PYRETHROIDS AND THEIR PREPARATION, THEIR PESTICIDAL COMPOSITION; INTERMEDIATES AND THEIR PREPARATION

Abstract: There are described 3-phenoxy-benzyl or α-cyano-­ 3-phenoxy-benzyl esters of 2,2-dimethyl­ cyclopropanecarboxylic acids substituted in position 3 by a dienic polyhalogenated chain, as well as their use as insecti­ cides and acaricides. Moreover, there are also described the intermediates for their preparation and the synthesis proces­ ses.

Description: The present invention concerns new insecticides and acaricides belonging to the class of pyrethroids, and more particularly, it relates to new cyclopropanecarboxylic esters, substituted in position 3 by a dienic chain having from 4 to 8 carbon atoms and which is halosubstituted, the use of these compounds as insecticides and acaricides, as well as the intermediates and synthesis processes. There are already known numerous pyrethroid insecticides, some of which combine a good insecticide activity with a sufficient persistence on the field (see for instance "Synthetic Pyrethroids" by M. Elliot - Editors ACS Simposium, Series No.42, Washington 1977). Likewise, there are known pyrethroids substituted in po sition 3 of the cyclopropylic ring by a dienic chain. M. Elliot and collaborators described 5-benzyl-3-furyl -methyl- esters of 2,2-dimethyl-3-butadienyl-cyclopropanecarboxylic acid Nature no. 244, p. 456 (1973)2. These compounds, endowed with a high insecticide activi ty, undergo, however, a fast degradation in the presence of air and light (photooxidation), wherefore they are not suit ed for the use in agriculture. In Japanese Patent Appln. nO 7411854 by Sumitomo EChe- mical Abstract NO 81, 34599 (1974)off there are described esters with lower alcohols of 2,2-dimethyl-3-cyclopropane- carboxylic acids substituted in position 3 by a branched dienic chain having from 4 to 8 carbon atoms, and not substituted by halogens. In Belgian Patent nO 858,137 (Bayer) there is described a method for the synthesis of intermediates for pyrethroids, among which also esters of 2-(ss, #, #, -trichloro-1,3-dienyl)- -2 ,2-dimethyl-cyclopropanecarboxylic acid. However, neither of this acid nor of its derivatives there have been given examples of their synthesis, nor the re have been indicated the insecticide properties or its characteristics. From the process, described in said patent, there can be deduced that the above mentioned carboxylic acid should be prepared starting from 1,1 ,3-trichloro-6-methyl-heptatriene. No indications are given regarding the preparation of this compound or of other trienes, nor is there said anything about their use in the synthesis of pyrethroids. We have now found, and this forms an object of this invention, compounds of the general formula: EMI2.1 wherein: R = OH, O-alkyl C1-C4, halogen, EMI2.2 (wherein R = H, CN, -C=CH ), R = F, C1, Br, CH3, CF3, Rê = F, Cl, Br, CF3, R3 = H, F, Cl, Br, CF3, R4 = H, F, Cl, Br, CF3; or R and R together form a third bond between the two carbon atoms to which they are bonded. The compound of general formula I, in which: EMI3.1 are insecticides and acaricides endowed with a high activity and which possess a high persistance of the action. The compounds of general formula I, wherein R = OH, O-alkyl, halogen, are intermediates for the synthesis of the insecticide compounds. The synthesis of the compounds, endowed with an insect cide and acaricide activity is achieved, for instance, by converting a cyclopropanecarboxylic ester or acid of formula I, in which R is respectively equal to O-alkyl C1-C4 or to OH, to the correspondent acyl-halide (I, R = halogen) and by reacting this latter with alcohols of the formula: EMI3.2 (R has the meanings reported in previous general formula I). As far as the preparation of the new intermediate of ge neral formula I is concerned, different procedures are possi ble, whose choice depends mainly on the nature of the substi tuents present in the dienic chain (R1, R2, R3 and 4 In the following will be described: a process for the synthesis of the compounds of general formula I, wherein R4 is different from H (method A); a process for the synthesis 3 of the compounds of formula I wherein R = H (method B), a process for the synthesis of the compounds of formula I whe rein R4 = H (method C), and an alternative process for the preparation of the compounds of formula I wherein R = H (method D). METHOD A: A lower alkyl ester of 2,2-dimethyl-3-formylcyclopropanecar boxylic acid (1) (caronic aldehyde), as a mixture of geometric isomers or as a single isomer, is made to react according to the Wittig reaction with the ylide (2) of a haloalke nyl of formula (3): EMI4.1 wherein: RÚ, Rê and R have the previously specified meanings: 4 R = F, Cl, Br, CF3; X and X' (equal to or different from each other) = Cl, Br. Scheme 1: EMI4.2 EMI5.1 As examples of such compounds of formula (3), there may be cited: EMI5.2 Some of the compounds of formula 3, and more particularly those of the general formula: EMI5.3 wherein: X and X' (equal to or different from each other) = = halogen, are new compounds and form ano ther object of this invention. Their preparation is achieved by dehydrohalogenation of 1,l,l-trifluoro-2,2,4,4,4-pentahalobutanes described in the following. Alternatively to the process indicated in scheme 1: the com 4 pounds of formula I, wherein R is a halogen atom, may be prepared by carrying out a Wittig reaction between a lower. alkyl ester of 2, 2-dimethyl-3-formyl-cyclopropanecarboxylic acid (1) and a polyhaloalkane of formula (4): EMI6.1 and by subjecting the resulting product of this reaction to a dehydrohalogenation with bases, according to Scheme lb. Scheme 1b EMI6.2 EMI7.1 ER6 = alkyl, phenyl. As a further alternative to the process indicated in 4 scheme 1, the compounds of formula 1, wherein R is either a chlorine or bromine atom, may be prepared by a Wittig reaction between allyl chloride or allyl bromide of the type: EMI7.2 and a lower alkyl ester of 2,2-dimethyl-3-formyl-cyclopro- panecarboxylic acid (1) and by then subjecting the therefrom resulting dienic product to a halogenation with Cl2 or Br2, followed by dehydrohalogenation. Scheme lc: EMI7.3 EMI8.1 EMI8.2 XR4 (wherein X an R4 are both HX Cl or Br atoms) I [R = O-alkylL7 METHOD B: A polyhaloalkane (propane or butane) (4) is additioned with an ester of 3,3-dimethyl-4-pentenoic acid (5, n=l) or 2-ethcxy carbonyl-3,3-dimethyl-4-pentenoic acid (5, n=2): EMI8.3 (n = 1 or 2), thereby obtaining adduct (6) which, treated with bases, undergoes in one or more stages, successive dehydrohalogenations with the elimination of three mols of halogenhydric acids optionally followed (in the case n = 2) by a decarboxylation. In the case the dehydrohalogenation is carried on and Rê is a halogen atom, there are obtained the compounds of formula 2 3 I in which R and R together constitute a third bond. Scheme 2: EMI9.1 EMI9.2 I (R = OH, o-alkyl; R = H) -HX", (-CO2) (- HO-alkyl) tX, X' and X" (equal to or different from each other) = = Cl, Br; n = 1 or 2; RÚ, Rê and R4 have the same meanings as those reported in general formula 12. The polyhaloalkanes of formula (4), suited for reacting according to reaction 3), are, for instance: 1,1,1,3,3,3-hexahalopropanes, 1,1,1,3,3, -pentahalobutanes, 1,1,1,2,2,4,4,4-octahalobutanes. Amongs these compounds there may be cited a few as exam ples: CCl3 - CH2 - CCl3 CH3 - CC12 - CH2 - CC13 CF3 - CCl2 - CH - CCl 3 CF3 - CBr2 - CH2 - CCl2Br CF3-CFBr-CH2-CCl2Br. Some of these compounds, the 1,l,1-trifluoro-2,2,4,4,4 -pentahalobutanes (IV), are new compounds and consist te a further object of the present invention. Their preparation, which likewise constitutes an object of this invention, is achieved by reacting a poly haloethane of formula (7): EMI10.1 with vinylidene chloride, according to equation 5): EMI10.2 therein X = F, Cl, Br; X' and X" (either equal to or different from each other) = Cl, Br]. Both reactions 3 and 5, in general, are achieved by re acting the halo-alkane (4 or 7) with the unsaturated ester (5) or with the vinylidene chloride, in a molar ratio from 1 to 4. The above indicated reactions are conducted in inert so vents at a temperature comprised between 500 and 2000C and in the presence of catalytic amounts of radical reaction promoters, such as organic peroxides (ter-butyl-peroxide, benzoyl-peroxide, diacetyl-peroxide), azo-derivatives (azo -bis-isobutyronitrile), U.V. radiation, or in the presence of redox-transfer systems or of metal-carbonyls, etc. Reaction 4 is conducted according to known techniques, either in one single or in plurality of successive stages, using organic bases (amines), alkaline alcoholates or inorganic bases (NaOH, KOH). METHOD C: A mixture of cis and trans isomers of esters with lower alcohols of 2 , 2-dimethyl-3-acetoxymethyl-cyclopropanecarboxi.- lic acid (8) is hydrolized with catalytic amounts of sodium ethylate in ethanol, thereby obtaining a mixture of ethyl ester of trans 2 ,2-dimethyl-3-hydroxymethyl-cyclopropane- carboxylic acid (9) and of the lactone of the same acid in the cis form (10). Compounds 9 and 10 may be separated by distillation, and each one may be independently converted into the correspond ing 3-bromomethyl derivative, i.e.: compound 9 by treatment with triphenylphosphine bromide (C6H5)3PBr2 and compound 10 by treatement with HBr, thereby obtaining respectively the 3-bromomethyl-derivative of trans ethyl ester (11-trans) and the 3-bromomethyl-derivative of the cis acid (12) which will then be converted to the corresponding alkyl ester (11-cis). Intermediates 11-cis and -trans, either separately or in admixture with each other, are converted to the corresponding phosphonium salts (13) by treatment with triphenylphosphine ( H ) P. Finally the phosphonium salts (13) are made to react with an aldehyde of the formula: EMI12.1 (RÚ R2 and R3 have the same meanings indicated for the general formula I)-. Thereby are obtained the compounds of formula 1 wherein: 4 R = O-alkyl and R = H. Scheme 3: EMI12.2 EMI13.1 The reactions from 6) to 9) are carried out by applying well known techniques in the transformations of hydroxy acid esters by hydrolysis and lactonization, in the substitution of an OH group by a bromine atom and in the formation of phosphonium salts from bromo-alkyl derivatives. The examples given in the present patent application give an adequate documentation of the sequence of these reactions. Wittig reaction 10), although known by itself, has never been applied to halogenated derivatives of acrolein. This reaction is conducted by suspending the phosphonium salt (13) in an anhydrous inert solvent (e.g.: tetrahydrofurane), in aa anhydrous and deoxigenated nitrogen atmosphere according to what described by L.F. Fieser in: "Reagents for Orga nic Synthesis" - J. Wiley & Sons Ed., 1967, page 149. To this suspension is then admixed a stoichiometric quantity of butyl-lithium dissolved in the same solvent, at a temperature comprised between -700 and -200C. As soon as the bu tyllithium has disappeared, g as can be checked by carrying out the Gilman test described in: "Organic Reactions", 6, (1951) page 352off to the ylide thus prepared is added the aldehyde (14) in sligth excess and is then allowed to react at a temperature of between -200 and OOC. Once the reaction has ended, the betainic complex that has formed is preferably decomposed by treatment with a stoichiometric quantity of phosphoric hexamethyltriamide and then with water, in order to obtain the dienic ester I (R = O-alkyl, R = H). The esters with lower alcohols of 2,2-dimethyl-3-acetoximethyl-cyclopropanecarboxylic acid (compound 8) have been described in Italian Patent Application No. 24,255 A/79. As examples of aldehydes of formula (14), suited for the reaction with phosphonic salts (13) according to the Wittig reaction (reaction 10), there may be cited: EMI14.1 EMI15.1 Some of the aldehvdes of formula 14, and more particularly, those having in ss a CF3 group and one halogen, of formula: EMI15.2 (X = F, Cl, Br) are new compounds and form another object of this invention. Their preparation is achieved by reacting l,1,1-trifluo ro-2,2,2-trihaloethane with a vinylether followed by dehydrX halogenation and hydrolysis. The addition reaction of 1,1,1-trifluoro-2,2,2-trihalo ethane to a vinylalkylether (or to another vinyloxiderivati ve, such as for instance vinyl acetate) is conducted in the presence of radical reactions promoters, at temperatures of between 0 and 200 C, by operating with an excess of polyha loethane, with or without solvents. As a radical reaction promoter there may be used one of the following agents: U.V. light, peroxides, transition metal salts such as for instance iron or copper salts, in the presence of either primary or secondary amines, or azo-derivatives such as for instance azo-bis-isobutyronitrile-. EMI16.1 wherein: X = F, Cl, Br; X' = Cl, Br; Y = an alkyl group with from 1 to 5 carbon atoms, EMI16.2 (R' = lower alkyl). Some further examples of the addition of other fluoro alkanes to vinyl ethers have been reported by P. Tarrant, E.C. Stump in the Journal of Organic Chemistry, 29, p.1198 (1964). Once there has been obtained the adduct, this is subject ed to dehydrohalogenation and hydrolysis of the i-haloethe group by treatment with boiling water or with bases or salts developing an alkaline action (e.g.: Na2CO3, NaHCO3) in an aqueous medium (equation 12). Alternatively, the dehydrohalogenation reaction may be carried out in a stage preceding the hydrolysis, for instance by heating up the adduct to a temperature at which there is a thermal elimination of the halogenhydric acid HX (equation 14). In its turn, the conversion of the i-haloetheric group (when R = alkyl) to an aldehydic group may be achieved by pyrolysis (equation 15) instead of by hydrolysis (equation 13). A further alternative consists in conducting the hydrolysis reaction in the presence of water, at the boiling tern perature, (equation 16), followed by a dehydrohalogenation in the presence of an aqueous base (equation 17). EMI17.1 EMI18.1 The thermal decomposition reactions (in the absence of wa. ter) are conducted at temperatures comprised between 7O0C and 25O0C. METHOD D Consists in a synthetic procedure alternative to Method B for the preparation of the compounds of formula I in which R = O-alkyl, R3 = H and R4 = H, F, C1, Br. The process reported under Method D results to be more convenient than that of Method B in as much as it is of easier execution affording higher yields. Moreover the products are isolated from the reaction mixture in a simple way and with a high degree of purity. Because of the fact that the substituent R4 values in the compounds which can be prepared by Method D is slightly limited with respect to the values of R4 in the compounds which can be prepared by Method B, and in order to avoid misunderstandings, in the description of Method D, the substituent R will be replaced by R6. Thus, the process of Method D is usefull for the preparation of some of the compounds of general formula I, having the following restricted general formula: EMI19.1 wherein RÚ and Rê have the meanings reported for general formula I, R = O-alkyl C1-C4 and R6 = H, F, Cl, Br. Said process consists in reacting, in the presence of a strong base, a 2-alken-phosphonate of the formula: EMI19.2 [wherein RÚ, Rê and R6 have the meanings given to them in formula VI; R7 and R8 (equal to or different from each other) represent an alkyl or a haloalkyl with C1-C4, or 7 8 R and R together form either a EMI19.3 group 7 with a lower alkylester of caronic aldehyde (1) (2,2-dimethyl-3-formyl -cyclopropanecarboxylic acid) of the formula: EMI19.4 (wherein: R = O-alkyl C1-C4). The above process, is illustrated by reaction 18): EMI20.1 The compounds of formula VII have been indicated as pho sphonates, thereby using this term in its more general meaning, that is, referred to organic compounds of the pentava lent phosphorus in which there is present a carbon-phospho rus bond. It must, however, be pointed out that the correct nomenclature for the compounds of formula VII (in which substi 7 8 tuents R and R together represent either a EMI20.2 or a EMI20.3 group and thus form with the EMI20.4 group either a pentaatomic or hexaatomic ring) foresees for these compounds the term 2-oxo-1,3,2-di oxaphospholane and respectively 2-oxo-1,3,2-dioxa-phosphori nane. In this contest, the compounds of formula VII will in the following be indicated by the term 'phosphonates", also comprising thereby the compounds of formula VII in which there occurs either a penta- or hexatomic ring. As far as we-know, only one example of a reaction between a 2-alken-phosphonate and an aldehyde was known from the literature. Said example concerns the reaction between methyl 3-chloro -2-butene-phosphonate and benzaldehyde tG. Lavielle, C.R. Acad. Sci., Ser. C, 86 (1970)2. The above cited reaction leads to the formation of three products, only one of them having a dienic structure: EMI21.1 It had thus to be expected that also from reaction 18 there would form compounds of little interest for the purpo ses of the desired structure. On the contrary, we surprisingly found that reaction 18 affords compounds of formula VI with high yields and al lows to separate(iso late) the desired product quite easily and with a high degree of purity. Reaction 18 is carried out using substantially equimolar quantities of phcsphonate VII and of the ester of caronic aldehyde (1), in the presence of substantially equimoku lar amounts of a strong base, in an inert solvent or diluent and at temperatures comprised between -500C and +1000C, but preferably comprised between -300C and room temperature Suitable strong bases may be hydrides or hydroxides of alk line metals such as sodium hydride, lithium hydride, sodium hydroxide, potassium hydroxide, etc. In case that as a base there is used sodium hydride, it is preferable to operate in the presence of catalytic amounts of suitable activators such as for instance ethyl alcohol or imidazole. As a reaction medium there may be used an ether such as for instance: dimethoxy-ethane or tetrahydrofurane, an aprotic polar solvent such as N,N-dimethXl- -formamide or a pair of protic-aprotic solvents such as e.g water and an aromatic hydrocarbon (in this latter case, as a base there must be used an alkaline hydroxide). In a practical embodiment, the reaction 18 may be conducted by preparing a mixture of phosphonate VII and of the ester of caronic aldehyde (1), in a molar ratio of about 1:1 and by then admixing slowly this mixture to a solution or a suspension of the base in a suitable inert solvent. In another practical form of embodiment, reaction 18 is conducted by slowly admixing a solution of phosphonate VII in an inert solvent to a mixture consisting of the base, of the ester of caronic aldehyde (1) and of an inert solvent. Reaction 18, in general, is carried out in an anhydrous medium and under an atmosphere of an inert gas when a base there is used an alkaline metal-hydride. The lower alkyl esters of caronic aldehyde (1) are known compounds that are separable in two isomeric forms, cis and trans (isomerism on the cyclopropane ring). The possibility to use in reaction 18 also only just oni of the two cis or trans forms, allows to obtain cyclopropanecarboxylic esters (VI) having the corresponding isomerism. As far as is known to us, the only 2-alkene-phosphonate of formula VII known previously, is methyl 3-chloro-2-butene-phosphonate (reaction 19). Thus a further object of this invention concerns the phosphonates of formula VII wherein R is different from 2 methyl when R is a chlorine atom. The preparation of the phosphonates of formula VII is carried out according to known techniques starting from a 2-alkenyl halide (15) and from a suitable phosphorus compound. Reactions from 20 to 27 hereunder reported, are representative examples of methods for the preparation of the various phosphonates of formula VII. EMI23.1 EMI24.1 In the above reported reaction RÚ, Rê, R6, R7 and R8, if not otherwise indicated, have the meanings reported for formula VII; X stands for chlorine or bromine while NBS indicates the N-bromo-succinimide compound. Reactions from 20 to 23 represent examples of methods for the preparation of the co 6 pounds of formula VII wherein R H. The compounds wherein 6 R = halogen, may be prepared in a similar way starting from suitable 2-alkenyl halides, or they may be prepared from the compounds of formula VII wherein R6 = H, by the methods illustrated by reactions from 24 to 27. All starting compounds of reaction 20 to 23 are known compounds or they can be easily prepared according to known methods. Reaction 24 concerns a standard halogenation in allylic position, carried out with N-bromo-succinimide. Reactions 25 to 27 represents an alternative to reaction 24, also useful for preparing compounds in which R6 = Cl. The addition of halogen (X2) to compounds VII wherein R6 = H (reaction 25) is carried out according to techniques that are standard in organic chemistry, using halogens or haloge nating agents such as S02Cl2. The dehydrohalogenation of adduct (16) (reaction 26) m be carried out either in the presence of inorganic bases or of organic bases such as secondary or tertiary amines. The reaction of the re-arrangement of adducts (17) (re action 27) is a new one and as such forms a further object of this invention. Said reaction accours quantitatively at a temperature comprised between 200 and 1500C, in the presence of catalytic quantities of a bivalent copper halide, by simple stirring of the mixture consisting of the adduct (17) and of cu pric halide. In case X = Cl , a suitable catalyst is cupric chloride in the commonly used foim of dihydraze. By means of the hereabove described methods A to D, the compounds of formula I in which R = OH or O-alkyl can be prepared. From these compounds, with methods known in the common practice of organic chemistry, it is possible to pre pare the acylic halides (I, R = halogen), for instance, by the reaction of the acids with thionyl chloride. From the acylic halides, by reaction with the alcohols of General Formula II, according to known techniques, there are obtained the compounds of formula I, wherein: EMI26.1 The compounds of general formula I, in general, are obtained as mixtures of geometrical and configurational isomers due to the particular structure of the molecule which contains asymmetric carbon atoms and double bonds. The separation of the various mixtures in the various diastereoisomers may be achieved following the techniques usually applied in the normal practice of organic chemistry, such as for instance chromatographic methods. Under the spirit of this invention falls the separation and the use of the single isomers or their mixtures or of the mixtures obtained by partial separation of the isomers of the compounds of general formula I. The compounds of general formula I, wherein R is an alcoholic residue of the 3-phenoxZ-benzyl alcohol optionally substituted, display a high insecticide activity against insects belonging to the most important species, from the point of view of their noxiousness in the agricultural and civil fields, such as hemiptera, lepidoptera, coleoptera and blattoidea, and possess, moreover, a high acaricide ac.tivity, particularly as ovicides. In this latter action they prove by far more active than the best pyrethroids known. Moreover, they are endowed with a high stability to pho to-oxidation, a property that ensures a sufficient persisted ce of their action thus allowing also their use in agriculture. The insecticide compounds of general formula I may be applied to a zone where insect control is desired both as technical materials or as suitable compositions or formulations. Suitable compositions comprise an insecticide compound of formula I as active ingredient in combination with one or more suitable inert carriers and/or surface active agent , and optionally other active compounds such as other insecticides, acaricides, nematocides etc. Suitable formulations include granules, dusts, eatable powders, emulsifiable concentrates, solutions, dispersions and the like. The active ingredient may be present in a suitable composition at a concentration of from 0.1 to 99 by weight. While the application rate of the formulations varies widely depending on the type of formulation, the active compound, the mode of application and the environment, an effective insecticidal amount of the active principle must be applied and the practical rate may vary in the range of 0.01 to 3 Kg/hectare. In order to even further illustrate this invention, in the following are given a number of examples. EXAMPLE 1: Preparation of CF3-CClz-CH2-CCl3. Into a Pyrex glass vial were introduced: 10 g of l,l,l-trichlorotrifluoroethae (0.05 mols), 5 g of l,l-dichloroethylene (0.05 mols), 0.2 g of diethylamine-chlorohydrate, 0.2 g of CuCl2.2H2 0 and 8 ml of acetonitrile. After sealing on a flame, the vial was heated for 24 hours at 1200C. Thereupon it was cooled down and opened and the content was diluted with 50 ml of methylene chloride and then washed with water (3 x 100 ml), after which it was anhydrified on sodium sulphate and subjected to distillation in order to remove the solvent and the more volatile fractions consisting mainly of unreacted trichlorotrifluoro ethane. As a residue there were gathered 5 g of a fluid yellowish liquid, mainly consisting of 1,1,1,3,3-pentachloro-4,4-tri fluorobutane. NMR (nuclear magnetic resonance) J - 3.8 ppm (CH2) in CDCl3. Mass spectrometry: (C H ClgF3) 42 53 247 (M+ - Cl) 211 (247 - HCl) 151 (CF3-CCl2+) 117 (CCl3+) 69 (CF3+) 3 EXAMPLE 2: Preparation of: CF3-CBr2-CH2-CCl2Br. Into a glass flask of 500 cc holding capacity, fitted with a reflux condenser1 there were introduced, under a nitrogen atmosphere, the following reactants: 339 g of 1,1,1-trifluoro-2,2,2-tribromoethane (1.056 mols) 51 g of l,1-dichloroethylene (0.526 mols), 0.5 g of CuCl and 10 ml of ethanolamine. This reaction mixture was then heated up at the reflux te perature for 4 hours. After cooling down, the reaction mixture was washed with water until attaining a neutral pH, whereupon it was subjected to distillation. After removal of the excess trifluorotribromoethane as a head, there were gathered 30 g of a fraction with b.p. com prised between 430 and 450C at 0.15 mm Hg, consisting for 90% of it of 1,1,1-trifluoro-2,2,4-tribromo-4,4-dichlorobu tane, as evidenced by mass spectrometry combined with gas -chromatographic separation. Mass spectrum: peak of molecular ion:C4H2F3Br3Cl2 + main fragments : CF3-CBr2 + CCl2Br and for 10% of it of the dehydrohalogenation product: Mass spectrography: peak of molecular ion: C4HF3Br2C12. EXAMPLE 3: Preparation of ethyl 3,3-dimethyl-4, 8, 8-tribromo-6,6-dichlo ro-9,9,9-trifluorononanoate. CF3-CBr2-CH2-CCl2-CH2-CHBr-C(CH3)2-CH2-COOC2H Into a quartz vial were introduced, under an atmosphere of nitrogen: - 41.8 g of CF3-CBr2-CH2-CCl2Br (prepared as described in example 2), - 15.6 g of ethyl 3,3-dimethyl-pent-4-enoate. The vial was then sealed and irradiated with a high pressure Hanau lamp for 15 hours at 650C. The content of the vial was then distilled in order to remove the unconverted reactants. The residue (12 g) proved to consist essentially of the desired product (gas-chromatographic analysis). Mass fragmentations: +/e = 269, 189, 161, 155 C13H18F3Cl2Br302 (main peak) 135, 129, 109, 88, 87. EXAMPLE 4: Preparation of ethyl 3-(2'-chloro-4'-bromo-4'-trifluorome- thyl-butadienyl)-2,2-dimethyl-cyclopropanecarboxylate. EMI30.1 The adduct prepared as described in example 3 (0.02 mols), was treated with 0.06 equivalents of sodium ethylate in 40 ml of absolute ethyl alcohol at a temperature of 600C for 2 hours. After removal of the solvent, the residue was diluted with methylene chloride, then washed with water, acidified with acetic acid, until obtaining a neutral pH, then anhydrified on CaCl2 and then, after removal of the solvent, subjected to fractioned distillation gathering - the fraction that boils at 620-630C at 0.2 mmHg. This fraction proved to consist for about 65% of the desired product. EXAMPLE 5: (method B) Preparation of ethyl 3,3-dimethyl-4,6,6,8,8-hexachloro-octa noate. CCl3-CH2-CCl2-CH2-CHCl-C(CH3)2 -CH2-COOC H Into a 50 cc flask, fitted with a stirrer and a reflux condenser, connected at the upper end to a calcium chloride valve, there were introduced: 12.5 g of l,l,l-3,3,3-hexachloropropane (0.05 mols), 8 g of ethyl 3,3-dimethyl-pent-4-enoate (0.05 mols), 1 g of diterbutylperoxide. The reaction mixture was then heated up to 1500C for 24 hours. After cooling down, from the mixture was drawn a sample of the product which, by gas-chromatographic analysis, proved to consist for about 50% of it of the addition product and of minor quantities of hexachloropropane and of ethyl 3,3-dimethyl-pent-4-enoate that had not reacted. The se latter were thereupon removed from the reaction mixture by distillation under vacuum, thereby gathering the fractions that boil until a temperature of the vapors of 1100C at 0.5 mmHg. The residue (11 g) was extracted with n-hexane, then purified with active charcoal and subjected to the removal of the solvent in order to give 7 grams of ethyl 3,3-dimethyl -4,6-6,8,8,8-hexachlorooctanoate. Mass spectrometry: (C12H18C16 0 2 404 (M+) 359 (M+ -OC H 25 333 (M+-OC H , -Cl, -HCl) 287 (M+ - CCl 3 129 (C (CH3)2-CH2-COOC2H5 117 (CCl +) 3 87 (CH2-COOC2H5 EXAMPLE 6: (method B) Preparation of ethyl 3,3-dimethyl-4, 6, 6, 8, 8-pentachloro-9, 9, 9 -trifluoro-nonanoate: CF3-CCl2-CH2-CCl2-CH2-CHCl-C(CH3)2-CH2-COOC2H5. Intoa.50nl flask fitted with a stirrer and a reflux condenser, connected by its upper end to a CaCl2 valve, there were introduced: 5.7 g of CF3-CCl2-CH2-CCl3 (0.02 mols). 3.1 g of ethyl 3,3-dimethylpent-4-enoate (0.02 mols) and about half of a solution obtained by dissolving 0.5 ml of Fe(CO)5 in 5 ml of isopropyl alcohol. This reaction mixture was thereupon heated up under a slight refluxing at about 1000C and additioned, in 3 hours, with the remaining iron-pentacrbonyl [Fe(CO)5] solution. After cooling down, the content was then diluted with 50 ml of methylene chloride, then washed with water, anhydrifièd and finally concentrated under vacuum in order to give 8.5 g of a raw product which was then distilled under vacuum gathering thereby the fraction boiling at 1150-1180C (0.15 mm Hg) and which consisted of the desired product. EXAMPLE 7: Dehydrohalogenation of ethyl 3,3-dimethyl-.4,6,6,8,8,8-hexa- chlorooctanoate (1). To a solution of 2.1 g of (1), (prepared as described in example 5) in anhydrous n.hexane (25 ml) there was added a solution of 2 grams of tetramethyl-guanidine in 25 ml of anhydrous n . hexane. The reaction mixture was then maintained under stirring for 24 hours at room temperature, whereafter it was poured into cold water. The hexanic phase was thereupon separated and the aqueous phase was extracted with diethyl ether (50 ml). The heteric phase was recombined with the hexanic phase. The resulting solution was washed with a dilute solution of HCI, until attaining a neutral pH. It was tf n anhydrified with CaCl2 and then concentrated until reaching a con stant weight thus obtaining a raw product (7 g) consisting of compound A (95d) and of compound B (5). Compound A: ethyl 3 > 3-dimethyl-4,6,8,8-tetrachloroocta-5,7- -dienoate. Cl2C=CH-CCl=CH-CHCl-C(CH3)2-CH2-COOC2H5 (mixture of cis and trans isomers). The IR analysis is consistent with the assigned structure. ÚH NMR (# ,ppm) : 1,2 (9H, methyl group::) 2,15-2,7 (m, 2H) 4,15 (q, 2H, 0-OH - CH I 3 4,6-5,2 (m, 1H) 5,9-6,5 (m, 2H) Mass fragmentation: (M+/e) C12H16O2Cl4 332 (M+) 296 (M+-HCl) 260 (M+-2HCl) 173 (M+-3HCl, -C2H5 96 Compound B: ethyl 2,2-dimethyl-3-(2', 4', 4'-trichlorobuta- -1',3'-dienyl)-cyclopropancarboxylate. EMI34.1 Mass fragmentation: C12H15O2Cl3 296 (M+), 260 (M+-HOl), 12 15 2 5 213 (M+-CHCl2) 177 (M+-HCl-COOV2H5) [an alternative synthesis of compound B is reported in Example 35]. EXAMPLE 8: hydrolysis of 2-acetoxymethyl-3,3-dimethyl-carbethoxy-cyclo propane for obtaining 2-hydroxymethyl-3,3-dimethyl-carbetho xy-cyclopropane trans and 6,6-dimethyl-3-oxa-bicyclo [3, 1, 0]-hexan (2) one EMI35.1 1 mol of (1) was dripped, at a temperature of between 0 and 100C, into a beaker containing 500 cc of 99% ethyl alco hol and 0.25 mols of metal sodium. This mixture was then kept under stirring at room temperature overnight. There after the solvent was evaporated at 15 mmHg until obtaining about 250 cc of solution. This was poured into 750 cc of wa ter and ice and was then extracted with methylene chloride (4 times, each time with 150 cc of solvent). The reunited organic phases were then washed with water until reaching a neutral pH, whereupon they were anhydrified and evaporated, thereby obtaining 140 g of an oil which by gas-liquid chromatographic analysis (GLC) appeared to consist for 35 of (3) and for 50% of (2) (yield about 80do). The raw product was distilled and rectified at 15 mmHg. There were obtained 0.37 mols of (3) (b.p. at 15 mmHg = = 112-1140C) and 0.33 mols of (2) (b.p. at 15 mmHg = 132 -1340C) -1 IR analysis of (3): 1780 cm -1 -1 IR analysis of (2): 3200-3600 cm , 1715 cm 1380-1370 cm-Ú, 1170 cm-Ú, 1020 cm-Ú EXAMPLE 9: (method C) Preparation of 2-bromomethyl-3,3-dimethyl-carbethoxy-cyclo- propane trans EMI36.1 About 0.3 mols of bromine are dripped into a solution of 0.27 mols of 2-hydroxymethyl-3,3-dimethyl-carboetoxycyclo propane (1), 0.28 mols of triphenylphosphine and 300 cc of dimethylformamide, maintaining the temperature at between 500 and 550C (dripping time about 30 minutes). Once the dripping has been completed, the mixture was main tained under stirring at 500C for 5 minutes. Thereafter it was cooled down and then poured into 1.2 litres of water and ice, after which it was extracted with benzene (5 times each time with 150 cc of solvent). The re-united organic extracts were then washed with an aqueous sodium sulphite solution at 5% concentration, then with a 5 sodium bicarbonate solution and finally with water until attaining a neutral pH. The mixture was thereupon anhydrified on sodium sulphate and then evaporated thereby obtaining a raw product of a rubbery appearance. It was then diluted with petroleum ether, and the white solid that precipitated (70 g of triphenyl-phosphoxide equal to 0.25 mols) was filtered. After evaporation of the solvent there were obtained about 0.25 mols of (2) (yield = 90-95). b.p. (at 0.05 mmHg) = 650 - 66 C NMR (S, ppm, TMS) : 4.1 [q, COOCH2i 3.4 [dd, CH2Br] 1.7-2.1 [m, H of cyclopropane] 1.2 Es, CH3 geminals] 3 1.2 [t, CH3-CH2O] (s = singlet, dd = doublet of doublet, t = triplet, q = quad tet, m = multiplet). EXAMPLE 10: (method C) Preparation of [(2-carbethoxy-3,3-dimethyl)-cyclopropyl] -methyl-triphenylphosphonium bromide. EMI37.1 Into a 2 litre autoclave were placed 0.163 mols of 2-bromo methyl-3,3-dimethyl-carbethoxy-cyclopropane-trans (1) 0.18 mols of triphenylphosphine and 500 cc of ethyl ether. The autoclave was then washed with nitrogen, heated up to about 120 C (inside pressure about 9.5 atm.) for 50 hours. The mixture was then cooled down and the white solid that was obtained was filtered. There were obtained 0.147 mols corresponding to a yield of 90d. The m.p. was about 182 - -184 C. The elemental analysis (in ge): C, theoretical: 64.56 C, found : 65.20 H, " " 6.05 H, " 6.08 Br, " " 16.07 Br, " 16.25 EXAMPLE 11 (method C): Preparation of 2-bromomethyl-3,3-dimethyl-carbethoxy-cyclo propane-cis, starting from 6,6-dimethyl-3-oxa-bicyclo [3,1, ,0 7-hexan-(2)-one. EMI38.1 A') Into a solution of lactone (1) (0.37 mols) and of 60 cc of 99.5% ethanol, were made to bubble through 0.98 mols of gaseous hydrogen bromide. The temperature was rigo rously maintained at between 0 and 2 C. (Bubbling time = 5 hours). The solution was then kept under stirring at OOC for another 19 hours. Cooling the solution down, there were added 160 cc of water and ice. The resulting white precipitate was filtered The filtrate was then washed with water until attaining a neutral pH (5 times, each tirne with 50 cc) and successively was washed with petroleum ether. It was then anhydrified and the petroleum ether was evaporated, thereby obtaining 0.055 mols of 2-bromomethyl-3,3-dimethyl-carbethoxycyclopro pane. From the washing waters, by extraction with methylene chloride there were obtained about 3 g of the starting product. The white solid filtrate which, after drying, weighted 50 g, showed a melt point (m.p.) of 1150-1170C, and proved soluble in 5% bicarbonate. The elemental analysis (in %) was: theor. C = 40.60; found C =40.71 " H = 5.35 " H = 5.37 " Br = 38.60 " Br =38.54 B') The 2-bromomethyl-3,3-dimethyl-carboxycyclopropane ob tained according to point A' (0.18 mols) was dissolved in 180 cc of chloroformium. Thereupon, by dripping, the re was added the thionyl chloride (0.36 mols) cooling with water and ice so that the reaction temperature did not exceed 10 C. The reaction mixture was then reflux heated until there is no more development of hydrochlo ric acid (about 5 hours). It was then evaporated at re duced pressure thereby obtaining a raw oil (yield = = about 95%). The raw product thus obtained partly decomposes by dis tillation and is then used as such in stage C). By a distillation test on a reduced quantity, there was obtained an 85% pure product (GLC) with a b.p. (at 0.15 -l mm Hg) = 50 -55 C. I.R. analysis: 1770 cm C') 0.18 mols of the raw acyl chloride prepared according to point B, were admixed to 5 cc cf anhydrous benzene. While cooling the mixture with water and ice, there we re dripped into it 0.36 mols of a 99.9% ethanol. Once the addition of the ethanol was accomplished, there were dripped in slowly, at about OOC, 0.18 mols of pyridine. The mixture was then allowed to rest overnight at roum temperature and the salt that had formed was filtered. The filtrate, after washing to a neutral pH with water, was anhydrified on sodium sulphate and then evaporated. Thereby were obtained 40 g of oil which was distilled. B.p. (at 15 mm Hg) = 1070 - 11000. -1 I.R. analysis: 1720 cm EXAMPLE 12 Preparation of R-trifluoromethyl- n -chloro-acrolein. A mixture of CF3 - CCl3 (450 G; 2.4 mols) and n. butyl-vinyl ether (80 g; 0.8 mols) was irradiated with a mercury-vapor U.V. lamp of the Hanau HP type, model TO 150, for 1.5 hours at 450C. The reaction mixture was then distilled in order to remove the unconverted reactants. Thereby was obtained a residue consisting of 1,1,3-trichloro-4,4,4-trifluorobu- tyl-butyl-ether, chromatographically pure (yield = 89%). 0.1 mols of this compound were thereupon dripped, at room temperature, into a solution containing 0.1 mols of sodium -carbonate decahydrate in 100 cc of water. This solution was maintained under stirring for 3 hours. Thereafter the organic phase was separated from the solution and anhydrified and then distilled at atmospheric pressure. The pure product boils at about 700C. I.R. analy sis: 3050, 1685, 1625 cm NMR (CDC13) ( , ppm) H 6.7 rd, C = C, J = 7 Hz] 10.1 i d, CHO, J = 7 Hz7. d = doublet, J = coupling constant. The preparation was then repeated in the absence of a base, operating in the following way: 50 g (0.174 mols) of 4,4,4-trifluoro-3,3,l-trichlorobutyl- -butylether were introduced into a 250 ml flask fitted with a stirrer and a reflux condenser. After the addition of 150 ml of water, the content was heated at reflux temperatu ture (temperature of the mixture = about 850C) for 1 hour. At this point the flask was connected to a Vigreux column and the content was distilled thereby gathering the fraction that boiled between 7100 and 75 C After anhydrification on Na2 SO4 and filtering, there were obtained 15 g of p ss-trifluoromethyl-ss-chloroacrolein. EXAMPLE 13 (method C) Preparation of 3-(4', 4'-dichlorobutadienyl)-2,2-dimethyl -carbethoxy-cyclopropane (trans) To a suspension of 0.01 mols of E(2-carbethoxy-3,3-dime- thyl)-cyclopropyl]-methyl-triphenylphosphonium bromide in 30 ml of tetrahydrofurane (distilled on lithium-aluminum -hydride), at -250C, by dripping were admixed 0.01 mols of a butyl-lithium solution in hexane (1.5 molar). The suspension was maintained under stirring for 20 min. at -20 C whereafter into it were dripped 0.014 mols of p -di chloro-acrolein in 2 ml of tetrahydrofurane. Then, the tem perature was allowed to rise to OOC. The mixture was maintained under stirring for 10 minutes and was then cooled down again to -200C adding to it 0.01 mols of phosphoric hexamethyltriamide. The mixture was then maintained under stirring at room tem perature 20 minutes. To it was then admixed 10 ml of water and it was then kept under stirring for 2 hours. After this period, the mixture'was poured into 50 ml of water, the pha ses were separated and the organic one was extracted with toluene (2 times, each time with 30 cc of solvent). The organic phase was thereupon washed with water until attaining a neutral pH. Thereupon it was anhydrified on anhydrous sodium sulphate and evaporated. Thereby were obtained 4.9 g of product (a dark oil) which was then passed through a cylindrical funnel of 5 cm diame ter, containing 70 g of alumina. The mixture was then eluted with 100 cc of hexane (lust fraction), then with 200 cc of a mixture hexane-ethyl acetate (9:1) (2nd fraction) and finally with 300 cc of a mixture of hexane-ethyl acetate (7:3) (3rd fraction). The three fractions were then evaporated separately. The 2nd (about 1.0 g) showed an I.R. spectrum coherent with the product. According to GLC there were present 2 isomers for a total of 50-55 of the fraction. This product was then bubble distilled (temperature: 1200- 14000) at a pressure of 1 mm Hg, thereby obtaining the pure product. I. R.: 1725, 1625, 1580 cm-Ú; NMR (#, ppm, CDCl3): 1.10-1.40 (CH3) 1.50-1.70 (m, -CH-CO) 2.00-2.25 (m, -CH-C=C) 4.15 (q, CH2O) 5.15-5.85 (m, CH=CH-CH=CCl2 6.0-6.5 (m, CH=CH-CH=CCl2) 6.6-7 (m, CH=CCl2). / alternative synthesis are reported in Examples 34 and 39] EXAMPLE 14 Preparation of the chloride of 3-(4',4'-dichlorobutadienyl)- -2,2-dimethyl-cyclopropanecarboxylic acid (trans), (3): EMI43.1 A) 0.002 mols of the product (1), obtained as described in the preceding example, were treated with 2.6 ml of a solution of KOH in methanol. It was then reflux heated for 4 hours by a water bath. Thereafter it was cooled down and then poured into 50 cc of water. It was then extracted with toluene (2 times, each time with 20 cc of sol vent). The organic phase was then washed with 20 cc of a 10% NaOH. The aqueous phases were then acidified with HC1 at 5% concentration and then extracted with toluene (3 times, each' time with 25 cc of solvent). The organic phase was thereupon washed with water until attaining a neutral pH, whereafter it was anhydrified on sodium sulphate and then evaporated, thereby obtaining 0.4 g of an oil consisting of the desired product (2). -1 I.R. (cm ): 3500 - 2500; 1700 - 1680; 1430; 1240; 1105; 890; 730; 690. B) The raw 3-(4', 4'-dichloro-butadienyl)-2,2-dimethyl-cyclo propanecarboxylic acid (2), obtained by means of the above described reaction, was dissolved in 3.5 cc of hexane. Then, at 0 -5 C, there were dripped in 3.5 m.molE of thionyl chloride. This mixture was then subjected to reflux and stirring for 4 hours. Thereafter the hexane was decanted from the tars and evaporated at 40 C under a pressure of 15 mmHg, thereby obtaining about 0.2 g of chloride of 2,2-dimethyl-3-(4', 4'-dichlorobutadienyl)-cy clopropanecarboxylic acid (3). -1 I.R., 9 (C = 0) : 1765 cm # (Cl2C = CH): 1580 cm-Ú 9(CH = CH) : 1615 cm EXAMPLE 15: Operating in the same way as that described in example 14, the following compounds were prepared: - Chloride of 3-(3', 4', 4'-trichlorobutadienyl)-2,2-dimethyl- -cyclopropanecarboxylic acid (trans) of formula: EMI45.1 or I.R. (cm ): 1765 (#C = 0) 1585 (#CCl2 = CCl) 1620 (#CH = CH); - Chloride of 3-(5', 5', 5'-trifluoro-4'-chloro-penta-1', 3'- -dienyl)-2,2-dimethyl-cyclopropanecarboxylic acid of for mula: EMI45.2 I.R. (cm-1): : 1765 () C = 0) 1580 (4 CF2-CCl = CH) 1630 (#CH = CH). EXAMPLE 16 Preparation of the i-cyano-3-phenoxybenzyl ester of the (#)-trans-3-(4', 4'-dichloobutadienyl)-2,2-dimethyl-cyclo propanecarboxylic acid (3) 7compound No. 1] EMI45.3 EMI46.1 0.2 g of the acylic chloride (1), prepared as described in example 15, were diluted with 1 cc of anhydrous ethylether. This mixture was cooled down to OOC and then there was drip ped into it a mixture of the cyanhidrine of phenoxybenzalde hyde (2) (180 mg = about 0.8 m.mols) in 0.5 cc of anhydrous ether. This mixture was subjected to stirring at room tem- perature for 1 hour, whereafter it was cooled down to OOC and into it was dripped a mixture consisting of 0.75 mols of pyridine and 0.5 cc of ether. Thereupon the temperature was allowed to slowly rise. The mixture was then maintained under stirring at room temperature overnight. The mixture was then diluted with 5 cc of benzene, washed with water up to a neutral pH (2 x 5 cc), anhydrified, filtered and evaporated whereby there was obtained an oily residue of about 400 mg. Thereupon was rapidly carried out a chromatography with 20 g of silica, eluting with hexaneethyl acetate (9:1). There were obtained 200 mg of a pure product (3). GLC titre = 90% (glass column, length = 1.2 mt., outside diameter = 6 mm, inside diameter = 4 mm; packed with Chromosorb W.H.P. 80-100 mesh, covered with silicon oil HCC - W 982; 3.8% by weight, temperature 280 C, isothermic). NMR (0D013 , ppm (TMS): 1.1-1.4 (CH3); 1.6-1.8 (m, /CH-CO) 2.0-2.5 (m, EMI47.1 - C=C); 5.0-5.8 (m, CH = CH-CH=CCl2); 6.2-6.5 (m, CH-CN and CH = OH - CH = CCl2); 6.9-7.6 (m, CH = CCl2 and aromatic protons). EXAMPLE 17 Preparation of the 3-phenoxy-benzyl ester of (+,trans), 2,2-dimethyl-3(4', 4'-dichlorobutadienyl)-cyclopropanecarboxylic acid (3) Compound No. 2]. EMI47.2 0.25 g of compound (1), prepared as described in example 14, were diluted with 0.5 cc of anhydrous benzene. It was then cooled down to 0 C and into it there was dripped a mixture consisting of 3-phenoxy-benzyl alcohol (2) (0.1 m.mols) and of 0.5 cc of anhydrous benzene. Then, still at OOC, there was dripped into it a mixture consisting of 0.9 m.mols of pyridine and 0.5 cc of anhydrous benzene. This mixture was then maintained under stirring at room temperature overnight Thereupon it was washed with water until attaining a neutral pH, anhydrified and finally evaporated, thereby obtaining 300 mg of raw product which was then purified by preparaory chromatography. GLC: 2 isomers, total 97% (glass column, length 2 metres, outer diameter 6 mm, inner diameter 4 mm; packed with Chromosorb W-HP of 80-100 mesh, covered with 3% by weight of silicon oil OV-210; isothermic temperature = 240 C). NMR CDCl3)#, , ppm (TMS): 1.1-1.3 (CH3); 1.5-1.7 (m, EMI48.1 2.0-2.3 (m, EMI48.2 5.05 (s, CH2-0); 5-5.8 (m, CH = CH-CH=CC12); 2 2 6.2-6.5 (m, CH = CH-CH=CCl2); 6.8-7.5 (m, CH=CCl2 and aromatic protons). EXAMPLE 18: Operating in the same way as that described in example 17, there was prepared the 3-phenoxy-benzyl ester of (+)trans -3-(3', 4', 4'-trichlorobutadienyl)-2,2-dimethyl-cyclopropane carboxylic acid [compound No. 3]: EMI48.3 IR (cm-Ú): 1715, 1620, 1580, 1480, 1250, 1210, 1160, 1110, 930, 780 and 690. NMR (CDCl3) #, ppm (TMS): 1.2-1.4 (CH3), 1.7-1.9 (m, EMI48.4 2.1-2.4 (m, 5.1 (s, CH2O), 5.5-6.2 (m, CH = CH - CC1 = CC1 2 6.9-7.6 (m, CH = CH - CCl and aromatic protons). EXAMPLE 19 Operating in the same way as that described in example 16, there was prepared i-cyano-3-phenoxy-benzyl ester of the (#)-trans-3-(5*, 5*, 5*-trifluoro-4'-chloro-penta-1', 3'-dienyl) -2,2-dimethyl-cyclopropanecarboxylic acid Compound No. 4] of the formula: EMI49.1 IR (cm ): 1725 (# C = 0); 1630 (# CH=CH). EXAMPLE 20 Preparation of 3-(E, Z-4', 4'-dichloro-2'-bromo-butadienyl) -2,2-dimethyl-carbethoxycyclopropane (trans): EMI49.2 The compound was prepared from the compound of example 13, [3-(4', 4'-dichlorobutadoienyl)-2,2-dimethyl-carbethoxycyclo propane] by bromination and dehydrobromination according to conventional methods (scheme lc). IR: 1730 cm-Ú (#C=0); 1595 cm-Ú (# C=C). [an alternative synthesis is reported in Example 37]. EXAMPLE 21: Preparation of the chloride of 3-(E,Z-4',4'-dichloro-2'-bro mo-butadienyl)-2,2-dimethyl-cyclopropanecarboxylic acid (trans): EMI50.1 The compound has been prepared in an analogous way to that described in example 14, starting from the corresponding ethyl ester (example 20). IR: 1775 cm-Ú (# C=0), 1595 cm-Ú (' C=C). EXAMPLE 22 Preparation of 3-phenoxy-benzyl ester of ro-2'-bromo-butadienyl)-2,2-dimethyl-cyclopropanecarboxylic acid (trans) Compound No. 5]: EMI50.2 The compound was prepared using the same method as that described in example 17, starting from the acyl-chloride of example 22 and from 3-phenoxy-benzyl alcohol. IR: 1730 cm-Ú (# C=00); 1590 cm-Ú (expanded band, # C=c + aro matics); NMR (CDCl3, TMS): # (ppm): 1.17( ) (6H, geminal methyls) 1.28) 1.65 (d, 1H, H A 2.02 (dd, 1H, H B 5.10 (s, 2H, CH2) 5.63-6.15 (d, d, 1H, HC) 6.40 (s, 1H, HD) 6.75-7.55 (m, 9H, aromatic protons) JHA-HB = 6.0 Hz JHB-HC = 10.0 Hz (s = singlet, d = doublet, dd = doublet of doublet, m = mul tiplet, J = coupling constant). EXAMPLE 23 Preparation of the # &alpha;-cyano-3-phenoxy-benzyl ester of the 3-(4' ,4'-dichloro-2-bromo-butadienyl)-2,2-dimethyl-cyclopro panecarboxylic acid(trans) compound No. 6 7. EMI51.1 The compound was prepared using the same method as that described in example 16, starting from the acyl-chloride of example 22 and from i-cyano-3-phenoxy-benzyl alcohol. IR: 1740 cm-Ú (# C=0=, 1590 cm-Ú (expanded band, # C=C + a romatics); NMR (CDCl3, TMS) g(ppm) : 1.0 - 1.45 (m, 6H, geminal methyls) 1.6 - 2.2 (m, 1H, H A 1.9 - 2.2 (m, 1H, H B 5.6-6.1 (d, d, 1H, HC) 6.3-6.45 (m, 2H, HD + CH-CN) 6.85 - 7.55 (m, 9H, aromatic protons) (d = doublet; m = multiplet). EXAMPLE 24 Preparation of the # i-cyano-3-phenoxy-benzyl ester of the 3-(E, Z-2', 4', 4'-trichloro-butadienyl)-2,2-dimethyl-cy panecarboxylic acid(trans) Compound No. 7]. EMI52.1 The compound was prepared starting from the ethyl ester of the 3-(E, Z-2', 4', 4'-trichloro-butadienyl)-2,2-dimethyl-cy clopropanecarboxylic acid (Compound B, example 7) which was converted to the corresponding acyl-chloride, operating in a similar way to that described in example 14, and then esterified with 4 -cyano-3-phenoxy-benzyl alcohol operating in a similar way to that described in example 16. NMR : (CDC13, TMS) g(ppm) : 1.05 - 1.45 (m, 6H, geminal methyls) 1.57 - 1.80 (m, 1H, H A 1.80 - 2.80 (m, 1H, H B 5.59 - 5.81 (d,d, Hc, E+Z) 6.35 (2H, HD + CH-CN) 6.87 - 7.65 (m, 9H, aromatic protons) (d = doublet; m = multiplet). EXAMPLE 25: Preparation of the ethyl ester of 3-(E,Z-4'-chloro-l',3' -pentadienyl)-2,2-dimethyl-cyclopropanecarboxylic acid: EMI53.1 The compound was prepared according to the same procedures that have been described in example 13, starting from [(2-carbethoxy-3,3-dimethyl)-cyclopropyl]-methyl-triphenylphosphoniumbromide and from ss-methyl-ss-chloro-acrolein EMI53.2 IR spectrum: meaningfull bands at: 1720, 1620, 1180 and -1 965 cm Ean an alternative synthesis is reported in Example 36]. EXAMPLE 26 : Preparation of the chloride of 3-(E,Z-4'-chloro-1' ,3'-penta dienyl)-2,2-dimethyl-cyclopropanecarboxylic acid: EMI54.1 The ethyl ester of the example nO 26 was subjected to an alkaline hydrolysis thereby obtaining the corresponding -1 carboxylic acid tIR: 1700 cm (o=O)ff and this latter, according to the methods described in example 14, was treated with thionyl chloride. IR of acyl-chloride: 1780 cm ( C=O) EXAMPLE 27 Preparation of i-cyano-3-phenoxy-benzyl ester of the3-(E, Z-4'-chloro-1', 3'-pentadienyl)-2,2-dimethyl-cyclopropanecarboxylic acid g Compound nO B]: EMI54.2 The compound was prepared by operating in an analogous way as that described in example 16, starting from acyl-chloride of example 26 and from i-cyano-3-phenoxy-benzyl alcohol. The product was obtained in the form of a mixture of cis -trans isomers on the cyclopropane ring, in a ratio of about 1:9. IR: 1720 cm-Ú (# C=0). EXAMPLE 28 (Method D): Preparation of the diethylester of 3,3-dichloro-2-propenephosphonic acid (reaction 20): EMI55.1 Into a 250 ml flask, fitted with a magnetic stirrer and a reflux condenser, there were introduced: 83 g (0.5 mols) of triethylphosphite [P (OC2H5)3] 73 g (0.5 mols) of 1,1,3-trichloropropene Cl2C=CH-CH2Cl. The reaction mixture was stirred for 5 hours at 160 C. It was then allowed to cool down to room temperature, wherein after it was distilled at reduced pressure thereby gathering the fraction with boiling point comprised between 145 and 15300 at a pressure of 18 mm Hg (104.7 g). The fraction thus gathered proved to consist of the product desired, having a purity of 96.6% (gas chromatographic titre GLC). IR (infrared spectroscopy), (cm-Ú): 1629 (# C=C); 1260 (# P = 0); 1025,. 965, 920. 1 S (ODOl ,TMS) H NMR (nuclear magnetic resonance): J , ppm EMI55.2 1.1-1.5 (t, 6H, OH 3 2.4-3.0 (dd, 2H, CH2-P) 3.8-4.4 (m, 4H, OCH 2 5.7-6.2 (m, 1H, CCl2=CH) JHA - HB = 7 Hz JHC - P = 22 Hz JHC - HD = 8 Hz (t = triplet; dd = doublet of doublet, m = multiplet; J = coupling constant). EXAMPLE 29: Preparation of the diethyl ester of 3,3-dichloro-1-bromo -2-propene-phosphonic acid (reaction 21): EMI56.1 Into a 1 litre flask, fitted with a mechanical stirrer and with a reflux condenser, closed by a calcium chloride valve, there were introduced: 125 g (0.5 mols) of diethylester of 3,3-dichloro-2-propene -phosphonic acid (obtained as described in example 28). 100 g (0.56 mols) of N-bromosuccinimide, 500 ml of carbon tetrachloride, 1.0 g of azo-bis-isobutyronitrile (A.B.N.). This mixture was then reflux heated, under constant stirring for 2 hours, after which there were admixed further 1.0 g of A.B.N. and refluxing was carried on under stirring for another 2 hours. After cooling down to OOC, the mixture was then filtered in order to remove the succinimide and from the filtrate was then evaporated the solvent. The residue was diluted in 500 ml of petroleum ether and then was cooled down to 0 C. Once again there precipitated a small quantity of succinimide which was removed by filter ing. From this filtrate, after evaporation of the solvent, there was obtained a residue which was purified by chromatography on a silica gel column (eluent: petroleum ether-CH2Cl2-ethy acetate in the ratio of 10:6:4). Thereby were obtained 135 g of the desired product. The product analysis showed: IR : in agreement with the assigned structure; Elemental analysis: C, in % : theoretical: 25.75 - found : 25.43 H, in % : " 3.71 - " 3.64 Cl,in % : " 21.75 - " 21.77 Br,in %: " 24.52 - " 25.39 P, in < 0 : " 9.50 - " 9.22 NMR , ppm (CDCl3, TMS) EMI57.1 1.35 (t, 6H, OH 3 4.22 (dq, 4H, O-CH2 4.68 (dd, 1H, CHBr) 6.16 (dd, 1H, =CH) JH -H H 7 Hz A B JHB - p = 8.5 Hz JHC - HD = 11.5 Hz JHC - p = 11.5 Hz JHD - p = 8 Hz. (t = triplet; dq = doublet of quartet; dd = doublet of doublet; J = coupling constant). EXAMPLE 30 Preparation of the diethyl ester of 2,3,3,3-tetrachloropro pane-phosphonic acid (Reaction 25) EMI58.1 Into a 500 ml flask, fitted with a mechanical stirrer, a thermometer and a reflux condenser connected with a H2 50 4 valve and with one column for the separation of the gases, there were introduced: 150 ml of benzene, 24.7 g of diethyl ester of 3,3-dichloro-2-propene-phospho nic acid (prepared as described in example 28), 13.5 g of sulphoryl chloride. This mixture was thereupon irradiated under stirring, with an Osram "Sonne" 300 Watt lamp, for 30 minutes, during which the internal (inside) temperature rose to 45 C shoing a development of gas. After cooling down to room temperature, the solvent was eva porated at reduced pressure, thereby obtaining a residue (32 grams) consisting of the desired product. Elemental analysis: Cl, in % : theoretical: 44.60 - found : 42.63 P , in % : " 9.79 - " 9.80 IR (cm 1265, 1230, 1170, 1025, 970. EXAMPLE 31 Preparation of the diethyl ester of 3,3,3-trichloro-l-propene-phosphonic acid: (Reaction 26) EMI59.1 Into a beaker of 300 ml holding capacity, fitted with a ma gnetical stirrer and a reflux condenser, closed by a calcium chloride valve, there were introduced 16 g of diethyl ester of 2,3,3,3-tetrachloropropane-phosphonic acid (prepared as described in example 30) 50 ml of n-hexane; 6 ml of diethylamine. This mixture was then subjected to stirring at room temperature for 3 hours whereafter it was allowed to rest overnight. After filtering the chlorohydrate that had formed, the filtrate was washed with 10 ml of HCl 2N, then with water until obtaining a neutral pH. After anhydration with anhydrous Na2SO4 and subsequent evaporation of the solvent at reduced pressure, there was obtained a residue (12.4 g) consisting of the desired product (b.p. = 84 -85 C at 0.08 mmHg). IR (cm-Ú): 1635; 1260; 1210; 1165; 1020; 970; NMR #, ppm, (CDCl3, TMS): EMI60.1 1.40 (t, 6H, CH3) 3 4.18 (dq, 4H, CH2) 6.32 (dd, 1H, HC) 7.10 (dd, 1H, HD) JHA - HB = 7 Hz JHB - p = 9 Hz JHC - HD = 16 Hz C D H -P = 14.5 Hz C JHD - p = 20 Hz (t = triplet; dq = doublet of quartet; dd = doublet of dou blet; J = coupling constant). EXAMPLE 32 Preparation of the diethyl ester of 1,3,3-trichloro-2-prope ne-phosphonic acid (Reaction 27) EMI60.2 Into a 100 ml beaker, fitted with a magnetical stirrer and with a reflux condenser closed by a clcium chloride valve, there were introduced: 2.8 g of diethyl ester of 3,3,3-trichloro-1-propene-phospho nic acid (obtained as described in example 31), 1 g of CuCl2. 2H2 0. This mixture was thereupon stirred for 1 hour and 15 minutes at 110 C. After cooling down to room temperature, it was additioned with 100 ml of ethyl ether and then filtered. The filtrate was then washed with water until achieving the full disappearance of the green colour, after which it was anhydrified on anhydrous Na2S04. The solvent was then evaporated under reduced pressure, thereby obtaining 25 g of the desired product (b.p. = 95 -96 C/0.08 mm Hg). Elemental analysis C , in S : theoretical = 29.87 - found = 29.21 H, in %: " = 4.3 - " = 4.01 P , in % : = 11.0 - " = 10.91 Cl, in % : " = 37.78 - " = 36.90 -1 ¯ (cm ) : 1615, 1270, 1025, 980, 920 NMR , ppm (CDCl3, TMS) EMI61.1 1.39 (t, 6H, CH3) 3.85-4.50 (m, 4H, CH3) 2 4.7 (dd, 1H, HC 6.08 (dd, 1H, HD JHA - HB = 5.5 Hz J H - HD = 10 Hz C HC - P = 13 Hz HD - p = 6 Hz (t = triplet, m = multiplet, dd = doublet of doublet, J = coupling constant). EXAMPLE 33 Preparation of diethyl ester of 3-chloro-2-butene-phosphonic acid. (Reaction 20) EMI62.1 Into a 100 ml flask, fitted with a magnetical stirrer and a reflux condenser, there were introduced 33.2 g (35 ml, 0.2 mols) of triethylphosphite 25 g (22 ml; 0.2 mols) of 1,3-dichloro-2-butene EMI62.2 The reaction mixture was thereupon subjected to stirring for 4 hours at 150 C, whereafter it was allowed to cool down to room temperature. Then it was distilled at reduced pressure, gathering the fraction with a b.p. of 145 -146 C at 15 mm Hg (37 g) and consisting of the desired product: NMR #, ppm (CDCl3, TMS) EMI63.1 1.1-1.5 (t, 6H, H A 2.0-2.2 (d, 3H, CH3-C=) 2.4-3.0 (dd, 2H, HC) 4.0-4.3 (dq, 4H, HB) 5.4-5.7 (m, 1H, HD) D J = 8 Hz H -H A B HB - p = 8 Hz HD - HC = 8 Hz H -P = 20 Hz HC - P (d = doublet; t = triplet; dd = doublet of doublet; dq - doublet of quadrouplet; m = multiplet, J = coupling constant). EXAMPLE 34 Preparation of ethyl ester of 2,2-dimethyl-3-(4,4-dichlorobutadienyl)-cyclopropanecarboxylic acid (Reaction 18): EMI64.1 Into a 500 ml flask, anhydrous and maintained under a nitrogen atmosphere, there were introduced 12.5 g of a suspen sion of about 50% of sodium hydride (0.26 mols) in paraffine oil. This suspension was then washed with anhydrous petroleum ether (2 x 50ml) and to it were then admixed 20C ml of anhydrous dimethoxyethane. To this mixture, kept under stirring at 5 -10 C under a ni trogen atmosphere, there was slowly dripped, in a period of 2 hours, a mixture consisting of: - 49.5 g (0.2 mols) of diethyl ester of 3,3-dichloro-2-pro pene-phosphonic acid (obtained as de scribed in example 28), - 0.24 mols of ethyl ester of the caronic aldehyde (cis -trans mixture in a ratio of 58:42). Once the admixture had been accomplished, the mixture was allowed to spontaneously heat up to room temperature whi le keeping it under constant stirring for 1 hour. The reaction mixture was then cooled down to 1000 and to it were then admixed dropwise 5 ml of ethyl alcohol and then 150 ml of a 1% hydrochloric acid. The mixture was then extracted with ethyl ether (2 x 100 ml). The reunited organic phases were then washed with water until reaching a neutral pH, anhydrified on anhydrous sodium sulphate and the solvent eliminated under reduced pressure. Thereby were obtained 76.2 g of a raw product (dark oil) which was distilled under reduced pressure thereby gathering the fraction with b.p. of 1050 - 109 C at 0.05 mm Hg (19 grams) consisting of the desired product (mixture of geometrical isomers) with a purity degree of 93 (GLC).. Elemental analysis C , in % : theoretical = 54.77 - found = 53.77 H , in % : = 6.13 - " = 6.18 Cl, in % : " = 26.95 - " = 25.65 The IR and NMR spectroscopic data were consistent with the assigned structure. EXAMPLE 35 Preparation of ethyl ester of the trans-2,2-dimethyl-3-(2, 4,4-trichloro-butadienyl)-cyclopropanecarboxylic acid (Reaction 18). Into a 250 ml flask, fitted with a mechanical stirrer, a reflux condenser and a dripping funnel, anhydrous and kept under a nitrogen atmosphere, there were introduced 2.5 g of a suspension of sodium hydride (50%) in paraffine oil. This suspension was washed with n.hexane (3 x 20 ml) whereafter it was additioned with 100 ml of anhydrous tetrahydrofurane (THF). This mixture was thereupon cooled down to -30 C and then additioned with 0.2 g of imidazol and 8.5 g of ethyl ester of trans-caronaldehyde. The mixture was then subjected to stirring and was additioned slowly over 30 minutes, by dripping, with a solu tion of diethyl ester of 1,3,3-trichloro-2-propene-phosphonic acid (obtained as described in example 32) in 30 ml of anhydrous THF. During the admixture, the temperature rose up to 1000. The mixture was allowed to spontaneously warm up to room temperature continuing to stirrer for 2 hours and 30 minutes. The reaction mixture was then poured into 100 g of water and ice; whereafter it was extracted with diethyl ether (3 x 100 ml). The reunited organic phases were then washed with water up to a neutral pH, thereupon anhydrified on anhydrous Wa2S04. The solvent was evaporated at reduced pressure, thereby obtaining a residue (16 g) which was purified by chromatography on a silica gel column (eluent n.hexane/ethyl aceta te = 8:2). There were obtained 13 grams of a product which was further purified by distillation and a fraction was gathered with b.p. = 1180-1220C at a pressure of 0.1 mmHg, and which con sisted of the desired product (9.8 g). -l IR (cm-) 1725, 1602 ÚH NMR#, ppm (CDCl3, TMS) EMI66.1 1.05-1.55 (m, 9H, methyl groups) 1.63 (d, 1H, HA) 1.98 (dd, 1H, HB) 5.62-5.85 (dd, 1H, HC, E + Z) 6.48 (s, 1H, HD) 4.13 (q, 2H, OCH2) JCH3-CH2 = 7 Hz JHA - HB = 5.5 Hz JHB - HC = 9.5 Hz (s = singlet; d = doublet; dd = doublet of doublet; q = quaX tet; m = multiplet; J = coupling constant). EXAMPLE 36 Preparation of ethyl ester of cis,trans-2,2-dimethyl-3-(4 -chloro-1,3-pentadienyl)-cyclopropanecarboxylic acid. Starting from: 7.2 g (0.04 mols) of ethyl ester of caronaldehyde (cis -trans mixture in a ratio of 1:8.5) and from 0.037 mols of diethyl ester of 3-chloro-2-butenphosphonic acid (prepared as described in example 33), and by operating in a way similar to that described in example 34, there were obtained 7.6 g of a raw substance which was then purified by chromatography on silica gel (eluent n.hexane/ethyl acetate in a ratio, of 85:15) obtaining 3.7 g of the desired product (a yellowish oil). IR (cm ) 1720, 1620, 1180, 965 NMRj, ppm (CDCl3, TMS) EMI68.1 1.1-1.4 (9H, CH3-CH2 and geminal methyls) 1.5-1.7 (1H, HA) 2.1-2.4 (4H, CH3-CCl and HB) 3.9-4.3 (2H, CH2) 5.0-6.8 (3H, HC, HD and HE) EXAMPLE 37 Preparation of ethyl ester of trans-2,2-dimethyl-3-(2-bromo -4,4-dichlorobutadienyl)-cyclopropanecarboxylic acid. Starting from: 8.5 g of ethyl ester of trans-caronaldehyde and 16.5 g of ethyl ester of 1-bromo-3,3-dichloro-2-propene-pho sphonic acid (obtained as described in example 29), and by operating in a way similar to that described in example 35, there were obtained 9.5 grams of the desired product (in this case it is not necessary a further purification by distillation). IR (cm-Ú) 1730 (# C = 0), 1595 (# C = C) NMR #, ppm (CDCl3, TMS) EMI69.1 1.26 (m, 9H, methyl groups) 1.63 (d, 1H, HA) 1.98 (dd, 1H, HB) 4.15 (q, 2H, CH2) 5.7-6.15 (dd, 1H, HC 6.37 (s, 1H, HD) J = 7.0 Hz CH - OH2 JHB - HA = 6.0 Hz JHB - HC = 9.0 Hz (s = singlet; d = doublet; dd = doublet of doublet; q = quartet; m = multiplet; J = coupling constant). EXAMPLE 38 : Preparation of 0-ethyl-0-(2'-chloroethyl)-3,3-dichloro-2 -propene-phosphonate. (Reaction 21) Into a 50 ml flask, fitted with a magnetical stirrer, a thermometer, a reflux condenser and connected with a H2S04 valve, under a nitrogen atmosphere and at room temperature, there loaded: - 14.5 g (0.1 mols) of 1,1,3-trichloro-propene - 13.5 g (0.1 mols) of 2-ethoxy-1,3,2-dioxaphospholane of the formula EMI69.2 The reaction mixture was then heated up to 140 C and then, in 2 hours and 30 minutes, the temperature was brought up to 165 C. The reaction mixture was thereupon allowed to cool down to room temperature and was then distilled at reduced pressure, gathering the fraction that distilled at between 1200 and 130 C at a pressure of 0.2 mmHg. The gathered fraction (15.3 g) proved to consist of the desired product showing a purity of 92% (GLC). IR (cm-Ú: 1620 (# C = C), 1260 (# P = 0), 1025, 970, 920 (# P-O-C) NMR (CDCl3, TMS) EMI70.1 # (ppm): 1.2-1.5 (t, 3H, CH3) 2.5-3.1 (dd, 2H, HB) 3.6-3.8 (t, 2H, HD) 4.0-4.5 (m, 4H, CH2-CH3 + HC) 5.7-6.15 (m, 1H, HA) JCH3-CH2 = 7 Hz JHB - p = 22 Hz JHB - HA = 8 Hz JHD - HC = 5 Hz (dd = doublet of doublet; t = triplet; m = multiplet; J = coupling constant). EXAMPLE 39 Preparation of ethyl ester of 2,2-dimethyl-3-(4,4-dichlorobutadienyl)-cyclopropanecarboxylic acid. (Reaction 18) Into a 100 ml flask, maintained in a nitrogen atmosphere, there were introduced 2 g of a 55% suspension of sodium hydride (NaH) in vaselin oil. The oil was then extracted by repeated washings (3 x 25 ml) with n.hexane, and there were then additioned 20 ml of tetrahydrofurane (THF). To this suspension, kept under stirring at 1000, there were then slowly admixed in 1.5 hours a mixture consisting of: - 3.4 g (0.02 mols) of caronic aldehyde (a cis-trans mixtu re). - 7.5 g (0.025 mols) of the phosphonate of example 38. - 5 ml of THF. Once the additions had been accomplished, the reaction mixture was subjected to stirring for further 30 minutes at 100C. Thereupon the reaction mixture was poured slowly into 100 ml of water and ice, after which it was extracted with diethylether (3 x 50 ml). The reunited extracts were then washed with cold water until attaining a neutral pH (3 x 50 ml), they were then anhy drified on anhydrous CaCl2 and the solvent was then removed by evaporation at reduced pressure. Thereby were obtained 6 grams of a raw oil which was chromatographied on silica gel (eluent n.hexane/ethyl ether in a ratio of 95:5). There were obtained 4 grams of the desired product in the form of mixture of geometric isomers having a purity degree t 95 (GLO). The elemental analysis, the IR and NMR values were consistent with the assigned structure. EXAMPLE 40 Insecticide activity of the compounds of the invention. The compounds of this invention were tested on larvae and adults of the following phytophagouses, according to the following methodologies. A) Biological activity on Macrosiphum euphorbiae (aphides): Pot-grown potato plants were infested with adult females of aphides and, after a few hours, were besprinkled with a hydroacetonic dispersion of the products under examina tion. The mortality percentage was determined 24 hours after treatment (mortality of the aphides on untreated plants was equal to 0). B) Biological activity on Pieris brassicae (Lepidoptera): Cut cauliflower leaves were submitted to besprinkling with a hydroacetonic dispersion of the products under examination. After drying, the leaves were infested with 5-days old larvae. The mortality percentage of said larvae (morta lity on untreated leaves = 0) was determined 48 hours after treatment. C) Biological activity on Leptinotarsa decemlineata (Cole optera). Small pot-grown potato plants were infested with 4-days old larvae and subsequently subjected to besprinkling with a hydroacetonic dispersion of the products under examination. The mortality percentage (untreated plants, mortality = 0) was determined 48 hours after the treat ment. D) Biological activity on Musca domestica (Diptera) 4-days old adults were treated, by topical application with a microsyringe, with an acetonic solution of the products under examination. The mortality percentage (mortality of the insects tre ated only with acetone = 0) was determined 24 hours af ter treatment. E) Biological activity on Blatta orientalis (Orthoptera) The bottom and walls of crystallizers of glass were uni formly treated with an acetonic solution of the products under examination. After evaporation of the solvent, in each crystallizer there were introduced 80-100 days old neanides, there upon closing the crystallizers with a metal net cover. 24 hours after treatment the insect were transferred in similar, untreated crystallizers and suitably fed. The mortality percentage (mortality of untreated in sects = 0) was determined 48 hours after the start of the treatment. F) Biological activity on Tetranychus urticae adults (Aca ri): Bean leaf discs were infested with adult acari and suc cessively besprinkled with a hydroacetonic dispersion of the products under examination. The mortality percentage was determined 24 hours after treatment (mortality of the acari on untreated foliar discs = O). G) Biological activity on Spodoptera littoralis Cut tobacco leaves were besprinkled with a hydroaceto nic dispersion of the products under examination. After drying, the leaves were infested with 5-days old larvae. The percentage of mortality of the larvae was determined 48 hours after treatment. (The mortality of the larvae on untreated leaves = 0). H) Biological activity on Tetranychus urticae eggs (Acari): Bean leaf discs, previously infested with ac-ari eggs, were treated by besprinkling with a hydroacetonic di spersion of the products under examination. The percen tage of unhatched eggs (equivalent to the mortality per centage) was evaluated, 6 days after treatment, in com parison with the percentage of unhatched eggs on the un treated foliar discs. The biological activity data of some representative co pounds have been recorded on the following Table 1 and are expressed as a mortality percentage at the indicat ed dose. T a b l e 1 Biological activity of compounds of the invention expressed as percentage of mortality of the pasts at the indicated doses. EMI75.1 Compound <SEP> n <SEP> Macrosiphum <SEP> e. <SEP> Pieris <SEP> b. <SEP> Leptinotares <SEP> d. <SEP> Spodoptera <SEP> l. <SEP> Musca <SEP> d. <SEP> Tetranichus <SEP> u. <SEP> Blatts <SEP> o. <tb> <SEP> (adults) <tb> (example <SEP> n ) <SEP> (0.1 <SEP> %.) <SEP> (0.1 <SEP> %.) <SEP> (0.1 <SEP> %.) <SEP> (0.1 <SEP> %.) <SEP> (0.1#/lns.) <SEP> (0.1%.) <SEP> (0.1 <SEP> %.) <tb> 1 <SEP> (16) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <tb> 2 <SEP> (17) <SEP> 80 <SEP> 62 <SEP> 100 <SEP> 100 <tb> 3 <SEP> (18) <SEP> 90 <SEP> 100 <tb> 4 <SEP> (19) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 70 <SEP> 100 <tb> 6 <SEP> (23) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <tb> 7 <SEP> (24) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 86 <SEP> 100 <SEP> 53 <tb> 8 <SEP> (27) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 40 <SEP> 100 <tb> In the following Table 2 there has been reported the biological activity against acari eggs (Tetranichus urticae) of Compound No. 4 (example 19) in comparison with that of known pyrethroids. TABLE 2 EMI76.1 <tb> Compound <SEP> dose <SEP> (o) <SEP> 0.1 <SEP> 0.05 <tb> <SEP> 4 <SEP> 100 <SEP> 100 <tb> Permethrin <SEP> (a) <SEP> 18 <SEP> 0 <tb> Cipermethrin <SEP> (b) <SEP> 11 <SEP> 0 <tb> Decamethrin <SEP> (c) <SEP> O <SEP> 0 <tb> Phenvalerate <SEP> (d) <SEP> 18 <SEP> 0 <tb> (a) Permethrin : 3-phenoxy-benzyl ester of 2,2-dime thyl-3-(ss, ss-dichlorovinyl)-cyclopro panecarboxylic acid; (b) Cipermethrin : i-cyano-3-phenoxy-benzyl ester of 2,2-dimethyl 3-(13,P-dichlorovinyl) -cyclopropanecarboxylic acid; (c) Decamethrin : &alpha; -cyano-3-phenoxy-benzyl ester of 2,2-dimethyl-3-(ss, ss-dibromovinyl) -cyclopropanecarboxylic acid; (d) Phenvalerate : i-cyano-3-phenoxy-benzyl ester of 1-(4'-chlorophenyl)-2-methyl-butyric acid. In the above formulae alkyl C1 -C4 is e.g. methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec.-butyl, tert.butyl. This also applies for more complex radicals like alkoxy or haloalkyl etc. If alkyl is not defined lower alkyl groups e.g. with 1 - 6 carbon atoms are preferred, especially alkyl groups with 1 - 4 carbon atoms. Alkyl C1-C5 also includes pentyl, i-pentyl etc. If halogen is not specified it is F, C1, Be or J.

Claims: CLAIMS 1) Compounds of general formula (I) EMI78.1 wherein: R = OH, O-alkyl C1-C4, halogen, EMI78.2 (R5 = H, CN, -C#CH) RÚ = F, Cl, Br, CH3, CF3 R2 = F, C1, Br, CF3 R = H, F, Cl, Br, CF 3 R4 = H, F, Cl, Br, CF3 êand R or R and R together form a third bond between the car bon atoms to which they are bonded. 2) Compounds of general formula I, according to claim 1, wherein: EMI78.3 and R5 = H, CN. 3) The &alpha;-cyano-3-phenoxy-benzyl ester of 3-( 4' ,4 '-di- chloro-butadienyl)-2,2-dimethyl-cyclopropanocarboxylic acid, of 3-(4',4'-dichloro-2'-bromo-butadienyl)-2,2-dimethyi cyclopropanecarboxylic acid or of 3-(2',4',4'-trichloro-butadienyl)-2,2-dimethyl- cyclopropanecarboxylic acid. 4) The 3-phenoxy-benzyl ester of 3-(4',4'-dichlorobuta dienyl)-2,2-dimethyl-cyclopropanecarboxylic acid, of 3-(3',4',4'-trichlorobutadienyl)-2,2-dsmethyl-cyclo- propanecarboxylic acid or of 3-(4', 4'-dichloro-2'-bromo-butadienyl)-2,2-di methyl-cyclopropanecarboxylic acid. 5) The & -cyano-3-phenoxy-benzyl ester of 3-(5' ,5' ,5'- trifluoro-4'-chloro-penta-1',3'-dienyl)-2,2-dimethyl- cyclopropanecarboxylic acid or of 3-(4'-chloro-1', 3'-pentadienyl)-2,2-dimethyl cyclopropanecarboxylic acid. 6) Compounds of general formula I, according to claim 1, wherein: R = OH, O-alkyl C1 -C4 , halogen. 7) Compounds according to claim 6), having the formula: EMI80.1 wherein: R = OH,OC2H5, Cl. 8) Compounds according to claim 6), having the formula: EMI80.2 EMI81.1 wherein R = OH, OC2H5, C1. 9) Compounds of the general formula: EMI81.2 wherein X and X' (equal to or different from each other) are equal to halogen. 10 ) Compounds of the general formula: EMI81.3 wherein: X = F, Cl, Br; X' and X" (equal to or diffe rent from each other) = Cl, Br. 11) Compounds of the general formula: EMI81.4 wherein: X = F, Cl, Br. 12) Compounds of the general formula: EMI81.5 wherein: R1 = F, Cl, Br, CH3, CF3; Rê = F; C1, Br, CF3; R = H, F, C1, Br; R7 and R8, equal to or different from each other, = alkyl or haloalkyl with C 1-C4, or R7 and R together constitute a EMI82.1 group or a EMI82.2 group, provided that when RÚ = CH3, Rê will be different from Cl. 13) Process for preparing the compounds of claim 1, whe rein R is different from hydrogen, characterized in that a compound of the formula: EMI82.3 [wherein R1, R2 and R3 have the meanings reported in claim 1; R = F, Cl, Br, CF3; X and X', either equal to or different from each other, = Cl, Br], is made to react with triphenyl-phosphine (C6H5)3P according to the equation: : EMI82.4 and the ylide (2) thus obtained is made to react with a lower alkyl ester of 2,2-dimethyl-3-formyl-cyclopro panecarboxylic acid (carbonic aldehyde) thereby obtain ing the compounds of general formula I, wherein R4 # H and R = O-alkyl, and from which, by hydrolysis, there 4 are prepared the compounds of formula I wherein R / H and R = OH, which in their turn are treated with thio nyl chloride (SOCl2) thereby obtaining the compounds of formula I wherein R4 # H and R = Cl, which finally, by reaction with an alcohol of the formula: : EMI83.1 wherein R5 = H, CN; -C # CH, give the compounds of formula I wherein R4 # H and where EMI83.2 (R5 = H, CN, -C=CH). 14) Process for preparing the compounds of claim 1, whe rein R = H, characterized in that an ester of 3,3-di methyl-4-pentenoic or 2-alcoxycarbonyl-3,3-dimethyl -4-pentenoic acid, having the formula: EMI83.3 (wherein n = 1' or 2), is made to react, in the presence of radical reaction promoters, with a polyhaloalkane (propane or buthane) of the formula: EMI84.1 wherein RÚ, Rê and R4 have the meanings indicated in claim 1, X, X' and X" = Cl or Br, thereby obtaining the compounds of formula: EMI84.2 (wherein RÚ, R2, R , X, X', X" and n have the meanings previously reported), which by treatment with bases undergo in one or more stages, three successive. dehydrohalogenations optionally followed (in the case n = 2) by a decarboxylation, affording the compounds of claim 1, wherein R3 = H, R = OH, O-alkyl, which are converted to the corresponding acyl-chlorides (form. I, R3 = H, R = cl) and finally, from these, by reaction with an alcohol of the formula: EMI84.3 (wherein Rb = H, CN; -C=CH) there are obtained the compounds of claim 1 wherein R3 = H and EMI85.1 (wherein R5 = H, CN, -C # CH). 15) Process for the preparation of the compounds of claim 1, wherein R4 = H, characterized in that a lo wer alkyl ester of 2,2-dimethyl-3-bromomethyl-cyclo propanecarboxylic acid of the formula: EMI85.2 is converted by treatment with triphenylphosphine (C 6H5)3P, to the phosphonium salt of formula: (C6H5)3P# - CH2 EMI85.3 COO-alkyl Br which, by reaction, in the presence of a strong base, with an aldehyde of the formula: EMI85.4 (wherein R , R2 and R3 have the meanings given to them in claim 1) affords the compounds of claim 1 of 4 formula I wherein R = H and R = O-alkyl; said com- pounds, by hydrolysis yield the compounds of formula A I wherein R = H, R = OH, and which, by treatment wit thionyl chloride (SOCl2) afford the compounds of formula I wherein R = H and R = Cl, and, finally, from these latter, by reaction with an alcohol of the for mula: EMI86.1 (wherein R5 = H, CN, -C#CH), there are obtained the compounds of formula I wherein R4 = H and EMI86.2 (wherein R5 = H, CN, -C # CH). 16) Process for the preparation of the compounds of daiml, in which R = H, R4 = H, F, Cl, Br, characterized in that a phosphonate of formula: EMI86.3 wherein R1 and R2 have the meanings reported in 6 = H, F, Cl and Br and R7 and R8 claim 1, R = H, F, Cl, Br and R and R , equal to or different from each other, represent an alkyl or a haloalkyl having from 1 to 4 carbon atoms, or R7 and R8 together form either a EMI87.1 group; is made to react at a temperature of between -50 and 100 C, in the presence of a strong base and in a suitable solvent or diluent, with a lower alkyl ester of 2,2-dimethyl -3-formyl-cyclopropanecarboxylic acid (caronic aldehyde) of following formula: EMI87.2 (wherein R = O-alkyl C1-C4) thereby obtaining the compounds of claim 1 in which R = H, R4 = H, F, C1, Br and R = O-alkyl C1-C4 which are then converted into the corresponding carboxylic acid (R=OH) and acyl-chloride (R=C1) which, in their turn, are made to react with an alcohol of formula: EMI87.3 thus obtaining the compounds of claim 1 in which: : EMI87.4 17) Process according to claim 16, characterized in that the reaction between phosphonate VII and the caronic aldehyde is conducted at a temperature comprised between -300C and room temperature and/or b) tie strong base is either a hydride or a hydroxide of aii alkaline metal and/or C) as an inert solvent or diluent there is used an ether, an aprotic polar solvent or a mixture of polar -apolar solvents and/or d) starting from lower alkyl esters of caronic aldehyde in the cis or transform, there are obtained the cy clopropanecarboxylic esters in the corresponding iso meric form and/or e) the reaction between phosphonate VII and the alkyl ester of the caronic aldehyde, is carried out by admixing a mixture of the aforesaid compounds to a suspension or solution of the strong base in a suit able solvent or f) the reaction between the phosphonate VII and the al kyl ester of the caronic aldehyde is carried out by adding a solution of phosphonate VII in a suitable solvent to a suspension or solution of the base and of the alkyl ester of caronic aldehyde in a suit able solvent. 18) Process for the preparation of the compounds of claim 10, characterized in that a compound of the formula: EMI89.1 Wherein X = F, C1, Br; X' and X", equal to or different from each other, = C1, Br] ] is made to react, in the presence of radical reaction promoters, with the vinylidene chloride (CH2 = CC12) in a molar ratio from 1 to 4 in inert solvents and at a temperature of between 500 and 20000, according to the equation: EMI89.2 wherein X, X' and X" have the meanings previously in dicated. 19) Process for the preparation of the compounds of claim 9, characterized in that a compound according to claim 10 , of formula: EMI89.3 is dehydrohalogenated in an inert solvent and in the presence of a base. 20) Process for the preparation of the compounds of claim 11, characterized in that a l,l,1-trifluoro-2,2,2-tri haloethane of the formula: CF3 - CXX'2 wherein X = F, Cl, Br; X' = Cl, Br, is added to a vinyl ether of the formula: OH2 = CH - 0 - Y (wherein Y = alkyl C1-C4 or EMI90.1 with R' = alkyl C1-C4) thereby obtaining the adduct of formula: EMI90.2 (wherein X, X' and Y have the meanings previously in dicated) and this adduct is subjected to dehydrohalo generation and hydrolysis of the &alpha;-haloetheric group by treatment with water at the boiling temperature, or with bases or with salts developing an alkaline action. 21) Process for the preparation of the compounds accord ing to claim 12, having the formula VII wherein R6 = C1, Br, characterized in that a compound of for mula: EMI90.3 R' X OR (wherein X = Cl, Br and RÚ, Rê, R7 and R8 have the meanings indicated in claim 21) is isomerized at a temperature comprised between 200 and 150 C, in the presence of a cupric halide. 22) Process according to claim 21, characterized in that the isomerization of compound XI is achieved by stir ring of a mixture of the above indicated compound with the cupric halide. 23) lnsecticide and/or acaricide compositions having as an active principle one or more of the compounds of claim 1, wherein EMI91.1

Inventors: BOSONE, ENRICO, DR., CAPRARA, GIUSEPPE, CAPRIOLI, VINCENZO, CORDA, FRANCESCO, GOZZO, FRANCO, DR., MENCONI, AUGUSTO, DR., PICCARDI, PAOLO
Applicants: MONTEDISON S.P.A.
Application year: 1980
Main classification: C07C69
IPC codes: C07F9, A01N53, C07C45, C07D307, C07C61, C07C255, C07C17, C07C47