DK161830B - ESTERS OF 2,2-DIMETHYLYCYCLOPROPANCARBOXYL ACID DERIVATIVES, PROCEDURES FOR THE PRODUCTION THEREOF, INSECTICID AND ACARICID AGENTS AND PROCEDURES TO FIGHT AGAINST PLANTS - Google Patents

Description

in

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The invention relates to a new class of pyrethroids, namely new esters of 2,2-dimethylcyclopropanecarboxylic acids substituted at the 3-position of the cyclopropyl ring with a three-carbon unsaturated polyfluorinated chain, a process for their preparation, an insecticide and acaricidal agent and a method of combating plant attacks.

The pyrethrins (or pyrethrums), i.e. esters of chrysanthemic acid (2,2-dimethyl-3-isobutenyl-cyclopropanecarboxylic acid) with a retronolone (2-alkenyl-3-methyl-cyclopent-2-en-4-olone) are natural insecticides origin whose properties are a fast and high insecticidal activity combined with a low mammalian toxicity.

15

However, pyrethrum can be readily degraded under the influence of atmospheric materials, and these properties render pyrethrum unsuitable for protecting culturally grown crops, limiting its use to 20 indoor applications. Furthermore, it has a high cost, partly because of the complexity of the extraction process and partly because of the requirements of a combination with appropriate synergistic substances.

In order to overcome all these problems, a very large number of substances which have been structurally related to pyrethrum (pyrethroids) have been synthesized to maintain the insecticidal activity and low toxicity to mammals and at the same time to obtain molecules which are 30 more resistant to atmospheric materials (see, for example, "Synthetic Pyrethroids" (M. Elliott Ed. ACS Symposium Series No. 42, Washington 1977).

Research has been directed towards the synthesis of new derivatives of 2,2-dimethylcyclopropanecarboxylic acid and analogues, as well as the synthesis of alcohols analogous to cyclopentenolones, and towards new groups of 2

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alcoholic functions to be esterified with the derivatives or analogs of 2,2-dimethylcyclopropane carboxylic acid. There are numerous derivatives of 2,2-dimethyl-cyclopropane carboxylic acid substituted at position 3.

5

Among these, the most promising from a stability point of view are those at position 3 carrying a / 5, β-dihalo vinyl group [J. Farkas et al., Chem. List 52, 688 (1958); M. Elliott et al., Nature (London) 246, 169.

10 (1973); M. Elliott et al., J. Chem. Soc., Perkin 1, 1974, 2470].

In the following Scheme 1 some of the synthetic pyrethroids having interesting properties have been compiled.

20 25 30 \ -35

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3

Scheme 1

H ^ C CHX

= V

¥ / X _C-Z

ti o

Generic name W Z Bibliographic source 10 δ- H5c _0 *

Pyrethrin I) - / \ / Natural Origin

H ^ C

H ^ c \ / „/ —f °

Allethrin \ = / -O y Schechter et al.

15 / \ - _ J.A.C.S. 71, 3165 H3C / (1949)

EUCV / C H

Rosmethrin) Elliott et al., Na- H r7 II Tours (London), 213, 0 493 (1967) - 2 ° / β

Tetramethrin / β 111 Kato et al., Agric.

H C ° ° N / V A J Biol. Chem. 28, 914 H-C ° (1964)

Phenothrin χ XO / Fujimoto et al., 25 h3c o-c6h5 2681 (1973)

Permethrin "Λ = / ~ 6 \ / y ~ y M. Elliott et al., Rr \ n-r H Nature (London), 246, 0 ° 6M5 169 (1973)

Ci Sci., 6, 537 (1975)

30 Cypermethrin / = ^ ~ ° \ / Q) M. Elliott - ACS

new A 'Symposium Series CN 0-CÆ ηδ. 42 - Washing-

Br, ton 1977 V / _0 / O)

Decamethrin / V '- (M. Elliott - ACS

and Br ρτ, τ- ο-Γ H Symposium Series n 3 CN υ c_h_ p Washington lg77 4

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It has now been found that there are novel pyrethroids of the general formula: H ^ C CHq _ 3 \ / 35 C (i) * / \ i

A-CH-CH-C-OR

II

O | 10.

F

where A = * CF2 -CsCH-, 15 ^ where R3 = 3 phenoxy or 3-benzyl.

The compounds of general formula I exhibit a high insecticide and a high acaricidal effect. In addition, it has been found that there are novel 2,2-dimethylcyclopropanecarboxylic acid derivatives of the following general formula (II):

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5 H3C CH3 \ / C (II) / \ 5 A - CH - CH - COOR "

where R '= H or C1-C4 alkyl and F

A = CF 3 -C = CH-.

The compounds of general formula II are useful as starting materials for use in the preparation of the novel pyrethroids of general formula I.

15

You know from DK ans. Nos. 347/78 and 5850/78, both published only after the priority date of the present application, in chemically related compounds covered by a general formula wherein A is CF3 ~ C (X) = CH-, with it is not apparent from these DK applications that the compounds in which X = F exhibit any particular position. However, according to the invention, it has surprisingly been found that precisely these compounds exhibit an extremely high insecticide and acaricidal activity.

25 1 35 6

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Scheme 2

Examples of compounds of general formula II are: Compound 11 Formula Characterization H3% / CH3 MS (a> yes CF - CF = CH - CH - - - CH - COOC ^ H (C ^ H ^ F ^) 10 + 254 (M, 1.6856) 226 (M -C H4) 209 (M. CH CH O) 188 (MT; -CFp 2).

l8l (M -COOC2H5, 100¾). —- (a)

3 nc / 3 MSV

b CF -CFBr-CH₂ -CH "-CH-COOC H (CH -F BrO) 3 2 25 11 15 4, 2 334-336 (m7o.66, 0.24 ^) 289-291 (MT CH3 CH2 O) 255 (M + -Br) 247,249,227,209) H3C \ / CI3 R, n (b) / \ 20 «cc CF-CF = CH-CH- CH-COOH n = 1.4180 Æ - 3 D 7 1 35 7

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Notes to Schedule 2 above; (a) MS = Mass spectroscopic data, only the major ions are reported.

(B) R.I. s Refractive index.

The pyrethroids of general formula I can be readily prepared from the cyclopropane carboxylic acids and esters of general formula II by methods which are quite common in the practice of organic chemistry.

It is e.g. possible of transforming the acids and esters of general formula II into the corresponding acyl halides, which upon reaction with alcohols of formula R-OH (where R has the same meaning as given in formula I) give rise to the formation of the compounds of the general formula I.

The particular structure of the acids and esters of general formula II enables the existence of various geometric configurational isomers, the existence of which is due to the presence of the following factors: 25 - the asymmetric nature of carbon atoms 1 and 3 of the cyclopropyl ring (enantiomer); relative spatial arrangement of COOR groups and of substituent A relative to the plane located by the cyclopropyl ring (cis or trans); - cis- or trans-isomerism of the substituents present by the double bond in the radical 35 A = CFq-C = CH-.

3 i

F

8

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The separation of the various isomer mixtures in the various stereoisomers and in their enantiomers can be achieved by using known chemical techniques such as e.g. chromatographic methods and precipitation of salts with optically active bases. The invention also encompasses the isolation and use for the synthesis of the compounds of general formula I of all steric and / or configurational isomers that can be prepared from the mixture of compounds of formula II, as well as the use of the compounds themselves and the materials themselves. derived on the basis of their partial or complete separation into stereoisomers.

Similarly, due to the presence of asymmetric centers and the possibility of cis-trans isomers, the novel pyrethroids of general formula I may also be mixtures of isomers. A particular feature of these mixtures is the fact that the separation of the components can be carried out by simple chemical techniques such as column chromatography or thin layer chromatography.

The invention also encompasses the isolation and use as insecticide of each steric or configurational isomer, as well as the direct use of the mixtures resulting from synthesis or by incomplete separation of the isomers.

The compounds of the general formula I according to the invention exhibit, besides a very high activity against insects 30, among species most important in terms of their detrimental effect on the agricultural and civilian areas, such as e.g. hemiptera, lepidoptera, cole-optera, diptera and blattoidea, also a satisfactory acaricidal activity which is definitely superior to the corresponding activity of the many known pyrethroids.

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The interest of the esters of the invention is particularly evident when one considers the high observed level of insecticidal activity, together with their low acute toxicity, as evidenced by the data given in Table 14, respectively, in which a comparison is made. with the two known synthetic pyrethroids, and Example 10.

The pyrethroids according to the invention also meet the requirement 10 for good stability, as shown in Example 11.

Particularly preferred embodiments of the esters of the invention are characterized by the features of claims 2-5.

15

The invention also encompasses a process for preparing the esters of the invention and this process is characterized by the method of claim 6.

20

The invention also encompasses an insecticidal and acaricidal agent, and this is peculiar to that of the characterizing part of claim 7.

The invention also encompasses a method for controlling infestation of plants from insects or mites, and this method is characterized by the method of claim 8. 1 35

A number of experiments were carried out to compare the in-secticidal and acaricidal activity of the esters of the invention with other esters which are chemically related to it. The compounds studied have the following general formula:

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10 hqc ch, 3 \ / dc / - \ CF3-C = CH-CH_CH-C-O-CH2 - (O) (a) 5 x 0 '- (fr \ ° - \ Oy where X represents a fluorine, chlorine or bromine atom.

10

The esters under investigation will be identified as follows: IFHm = 3-phenoxybenzyl ester of (+) - cis, trans-2,2-dimethyl-3- (0-fluoro-0-tri-fluoromethyl-vinyl) -cyclopropane carboxylic acid (formula I, X = F, mixture of cis and trans isomers on the cyclopropane moiety in the approximate 1: 1 ratio); IFHt = 3-phenoxybenzyl ester of (+) - trans-2,2-dimethyl-3- (3-fluoro-5-trifluoromethyl-vinyl) -cyclopropane carboxylic acid (Formula I, X = F, trans isomer of cyclopropanndelen); 1 2 3 4 5 6 35 I-Cl-Hm = 3-phenoxybenzyl ester of (+) - cis, trans-2,2-2 ~ dimethyl-3- (O-chloro-β-trifluoromethyl-vinyl) - 3 cyclopropane carboxylic acid (formula 1, X = C1, 4 mixture of cis and trans isomers on the cyclopropane portion in the approximate 1: 1 ratio); 6 I-Cl-Ht = 3-phenoxybenzyl ester of (+) - trans-2,2-dimethyl-3- (O-chloro-β-trifluoromethyl-vinyl) -cyclopropane carboxylic acid (Formula I, X = C1, trans isomer on the cyclopropane moiety); 11

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I-Br-Hm = 3-phenoxybenzyl ester of (+) - cis, trans-2,2-dimethyl-3- (O-bromo-5-trifluoromethyl-vinyl) -cyclopropane carboxylic acid (Formula I, X = Br, mixture of cis and trans isomers on the cyclopropane portion in the approximate ratio 1: 1); I-Br-Ht = 3-phenoxybenzyl ester of (+) - trans-2,2-dimethyl-3- (O-bromo-O-trifluoromethyl-vinyl) -cyclopropane carboxylic acid (Formula I, X = Br, trans -10 isomer on the cyclopropane moiety);

Biological tests were performed in the laboratory to assess the insecticidal and acaricidal activity of the aforementioned esters.

15

The following insect or mite species were used: A - Spodoptera littoralis (larvae), of the order Lepidoptera 20 B - Pieris brassicae (larvae), of the words Lepidoptera C - Leptinotarsa decemlineata (larvae), of the order Coleoptera 25 Οχ - Culex pipiens ( larvae), of the order Diptera d2 - Culex pipiens (adults), of the order Diptera E - Blatta orientalis (adults), of the order Orthoptera 30 F - Musca domestica (adults), of the order Diptera - Tetranychus urticae (eggs), of the order Acarina 35 G2 ~ Te'tranyctlus urticae (adults), of the order Acarina.

12

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The insecticidal or acaricidal activity of the investigated compounds against the aforementioned harmful organisms designated as B, C, E, F and G2 was determined according to the methods described in Example 7 of this specification. Activity against the remaining harmful organisms was determined according to the methods set forth below.

Determination of insecticidal activity against Spodoptera littoralis (larvae) (A)

Cut tobacco leaves were sprayed with an acetone / water dispersion of the product to be tested. After drying, the leaves were infected with 5-day-old larvae.

15 In the same way, untreated tobacco leaves were infected in a similar manner. The mortality rate of larvae was evaluated 48 hours after infection compared to the mortality rate of the larvae on the untreated leaves.

20 Determination of activity against Culex pipiens (larvae) l ° ll

Mosquito larvae in the 3 'and 4' stages were introduced into glass containing an acetone / water dispersion of the product being examined. As a blank test, mosquito larvae were introduced into glass containing waterworks water and acetone / water solution, respectively. The mortality rate of the larvae was determined 24 hours after the start of the sample with reference to the blank.

30

Determination of activity against Culex pipiens (adults) ()

With an acetone solution of the product to be tested, rectangles of Whatman No. 1 paper were uniformly moistened. After evaporation of the solvent, the paper rectangles were used to penetrate the inner wall 13.

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of a perspex cylinder (model WHO). 2-3 days old female mosquitoes were introduced into the cylinders, which were then closed with a net. As a blank test, adult female mosquitoes were introduced into cylinders lined with untreated paper. One hour after the start of contact, the insects were transferred to cylinders lined with untreated paper and to which a sugar-water solution was added as a nutrient. The mortality rate was determined 24 hours after the start of treatment in comparison with the mortality rate of the insects serving as a blind sample.

Determination of activity against Tetranychus urticae (eggs) (Gil 15 Leaf slices cut from bean leaves were infected with adult female mites for egg laying, and the adult individuals were then removed and the eggs counted. The slices were treated by spraying with an acetone / water dispersion ( 10% by volume of acetone) of the product being examined 20. Blank infections treated only with acetone / water solution as a blind sample. The percentage of un hatched eggs (corresponding to the mortality rate) was evaluated 7 days after treatment compared to the percentage of hatching eggs at the 25 blank test.

The insecticidal or acaricidal activity of the compounds tested is expressed as relative potency as follows.

30

For each of the compounds studied, the value of LDj-q (lethal dose for 50% of insects or mites) was determined.

The number 100 was assigned to the activity (LD ^g value) of the fluorine analog (compound of formula I, where X = F) in each series of compounds, and the relative potency of 14

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its chlorine and bromine analogs were determined by the following formula: (UW v = p

Relative power = - x 100 j (LD 50) X = Cl or Br (for X = Cl or Br).

The results reported in the following Tables 1 to 4 are expressed as relative potencies relative to the fluorine analog in each series of compounds according to the foregoing.

In these experiments, each series of compounds was examined separately.

Table 1 2® Relative potencies (fluorine analog = 100) against Spodoptera littoralis

Connection Relative power 25 I-F-H-m 100 I-Cl-H-m 20 I-Br-H-m 19 I-F-H-t 100 I-Cl-H-t 28 I-Br-H-t 21 30 -------- 35 15

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Table 2

Relative potency (fluorine analog = 100) against Pieris brassi cae.

5

Compound Relative power I-F-H-m 100 I-Cl-H-m 42 I-Br-H-m 31 10-- I-F-H-t 100 I-Cl-H-t 88 I-Br-H-t 40 15

Table 3

Relative potencies (fluorine analog = 100) against Musca dornestica.

20

Compound Relative power I-F-H-m 100 I-Cl-H-m 72 I-Br-H-m 83 25 I-F-H-t 100 I-Cl-H-t 64 I-Br-H-t 50 1 35 16

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Table 4

Relative potencies (fluorine analog = 100) against Tetranychus urticae adults (acarina). IN

5

Compound Relative Potency I-F-H-m 100 in I-Cl-H-m 43 \ I-Br-H-m 36 10-- I-F-H-t 100 I-Cl-H-t 85 I-Br-H-t 97 The following examples are intended to further illustrate the invention. Some examples illustrate the preparation of the esters of the invention, and other examples illustrate the preparation of the intermediates II.

Example 1

Preparation of the intermediate ethyl ester of 3,3-dimethyl-4,6-dibromo-6,7,7,7-tetrafluoro-heptanoic acid In a 200 ml volume autoclave, the following reagents were introduced into a nitrogen atmosphere: 17 g of ethyl ester of 3,3-dimethyl-4-pentenoic acid (0.105 mol); 55 g of 1,1,1,2-tetrafluorodibromoethane (0.21 mol); 0.5 ml of tert.-butyl peroxide.

30

The autoclave was then immersed in an oil bath and kept under mechanical stirring for 5 hours at a temperature of 120 ° C. After cooling, the contents were diluted with 100 ml of CH 2 Cl 2. This solution was then washed with (3 x 35 17)

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50 ml) containing small amounts of FeSO4 and dried with anhydrous CaCl2 and the solvent was evaporated under vacuum. There was thus obtained 43.3 g of crude product which was distilled under vacuum, collecting the fraction boiling between 97 ° and 99 ° C at 0.25 mm Hg. There were thus obtained 39 g of ethyl 3,3-dimethyl-4,6-dibromo-6,7,7,7-tetrafluoroheptanoate.

Elemental analysis: 10

Bromine: theoretical: 38.41%; found: 37.83%.

Example 2 Preparation of the ethyl ester of 2,2-dimethyl-3- (1-fluoro-g-trifluoromethyl-vinyl) -cyclopropane carboxylic acid and the free acid.

To a solution of ethyl 3,3-dimethyl-4,6-dibromo-6,7,7,7-tetrafluoroheptanoate (25 g, 0.06 mol), obtained as described in Example 1, in ethanol (50 a solution of sodium ethylate (0.132 mol) in ethanol (150 ml) was added at a temperature between 23 and 32 ° C.

25

After completion of the addition, the resulting solution was kept at room temperature for 3 hours.

Then, 50 ml were taken from the solution, which was concentrated to a reduced volume. The resulting solution was then poured into water and ice. The solution was then extracted with CH 2 Cl 2 (50 mL) and the organic phase washed with water to give a neutral pH, then dried with anhydrous CaCl 2 and the solvent removed under vacuum.

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18

There was thus obtained 3.6 g of crude reaction product which, after analysis by gas chromatography together with mass spectrometry, was found to consist mainly of the ethyl ester of 2,2-dimethyl-3- (0-fluoro-0-trifluoromethyl-vinyl) cyclopropane-5-carboxylic acid (Compound a, Scheme 2) which could be isolated from the crude product by column chromatography and by the ethyl ester of 2,2-dimethyl-3- (O-bromo-O, r, r, r-tetrafluoropropyl) cyclopropane carboxylic acid ( about 20% of the crude product) (Compound b, Scheme 2).

10

The remaining portion of the ethanol solution from which 50 ml was taken was treated with 6 g of KOH at 85% concentration in 30 ml of ethanol.

The reaction mixture was then heated for 2 hours at reflux temperature to carry out the hydrolysis of the ester and to complete the dehydrobromination of the β-bromo-O, r, r, r-tetrafluoropropyl group. The reaction mixture was then concentrated to a reduced volume and then poured into water and ice. The mixture was acidified with dilute H 2 SO 4 and then extracted with Cl 2 C 2 (3 x 50 mL), and the organic phase was then washed with an aqueous solution of NaCl (2 x 100 mL) and dried over anhydrous Cad

The solvent was removed in vacuo to give 8 g of 2,2-dimethyl-3- (O-fluoro-β-trifluoromethyl-vinyl) -cyclopropanecanboxylic acid in the form of a viscous straw yellow oil (Compound c, Scheme 2).

30

Example 3

Preparation of CF3-CFBr-CH2-CHBr-C (CH3) 2 ~ CH (CO ^ H ^ 35 In a 250 ml Hastelloy C autoclave equipped with a lever rocker is introduced under a nitrogen atmosphere:

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19 208 g CF3-CFBr2 (0.8 mole) 91.2 g CH2 = CH-C (CH3) 2-CH (CO2Et) 2 (0.4 mole) 6 ml of ditert.-butyl peroxide.

The autoclave was heated to 140 ° C and kept at this temperature for 2 hours. After cooling, the contents were removed and the excess CF3 ~ CFBr2 was removed by evaporation, after which the contents of the autoclave were subjected to molecular distillation, collecting the fraction 10 with kp. 90 ° C (10 ~ mm Hg) consisting of 120 g of ethyl (1,1-dimethyl-2,4-dibromo-4,5,5,5-tetrafluoro) -pentyl malonate.

22 ° n ^ = 1.4513 I.R. analysis corresponded to the structure indicated.

Elemental analysis: C found = 34.9%; teoret. C = 34.5% H found = 4.2%; teoret. H = 4.1% F found = 15.4%; teoret. F = 15.6%

Br found = 31.9%; teoret. Br = 32.8% Example 4

Preparation of CF, -CFBr-CHo-OH - C - COoCoHc and of

D £ i 2 2 D

CO 2 C 2 Hc 25 CH 2 Hj 225 CF, -CF = CH-CH ~ C-COOCoHc 3 j 2 2 5 00 0 OO, -2 2 5 30 48.8 g (0.1 mole) of ethyl (l) 1-Dimethyl-2,4-dibromo-4,5,5,5-tetrafluoro-pentyl-malonate, prepared as described in Example 3, was added dropwise in 100 ml of anhydrous ethanol and with stirring to an ethanolic solution of sodium methylate, prepared from 2.4 g of sodium and 100 ml of anhydrous ethanol.

20

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When the addition was first completed, a sample was taken from the mixture, which was then gas-mass-analyzed, the results thereof showing that the cyclization reaction was already completely completed to form the compound in 10. CH3 / CH3! CF ^ -CFBr-CHg-CB ^ C - CO ^ E ^ CO2C2H5 15

Mass fragmentation: (C 14 H 19 F 4 BrO 4): 406 (M +) 327 (M + -Br) 20 361 (M-C 2 H 50) 213 (M + -C 3 F 4 Br 2 (equal to the previous one) and the reaction mixture was kept under stirring at 40 ° C for 5 hours.

After neutralization with HCl, 1: 1 and subsequent filtration, the solution was concentrated to a small volume.

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then 200 ml of water was added to the solution and extracted with CHCl 3 (2 x 150 ml). The chloroform extract was then dewatered on CaCl 2 and then evaporated to give 31.4 g of diethyl ester of 5,2,2-dimethyl-3- (β-fluoro-O-trifluoromethyl-vinyl) -cyclopro-22 ° pan-1, 1-dicarboxylic acid, = 1.4303 CEL · CH, CF 2 - CF = CH-CH-C ~ C 02 C 2Η 2 CO 2 C 2 H 5

Mass fragmentation: (C 14 H 18 VV: 326 ^ 281 (M-C 2 H 50) 253 (m + -C 3 H 5 O 2) 225 (253-C 2 H 4) 20 235 207 179 167 160 160 115

Example 5

Preparation of CH, / CH, 30 3> C. 3 CF3-CF = CH-CH-CH-CO 2 CO 2 H 5 In a container immersed in an oil bath and provided with a reflux condenser, a nitrogen atmosphere was introduced: 22

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CH * CH ^ V 3 5 5 g CF -, - CF = CH-CH-C-COCO, -) Hc-, prepared as described in DI 5 EX * 4 COCOH. ~ 2 2 d 10 1 g NaCl, 12 ml dimethyl sulfoxide, 0.6 ml of water

The reaction mixture was then heated at reflux for 9 hours at 165 ° -167 ° C.

After cooling, the gas chromatographic analysis showed that the compound formed with a conversion of 75% and with a cis / trans ratio on the ring of approx. 1: 1.

Examples 6 - 20

Preparation of the m-phenoxybenzyl ester of (±) -cis, trans-2,2-dimethyl-3- (g-fluoro-O-trifluoromethyl-vinyl) -cyclopropanecarboxylic acid and partial separation of the geometric isomers 9.5 g of 2 2-Dimethyl-3- (5-fluoro-3-trifluoromethyl-vinyl) -cyclopropanecarboxylic acid was converted to the chloride of the acid by treatment with 9.7 g of PC15 in 200 ml of CCl 2 at 23-24 ° C. On distillation under vacuum, 6.2 g of chloride was collected from the acid (elemental analysis: found Cl = 14.29%, theoretical Cl = 14.49%).

2.2 g of chloride of the acid thus obtained was esterified by treatment with 2.2 g of 3-phenoxybenzyl alcohol in 100 ml of anhydrous benzene containing 2 ml of pyridine at a temperature between 18 and 24 ° C.

23

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After filtration of the pyrodinium salt, the solution was washed with 80 ml of an aqueous solution of HCl and then with water at 0 ° C until a neutral pH was obtained.

After dehydration, the solvent was evaporated under vacuum to give 4.1 g of crude 3-phenoxy-benzyl ester of (+) - cis, trans-2,2-dimethyl-3- (ε-fluoro, methyl vinyl) cyclopropane carboxylic acid.

To obtain a partial separation of the geometric isomers, the resulting product was chromatographed on a silica gel column [filler: silica gel Kieselgel G

(Type 60) product of Merk and analog product of C. Erba code. 45332, a weight ratio of 1: 2, column length: 20 cm, 15 diameter of column: 2.4 cm? eluent: n-hexane-benzene (2: 1), at room temperature], collecting the following fractions: - Fraction I: Sample 1-A (1 g) 20 - Fraction II: Sample 1-M (0.6 g) - Fraction III: Sample 1-B (1,2).

Based on Nuclear Magnetic Resonance (NMR) analysis, Sample 1-A was found to consist mainly (at least 90%) of the isomeric 3-phenoxybenzyl ester of (+) - cis-2,2-dimethyl-3- (E-fluoro, E-trifluoromethyl (E) vinyl) -cyclopropane carboxylic acid.

Sample 1-B was found to consist mainly (at least 80%) of the isomeric 3-phenoxybenzyl ester of (+) - trans-2,2-dimethyl-3- (5-fluoro, 0-trifluoromethyl (E) vinyl) cyclopropane-carboxy1syre.

Sample 1-M was found to consist of a mixture of the above-mentioned isomers in a cis: trans ratio of ca. 1: 3.

Properties of these samples are given below.

24

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NMR (S - ppm) (*)

HA v 'HB 2 (m, H. + H J

v _ f Å B

5 F \ / \ / ^ COO-CH? - / o \ 6.1 (dd3 Hc> F <T '' CH CH ^ X · 3 '33 OC.H 1.23 (s, geminal methyler) !! c _ / 05 - Connection-1i S * p6 '(s, j 6.8- 7.5 Cm3 aromatic protons) J (H ^, F trans) = 33 Hz JV = 9 Hz FCH' 15 3V_ / H 1.7 (d / V

/ - \ / B B

Tf '/ - \: 2.33 (dd, H.) h, aY coo-ch- (o) - c <V 2M S.23 (dd, H) 3 3' O-C.H. -. - ° 5 1-16 (s-, CH)

20. "Compound 1-B

1.25 (s, CH 3) 5.05 (s, CH 2) 6.8- 7.4 (m, aromatic protons) 25 J (Hc, Ha) = 9 Hz

J (IV V = 5 HZ

J (H j F currently) = 31 Hz 30 - s = singlet; d = doublet; dd = duplicate of duplicate; m = multiplied; J = coupling constant 25

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Example 7

Insecticidal Activity of the Compounds of the Invention 5 The compounds of the invention have been studied on larvae and adult individuals of the following species of phytophagous, following the methods set forth below (the data in question are reported in Table 5).

A) Biological activity on Macrosiphum euphorbiae (aphids)

Small potato plants that are propelled in pots were infected with adult female aphids and after a few hours were sprayed with an aqueous dispersion of the products to be examined (see Table 5). The mortality rate was evaluated 24 hours after treatment (aphid mortality on untreated 20 plants = 0).

B) Biological activity on Pieris brassicae (lepydoptera)

Cut cauliflower leaves were sprayed with an aqueous dispersion of the product under study (see Table 5). After drying, the leaves were infected with 5-day-old larvae.

Mortality rates of the larvae (mortality of untreated leaves = 0) were determined 48 hours after treatment.

C) Biological activity on Leptinotarsa decemlineata (Coleoptera)

Small potato plants that were propelled in pots were infected with 4-day-old larvae and then exposed 35 26

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for spraying with an aqueous dispersion of the products tested (see Table 5). The mortality rate (mortality of untreated plants = 0) was determined 48 hours after treatment.

5 j D) Biological activity on Musca domestica (Dyptera) 4-day-old adult subjects were treated by topical application with a microinjection syringe with an acetonic solution of the products under investigation (see Table 5). The mortality rate (mortality of insects treated with acetone only) was determined 24 hours after treatment.

E) Biological activity on adult individuals of Culex pipiens (Dyptera)

Rectangular strips of Whatman Paper # 1 were treated uniformly with an acetone solution of the products under investigation (see Table 5).

After evaporation of the solvent, the inner or internal part of a Perspex cylinder (model OMS) was lined with each treated paper and closed with a net.

25 Then two to three days old female animals were introduced into the cylinder.

After an hour from the beginning of contact, the insects were transferred to an identical cylinder, which is also lined with untreated paper and to which a sugar solution was added.

30

The mortality rate (mortality of untreated insects = 0) was determined after 24 hours from the start of treatment.

F) Biological activity on Blatta orientalis (Ortoptera)

The bottom and walls of glass crystallizers (cylinders) 27

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were treated uniformly with an acetone solution of the products under investigation (see Table 1).

After evaporation of the solvent, 80-100 days old neanides were introduced into each crystallizer, after which the crystallizers were closed with a metallic mesh cover. Twenty-four hours after the initiation of the treatment, the insects were transferred to similar, untreated crystallizers where they received appropriate nutrition.

10

Mortality rate (Mortality of untreated insects = 0} was determined 48 hours after the start of treatment.

O) Biological activity of adult individuals of Tetranychus urticae (mites)

Small slices of bean leaf leaves were infected with adult individuals of mites and then sprayed with a 20 aqueous dispersion of the products under investigation (see Table 5). The mortality rate was determined 24 hours after treatment (mortality of mites on untreated small slices = 0).

25 1 35

DK 161830B

~ · 0 ^ -s P O O vo Λ · U '"O O' 00

µ 0Ό 0 # H

0> search— CO C —----

O (0 · CQ

Ό μθ · Η / ~ 'i — ί ϊ — i H

[0 O V v ·.

0 0 O on O O O

c ft ΰ ^> ----- • ri · bi -µ oo oin oo β o µ ~ oo OvD oo

0 OdP HiH H HH

0 5'— 0 P --- i--

Ό -PØ i — ii — i H

0 -H ^ HO HO HO

• ri H 10 ° s s s s s s s

CQ 0 df> OO OO OO

p ό «- C ---- 0 ·

O ^ P O l> O

o · µ- 'o w o

U ΧΌ OdP H H

a island gw co h —---- pø · «

0 Oft-H M M M

p m o s s s

ri O df> O O O

Η Ό '- 0 ----

P

μ p ~ oo to oo o μ <κ> o o o oo oco

E 0 o— HH Η H

o ε E 10D CQ ----

0 O -ri LOH into IOH

CO 2 «o oo OO OO

00 O C? P s s s s SK

Μ P Ό - oo OO OO

X ------> 1 ø μ co p μ P'- 'o o o Ό 0 μ <Λ »o o o

0 p 0-— Η Η H

o ε P co ---- 0 -ri ra

p p-H '-' H Η H

• H ft CQ o O O O

> 0 0 dP s s s s

• Η Ο Ό - O O O

P ----

X

ø p- '' oo om oo CO μ <Λ »OO OCTv oo

Ό "H O'— HH H HH

• ri μ ε o tender ----

ri -ri CQ IDH IDH IDH

μ cu -H - oo oo oo ø ra o oo oo oo

0 Odf * SK S S SS

0 Ό W oo OO OO

o ε O 0 p-- 'oo oo oo δ μ <κ> oo oo oo

0 ft O'— HH HH HH

• H -ri s o CQH ---- • ri O to in in in

P µ H ^ HO HO HO

X o CO O oo oo oo

0 0 0 dP s S SS SS

M 2 Ό - OO OO OO

C - -

• H

in <m s

Η III

0 Η Η H

Λ 0 E-t ---- 29

DK 161830 B

Example 10

Acute toxicity to rats by oral administration 5 Laboratory animals: albino rats? Wister branch, 50% males and 50% females.

The animals were fasted after a staging period from 6 hours before to 2 hours after treatment and 10 were kept under observation for 14 days, during which time they were fed calibrated feed in tablets and water ad libitum. The treatment was carried out by introducing established quantities of the products into the stomach of the animals through a gastric probe connected to a precision injection syringe.

Throughout the observation period, mortality and all possible symptoms of intoxication were recorded.

Compound 1-B was tested in rats according to the above method, at a dose of 200 mg of active substance / kg live weight, without observing any mortality of the test animals after the test.

Example 11

Activity and efficacy test on acary in open field 30 The experiment was conducted in open field to investigate the activity and efficacy of a number of representative compounds against acari (Tetranychus urticae) resistant to commonly used insecticides.

The compounds were applied in the form of a hydroacetonic dispersion with the addition of a wetting agent ("Phytophilic" Montedison at a concentration of 0.5%),

DK 161830B

They were sprayed uniformly on the culture plants until there was just drip (concentration of the active substance = 0.3%).

5 Data were recorded at time intervals from the beginning of the treatment by counting the number of adult mites present on leaves taken as samples appropriately.

It is known that all the pyrethroids listed in Scheme 1, under the above conditions, except Permethrin, Cypermethrin and Decamethrin, undergo rapid decomposition, becoming totally inactive after a very short period of time.

15 On the basis of our experiments, it was found that Permethrin and j

Cypermethrin becomes totally inactive after 14 days. In contrast, the compounds of the invention still showed considerable activity after the same period of time.

'20 25 1 35

Claims (8)

Esters of 2,2-dimethyl-cyclopropanecarboxylic acid derivatives, characterized in that they have the general formula: HqC CHq 3 \ / 3 C (I) 10 / \ A - CH - CH - C - OR II o F where: A = CF 2 -C 2 H-, and 20 / - \ R = -CHL- (f "" ') \ where: R 2 = 3-phenoxy or 3-benzyl. Fri ^ R2 25 Ester according to claim 1, characterized in that 2R is 3-phenoxy. The ester according to claim 2, characterized in that it is the 3-phenoxybenzyl ester of (±) -cis-2,2-dimethyl-3- (O-fluoro-β-trifluoromethyl (E) vinyl) -cyclopropane carboxyl acid. DK 161830 B Ester according to claim 2, characterized in that it is the 3-phenoxybenzyl ester of (+) - trans-2,2-dimethyl-3- (5-fluoro-O-trifluoromethyl (E) vinyl) -cyclopropane carboxylic acid . 5 Ester, characterized in that it is a mixture of the two isomeric compounds of claims 3 and 4. Process for the preparation of an ester according to claim 1, characterized in that a compound of the formula IUC CHq 3 \ / 3 c (II) 15 / \ A - CH - GH - COOR 'wherein A has the already stated conversion meaning, and R '= H or a C 1 -C 4 alkyl, to the corresponding acyl halide, 20 ° C raises this to react in an inert solvent and in the near room of a base which can take up a hydrogen halide acid with an alcohol of the general formula R-OH, where R has the meaning already given. 7. Insecticidal and acaricidal agent, characterized in that it contains as one active principle one or more esters according to claim 1. Method for controlling infestation of plants from insects or mites, characterized in that one or more of the esters according to claims 1 to 5 are distributed as such or in the form of suitable mixtures. 35