 mol) was added in portions to the stirred solution. After stirring for 3.5 hours, the mixture was poured into water (50 ml) and extracted with ethyl acetate (3 × 25 ml). The collected organic fractions were washed with brine (50 ml), dried (with magnesium sulfate) and evaporated under reduced pressure to give a pale yellow oil (1.15 g, 88%) as product.

¹ H NMR (CDCl ₃ ): δ 3.22 (m, 1 H), 2.19-2.70 (m, 6H) ppm. M + = 109.

Example 2

This example describes the preparation of N-benzyl-3-cyano-cyclopentylamine.

Benzylamine (1.57 g, 14.68 mmol) was stirred in methanol (2 mL) at room temperature and a solution of 3-cyanocyclopentanone (0.80 g, 7.34 mmol) dissolved in methanol (10 mL) was added dropwise. The solution was stirred for 80 minutes and a solution of sodium cyanoborohydride (0.37 g, 5.87 mmol) dissolved in methanol (10 ml) was added dropwise. After 18 hours of continued stirring, the mixture was acidified to ˜pH 2 by addition of concentrated hydrochloric acid prior to concentration under reduced pressure. This residue was partitioned between 2M hydrochloric acid (40 ml) and diethyl ether (15 ml) and its aqueous phase was further extracted with diethyl ether (2 × 10 ml). The aqueous layer was basified to pH 10-11 with the addition of solid potassium hydroxide and extracted with diethyl ether (4x15 ml). The latter extract was collected, washed with brine, dried using potassium carbonate / magnesium sulfate and evaporated under reduced pressure to leave a yellow oil (2.03 g). The remaining benzylamine was removed at 50 ° C. under a pressure of 0.4 mm of mercury (53.3 Nm ⁻² ) to give a light brown oil (1.6 g) as product.

Example 3

This example describes the preparation of N-benzyl-N-t-butyloxycarbonyl-3-cyanocyclopentylamine.

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

MH + = 301.

Example 4

This example describes the preparation of N-benzyl-N-t-butyloxycarbonyl-3- (5-bromopyrid-3-yl) -3-cyanocyclopentylamine.

Lithium bis (trimethylsilyl) amide (1M solution in THF (4.58 ml), 4.58 mmol) was stirred under nitrogen and cooled to 5 ° C. and N-benzyl-Nt-butyloxycarbonyl-3-sia in THF (5 ml) Nocyclopentylamine (550 mg, 1.83 mmol) was added dropwise. The reaction mixture was heated to 15 ° C., 3,5-dibromopyridine (477 mg, 2.01 mmol) in THF (5 ml) was added dropwise, and the reaction mixture was warmed to room temperature. The reaction mixture was stirred for 5 hours and left overnight. The mixture was carefully poured into water (20 ml) and extracted with ethyl acetate (4x20 ml). The collected organic extracts were dried over potassium carbonate / magnesium sulfate and the solvent was removed under reduced pressure to give a brown oil (820 mg). This product was purified by filtration chromatography on silica using gradient elution of 5% -20% ethyl acetate in hexanes to afford the desired product as a mixture of asymmetric stereoisomers (130 mg).

Example 5

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

N-benzyl-Nt-butyloxycarbonyl-3- (5-bromopyrid-3-yl) -3-cyanocyclopentylamine (120 mgs, 0.263 mmol) was stirred in dichloromethane (2 ml) and trifluoro Acetic acid (1 ml) was added dropwise. The solution was stirred at rt for 5 h and the solvent was evaporated under reduced pressure. This residue was treated with toluene (92 ml) and evaporated to give a light brown solid (134 mg). The material was partitioned between dichloromethane (20 ml) and saturated sodium bicarbonate (20 ml). The organic layer was separated and this aqueous phase was extracted with additional dichloromethane (2x20ml). The collected organic layer was dried using potassium carbonate / magnesium sulfate, and this solvent was removed under reduced pressure to give a yellow oil (75 ml). This was purified by filtration chromatography on silica using a dichloromethane (1-4%) gradient eluent of 10% aqueous ammonia solution in methanol to give the intended product as a mixture of asymmetric stereoisomers (55 mg).

Example 6

This example describes 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 (24 mg, 0.067 mmol) was stirred in acetonitrile (2 ml) at room temperature and 37% aqueous formaldehyde (0.06). ml, 0.674 mmol) was added followed by sodium cyanoborohydride (8.5 mg, 0.135 mmol). The mixture was stirred overnight and concentrated under reduced pressure, then partitioned between 2M caustic soda (10 ml) and dichloromethane (10 ml) and its aqueous layer was extracted with additional dichloromethane (3x10 ml), and the collected organic phase was extracted with potassium carbonate. Dried using magnesium sulfate, and the solvent was evaporated under reduced pressure to give a colorless oil (25 mg). This was purified by filtration chromatography on silica using a dichloromethane (1-4%) gradient eluent of 10% aqueous ammonia solution in methanol. This gave the intended product as asymmetric stereoisomer (colorless oil, 20 mg).

Example 7

This example describes the preparation of N, N-dimethyl-3-cyanocyclopentylamine.

Dimethylamine hydrochloride (46.45 g, 0.57 mmol) was stirred in methanol (250 ml) at room temperature and a solution of 3-cyanocyclopentanone (6.25 g, 0.057 mmol) dissolved in methanol was added dropwise. After 55 minutes, a solution of 3-cyanocyclopentanone (6.25 g, 0.057 mmol) dissolved in methanol (25 ml) was added dropwise. Agitation was continued and after 4 hours the mixture was concentrated under reduced pressure. The residue was dissolved in 2M sodium hydroxide (200 ml) and extracted with diethyl ether (3 × 100 ml). The collected organic extracts were washed with brine, dried over potassium carbonate / magnesium sulfate and evaporated under reduced pressure to give an orange oil (4.50 g). It was dissolved in ethyl acetate (50 ml) and extracted with 2M hydrochloric acid (1 × 50 ml, 1 × 10 ml). The collected acid extracts were basified to pH 10-11 by addition of solid potassium hydroxide, which was extracted with diethyl ether (3 × 50 ml). The organic extracts were collected, dried using potassium carbonate / magnesium sulfate and evaporated under reduced pressure to give the product as a mixture of asymmetric stereoisomers (yellow oil, 3.35 g).

M + = 138.

Example 8

This example describes the preparation of N, N-dimethyl-3- (5-bromopyrid-3-yl) -3-cyanocyclopentylamine (Compound No. 14).

N, N-dimethyl-3-cyanocyclopentylamine (0.52 g, 3.77 mmol) and 3,5-dibromopyridine (0.983 g, 4.15 mmol) were stirred together in dry THF (10 ml) under nitrogen and 0 ° C. Cooled to. Nitrile bis (trimethylsilyl) amide (1M solution in THF (5.65 ml, 5.65 mmol) was added dropwise at a rate of 2.7 ml per hour using a syringe pump.The reaction mixture was stirred for 30 minutes Lithium bis (trimethylsilyl) amide (2.83 ml, 2.83 mmol) was then added similarly, stirring continued for 1.5 h under low temperature, then the mixture was carefully poured into water (30 ml) and extracted (3 × 30 ml of Ethyl acetate) .The collected organic extracts were dried using potassium carbonate / magnesium sulfate and evaporated under reduced pressure to give a brown oil (1.30 g) Residual 3,5-dibromopyridine and N, N-dimethyl-3 Cyanocyclopentylamine was partially removed at 100 ° C. and 0.6 mm mercury pressure (80 Nm ⁻² ), and the product (brown oil, 0.96 g) was further removed with dichloromethane (1%) of a 10% solution of aqueous ammonia in methanol. -3%) slope It was made the filtration was purified by silica chromatography using a Reactor yellow gum (gum) is obtained. Residual N, N- dimethyl-3-cyano-cyclopentylamine to 100 ℃ and 0.3mm of mercury pressure (40Nm ^-2) Removal under gave the product as a mixture of asymmetric stereoisomers (160 mg).

Example 9

This example describes the preparation of N-methyl-N-t-butyloxycarbonyl-3- (5-bromopyrid-3-yl) -3-cyanocyclopentylamine (Compound No. 22).

Sodium amide (109 mg, 2.79 mmol) was suspended in THF (2 ml) and stirred under nitrogen at room temperature. N-methyl-N-t-butyloxycarbonyl-3-cyanocyclopentylamine (0.50 g, 2.23 mmol) dissolved in THF (2 ml) was added dropwise. The reaction mixture was stirred for an additional 30 minutes, cooled to 0 ° C., and then 3,5-dibromopyridine (581 mg, 2.45 mmol) dissolved in THF (2 ml) was added dropwise. Stirring was continued under low temperature for 1.5 hours and then left overnight at room temperature. The reaction mixture was carefully poured into water (30 ml) and extracted with 3 × 30 ml of ethyl acetate. The collected extracts were dried using potassium carbonate / magnesium sulfate and then evaporated under reduced pressure to give a brown semi-solid (810 mg). This product was purified by filtration chromatography on silica using a gradient eluent of 5% -15% ethyl acetate in hexanes to afford the desired product as a mixture of asymmetric stereoisomers (205 mg).

Example 10

This example describes the preparation of N-methyl-3- (5-bromopyrid-3-yl) -3-cyanocyclopentylamine (Compound No. 2).

N-methyl-Nt-butyloxycarbonyl-3- (5-bromopyrid-3-yl) -3-cyanocyclopentylamine (185 mg, 0.49 mmol) was stirred in dichloromethane (3 ml) and tri Fluoroacetic acid (1.9 ml) was added dropwise thereto. The solution was stirred at room temperature for 2 hours and then left overnight. The solvent was removed under reduced pressure and the residue was partitioned between saturated sodium bicarbonate (15 ml) and dichloromethane (15 ml). Its organic layer was separated and the aqueous layer was extracted with additional dichloromethane (2x15 ml). The collected organic layer was dried using potassium carbonate / magnesium sulfate and the solvent was removed under reduced pressure to give a yellow oil (135 mg) which was obtained using a 10% solution in dichloromethane with a 10% solution of aqueous ammonia in methanol. Purification by preparative thin layer chromatography on silica yielded the intended product as a mixture of asymmetric stereoisomers (70 mg).

Example 11

This example describes 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 (115 mg, 0.39 mmol) was stirred in 1,2-dichloroethane under reflux nitrogen. Vinylchloroformate (125 mg, 1.17 mmol) was added dropwise, and the reaction mixture was kept at reflux for 5 hours and then allowed to stand overnight at room temperature. The reaction mixture was concentrated under reduced pressure to give a brown gum (150 mg). The product was purified using filtration chromatography on silica using 20% ethyl acetate in hexanes to afford the desired product as a mixture of asymmetric stereoisomers (75 mg).

Example 12

This example describes 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 (110 mg, 0.39 mmol) was stirred in methyl formate (2 ml) for 2 hours and then left overnight. The reaction mixture was concentrated under reduced pressure to give a yellow oil (120 mg). After the reaction was completed the oil was stirred for additional 6 hours with methyl formate (2 ml) and left overnight. Additional methyl formate (3 ml) was added and the mixture was left to stir overnight for another 6 hours. Stirring was continued for an additional 6 hours and the mixture was left overnight. Additional methyl formate (2 ml) was added and the reaction mixture was left to stand for 7 days, concentrated under reduced pressure, to give a yellow oil (130 mg). This product was purified by filtration chromatography on silica using dichloromethane followed by 10% solution of aqueous ammonia in methane and 2% solution in dichloromethane to give the desired product as a mixture of asymmetric stereoisomers (95 mg). Was obtained.

Example 13

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

N-methyl-3- (5-bromopyrid-3-yl) -3-cyanocyclopentylamine (100 mg, 0.36 mmol) and 2-bromo-1,1-difluoroethane (79 mg, 0.54 mmol ) Were stirred together in dimethylformamide (DMF) (3 ml) at room temperature. Some potassium carbonate (75 mg, 0.54 mmol) was added, followed by successively addition of potassium iodide (15 mg, 0.09 mmol), and the reaction mixture was heated to 50 ° C. After 24 hours, additional 2-bromo-1,1-difluoroethane (79 mg, 0.54 mmol) was added in DMF (1 mL) followed by potassium carbonate (75 mg, 0.54 mmol). The reaction mixture was kept at 50 ° C. for 24 hours and additional 2-bromo-1,1-difluoroethane (79 mg, 0.54 mmol) was added in DMF (1 ml). After 3 days at 50 ° C., the reaction mixture was cooled, diluted with dichloromethane, filtered to remove inorganic compounds and evaporated under reduced pressure to give a yellow gum (110 mg). After completion of the reaction, the mixture was stirred with 2-bromo-1,1-difluoroethane (522mg, 3.60mmol) in DMF (3ml) and potassium carbonate (75mg, 0.54mmol) followed by potassium iodide Part (60 mg, 0.36 mmol) was added. The reaction mixture was heated to 50 ° C. and allowed to stand overnight at room temperature, then additional 2-bromo-1,1-difluoroethane (522 mg, 3.60 mmol) in DMF (3 ml) was added successively to potassium carbonate (75 mg, 0.54 mmol) was added. After an additional 3 days, the reaction mixture was cooled down, filtered to remove minerals, washed thoroughly with DMF and concentrated under reduced pressure to give a yellow oil (310 mg). This oil was purified by preparative thin layer chromatography on silica using a 10% solution of dichloromethane in a 10% solution of aqueous ammonia in methanol to afford the desired product as a mixture of asymmetric stereoisomers (65 mg).

Example 14

This example describes the preparation of N-methyl-N- (4-ethoxybenzyl) -3- (5-bromopyrid-3-yl) -3-cyanocyclopentylamine (Compound No. 24). do.

N-methyl-3- (5-bromopyrid-3-yl) -3-cyanocyclopentylamine (160 mg, 0.57 mmol) was stirred in methanol (2 ml) at room temperature and 4- in methanol (2 ml) Ethoxybenzaldehyde (171 mg, 1.14 mmol) was added dropwise. After 90 minutes, some sodium cyanoborohydride (36 mg, 0.57 mmol) was added. After stirring for 24 hours at room temperature, additionally sodium cyanoborohydride (36 mg, 0.57 mmol) was added and after an additional 24 hours, 4-ethoxybenzaldehyde (86 mg, 0.57 mmol) in methanol (1 ml) was added dropwise. After addition, sodium cyanoborohydride (36 mg, 0.57 mmol) was added subsequently. After 4 days, the reaction mixture is concentrated under reduced pressure, and the residue is partitioned between 2M sodium hydroxide (5ml) and diethyl ether (5ml), and the aqueous phase is further diluted with ethyl ether (2x5ml). Extracted. The collected organic extracts were washed with water (1 × 10 ml), dried over potassium carbonate / magnesium sulfate and concentrated under reduced pressure to give a yellow oil (460 mg). It was dissolved in dichloromethane (10 ml) and extracted with 2M hydrochloric acid (3 × 5 ml). The collected acid extracts were basified to pH 10-11 with the addition of solid potassium hydroxide, which was extracted with dichloromethane (4 × 10 ml). The organic extracts were collected, dried using potassium carbonate / magnesium sulfate and evaporated under reduced pressure to give a colorless oil (140 mg) as product. This oil was purified by preparative thin layer chromatography on silica using a 10% solution of dichloromethane in a 10% solution of aqueous ammonia in methanol to afford the intended product as a mixture of asymmetric stereoisomers (120 mg).

NMR data for the intermediate N-allyl-Nt-butyloxycarbonyl-3-cyanocyclopentylamine are as follows: ¹ H NMR (CDCl ₃ ): δ5.80 (m, 1H), 5.12 (m, 2H), 3.78 (d, 2H), 1.80-4.50 (m, 8H), 1.47 (s, 9H) ppm.

Example 15

This example describes an emulsifiable concentrated composition that can be diluted with water and readily converted into a liquid formulation suitable for spraying use. This concentrate comprises the following composition:

weight% Compound 1 25.5 SYNPERONIC NP13 2.5 Calcium Dodecylbenzenenesulfonate 2.5 AROMASOL H 70

Example 16

This example describes a wettable powder composition that can be diluted with water and readily converted into a liquid formulation suitable for spraying applications. This wettable powder comprises the following composition:

weight% Compound 2 25.0 Silica 25.0 Sodium lignosulfonate 5.0 Sodium Lauryl Sulfate 2.0 Kaolinite 43.0

Example 17

This example describes a spraying agent comprising 1% of the first compound and 99% by weight of talc that can be used directly on a plant or other surface.

Example 18

This example describes concentrated liquid formulations suitable for application in ultra low volume techniques after mixing with paraffin diluents.

weight% Compound 1 90.0 SOLVESSO 200 10.0

Example 19

This example describes a capsule suspension concentrate that can be diluted with water and readily converted into a suitable product for application as an aqueous spray.

weight% Compound 1 10.0 Alkylbenzene solvents (eg AROMASDL H) 5.0 Toluene di-isocyanate 3.0 Ethylenediamine 2.0 Polyvinyl alcohol 2.0 Bentonite 1.5 Polysaccharides (eg, KELTROL) 0.1 water 76.4

Example 20

Preparation for Using Granule Formulations

weight% Compound 1 0.5 SOLVESSO 200 0.2 Nonylphenol Ethoxylate (eg, Synperonic NP8) 0.1 Calcium Carbonate Granules (0.3-0.7mm) 99.2

Example 21

Aqueous Suspension Concentrate:

weight% Compound 1 5.0 Kaolinite 15.0 Sodium lignosulfonate 3.0 Nonylphenol Ethoxylate (eg, Synperonic NP8) 1.5 Propylene glycol 10.0 Bentonite 2.0 Polysaccharides (eg, KELTROL) 0.1 Fungicides (eg, Proxel; Proxel is a registered trademark) 0.1 water 63.3

Example 22

This example describes a water dispersible granule formulation.

weight% Compound 1 5 Silica 5 Sodium lignosulfate 10 Sodium dioctylsulfosuccinate 5 Sodium acetate 10 Montmorillonite powder 65

Example 23

This example describes compounds of insecticide properties of formula (1). The activity of the individual compounds of formula (1) was measured using various pests. The pests are treated with a liquid composition containing 500 parts per million (ppm) per weight of the compound, unless otherwise specified. Each composition was dissolved in the compound in an acetone and ethanol (50:50) mixture and the solution contained 0.05% by weight of the wetting agent sold under the trademark "SYNPERONIC NP8" in the concentration of the compound for which this liquid composition was required. It is prepared by diluting until it contains. "SYNPERONIC" is a registered trademark.

The test procedure adopted for each pest is basically the same, supporting a plurality of pests in a medium that is a substrate, host plant or food to be supplied to the pest, and treating the composition both or both of the medium and the pests. Steps. The mortality of the pests was analyzed following various periods of 2-5 days after treatment.

The results of the test on peach aphid (Myzus persicae) are shown below. This result is indicated according to the grade designated as A, B or C, where C represents a mortality of less than 40%, B represents a mortality of 40-79% and A represents a mortality of 80-100%. In this test, Chinese cabbage leaves were swarmed with aphids, and then the infested leaves were sprayed with the test composition to determine their mortality after standing for 3 days.

Compounds 2, 3, 5, 9, 14, 16, 17, 18, 23, 24, 25, 39, and 52 each had grade A mortality, while compound 82 had a grade B.

In addition, in the above similar test against the red spider mite (Tetranychus urticae), compounds 9 and 88 each showed grade B mortality.

Claims (9)

A compound of formula (1) or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom: [Formula 1] [Wherein R ¹ is Ar— (CH ₂ ) _n − (where n is 0 or 1 and Ar is optionally substituted phenyl or contains 1 to 3 heteroatoms each selected from nitrogen, oxygen and sulfur atoms An optionally substituted 5- or 6-membered heterocyclic system containing one or more unsaturated (double bonds) between adjacent atoms in the ring, in which the substituent is a halogen atom, alkyl having up to 6 carbon atoms, al Kenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, haloalkoxy, alkylthio and alkyl amino groups); Wherein R ² and R ³ are each hydrogen or alkyl, aryl, heteroaryl, aralkyl, formyl, alkylcarbonyl, arylcarbonyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, Alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl or dithiocarboxyl groups; The alkyl moiety of R ² and R ³ contains 1 to 15 carbon atoms and includes halogen, cyano, carboxyl, carboxylic arsyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, Optionally substituted with one or more substituents selected from amino, acylamino, imidate and phosphonato groups; Aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, phenylsulfonyl, alkenyloxycarbonyl, aralkyloxycarbon of R ² and R ³ Neyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl and dithiocarbonyl moieties include halogen, cyano, carboxyl, carboxylic arsyl, formyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, Optionally selected from nitro, haloalkyl, alkyl, amino, acylamino, imdate and phosphonato groups with one or more substituents. The benzene of claim 1, wherein R ¹ is Ar— (CH ₂ ) _n −, wherein n is 0 or 1 and Ar contains 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur. A compound of formula (1) which is a 5- or 6-membered aromatic heterocyclic system optionally substituted with halogen, haloalkoxy or haloalkyl optionally fused to a ring. 3. A compound according to claim 1 or 2 wherein R ² and R ³ are each hydrogen; Alkyl comprising 1 to 15 carbon atoms optionally substituted with halogen or alkoxy; Phenylalkyl optionally substituted with halogen or alkoxy; Alkenyl; Formyl; Alkoxycarbonyl; Or alkenyloxycarbonyl. 4. The compound of claim 1, 2 or 3, wherein R ¹ is Ar— (CH ₂ ) _n −, wherein n is 0 or 1 and Ar contains 1 to 3 nitrogen atoms optionally substituted with halogen atoms. Is a 6-membered aromatic heterocyclic system); R ² and R ³ are each hydrogen; Alkyl optionally substituted with halogen or alkoxy; Phenylalkyl optionally substituted with halogen or alkoxy; Formyl; Alkoxycarbonyl; Or alkenyloxycarbonyl. Intermediate of formula (1), wherein R ¹ is hydrogen and R ² and R ³ as claimed in claim 1. Method for preparing a compound of formula (1) as claimed in claim 1, (a) reacting 3-cyanocyclopentylamine of formula (8) with a compound of formula R ¹ -X, wherein X is a leaving group, in the presence of a base: [Formula 8] Or (b) reacting the 3-cyanocyclopentylamine of formula (7) with an alkylating agent of formula R ³ -X ¹ , wherein X ¹ is a leaving group: [Formula 7] Or (c) reductively coupling the 3-cyanocyclopentylamine of formula (7) with a carbonyl compound of formula R ³ CHO Or (d) when R ³ is hydrogen, decarboxylating a compound of formula (6): [Formula 6] Or (e) replacing the amine group of the compound of formula (13): [Formula 13] Or (f) aminating the compound of formula (11) to reductively: [Formula 11] How to include. A pesticide, acaricide, nematicide composition comprising a compound of formula (1) as claimed in claim 1 and an appropriate carrier or diluent thereof in an effective amount for insecticide, acaricide, nematode. Insects, ticks or nematode pests at the locus comprising the step of treating the pest or locus of the pest with an effective amount of the composition of the insecticidal, tick or nematode according to claim 7. Eradication and control. The method according to claim 8, wherein the place of activity is a plant growing and the pest is a plant pest.