INSECTICIDES. HALOGENATED ESTERS, THEIR PREPARATION PROCESS AND THEIR USE AS

Description

TITLE HALOGENATED ESTERS / THEIR PROCESS PREPARATION AND THEIR USE AS INSECTICIDES. t PRIORITY GREAT BRITAIN PATENT DOCUMENT NO. 2763 / 77 OF 24 JANUARY 1977 PATENT DOCUMENT NO. 12210 / 77 OF 23 MARCH 1977 PATENT DOCUMENT NO. 36714 / 77 - 36715 / 77 OF 2 SEPTEMBER 1977 Rome, there WUJB. W Chicee - TJvOll 4 / 603 59 ve ì_Pr ofoc.nl lo h° 536 A / 78 MINISTRY OF INDUSTRY, COMMERCE AND F. L L'A R TJCI AH AT 0 3ύ*''ίί* w , 1 · - ,> - ( J. -» · , · ' ' . . , ,! iLUV Ul Ivo ItAI t » COPY OF THE MINUTES OF FILING FOR INDUSTRIAL INVENTION PATENT In the year 1978, on the TWENTY-THREEth day of the month of JANUARY forty-six, the Company IMPERIAL CHEMICAL INDUSTRIES LIMITED, having its registered office at Imperial Chemical House, ΣΤί / ΡΐΤϊυ, in Millbank, London SW1V, Great Britain, of British nationality. Via through the agent International Patent Office Eng. C. GREGORJ and with domicile for legal purposes in Milan - Via Dogana l at the agent himself has presented to me, the undersigned: - Stamped application for the granting of a PATENT FOR INDUSTRIAL INVENTION MAIN having as title: HALOGENATED ESTERS, THEIR PREPARATION PROCESS AND THEIR USE AS INSECTICIDES Inventor designat f * Priority - of the patent application in: GREAT BRITAIN No. 2763 / 77 of 24 January 1977 No. 12210 / 77 of 23 March 1977 No. 36714 / 77 of 2 September 1977 No. 36715 / 77 of 2 September 1977 supplementary to patent no. (application __ ) filed with the granted party accompanied by: - Description in duplicate of η. 101 pages of writing. - Letter of appointment - Priority document and Italian translation (reservation) - Proof of payment on postal account no. 1 / 11770 in the name of the Tax and Concession Registry Office Rome of L.22 2 , OOO issued by the Post Office of Milan - Revenue stamp of L, 1,500.32 on January 23, 1978 229 The application, descriptions and drawings listed above have been signed by the applicant and countersigned by me and stamped with the official seal. The UEEICIaTe '^·'' ' Z' Peter Mecsineus For a true copy of the original.\rijUT Director (Federico Nappi) RfiEVEUl dall) THE HEAD OF (Dr. He: MARC 4 / 60359 ve. 1953 and A / 78 Hon. MINISTRY OF INDUSTRY, TRADE AND CRAFTS Central Patent Office - ROME to company IMPERIAL CHEMICALINDUSTRIES LIMITED with headquarters at: Imperia Chemical House, Millbank, London SW 1 -Great BritainTò of British nationality through agent and domiciliary PATENT OFFICE ING. C. GREGORJ, Milan, Via Dogana 1 - requests a patent certificate for an industrial invention entitled: « HALOGENATED ESTERS, THE PROCESS OF THEIR PREPARATION AND THEIR USE AS INSECTICIDES PRIORITY* OF THE PATENT APPLICATION IN GREAT BRITAIN No. 2763 / 77 of 24 January 1977 No. 12210 / 77 of 23 March 1977 No. 36714 / 77 of 2 September 1977 No. 36715 / 77 of 2 September 1977 the following documents are attached to this document: 1. - Description in duplicate. 3. - Letter of appointment. na&aw 4. - Att / n of version. in o / o L. plus one of L. 1,600. 5. - Priority document with Italian translation, (reservation) Milan, January 23, 1978 ICI Case No ϊ PP 29295 / 29427 / 29775 / 29776 4 / 60559 ve. Description of the invention entitled: HALOGENATED ESTERS, PROCESS FOR THEIR PARALYSIS AND THEIR USE AS INSECTICIDES ￂﾷ' a none: IMPERIAL CHEMICAL INDUSTRIES LIMITED a: Imperial Chemical House, Millbank, London SII - Great Britain of British nationality and elected domicile for all legal purposes in Milan - Via i Dogana,! - at the office of the Patent Agent Ing.C.GregorJ 2 P / 1Q fe, VV à-i'l Mj | (Deposit. on January 1978 - No. volume > U' oc co OR O ί ; ZJ : The present invention relates to new cyclopropane derivatives usable as insecticides, to processes for their preparation and to methods for combating infestations by insects and similar invertebrates using the same. It has long been known that certain naturally occurring cyclopropanecarboxylic acid esters possess insecticidal properties, but these compounds are too easily degraded by ultraviolet light to be used extensively in agriculture. PATENT OFFICE ING. C. GREGORJ r -2Numerous groups of synthetic compounds based on cyclopropanecarboxylic acids (for example those described in British patents No. 1,243,85β) are No. 1,413*491 were examined in an attempt to discover compounds of sufficient light stability for use as insecticides in agriculture. The Applicant has now discovered that compounds according to the general formula: R 1R 2C sCH-CH-CK-CR \ / 6Hj 'cHj 2 where R and R both represent haloalkyl groups containing 1 or 2 carbon atoms, ojd 1 2 where one of R and R is a haloalkyl group • · • · ·. · » • · · ·>· • · · • a * of this type and the other is a halogen atom or even a methyl group, / in which R represents a phenoxybenzyloxy group optionally substituted in the a position with a cyano or ethynyl group, show very good insecticidal characteristics associated with good resistance to degradation by light, and that similar compounds in which R represents a hydroxyl group or an alkoxy group containing up to 6 carbon atoms, or a halogen atom are usable as <!......σι ’ ! -3 intermediates for the preparation of insecticides. R represents a phenoxybenzyloxy or phenoxybenzyloxy group, it is preferably a 3-phenoxybenzyloxy, or 5-phenoxy group. α-substituted benzyloxy. ι i In one aspect, therefore, the present invention provides compounds according to the general formula: At 2C. CH, CH, V / \ °o 6h 5 • · ·· (I) *>· • ee • *·· e · • e · 2 where one of R and R represents a group of formulas W-(CF ) « 2'm | where W represents a hydrogen, fluorine ! or chlorine atom and m has the value of 1 or 2, and ί i 2 | the other of R and R represents a fluorine atom, I ì chlorine or bromine, or a group of formula: ! Ϊ xc* z where each of X» Ϊ and Z independently represents a hydrogen, fluorine, or chlorine atom, and R represents a hydrogen atom or ι i Sho, 0 Gii. GOB -4cyano or ethynyl group. One of the preferred groups of compounds according to the invention is represented by those compounds according to the general formula I, given above, 1 2 wherein one of E and E represents a group of formula: wcf 2 where W represents a hydrogen, fluorine, or 1 2 chlorine atom, and the other between E and E represents a formula group: *· · ** • 4 to « · 4 4 4 4 4 :· 4 4 4 4 • G • · >4 y XC« z · 4 ·>· • 4 4 4 4 • 4' » •ρ where X, Y and Z have the meaning previously established 5» and E represents a hydrogen atom or the cyano group. Within this preferred group of compounds, those which are particularly 2 preferred are those where E and E are both trifluoromethyl groups. Another preferred group of compounds according to the invention is represented by those compounds according to the general formula I given above, 2 where one of E and E represents a formula group WCE„PATENT OFFICE <NG. C. GREGORJ —5— #· ? where W represents a hydrogen atom, fluorine, or chlorine, and the other of E and E represents a fluorine atom, chlorine, or bromine, and E represents a hydrogen atom or the cyano group. Particularly preferred compounds within this group are those in which one of E and E represents the trifluoromethyl group and the other represents a chlorine or bromine atom. It should be kept in mind by specialists in the field that the compounds represented by formula I are capable of existing in various geometric forms and stereoisomers. Therefore, cis and trans isomers can exist resulting from the substitution scheme of the cyclopropane ring, and 0 0 0* • · * e · e * ♦ 0000· • · ·· • · · e ...e 4 • 00 0 0 ·.·· 0 0· ·;·. • » 0 E and Z isomers derived from the vinyl group 1 2 substituted when E is not equal to E . Furthermore, two since they are substituted asymmetrically 3 of the three carbon atoms of cyclopropane are ι capable of existing in either the E or S configuration, or» and when R' is not hydrogen, the carbon atom to which it is attached is also capable of existing in either the R or S configuration. Thus, for a compound according to the formula I in 12 5 where E and E are equal and R is hydrogen» there are four possibilities of isomerism, arising from our -6cyclopropane ring substitution« These can be indicated by reference to their absolute configuration, such as (1R,5R), (1R,5S), (1S,3S) (1S,3R). When R is not hydrogen, there are eight possible isomers, since each of the four possible cyclopropane ring configurations must exist in two forms, one corresponding to the S configuration and the other to the R configuration of the carbon atom bearing the R group. In all alternative if R is hydrogen and R is not equal to 2 R there are again eight possibilities of isomerism, since each of the four possible configurations of the cyclopropane ring must exist in two forms, one corresponding to the Z configuration and the other to the E configuration of the vinyl group. 2 5 Finally, when R is not equal to R » and R ι ι it is not hydrogen, each compound can exist in 1, sixteen isomeric forms. Table I lists compounds according to the invention. Each of the compounds listed is a racemic mixture of (+) and (-) isomers although a distinction is made between cis and trans substitution on the cyclopropane ring and E and Z substitution in the vinyl group in which it is present. VX C. fin -7The compounds in Table I all conform to the following formula: “C=C OC -H6 5 TABLE I ****** COMPOUND No, R1 ciif 2 CIIF 2 II trans 7 chf 2 CUF 2 CN cis 8 CIIP 2 cuf 2 CN trans 9 CF 2C1 CF 2C1 II cis IO CF 2C1 CF 2C1 II trans 11 CF 2C1 CF 2C.l CN cis 12 Cf 2Cl CF ?C1 CN trans β. TABLE 1' (continuation) compound E 1 P 2 P? COLF IGURATION No. OF SUBSTITUENTS ♦ · 1 0 ON THE CYCLOPROPANE RING • *· • 0· t· 0 »· 0 0 . .· 0 0> 0 0 · 13 CP 3 CF 3 C;CII cls 0 0 1 ... V ;· 0 0 1 0 0 0 0 0 14 cp 3 CF ci 3 CsCII trans 0 0 • · 0 15 CIIP 2 CF- 3 CN cls ·:: • 0 • 0 0 • 16 CF 3 CIIF 2 CN cis 0 0 *· • ι · 17 chf 2 cf 3 CN trans 0 0 0 18 cf 3 chf 2 CN trans 0 0 0 0 . • · 19 ch 3 cf 3 CN cis 20 cf 3 ch 3 CN cis 21 ch 3 C13 CN trans 22 cf 3 CII3 CN trans 23 CIL· 3 cf 3 II cis 24 CF3 CU 3 II cis 95?ju13LLA I ( contiRuasiono ) PATENT OFFICE ENG. C. GREGORJ -10ΤΑΰΒΝΝΑ I (cpn.ttuition ) composed 1 IT R 2 3 le CO?n?IGWAZIGHE t No. DI SUBSTITUENTI 1 « 9 9 · 3υΐΛ»ΛΝ£ΐώΟ • · * · » 0 0 CYCLOPROPANEICO • · » 0 · ,»0 · 0 * · —»0 0 · 37 CF„ Cl II trans • · • 0 0 <·· 0 • * • • · · 0 · 38 Cl Cl? II trans 0 u.. II 39 Cl? Cl 3 Cl H txim ·: . · · * · r.. · 2 • .· ··' 40 Cl Cl'“ Cl II cis ·« • * 0 0« 0 1 2 • 0t ·' f·; ·. 41 CF„C1 Cl li trans • 1 • 0 0 0 » ·· z 0 · » 0 0 42 Cl Cf' Cl II trans 0 0 ► 0 2 0 · ► 0 * 43 CF ?C1. Cl CN cis 44 Cl C1-' 2C1 CN cis 45 CF 2C1 Cl CN trans 46 Cl CP 2C1 CN trans 47 CF 2C1 1? CN cis 4 8 CP 2C1 F CN trans ιΐΓποϊπ ΠίτΓνη......γ -31__£ (coatiniVìMone» ) COMPOUND Νθ· κ 1 P? 3 P CO'ÌPICuPJrlIQIK ,, t DI S0STITTK5IìTÌy / GULI'jWLLO XiC ,ι CYCLOHYOPA3IC 0*: * 49 CF 2C1 FH cis .........-? • • 4*4* 4 4 4 4 4 50 CF„C1 FH · trans 4 4 4 4 :· 2 • 51 cicf 2cf 2 Cl CN cis ···» 4 52 C1CF 2CF 2 Cl CN trans 4 » *4 c2 trans 4 Cl 4 C53 4 4 4 4 4 4 54 of 3 Br CN cis • ·* · is 4 4 4 4 * 55 Br CN trans 57 Br cf 3 CN trans 58 CF 3 Cl C=CII cis 3 CF C 39 Cl C'^CII trans 61 Cl CF 3 CslCH trans JN Today Kb:-.. ING. G GüKGu -12Particularly useful compounds of formula I according to the invention include: C+)-cyano-3-phenoxlbenzyl (+)-£Ìs / trans-3-(2-chloro3.3.3-trifluoroprop-l-en-l-yl)-2,2pro-dimethyl pan carboxylate, (+)-a-cyano-3-phenoxybenzyl (+>cis / tran8-3+(3,3,3-j tr fluoro-2-trÌf fluoromethylprop-l-en-l-yl )-2,2-dimethylcyclopropane carboxylate, | i ι (+)-a-cyano-3-phenoxybenzyl (+)-cls / trans-3-(3-chloro2.3.3- trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane I carboxylate, (+)-a-cyano-3-phenoxybenzyl (+)-cis / trans-3-(3-bromo3.3.3- trifluoroprop-l-en-l-yl)-2,2-dimethylcycloprotean carboxylate, and 3-phenoxybenzyl (+)-cis / trans-3-(2-chloro-3,3,3- | trifluoro-prop-l-en-l-yl)~2,2-dimethylcyclopropane j carboxylate, and | 3-phenoxybenzyl (+)-eiB / trans-3-(3,3,3-trlfluoro-2trifluoromethylprop-l-en-1-11)-2,2-dimethylcyclopropcn carboxylate· j ι The compounds of the invention according to the formula are esters and may be prepared by esterification processes, of which the following are examples. Ϊ· eeaeee ···· • I · •••e • and « and ·♦·· • eeeeaeeea aaaav • eaa · a · • eea · .* ea · e·· and « a · · A 2c “CH-CH-CH-C-OH \ / c X\ CHj CH^ Where R and R have any of the meanings previously given herein, can be reacted directly with an alcohol of formula ♦ ··· '· *** • * · e · a ··· • 44 · · HO-CH(ir) OCA / 65 where R represents the hydrogen atom, or the cyano or ethynyl group, the reaction taking place preferably in the presence of an acid catalyst, e.g., dry hydrogen chloride. (b) An acyl halide of the formula rVcxxCH-CH-CH-CQ \z CH \iH, 3 where Q represents a halogen atom, preferably a chlorine atom, and R and R have any of the meanings previously given here, can be reacted with an alcohol of the formula: 4··· a··· ·· « · ····, 4 a · « ' * ·* 4 4 ·*· • · 4 4 4 jrulO BRBVL. .. ENG. C. GREGORJ where λ represents the hydrogen atom or the ; cyano or ethynyl group» the reaction taking place j ! I preferably in the presence of a base, e.g., pyridine, alkali metal hydroxide or carbonate, or alkali metal alkoxide. As an alternative when R is to be the cyano group, a mixture of alkali metal cyanide and 3-phenoxybenzaldehyde may be employed in place of α-cyano-3-phenoxybenzyl alcohol. (c) An acid of the formula . ····< • · e · 1 e · e tee A^sCH-CH-ChJì'-QH V '3 CH, CH^ or, preferably, an alkali metal compound thereof, can be reacted with a halogen of formula» °°6 H5 where Q* represents a halogen atom, preferably the chlorine atom, and R represents the atpη Ρ' 1' '.,'Η I -15mo of hydrogen, or the cyano or ethynyl group or with quaternary ammonium salts derived from such halides with tertiary amines, for example pyridine, or trialkylamines such as triethylamine. (d) A lower alkyl ester, of formula: A 2c =CH-CH-CH-C-QR 5 V s \ CH CHj in which R represents a lower alkyl group containing up to 6 carbon atoms, preferably methyl or ethyl group, and R and R have any of the meanings previously given here, is heated with an alcohol of the formula: ···· • · • aa · a » aa · ·** • aaa · a ··* •I * • ♦ aaa · aa :· • aaaa ·:·:· • · a · aaaa · .· aaaaaa 6 H5 in order to carry out a transesterification reaction. Preferably, the process is carried out in the presence of a suitable esterifier, e.g., an alkali metal alkoxide, such as sodium methoxide, or an alkali derivative of titanium, such as tetramethyl titanate. ( |Γ ' ' ' - ! r' Π Γ'Γ\ / Il | —54— The resulting extract was stirred for a period of 16 hours at room temperature. Water (20 ml) was added and the mixture was extracted with diethyl ether (3 x 10 ml). The combined extracts were washed with water, saturated sodium bicarbonate solution, and water, and were dried over anhydrous sodium sulfate.After removal of the ether by evaporation under reduced pressure, the residual oil was subjected to preparative thin-layer chromatography, using 2 mm thick silica on glass with chloroform as the eluent, to obtain (je )·«-cyano5-phenoxybenzyl (+)-cjLg / trane-3-(3,3,3-trifluoro-2trifluoromethylprop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate (Rf 0.53) containing 20% ​​of the cis isomer and about 80% of the trans isomer. Spectroscopic data: infrared, 1755, 1680, 1600, 1490, 1500, 1160; 0.9-2.5^ , 6.0-6.15 Γ , 6.55-7»2T ; mass spectrum, M + 483(275, 259, 251, 209, 208, 181). EXAMPLE 17 This example illustrates the preparation of (·>·)-cis / trans-5-(2-chloro-5,3,3-trifluoroprop-1en-l-yl)-2,2-dimethyl-cyclopropane carboxylic acid. A mixture of ethyl (+)-cjLs / tr^s-3-(2~chloro! 3,3 » 3-trifluoro-prop-1-en-1-yl)-2,2-dlmethyl cycloprbpan ♦ · · · ******* ***** ···· • » · • · · · *··. « · *· • « * ··* * * * « · ..... • » · · * UFHC'O P7 rVFTTI P , , : -57chloro-3,3,3-trifluoroprop-l-en-l-yl)-2,2-dimethyloiclopropane carboxylate (Rf 0.52), and the corresponding trans isomers (Rf 0.4-2), each containing approximately 90-95% of the Z-isomer. Spectroscopic data: infrared (ΟΗΘΙ^) 1740, 1660 1590, 1480, 1460 cm** 1; NMR (OC1 4): 6.90-7.50 ' 1.60-2.70 C*, 1.50-1.00 T, and specific peaks at 6.3 (bensylic H), 6.85, 6.50, 6.11 and 5.84^ (vinylic H) assigned experimentally to the 2-ois, E-cls, Z-trans and E-trans isomers, respectively · ► 0 · 0 0 0 - ··· 0 0 ·;·· EXAMPLE 20 i By the use of procedures analogous to those illustrated in Example 14 and Example 17, the following carboxylic acids were i | prepared from the corresponding ethyl esters, i (i) Àcido (+)-c is / trans-3-(3,3-difluoro-2-tri i ι ì fluoromethyl-prop-1-en-1-yl)-2,2-dimethyl-cyolopropane carboxylium Infrared (liquid film) 3500-2400, 1700, 1665 cm** 1. (ii) Acid ( 4-)-ci s / trans-3-(3,3-difluoro-2difluoromethyl-prορ-1-έ nl-yl)-2,2-dimethylopropane carboxylic acid I ί NMR (COI.) ppm 1.30-1.50 (m,6H)i UFRCIQ BIT V ING, G. GR G HO-CH(R 2) OC^ 3 wherein R , R and R have the meaning set forth in claim 1« 23. Process for preparing a compound according to: claim 1, characterized in that an acyl halide of formula is reacted: ···· ·· · • · · ♦ AA =CH-CH-CH~CQ V R\ with an alcohol of formula: HO-CH(R 2), OCA 6 5 3 where R » R and R have the meaning established' ! in claim 1 and Q represents a chlorine or bromine atom. 24. Process for preparing a compound according to claim 1, where R represents the cyano group, characterized in that an acyl halide of formula is reacted: r¥c =CH-CH-CR—CQ ' ιΟιϋ BEASTS ί ι 'NG. C. GREGORJ —16— All of these conventional processes for the preparation of esters can be carried out using solvents and diluents for the various reagents, if appropriate, and can be accelerated or increased to higher product yields when carried out at elevated temperatures or in the presence of appropriate catalysts, e.g., phase transfer catalysts. The preparation of single isomers can be carried out in the same way, but starting from the corresponding single isomers of compounds of formula II. These can be obtained by conventional isomer separation techniques from mixtures of isomers. Thus, cis and trans isomers can be separated by fractional crystallization of carboxylic acids or their salts, while the various optically active species can be obtained by fractional crystallization of salts of the acids with optically active amines, this operation being followed by regeneration of the optically pure acid. optically pure isomeric form of the acid (or equivalent ester or acyl chloride) can then be reacted with 3-phenoxybenzyl alcohol to produce the compounds of formula I in the form of a 4** *44* * 4 * 4 · • ♦ · • •44 * 4 « • * 4 · • · • · · V · .· • « · ·** · • 4 · -17 single optically pure isomer of the same. In the case of α-cyano-3-phenoxybenzyl alcohol the product will consist of a mixture of two isomers since it is not possible to react optically pure α-cyano-3-phenoxybenzyl alcohol with the acid or its equivalent without chromatization of the alcohol present. Typical products of this process include: (+)-a-cyano-3-phenoxybenzyl (IR, 3R)-3-(3,3,3-tri_fluoro-2-trif luoromethylprop-len-1-yl)-2,2-dimethylcyclopropane carboxylate, and (+)-a-cyano-3-phenoxybenzyl (IR,3S)-3-(2-chloro-3,3j3trifluoroprop-1-sn-1-yl)-2,2-dimethyleiciopropane oaa^ boxylate· These compounds are thought to be particularly useful as insecticides. The preparation of single isomers of these i ; compounds can be obtained by preparing optically pure acyl chloride and reacting it with (+)-3-phenoxymandelamide, so as to obtain the corresponding (+)-α-carboxamide ester. The two isomers can be separated by fractional crystallization, and individually subjected to dehydration to the corresponding α-cyano-3-phenoxybenzyl ester. In this way, the following can be obtained: 0* 0 -18UFFICIO BBuvu ING. C. GREGOFU following single isomers. (S)-a-cyano-3-phenoxybenzyl (1R,3R)-3(3,3,3-trìfluoro-2-trifluorometilprop-l-en-l-yl)2,2-dimetilcyclopropane carboxylate, and (S)-a-cyano-3-phenoxybenzyl (1R,3S)-3-(2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-2,2-dimetilcyclopropane ·· · • * » · ♦ . · · · carboxylate, which are believed to be the most effective isomers as insecticides of these particular compounds. | The various cyclopropane compounds mentioned above cited because they can be used as intermediates in the processes through which the compounds of formula I according to the invention can be prepared, they themselves represent new compounds. In a further aspect, therefore*, the present invention provides compounds according to the general formula: ♦ MM . ··· • e • · ·· · ♦ t E • aei II tArc.CH-CH-CH-OQ V c z\ mi (II) CH. 2 , where one of R and R represents a formula group: where V represents a hydrogen atom, fluorine ) j ί or chlorine and m has the value of 1 or 2, and the other • ♦ ♦ and * .* • and · ··· and * • * · Uf i IGIU SHORTι ,, ING. C. GREGORJ -191 2 between R and R represents a fluorine, chlorine, or bromine atom, or a group of formula: Y x-cz where each of X, Y and Z independently represents a hydrogen, fluorine or chlorine atom, and Q represents the hydroxyl group, a lower alkoxy group containing up to 6 carbon atoms, ! the I or the chlorine or bromine atom. ί ; A preferred group of intermediates according to the invention consists of those compounds according to the general formula II, previously given, wherein 1 2 one of R and R represents a group of formula: WCF, where W represents a hydrogen, fluorine 1 2 or chlorine atom, and the other between R and R represents a formula group: Y X-Ci Z 1 where X, Y and Z have the meanings previously given ι ! established, and Q represents the hydroxyl group, a lower alkoxy group containing 1 to 3 carbon atoms, or the chlorine or bromine atom. Fra ,-f ri -20— this favorite group of compounds, those that are 1 particularly preferred are those in which E and ì And they are both fluoromethyl groups. Another preferred group of intermediates according to the invention are those according to the general formula II, previously given, wherein one of E and E represents a group of formula; vcp 2 wherein W represents a hydrogen atom, fluorine 2 ί chlorine, and the other between E and E represents a fluorine, chlorine, or bromine atom, and Q represents the. ι hydroxyl group, a lower alkoxy group c <Jm~ i containing 1 to 3 carbon atoms, or the chlorine or bromine atom. Compounds particularly i Preferred within this group are those in which one between E 1 and E 2 represents the trifluoromethyl group and the other represents a chlorine or bromine atom. the The compounds represented by the formula II i are also capable of existing in various geometric forms and stereoisomers, similarly to compounds of formula I. Therefore, cis and trans isomers derived from the substitution scheme of the cyclopropane ring can exist, and E and Z isomers derived from the vinyl group substituted *ip when R x is not* equal to E . Furthermore, two of the three -21 carbon atoms of cyclopropane are capable of existing in either the R or S configuration, since they are asymmetrically substituted. Examples of specific intermediate compounds according to the invention include those represented by the following general formula: where R and R have the specific meanings given in Table I, shown here above, for the corresponding compounds of formula I, and in j ì where Q represents a chlorine atom, a hydroxyl group, or an ethoxy group. ! Compounds of formula II where Q represents hydroxyl can be obtained by hydrolysis of compounds of formula II, where Q represents lower alkoxy, and can be converted to compounds of formula II where Q represents chlorine or bromine by reaction with, for example, thionyl chloride or thionyl bromide, respectively. All compounds of formula II can be used directly or indirectly for the preparation of hydroxylated ... —22— to prepare the active esters as insecticides, of formula I, as previously described. Compounds of formula II where Q represents the lower alkoxy can be prepared by a variety of processes. One method involves the reaction of a diene of the formula: CH. CH, (V) with a lower alkyl ester of diazoacetic acid. the This reaction directly provides the compound I of formula II required. The process is conducted appropriately using an excess of the diene dome. The solvent for alkyl diazoacetate in the presence of a metal catalyst, such as powdered copper or copper bronze. In a variation of the above process, a compound of formula III can be obtained ί by reaction of the unsaturated alcohol of formula ±V with a lower alkyl diazoacetate and can be converted to a compound of formula II where Q represents lower alkoxy by dehydration with a chemical dehydrating agent, e.g., phosphorus pentoxide. -23(I! ί I KNOW fi / :· ·'' Ί C., ί·;Λ : Γ,: ί 0 0 R 1E 2C-CH -CH-CH-CQ 2 \ / C CH, \η. (III) (IV) This variant of the diazoacetate process: is not applicable to the preparation of compounds 1 2 m in which one of R and R represents an atom of J halogen, but it is very useful for the preparation of; compounds in which R 1 and R 2 are both tri-groups? 2 fluoromethyl, or where one of R and R is trifluoromethyl and the other is difluoromethyl. In a still further aspect, the invention provides compounds of formula: ... where R and R have the meaning given above; —+ I established for compounds of formula I, and j compounds of formula: SHORT OFFICE! Π ING. C. GREGORJ 2 I where R is trifluoromethyl, and R is* trifluoromethyl or difluoromethyl· Compounds of formula IV can be obtained by reacting a ketone of formulas: Τ Η p R -CR (Vi) with 3-methylbut-l-ene, preferably under pressure. The corresponding compounds of formula V ί can be obtained by dehydrationJ ι for example with phosphorus pentoxide, compounds of formula IV. 2 Compounds of formula V where R and R are both haloalkyl groups, or 1 2 where one of R and R is* a haloalkyl group and the other is* a methyl group can also be obtained by reacting the corresponding ketone of formula: *' 2 R —CR with the ylide obtained by treating a halide of i 3,3-dimethylallyl triphenylphosphonium, preferable-' UH F'.Hl V· ! Il ENG. G. GUIGGE' 25chloride or bromide, with a suitable dehydrohalogenation agent, such as an alkyllithium compound such as n-butyllithium. Phosphon halide can be obtained by reacting triphenyl phosphine with a 3,3-dimethylallyl halide. Dienes that can be obtained by this process include those of formula V where R and ! R have the meaning established in the following: Table: 1 2 RR CF, CF, 3 3 CHFg chf 2 CF3 chf 2 CF, CH. 3 3 CF Cl CF 2C1 CHF^ CF Cl 2 2 Examples of compounds of formula IV are 5-hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoromethylhex-2-ene and 5-hydroxy-2-methyl-6,6-difluoro-5-trifluoromethylhex-2-ene, and they can be dehydrated to 2-methyl-6,6-6-trifluoro-5-trifluoromethylhex-2,4-diene and 2-methyl-6,6-difluoro-5-trifluoromethylhex-2,4-diene, as examples of compounds of formula V. r —26— Another method for preparing compounds of formula II, where Q represents alkoxy, involves: base-induced ring closure of a compound of formulae CH . 3 II V r'Lc-ch -CH—C-CH -CQ (VII) »2 R W” CH, where R 1 and R 2 have any of the meanings previously given, Q represents alkoxy, and W' and W each represent fluorine, chlorine, or bromine, provided that W' is bromine when R is bromine. Suitable bases for carrying out the process include tertiary amines, such as pyridine, triethylamine, diethylaniline, and N-methylpyridine, as well as lower alkali metal alkoxides, i.e., those containing up to 6 carbon atoms, such as sodium methoxide, sodium ethoxide, and sodium and potassium t-butoxide. The step is conveniently carried out in a diluent or solvent for the reagent and the base. A particularly convenient way of carrying out this process is to treat a solution of the compound of formula III in an alcohol corresponding to the alkoxide of the alkali metal being used for a period of 0.5 to 20 hours. At least 2 moles of base are required to convert the compounds of formula III to 2000. ENG. C. GREGORJ -27mula VII to compounds of formula II in which R stands for alkoxyl, and this involves two separate stages 1, ί cyclization and β-elimination of hydrogen halide, but it is not clear in what order these two steps proceed, or whether they proceed simultaneously. When the process is carried out using only one molar equivalent of base, three different products are obtained corresponding to the following formulas: • · * « • · « t “ ·......... » k » lr « » :· ► · » * • . « · * « ... R' CH. li .7 C=CH-CH-C-CH.-CQ I 2 CH-, (A) ua. II R j--C-CH=CH-C-CH 2C-Q CH. (B) RC-CH^-CH-CH-CQ K 2 \ / CH. CH. (C) Each of these species, following treatment with an additional molar equivalent of base, PATENT OFFICE ENG. C. GREGOR.l -28provides the compound of formula III, and, in a further aspect, therefore, the invention provides a process for preparing the compounds of formula II wherein Q represents alkoxy by treating a compound of formula A, Β or C, with at least one molar equivalent of a base. Although the process can be used to prepare all compounds of formula II in which Q is alkoxy, it is particularly useful for the preparation of compounds in which one of R and R* is a halogen atom. compounds of formula VII that can be used as intermediates in the preparation of compounds of formula VII can be prepared by making the formula: react a compost i ί ch 2=ch-c(ch 3) 2~ch 2· tl CQ (vili) where Q represents alkoxy formula: R 1-CW I with a compound of (XX) • τΛ m whose R , ficati here initiator V R, V and W have any of the previously given meanings, in the presence of a radical type. This can be co i » J -25Ji ! ί ί GG '-fO Fu: consisting of a physically active initiator, for example irradiation with a suitable light source, for example ultraviolet light, or by a traditional chemically active radical catalyst, such as benzoyl peroxide or azo-bisisobutyronitrile. The process can be conveniently carried out using an excess of the compound of formula V as a diluent, at temperatures in the range between 50°C and 150°C, preferably between 80 and 120°C for periods between 1 and 20 hours, optionally in a hermetically sealed system and under the autogenous pressure of the reaction. A particularly useful compound of formula VIII is ethyl 3,3-dimethylpent-4-eijoate, although other lower alkyl esters may also be used. the ester of 3,3-dimethylpent-4-enoic acid represented by the formula VIII may be substituted with other compounds in which the carboxylic acid function is replaced by an equivalent function, by which Applicant means a functional group which does not interfere with the process described above, but which can subsequently be chemically modified by oxidation or hydrolysis to yield the carboxylic acid, SHORT OFFICE! The ENG. C. GREGORJ 30for example, the nitrile, acetyl, or formyl group. Alternatively, the compound of formula VIII can be replaced by a compound of formula: CH 2cCH-C(CH ) 2-CH-Q where Q* is chosen from alkoxycarbonyl, cyano» and acetyl and Q” represents cyano or alkoxy- j carbonyl. j A still further process by which compounds of formula II, wherein Q and 1 alkoxy, may be prepared, involves the reaction of a diene of formula V with an alkyl monomer in the presence of a reducible copper salt, and optionally in the presence of another salt selected from halides of Group I and Group II metals. Group II, e.g. lithium chloride or calcium chloride. The initial product, which has the formula: I Q 0 12 ih RRC=CH-CH-C “CQ yield provided and Q represents alkoxy, can be converted to the required products of formula II by traditional hydrolytic processes 31sNG- G, G and esterification. ί Examples of compounds of formula IX that may be used in the above processes include hexafluoroethane, chloropentafluoroethane, 1,1-dichlorotetrafluoroethane, 1,2-dichlorotetrafluoroethane, 1,1, 1-trichlorotrifluoroethane, 1,1,2-trichlorotrifluoroethane, 1,1,1-tribromotrifluoroethane, 1,1,1,3-tetrachlorotetrafluoropropane and 1,1,3-trichloropentafluoropropane. When the various processes are carried out for the preparation of intermediates of formula II, the products are ordinarily made up of mixtures of of the various geometric isomers. That is, the processes can lead to a mixture of cis and isomers; trans, in which one of the forms often predominates, and 1 2 in cases where R is not 1 equal to R , of isomers Z and E both in cis and trans form, where, again, one of the forms often predominates. Unless such forms are separated by some physical process, e.g. by fractional crystallization of the carboxylic acids, the final products of formula I will also consist of mixtures of various isomers, containing more than one of the compounds in Table 1. Typical examples of products active as insecticides, most of which are mixtures of more than one compound, -32which have been obtained, include the compounds listed below. Product No.l: Mix 1 part of compound No.l with 4 parts of compound No.2. Product No.2: mixture of 1 part of compound No.1 I with the part of compound No. 2, Product No.3: Compound No.2 only. Product No.4; compound No.1 only. T* i Product No. 5: Mixture of 19 parts of compound No.31 with 1 part of compound No.32. Product No.6; mixture of 19 parts of compound; No.31, 1 part of compound No.32, parts of compound No.33, and 1 part of compound No.34. the Product No.7: mixture of 11 parts of compound No.3 with 14 parts of compound No. 4 . Product No.8: mixture of compounds No.15, 16, 17 and 18 (composition undetermined) Product No.9: Mixture of 1 part of compound No.39 with 1 part of compound No„41. Product No.10: mixture of 19 parts of compound No.43, 1 part of compound No.44 :, parts of compound No.45 θ 1 p^rte Uh' ivH SHORTih ING. C. GREGORJ -33Product Product Product i Product Product Product Product Product Product Product Compound of compound No.46. Ho.11: Mix 19 parts of compound No.43 with 1 part of compound No.44. No.12: mixture of 19 parts of compound No.39 I with 1 part of compound No.40. ί No.13: mixture of 1 part of compound No.19, parts of compound No.20, 1 part of compound No.21 and 9 parts of compound No.22. No.14: mixture of 1 part of compound No.23, 9 parts of compound No.24, 1 part of compound No.25 and 9 parts of compound No.26. wo.l5i mixture of 1 part of compound No.47 with 1 part of compound No.48, No.16: compound No.47. the No. 17: Mixture of 1 part of compound No. 49 with 1 part of compound No. 50. No.18: mixture of 1 part of compound No»1 with 2 parts of compound No,2. No.19: Mix 3 parts of compound No. 5 with 2 parts of compound No.6. No.20: mixture of 3 parts of compound Ho. / with 2 parts of compound N o.8. ! No.21: mixture of 9 parts of compound No.^5, 1.. jr * ι · ί ? the -341 parts of compound No.36, 6 parts of compound No.37 and 4 parts of compound No.38. j Product No.22: mixture of 9 parts of compound No.51 I with 1 part of compound No.52. j | Eyo^otto No.23: compound No.53 alone. ; j Product No. 24: Mixture of 7 parts of compound No. 9 with 13 parts of compound No. 10. jj Product No. 25: Mixture of 7 parts of compound No. 11 with 13 parts of compound No. 12. Product No.26: mixture of undetermined composition containing compounds 27, 28, 29 and 30. Product No.27: mixture of 10 parts of compound No<54, 2 parts of compound No.55, 10 parts of compound No.56 and 1 part of compound No.57. : ί ί Product No.28: mixture of 10 parts of compound No.58, one part of compound No.59, 10 parts of compound No.60 and 1 part of compound No.61. Product No.29 mix 2 parts of compound No.13 with 3 parts of compound No.14. The compounds of formula 1 can be used to combat and control infestations by parie (insects) and also other inverted pests. ' 'Gin pr;| 'j -35bratì, for example, infestations by mites. THE Infestations by insects and mites that: ι i can be fought and controlled by j I ì The use of the compounds of the invention includes infestations associated with agriculture (which term includes the growth of food crops and fibrous products, horticulture and animal husbandry), forestry, storage of plant products, such as fruit, grains and timber, as well as infestations associated with the transmission of human and animal diseases. For administration of the compounds to the infested site, they are ordinarily formulated to obtain compositions which include, in addition to the active ingredient or ingredients such as insecticides, of formula I, suitable diluents and aggregates or support materials, and / or tensile agents active ingredients· The compositions may also comprise other pesticidal substances, for example another insecticide or acaricide, or a fungicide, or they may also comprise a synergistic insecticidal agent, such as dodecyl imidazole, safroxan, or piperonyl butoxide. Compositions can be found in the form; THE I ' ι: ργ'Γ >.....>τ, —36· of fine powders for sprinkling, in which the active ingredient is mixed with a solid diluent or vehicle, for example kaolin, bentonite, kieselguhr, or talc, or they may be under In the form of granules, where the active ingredient is absorbed into a porous granular material, e.g. pumice. ι Alternatively, the compositions may be in the form of liquid preparations to be used by immersion or spraying, which generally consist of aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents (surfactants). Wetting agents, dispersing agents, and emulsifying agents may be of the cationic, anionic, or nonionic type. Suitable agents of the cationic type include, for example, quaternary ammonium compounds, e.g., cetyltrimethylammonium bromide. Suitable agents of the anionic type include, for example, soaps; salts of aliphatic monoesters of sulfuric acid, e.g., sodium lauryl sulfate; salts of aromatic sulfur compounds, e.g., sodium dodecylbenzenesulfonate; sodium, calcium, or ammonium. lignosulfonate, butylnaphthalene sulfonate, and an I -37BREVI OFFICE-' ING- C. GREGORJ of the mixture of sodium salts / diisopropyl- and triisopropylnaphthalene sulfonates. Suitable non-ionic agents These include, for example, condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols. such as octyl phenol, nonyl phenol, and octyl cresol. Other non-hypnotic agents include partial esters derived from long-chain fatty acids and hexitol anhydrides, the condensation products of the aforementioned partial esters with ethylene oxide, and lecithins. Compositions may be prepared by dissolving the active ingredient in a suitable solvent, for example, a ketone solvent such as diacetone alcohol, or an aromatic solvent such as trimethylbenzene, and adding the resulting mixture to water, which may contain one or more known wetting, dispersing, or emulsifying agents. Other organic solvents include dimethyl formamide, ethylene dichloride, isopropyl alcohol, propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, white spirit, methylnaphthalene, xylenes and trichloroethyl(s), N-methyl-2-pyrrolidone, and tetrahydrofurfuryl alcohol (THFA). The compositions to be used by spraying can be: ,ClG 8'υ \ Ki G. C|\!o, -38also be found in the form of an aerosol in which the formulation is kept in a container I under pressure in the presence of a propellant such as fluorotrichloromethane or dichlorodifluoró· methane. The compositions to be used; in the form of aqueous dispersions or emulsions | are generally supplied in the form of a concentrate containing a high proportion of the active ingredient or ingredients, the latter (said concentrate having to be diluted with water J before use, These concentrates are often required to withstand storage for prolonged periods of time and to be, after such storage radius, susceptible to dilution with water to form aqueous preparations that remain homogeneous THE I 1 for a period of time sufficient to make it possible to apply it by conventional spraying devices. Concentrates may contain 10-8% by weight of the active ingredient(s). When diluted to form aqueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending on the use for which they are to be used. For agricultural or horticultural uses, an aqueous preparation containing 0.0001% to 0.1% by weight. SHORT OFFICE. ENG. C. GREGORJ -39of the active ingredient is particularly useful, | In use, the compositions are [administered to the pests, the infested location, the habitat of the pests, or to growing plants subject to infestation. I j tion by pests, by: A : any of the known methods of administration of pesticide compositions, for example, by j dusting or spraying. The compositions of the invention are highly toxic to a wide variety of insects and other invertebrate pests, including, for example, the following: Aphis fabae (aphids) Megoura viceae (aphids) Aedes aegypti (mosquitoes) i --- — ' Π .1,· ] Dysdercus fasciatus (capsids) Musca domestica (houseflies) Pieris brassicae (cabbage, larvae) Plutella maculipennis (cabbage leafworm, larvae) Phaedon cochleariae (watercress leafworm) Telarius cinnabarinus (red orb weaver spider) Aonidiella spp, (coccidia) Trialeuroides spp. (whiteflies) -40• jf-r : Din · ι n Blattella germanica (cockroaches) ι Spodoptera littoralis (cotton leaf maggot) Chortiocetes terminifera (locusts) Compounds of formula I and compositions comprising them have been shown to be particularly useful in the control of lepidopteran-type pests on cotton, e.g., Spodopter spp. and Heliothis spp. They are also very useful in fighting infestations by insects and mites that infest domestic animals, for example Lucilia sericata, ί i and ixodid ticks such as Boophilus spp., Ixodes spp.,; Amblyomma spp., Rhipicephalus spp., and Dermaceutor spp. They are effective in combating both susceptible and resistant strains of these pests at their adult, larval, and intermediate growth stages, and can be applied to the infested host animal by topical, oral, or parenteral administration. The following examples illustrate | ì various aspects of the invention. EXAMPLE 1 This example illustrates the preparation of 1-chloro-1,1-difluoro-2-chlorodifluoromethyl-5-methylhexa2,4-diene, of formula: (a) Preparation of 3,3-dimethylallyl triphenylphosphonium bromide. A mixture consisting of 3,3-dimethylallyl bromide (50.0 g), triphenylphosphine (88.0 g), and dry toluene (500 ml) was stirred and heated to reflux temperature for 1 h, and then held at room temperature for 18 h. The white precipitate of 3,3-dimethylallyl triphenylphosphonium bromide (mp 24°C) was collected by filtration, washed with diethyl ether, and dried. (b) Preparation of 1-Chloro-1,1-difluoro-2-chloro-difluoro-methyl-5-(J-Kethylhexa-2,4-diene) n-Butyl lithium (65.0 ml) of a 15% solution by weight in hexane) was slowly added to a vigorously stirred suspension of 3,3-Dimethylallyl triphenylphosphonium bromide (65.0 g) in a dry petroleum solution (boiling range 0—40°C, 500 ml) at 0°C in a nitrogen atmosphere, after which the mixture was kept at room temperature for <ir 48 ore. La miscela venne poi raffreddata fino a O°C,je $i aggiunge 1,3-dￃﾬclorotetrafluoroacetone (31,44 g).j Ij,a miscela venne lasciata arrivare a temperatura amb^en4 SHORT OFFICE ENG. C. GREGC -42te over a period of two hours, and the precipitate was removed by filtration. The filtrate was concentrated by evaporation until the volume was about 70 ml, and passed through a short alumina column, after which the remaining solvent was evaporated under atmospheric pressure at a temperature of 69°C. The residual liquid was subjected to fractional distillation, and the fraction boiling at 79 - 80°C / 20 mm Hg was collected and identified by infrared and nuclear magnetic resonance spectroscopy as 1-chloro-1,1-difluoro-2-chlorodifluoromethyl-5-methylhexa-2,4-diene. NMR (CC1 4) ppm 1.88-1.94 (m,6H); 6.3 (d,ltì)j 7.08 (d, IH). EXAMPLE 2 By procedures analogous to those illustrated in Example 1, other dienes were prepared from the appropriate ketones, as follows: (i) 2-methyl-5-trifluoromethylhexa-2,4-diene was prepared from 1,1,1-trifluoroacetone. NMR (CC1 4) ppm 1.76-1.82 (m,9H); 5.85-6.00 (m, IH)? 6.62-6.78 (m,lH). (ii) l,l-Difluoro-2-chlorodlfluoromethyl-5-methylhexa2,4-diene was prepared from l-chloro-1,1,2,2-43tetrafluoroacetone. Infrared (liquid film) - 3000, 1650, 1265 cm \ (iii) l»l-Difluoro-2-difluoromethyl-5-methylhexa-2,4diene was prepared from 1,1,3,3-tetrafluoro! acetone. ! NMR (CC1 4) ppm 1.90-2.02 (m,6H)j 5.65-7.10 (m,4H). EXAMPLE 3 This example illustrates the preparation of 5-hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoromethyles-2,ene. A stirred mixture of hexafluoroacetone (235 g) and 3-methylbut-1-ene (100 g) was heated to 125°C under a pressure of 17 atmospheres for a period of 20 hours. Distillation of the product mixture under reduced pressure produced 5-Hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoro-methylhex-2-ene as a colorless liquid, mobile, b.p. 43°C / 15 mm Hg. NMR (CC1 4) ppm 1.77 (d,6H); 2.58-3.00 (m,3H); 5.0-5.4 (m, IH). EXAMPLE 4 By using a procedure analogous to that illustrated in Example 3, 5-Hydroxy-2-methyl-446.6-difluoro-5-trifluoro-methylhex-2-ene was prepared from pentafluoroacetone. NMR (CC1 4) ppm 1.76 (d,6H)j 2.5-2.75 (m,3H); 5.18 (m,lH)j 5.80 (t,lH). EXAMPLE 5 This example illustrates the preparation of ethyl (+) cis / trans-3-(2-hydroxy-3,5,5-trifluoro-2trifluoro-methylprop-l-yl)-2,2-dimethylcielopropane cprboxylate. A solution of ethyl diazoacetate (9.12 g) in dichloromethane (400 ml) was added dropwise over a period of 48 h to 5-hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoro-methyl-2-ene (18.9 g) in the presence of a catalytic amount of anhydrous copper(II) sulfate at 110-120°C. The resulting mixture was washed with water, dried over anhydrous magnesium sulfate, and distilled to yield numerous fractions within the range of 68-90°C at 0.15 mm<> NMR* (nuclear magnetic resonance) infrared spectroscopic and mass spectroscopic analysis indicated that these fractions consisted primarily of the (+)-cis and (+)-trans isomers of ethyl 3-(2-hydroxy-3-3-trifluoro-2-trifluoromethylprop-1-yl)-2,2-dimethylcyclopropane carboxylate in different proportions. -45N.MR (ODCl^) ppm 1.04-1.40 (m,9H); 1.55-2.43 (m,4H)i 4.00-4.37 (m,2H). EXAMPLE 6 By using a procedure analogous to that illustrated in Example 5, 5-hydroxy-2-methyl-6,6-difluoro-5-trifluoro-methylhex-2-ene was converted to ethyl (+)-cis / trans-3-(2-hydroxy-3,3-difluoro-2-trifluoromethylprop-1-yl)-2,2-dimethylcyclopropane carboxylate. NMR (CC1 4) ppm 1.3-2.4 (m,13H)j 4.0-4.35 (m,2H)j 4.6-4.8 (m,lH)i 5.2-6.4 (m,lH)o EXAMPLE 7 This example illustrates the preparation of ethyl (+)-cis / trans-(3,3,3-trifluoro-2-trifluoromethylprop1-en-1-yl)-2,2-dimethylcyclopropane carboxylate. A mixture of ethyl (+)-cis / trans-3-(2-hydroxy-3.3.3-trifluoro-2-trifluoromethylprop-1-yl)-2,2-dimethylcyclopropane carboxylate (4.62 g), phosphorus oxychloride (2.2 g), and dry pyridine (5.3 ml) was heated to 110°C for a period of 65 hours, after which it was poured into ice-cold water and stirred for 5 hours. The resulting mixture was extracted with diethyl ether, and the extracts were washed with water and dried over anhydrous sodium sulfate. After removal of the ether by a short reaction, the mixture was dissolved in water. -46©evaporation at reduced pressure, the residual oil was distilled under reduced pressure, and ethyl (+)-oie / trang-5-(3,3,3-trifluoro-2-trifluoro6methylprop-1-en-1-yl)-2,2-dimethylcyclopropane c serbo £isylate was obtained in the form of a colorless oil, bp 60-65°^0.5 NM.R. (CDC1 5) pp*m. 1.15-1.39 (m, 9H)j 1.75-2.60 (m, 2H); 4.02-4.34 (m, 2H)j 6.36 and 7.36 (dd, 1H). EXAMPLE 8 By using a procedure analogous to that illustrated in Example 7 ethyl (*)-cÌ3 / ì;rans3-(3,3-difluoro-2-trifluoro-methylprop-1-en-1-yl)2,2-dimethylcyclopropane carboxylate was obtained from the product / from Example 6. NMR (CC1 4) ppm 1.2-1.4 (m,9H)j 1.6-2.6 (m,2H); 4.0-4.4 (m.2H)j 5.4-7.2 (m.2H). EXAMPLE 9 Using procedures similar to that illustrated in Example 5, the following ethyl esters of formula II were obtained from the dienes considered by reaction with ethyl diazoacetate. (i) Ethyl (+)-cis / trans-3-(3,3-difluoro-2-dÌfluoromethylprop-1-sn-1-yl)-2,2-dimethylcyclopropane carboxylate, from 1,1-difluoro-2-difluoroethyl5-methylhexa-2,4-diene· NMR (CC1 4) ppm 1.25-1.44 (m,9H); 1.60^.40 mia •5è>· » aaa · :· » · aa · a*· a · aaa U' -τη -47(m,2H); 4.0-4.30 (m,2H)j 5.58-7.34 (complex, 3H). (il) Et il (+)-ci s / trans-3- (Ε / Ζ-2-trifluoromet ilpr c pί 1-en-l-yl ) -2,2-dìmetilciclopropali carboxylate, from 2-trifluoromethyl«5-methylhexa-2,4-diene. JLM.R. (CCl^) ppm· 1.10-1.40 (m.9H); 1.50-2.10 (n,5H)> 4.0-4.38 (m,2H)j 5.24-6.46 (m,lH). (yl) Ethyl (+)-c is / trans-3-(3-chloro-3,3-difluoro-2chlorodifluoromethylprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate, from 1-chloro-1,1difluoro-2-chlorodifluoromethyl-5-methylhexa-2,4diene. NMR (CC1 4) ppm 1.28-1.42 (m,9H); 1.78-2.60 (m,2H)j 4.06-4.26 (m,2H)j 6.20 and 7.1 6 (dd, IH). ! (iv) Ethyl (+)-cis / tr«ns-3-(E / 2-3,3»difluoro-2-oIo^o! difluoromethylprop-1-en-1-yl)-2,2-dimethylcitric acid / propane carboxylate, from 1,1-difluoro-2-chlorodifluoromethyl-5-methylhexa-2,4-dlene· KM.R. (CC1 4) pp-m. 1.24-1.52 (m,9H)jl,64»2.5O (m,2H)j 3.90-4.30 (m,2H); 5.50-7.04 (m,2H), EXAMPLE 10 This example illustrates the preparation of ethyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluorohepteinoate, of formula • aa •••aa aa • « ♦ · a · aaaa « .* » aa *4 · CP5 CC12 CK2 CHC1C < CH5 )2 CH2 C °2 C2 H5 ..r' / :<·'Ώ rTi'T s ING,. C. uuEGUh.i 4θXJ A mixture of ethyl 3,3-dimethylpent-4-enoate (7.0 g), 1,1,1-trichloro-2,2,2-trifluoroethane (20.0 g), and benzene peroxide (0.1 g) was heated in a sealed glass tube for 5 h at 100°C. The resulting mixture was carefully distilled, and ethyl 3,pdimethyl-4,6,6-trichloro-7,7,7-trifluoro-heptanoate was collected as a boiling fraction at 112-114°C / 2 mm Hg, and its identity was confirmed by nuclear magnetic resonance and infrared spectroscopy. EXAMPLE 11 00*1 ·· · ' ri* ' * · · • ( ( Il • · • I II I a 0 .· • · 0 0*· 0 0 0 0 By using procedures similar to that presented in Example 16, certain other halogenated esters were prepared by reacting haloalkanes with ethyl 3,3-dimethylpent-4-enoate as follows: (i) Ethyl 3,3-dimethyl-7,7-difluoro-4,6,6,7-tetrachloroheptanoate from 1,1-difluorotetrachloroethane. NMR <ci>£1 5) ppm 1.10-1.35 (m,9H)i 2.10-3.00 (m,4H); 4.12 (q,2H) ; 4.52 (dd,XH). (ii) Ethyl 3,3-dimethyl-6,7,7-trifluoro-4,6,7-trichloro· heptanoate from 1,1,2-trifluorotrichloroethane· The boiling point of the product was 75-76°C / 0.05 mm Hg PATENT OFFICE NG. C. GREGORJ ; -49ì (iii) Ethyl 3,3-dimethyl-4,6,6-tribromo-7,7,7-tri M | fluoroheptanoate from 1,1,1-tribromotrifluoroethene. KM.R. (CDCip ppm 1.16-1.44 (m,9H)j 2.50 (q,2H)j 3.04 (q,2H)j 4.18 (q,2H)j 4.60-4.74 Cm,lH). (iv) Ethyl 3,3-dimethyl-7,7,8,8,8-pentafluoro-4,6,6trichloroctanoate from 1,1,1-trichloropent©fluoropropane· ί NMR (CC1 4;) ppm 1.13-1.40 (m,9H); ' 2,14-2,92 <m,4H)s 3,96-4,25 (q,2H)ì 4,5-4,62 (m,lfl). (v) Ethyl 3,3-dimethyl-7»7,8»8-tetrafluoro-4,6,6,8! tetrachloroctanoate from 1,1,1,3-tetrachloro- j ! ί tetrafluoropropane. I EXAMPLE 12 ! the This example illustrates the preparation of 1-ethyl(0)-cys / trans-3-(E / Z-2-chloro-5,3,3-trifluoroprop:1-en-1-yl)-2,2-dimethyleicyclopropane corboxylate. The ethyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoroheptanoate obtained in Example 10 was dissolved in dry tetrahydrofuran (30 ml) and the solution was added dropwise to a suspension of sodium t-butoxide (2.75 g, prepared in situ from sodium hydride and t-butyl alcohol) in uranium tetrahydrofuran. I dry (120 ml) * 0°C. When the addition was complete®, ·♦·· • 0 ·· ♦♦ ·· · 0*000 • · 0 · * e · * * :· * 0 * * 0 *•00 * t» * 0 •0 0· ·*··. * * * * 1 * *00 0*0 0 « »·· * -50ur ih the mixture was stirred for a period of 2 hours at 0°C and then acidified with ethenol hydrogen chloride. After dilution of the mixture with ethereum, it was washed with water, dried over anhydrous magnesium sulfate and concentrated by evaporation of the solvents under reduced pressure. The residual yellow oil was carefully distilled off under reduced pressure, affording ethyl (C+)-cis / trans 3-(2-chloro-3,3,3-trifluoropropyl-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate, pe70°C / 0.5 mm Hg, Nuclear magnetic resonance analysis indicated* that the product consisted of a mixture of approximately 60% of the e isomers and approximately 40% of the trans isomers (with respect to the cyclopropane ring), with approximately 90-95% of the isomer in which the trifluoromethyl group is in the trans position with respect to the cyclopropane ring at the legal pair (the Z isomer), and approximately 5-10% of the isomer in which it is in the cis position (the E isomer). EXAMPLE 13 Using procedures similar to that illustrated in Example 12, other ethyl esters of formula II were prepared as follows! (i) Ethyl (+)-cis / trane-3- (E / Z-2,3-dichloro-3,3• · · 4 :· • 4 4 * e •e · · eee • · ··· • e • » * UiHGO Bill GG. e. GG iW I ì(ii> (ili) !(ÌV) -51difluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate, from ethyl 3,3-dimethyl7.7- difluoro-4 » 6,6,7-t anoated etrachloroept. HMR (CDClj) ppm 1.15–1.55 (m,9H); I, 55-2.50 (m,2H)> 4.00-4.33 (m,2H)j 6.13 4 6.95 (ad,IH). Ethyl (+)-oÌB / trans-3-(E / Z-5-chloro-2,3,3trif luori-prop-l-en-l-yl)-2,2-dimeth ile icl^propane carboxylate, from ethyl 3,3-dimethyl6.7.7- trifluoro-4,6,7-atotrichloroethylene NMR (CC1 4) ppm 1.20–1.58 (m,9H); 1.58–2.33 (m,2H); 4.15 (q.2H)j 5.10, 5.41 5.91 and 6.26 (4ά,1Η). Ethyl (+)-cis / trans-3-(2-bromo-3,3,3-trif j.uroprop-l-en-l-yl)-2,2-dimethyl iclopropane carboxylate, from ethyl 3,3-dÌmetll-4,6,6tribromo-7,7,7-trifluoroeptanoate. NMR (CC1 4) ppm 1.10–1.40 (m,9H); 1.60–2.44 (m,2H)f 3.96–4.28 (m,2H)j 5.96–7.26 (m,lH). Ethyl (+)-cÌs / trans-3-(2-chloro-3,3,4,4,4penta-fluorobut-l-en-1-11)-2,2-dimethylcyclopropane carboxylate from ethyl 3,5-dimethyl-7,7,8,8,8lopentafluoro,6anotric-4 NMR (CC1 4) ppm 1.15–2.53 (complexes” · » · · :· • · ft · · « ··*· ·! · • · ·· • · • · • · · · ·*· • «·* PATENT OFFICE and ING. C. GREGORY -52so,llH); 3.92–4.30 (m,2H); 6.12 and 6.92 (dd^lH). (v) Ethyl (+)-cls / trans-3-(2,4-dichloro-3,3,4,4tetrachlorobut-l-cn-l-yl)-2,2-dimethylcyclopropane carboxylate, from ethyl 3,3-dimethyl-7^7,8,6- .... tetrafluoro.6o-8,6-tetrate EXAMPLE 14 This example illustrates the preparation of (+)-cis / trans-3-(3,3,3-trifluorineο-2-trifluoromethylprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxysilicon. *·". A mixture of ethyl (+)-oxy / trans-3-(3,3,3t r if luor ο-2-tr if luor ometylprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate (0.52 g), glacial acetic acid (2.52 ml), hydrobromic acid (48 wt. % / yol. 3.36 ml), and water (1.12 ml) was heated to reflux temperature for a period of 10 h. After cooling, the mixture was diluted with water (50 ml) and extracted several times with diethyl ether. The extracts were combined, washed with water, dried over anhydrous sodium sulfate, and concentrated by evaporation of the ether under reduced pressure. The residual oil was found, by spectroscopic analysis, to consist mainly of (+)-ois / trans-3-(3,3,3-trifluoro2-trifluoromethylprop-1-en-1-yl)-2,2-dimethylcyclopropanol carboxylic acid. -53Uf-FIGIO SHORT hi «NG. C. GREGORJ ·· · · • · ·· ·· *♦·*·* <·:· ·· ·. * • * • * •n· 4* 4 4 4 ····, 4 » « · 1 EXAMPLE 15 This example illustrates the conversion of (+)-cis / trans-3-(3,3 » 3-trifluoro-2-trifluoromethylprop-len-l-yl )-2, 2-dimethylcyclopropane carboxylic acid to its acyl chloride. A mixture of (+)-cis / trans-3-(5,5-3trifluoro-2-trifluoromethyl-prop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylic acid (0.4 g) and thionyl chloride (5.0 ml) was heated to reflux temperature for a period of 2 h, after which the excess thionyl chloride was removed by distillation under reduced pressure, affording (+)-cis / trans-1-chlorocarbonyl-3-(3,3,3-trifluoro-2-trifluoromethyl-prop-l-en-l-yl)-2,2-dimethylcyclopropane. EXAMPLE 16 This example illustrates the preparation of (+)-ot-cyano-3-phenoxybenzyl (+ )-cis / trans-3-(5,3,^trifluoro-2-trifluoromethylprop-l-en-l-yl)-2,2-dimethyl cyclopropane carboxylate, referred to herein by the text as Product »ol To the residue of (+)-cis / trans-3.-chlorocarbonyl-^(3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl)-2,2dimethylcyclopropane (obtained in example 15) a mixture of pyridine (0.12 g) and (+)-α-oiano3-phenoxybenzyl alcohol (0.33 g) was added and the mixture was -55carboselate (0.52 g), glacial acetic acid (2.52 ml), ι Hydrobromic acid (48% wt / vol; 3.36 ml), and water (1.12 ml) were heated to reflux temperature for a period of 10 hours. After cooling, the mixture was diluted with water (50 ml) and extracted several times with diethyl ether. The extracts were combined, washed with water, dried over anhydrous sodium sulfate, and concentrated by evaporation of the ether under reduced pressure. The residual oil was found, by spectroscopic analysis, to consist primarily of (+)-cls / trans-3-(2-chloro-3,3,5-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropanecarboxylic acid. EXAMPLE 18 This example illustrates the conversion of (+)-cis / trans-3-(2-chloro-3,3,3-trifluoroprop-l-en-lyl)-2,2-dimethyl-cyclopropane carboxylic acid to the related acyl chloride. A mixture of (+ )-cis / trans-3-(2-oloroi-3,3,3trifluoro-prop-l-en-l-yl)-2,2-dimethylcyclopropane ι acid carboxylic acid (°.4 g) and thionyl chloride (5.0 ml) were heated to reflux temperature for a period of 2 hours, after which the excess thionyl chloride was removed by distillation at reduced pressure, leaving (+)-cis / trans-1-chlorocarboxy ... -56 υΓΓBREVE, j, ,NG- C. GREGORJ 3-(2-chloro-3,3 » 3-trifluoroprορ-1-en-l-yl)-2,2dimethylcyclopropane. j EXAMPLE 19: the This example illustrates the preparation of (+)-a-cyano-3-phenoxybenzyl (+)-ois / trans-3-(2chloro-3,313-trifluoroprop-l-en-l-yl)-2,2-dimethyl cyclopropane carboxylate, reported herein as product No. 6. To the residue of (+)-αs / trans-1-chlorocarbonyl43(2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane (obtained in Example 18) a mixture of pyridine (0.12 g) and (+)-α-cyano-3-phenoxybenzyl alcohol (0.33 g) was added and the resulting mixture was stirred for a period of 16 hours at room temperature. Water (20 ml) was added and the mixture was extracted with diethyl ether (3 x 10 ml). The combined extracts were washed with water, saturated sodium bicarbonate solution, and water, and dried over anhydrous sodium sulfate. After removal of the ether by evaporation at reduced pressure, the residual oil was subjected to preparative thin-layer chromatography, by coating a 2 mm thick layer of silica on glass with chloroform as the eluent, to obtain (+)-a-cyano-3-phenoxybenzyl (+)-α-s-3-(2 x 00 ml). 0 0 • * » « ♦ « * » 0 · • · Λ 0 0 :· • 0 00 » ·:** ·· ·0 0 ♦ 0 «00* 0 0 0 0 mi). (iii) (iv) (v) (vi) (vii) G. GRFGOR -581.70-2.60 (complex, 2H)j 5.70-7»13 (complex, 3H). (+)-cis / trans-3-(E / Z-2-trifluoromethyl^prop-l-en1- il)-2,2-dimethylcyclopropane carboxylic acid. ; ….. *· · 4 * KMR (COI.) ppm 1.22-1.44 (m,6H)j »?'. ·»·· 4 :··· 1.6–2.3 (m,5H)j 5.36–6.6 (m,lH)} 11.9 (e,IH). :... | 4 4 4 · · 4 E · 4 · 4 4 of Acid (+)-£Ìs / tr ans-3-(3-chloro-3,3-dif fear- > ttt '·· * · , .· · *·* 2- chloro-difluoromethylprop-l-en-l-ìl)-2,2• · · * · ·* *· · * ,· dimethylcyclopropane carboxylic· *·**· ΪΛ. *···· ​​.*·.'· NMR (CC1 4) ppm 1.24–1.42 (m,6H); 1.80–2.68 (m,2H)j 6.16 and 7.12 (dd,lH); 11, …. (e,IH). Acid (+)-oiB / trang-5-(E / Z-5,3-difluoro-2chlorodifluoro-methylprop-l-en-l-yl)-2,2dimethylcyclopropane carboxylic acid. Infrared (OHOlj) 3450-2500, 1705, 1675 ci* Acid (+)-cis / trans~3-( 2-bromo-3,3,3-tr i_ fluoroprop-l-en-l-yl)-2,2-dimet ileiclopropine carboxylic. Infrared (CHCip 3400–2450, 1700, 1650, 1275, 1140 cm” 1·. Acid (+)-cis / tran3-5-(5-odoro-2.5,3-trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane car bossilic. Infrared (oil film) 3400–2200, -59(viii) 1700, 1450, 1140, 1070 cm Acid (ft)-cÌs / trans-3-(2,3-dichloro-3,3difluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane j (ix) carboxylic. | Infrared (CHClj) 3400–2200, 1700 cm 1” Pure (£)-ois-3-(2,3-dichloro-3,3-difluoroop-l-en-l-yl )-2, 2-dimethyl cyclopropyl carboxylic acid was precipitated in six columns on cooling from a solution co^i_ The centrata of mixed cis and trans acids in hexane· • * ft ft • · · « ft • «•ftft ·:· : ' · · · . •ftft· « • · » · · « · • ft * ·' • ftft 1 ··· • · 1 • ftft NMR (CDC;^) ppm 1.25 (s,6H); 1.80.-2.25 (m,2H); 6.73 (d, IH). (x) (+)-cls / trane-5-(2-chloro-5,3,4,4,4pentafluorobut-l-en-l-yl)«2,2-dimethylcyclopropanecarboxylic acid· NMR (CDClj ppm 1.10-1.50 (m,6H); 1.68-2.58 (m,2H); 6.14 and 6.85 <dd,lH). (xi) (ft)-ois / trans-3-(2,4-dichloro-3,3,4,4~ tetrafluoro-but-l-en-l-yl)-2,2-dimethylcyclippropane carboxylic♦ EXAMPLE 21 The various carboxylic acids of example 20 were converted to the insecticidal ester products of formula I by reacting ι · ί . V I.... ί -60! ί acyl chlorides with 3-phenoxy-benzyl alcohol, (+)-α-cyano-3-α-enoxybenzyl alcohol or (+)-α-ethynyl-3-phenoxybenzyl alcohol. The products of these reactions (herein referred to as products Nos. 2-5 and 7-29) are mostly mixtures of more than one of the compounds in Table I, as indicated below. Product No. 2: (+)-a-cyano-3-phenoxybenzyl (+)cis / trans-3-(3,3,3-trylfluoro-2-trifluoro-methylprop-1-en-1-yl)-2,2-dimethyl cyclopropane carboxylate, and* a mixture of 1 part of compound No. 1 with 1 part of compound No. 2. NMR (COI.) ppm 1.20-1.40 ! (m,6H)i 1.80-2.30 (m,2H); 6.17-6j37 and 6.85-7.42 (mm,HH). i ! Product No.3s (+)-a~cyano-3-phenoxybenzyl (+)! trans-3-(3,3,3-trifluorο-2-trifluoromethylprop-1-en-1-11)-2,2.... • · · 0*00 99··· _ .·;· ··«« ···· · • · • · · * · • · 9 9 · B «..... · 99999 ··* ζ · · · · · MM* · > * ζ * .... · · : · · · • . · * · . · . • · ··, ·*·· · · * · * * · ..... .... • * * · · · . . · · · · MM, dimethylcyclopropane carboxylate] is Product No.4i compound No.2 only. (+)-a-cyano-3-phenoxybenzyl (+)-óis3-(3,3,3-trlfluoromethylprop-1-en-11)-2,2-dimethylcyclopropane carboxy. side, is the only compound No. 1. -611” V ' f -ITI Product No.5: (+)«a-cyano-3-phenoxybenzyl (+)-cji.s Product No.7: Product No.8: Product No.9: 3-(2-chloro-?,3,3-trifluoroprop-1-en1-yl)-2,2-dimethylcyclopropane carboxylate, is a mixture of 19 parts of compound No. 31 with 1 part of compound! this No.32. 3-Phenoxybenzyl (+)-cis / trans-3-(3,3,3-trifluoro-2-trìfluoromethylprop-len-1-yl)-2,2-dimethylcyclopropane carboxylate, is a mixture of 11 parts of compound No. 3 with 14 parts of compound No. 4. NMR (CC1 4) ppm 1.18-1.40 (m,6H); 1.75-2.55 (m,2H)> 5.15 (s,2H); 6.30 and 6.70-7.40 (dm,10H). (+)-α-c iano-3-fe no s sibenzyl (+)-£is / i trans-3-(3,3-difluorο-2-trifluoro [ THE I methyl-prop-1-en-1-yl)-2,2-dimethyl / cyclopropane carboxylate, and a ; i mixture of compounds Nos. 15, 16, 1^7 and 18 (composition undetermined) Infrared (liquid film) 17^5, 1665, 1595 cm 1. 3-phenoxybenzyl (+)-cis / tran3-3(Z-2,3-dichloro-3,3-difluoroprop-1% 4**4 ?.·.· / ··· ···· •4 44 · • · • 4 4 4 4 444*4 4 · · « · 4 · 44444 4 4 * ζ · 4 · 4 4 44444 4 . * Ϊ* .4»« a·* •i-· · * . · · · * 4 4 4 * 4 • 4 4 · * ···4 · 4* • 4 4 4 4 ..... .. · · · · · , . .... 4 4 4 φ ····* Product No.10: Product No.11: UbLIGiO ΒΒ.,λ , ING G. Ghi G r' s' —62— en-1-yl)-2,2-dimethylcyclopropane carboxylate is a mixture of 1 part of compound No.39 with 1 part of compound No.41. NMR (CDCip pp-m. 1.20-1.37 (m,6H); 1.73-2.50 (m,2H) | 5.10 (d^H); 6.12 and 6.88-7.48 (dm,10H). (+)-a-cyano-3-phenoxybenzyl (+)-03.8 / trans-3- (Ζ / Ϊ3-2,3-dichloro or-3,3-difltLoroprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate is a mixture of compound 19.4 of this subclass. 19 parts of compound No.45 and 1 part of compound No.46. NM.R. (CC1 4) pp*m. 1.18–1.45 (m.6H); 1.73–2.50 (m,2H); 6.32 (m,lH)j 6.08 and 6.81 (dd,lH)j 6.90–7.44 (m.9H). (+)-ocyano-3-phenoxybenzyl (+)-cis3-(Z / E-2,3-dichloro-3,3-dif luoproclpl-en-l-yl)-2,2-dimethylcyclopropane carboxylate and* a mixture of 19 parts of compound No.44 with pair No.43 NMR (CC1 4) ppm 1.18–1.40 (J,6H)j 1.92–2.32 (a, 2H): 6.31 (d,lH)s 6.81 …. • * « 4 4 · '•Ve · * * 4 « « 4 4 * > · 4 4 » 4 « ;· 4 4 4 4 • ♦ » 4 « 4 * 4 «4 4* • •44 · 4 · • · 4 · · • 444 ·*·, 4· 4·· -65( ir-f Product #12: (d,lH; 6.90-7.45 (m,9H). 5-phenoxybenzyl (+)-ois-3-(Z / E-2 3Product No.15iProduct No.14: dichloro-3,3-difluoroprop-1-en-1-yl 2.2-dimethylhexylpropanol carboxylate, is a mixture of 19 parts of compound No.39 with 1 part of compound No.40. NMR (CC1 4) ppm l,05r!48 (m,6H)i 1.84-2.36 (m,2H); 5.02 (s,2H)ì 6.72-7.45 (m,10H) · (+)-α-cyano-3-phenos s ibenzyl (+)-cis / trans-5-(Z / fe-2-trifluoromethylproi(-len-1-yl)-2,2-dimethylcyclopropane carboxylate is a mixture of 1 part of compound No.19, 9 parts of compound No.20, 1 part of compound No.21 and 9 parts of compound No.2^'. NMR (CC1 4) ppm 1.22-1.40 (m,6H); 3-phenoxybenzyl (+)-clg / tran.s-3(Z / E-2-trifluoromethylpropane op-1-en-1-yl)2,2-dimethylcyclopropane carboxylate is a mixture of 1 part of compound No.25, 9 parts of compound Product No.15: Product No.16: Product #17: ~ rriClO BRIEF ιι ING. C. GREGORY -64— No.24, 1 part of Compound No.25 9 parts of Compound No.26. NMR (CC1 4) ppm 1.22-1.40 (m,6H)j 1.58-2.2 (m,5H)} 5.02 (s,^H); 5.2–6.45 (m,lH); 6,85-7.42 (m.9H) (+)-a-cyano-3-phenoxybenzyl (+)-£is / trane-3-(Z-5-chloride-2,3,3-trifluoroprop-l-en-l-yl)-2,2-dimethyl dimethyl cyclopropane dicarboxylate compounded with part No. 1, and a mixture of part No. 14 compound No.48. NMR (CC1 4) ppm 1.15–1.40 j (m,6H); 1.65–2.40 (m,2H)> 5.08, | I 5.39, 5.80, and 6.12 (4d,lH); 6.35 | (m,lH); 6.92–7.50 (m.9H). I (+)-a-cyano-3-phenoxybenzyl (+)~cis3-(Z-3-chloro-2,3,3-trifluoroprop-len-l-yl ) -2 ,2-dimethyl hyclopropane carboxylate, and* the compound Ho. NMR (CC1 4) ppm 1.18–1.40 (m,6H); 1.85–2.33 (m.2H)} 5.80 and 6.11 (dd, IH); 6.35 (d,lH)} 6.95–7.60 (m.9H). 3-phenoxybenzyl (+)-cis / t_rans-3-(Z3-chloro-2,3,3-trifluoroprop-l-en-10 0··· • 000 0 10*01 y ·*· • * 0 0 -65Product No.18» Product No. 19» Product No.20i (1)-2,2-dimethylcyclopropane carboxylate, is a mixture of 1 part of compound No.49 with 1 part of compound No.50. NMR (CC1,) ppm 1.15-1.30 (m,6H)ii 1.65-2.40 (m,2H)j 5.10, 5.40, 5.9½ and 6.23 (m,3d,3H)j 6.90-7.45 (m,9H). (+)-a-cyano-3-phenoxybenzyl (+)-cis / trans-3-(3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl)-2,2-dimethylcyclopropanecarboxylate, and* a mixture of 1 part compound No.1 with 2 parts compound No.2. 3-phenoxybenzyl (+)-cis / trans-5(3,3-difluoro-2-difluoromethylprop-len-1-yl)-2,2-dimethylcyclopropane carboxylate is a mixture of 3 parts of compound No. 5 with 2 parts of compound No. 6. NMR (CCl^) ppm 1.18-1.37 (m,6H); 1.60-2.45 (m,2H)j 5.03-5.ί (m,2H)j 5.13-7.47 (complex, 12H). (+)-a-cyano-3-phenoxybenzyl (ft)-ois / trens-3-(3,3-difluoro-2-difluoromethylpr ορ-1-en-l-yl)-2,2-dimethylcyclopropane « · « ♦ 1 ft ··· ' · · ft ft ft · » · · ft · ♦ · ft • ••ftft « .ft·· • •ftft, • · ftft ' p; ··.· • ftft THE TTI Product No.21: Product No.22: Product No.23: -66carboxylate is a mixture of 3 parts of compound No.7 with 2 parts of compound No.8. NM.R. (CCl^) ppm 1.20—1.40 (m.6H); 1.80-2.47 (m,2H)> 6.17-6.37 and 6.85-7.43 (mm,13H). 3-phenoxybenzyl (+)-cys / trans-3(Z / te-2-chloro-3,3,3-trifluoroprop-^en-1-yl)-2,2-dimethylcyclopropane carboxylate, and 1 a 9-part mixture of thio compound. 35, 1 part No.36 compound, 6 parts No.37 compound, and 4 parts No.38 compound. (+)-a-cyano-3-phenoxybenzyl (+)-o,is / trans-3-(2-2,4-dichloro-3,3,4,4-tetrafluorobut-1-en-1-yl)-2,2-dimethyl-j ! cyclo-propane carboxylate, and* a; a mixture of 9 parts of compound No.51 with 1 part of compound No.52* (+)-oc-cyano-3-phenoxybenzyl (+)-trans3-(Z-2-chloro-3,3,4,4,4-pentafluorobutyl-en-1-yl)-2,2-dimethylcyclopropane carboxylate and* compound No.53 » NKR (CC1 4) ppm 1.16-1.42 ··· ' · · · · · · .·· » · un '< - · : · 'PΠΊΤ Product No.24: Product No.25j -67(m,6H); 1.74-2.60 (m,2H)> 5.98-6.40 and 6.77-5.55 (m,11H). ; the 3-Phenoxybenzyl (+)-cig / trans-3-(5chloro-3»>-difluoro-2-chloroalfluoroqroethylproρ-l-en-l-yl )-2,2-dimethylcyclopropane carboxylate, is a mixture of 7 parts of compound No. with 13 parts of compound No.,10. NMR (CC1 4) p.p'm. 1.24-1.42 (m.6H)j 1.76-2.60 (m.2H); 5.02 (s^ìi); 6.16 and 7.12 (da,IH); 6.76-7.40 (m*9H). (+)-a-cyano-3-phenoxybenzyl (+)-£j^ / trans-3(3-chloro-3,3-difluoro-2-chloro I difluoromethylprop-l-en-l-yl)-2,2-; and < dimethylcyclopropane carboxylate, e* i a mixture of 7 parts compost^ No.11 oon 13 parts of compound ^0^.12. I NMR (CC1 4) p*p*m. 1.24-1.42 h ·· ·· to 0 •00· ·· · 00000 ··* •Z · ···. 0 • 0 ···♦ Product No.26s (m,6H)i 1.64-2.70 (m,2H)j 6.16 e 7.12 (dd,lH)and 6.36 (ss,IH); 6.90-7.50 (m.9H). (+)-a-cyano-3-phenoxybenzyl (+)-eie / ì trans-5-(Z / E-5,3-difluoro-2-chlorodifluoromethylprop-l-en-l-yl)-2,2dimethylcyclopropah carboxylate,· and 000 0 0 0 0 ·.·· 0 0 0 ·;·. 0 0 0 πι Product No.27s Product No.28: -68a mixture of undetermined composition containing compounds 27 , 28 , 29 , and 30 . NMR (CC1 4) ppm 1.24–1.52 (m,6H); 1.76–2.70 (m,2H); 5,6-7,6 (m,l2Hk (+)-a-cyano-3-phenoxybenzyl (+)-£Ìg / trans-5-(2 / B-2-bromo-3,3,3-trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane a carboxylated oo4 particle, and* 1 part of compound No.55, parts of compound No.56 and 1 part of compound No. NMR (CC1 4) ppm 1.24–1.50 (m,6H)and 1.75–2.55 (m,2H)j 5.96–706 (m,lH)| 6,36-6.56 (m,lH)j 7,0-7i (m,9H)· (+)-a-ethynyl-3-phenohexybenzyl (+)-ois / trans-3-(Z / E-2-ohoro-3,3,3-trifluoroprop-l-en-l-l-yl carboxyl unacycl )-2,2,2- 10 parts of No.58 compound, 1 pail of No.59 compound, 10 parts of No.60 compound and 1 part of compost^ No.61. .· · · • A * « * .·· a · · · · • · A « · a * « A · · * A « A * · * aaa aaa A « AA « • * A · A··* AA AA· f 'PINK Β V ! ΪΊ ìng G, GHFGOR -69N.MR (CC1 4) ppm 1.16-1.44 (m,6H); 1.64–2.56 5.7–7.0 (m,lH)j 6.28–6.40 (m,lH); 6.70-7.40 Product No.29s (+)-a-ethynyl-3-phenoxybenzyl (+)-cts / trans-3-(3,3,3-trifluorideο-2-trifluorocmethylprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate, comprising a mixture of compound No. compound No.14. NMR (CC1 4) ppm 1.16-1.44 (m,6H)j 1.76-2.56 (m,3H)j 6.12-7.04 (m,lH)f 6.24-6.40 (m,lH); 6.76–7.36 (m.9H). EXAMPLE 22 This example illustrates the insecticidal properties of (+)-a-cyano-3-phenoxybenzyl (+)-cis / trans· 4 4 4 4 4 4 4 · 4* 4 4 * * · • 4 · 3-(2-chloro-3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate (containing 60% of the cis isomer) (Product No. 6) and (+)-α-cyano-3-phenoxybenzyl (+)-cis / trans-3-(3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate (containing 20% ​​of the cis isomer) (Product No. 1) as representative examples of esters according to the invention. The activity of the products was tested against a variety of insects and other invertebrates. Each product was used as a liquid preparation, containing, in the case of product No. 1, 1000, 500, 125, and 62.5 ppm, and in the case of product No. 6, 50, 25, 12.5, and 6.25 ppm by weight of the product itself. The preparations were obtained by dissolving the compound in a solvent mixture consisting of 4 parts by volume of acetone and 1 part by volume of diacetone alcohol, the solutions were then diluted with water. containing 0.01$ by weight of a wetting agent marketed under the trade name USSArOl NX until the liquid preparations contained the required concentration of the compound* lissapol is a registered trademark. The test procedure adopted for each pest was basically the same and involved placing a number of the pests on a support medium which usually consisted of a host plant or food product on which the pests fed, and treating the pests or the support medium, or both, with the preparations. the mortality of the infesting agents was then evaluated at periods normally varying between 1 and 3 .·· • 4 4 4 · • 4 · 4 4 :· 4« ·· ·· ·· • · • · • » 4 · » 4· Lfrl SHORT THURSDAY! yes, ENG. C. GREGORJ -71 days after treatment. The test results are provided below in Tables II and III. In these Tables, the first column indicates the name of the pest species. Each of the subsequent columns indicates the plant or host medium on which it was supported, the number of days that were allowed to elapse after treatment before assessing pest mortality, and the number of days that were allowed to elapse after treatment before assessing pest mortality. The values, and the results obtained for each of the concentrations given above. The evaluation is expressed in whole numbers ranging from 0 to 3. represents a mortality rate of less than $30 represents a mortality rate of $30-49 represents a mortality rate of $50-90 represents a mortality rate of more than $90. A line (-) indicates that no testing was performed. A contact test indicates that both the pest and the medium were treated, and a residual activity test indicates that the medium was treated prior to infestation with the pest. The results for product No.1 are presented in Table II and those for product No.6 in Table III. • · · · • · ·**· • · · a · !· • aa · · a .··· • ftft·, • ft · · 1 ··· « · · ··· • ft • · · Η Η TO TO TO TO VF f'ìCiO Vf l ì I 73H TO H <4 TO TO TO .'•nr·.,-. -74ESSifPIC 23 _ This example illustrates the characteristics of insects and the products of the I ' and snakes 0 21. The tests were conducted under the same conditions of the? nei'!pio 22. T ri nnl tates not provided, ri (ìli to febei 1 to IV, cone per reen tirale of mortality dogli. G'i'j G- TL Lj »4. The noetic symbols in Table IV have different meanings. P Ho. Indine. Product No, as defined in * and if υ,pio 21. Level indicate the concentrated one eopreoon The parts per million of the active ingredient in the preparations used in the test. I 0 Symbols from A to ÌJ Iridium;.;,no the types of infesting agent used in the tests, which are the following: *· · · • * • 44· 4 4 4 4 4 »· * · « · 4 > a • • « 4 » > 4 4 4 4 4 • 4 * » 4 :· 4 4 4 4 « *•44 ·· · 4 4 « 4 » • 4 * • 4 • 44 4 « • 4 4 v 4 4 4 4* 4 • 4 * 4 4 4 • 4* 4 4 4 ··♦ THE -75 A ” Tetranychus telarius (red orb weaver spider - adults) ” B - Tetr&nychus tebarius { red orb weaver spider - eggs) C ~ Aphis fabas (black bean aphid) D _ Megoura viceae (green aphid) E” - Aedes aegypti (; mosquitoes) F - Musca domestica (houseflies) - contact activity G - Musca domestica (houseflies) - residual activity 5 H - Plutella xylostsila - residual activity (3 days) I - Patella 2Svl£st_ehk4 - residual activity (10 days) J” - Ziri iii (cress chrysomelus) K - Calandra granaria (corn calandra) ” L castaneum (calander) m ~ spodoptora littoralis (cotton leaf maggot) An asterisk (-t) in the Table indicates that, in addition to the mortality indicated, the remaining live insects were all severely affected and would likely have died if the duration of the test had been extended. >ì TABLE A| OA>1.. fu r~ί <-4 ι / π·ϊθίθ i.-'Rì·vff ir Iu£, m CN * oo ro * O oo ro O co O o 1-1 ooo O in O in 1 1 1 t 1 1 1 1 I t tn kO -k * ro l'' CM co in ro cn ro rA 1 ot co P—1 oo in ao σ> rA ro o co ro oo CN 1 CN I rA rH rA * O ooo •fc * koo ro ooooto kO i—1 rl ro oo O ro oo Γ 1 1 1 t O 1 kO ro rA rf -XO oooo * o KO in ooooooo * CO r—1 rl rA iN co —1 CM o * oo O ooooo CM o kD ooo CM oo <0 rH PA rA rA oooo * ooooooooooo in ooa tH <—1 rl kO r"! rA oo O oooo Γ moooooooo co CM kO rl rH rA H r—1 rA rA ooo C3 ooooooooo O ooaooop—ì rA «—l rN rA rA iA «-A »~A i—loooooooooooooooooo eh oo rA rA f—1 Γ—1 rA 1-1 1 rH rA ooo C! oo CJ o O o O o H ooooo co O ooo rl o cn 1 kO G\ CO CM CM rA ooooooo ro in oao LO moa CM CM CM «-A rl rA rA r—1 .__ -— ________ CM CO 'X LtA CO CA o 1—I ι—I il o ro CN K O o o ,-ì o man CN CN 100 3 3 100 0 100 f "77" TABLE IV (continuation) oooooo 2 oooooor—J rH 0 0 0 r—t 0 oooooo in ooooo « 0 + * * * * h) oooooo 0 H ! 1 tll 1 * 4t H * * * oooooo 04 r-~ r* in -cr rH uooo 0 J o -» * * * Cm oooooo Γ tt xr m CO in oooooo W ooo cr 0 CM 0 0 oooooo 0 ooo o unΓ o x— LO oo —1<n o cn o Cì r-4 rM a o o o O o O o o o o o O LO GD 0 04 Al in m in m in in S> o CM 0 04 0 04 04 aao £•4 mn lo Cl o —ic~i rH tH rl CM CJ ----- ----—— ——- ---— -----— o O 0 o 0 oooo *—1 0 oooo 1 1 1 0 in ool JI cc oor*i * o co « omo 0 oo 0 O σ» o O o σι 1 1 JI 0 o * ooo O o O o rM o 0 co 0 0 0 * 0 O ot 1 1 0 -k * ooo 0 o O 0 ooo 0 gì o 0 r—J oo0 O0 J 0 o 0 o 0 ί-Η 0 0 0 0 oooo 0 o 0 oooor—1 r—ì rH 0 0 0 o in oo 0 oo Gì o rH rH oo 0 o Cl o in Cl on in O LO O n CM CM in CM CM m n r- co cn CM CM CM CM rH cm CM CM cn CM 100 100 100 - 56 - 90 - 100 OFFICE ΒΗι-, . Η'Ήλ, c -78EXAMPLE 24 This example illustrates the ixodic activity of product No.2 / product No.6 against cattle ticks (Boophilus microplus). The suspension of each of the products was prepared by ball milling 10 parts of the product with 985 parts water and 5 parts Terip N9 (Teric is a registered trademark and is a registered trademark. N9 is a non-ionic surfactant obtained by condensation of nonylphenol with ethylene oxide in a 1:9 molar ratio) to give a composition containing 1.0% of the active ingredient. A portion of each of the above suspensions was then diluted with water to give compositions containing 0.1% to 0.01% of the active ingredient. The efficacy of each product against adult female ticks gorged on Yeerongpilly strains was assessed by administering a microdrop of suspension of the appropriate concentration to each of approximately twenty ticks. After 14 days, the mortality of adult ticks was calculated by counting the eggs laid by the ticks and the percentage of those eggs that hatched. The results • a ·♦ ·* * AAAAAA ·** ♦♦ A · aaa AAA a·* • A AAA -79θοηο provided in Table V. the effectiveness of each of the products in the con Γ r« URICO ΒΠ'ΎΠ ri ING. C„ G RUGGHI fronts of tick larvae of the Yeerongpilly strain were evaluated as follows: a sheet of filter paper was soaked in the suspension of the appropriate concentration and then allowed to dry. The treated paper was converted into the form of an envelope and approximately 100 tick larvae of the Yeerongpilly strain were enclosed in it. Mortality counts were performed on the tick larvae 48 hours after they had been placed in the envelope and the data were classified on a scale of 0 to 5, in crii ! represents a mortality of 0-20# represents a mortality of 20-50# represents a mortality of 50-80# represents a mortality of 80-95# represents a mortality of 95-99# represents a mortality of 100#. The results are provided in Table V. In a further test, an emulsion of each of the products was prepared by mixing 25 parts of the compound with 75 parts of cyclohexanone and 25 parts of Teric N9 and diluting the mixture with water to give 10,000 parts by volume of a >· ·. » · · ' • · · • » 0 0 » » ··· » * ♦♦ 00 ····, • 0 00 1 SHORT OFFICE r ING, C, GNEGOnJ -80 emulsion. Each of the emulsions thus obtained was sprayed, to the dripping point, on calves heavily infested with various stages of the resistant Biarra strain of cattle tick. The efficacy of each of the products was evaluated. as follows: (i) all adult female ticks that were completely satiated (or saturated with blood) at ! The calves were collected immediately after spraying. They were then placed in a 4-meter dish in an incubator for mortality assessment based on the ability to lay eggs and, if eggs were laid, on the viability of the eggs, demonstrated by the ability to produce viable larvae. Satiated adults, if any, were collected 24 and 48 hours after spraying and the same mortality assessment was performed. This assessment is reported I as mortality - saturated adults (i.e. blood-saturated), and the results are given in Table VI. (ii) At 1-day intervals, pre-established sampling zones on each calf were .*· MM* .·♦· >··< • S · • 00 *··· * · *· · · 000, 0 0 0 0* • · • 00 -81examined for the effect of the active ingredient on immature adults and nymphs. This evaluation was scored on the 0 to 5 scale defined in the example and is reported as Mortality - Immature Adults and Mortality - Nymphs. The results are provided in Table VI. The symbol is used to indicate that no saturated adult individuals were present. In these tests, permethrin (3-phenoxybenzyl (+)-cis / trans-5(2,2dichlorovinyl)-2,2-dimethylcyclopropane carboxylate) was used as a standard» · * I « ·! · 4* • · * • · · ..... . . . · ' -02 in vitro ixodic activity against adults and larvae 8 H s Pi Gl, ri* so •H Ό ÓP rd LO 1 y •H g 1 g * tl ' «n in H rd CO vv ì not there ; oi=> M •ri » T? and 1 lo if) &> ·«· h 1<ri Oh « H CS • ! tì •ri q •ri •tl o o • w tip ΟΊ o o rH ---1 > A *s •H ' ; o ·» +> -=4 • •5 Cj EH H Φ H =4 Ή *ri 100 100 ri (1) •ri o •fe—< Where 3 tH Φ ri L< I? PATENT OFFICE Eng» G GREGORJ or ι three e. I CJ • _______ -----— --------- -S3 PATENT OFFICE I Eng. C. GREGORY TABLE VI live activities in the communities of saturated adults, unsaturated adults -84BRtv OFFICE. WG. C. GREGORv< / ci>

Claims

1. CLAIMS 1. A compound of formula: rVc^CH-CH-CH-CR CH. 1 2 wherein one of R and R represents a haloalkyl group containing one or two carbon atoms^, 1 2 and the other of R and R represents a halogen atom, a methyl group or a haloalkyl group containing 1 or 2 carbon atoms and R represents hydroxyl, alkoxy containing up to 6 carbon atoms, a halogen atom, a phenoxybenzyloxy group which may optionally be substituted in the a position with a cyano or ethynyl group.

2. Compound according to claim 1, characterized in that R stands for 3-phenoxybenzyloxy, α-cyano-3-phenoxybenzyl or α-ethynyl-3-phenoxybenzyloxy.

3. 6ompound formula: ···· • * * · · · · ♦·;· !... * · · a · • · 0 0 0 0 00··· 0 • • 0 00 » · 0 · · 0 0 0 *0 J 0 · · 0 0 ♦··♦♦ 00. • I · ,»·· .·· *0 ·* * : · · · 0 *00« 0 0 . 0 0 0 ·.· »0·· · · 0 0 0 0 0 ***** ..·· · · · · • · · » · ♦ • · · · * 1 T,2 where one of R and R represents a group of -85 formula: W(CP 2) 5 where W represents a hydrogen, fluorine or chlorine atom and m has the value of one or two, Luoro, 1 2 and the other of R and R represents a chlorine or bromine atom or a group of formula: XC. r,F'VF .· ·· ·· ♦· • a · · · IH 4 · · *••44 lit· ►:· ·· ·| • · · a · ». · 4 4 4 I · _· wherein each of X, Y and Z independently represents a hydrogen, fluorine or chlorine atom, and R represents a hydrogen atom, or the cyano or ethynyl group* 4. Compound according to claim 3, characterized in that one of R and R represents a group of formula: wgf 2 wherein W represents a hydrogen, fluorine or chlorine atom, and the other of R and R represents a group of formula: Y XC» Z wherein each of X, Y and Z independently represents a hydrogen, fluorine or chlorine atom, and UFFICIO BREVE, ING. C. GREGORJ -863 R represents a hydrogen atom or the cyano or ethynyl group.

5. Compound according to claim 4, characterized in that R and R each represent the trifluoromethyl group.

6. Compound according to claim 3, characterized in that one of R and R represents a group of formula: WC3? 2~ where W represents a hydrogen, fluorine or chlorine atom, and the other of R and R represents a fluorine, chlorine or bromine atom, and R represents a hydrogen atom or the cyano group.

7. Compound according to claim 6, characterized by the fact that one of R and R represents a trifluoromethyl group and the other of R and R represents a chlorine or bromine atom.

8. (+)-a-cyano-3-phenoxybenzyl (+)-ois / trang-3-(i2chloro-3,3,3-trìfluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate.

9. (+)-a-cyano-3-phenoxybenzyl (+)-cya / tran.s-5(3,3,3-trifluoro-2-trifluoromethylprop-l-en-l-yl)-2,2dimethyl-cyclopropane carboxylate.

10. (+)-a-cyano-3-phenoxybenzyl (t)-o,is 7 / tran8-3-j(5« I chloro-2,3,3-trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate· 11. (+)-a-cyano-3-phenoxybenzyl (O-cis / trans3-(2-bromo-3, 3,3-trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate.

12. 3-Eenoxybenzyl ,( +)-cis / trans-3-(2-olo· 3,3,5-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate.

13. 3-Eenoxybenzyl (+)-c is / trans-3-(3,3,3-t j&fluoro-2-trifluoromethylprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate· 14. A compound according to any of the terms 1 to 7, characterized in that the hydrogen atoms of the cyclopropane ring have the trans♦ configuration.

15. Compound according to any of claims 1 to 7, characterized in that the hydrogen atoms of the cyclopropane ring have the cis configuration.

16. Compound according to any of the preceding claims, characterized in that the absolute configuration of the cyclopropane ring© is of the (1R,3R) or (2R,3S) type.

17. Compound according to any of the preceding claims, characterized in that R is not a hydrogen atom in which the absolute configuration of the carbon atom to which R is attached is of type (S), 18* (+)-a-cyano-3~phenoxybenzyl (IR,3R)-3-(3,3,3trif luoro-2-trif luoromethylprop-1-en-1-yl )-2,2-dimethylchloropropane carboxylate.

19. (+)-a-cyano-3-phenoxybenzyl (IR,3S)-3-(2-chloro^o3,3,3-trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate.

20. (S)-a-cyano-3-phenoxybenzyl (lR,3R)-3-(3,3-! j trifluoro-2-trifluoromethllprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate.

21. (S)-oc-cyano-3-f enosybenzyl (IR,3S)-3-(2chloro-3,3»3-trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate.

22. Process for preparing a compound according to claim 1, characterized in that an acid of formula: ··»« and • · · ' 4 4 4 • 44 A 2C==CH-CH-CH-C-0H \ / C z\ [3 CH, CH^ is reacted with an alcohol of formula: -90UFFICIO PATENT . ING. C. GREGORJ ϊ with a mixture of an alkali metal cyanide and ί 3-phenoxy-benzaldehyde, wherein R , R and Q have the meanings established in claim 23. j 25. Process for preparing a compound according to | claim 1, characterized in that £i reacts an acid of formula: 00000 ···♦ A 2C=CH~CH~CH-C~OH V cì^ or an alkali metal salt thereof with a halide of formula: Q»-CH(R 2) OCA 6 5 ♦ 0 · · 0 !· • · · · · · ··< • · 0 · ' wherein Q' represents a halogen atom, and R » Ri 3 1 and R have the meaning established in claim 1.

26. A process for preparing a compound according to claim 3, characterized in that a lower alkyl ester of the formula: rVc »0H-CH-CH-O-QR 4 V CHj CHj 91 is heated with an alcohol of the formula: H0-CH(R 2) -°°6 η5 12 3 wherein R t R and R have the meanings set forth in claim 3 and R is a lower alkyl group containing up to 6 carbon atoms.

27. Process according to claim 26, characterized in that it is carried out in the presence of an alkali metal alkoxide* 28. Process according to claim 26, characterized in that it is carried out in the presence of an alkylated titanium derivative.

29. Insecticide composition, characterised in that it comprises, as an active ingredient, a compound according to any of claims 3 to 21 in association with a material having the character of a diluent or vehicle, inert as an insecticide.

30. Composition according to claim 29, characterized in that it comprises a surfactant.

31. Composition according to one or the other of claims 29 and 30, characterised in that it comprises a synergistic agent such as an insecticide.

32. A method for combating infestations by insects or mites in a given location, characterized in that the location is treated with an insecticidal or acaricide-effective amount of a compound according to any of claims 3 to 21 or a composition according to any of claims 29 to 31.

33. A method according to claim 52, characterized in that the location is a growing plant or plants.

34. A method according to claim 32, characterized in that the location is a domestic animal or animals.

35. Method according to claim 34, characterized in that the domestic animals are cattle infested with ticks of the ixodidae family. • ·· I · ·:···' • · 4 » 4 4· 4 4 4 4 ♦ 4* 4 4 4 i 36. Compound of formula rVc^ch-ch-ch-cq \ / c X\ ci^ CHj wherein one of R^ and R 2 represents a group of formula: Wherein W represents a hydrogen atom, fluorine -93PATENT OFFICE. ING, C. GREGORJ or chlorine and m has the value of one or two, and the other 1 2 between R and R represents a fluorine, chlorine or bromine atom, or a group of formula: XC« Z wherein each of X, Y and Z independently represents a hydrogen, fluorine or chlorine atom, and represents the hydroxyl group, a lower alkoxy group containing up to 6 carbon atoms or a chlorine or bromine atom.

57. Compound according to claim 56, characterized in that one of R and R represents a group of formula: I ·· · · · · · · · · · · · · · · A » A . a·· , A· » • a.»♦ A AA « AAAA AA • AA • AAA AAA A AAA • AAA • AAA A* AAA .·· TO' - ; £ I wherein V represents a hydrogen, fluorine or chlorine atom, and the other of R and R represents a group of formula: Y XC» z wherein each of X, Y and Z independently represents a hydrogen, fluorine or chlorine atom; Q represents the hydroxyl group, a lower alkoxy group containing from 1 to 5 carbon atoms, -r T -94 or 1 chlorine or bromine atom.

38. Compound according to claim 36, characterized in that one of R and R represents a group of formula: where W represents a hydrogen, fluorine 1 2 or chlorine atom, and the other of R and R represents a fluorine, chlorine or bromine atom, and Q represents the hydroxyl group, a lower alkoxy group containing 1 to 3 carbon atoms, or the chlorine or bromine atom.

39. A compound according to claim 36 or claim 37, characterized in that R 1 and R 2 are both trifluoromethyl groups.

40. A compound according to claim 36 or claim 38, characterized in that one of R 1 and R 2 represents the trifluoromethyl group and the other represents a chlorine or bromine atom.

41. (+)-cis / trans-3-(2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylic acid.

42. (+)-cis / trans-3-(2-bromo-3,3,3-trifluoromethylprop-l-en-l-yl)-2, 2-dimethylcyclopropane carboxylic acid.

43. (»)-ois / tra»s -3-(5,5,3-trifluoro-2t ref fluoromethylprop-l-en-l-yl )-2,2-dimethylcyclopropópane 4 · * • 4 4 # » . ··* • · · I · *1 M » 4 .;·:· 4. 4 4 • 4 *4»· 4 · · > « 4. * 4 4 4 4 4 4« • ·** 4 4 4 4 4 * • 4 '4 4 4 4 4 -95BREVl. ING. C. GREGORJ carboxylic acid. 44.(+)-cis / trans-3-(3-chloro-2,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylic acid 45. Compound according to any of claims 41 to 44, characterized in that it is found in the form of the relevant ethyl ester.

46. Process for the preparation of a compound according to claim 36, wherein Q represents a lower alkyl group containing up to 6 carbon atoms, characterized in that a diene of formula: ,1 '0 0 0 0 . ··· R' CH_ C=CH-CH-C / \ CH„ se• · · · 0 ·· ·. »00« '··< 0 0· 0 0« 0 0 0 0 · 0 0 0 Β· 0 * .* 0 0 0 ··· 0 » with a lower alkyl ester of diazoacetic acid.

47. Process according to claim 46, characterized in that the lower alkyl ester of diazoacetic acid is ethyl diazoacetate.

48. Process according to either of claims 46 and 47, characterized in that the diene is used in excess. 49.

50. A process according to any of claims 46-48, characterized in that it is carried out in the presence of a metal catalyst.

51. A process for preparing a compound according to claim 6, wherein R and R are both trifluoromethyl or one of R and R is trifluoromethyl and the other is difluoromethyl, and Q is a lower alkyl group containing from 1 to 6 carbon atoms, characterized in that it comprises the steps of (a) treating a compound of the formula OH rVo-CH 2 CK sC CH 5 CH 5 with a lower alkyl ester of diazoacetic acid. (b) subjecting the compound of the formula OH 0 -CH 2 ... 3 3 thus produced by dehydration with a chemical dehydrating agent.

51. A process according to claim 50, characterized in that the chemical dehydrating agent is phosphorus pentoxide. 52.

53. A diene according to claim 52, characterized in that R and E are selected independently from trifluoromethyl, difluoromethyl and chlorodifluoromethyl, and in that one of R 1 2 and R 2 may be, in addition, methyl.

54. A process for preparing a diene according to claim 51, characterized in that a ketone of formula: 1 2 R X 2 C-R is reacted with the ylide obtained by dehydrohalogenation of a difluoromethyl halide. 3,3-Dimethylallyl triphenylphosphonium, 55* Compound of formula: OH , r 1r 2c~ch 2-ch=cs CtL 0H5 1 2 wherein one of R and R is trifluoromethyl and the other is trifluoromethyl or difluoromethyl 56· Process for the preparation of a compound according to claim 55, characterized by nl-io + nWo Η4 “ΡηΤΐΜίΤ fi · [irr ·- jt- '0τγ| ·· · » • · • ·.· * · · · · , ft ·* · • : · · · · » • · · · · • « ft » · · · ••ft·» · • · · ♦ » φ » ........ • · · · · ♦ .··· .·· . · · · » , ··.·· • · · · · » » · · « · • * · · · ft · ft · ft • ···· • ft * ft · · • ft ft · · ft • · · « · • . » * ft -98Hi' .· sr!, : , / rn, ING. 1 ” 2 R -CR 1 «2 wherein R and R have the meaning established in Claim 55, with isobutene. 57· Process according to claim 56, characterized in that it is carried out under pressure. 58· Process for preparing a diene of formula: , · »1 ►a A 1 • ··«· . A ··· ΕCH, *''C»CH-CH=C CH, ► ♦ · • ·· ••A « AAAAAA* AAAA** A * AAA 1 2 I wherein R and R have the meaning established in * ·**. AAAA 1 claim 55, characterized in that it comprises the dehydration step of the corresponding compound of formula: OH R^R^C -ch 2-ch=c CH, CH^ by treating the same with phosphorus pentoxide.

59. A process for preparing a compound according to claim 56, wherein Q represents a lower alkoxy group containing up to 6 carbon atoms, characterized in that it is a compound of the formula: » -99r* t Ì W· CH^ 0 ^JC-CH -CYL-C-CH 9-CQ * » ι * ir 2 W CHj 1 2 wherein R ©à R have the meaning set forth in claim 36 and Q represents a lower alkoxy group containing up to 6 carbon atoms, and VP and F each represent fluorine, chlorine or bromine, provided that W* is bromine when 2 j R is bromine, with at least two molar equivalents of j a base. ' 60. A process according to claim 59, characterized in that the base is the lower alkali metal alkoxide containing up to 6 carbon atoms.

61. Process for preparing a compound according to claim 36, characterized in that it is a compound according to one of the formulas R' .O-CH=CH-C-CH 2-CQ È 2 ÌH5 ···· • · ·· · * ···· • · *.· • 4 4 4 4 4 4 • 4 4 4 4 « 4 4 4 4 4 * ·.·.· ..... • * · · · * ····· • : · . ·· · · · 4 *·** 4 4 * 4 4 4 4 4 4 4 4 M··. 4 4 4 4 · •100W* ο R 1-C-CH O-CH-CH-CQ *2 \ / R 2 0 CHj CH, wherein R 1, R 2, Q, W» and W have the meaning established in claim 59, is treated with at least one mole of a base· 62. Compound of formula: · ·· · • ··· * • * · · · · 1 ·· ·· · ·.·...... • · t ♦ is ..... ... ;·· ···. ? *> w» kLÒ-oh-ch » · e2 W» OH, 0 O-CH pCQ » c CH, wherein r\ R 2, Q, W* and WM have the meaning established in claim 59.

63. Process for preparing a compound according to claim 62, characterized in that a compound of the formula: CH, . 5 ti CH 2«CH-C-CH 2-CQ CH, ·· · · « ..... • · . · 1 ... is reacted with a compound of the formula: βM.I· » W* lo wherein R , R , Q, w* and W” have the meaning established in claim 59, in the presence of a radical-type initiator. 64.

65. Compounds according to claim 1, and processes for their preparation, substantially as described herein, with particular reference to any one of examples 16, 19 and 21.

66. Compounds according to claim 36, and processes for their preparation, substantially as described herein, with particular reference to any one of examples 16, 19 and 21. any of examples 1 to 15, 17, 18, and 20, taken separately or in combination. Milan, January 1978 PATENT OFFICE ING. C. GREGORJ • · · · 9 · ·· ·· • · * 0 0 0 ·· ·· ·.« a 0 4 0 1 •*000 :· t « • « 0 »··· Φ 1 0 0 · • 0 • · 0 *0 0 0 0 0 0 • 0 0 0 0 0 0 0 * · « • » » 0 * » · « 0 · »·♦ a · • 0 ·.