FR2531074A1 - Pesticide and process for its preparation and for its use. - Google Patents

Abstract

Pesticide compounds of formula: in which: D denotes hydrogen or a cyanogen or ethynyl group, B denotes hydrogen or an alkyl or alkenyl group, A denotes an alkyl group or a halogen group or a CF3 group, n is equal to 0 or to an integer between 1 and 4, RCOO being the residue of an acid RCOOH which is a 2,2-dimethylcyclopropanecarboxylic acid carrying a dihalovinyl, an alkenyl or an alkoxycarbonylalkenyl group in position 3, on condition that when the -CH2CH=CHB group is situated in position 4 on the ring in relation to the ester bond, D must then be hydrogen and the group arranged in position 3 on the cyclopropane ring of the acid must be a -CH2CH=CHB is arranged in position 3 on the ring and that D is a CN group, n must then be equal to 0. [sic]

Description

Pesticide and methods for its preparation and for its use The invention relates to pesticides and in particular pesticide compounds, the preparation of such compounds, to intermediates which can be used for their preparation, of compositions containing such compounds and the use of such compounds and compositions for control insects, for example insects in the soil.

dans laquelle
D représente llhydrogène ou un groupe cyanogène ou un groupe ithynyle,
B représente lDhydrogèneR un alkyle ou un aikényle;
A représente un groupe alkyle (typiquement an groupe alkyle
eh C1 à C6 > ou un groupe halogène, par exempe F, c-I ou
Br ou un groupe CF3; n est compris entre 0 et 4;
RCOO est le-résidu d'un acide 2,2-diméthylcyclopropane-
carboxylique portant en position 3 un dihalogénovinyle,
un alkényle ou un groupe carboalkoxyalkényle; à condition que (1) lorsque le groupe -CH2CH=CHB est disposé sur le cycle en position 4 par rapport à la liaison ester,
D soit alors de l'hydrogène et le groupe disposé en position 3 sur le cycle cyclopropane de l'acide doit être un groupe dihalogénovinyle et (2) lorsque le groupe -CH2CH=CHB est disposé sur le cycle en position 3 et D représente un groupe cyanogène-, n doit etre alors égal à 0. The invention provides a compound of formula (I):

in which
D represents hydrogen or a cyanogenic group or an ithynyl group,
B represents hydrogen, alkyl or akenyl;
A represents an alkyl group (typically an alkyl group
eh C1 to C6> or a halogen group, for example F, cI or
Br or a group CF3; n is between 0 and 4;
RCOO is the residue of a 2,2-dimethylcyclopropane acid
carboxylic bearing in position 3 a dihalogenovinyl,
an alkenyl or a carboalkoxyalkenyl group; provided that (1) when the group -CH2CH = CHB is placed on the ring in position 4 relative to the ester link,
D is then hydrogen and the group placed in position 3 on the cyclopropane ring of the acid must be a dihalogenovinyl group and (2) when the group -CH2CH = CHB is placed on the ring in position 3 and D represents a cyanogenic group-, n must then be equal to 0.

 When the group placed in position 3 on the cyclopropane ring is an alkenyl or a carboalkoxyalkenyl, the alkenyl is an alkmonoenyl, usually branched, such as isobutenyl or 2-methoxyvarbonylpropenyl, so that the preferred acid residue of this type is that of chrysanthemic acid, especially when it is in the trans form and in particular in the form (IR, trans) or pyrethric acid.

The preferred acids are 2,2-dimethyl-3- (2,2-dihalo genovinyl) -cyclopropanecarboxylic, 2,2-dimethyl-3- (2,2-dibromovinyl) -cyclopropanecarbonylic acid, especially in the form ( IR, cis), being particularly interesting.

When B represents an alkyl or an akenyl group, the configuration in the vicinity of the double bond of the substituent group -CH2CH = CHB may be in the E or Z form and the compounds in which the configuration is in Z form are preferred as are mixtures of geometric isomers in which the Z-form isomer predominates. The compounds in which B represents methyl, ethyl or vinyl, are particularly interesting, especially
this last. The preferred position on the cycle relative
to the ester bond for the substituent group -CH2CH = CHB
is position 3 or 4, position 3 for compounds in
which D represents a cyanogenic group being particularly interesting.

Group A, when present, is. typically arranged in position 2 on the ring with respect to the ester bond and, when it is alkyl, generally represents methyl. Two groups, for example methyl groups, when they are present, are usually placed on the ring in positions 2 and 6 with respect to the ester bond. Such compounds are particularly advantageous when B, in the group -CH2CH = CHB represents hydrogen, the group preferably being placed on the ring in position 3 or 4.

dans laquelle Y représente le groupe hydroxyle ou un halogène, par exemple le chlore et De A, n et B sont comme définis ci-dessus.As described above, the esters (I) of 2,2-dimethyl-3- (dihalyogenovinyl) -cyclopropanecarbonylic acid, typically an acid in which the two halogens, which are fluorine, chlorine or bromine are identical, are preferred and especially the esters of 2, 2-dimethyl-3- (dibromovinyl) -cyclopropanecarboxylic acid. The following esters of the latter acid, especially when they are in the form (IR, cis), are particularly interesting o a-cyano-3-allyl-benzyliques (D = CN, B = H); α -cyano-3-methylallyl-benzyliques (D = CN, B = CH3); 3-methylallyl-benzyls (D = H, B = CH3); 3-pentadienyl- and 4-pentadienyl-benzyls (D = H, B = -CH = CH2); a-cyano-3-pentadienylbenzyls, α (D = CN,
B = -cyano-3-ethylallyl-benzyls 2-methyl-3-allylbenzyls (D = H, B = H, A = CH3 n = 1) 2,6-dimethyl-4-allyl-benzyls (D =, B = H, -CH2CH3); n = 2) and luron will particularly prefer that the latter omposed, when possible, exist in the form
Esters A = CH3 can be prepared by reaction of an acid
RCOOH or an esterifiable derivative thereof with an intermediate of formula (II)

in which Y represents the hydroxyl group or a halogen, for example chlorine and De A, n and B are as defined above.

Intermediaries of formula (II) are also included in a second aspect of the present invention, provided that (1), when the group -CH2CH = CHB is placed on the ring in position 4 relative to the group -CHDY, D must then be hydrogen and B must be alkyl or alkenyl and the configuration in the vicinity of the double bond in the group must be of form Z, and so far.

that (2), when the group -CH2CH = CHb is placed in position 3 relative to the group -CHDY and D represents a cyanogenic group, n must then be equal to 0
It is generally preferred that the configuration in the vicinity of the double bond in the intermediates of formula (II) is of form Z and the following compounds are particularly interesting (a) (II), D = H, n = 0, B- - CH = CH2, Z-isomer, position 3
on cycle (b) (II), D = H, n = 0, B = -CH = CH2, isomer E, position 3
on cycle (c) (Il), D = CN, n = 0, B = -CH = CH2, Z isomer, position 3
on cycle (d) (II), D = H, n = 0, B = -CH = CH2, Z isomer, position 4
on cycle (e) (II), D = H, n = O, B = -CH3, Zp isomer position 3 on the
cycle (f) (II), D = CN, n = 0, B = -CH3, Z isomer, position 3 on the
cycle (g) (II), D = CN, B = -CH2CH3, Z isomer, position 3 on the
cycle (h) D = H, n = 1, A = CH3 position 2 on the cycle, B = II in position 3. In these latter compounds, Y-typically represents a hydroxyl group.

The production of intermediates of formula (II) in which n = 0 is illustrated by the following reaction schemes.

Intermediaries in which n = 1 to 4 can be obtained from the appropriate reagent substituted in the ring.

The cyanohydrins or the intermediate ethynylic compounds ((II), Y = OH, D = CN or C = CH) are generally obtained from the corresponding aldehydes by treatment of the latter with an alkali metal cyanide in an acid medium or using an acetylide. magnesium. The necessary aldehydes are usually obtained by oxidation with pyridine dichromate of the corresponding alcohols obtained by methods analogous to those which are represented in the diagrams above.

The intermediates of formula (II) in which Y represents a halogen and D represents hydrogen can be obtained from intermediates of formula (II) in which Y represents the radical -OH and D represents the hydrogen, in accordance with another aspect of the present invention by treatment of these latter intermediates with a duhalogenation reagent of the class used to convert the carboxylic acids to acyl halides, for example SO (hal) 2, typically with pyridine or P (hal) 3 , hal representing chlorine or bromine
As described above, the compounds of the present invention can be prepared by an esterification involving the reaction of an alcohol of formula (II) or of an esterifiable derivative thereof with a carboxylic acid of formula
RCOOH or an esterifiable derivative thereof. It is so convenient in practice to react an alcohol of formula (with a chloride of Formula RCOCl chloride or to react a salt of the carboxylic acid, for example a silver salt or a triethylammonium salt with a derivative of 'benzyl halogen, or a cyanobenzyl halide which can be ring-alkylated or esterified with carboxylic acid with alcohol in the presence of N, N-dicyclohexyl-carbodiimide and a catalyst.

Alternatively, the esters of the invention can be prepared by transesterification by reacting a C1 to C6 alkyl ester of lucid carboxylic with a benzyl alcohol of formula (II) in the presence of a basic transesterification catalyst. This process is usually not satisfactory when one or the other of the molecules contains another residue sensitive to bases, for example when the carboxylic acid is pyrethric acid.

The compounds according to the invention exhibit an optical isomerism in that the carbon atom carrying the substituent D can exist in the R form or the S form and the present invention encompasses the compounds in which the configuration is practically totally of R form or in which the configuration is practically totally S-shaped or mixtures thereof.

The compounds according to the invention can exist in the form of both geometric and optical isomers. The cause is the asymmetric substitution in C1 and C3 on the cyclopropane ring. The compounds of the present invention include those of these isomers in which the C1 and C3 hydrogen atoms on the cyclopropane ring are substantially completely in the cis configuration or substantially completely in the trans configuration or their mixtures.

The present invention also includes compounds in which the C1 configuration is almost completely R or almost completely S and mixtures thereof. In the compounds of the invention, the optical configuration in C1 and C3 cannot vary independently of the geometric configuration of the hydrogen atoms in C1 and C3 on the cyclopropane ring.

As a result, the configuration of the cyclopropane ring can be defined only by specifying the optical configuration in C1 and the geometric configuration of the hydrogen atoms in
C1 and C3 and, for definition purposes, we have adopted a nomenclature of the form (IR) -cis, (IR) -trans, etc., the indication of the optical configuration in C # is not necessary because it is set when the other two variables are defined. The adoption of this nomenclature avoids the confusion which could arise if one designated by R or S the same optical configuration in C3 according to the nature of the substituents of the cyclopropane cycle and even those of the side chain.

When R is a group in which the substitution on the ethylenic bond is acymetric, the configuration of this part of the molecule can then be practically completely in the E form or practically completely in the Z form or a mixture of these
The compounds of the present invention may be in the form of the single isomers but, in view of the fact that the compounds have at least one center of asymmetry and often more than one, the compounds of the invention are normally in the form of mixtures of isomers, although these mixtures of isomers can be optically active and / or practically completely in a single geometric form.

One or more of the pesticidal esters of formula I can be formulated with an inert carrier or diluent to give pesticidal compositions and such compositions constitute another aspect of the present invention. These compositions can be in the form of lungs and granular solids, wettable powders, mosquito coils and other solid preparations, or of emulsions, emulsifiable concentrates, liquids to be sprayed and aerosols and other liquid preparations after addition of suitable solvents, diluents and surfactants.

The compositions suitably formulated for controlling soil insects, in particular by treating the soil, are particularly advantageous. For this application, the compositions containing the compounds I described above are particularly suitable because they generally have lower molecular weights than many of the pyretbroldes described above, and it is envisaged that their relatively high vapor pressures allow them to diffuse through the soil.

The pesticidal compositions of the invention normally contain from 0.001 to 252 by weight of the compound of formula I but the compositions may contain higher concentrations of active ingredients of formula I, for example up to 95 for the compositions sold in the form of concentrates to dilute before use by the end user.

The compositions of the invention may contain diluents such as hydrocarbon oils, for example xylene or other petroleum fractions, water, anionic, cationic or nonionic surfactants, antioxidants and other stabilizers as well as perfumes and dyes. The type and proportions of these inert ingredients can be those traditionally used in pesticidal compositions containing compounds of the genus pyrethro i.

In addition to these inactive ingredients, the compositions of the present invention may contain one or more other active ingredients which may be other pesticidal compounds of the pyrethroid type or of other types and the composition may also include synergists of the type capable in known manner of 'enhance the activity of natural pyrethrin and pyrethroid insecticides. Synergists of this type include piperonyl butoxide, tropital and sesame.

The compounds of formula I can be used to fight against insect invasions in the domestic, horticultural, agricultural and medical fields, including veterinary. The compounds or compositions of the invention can be used to combat insect invasions by treating insects or surfaces or environments liable to be infested by insects with effective amounts of active compounds of the Bizou formula of compositions containing them .

For example, they can be used in a domestic environment to vaporize rooms and fight invasions of flies or other insects, they can be used to treat crops or dry cereals stored to fight invasions of insects or others, they can be used to spray standing crops, for example cotton or rice, to combat common insect invasions and they can be used in the medical or veterinary field, for example in livestock sprays to prevent or treat invasions of insects or others
Although, as indicated above, they are particularly advantageous for the treatment of soils with a view to controlling insects such as Delia antiqua, or Delia Coare tata, the compounds can find application in the control of a wide variety of insects including those of the class of Isopods, for example Oniscus asellus,
Armadillidium vulgare and Porcellio scaber; of the Diplopod class, for example Blaniulus guttulatus; of the class of Chilopods, for example Geophilus carpo phagus and Scutigera aspect; of the Symphylae class, for example Scutigerella immaculata; of the order Thysanoures, for example Lepisma saccharina; of the order of Collemboles; for example Onychiurus armatus; Orthopters, for example Biatta orientalis,
Periplaneta americana, Leucophaca madarae, Blattela germanica,
Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Helanoplus differentialis and Schistocerca gregaria;
of the order Dermaptera, for example Forficula auricuiaria;
of the order Isoptera, for example Reticulitermes spp. ;
of the order of Anoploures, for example Phylloxera vastatrixr
Pemphigus spp., Pediculus humanus corporis, Haematopinus spp.

and Linognathus spp. ;
of the order Mallophages, for example Trichodectes spp
and Demalinea spp .;
of the order of the Thysanoptera, for example Hercinothrips
femoralis and Thrips tabaci;
of the order Heteroptera, for example Eurygaster spp.,
Dysdercus intermedius, Piesma quadrata, Cimex lectularius,
Rhodnius prolius and Triatoma spp. ;;
of the order Homoptera, for example Aleurodes brassicae,
Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii,
Breuvicoryne brassicae, Cryptomyzus ribis, Doralis fabae,
Dorais pomi, Eriosoma lanigerum, Hyalopterus arundinis,
Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopaio
siphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix
cincticeps, Lecanium corni, Saissetia oleae, Laodelphax
striatellus, Nilaparvata lugens, Aondiiella aurantii, Aspidiotus hederae, Pseudococcus spp D -and Psylla spp. ;;
of the order Lepidoptera, for example Pectinophora
gossypiella, Bupalus piniarius, Cheimatobia brumata,
Lithocolletis blancardella, Hyponomeuta padella, Plutella
maculipennis, Malacosoma neustria, Euproctis chrysorrhoea,
Lymantria spp., Bucculatrix thurberiella, Phyllocnistis
citrella, Agrotis app., Euxoa spp., Feltia spp., Earlas insulana, Helitothis spp., Laphygma exigua, Mamestra brassicae,
Panolis flammea, Prodenia litura, Spodoptera spp., Trichlo plusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp.,
Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella,
Cacoecia podana, Capua reticulana, Cnoristoneura fumiferana,
Clysia ambiguella; Homona magnanima and Tortrix viridana; of the order Beetles, for example Anobium punctatum,
Rhizopertha dominiéa, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atinusus spp.
Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp.,
Anthrenus spp., Attagenus spp, Lyctus spp., Meligether aeneu:
Ptinus spp., Niptus holoeucus; Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp.,
Melolontha melolntha, Amphimallon solstitialis and Costelytra zealandica; the order of Hymenoptera, for example Diprion spp
Hoplacampa spp., Lasius spp., MOnomorium pharaonis and Vespa spp. ; of the order Diptera, for example Aedes spp ,, Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp.,
Fannia spp., Calliphora erythrocephala, Lucilia spp.,
Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp D Stomoxys spp., Oestrus spp, Hypoderma spp.
Tabanus spp., Tannia spp., Bibio hortulanus, Fried Osicinella,
Phorbia spp., Pegomyia hyoscyami, Ceratitis capita, Dacus oleae and Tipula paludosa; of the order Siphonoptera, for example Xenopsylla cheopi.

and Ceratophyllus spp., from the Arachnid class, for example Scorpio maurus and
Latrodectus mac tans; of the order of the Mites, for example Acarus siro, Argas app.

Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis,
Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp.,
Amblyomma spp. Hyalomma spp., Ixodes spp., Pscroptes spp.,
Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp.- and Tetranychus spp.

The invention is illustrated by the examples below.

The temperatures are in OC.

Pesticide activity is assessed for houseflies and watercress beetles using the following techniques
House flies (Musca domestica)
Female flies are treated on the chest with a drop of a microliter of insecticide dissolved in acetone. Two samples of 15 flies are used for each dose and 6 doses per test compound. After treatment, the flies are kept at a temperature of 200 + 10 and the destruction is evaluated 24 and 48 hours after treatment. The LD50 values are calculated in micrograms of insecticide per fly and the relative toxicities are calculated as an inverse function of the LD50 values (see-Sawicki et al., Bulletin of the
World Health Organization, 35, 893 (1966) and Sawicki et al.,
Entomologia and Exp.Appli. 10, 253 (1967)).

Watercress beetles (Phaedon cochleariae Fab)
Solutions in acetone of the compounds to be tested are applied to the belly of adult beetles using a microdrop applicator. The treated insects are kept for 48 hours, after which the destruction is assessed. Two samples of 40 to 50 beetles are used for each dose and 5 doses for each compound. The LD50 values are again calculated and the relative efficiencies are calculated as an inverse function of LD50 (see Elliott et al.,
J. Sci.Food Agric. 20, 561 (1969))
The relative efficiencies are calculated by comparison with the (IR) - 5-benzyl-3-furylmethyl trans-chrysanthemate (Bioresmethria), which is one of the most toxic known chrysanthemum esters in respect of house flies and watercress, its toxicity being approximately 2 times that of allethrin for houseflies and 65 times that of allethrin for watercress beetles.

The invention is illustrated by the examples below
EXAMPLE 1 (IR) cis-3- (2,2-dibromobinyl) -2,2-dimethylcyclopropane carboxylate of 3- (2E, 4-pentadienyl) benzyl (a) Grignard reagent from 3-bromobenzal acetal-
ethylene dehyde
Covered with 10 ml of THF 0.74 g of dry magnesium placed under dry nitrogen in a flask and a dipod crystal is added. Adding 5 ml gives a solution of 7.0 g of acetal of 3-bromobenzaldehyde ethylene in 30 ml of THF maintained until it warms up, after which it is cooled to 150C, and the rest of the solution is added. acetal over a period of 15 min, after which the mixture is stirred for an additional 1 hour.

(b) 3 (2E, 4-pentaldienyl) benzaldehyde
Grignard reagent of 3-bromobenzaldehyde ethylene acetal (3.0 g) is added to a mixture of 2.2 g of 1-bromo-2E, 4-pentadiene, of 0.02 g of copper bromide (I ) and 20 ml of THF cooled to -20 C. The mixture is then allowed to warm to 200C while stirring for 1 hour.

The mixture is treated as usual by adding ammonium chloride and HPLC. Yield 0.05 g (22%), n20 1.5723.

D (c) 3 (2E, 4-pentadienyl) benzyl alcohol
0.50 g of the aldehyde in ether are added to 0.08 g of lithium aluminum hydride in 20 ml of ether and the mixture is stirred at 20 ° C. for 1 hour. After having successively added dropwise 80 l of water, 80 ssQ of NaOH at 15 t and 240 l of water, the clear ether layer is evaporated (plus washes) in an alcohol residue 3- (2E, 4-pentadienyl) benzyl.

Yield 0.48 g (95%), n20 1.5654.

(d) (IR) cis-3 (2,2-dibromovinyl) -2,2-dimethylcyclopropane
3- (2E, 4-pentadienyl) benzyl carboxylate
0.11 g of alcohol in 5 ml of benzene is added to 0.20 g of cis-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarbonyl (IR) chloride in 5 ml of benzene. 0.075 ml of pyridine is then added and the mixture is stirred at 200C for 16 hours. This is run by chromatography on florisil and the fraction eluted with 7% ether in gasoline is evaporated to a residue of the title compound. Yield 0.20 g (70%), n20 1.5769.

EXAMPLE 2 (IR) cis-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropane carboxylate of 3- (2z, 4-pentadienyl) benzyl ga) Acetal of 3,3- (2-propynyl) benzaldehyde ethylene cover with 10 ml of THF 0.74 g of dry magnesium placed under dry nitrogen in a flask and an iodine crystal is added.

5 ml of a solution of 7.0 g of acetal of 3-bromobenzaldehyde ethylene in 30 ml of THF are added and after having allowed to heat, the mixture is cooled to 150C, and the remainder of the acetal solution is added over a period of 15 min, after which the mixture is stirred for an additional 1 hour. A mixture of 2.55 g of methoxyallene, 0.30 g of copper (I) chloride and 30 ml of THF is cooled to -200C. The above Grignard solution is then added (under conditions excluding humidity) to this solution for 5 min, and the mixture is left to warm up to 200C with stirring for 30 min. A saturated aqueous solution of ammonium chloride is added and the product is extracted with ether. The ether layer is washed with water, dried (MgSOa) and the residue is distilled under vacuum.

Yield 4.3 g (75%), 89-96 (0.03 m Hg), 1.5422.

 nD (b) Acetal of 3 (bent-4-en-2-ynyl) benzaldehyde ethylene 0.10 g of copper iodide - (I), 0.6-0 g of pallet tetrabistriphenylphosphine - (0) and 1.6 ml of n-butylamine are added to a solution of 2.0 g of acetylene acetal in 50 ml of benzene at 10 C. 5 ml of vinyl bromide are added and the mixture is stirred at 20 ° C. for 16 hours. It is evaporated off under reduced pressure, the residue is extracted with carbon tetrachloride and passed by chromatography on florisil. The fraction eluted with 10% ether is collected in gasoline. Yield 1.9 g (83%), n20 1.5610.

(C) 3- (2Z, 4-pentadienyl) benzaldehyde
1.9 g of acetal enyne are stirred with 75 g of zinc powder and 6.5 g of potassium cyanide in a 1/1 mixture of 250 ml of t-propanol and water at 200 ° C. under nitrogen for 16 hours. The mixture is then filtered through celite and the filtrate is partitioned between ether and water. The organic layers are washed with a saturated aqueous solution of NaCl, then dried (MgSO4) The residue is taken up in benzene (20 ml) and 0.10 g of tetracyanoethylene is added. The mixture is stirred at 200 ° C. for 15 min and then passed through a column of florisil. The fraction eluted with 10% ether in gasoline is collected. The residue is hydrolyzed by treatment with 3N HCl and the product is purified by HPLC.

Yield 0.23 g (-15%), nD 1.5613.

(d) 3 (2Z, 4-pentadienyl) benzyl alcohol
The aldehyde is reduced to alcohol by means of aluminum and lithium hydride, following the procedure of Example 1 (c).

(e) (IR) cis-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropane
3 (2Z, 4-pentadienyl) benzyl carboxylate
The alcohol is esterified following the procedure of Example 1 (d) to release the ester. Yield 88%, nD 1,
EXAMPLE 3 (IR) cis-3-dibromovinyl -2,2-dimethylcyclopropane carboxylate of 3- (Z, 2-butenyl) benzyl (a) 3 (2-butynyl) benzaldehyde 1.5 g of acetylenic acetal of example 2 (a) in 10 ml of THF is cooled to -780C under nitrogen. A mixture of 5.1 ml, 1.55 m of n-butyl lithium (in hexane) and 7 ml of THF is added dropwise for 5 min, and the mixture is stirred at -780C for 30 min. A mixture of 2.3 g of methyl iodide and 4 ml of THF is then added for 2 min and the reaction mixture is allowed to heat to 200C with stirring for 1 hour. A saturated aqueous ammonium chloride solution is added and the organic layer is evaporated under reduced pressure until an acetal residue of 3 (Z, 2-butynyl) benzaldehyde ethylene is obtained. This is dissolved in 20 ml of THF and treated with 10 ml of 3N HCl at 200C for 1 hour. The product is separated between ether and water, and the ether layer is washed with an aqueous solution of NaHCO3 and water, then dried (MgSO4). The residue is purified by preparative HPLC.

Yield 1.13 g (90%), n20 1.5575.

(b) 3- (Z, 2-butenyl) benzaldehyde 0.50 g of acetylenic acetal of Example 3 (a) is dissolved in 15 ml of pyridine 0.10 g of palladium is added to barium sulphate and the mixture is stirred under an atomosphere of hydrogen $ until the absorption of hydrogen is complete The mixture is filtered, then 50 ml of THF and 150 ml of 3N HCl are added to the filtrate and the mixture is stirred at 200C for 1 hour The THF is evaporated under reduced pressure and the product is extracted with ether.

The ether layer is washed with an aqueous solution of
NaHCO3, water, then dried (MgSO4). The residue is purified by preparative HPLC. Yield 0.20 g (50%), n20 1.5389.

(c) Alcohol 3- (Z, 2-butenyl) benzyl Lualdehyde is reduced in the form of the corresponding alcohol with lithium aluminum hydride following the procedure of Example 1 (c) (d) (IR ) cis-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropane
3- (Z, 2-butenyl) benzyl carboxylate
The alcohol is esterified by following the procedure of Example 1 (d) to release the ester Yield 76%, n20 1.5627.

 EXAMPLE 4 (IR) cis-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropane carboxylate α -cyano-3- (2Z, 4-pentadienyl) benzyl (a) Cyanohydrin of 3 (2Z, 4-pentadienyl) benzaldehyde 0223 g of 3 (2Z, 4-pentadienyl) benzaldehyde produced as described in Example 2 ( c) and 0.40 g of potassium cyanide in 1.0 ml of water and 4.0 ml of THF are treated with 1.2 ml of 40% sulfuric acid while cooling to 3 to 8 C. After 1 hour at 20 C, the reaction mixture is extracted with ether, which is washed, dried and evaporated in the form of a cyanohydrin residue of 3 (2Z, 4-pentadienyl) benzaldehyde. Yield 0.25 g, 94%, nD 1.5574.

(b) (IR) cis-3-92,2-dibromovinyl) -2,2-dimethylcyclopropane
α -cyano-3- (2Z, 4-pentadiétnyl) benzyle
The cyanohydrin is esterified following the procedure of Example 1 (d) to release the ester 26% yield, nD201, S639
EXAMPLES 5 to 32
Table I shows the constants for esters (I) and intermediates ((II), Y = OH) produced by following, with appropriate modification, the procedures of examples 1 to 4 with results of biochemical tests for esters (I). The esters (I) are produced from intermediates (II) following the procedure of Example 1 (d). For convenience, reference is made to Examples 1 to 4.

The symbols BR and CR represent respectively the acid residues (R) (IR) cis-2,2-dimethyl-3- (2 t 2-dibromovinylicyclopropane carbonyl and tIR) trans-chrysanthemylen TABLE I
COMPOUNDS I and II Powers
Position B in relative Procedure n20 (II) Position
Ex. On -CH2CH = CHB on R (I) followed for n20 (I) or (Bioresmé
No D (A) n cycle (isomer) cycle (II) (ex.) Mp (C) thrine = 100)
HF MB 5 HH - -CH = CH2 (E) 3 CR 1 1.5362 1.5654 5 0.3 1 HH - -CH = CH2 (E) 3 BR 1 1.5697 - "- 70 5 6 CN H - -CH = CH2 (E ) 3 CR 1 + 4 1.5338 1.5561 2. 6.5 7 CN H - -CH = CH2 (E) 3 BR 1 + 4 1.5673 - "- 45 14 8 HH - -CH = CH2 (E) 4 BR 1 1.5764 41-41.5 51 1 9 HH - -CH = CH2 (Z) 3 CR 2 1.5355 1.5647 4 0.6 2 HH - -CH = CH2 (Z) 3 BR 2 1.5710 1.5647 90 7.3 10 CN H - -CH = CH2 (Z) 3 CR 2 + 4 1.5296 1.5574 - 9 4 CN H - -CH = CH2 (Z) 3 CR 2 + 4 1.5639 - "- 170 14 11 HH - -CH = CH2 (Z) 4 BR 2 1.5714 1.5647 170 9 12 HH - -CH3 (Z) 3 CR 3 1.5211 1.5379 2.4 1.5 3 HH - -CH3 (Z) 3 BR 3 1.5627 - "- 56 10 13 CN H - -CH3 (Z) 3 CR 3 + 4 1.5143 1.5334 26 17 14 CN H - -CH3 (Z) 3 BR 3 + 4 1.5507 - "- 61 52 15 HH - -CH3 (Z) 4 BR 3 1.5610 1.5367 30 3.0 16 HH - -CH2CH3 (Z) 3 CR 3 1.5176 1.5304 0.5 approx. 0.2 TABLE I (continued)
COMPOUNDS I and II
Position B in Procedure Position No. 20 (II) Powers
Ex. On -CH2CH = CHB on R (I) followed for n20 (I) or relative
No D (A) N cycle (isomer) cycle (II) (ex.) Mp (C) (Bioresmé
thrie = 100)
HF MB 17 HH - -CH2CH3 (Z) 3 BR 3 1.5575 1.5309 12 4 18 CN H - -CH2CH3 (Z) 3 CR 3 + 4 1.5162 1.5292 34 12 19 CN H - -CH2CH3 (Z) 3 BR 3 + 4 1.5533 - "- 110 12 20 HH - -CH2CH3 (Z) 4 BR 3 1.5540 1.5277 34 3 21 H CH3 2 -CH = CH2 (E) 3 CR 1 1.5357 1.5680 1.8 0.6 22 H CH3 2 -CH = CH2 (E) 3 BR 1 1.5676 - "- 4.5 7.7 23 H (CH3) 2 2.6 -CH = CH2 (E) 4 BR 1 1.5757 54-5 11 4.3 24 H CH3 2 -CH2CH3 (Z) 3 CR 3 1.5178 1.5370 1.4 0.7 25 H CH3 2 -CH2CH3 (Z) 3 BR 3 1.5573 - "- 9.6 9.1 26 H CH3 2 H 3 CR 1 1.5219 1.5456 15 3.9 27 H CH3 2 H 3 BR 1 1.5645 -" - 120 43 28 H (CH3) 2 2.6 H 3 CR 1 1.5232 1.5441 8.5 5.2 29 H (CH3) 2 2.6 H 3 BR 1 1.5637 - "- 45 23 30 H (CH3) 2 2.6 H 4 BR 1 1.5608 1.5434 180 95 31 CN H - H 3 CR 1 + 4 1.5218 1.5327 18 18 32 CN H - H 3 BR 1 + 4 1.5549 - "- 34 44

Claims (9)

Claims 1.- Compound of general formula characterized in that D represents hydrogen or a cyanogenic or ethynyl group; B represents hydrogen or an alkyl or allkenyl group; A represents an alkyl group or an alkyl group or a halogen group or a CF3 group, n is equal to O or an integer between 1 and 4; and RCOO is the residue of an RCOOH acid which is a 2,2-dimethylcyclopropane carboxylic acid carrying in position 3 a dihalogenovinyl an alkenyl or a carbo alkoxyalkenyl group, provided that (1) when the group -CH2CH = CHB is located in position 4 on the ring with respect to the ester1 D bond must then be hydrogen and the group carried in position 3 on the cyclopropane ring of the acid must be a dihalogenovinyl group and (2) when the group -CH2CH = CHB is located in position 3 on the cycle and that D is a group CM1 n must then be equal to 0 2.- Compound according to claim 1, characterized in that the group -CH2CH = CHB is arranged in position 3 or 4. 30- Compound according to 1 or one of the claims 1 and 2, characterized in that B represents H, A represents methyl and n is equal to 1 or 2 4.- Compound according to either of claims 1 and 2, characterized in that B represents ethylene or vinyl and that the configuration at the level of the double bond its in -CH2CH = CHB is of form Z. 5.- Compound according to any one of the preceding claims, characterized in that D is H or CN 6.- Compound according to any one of the preceding claims, characterized in that R represents

 7 * - Compound according to Claim 6, characterized in that the hydrogen molecules in C1 and C3 of the cyclopropane cycle are practically completely in the cis configuration or practically completely in the train configuration and that C1 on the cyclopropane cycle is practically completely in the configuration R. 8.- Compound according to any one of the preceding claims, characterized in that D represents CN and that the carbon atom to which the CN group is linked is practically completely in configuration R or practically completely in configuration S 9.- Compound according to claim 1, characterized in that it is chrysanthemum α -cyano-3- (2,4-pentadienyl) -benzyl, or ester 4- (2,4-pentadienyl) -benzyl, ester α -cyano-3- (2-pentenyl) -benzylic, 3-allyl-2methylbenzyl ester or 4-allyl-2,6-dimethylbenzylic ester of 2,2-dimethyl-3- (2 , 2-dibromobinyl) cyclopropanecarboxylic. 10. - Process for the preparation of a compound of the formula (I) defined in claim 1, characterized in that it comprises a phase consisting in reacting a carboxylic acid RCOOH or an esterifiable derivative thereof with an alcohol of formula

 or an esterifiable derivative thereof, wherein R, D, A, B and n are as defined in claim 1. 11. - Process according to claim 10, characterized in that one reacts an RCOCl acid chloride with alcohol or in that one reacts a salt of RCOOH acid with a compound of formula

 in which Y is a halogen group, or in that an alkyl ester of RCOOH acid is reacted with alcohol in the presence of a basic catalyst. 12. A pesticidal composition, characterized in that it comprises a compound according to any one of claims 1 to 9 with an inert carrier or solvent. 13.- Composition according to claim 12, characterized in that it comprises an additional pesticidal compound. 14.- A method of fighting against insect invasions, characterized in that it consists in applying to an insect or to a surface or medium capable of being invaded by insects a compound according to any one of claims 1 to 9 or a composition according to either of claims 12 and 13. 15.- Compound of formula

 characterized in that Y represents OH or a halogen group; D represents hydrogen or a cyanogen or ethynyl group; B represents hydrogen or an alkyl or alkenyl group; A represents an alkyl group or a halogen group or CF3; and n is equal to O or an integer between 1 and 4; and that (1) when the group -CH2CH = CHB is in position 4 relative to the group CHDY, D must then be hydrogen and B must be alkyl or alkenyl and the configuration at the double bond in the group CH = CHB must be of form Z, and that (2) when the group -CH2CH = CHB -is in position 3 relative to to the group CHDY and that D is CX, n must then be equal to 0. 16.- Compound of formula

 characterized in that A, B and n are as defined in claim 15.