PROCEDURE FOR the PRODUCTION OF NEW ONE 3 (2 ' PERHALOGENALKYLVINYL) - 2,2-DIMETHYLCYCLOPROPANCARBONS [UREESTERN

The invention refers to a procedure for the production of new 3 (2 ' - Perhalogenalkylvinyl) - 2,2-dimethylcyolopropancarbonsäureestern of the general formula CI) where Y Perhalogenalkyl with I to 4 C-atoms and Z hydrogen, halogen, nied. Alkyl, Phenyl, Phenylthio or benzyle mean, or and R for a group of the formulas R-S - CHRil iR3, - form a Perhalogencyclopentylidengruppe with one another for Y and Z CHz -- - Stands for CH2 ß R7 ù - CH, R or Cl, whereby R' for hydrogen, cyanogen or tri fluorine methyl, R2 for hydrogen, chlorine, methyl tert or. Butyl, H3 and R independently stand for hydrogen or chlorine or with one another Methylendioxy form, R5 and R6 hydrogen, halogen or methyl are independent, R hydrogen, chlorine or methyl are, R8 and R9 hydrogen, chlorine or Niethyl are independent or Methylendioxy form with one another and R ° hydrogen, bromine, Methoxy, Phenyl or Nitro are, with insektizider effectiveness. Pyrethrine, naturally occurring excerpts of chrysanthemums, are for a long time as insecticides of interest. Since the clearing-up of the structures of these connections, one strove to synthesize related connections with increased insektizider effectiveness and improved stability against air and light. A remarkable progress in this area was the discovery of Elliott et al. more intended highly active connections, for example Dihalogenvinylcyclopropancarboxylaten, like Permethrin, the general name for 3-Phenoxybenzyl-3 (- dichlorvinyl) - -2,2-dimethylcyclopropancarboxylat. This in the US-PS Nr.4, 024.163 descriptive Klass of connections shows in the comparison with the available Cyelopropanoarboxylaten, like the Chrysan25thematen, i.e. the connections of the formula (I), where Y and Z mean both methyl, substantial improved photo stability. Those so far did not admit Cyelopropancarboxylate, as they are descriptive in the oberwähnten US-PS, showed a high extent at effectiveness against insects of the kind Lepidoptera, but many of these connections commercially satisfying extent at effectiveness against insects of the kind Homoptera, e.g. of sheet lice, showed. Now new Perhalogenalkylvinyldimethylcyclopropancarbonsäureester is manufactured according to invention, which generally a high extent at insektizider effectiveness, an improved effectiveness against insects of the kind Homoptera, like sheet lice, and an improved photo stability to show. The expression used here “nied.” in connection with alkyl means a content of 1 to 6 C-flavours, preferably 1 to 4 C-flavours. The expression “halogen” means bromine, chlorine or fluorine. In connection with a Perhalogenalkylgruppe the halogen atoms know directly or differently, be suitable-prove fluorine and chlorine, preferably however fluorine, to be. These definitions are valid here continuous, if not expressly is indicated to something else. B means the indicated alcohol remainders, those together with Chrysanthemsäure [3 (2,2-Dimethylvinyl) - 2,2-dimethylcyclopropancarbonsäure] or the Dihalogenvinylcyclopropancarbonsäuren of the US-PS Nr.4, 024.163, as Permethrin, insecticide form effective esters. Thus R is a group, which is in the Cyclopropancarboxylatinsektizidtechnik esters effective for the production of insecticide together with a suitable well-known Pyrethroidsäure usable. By these alcohols those, where R 3-Phenoxybenzyl, - Cyano-3-phenoxybenzyl, means 3-Phenylbenzyl or 5-Benzyl-3-furylmethyl, are either easily available or easily and cheaply synthesizable from easily available raw materials. In addition show connections of the formula (I), which this AIkoholreste contains in combination with an acid component, where one of the groups is Y tri halogen methyl, preferably tri fluorine methyl, and Z halogen, unexpectedly high effectiveness against insects generally, remarkable effectiveness against sheet lice and along of exception of 5-Benzyl-3-furylmethyl - unusual photo stability. Available the according to invention connections and certain output products to their production exist as cisund trans geometrical isomers; the Carboxyund the substituted Vinylgruppe in the positions 1 and 3 of the Cyclopropanringes is in purchase either ice one on the other or trans. The production of such connections results in usually a mixture of cisund trans isomers, ice, trans designation, where the relationship of cis to trans over a wide range can vary. The designations cis and trans correspond to P.E. Burt et el., Pestic. Sci, 5, 791-799 (1974). Available the according to invention connections can also as Eoder Z-isomers or as their mixtures, E, Z designation, depending upon the spatial relation of the substituents to “- carbon atom of the Vinylgruppe to those at the 8-Kohlenstoffatom of the Vinylgruppe exist. In the Cyclopropancarboxylattechnik is well-known it that in the extent the insecticides effectiveness between cisund the trans isomers substantial differences can be present. Generally trans mixture is usually more active from cisund the trans isomers of a certain Cyclopropancarboxylats an isomer than other and also more active than cis. Which concerns available the according to invention connections, that is usual cis isomers the more active. hn 0 liche differences in the effectiveness can be present also regarding the Eund Z-isomers. If nothing else is indicated, the invention covers the production of all connections, where the Carboxyund is the substituted Vinylgruppe one on the other in the positions I and 3 of the Cyclopropanringes ice or Iran or a mixture of cisund trans configuration in purchase. Although further the invention illustrates 5 on the basis a mixture of the Eund Z-isomers becomes, also individual isomers as well as the mixtures fall under the save area of the invention; in the same way the Enantiomeren this isomers. The procedure according to invention consists of that one a Alkanoat of the general formula x z --COOAIk (II) where X CH! or or bromine meant, Y and Z the above meaning have, and alkene C, - C - alkyl is, in an not-aqueous solvent by shifting with a strong base to a Alkylcyclopropancarboxylat of the general formula (eyelid where Y, Z and alkene the above meaning to have, dehydrohalogen ert and this alkyl ester directly or after preceding transfer into the appropriate Säurechlorid with the alcohol of the general formula HO-R, (IV) IP where B the above meaning have, umestert. In mode of production i a procedure for the production of the preferential parent compounds of the formula (IL) is by shifting one nied. Alkyl-3,3-dimethyl-4-pentenoats with a connection of the formula X2 - C (Y) (Z), where X, Y and Z have the above meaning, indicated. The Dehydrohalogenierung according to invention can in several steps over the intermediate connections X COOAIk X --COOAIk Y (Iv) (v) (vb and in only one step by distance of two Halogenatemen or to be gradually accomplished. These intermediate products or mixtures hievon can, if are wished, isolated. The connection of the formula (III) becomes then also ago into the connection of the formula (I) transferred. The following examples are to describe the invention more near, without this is to be limited however on that. If differently not indicated, the decreased pressure for restricting liquid caused by a water-operated vacuum pump. First the production of connections of the formula (II) becomes described on the basis the mode of production 1: Mode of production 1: Production of Äthyl-3,3-dimethyl-4,6,6-triohlor-7,7,7-trifluorheptanoat: An agitated solution of 44,6 g (0.267 4oi) Äthyl-3,3-dimethyl-4-pentenoat, 100 g (0.533 mol) l, l, l-Trichlortrifluoräthan, 0.27 g (0.0027 mol) copper (I) chlorld and 8.2 g (0.134 mol) ethanol amine in 270 ml tert. Butyl-alcohol was heated up 16 h long under nitrogen atmosphere at the return flow. Then the reaction mixture on ambient temperature was cooled down and extracted three times with for each I00 ml diethylether. In the excerpts formed a precipitation, which was removed by Vakuumfiltration. The filter cake was washed twice with ever 25 ml diethylether. The ether excerpts were combined with the washing liquids and the whole under decreased pressure to oily arrears was concentrated. The remaining volatile components were removed from the arrears under far decreased pressure with application a vaccum pump. The arrears were distilled 3s under decreased pressure, whereby 78.3 g Äthyl-3,3-dimethyl-4, ö, became to receive 6-trichlor-7,7,7-trifluorheptanoat, kp. 85 to 870C/0,16 up to 0.20 mbar. The N 4R-Spektrum agreed with the attributed structure. Further parent compounds of the formula (II), which will receive in accordance with above procedure, are indicated in the following table I. Table I mode of production 1 ith ia) 1.2a} 1.3a} 1.4a} 1.5a) 1.6a) 1.7a} 1.8b) Br Cl c1 c1 C! Cl Cl c1 CF3 CF3 CF3 CF2C1 CF2C1 CFCl2 CFùCF2C1 C2Fs z Br F H c1 F F c1 Cl a) kp. (C/mbar): I.I: 63/0,106; 1.2: 71/12 mbar; 1,3: i12-115/9,31; 1.4: 95-I06/0,133-0,1662; 1.5: 58-60/0,0067; 1.6: 183/0,266 0,399; 1.7: 98-102/9,067. b) Structure by NMR confirms. The modes of production 2 and 3 describe the production nied. Alkyl ester of the formula (III). Mode of production 2 is a two-stage procedure over the Zwisehenprodukt of the formula (VI). Mode of production 3 is a classification procedure. Mode of production 2: Production of methyl cis, trans-3 (2-ehlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarboxylat A) production of methyl ice, trans-3 (2,2-dichlor-3,3,3-trifluorpropyl) - 2,2-dimethylcyclopropancarboxylat as an intermediate product: An agitated solution of 37,0 g (0.112 mol) Methyl-3,3-dimethyl-4, 6-trichlor-7,7,7-trifluorheptanoat, 50 ml tert. Butyl-alcohol, 50 ml dimethylformamide and 50 ml hexane was cooled under argon atmosphere on -5°C. To the agitated solution drop by drop a solution was tert of 16,4 g (0.14 mol) potassium tert.butoxyd in 200 ml. Butyl-alcohol with a such speed added that the reaction mixture temperature remained with -3 to -5°C. After terminated additive the reaction mixture 4 h was agitated long with -3 to -5°C and poured then into a solution by 8,0 g ammonium chloride in 250 ml water. The mixture was extracted twice with ever 280 ml diethylether. The united ether excerpts were washed twice with 200 each ml water. The ether layer was dried and filtered with sodium sulfate. The filtrate was evaporated under decreased pressure to an oil. This oil was distilled under decreased pressure, whereby methyl cis, trans-3 (2,2-dichlor-3,3,3-trifluorpropyl) - 2,2-dimethyleyclopropancarboxylat 19.8 g became to receive, kp. 55 to 57°C/0,12 mbar. The IRund NMR spectra agreed with the attributed structure. Elementary analysis: - ü - Nr.367391 computes 0 H, gCI2 F O for C: found: C 40,98; H 4.47% C 41,50; H 4.41%. B) Production of methyl cis, trans-3 (2-chlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarboxylat: An agitated solution of 30,6 g (0.105 mol) methyl cis, trans-3 (2,2-dichlor-3,3,3-trifluorpropyl) - 2,2-dimethylcyclopropancarboxylat and 17.6 g (0.116 mol) 1,5-Diazabicyclo [5,4,0] undec-5-en in 100 ml dimethylformamide one heated up 4 h on 100°C. The Reaktionsmisehung was cooled and into a solution von37,2 ml konz. Hydrochloric acid in 300 ml water poured. The mixture was extracted I0 three times with ever 200 ml diethylether. The united ether excerpts were washed with an aqueous solution satisfied with sodium chloride. Therschicht with sodium sulfate one dried and one filtered. The filtrate was evaporated under decreased pressure to an oil. This oil was loosened in hexane, treated and filtered with decolorizing coal. The filtrate was evaporated under decreased pressure to an oil. This oil was distilled under decreased pressure, whereby in three parliamentary groups methyl cis, trans-3 (2-chlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarboxylat 10.0 g became to receive, kp. 40 to 6fl°C/0,067 mbar. The IRund NMR spectra agreed with the attributed structure. The NMR spectra showed 88: 12-Mischung of cis: Trans isomers on. Analysis: Computed for C, 0 H, 2 CIFsO2: found: C 48,80: H 4.71% C 46,91; H 4.79%. Mode of production 3: Production of ethyl cis, trans-3 (2-chlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarboxylat: To an agitated solution ethanol distilled by 78,3 g (0.228 mol) Äthyl-3,3-dimethyl-4,6,6-trichlor-7,7,7-trifluorheptanoat in 200 ml were added to metallic sodium drop by drop with ambient temperature 500 ml äthanolische Natriumäthoxydlösung, manufactured from 11,5 g (0.50 mol). After terminated additive the Beaktionsmischung i h was agitated long with ambient temperature and let long then for 18 h stand. Those cloudy reaction mixture was filtered and the filtrate under decreased pressure was evaporated, whereby arrears became to receive. The arrears were mixed into a paste with in 200 ml water and the mixture three times with ever 50 was extracted ml diethylether. The united excerpts were dried and filtered with sodium sulfate. The filtrate was evaporated under decreased pressure, whereby as remaining oil 58.5 g became to receive ethyl cis, trans-3 (2-chlor -3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarboxylat. The NMRund IR spectra agreed with the attributed structure and showed that the product was a mixture of approximately same parts cisund trans isomers. Further intermediate products of the Formol (VI), manufactured in accordance with the procedure described in mode of production 2 A) are indicated in table [...]. Table [...] --COOCH8 mode of production X Y Z 2.1a) Br CF3 Br 2,2 c1 CF3 F 2.3b) c1 CF3 H 2,4 CI CF c1 Cl 2.5a) Cl CF2 CI F 2,6 c1 CFCI2 F 2.7b) c1 CF2 CF, CI c1 a) kp. (°C/mbar): 2.1: I00-133/0,12-fl, 133; 2.5: 45-47/0.27 b) structure by N 4B confirms. Further one nied. Alkyl ester of the formula (III), manufactured in accordance with mode of production 2 or 3, are indicated as connections 3,1 to 3,8 in table [...]. The connections 3,1 to 3,7 were received in accordance with mode of production 2. The connection 3,8 was made in accordance with mode of production 3. Mode of production 4: Production of transund cis, trans-3 (2-Chlor-3,3,3-trifluorprepenyl) - -2,2-dimethylcycloprop ancarbonsäure: A solution of 16,2 g (0.06 mol) Kthyl cis, trans-3 (2-chler-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarboxylat containing in 94 ml (0.078 mol) a supply solution, 3.34 g sodium hydroxide, 94 ml ethanol and 6 ml water, was agitated, whereby them became 18 h long at the return flow heated up i0. The Reaktiensmischung was restricted under decreased pressure, added to 25 ml water and acidified the mixture with 6n hydrochloric acid on pH 1. The acidified mixture was extracted twice with ever 50 ml diethylether. The united excerpts were dried and filtered with magnesium sulfate. The filtrate was evaporated under decreased pressure, whereby arrears became to receive, which were heated up with 50 ml hexane. The hot hexane was decanted and cooled by teerigen arrears, whereby a firm precipitation became to receive, which was collected by filtering and dried then; 3.3 g of a solid were received, Fp. 97 to 103°C. With concentrating the butter lamp a second parliamentary group of a solid with a mass was received from 0,8 g, Fp. 96 to 103°C. The NMB spectra of the two parliamentary groups showed that the solids in each case trans-3 (2-Chlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarbonsäure were. The mother liquor was evaporated to arrears. The arrears were taken up to 50 ml hexane and the solution in a Gefrierschrank 18 h was long cooled. A firm precipitation was collected and dried by filtration, whereby 4.3 g of a solid became to receive, Fp. 64 to 74°C. A NMB spectrum showed that the solid a 50/50-Mischung of cisund trans isomers of 3 (2-Ch] or-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarbonsäure was. Further free acids of the formula (III), manufactured in accordance with mode of production 4, are likewise in table [...] shown with 4.1 to 4,7. Mode of production 5; Production of trans-3 (2-Chlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarbonylchlorid: To an agitated solution of 4,1 g (0.173 mol} trans-3 (2-Chlor-3,3,3-trifluorpropenyl) - -2,2-dimethylcyclopropanearbonsäure in 40 ml toluol with ambient temperature became 1.7 g (0.022 mol) Pyridin and whereupon 2.6 g (0.022 Mel) Thiony] chloride in 25 ml toluol added. After completion of the additive the reaction mixture 17 h was agitated with ambient temperature. The reaction mixture was filtered by Diatomeenerde and the filtrate under decreased pressure was evaporated, whereby 3.8 g became to receive trans-3 (2-Chlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarbonylchlorid. The eating spectrum agreed with the attributed structure. Further connections of the formula (III) are likewise in table [...] shown. Table [...] mode of production Y Z of isomer 3.1b) CFs Br c/t 3.2b) CF s F c/t 3,3 CF 3 H c/t 3.4b) CF2 CI c1 c/t 3.5b) CF2 c1 F G/t 3.6b) CFCI2 F C/t 3.7b) CF, CF, CI c1 C/t 3.8b) C2 F5 c1 c/t a) NMR spectrum agrees with attributed structure. b) Kp. (°C/mbar): 3.1: 44-47/0,093-0,106; 3.2: 71/39,57; 3.4: 84-88/1,663-1,862; 3.5: 90-92/14,63; 3.6: 60-71/0,106; 3.7: 59-65/0,093; 3.9: 98-110/9,31; 5.7: 42-51/0,133. c) Fp. °C: 4.1: 110-116; 4.5: 80-87; 4.6: 67-69. The following examples 1 to 4 describe the production of connections of the formula (I). Example 1: Production of 3-Phenoxybenzyl-tr ans-3 (2-chlor-3,3,3-trifluorpropenyl) -2,2-dimethylcyclopropancarboxyI RK: To an agitated solution of 1,8 g (0.007 mol) trans-3 (2-Chlor-3,3,3-trifluorpropenyl) - -2,2-dlmethylcyclopropancarbonylchlorid in i0 ml dichloromethane with ambient temperature was added a solution by 1,6 g (0.008 mol) to 3-Phenoxybenzylalkohol and 0.73 g (0.009 mol) Pyridin in 5 ml dichloromethane. In the case of completion of the additive the reaction mixture 3 h fuel element ambient temperature was agitated and poured then in 50 ml water. The organic layer was separated and the more wässer ge layer three times with ever 50 was extracted ml dichloromethane. The united excerpts were dried with Natrinmsulfat and removed filtered and the filtrate under decreased pressure evaporated, whereby an oil stayed, the volatile components from the oil with 125 “C/0,0B7 mbar using a Kuge] of tubing distillation system. The Trepfrückstand became by gas-chromate-graphic analysis as 99% 3-Phenoxybenzyl-trans-3 (2-chlor-3,3,3 - trifluorpr0penyl) - 2,2-dimethylcyclopropancarboxylat determined, the mass of the product was 2.0 G. The NMRund IR-FR “ktr “n agreed also attributed structure. Analysis: Computed for C22 H, ùCIFù 0ù: found: C 62.05, H 4.73% C 62.29, H 4.80%. Example 2: Herstsllung of =-Cyano-3-phenoxybenzyl-trans-3 (2-chlor-3,3,3-trifluorpropenyl) - -2,2-dimethyloycloprop ane arboxyl RK: This connection was made in the way described in example 1 using 1,6 g (0.007 mol) irans-3 (2-Chlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcy cloprop anc arbonylchlorid, manufactured in accordance with mode of production 4, 1.7 g (0.008 mol) a-Cyano-3-phenoxybenzylalkohol and 0.73 g (0.009 mol) Pyridin in 15 ml dichloromethane. The pot arrears were with gasohromatographisoher analysis 98.9% a-Cyano-3-phenoxybenzyl-trans-3 (2-ohlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarboxylat. The mass of the product amounted to 2.4 G. the NMBund eating spectra agreed with the zugesohriebenen structure. Analysis: Computed for C2 ù HIù CIFù NOù: found: C 61.27, H 4.25 ½ C 61.57, H 4.38 example 3: Production of 3-Phenoxybenzyl-ois, trans-3 (2-chlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcycloprop ancarboxylat: This connection became on in Beispie! 1 descriptive way using 1,8 g (0.006 mol) cis, trans-3 (2-Chlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarbonylchlorid (manufactured by mode of production 4), 1.4 g (0.007 mol) 3-Phenoxybenzylalkohol and 0.66 g (0.008 mol) Pyridin in 15 ml dichloromethane. The pot arrears were with analysis by gas chromatography 99% 3-Phenoxybenzyl-cis, trans-3 (2-chlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarboxylat. The mass of the product amounted to 1.0 G. the NMBund IR spectra agreed with the zugesehriebenen structure. Analysis: Computed for C22 H20 CIFsD: found: C 62.01, H 4.49% C 62.11, H 4.58 example 4: Production of “- Cyano-3-phenoxybenzyl-ois, irans-3 (2-chlor-3,3,3-trifluorpropenyl) - -2,2-dimethylcyclopropancarboxylat: This connection became in described the way in example the i using l, B g (0.006 mol) cis, trans-3 (2-Chlor-3,3,3-trifluorpropenyl) - 2,2-dimethyloyclopropancarbonylchlorid (of mode of production 4), 1.6 g (0,0B7 mol) - Cyano-3-phenoxybenzylalkohol and 0.66 g (0,00B mol) Pyridin manufactured in 15 ml dichloromethane. The pot arrears were with analysis 99% a-Cyano-3-phenoxybenzyl-cis, trans-3 (2-ohlor-3,3,3-trifluorpropenyl) - 2,2-dimethylcyclopropancarboxylat. The mass of the product amounted to 0.9 G. the NMRund eating spectra agreed with the zugesehriebenen structure. Elementary analysis: Computed for Czù H ClFù NO3: found: C 61.46, H 4.26% C 61.47, B 4.48%. The connections shown in the following table IV were manufactured in accordance with the preceding examples. Table IV Y Verbindunga) 6,1,6,2,6,3,6,4,8,5,6,6,6,7,6,8,6,9 CFa CF3 CP CP3 CPa CP3 CFa CF3 CF3 c1 Cl c1 Br Br Br G1 c1 R eat. .o EN I ° EN of isomer c/t e/t /t table IV (continuation) Verbindunga) Y E.G. isomer 6,10 6,11 6,12 6,13 6,14 6,15 6,16 6,17 6,18 CFs CF3 CPs CFs CFs CFs CPs CFs CFs CI Br Br c1 Br Br - OH J CN - CH CN - CH [...] CN - CH J CN - CH CN c.©© c/t e*) c*) table IV (continuation) Verbindunga) Y Z R of isomer 6,19 6,20 6,21 6,22 6,23 6,24 6.25 6.26 6,27 6,28 CF3 F CFs F CF s c1 - CH z CF c1 - CHz CFzCI c1 CF2C1 - CH20B CFCI 2 F CzFs CF2CF2CI CF3 c1 - CI 2 whether clt table IV (continuation) clt Verbindunga) 6,29 6,30 6,31 6,32 6,33 6,34 6,35 6,36 6,37 CFs CFs CF3 CF=C1 CF=CI C2Fs CF2CF2CI CFs CFs CHs CFs c1 Cl Cl H H R - GH2 - GH20B - CH i CN - CH • i CN - CH - I CN - CH • i CN - CH I CN - CH i CN of isomer c/t clt c/t Verbindunga) 6.38b) 6.39b) 6,40 6.41d) 6,42 6,43 6,44 6,45 6,46 Y table IV (Continuation) z R CFaCI c1 CF CI C2Fs Cl CF CI CI c1 CF H CF3 c1 CHs - CH CHs CHs CFù c1 c1 - CH2 Gl CF3 c1 - CH c1 CF3 c1 O CF= of isomer c/t c/t c/t 6,47 CF3 c1 c/t table IV (continuation) Verbindunga) CF3 c1 6,48 6,49 6,50 6,51 6,52 6,53 ß.54 6,55 6,56 CF3 CF3 CF3 CF3 CF3 CFù CFù GF3 c1 c1 c1 c1 c1 c1 CI c1 0 c1 el 0 c1 - CH =--< CI-Iù CHù CH CH=GH2 OCH C (CH3) of 3 isomer c/t c/t c/t c/t c/t o/t table IV (continuation) Verbindunga) Y Z R of isomer 6,57 6,58 6,59 CFù CFs CF3 c1 c1 c1) separate one dia. stereoisomers a) Zugesehriebene structure by NMRund elementary analysis confirmed b) kp. 100-102°C/0,00665 mbar of c) kp. 110°C/1,197 mbar of d) only NMR analysis