FR2751644A1 - Aromatic amide(s) with insecticidal and acaricidal activity - Google Patents

Abstract

Aromatic amides of formula Q(CH2)a(X1)bQ1Q2C(X2)N(R1)(R2) (I) in all stereoisomeric forms, and their mixtures, are new. Q = aryl or a radical derived from a condensed bicyclic hydrocarbon having a benzene ring, which is attached to the adjacent methylene group by a carbon of the benzene ring, Q having 6-12C atoms and optionally being substituted; a, b = 0 or 1; X1 = oxy, thio, sulphinyl, or sulphonyl; X2 = O or S; Q1 = optionally substituted cyclopropane-diyl; Q2 = arylene or a radical derived from a condensed bicyclic hydrocarbon having a benzene ring, which is attached to the adjacent groups by two carbon atoms of the benzene ring, Q2 having 6-12C atoms and optionally being substituted; R1 = H; a radical derived from a cyclic or acyclic, saturated, unsaturated or aromatic hydrocarbon of 1-12 C atoms, which may be substituted; a radical derived from a straight or branched structure of 1-20C atoms and 1-6 hetero atoms (O, N, S), which may itself be substituted by an aromatic or non-aromatic heterocycle (having 1-5C, 1-4 hetero atoms and being optionally substituted); R2 = WZ, a group R3C(=X3) (A), a group (R3)2P(=X3) (B), or a group S(?>O)nY (C); NWZ may form a nitrogen heterocycle which may contain further hetero atoms (O, N, S), may be (partially) unsaturated and may be substituted; or W = O, NH or N-(1-8C alkyl); and Z = H, or saturated or unsaturated optionally substituted alkyl of up to 8C; X3 = O or S; R3 = H or R4(T1)i; i = 0 or 1; T1 = bivalent oxy, carbonyl or oxycarbonyl; R4 = H, or 1-20C group derived from a cyclic or acyclic, saturated, unsaturated or heterocyclic hydrocarbon, which may be substituted; n = 0 or 2; and Y = methyl or ethyl. Also claimed are: (1) 2-methyl-N-hydroxy-benzenamine, an intermediate in preparation of (I); (2) pesticide compositions containing (I).

Description

 The present invention relates to new aromatic amides, their preparation process and their use as pesticides.

The subject of the invention is in all their stereoisomeric forms or in the form of mixtures of these stereoisomers, the compounds of formula (I)
Q- (CH2) a (Xl) b-Ql-Q2-C (X2) -N (R1) (R2) (I) in which
Q represents an aryl radical or a radical derived from a condensed bicyclic hydrocarbon comprising a benzene ring, which is linked to the adjacent group (CH2) a by a carbon atom of said benzene ring, Q comprises from 6 to 12 carbon atoms and can be either unsubstituted or substituted, a and b are identical or different and are, independently of one another, equal to 0 or to 1, X1 represents a bivalent oxy, thio, sulfinyl or sulfonyl radical,
X2 represents an oxygen atom or a sulfur atom,
Q1 represents a cyclopropanediyl radical, which is either unsubstituted or substituted.

Q2 represents an arylene radical or a radical derived from a condensed bicyclic hydrocarbon comprising a benzene ring, which is linked to the adjacent groups Q1 and C (X) 2 by two carbon atoms of the said benzene ring, Q2 contains from 6 to 12 atoms carbon and may independently of Q, be either unsubstituted or substituted.

R1 represents either a hydrogen atom or a radical derived from a cyclic or acyclic hydrocarbon, aromatic or non-aromatic, linear or branched, saturated or unsaturated, and comprising from 1 to 12 carbon atoms, itself being either unsubstituted, either substituted, or a radical derived from a linear or branched structure comprising from 1 to 20 carbon atoms and from 1 to 6 heteroatoms chosen from oxygen, nitrogen or sulfur atoms, itself capable of be either unsubstituted or substituted, or a radical derived from an aromatic or non-aromatic heterocycle containing from 5 to 9 carbon atoms and from 1 to 4 heteroatoms chosen from oxygen, nitrogen or sulfur atoms, this radical can be unsubstituted or substituted.

dans lequel X3 représente un atome d'oxygène ou un atome de soufre, et R3 représente un atome d'hydrogène ou un groupe R4-(Tl)i dans lequel i est égal à O ou à 1, T1 représente un groupe bivalent oxy, carbonyle ou oxycarbonyle et R4 représente un atome d'hydrogène ou un radical dérivé d'un hydrocarbure cyclique ou acyclique, aromatique ou non aromatique, linéaire ou ramifié saturé ou insaturé, et comportant de 1 à 20 atomes de carbone, lui-même pouvant être soit non substitué, soit substitué.R2 represents a group WZ in which - either W and Z can together form a nitrogen ring linked to the nitrogen atom of the radical N (R1) (R2) by the nitrogen atom and can contain one or more other heteroatoms chosen from oxygen, nitrogen and sulfur, which may contain one or more other unsaturations and which may be optionally substituted, - either W represents an oxygen atom or an NH or N alkyl radical containing up to 8 carbon atoms and Z represents a hydrogen atom, a linear or branched, saturated or unsaturated alkyl radical containing up to 8 optionally substituted carbon atoms, ie a group (A)

in which X3 represents an oxygen atom or a sulfur atom, and R3 represents a hydrogen atom or a group R4- (Tl) i in which i is equal to O or to 1, T1 represents a bivalent oxy group, carbonyl or oxycarbonyl and R4 represents a hydrogen atom or a radical derived from a cyclic or acyclic hydrocarbon, aromatic or non-aromatic, linear or branched saturated or unsaturated, and comprising from 1 to 20 carbon atoms, itself possibly being either unsubstituted or substituted.

dans lequel R3 et X3 sont tels que définis plus haut ou un groupe (C)

dans lequel n représente le nombre 0 ou 2, y représente un radical alkyle renferment jusqu'à 2 atomes de carbone.or a group (B)

in which R3 and X3 are as defined above or a group (C)

in which n represents the number 0 or 2, y represents an alkyl radical containing up to 2 carbon atoms.

 The term “compound of formula (I)” denotes all the geometric isomers and possible stereoisomers taken individually or as a mixture.

 By radical derived from a condensed bicyclic hydrocarbon comprising a benzene ring, is meant in particular for the definition of Q the indanyl, indenyl, naphthyl, dihydronaphthyl or tetrahydronaphthyl radicals and for the definition of Q2 in particular the ortho-phenylene, meta-phenylene radicals, para-phenylene, 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, 4,5-indenylene, 4,6-indenylene, 4,7-indenylene, 4,5indanylene, 4,6-indanylene, 4,7-indanylene, 1,2,3,4-tetrahydro 5,6-naphthylene, 1,2,3,4-tetrahydro 5,7-naphthylene, 5,8tetrahydronaphtylene.

 By radical derived from a saturated or unsaturated, aromatic or non-aromatic, cyclic hydrocarbon, is meant in particular the phenyl radical, the cycloalkyl radicals, such as the cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl radicals as well as the alkyl radicals substituted by a cyclic radical such as the benzyl or cyclopropylmethyl radical.

 By radical derived from an acyclic hydrocarbon, linear or branched, saturated or unsaturated, is meant alkyl radicals such as in particular methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl , tert-pentyl, hexyl or isohexyl, alkenyl radicals, such as in particular vinyl, 1-propenyl, 2-methyl 2-propenyl, isoprenyl, alkynyl radicals such as in particular ethynyl, 1-propynyl, 2-propynyl radicals as well as the radicals comprising several unsaturations such as the alkadienyl radicals such as 1,3-butadienyl or the pent-2-ene-4-ynyl radical.

 The term radical derived from a linear or branched structure, comprising from 1 to 20 carbon atoms and from 1 to 6 heteroatoms, denotes in particular radicals derived from alkanes, certain carbon atoms of which are replaced by oxygen or sulfur atoms or a group -NH-, such as hydroxymethyl, methoxymethyl, ethoxymethyl, 2-hydroxyethyl, 2-methoxyethyl, 2- (2-methoxy ethoxy) ethyl, (2-methoxy ethoxy) methyl, [2- (2-methoxy) ethoxy) ethoxy] methyl, ethoxymethyl, [2- (2-buthoxy ethoxy) ethoxy] methyl, 2-methylthio ethyl, 2- (methylamino) ethyl, methylamino-methyl, butylaminobutyl or propoxymethyl.

 By radical derived from an aromatic or non-aromatic heterocycle, is meant in particular the thienyl, furyl, pyrannyl, pyrrolyl, 2H-pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, isothiazolyl, isoxazolyl, furazannylylazyl radicals. , pyrrolidinyl, pyrrolinyl, imidazolidinyl, pyrazolinyl, piperidyl, piperazinyl, morpholinyl, azepinyl, thiazinyl, tetrazinyl, oxathiolannyl or thiadizinyl.

When Q is substituted by one or more substituents, these substituents are chosen in particular from halogen atoms or groups or methylenedioxy, difluoromethylenedioxy, tetrafluoroethylenedioxy, cyano, nitro, cyanato, thiocyanato, pentafluorothio, fluorosulfonyl or R- (T) C - in which R represents a hydrogen atom or a radical derived from a cyclic or acyclic hydrocarbon, aromatic or non-aromatic, linear or branched, saturated or unsaturated, and comprising from 1 to 8 carbon atoms, which can itself be either unsubstituted or substituted by one or more halogen atoms, c is 0 or 1 and T represents a bivalent oxy, carbonyl, carbonyloxy, oxycarbonyl, thio, sulfinyl, sulfonyl, or sulfonyloxy group, - (CO) dN (R ') - (CO) e- (O) f- or -N (R ") -S (O) g in which R' and
R "independently of R represent a hydrogen atom, or a radical derived from a cyclic or acyclic hydrocarbon, aromatic or non-aromatic, linear or branched, saturated or unsaturated, and having from 1 to 8 carbon atoms, itself can be either unsubstituted or substituted by one or more halogen atoms, d, e and f are equal to O or 1, f is equal to 0 when e is equal to 0, the sum e + d is equal to 0 or 1 and g is 0, 1 or 2.

 When Q1 is substituted, the substituents are chosen in particular from halogen atoms, cyano, azido or aliphatic radicals, saturated or unsaturated comprising from 1 to 4 carbon atoms unsubstituted or substituted by one or more halogen atoms, such as methyl, vinyl or ethynyl radicals.

 When Q2 is substituted, these substituents are chosen in particular from halogen atoms or methyl lenedioxy, difluoromethylenedioxy, tetrafluoro ethylenedioxy, cyano, nitro, amino, alkylamino, alkenylamino, cyanato, thiocyanato, pentafluorothio, fluorosulfonyl or R- (T) groups. C- in which R represents a hydrogen atom or a radical derived from a cyclic or acyclic hydrocarbon, aromatic or non-aromatic, linear or branched, saturated or unsaturated, and comprising from 1 to 8 carbon atoms, itself capable of be either unsubstituted or substituted by one or more halogen atoms, c is 0 or 1 and T represents a bivalent oxy, carbonyl, carbonyloxy, oxycarbonyl, thio, sulfinyl, sulfonyl, or sulfonyloxy group, - (CO ) dN (R ') - (CO), (O) f- or -N (Rl) -S (O) g- in which R' and R ", d, e, f and g are as defined above.

 When, in the foregoing or in the following, it is indicated that a radical may be substituted by one or more halogen atoms, these halogen atoms may be fluorine, chlorine, bromine or d 'iodine. When it is a polysubstituted radical with fluorine atoms, the perfluorinated radicals are especially designated.

 When, in the above, a radical derived from a cyclic or acyclic, aromatic or non-aromatic, linear or branched, saturated or unsaturated, hydrocarbon is substituted, these substituents are chosen in particular from halogen atoms or methylenedioxy groups, difluoromethylenedioxy, tetrafluoro ethylenedioxy, cyano, nitro, cyanato, thiocyanato, pentafluorothio, fluorosulfonyl or R- (T) C- in which R represents a hydrogen atom or a radical derived from a cyclic or acyclic, aromatic or non-aromatic hydrocarbon, linear or branched, saturated or unsaturated, and having from 1 to 8 carbon atoms, and possibly 1 or more heteroatoms, itself being either unsubstituted or substituted, by one or more halogen atoms, c is equal to 0 or 1 and T represents a bivalent oxy, carbonyl, carbonyloxy, oxycarbonyl, thio, sulfinyl, sulfonyl, or sulfonyloxy group, - (CO) aN (R ') - (CO), (O) f- or -N ( Rl) -S (O) g- in which R 'and R ", d, e, f and g are as defined above.

 A more particular subject of the invention is the compounds of formula (I) in which a and b represent the number 0.

 A subject of the invention is in particular the compounds of formula (I) in which Q is unsubstituted or substituted by one or more substituents chosen from halogen atoms or methylenedioxy, difluoromethylenedioxy, tetrafluoroethylenedioxy, cyano, nitro, cyanato, thiocyanato groups , pentafluorothio, fluorosulfonyl or R- (T) C- in which R represents a hydrogen atom or a radical derived from a cyclic or acyclic hydrocarbon, aromatic or non-aromatic, linear or branched, saturated or unsaturated, and comprising of 1 with 8 carbon atoms, itself being either unsubstituted or substituted by one or more halogen atoms, c is equal to 0 or to 1 and T represents a bivalent oxy, carbonyl, carbonyloxy, oxycarbonyl, thio, sulfinyl, sulfonyl, or sulfonyloxy, - (CO) dN (R ') - (CO) e- (O) f- or -N (RIl) -S (O) g- in which R' and R "independently represent R a hydrogen atom, or a radical derived from a cyclic hydrocarbon eu or acyclic, aromatic or non-aromatic, linear or branched, saturated or unsaturated, and containing from 1 to 8 carbon atoms, itself being either unsubstituted or substituted by one or more halogen atoms, d, e and f are equal to 0 or 1, f is equal to 0 when e is equal to 0, the sum e + d is equal to 0 or 1 and g is equal to 0, 1 or 2.

Q1 is unsubstituted, or substituted by one or more substituents chosen from halogen atoms, cyano, azido, or aliphatic, saturated or unsaturated radicals containing from 1 to 4 carbon atoms unsubstituted or substituted by one or more atoms halogen and Q2 is unsubstituted or substituted by one or more substituents chosen from halogen atoms or methylenedioxy, difluoromethylenedioxy, tetrafluoroethylenedioxy, cyano, nitro, amino, alkylamino, alkenylamino, cyanato, thiocyanato, pentafluorothio, fluorosulfon groups R- (T) C- in which R represents a hydrogen atom or a radical derived from a cyclic or acyclic hydrocarbon, aromatic or non-aromatic, linear or branched, saturated or unsaturated, and comprising from 1 to 8 carbon atoms , itself being either unsubstituted or substituted by one or more halogen atoms, c is 0 or 1 and T represents a bivalent oxy, carbon group yl, carbonyloxy, oxycarbonyl, thio, sulfinyl, sulfonyl, or sulfonyloxy, - (CO) dN (R ') - (CO) e- (O) f- or -N (R ") S (O) in which R' and R ", d, e, f and g are as defined above.

Among the preferred compounds of the invention, mention may be made of the compounds of formula (I) in which Q is a phenyl radical or a naphthyl radical, unsubstituted or substituted with 1 to 3 substituents, for example, the compounds of formula (I ) in which Q represents a radical chosen from the phenyl, 2-chloro phenyl, 3-chloro phenyl, 3-bromophenyl, 3- (trifluoromethyl) phenyl, 4-chloro phenyl, 4-bromo phenyl, 4-iodo phenyl, 4 radicals - (trifluoromethyl) phenyl, 4nitrophenyl, 4-methoxy phenyl, 4- (difluoromethoxy) phenyl, 4- (trifluoromethoxy) phenyl, 3-bromo 4- (difluoromethoxy) phenyl, 4- (2,2-dibromo ethenyl) phenyl, 4 -ethynyl phenyl, 4-benzyl phenyl, 3,4-dibromo phenyl, 2,4-dichioro phenyl, 3,4-dichloro phenyl, 3,4-difluorophenyl, 3-chloro 4-iodo phenyl, 4-bromo 3-chloro phenyl, 4-bromo 2-fluoro phenyl, 4-bromo 3 fluoro phenyl, 4-bromo 3- (trifluoromethyl) phenyl, 4-chloro 3- (trifluoromethyl) phenyl, 3,5-bis (( trifluoromethyl) phenyl, 3,4,5-trichloro phenyl, 4-bromo 3,5-dichloro phenyl, 3-phenoxyphenyl, 4- (fluoro 3-phenoxy) phenyl, 3-bromo 4- (trifluoromethylsulfonyloxy) phenyl, 3,4 -bis (trifluoromethylsulfonyloxy) phenyl, 2 -naphthyl or 5-bromo 2naphthyl or 6-bromo l-naphthyl.

A subject of the invention is very particularly the compounds of formula (I) in which the steric configuration of
Q1 is such that the group Q- (CH2) a- (X1) b- is in the trans position relative to the group Q2-C (X2) -N (R1) (R2).

Among the preferred compounds, mention may be made of the compounds of formula (I) in which Q1 is unsubstituted or substituted by 1 or 2 halogen atoms or 1 or 2 methyl radicals.

Q1 can represent, for example, a radical chosen from the radicals 1,2 - cyclopropanediyle, i - fluoro 1,2-cyclopropanediyle, l-chloro 1,2-cyclopropanediyle, 1-bromo 1,2-cyclopropanediyle, 1-methyl 1,2 -cyclopropanediyle, 3,3-dibromo 1,2cyclopropanediyle and 1,2-difluoro 1,2-cyclopropanediyle.

 The subject of the invention is particularly the compounds of formula (I) in which Q2 represents one of the orthophenylene, meta-phenylene, para-phenylene, 1,2-naphthylene, i, 3-naphthylene, 1,4-naphthylene, 1 radicals , 5-naphthylene, 2, 5-naphthylene, 4,5-indenylene, 4,6-indenylene, 4,7-indenylene, 1,2,3,4tetrahydro 5,6-naphthylene, 1,2,3, 4-tetrahydro 5,7-naphthylene, 1,2,3,4-tetrahydro 5,8-naphthylene, unsubstituted or substituted with 1 to 4 substituents.

Q2 can represent, for example, one of the radicals 2-methyl 1,4-phenylene, 2,3,5,6-tetrafluoro 1,4-phenylene, 3-methyl 1,4-phenylene, 2-chloro 1,4-phenylene, 2-acetylamino 5-chloro 1,4-phenylene, 2-amino 5-chloro 1,4-phenylene, 2-dimethylamino 5-chloro 1,4-phenylene.

 A very particular subject of the invention is the compounds of formula (I) in which R1 represents an optionally substituted aryl radical.

Among the preferred compounds of the invention, mention may be made of the compounds of formula (I) in which W represents an oxygen atom, as well as those in which Z represents a hydrogen atom, an alkyl or Co2 alkyl radical containing juice than 18 carbon atoms.

dans lesquels Z conserve sa signification précédente, les noyaux phényle pouvant être éventuellement substitués par un ou plusieurs substituants, choisis parmi les atomes d'halogène et les radicaux alkyle renfermeront jusqu'à 4 atomes de carbone linéaire, ramifiés ou cycliques, saturés ou insaturés, éventuellement substitués par un ou plusieurs atomes d'halogène.The subject of the invention is in particular the compounds of formula (IA)

in which Z retains its previous meaning, the phenyl rings possibly being substituted by one or more substituents, chosen from halogen atoms and the alkyl radicals will contain up to 4 linear, branched or cyclic, saturated or unsaturated carbon atoms, optionally substituted by one or more halogen atoms.

 A more particular subject of the invention is the compounds of formula 1, the preparation of which is given below in the experimental part.

A subject of the invention is also a process characterized in that the corresponding acid or acid derivative of formula (II): Q- (CHZ) a (Xl) b Q1-Qâ-C (O) -Z ( 11) in which Q, X1, a, b, Q1 and Q2 are as defined in claims 1 to 12 and Z represents a hydroxy group, a halogenated group, an alkoxy radical containing from 1 to 4 carbon atoms or a group -P (O) (O) -NH, in which O represents a phenyl group, is reacted with an amine of formula (III)
HN (R1) (R2) (III) in which R1 and R2 are as defined above to obtain a product of corresponding formula (I), in which X2 represents an oxygen atom which, if necessary, is converted into a product of formula (I) in which (X2) represents a sulfur atom, then optionally functionalizes the OH group in the case where R2 represents a hydroxyl group to obtain the desired compound of formula I.

 According to the preferential conditions for implementing the process for preparing the compounds of formula (I), the reaction between processes II and III is carried out at a temperature between -25 ° C. and + 150 ° C. in an anhydrous and atopic solvent such than ether, dichloromethane, toluene or benzene.

 Detailed examples of the preparation of the compounds of formula (II) and of formula (III) are given below in the experimental part.

 When the acid derivative of formula (II) is an acid halide, for example acid chloride, it is prepared from the acid by reaction with the appropriate reagent such as oxalyl chloride or thionyl chloride. When Z represents a group -P (O) (OO) -NHO, the corresponding derivative is prepared from the acid by reaction with C1-P (O) (Oo) -NHO. The acid of formula (II) in which Z represents a hydroxy group can be prepared by hydrolysis of an ester.

dans laquelle Z1 représente un radical alcoxy, pour conduire au composé de formule (II) dans laquelle Q1 représente un radical cyclopropanediyle en position 1 par un atome de fluor.The preparation of the compound of formula (II) in which
Z represents an alkoxy radical can be made in particular a) by cyclopropanation of a compound of formula (IV)
Q- (CH2) a- (X1) bC (R9) = C (Rlo) Q2 C (0)) (IV) in which Q, a, X1, b, Q2 and Z are as defined above and Rg and R1o represent, independently of one another, a hydrogen atom, a halogen atom or an aklyl radical, with a carbon generator, such as diazomethane, dibromomethane or diiodomethane in the presence of diethylzinc; b) by cyclocondensation of a derivative of formula (V)
Q- (CH2) a (Xl) bC (R9) = CH (R10) (V) in which Q, a, X1, b, Rg and R10 are as defined above with a compound of formula (VI)

in which Z1 represents an alkoxy radical, to lead to the compound of formula (II) in which Q1 represents a cyclopropanediyl radical in position 1 by a fluorine atom.

pour conduire au composé de formule (VIII) Q-(CH2)a(Xl)b-Ql-Q2 (VIII) dans laquelle Q, a, X1, b, Q2 sont tels que définis précédemment, Hal représente un atome de brome ou d'iode et Q1 représente un radical cyclopropanediyle non substitué, produit de formule (VII I) qui est transformé en dérivé cyano de formule (IX)
Q-(CH2)a(X1)b-Ql-Q2-C-N (IX) lequel est ensuite converti en acide correspondant de formule (Il)
Le composé de formule (VII) est préparé par réaction de l'hydrazine avec le composé de formule (X)

The acid of formula (II) in which Z represents a hydroxy radical can also be prepared by elimination of nitrogen from a compound of formula (VII)

to lead to the compound of formula (VIII) Q- (CH2) a (Xl) b-Ql-Q2 (VIII) in which Q, a, X1, b, Q2 are as defined above, Hal represents a bromine atom or of iodine and Q1 represents an unsubstituted cyclopropanediyl radical, product of formula (VII I) which is transformed into cyano derivative of formula (IX)
Q- (CH2) a (X1) b-Ql-Q2-CN (IX) which is then converted into the corresponding acid of formula (II)
The compound of formula (VII) is prepared by reaction of hydrazine with the compound of formula (X)

The compound of formula (X) is prepared by condensation in basic medium of a compound of formula (XI)
Q (CH2) a (Xl) b-CO-CH3 (XI) with an aromatic aldehyde of formula (XII)
Hal-Q2-CHO (XII) products of formulas (XI) and (XII) which are either commercial or easily synthesizable by the skilled person.

The compound of formula (VI) is prepared by bromination of a compound of formula (XIII)
F-CH2 -Q2 -COZ1 (XIII) which itself is prepared from a compound of formula (XIV)
HO-CH2 -Q2 -COZ1 (XIV) which is commercial or easily synthesizable by a person skilled in the art.

 The compounds of formula (IV) and (V) are known or can be obtained according to the usual methods known to those skilled in the art.

dont la préparation est donnée ci-après dans la partie expérimentale.A subject of the invention is also, as a new chemical, the compound of formula (III) A

the preparation of which is given below in the experimental part.

 The compounds of formula (I) can be used to fight against harmful organisms such as arthropods, for example insects and mites, and helminths, for example nematodes, or molluscs, for example slugs. The subject of the present invention is therefore a process for combating arthropods and / or helminths and / or molluscs, which comprises the administration to the arthropods and / or molluscs or their environment of a quantity of a compound of formula ( I) sufficient to destroy the pest. The present invention also relates to a method for controlling and / or eradicating infestations by arthropods and / or helminths and / or molluscs, in animals (including humans) and / or plants (including trees) and / or stored products which comprises the administration to the animal and to the site of an effective amount of a compound of formula (I). A subject of the invention is also the compounds of formula (I) to be used in human and veterinary medicine, in public health and / or in agriculture for the fight against harmful arthropods and / or helminths.

 The compounds of formula (I) are of particular value for the protection of standing crops, fodder, plantations, greenhouse crops, orchards and vineyards, ornamental plants and trees in plantations and in the forest, for example cereals (such as corn, wheat, rice and sorghum), cotton, tobacco, vegetables and salads (such as beans, cabbage, cucurbits, lettuces, onions, tomatoes and peppers), food crops (for example, potatoes, sugar beets, peanuts, soybeans and rapeseed), sugar cane, grasslands and fodder crops (such as corn, sorghum and alfalfa), plantations (such as those producing tea, coffee, cocoa, banana, palm oil, coconut, rubber and spices), orchards and woods planted (such as those producing stone and seed fruits, citrus fruits, kiwis, avocados, mangoes, olives and nuts), vineyards, ornamental plants, flowers and bushes in the greenhouse and in gardens and parks, forest trees (both deciduous and evergreen) in forests, plantations and nurseries.

 They are also valuable for the protection of timber (standing, felled, transformed, stored or in buildings) against attack by sirex (for example Urocerus), beetles (for example, scolytidae, platypodidae , lyctidae, bostrychidae, cerambucidae and anobiidae) and termites.

 They find their application in the protection of stored products, such as grains, fruits, nuts, spices and tobacco, whole, ground or processed into products, against attack by mites, beetles and weevils . They also protect stored animal products, such as skins, body hair, wool and feathers, in natural or converted form (for example, carpets or textiles), from attack by mites and beetles, similarly than meat and fish against attack by beetles and flies.

 The compounds of general formula (I) are of particular utility in the fight against arthropods, helminths and molluscs which are harmful to humans and domestic animals or are the propagators or vectors of diseases striking the latter, for example. example, those described above, more particularly in the field of the fight against ticks, scabies, lice, fleas, midges and flies, causes of bites and nuisances.

 The compounds of formula (I) can be used for such purposes by applying the compounds as such or in diluted form in a known manner in the form of a bath, spray, mist, varnish, foam, powder, powder, aqueous suspension, paste, gel, shampoo, ointment, combustible solid, spray mat, combustible spiral, bait, dietary supplement, wettable powder, granules, d aerosol, emulsifiable concentrates, oily suspensions, oily solutions, pressure bomb, impregnated article, lotion or other standard compositions well known to those skilled in the art. Bath concentrates are not applied as is, but diluted with water and the animals are immersed in a tank containing the bath.

 The sprays can be applied by hand or using a lance or spray bar. The animal, the earth, the plant or the surface can be saturated with the spray by application in large volume or be coated superficially with the spray by application in small or ultra-small volume. The aqueous suspensions can be applied to the animal in the same way as sprays and baths. Powdered powders can be dispensed using a powder applicator or, in the case of animals, incorporated into perforated bags attached to trees or poles. The pastes, shampoo and ointments can be applied by hand or spread over the surface of an inert material against which the animals rub and thus transfer the material to their skin. Lotions are dispensed as a small dose of liquid on the back of the animals, so that all or most of the liquid remains on the animals.

 The compounds of formula (I) can be presented in the form of compositions ready for use on plants, animals and surfaces or in the form of compositions which must be diluted before application, but the compositions of two types comprise a compound of formula (I) in intimate mixture with one or more excipients or diluents.

The excipients can be liquid, solid or gaseous or can comprise mixtures of such substances and the compound of formula (I) can be present in a concentration of 99 to 0.025 W w / v, depending on whether the composition must be more diluted.

 Powdered powders, powders and granules comprise the compound of formula (I) in intimate mixture with an inert solid powdery excipient, for example, suitable clays, kaolin, bentonite, attapulgite, carbon black adsorbent, talc, mica, chalk, gypsum, tricalcium phosphate, cork powder, magnesium silicate, plant excipients, starch and diatomaceous earth. These solid compositions are generally prepared by impregnating the solid diluents with solutions of the compound of formula (I) in volatile solvents, evaporating the solvents and, if desired, grinding the products to obtain powders and, if the something is desired, by granulating, pressing or encapsulating the products.

 The sprays of a compound of formula (I) may comprise a solution in an organic solvent (for example, those listed below) or an emulsion in water (bath or shower) prepared in the field from approximately 32 mm by 22 mm by 3 mm treated with an amount up to 0.3 ml of a concentrate which contains the active ingredient in an organic solvent and, optionally, an antioxidant, a colorant and a perfume.

 The insecticide is vaporized by a heat source, such as an electric heater for mats.

 Combustible solids normally include sawdust and a binder in admixture with the active ingredient and in the form of ribbons (usually helical). A colorant and a fungicide can also be added.

 The wettable powders comprise an inert solid excipient, one or more surfactants and optionally stabilizers and / or antioxidants.

 Emulsifiable concentrates include emulsifiers and often an organic solvent such as kerosene, ketones, alcohols, xylenes, aromatic naphtha and other known solvents.

 Wettable powders and emulsifiable concentrates normally contain 5 to 95 W by weight of the active ingredient and are diluted before use, for example with water.

 The varnishes comprise a solution of the active ingredient in an organic solvent, together with a resin and optionally a plasticizer.

 The baths can be prepared not only from emulsifiable concentrates, but also from wettable powders, soap-based baths and aqueous suspensions comprising a compound of formula (I) in intimate mixture with a dispersant and one or more surfactants .

 The aqueous suspensions of a compound of formula (I) can comprise a suspension in water, together with a suspending, stabilizing or other agent. The suspensions or solutions can be applied as such or in a diluted formula in a known manner.

 Ointments (or fats) can be prepared from vegetable oils, synthetic esters of fatty acids or lanolin, together with an inert base such as soft paraffin. A compound of formula (I) is preferably distributed uniformly in the mixture in solution or suspension. Ointments can also be obtained from emulsifiable concentrates by diluting them in an ointment base.

 Pastes and shampoos are also semi-solid compositions in which a compound of formula (I) can be present in the state of uniform dispersion in an appropriate base, such as liquid or soft paraffin, or else in a non-greasy base. with glycerol, glue or suitable soap. Since ointments, shampoos and pastes are usually applied without further dilution, they must contain the appropriate percentage of the compound of formula (I) required by the treatment.

 Aerosol sprays can be prepared as a simple solution of the active ingredient in the aerosol propellant and a cosolvent such as a halogenated alkane and the solvents mentioned above, respectively. The lotions compositions can be presented in the form of a solution or suspension of a compound of formula (I) in a liquid medium. A host bird or mammal can also be protected against infestation by ectoparasitic mites by wearing a manufactured product made of suitably molded plastic material which is impregnated with a compound of formula (I). These manufactured products include necklaces, ear tags, bands, canvases and ribbons properly attached to the appropriate part of the body. The plastic material is advantageously a poly (vinyl chloride).

 The compounds of formula (I) are to be used in the protection and treatment of plant species, in which case an effective amount of insecticide, miticide, mollusc, nematocide of the active ingredient is applied. The dose of application varies with the chosen compound, the nature of the composition, the mode of application, the plant species, the density of plantation, the probable infestation and various other factors, but in general a dose suitable for the agriculture ranges from 0.001 to 3 kg per hectare and preferably between 0.01 and 1 kg per hectare. Typical compositions for agricultural use contain between 0.0001 and 50 W of a compound of formula (I) and advantageously between 0.1 and 15 by weight of a compound of formula (I).

 The concentration of the compound of formula (I) for application to an animal, premises or outdoor places varies with the chosen compound, the interval between treatments, the nature of the composition and the likely infestation, but in general the compound must be contained in the composition applied in an amount from 0.001 to 20.0% w / v, preferably from 0.01 to 10 W w / v.

 The amount of the compound deposited on an animal varies with the mode of application, the size of the animal, the concentration of the compound in the composition applied, the dilution factor of the composition and the nature of the composition, but is generally in the range of 0.0001 W to 0.5 W w / w, except for undiluted compositions, such as lotion compositions which are generally deposited at a concentration in the range of 0.1 to 20.0 W and preferably from 0.1 to 10%. The amount of the compound to be applied to the stored products is generally in the range of 0.1 to 20 ppm. Sprays in spaces can be carried out to arrive at an average initial concentration of 0.001 to 1 mg of the compound of formula (I) per m3 of space treated.

 Ointments, fats, pastes and aerosols are usually applied randomly as described above and concentrations of 0.001-20% w / v of a compound of formula (I) in the applied composition can be used.

 The compounds of formula (I) have been found to have activity against the ordinary fly (Musca domestica). In addition, certain compounds of formula (I) have activity against other harmful arthropods, in particular Myzus persicae, Tetranychus urticae, Spodoptera littoralis, Heliotuis virescens, Plutella xylostella, Culex spp., Tribolium castaneum, Sitophilus granarius, Periplaneta americana and Blattella germanica. The compounds of formula (I) are therefore useful for the fight against arthropods, for example insects and mites, in any environment where they constitute a nuisance, for example in agriculture, breeding, public health and in the home.

Insect pests are in particular members of the orders of beetles (for example Anobium, Ceuthorrhynchus,
Rhynchophorus, Cosmopolites, Lissorhoptrus, Meligethes,
Hypothenemus, Hylesinus, Acalymma, Lema, Psylliodes, Leptinotarsa, Gonocephalum, Agriotes, Dermolepida, Heteronychus,
Phaedon, Tribolium, Sitophilus, Diabrotica, Anthonomus or
Anthrenus spp.), Lepidoptera (e.g. Ephestia,
Mamestra, Earias, Pectinophora, Ostrinia, Trichloplusia,
Pieris, Laphygma, Agrotis, Amathes, Wiseana, Tryporyza,
Diatraea, Sparganothis, Cydia, Archips, Plutella, Chilo,
Heliothis, Spodoptera littoralis, Helrotuis virescens, Spodoptera or Tineola spp.), Diptera (e.g. Musca,
Aedes, Anopheles, Culex, Glossina, Simulium, Stomoxys, Haematobia, Tabanus, Hydrotaea, Lucilia, Chrysomyia, Callitroga,
Dermatobia, Gasterophilus, Hypoderma, Hylemyia, Atherigona,
Chlorops, Phytomyza, Ceratitis, Liriomyza and Melophagus spp.), Phtiraptera (Mallophaga, for example Damalina spp., And Anoplura, for example Linognathus and Haematopinus spp.), Hemiptera (for example Aphis, Bemisia, Phorodon,
Aeneolamia, Empoasca, Parkinsiella, Pyrilla, Aonidiella,
Coccus, Pseudococcus, Helopeltis, Lygus, Dysdercus, Oxycarenus, Nezara, Aleyrodes, Triatoma, Psylla, Myzus, Megoura,
Phylloxera, Adelges, Nilaparvata, Nephotettix or Cimex spp.), Orthoptera (for example Locusta, Gryllus, Schistocerca or Acheta spp.), Dictyoptera (for example Blattella,
Periplaneta or Blatta spp.), Hymenoptera (for example
Athalia, Cephus, Atta, Solenopsis or Monomorium spp.), Isoptera (for example Odontotermes and Reticulitermes spp.), Siphonapters (for example Ctenocephalides or Pulex spp.), Thysanides (for example Lepisma spp.), Dermapters ( for example Forficula spp.) and psocoptera (for example Peripsocus spp.) and thysanoptera (for example
Thrips tabaci).

Harmful mites include ticks, for example members of the genus Boophilus, Ornithodorus, Rhipicephalus, Amblyomma, Hyalomma, Ixodes, Haemaphysalis, Dermacentor and Anocentor, and mites and scabies such as
Acarus, Tetranychus, Psoroptes, Notoednes, Sarcoptes, Psorergates, Chorioptes, Eutrombicula, Demodex, Panonychus, Bryobia, Eriophyes, Blaniulus, Polyphagotarsonemus, Scutigerella and Oniscus spp.

The nematodes that attack plants and trees important in agriculture, forestry and horticulture, both directly and by propagating bacterial, viral, mycoplasmic or fungal plant diseases, are in particular nematodes of root scabies, such as Meloidogyne spp. (for example M. incognita); root nematodes, such as Globodera spp. (for example, G. rostochiensis); Heterodera spp. (for example H. avenae); Radopholus spp. (for example R. Similis); grassland nematodes, such as Pratylenchus spp. (for example P. pratensis); Belonolaimus spp. (e.g. B. gracilis); Tylenchulus spp. (for example T. semipenetrans); Rotylenchulus spp. (for example
R. reniformis); Rotylenchulus spp. (e.g. R. robustus) Helicotylenchus spp. (e.g. H. multicinctus); Hemicycliophora spp. (for example H. gracilis); Criconemoides spp. (for example C. similis); Trichodorus spp. (for example
T. primitivus); xiphophoric nematodes, such as Xiphinema spp. (e.g. X. diversicaudatum), Longidorus spp. (for example L. elongatus); Hoplolaimus spp. (e.g. H.

coronatus); Aphelenchoides spp. (e.g. A. ritzemabosi,
A. besseyi); and bulb nematodes, such as Ditylenchus spp. (e.g. D. dipsaci).

 The compounds of the invention can be combined with one or more other active pesticidal constituents (for example pyrethroids, carbamates and organophosphates) and / or with attractants, repellents, bactericides, fungicides, nematocides, anthelmintics And so on. In addition, it has been observed that the activity of the compounds of the invention can be increased by the addition of a synergistic or potentiating agent, for example a synergistic agent from the class of oxidase inhibitors, such as piperonylbutoxide or propyl 2-propynylphenylphosphonate, by the addition of a second compound of the invention or of a pesticidal pyrethroid. When an oxidase inhibiting synergist is present in a composition of the invention, the ratio of the synergist to the compound of formula (I) is in the range of 25: 1 to 1:25 , for example at about 10: 1.

 Stabilizers to prevent any chemical degradation that the compounds of the invention may undergo include, for example, antioxidants (such as tocopherols, butylhydroxyanisole, butylhydroxytoluene), vitamin C (ascorbic acid) and oxygen sensors ( such as epichlorohydrin), as well as organic and inorganic bases, for example trialkylamines such as triethylamine, which can act as basic stabilizers and sensors.

 The compounds of the present invention have increased pesticidal properties and / or photostability and / or reduced toxicity to mammals.

 The following examples illustrate, without limitation, preferred aspects of the invention.

EXAMPLE 1: 4- [2- (3,4-dichlorophenyl) -1-fluorocyclopropyll-N- hydroxy-N- (2-methylphenyl) -benzamide (cis isomer)
0.83 g of the product of Preparation 1 is introduced into a mixture of 40 ml of methylene chloride and 15 ml of water.

1.1 g of sodium hydrogen carbonate are added. The mixture is cooled to 0 ° C. and 1.86 g of an acid chloride solution from preparation 2 are added dropwise.

 The mixture is left to return to ambient temperature and stirred for 4 hours at ambient temperature. The reaction medium is poured onto a mixture of water and hydrochloric acid and extracted with ethyl ether. The organic phases are combined, washed with an aqueous sodium chloride solution, dried, filtered and evaporated to dryness. 2.28 g of an oil are isolated and purified by chromatography. Eluent, heptane / ethyl acetate 6-4. 1.45 g of the desired product are obtained.

Rf = 0.18.

EXAMPLE 2 4-C2- (3,4-di chlorophenyl) -lf luorocyclopropyl 1 -N- methoxy-N- (2 -methylphenyl) -benzamide (cis isomer)
0.5 g of the product of Example 1 is introduced into 15 ml of THF. It is cooled to 0 C and 65 mg of sodium hydride is added at 50 C. It is stirred for 15 minutes at room temperature and 0.10 ml of methyl iodide is added dropwise. The mixture is stirred for 3 hours at 10 C. The reaction medium is poured onto a saturated aqueous solution of potassium acid phosphate, extracted with hydrochloric ether, the organic phases are combined, washed with a saturated solution of sodium chloride, dry, filters and evaporates. 0.57 g of a product is obtained which is purified by chromatography eluting with a heptane ethyl acetate mixture 7 3. 0.33 g of the desired product is isolated. Rf = 0.17.

EXAMPLE 3 (iR, cis): (1R, cis) -4-t2- (3,4-dichlorophenyl) -1-fluorocyclo- propyll-N- (acetyloxy) -N- (2-methylphenyl) -benzamide
0.5 g of the product of Example 1 is introduced into 10 ml of methylene chloride. 0.35 ml of pyridine and 0.20 ml of acetic anhydride are added. The mixture is left stirring for 4 hours at room temperature. The reaction medium is poured onto a saturated aqueous solution of potassium acid phosphate, extracted with methylene chloride, the organic phases are combined, washed with hydrochloric acid with a saturated solution of sodium chloride, dried, filtered and evaporated. 0.29 g of a product is obtained which is washed with pentane. Dried at 30 C, isolated 0.26 g of the desired product.

F = 140 C.

Prenaration 1: 2-methyl-N-hydroxy-benzenamine
1 g of 2-methyl-nitrobenzene is introduced into 40 ml of THF.

Cooled to 0 ° C., add 0.16 of rhodium to charcoal and introduce dropwise 1.35 ml of hydrazine hydrate (64% solution). Stirred at 0 C for 30 minutes and stirred for 4 hours at room temperature. It is filtered, the catalyst is washed with ethyl ether and then with water. The filtrates are combined, extracted with ethyl ether, washed with water, dried, filtered and evaporated to dryness. 0.88 g of the desired crude product is thus obtained which is used as it is in Example 1.

NMR: Aromatic H 7.26 ppm
Methyl H 2.15 ppm
H of hydroxyl 1.6 ppm
Preparation 2: 4- [2- (3,4-Dichloro phenyl) l-fluoro cyclopropyl 1 benzoic acid
Stage A: tert-butyl 4-formyl benzoate a) 4-formyl benzoic acid chloride
15 g of commercial 4-formyl benzoic acid, 200 cm3 of dichloromethane are mixed at 0 ° C. under inert gas, then 9 cm3 of commercial oxalyl chloride and 0.2 cm3 of dimethylformamide are added, leaving 0.5 hours at 0 C then 20 hours at room temperature, brings to dry acid chloride obtained.

b) tert-butyl 4-formyl benzoate
20 cm3 of tert-butanol and 100 cm3 of pyridine are mixed at 6 ° C. under inert gas, then a solution of the residue obtained in stage a) is introduced into 200 cm3 of dimethylformamide.

After 1 hour at room temperature, the mixture is heated at reflux for 4 hours and then allowed to return to room temperature, the solvent is removed, the residue is taken up in ethyl acetate, washed and chromatography on silica. The terbutyl ester is thus obtained with a yield of 48.5 W.

TLC: Rf = 0.3 (eluent: heptane-ethyl acetate (8-2)).

Stage B: tert-butyl 4- (hydroxymethyl) benzoate
5.23 g of tert-butyl 4-formyl benzoate obtained according to stage A are mixed with 100 cm3 of tetrahydrofuran and cooled to 0 C; 1 g of sodium borchhydride is then added, the temperature is allowed to rise to 20-25 ° C., agitation is carried out for 3 hours, then hydrolysis with 100 cm 3 of a 10 W aqueous solution of ammonium chloride, extracted with acetate ethyl, wash, dry, bring to dry and chromatography on silica.

(eluent heptane - ethyl acetate (1-1)).

 5 g of the expected hydroxymethyl derivative are thus isolated.

TLC: Rf = 0.3 (eluent: heptane-ethyl acetate (1-1)).

Microanalysis: C12H1603 = 208.3
CWH t
Calculated 69.2 7.7
Found 68.9 7.8
Proton NMR in CDCl3 at 250 MHz (in ppm) 1.59 (s): CO2tBU; 2.01 (t): o-CH2-OH; 4.75 (d): bC ~ 2-OH 7.40 and 7.96 (AA'BB '): Aromatic H.

IR IN CHCl3 in cm-1 3610: OH; 1708: C = O ester; 1613-1576-1505: aromatics.

Stage C: tert-butyl 4- (fluoromethyl) benzoate
4.5 g of tert-butyl 4- (hydroxymethyl) benzoate obtained according to stage B are mixed with 100 cm3 of dichloromethane under inert gas and cooled to 0 C. Then 3.56 g of diethylaminosulfur trifluoride (C2H5) are added 2NSF3 commercial and known under the abbreviation DAST, stirred for 1 hour at 0 -5 ° C., then 1 hour at 20-25 ° C., poured onto a 10 W aqueous solution of sodium bicarbonate, dichloromethane extract, dried, brought to dry and chromatography on silica (eluent methylene chloride). 3 g of the expected fluoromethylated derivative are isolated.

TLC Rf = 0.37 (eluent: heptane-ethyl acetate (8-2)).

Microanalysis: for C12H15F02 = 210.25
C% H% pZ
Calculated 68.6 7.2 9.0
Found 68.3 7.3 9.1
Proton NMR in CDCl3 at 250 MHz (in ppm) 1.60 (s): CO2tBU; 5.43 (d, j = 47): CH2-F; 7.40 and 8.01 (AA'BB '): Aromatic H.

IR IN CHCl3 in cm-1 1712: C = O ester; 1618-1582-1512: aromatic.

Stage D: tert-butyl 4- (bromofluoromethyl) benzoate
2.3 g of tert-butyl 4- (fluoromethyl) benzoate obtained according to stage C are mixed with 30 cm3 of tetrachloromethane. 0.1 g of 2,2'-azobisisobutyronitrile, commercial and known by the abbreviation AIBN, is added thereto, 2 g of N-bromosuccinimide, then brought to reflux and irradiated for 4 hours, again added 0.2 g of AIBN , irradiates again for 4 hours, then leaves to stand for 48 hours at room temperature. After filtration and chromatography on silica, 1.7 g of the expected bromofluorinated derivative are obtained.

Fusion: 39.4 C
TLC: Rf = 0.32 (eluent: heptane-dichloromethane-tert-butyl methyl ether (90-5-5).

Microanalysis: for C12H14B2F02 = 289.15
C% HW Br% F Cc
Calculated 49.85 4.9 27.6 6.6
Found 50.0 4.9 27.4 6.9
Proton NMR in CDCl3 at 250 MHz (in ppm) 1.6 (s): CO2tBU; 7.43 (d, j = 49.5): CHB2F; 7.53-8.04 (AA'BB '): Aromatic H.

IR IN CHCl3 in cm 1 1711: C = O ester; 1613-1580-1506: aromatics.

Stage E: 4- [2- (3,4-dichlorophenyl) -fluorocyclopropyl benzoate tert-butyl benzoate
2.9 g of the product from stage D, 2.6 g of 3.4 dichlorostyrene and 7 cm 3 of toluene are mixed under inert gas. The mixture is heated to 80 ° C. and 13.5 ml of a 0.955 mol solution of sodium tert-pentoxide in toluene are introduced.

 The mixture is allowed to return to room temperature and the reaction medium is poured into an ice-cold solution of sodium hydrogen phosphate. Extraction is carried out with ethyl acetate, the organic phases are combined, dried, filtered and concentrated.

 6.74 g of crude desired product are obtained which is chromatographed on silica eluting with a heptane ethyl acetate 25-5 mixture. 0.82 g of trans product and 0.48 g of CIS product are obtained.

Stage F: 4- [2- (3,4-dichlorophenyl) 1-fluorocyclopropyl] benzoic acid (cis isomer)
1.32 g of the product from the preceding stage, 10 cm 3 of toluen and 0.15 g of paratoluenesulfonic acid are mixed. The mixture is refluxed for 2 h 30 min, allowed to return to room temperature and the reaction mixture is poured into ice water. Extraction is carried out with ethyl acetate, the organic phases are combined, dried and concentrated. 1.04 g of crude desired product are obtained.

 The acid chloride was prepared by the action of oxalyl chloride on the acid.

EXAMPLE 4
Pesticide compositions having the formula have been prepared
Soluble concentrate
A homogeneous mixture of
Active ingredient 0.25
Piperonyl butoxide 1.00
Tween 80 0.25
Topanol A 0.1
Water 98.40
EXAMPLE 5
We have prepared compositions corresponding to the formula
Emulsifiable concentrate
We mix intimately
Active ingredient 0.015
Piperonyl butoxide 0.5
Topanol A 3.5
Tween 80 0.1
Xylene 95,885
BIOLOGICAL STUDY
A) Study on Phaedon cochleariae
The product is dissolved at the desired concentration in an acetone-water mixture (50-50). Leaf discs of Chinese cabbage (Brassica pekinensis) are immersed for five seconds in the solution, then left to dry for one hour.

Ten adults (males and females mixed) are added to a Petri dish each concerning a leaf disc.

These are stored at a temperature of 25 C, with a twelve-hour photoperiod. After seven days, the mortality of the insects is controlled and the leaf area consumed is evaluated.

 The product of Example 1 exhibits good activity from the dose of 300 ppm.

B) Study on Spodoptera littoralis
The product is dissolved at the desired concentration in an acetone-water mixture (50-50). Bean leaves (Phaseolus vulgaris, var. Delinel) are immersed for five seconds in the solution, then left to dry in a box of
Kneaded for an hour. Ten larvae of Spodoptera littoralis are then added to each box. These are stored at a temperature of 25 C, with a twelve-hour photoperiod. After seven days, the larval mortality is checked and the leaf area consumed is evaluated.

 The products of Examples 1, 2 and 3 exhibit good activity from the dose of 100 ppm.

C) Study on Heliothis virescens
The product is dissolved at the desired concentration in an acetone-water mixture (50-50). 50y1 of solution are deposited on the surface of a small well containing about 2 grams of plant-based artificial medium. A neonate larva of
Heliothis virescens is then introduced into each well, which is closed with a cellophane sheet. The tests are stored at a temperature of 25 ° C. with a twelve hour photoperiod. The larval mortality is checked after seven days.

 The products of Examples 1 and 2 exhibit good activity from the dose of 300 ppm.

Claims (21)

1.- In all their stereoisomeric forms or in the form of mixtures of these stereoisomers, the compounds of formula (I)  Q- (CH2) a (Xî) b-Qî-Q2-C (X2) -N (R1) (R2) (I) in which Q represents an aryl radical or a radical derived from a condensed bicyclic hydrocarbon comprising a benzene ring, which is linked to the adjacent group (CH2) a by a carbon atom of said benzene ring, Q comprises from 6 to 12 carbon atoms and can be either unsubstituted or substituted, a and b are identical or different and are, independently of one another, equal to 0 or 1, X1 represents a bivalent oxy, thio, sulfinyl or sulfonyl radical, X2 represents an oxygen atom or a sulfur atom, Q1 represents a cyclopropanediyl radical, which is either unsubstituted or substituted. Q2 represents an arylene radical or a radical derived from a condensed bicyclic hydrocarbon comprising a benzene ring, which is linked to the adjacent groups Q1 and C (X) 2 by two carbon atoms of the said benzene ring, Q2 contains from 6 to 12 atoms carbon and may independently of Q, be either unsubstituted or substituted. R1 represents either a hydrogen atom or a radical derived from a cyclic or acyclic hydrocarbon, aromatic or non-aromatic, linear or branched, saturated or unsaturated, and comprising from 1 to 12 carbon atoms, itself being either unsubstituted, either substituted, or a radical derived from a linear or branched structure comprising from 1 to 20 carbon atoms and from 1 to 6 heteroatoms chosen from oxygen, nitrogen or sulfur atoms, itself capable of be either unsubstituted or substituted, or a radical derived from an aromatic or non-aromatic heterocycle containing from 5 to 9 carbon atoms and from 1 to 4 heteroatoms chosen from oxygen, nitrogen or sulfur atoms, this radical can be unsubstituted or substituted.  in which X3 represents an oxygen atom or a sulfur atom, and R3 represents a hydrogen atom or a group R4- (T1) i in which i is equal to 0 or to 1, T1 represents a bivalent oxy group, carbonyl or oxycarbonyl and R4 represents a hydrogen atom or a radical derived from a cyclic or acyclic hydrocarbon, aromatic or non-aromatic, linear or branched saturated or unsaturated, and comprising from 1 to 20 carbon atoms, itself possibly being either unsubstituted or substituted.

R2 represents a group WZ in which - either W and Z can together form a nitrogen ring linked to the nitrogen atom of the radical N (R1) (R2) by the nitrogen atom and can contain one or more other heteroatoms chosen from oxygen, nitrogen and sulfur, which may contain one or more other unsaturations and which may be optionally substituted, - either W represents an oxygen atom or an NH or N alkyl radical containing up to 8 carbon atoms and Z represents a hydrogen atom, a linear or branched, saturated or unsaturated alkyl radical containing up to 8 optionally substituted carbon atoms, ie a group (A)  in which n represents the number 0 or 2, y represents an alkyl radical containing up to 2 carbon atoms.

 in which R3 and X3 are as defined above or a group (C)

or a group (B) 2.- The compounds of formula 1 defined in claim 1 in which a and b represent the number 0. 3.- The compounds of formula 1 defined in claim 1 or 2 in which Q is unsubstituted or substituted by one or more substituents chosen from halogen atoms or methylenedioxy, difluoromethylenedioxy, tetrafluoroethylenedioxy, cyano, nitro, cyanato groups, thiocyanato, pentafluorothio, fluorosulfonyl or R- (T) C- in which R represents a hydrogen atom or a radical derived from a cyclic or acyclic hydrocarbon, aromatic or non-aromatic, linear or branched, saturated or unsaturated, and comprising of 1 to 8 carbon atoms, itself being either unsubstituted or substituted by one or more halogen atoms, c is equal to O or to 1 and T represents a bivalent oxy, carbonyl, carbonyloxy, oxycarbonyl, thio group , sulfinyl, sulfonyl, or sulfonyloxy, - (CO) dN (R ') - (CO) e- (O) f- or -N (R ") - S (O) g- in which R' and R" represent independently of R a hydrogen atom, or a radical derived from a cyclic hydrocarbon ic or acyclic, aromatic or non-aromatic, linear or branched, saturated or unsaturated, and containing from 1 to 8 carbon atoms, itself being either unsubstituted or substituted by one or more halogen atoms, d, e and f are equal to 0 or 1, f is equal to 0 when e is equal to 0, the sum e + d is equal to O or to 1 and g is equal to 0, to 1 or to 2. Q1 is unsubstituted, or substituted by one or more substituents chosen from halogen atoms, cyano, azido, or aliphatic, saturated or unsaturated radicals containing from 1 to 4 carbon atoms unsubstituted or substituted by one or more atoms of halogen and Q2 is unsubstituted or substituted by one or more substituents chosen from halogen atoms or methylenedioxy, difluo romethylenedioxy, tetrafluoroethylenedioxy, cyano, nitro, amino, alkylamino, alkenylamino, cyanato, thiocyanato, pentafluorothio, fluorosulfon groups R- (T) C- in which R represents a hydrogen atom or a radical derived from a cyclic or acyclic hydrocarbon, aromatic or non-aromatic, linear or branched, saturated or unsaturated, and comprising from 1 to 8 carbon atoms , itself being either unsubstituted or substituted by one or more halogen atoms, c is 0 or 1 and T represents a bivalent oxy, carbon group yl, carbonyloxy, oxycarbonyl, thio, sulfinyl, sulfonyl, or sulfonyloxy, - (CO) dN (R ') - (CO) e- (O) f- or -N (R ") S (O) in which R' and R ", d, e, f and g are as defined above. 4.- The compounds of formula (I) as defined in claim 1, 2 or 3 in which Q is a phenyl radical or a naphthyl radical, unsubstituted or substituted by 1 to 3 substituents. 5.- The compounds of formula (I) as defined in claim 4 in which Q represents a radical chosen from phenyl, 2-chloro phenyl1 3-chloro phenyl, 3bromophenyl, 3 - (trifluoromethyl) phenyl, 4-chloro radicals phenyl, 4-bromo phenyl, 4-iodo phenyl, 4- (trifluoromethyl) phenyl, 4-nitrophenyl, 4-methoxy phenyl, 4 - (difluoromethoxy) phenyl, 4- (trifluoromethoxy) phenyl, 3-bromo 4- (difluoromethoxy) phenyl, 4- (2,2-dibromo ethenyl) phenyl, 4-ethynyl phenyl, 4-benzyl phenyl, 3,4-dibromo phenyl, 2,4-dichloro phenyl, 3,4-dichloro phenyl, 3,4-difluorophenyl , 3-chloro 4-iodo phenyl, 4-bromo 3-chloro phenyl, 4-bromo 2-fluoro phenyl, 4-bromo 3 fluoro phenyl, 4-bromo 3- (trifluoromethyl) phenyl, 4-chloro 3- (trifluoromethyl) phenyl, 3,5-bis ((trifluoromethyl) phenyl, 3,4,5-trichloro phenyl, 4-bromo 3,5-dichloro phenyl, 3-phenoxyphenyl, 4- (fluoro 3 -phenoxy) phenyl, 3-bromo 4 - (trifluoromethylsulfonylo xy) phenyl, 3,4-bis (trifluoromethylsulfonyloxy) phenyl, 2-naphthyl or 5-bromo 2naphthyl or 6-bromo 1-naphthyl. 6.- The compounds of formula (I) as defined in any one of claims 1 to 5 in which the steric configuration of Q1 is such that the group Q- (CH2) a- (Xl) b- is in position trans with respect to the group Q2-C (X2) -N (R1) (R2). 7.- The compounds of formula (I) as defined in any one of claims 1 to 6 in which Q1 is unsubstituted or substituted by 1 or 2 halogen atoms or 1 or 2 methyl radicals. 8.- The compounds of formula (I) as defined in claim 7 in which Q1 represents a radical chosen from 1,2-cyclopropanediyl, l-fluoro 1,2-cyclopropanediyle, l-chloro 1,2-cyclopropanediyle radicals , l-bromo 1,2cyclopropanediyle, methyl 1,2 - cyclopropanediyle, 3,3dibromo 1,2-cyclopropanediyle and 1,2-difluoro 1,2-cyclopropanediyle. 9.- The compounds of formula (I) as defined in any one of claims 1 to 8 in which Q2 represents one of the ortho-phenylene, meta-phenylene, paraphenylene, 1,2-naphthylene, 1,3-naphthylene radicals , 1,4-naphthylene, 1,5-naphthylene, 2,5-naphthylene, 4,5-indenylene, 4,6-indenylene, 4,7-indenylene, 1,2,3,4-tetrahydro 5,6- naphthylene, 1,2,3,4-tetrahydro 5,7-naphthylene, 1,2,3,4-tetrahydro 5,8naphthylene, unsubstituted or substituted by 1 to 4 substituents. 10.- The compounds of formula (I) as defined in any one of claims 1 to 9 in which Q2 represents one of the radicals 2-methyl 1,4-phenylene, 2,3,5,6-tetrafluoro 1,4 -phenylene, 3-methyl 1,4-phenylene, 2-chloro 1,4phenylene, 2-acetylamino 5-chloro 1,4-phenylene, 2-amino 5chloro 1,4-phenylene, 2-dimethylamino 5-chloro 1,4 -phenylene.  11.- The compounds of formula (I) as defined in any one of claims 1 to 10 in which R1 represents an optionally substituted aryl radical. 12.- The compounds of formula (I) as defined in any one of claims 1 to 11 in which W represents an oxygen atom. 13.- The compounds of formula (I) as defined in any one of claims 1 to 12 in which Z represents a hydrogen atom, an alkyl or Co2 alkyl radical containing up to 18 carbon atoms. 14.- The compounds of formula (I) defined in claim 1 corresponding to formula (IA)

 in which Z retains its previous meaning, the phenyl rings possibly being substituted by one or more substituents, chosen from halogen atoms and the alkyl radicals will contain up to 4 linear, branched or cyclic, saturated or unsaturated carbon atoms, optionally substituted by one or more halogen atoms. 15.- The compounds of formula I defined in claim 1, the following names: - 4- [2- (3,4-dichlorophenyl) -1-fluorocyclopropyl] -N-hydroxy-N (2-methylphenyl) -benzamide ( cis isomer), - 4- [2- (3,4-dichlorophenyl) -1-fluorocyclopropyl] -N-methOxy-N- (2-methylphenyl) -benzamide (cis isomer) - 4- [2- (3,4 -dichlorophenyl) -1-fluorocyclopropyl) -N- (acetyloxy) -N- (2-methylphenyl) -benzamide (cis isomer). 16.- A process for preparing the compounds of formula (I) as defined in any one of claims 1 to 15 characterized in that the acid or the corresponding acid derivative of formula (II) Q- (CH2) a (Xl) b-Ql-Q2-C (O) -Z (II) in which Q, X1, a, b, Q1 and Q2 are as defined in claims 1 to 12 and Z represents a hydroxy group, a halogenated group, an alkoxy radical containing from 1 to 4 carbon atoms or a group -P (O) (OO) -NHb, in which b represents a phenyl group, is reacted with an amine of formula (III)  HN (R1) (R2) (III) in which R1 and R2 are as defined above to obtain a product of corresponding formula (I), in which X2 represents an oxygen atom which, if necessary, is converted into a product of formula (I) in which (X2) represents a sulfur atom, then optionally functionalizes the OH group in the case where R2 represents a hydroxyl group in order to obtain the desired compound of formula I. 17.- As a new chemical, the compound of formula (III) defined in claim 16 whose name follows 2-methyl N-hydroxy-benzeamine. 18. Use of the compounds of formula (I) as defined in any one of claims 1 to 15 as pesticides, in particular as insecticides, acaricides and nematicides in the protection of crops, especially rice crops and cotton, or for the treatment of storage places for products of said crops and in particular as insecticide or acaricide in domestic or public premises. 19. A pesticidal composition comprising a) a compound of formula (I) as defined in any one of claims 1 to 15, b) excipients suitable for use as a pesticide of said product of formula (I). 20.- Pesticide composition comprising a) a compound of formula (I) as defined in any one of claims 1 to 15, b) inert excipients suitable for use in the veterinary field of said product of formula (I) . 21.- Compound of formula (I) as defined in one of claims 1 to 15, for the implementation of a method of treatment of the human or animal body characterized in that a pharmaceutically acceptable formulation of said compound is applied to said body.