CH616313A5 - Process for the preparation of novel phenoxybenzyl esters of spirocarboxylic acids and their optical and geometric isomers - Google Patents

Description

The invention relates to a process for the preparation of new phenoxybenzyl esters of spirocarboxylic acids of the formula:

CH3 0

oi; r-k “^

O-i

(I)

where A is a grouping of the formula:

or fy

35

40

represents, Ri represents hydrogen, cyano or ethynyl and == ■ represents a single bond or a double bond, and the optical and geometric isomers of these compounds.

The invention further relates to the use of new compounds of the formula I or their optical or geometric isomers for controlling insects, including earth insects, and mites by bringing the insects or mites into contact, their habitat or their food with an insecticidal or acaricidally effective amount of a compound of formula I.

The invention thus lies in the field of new pyre-throids which are suitable for controlling pests.

Pyrethrin-like compounds (pyrethroids) are known to the chemist. Many of these compounds are insecticidal; however, most do not result in satisfactory control of insects and / or mites. So far, there is no such compound that can be used to control insects in the ground. With a few exceptions, all known pyrethroids are also broken down fairly quickly to non-toxic substances, and this is one of the main disadvantages of the pyrethroids. These compounds give excellent insect extermination, but their rapid degradation means that they are not effective for even a few days.

50

60

Pyrethrins and synthetic pyrethroids are generally so unstable against air and light that they cannot be used for a reasonable control of field and forest insects [J. Agr. Food Chem. 17, 208 (1969) 1. From the environmental point of view, this rapid degradation may be desirable. However, there must still be enough active ingredient left to ensure adequate control of a particular pest is ensured.

The new compounds of formula I now have an astonishingly strong insecticidal action and a surprising resistance on plant surfaces. They therefore have a combination of effectiveness and stability that has long been desired, but is extremely difficult to achieve.

In contrast to the known compounds from the series of pyrethroids, the new compounds of the formula I are also not those in which the methyl groups to be regarded as essential have been replaced by chlorine atoms in order to achieve better resistance. The new compounds thus consist only of carbon, hydrogen and oxygen. It is therefore surprising that the new esters are not sensitive to the instant light-accelerated oxidative degradation, which limits the effectiveness of most of the pyrethroids known to date in agriculture.

The process according to the invention is characterized in that approximately equimolar amounts of a spirocarboxylic acid halide of the formula:

65

(II)

616313

4th

where X is halogen, with an m-phenoxybenzyl alcohol of the formula:

HIGH-

A

(III)

implements. You can e.g. B. proceed in such a way that approximately equimolar amounts of an acid halide, preferably the acid chloride, of formula II and an m-phenoxybenzyl alcohol of formula III in the presence of a suitable solvent, such as benzene, toluene or diethyl ether, at temperatures between about 10 and 30 ° C and in the presence of an acid-binding

10th

By means of, for example, an organic tertiary amine such as triethylamine, trimethylamine or pyridine.

The spirocarboxylic acid halides of the formula II can be prepared by the corresponding spirocarboxylic acid of the formula IV with a thionyl halide, such as thionyl chloride, thionyl bromide or thionyl fluoride, or a phosphorus halide, such as phosphorus trichloride, or phosphorus oxychloride in the presence of an organic solvent such as toluene, benzene or a mixture of benzene and hexane. The reaction can be carried out at room temperature; however, a temperature of 60 to 90 ° C is preferably used. The reaction can be represented by the following equation:

CH-

(IV)

S02x

CH-

CIL

~ 7

0

il

CK

A

(II)

The 25 compounds of the formula I are obtained in the form of various geometric and optical isomers by the process according to the invention. In the synthesis of the 3,3-Dimethylspiro- [cyclopropan-l, l'-inden] -2-carboxylic acid ester and 3,3-Dimethylspiro- [cyclopropan-l, l'-indan] -2-car-bonic acid ester of m-Phenoxybenzylalkohol arise for. B. 30 pairs of d and 1 isomers. A further center of asymmetry is introduced in the preparation of the esters of β-cyano and a-ethynyl-m-phenoxybenzyl alcohol, which can result in additional d, l pairs. The above esters of 3,3-dimethylspiro- [cyclopropan-l, l'-indene] -2-carboxylic acid and 35 3,3-dimethylspiro- [cyclopropane-l, l'-indane] -2-carboxylic acid are added further complicated by the presence of ice and trans isomers.

Of course, the isomers differ somewhat in the strength of their insecticidal and acaricidal activity against a given pest; in any case, they can be used as insecticidal and / or acaricidal agents.

For use as systemic insecticides and acaricides, the new compounds of formula I can be administered to the host animal either orally or parenterally. 45 Any suitable form of administration can be used for oral administration, for example a bolus, a capsule,

a tablet or a medicine drink. The active ingredient can also be added to animal feed. For example, a nutritionally balanced feed can be prepared which, based on the feed, contains 0.01 to 3.0% by weight, preferably 0.01 to 1.5% by weight, of the active ingredient. For oral or parenteral administration, amounts of active ingredient from 25 to 1000 mg per kg of animal body weight are expedient.

A systemic insecticidal and acaricidal agent can, if desired, also be administered to the animal's body by subcutaneous, intramuscular or intraperitoneal injection, so that it is distributed through the animal's circulatory system in the animal's body. A systemic agent for administration is usually dissolved or dispersed in a pharmaceutically acceptable carrier such as water, propylene glycol, vegetable oil or glycerin formal.

The systemic agents have the advantage of a relatively low toxicity to humans and mammals and are suitable for protecting a number of animals, in particular 6s domestic and domestic animals such as cattle, sheep, horses, dogs or cats, against infestation by fleas, mosquitoes, flies or ticks.

To combat insects, including insects living in the soil, which attack growing plants and / or harvested crops, including stored cereals, the new insecticidal compounds can be applied to the leaves of plants, the habitat of insects and / or the food of insects. The active ingredient is generally applied in the form of a diluted liquid spray; however, it can also be applied as an aerosol, dusting agent or wettable powder.

When applied to the soil, the new active compounds of the formula I are preferably used in amounts of 11.5 to 57.5 kg per ha. The application to the leaves of plants is expediently carried out in amounts of active ingredient from 28 g to 228 kg per ha, preferably up to 113.4 kg per ha.

Particularly suitable liquid sprays are oil sprays and emulsifiable concentrates, which can be further diluted for use.

A typical emulsifiable concentrate which can be used to protect a number of useful plants, such as cereals, cabbages, pumpkins, ornamental plants or shrubs, contains about 24% by weight of active ingredient, 4% by weight of an emulsifier which is customary in the preparation of pyrethroid formulations, 4 % By weight of a surfactant, 23% by weight of an organic solvent, such as cyclohexanone, and approximately 45% by weight of a petroleum solvent with a minimum aromatic content of approximately 93% by volume.

The new compounds of formula I are extremely effective contact and stomach poisons for ticks and a wide variety of insects, in particular Diptera, Lepi-doptera, Coleoptera and Homoptera insects. These compounds are also unique pyrethroids because their residual insecticidal activity lasts longer and because they are surprisingly also suitable for controlling insects living in the soil. They do not have to be mixed with phenol derivatives such as bisphenols, BHT or arylamines to stabilize them to produce more resistant insecticidal and acaricidal agents. If desired, however, they can be used in combination with other biologically active chemicals, for example with synergists for pyrethroids, such as piperonyl butoxide, sesamex or sulfoxides (which is produced by adding octyl mercaptan to safrol and subsequent oxidation to the sulfoxide).

The invention is further illustrated by the following examples.

5

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example 1

3,3'-Dimethylspiro- [cyclopropan-l, l'-inden] -2-carboxylic acid-m-phenoxybenzyl ester ch3 o

C-0-CH2-f

4.3 g (0.02 mol) of 3,3-dimethylspiro- [cyclopropan-l, l'-in-den] -2-carboxylic acid are added in hexane / benzene or in benzene with 8 ml of thionyl chloride. The solution obtained is then stirred for 12 hours at room temperature. After removing the solvent in vacuo, 4.7 g of an orange liquid (theoretical yield) remain. An acid chloride carbonyl at 1790 cm-1 is shown in the infrared spectrum.

The above acid chloride and 4.0 g (0.02 mol) of m-phenoxy-benzyl alcohol are dissolved in 20 ml of ether, and a solution of 2.1 g (0.05) is added dropwise to this solution at a temperature of 20.degree. 02 mol) triethylamine in 8 ml ether. A solid precipitates out of the solution immediately. The resulting mixture is stirred for 12 hours at room temperature. The resulting crude product is distributed between a mixture of ether and water, whereupon the ether layer is dried over magnesium sulfate and concentrated in vacuo. This gives 7.7 g (96% of theory) of a brown liquid.

The above crude product is purified by dry column chromatography over silica gel, using a mixture of 25% methylene chloride in hexane as solvent. 4.4 g of a pale yellow liquid are obtained. In the infrared spectrum, an ester carbonyl band appears at 1720 cm-1. The nuclear magnetic resonance spectrum (CC14) shows the following data: delta = 1.41.1.45.1.58.1.66 (4S, 6H, methyl), 2.61, (S, 1H, cyclopropane-H), 4 , 85-5.10 (m, 2H, 0-CH2), 6.12 (d, 0.5H, J = 5.5Hz, vinyl), 6.66-7.76 (m, 14.5H aromatic and Vinyl).

Analysis for C27H24O3:

calculated: C 81.83 H 6.06 found: C 82.14 H 6.29

Example 2

3,3-Dimethylspiro- [cyclopropan-l, l'-inden] -2-carboxylic acid alpha-cyano-m-phenoxybenzyl ester

3.4 g of 3,3-dimethylspiro- [cyelopropan-l, l'-inden] -2-car-bonic acid are dissolved in 100 ml of a 4: 1 mixture of hexane and benzene. 15.0 g of tionyl chloride are then added, and the solution is stirred for 12 hours. The whole is then heated to reflux temperature for 20 minutes, after which the solvents and the excess thionyl chloride are removed under vacuum. The acid chloride obtained as a reaction product is used without purification. The acid chloride is taken up in 20 ml of benzene and added dropwise to a solution of 3.1 g of alpha-cyano-m-phenoxybenzyl alcohol and 1.0 g of pyridine in 100 ml of benzene. The precipitate obtained after 4 hours of reaction is filtered off and the filtrate is concentrated in vacuo to a viscous oil. Purification by column chromatography over silica gel and elution with a 1: 2 mixture of chloroform and hexane gives 1.3 g of a pale yellow oil

5 with the following spectral properties: IR spectrum (pure film) 1730 cm-1, nuclear magnetic resonance spectrum (CDCI3) delta = 6.8-7.6 (m, 14.5H, aromatic and vinyl),

CN

1

10 6.37 (m, IH, -C-0), 6.22 (d, 0.5H, vinyl),

I.

H H O

's. t «

15 2.73 (m, IH "^ C-C-C-), 1.72-1.43 (m, 6H, methyl).

Example 3

3,3-Dimethylspiro- [cy clopropen-1,1 '-indan] -20 2-carboxylic acid-m-phenoxybenzyl ester

25th

30th

40

The process described in Example 1 is carried out using 3,3-dimethylspiro- [cyclopropan-l, l'-indan] -2-carboxylic acid instead of 3,3-dimethylspiro- [cyclopropan-l, l'-indenl-2- carboxylic acid repeated. This gives an oil as a raw product. The pure ester obtained by chromatographic purification has the following spectral properties: IR spectrum (pure film) 1720cm-1, nuclear magnetic resonance spectrum (CCI4) delta = 6.7-7.6 (m, 13H, aromatic), 4.8-5, 1 (m, 2H, 0-CH2), 1.1-3.2 (m, UH, CH3, indane-CH2 and cyclopropane-H).

Example 4

3,3-Dimethylspiro- [cyclopropan-1,1 '-indan] -2-carboxylic acid alpha-cyano-m-phenoxybenzyl ester

50

55

60

65

C-O-CH-

CN

The procedure described in Example 2 is carried out using 3,3-dimethylspiro- [cyclopropan-l, l'-indanl-2-carboxylic acid instead of 3,3-dimethylspiro- [cyclopropan-l, l'-indenl-2-earbonic acid repeated, whereby the crude product of the compound mentioned in the title is obtained.

c>

Example 5 2,2-Dimethylspiro [2,4] hepta-4,6-diene-1-carboxylic acid m-phenoxybenzyl ester

CII3 O

CH

3—

C-O-CH2

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6

Level I

4.3 g of 2,2-dimethylspiro [2,4] hepta-4,6-diene-1-carboxylic acid in 75 ml of n-hexane are mixed with 10 ml of thionyl chloride. The solution is then stirred at room temperature for 2 days.

The clear, pale orange solution obtained in this way is concentrated under vacuum, giving 4.7 g (100% of theory) of an orange liquid. A carbonyl band at 1780 cm-1 can be seen in the IR spectrum, which is typical for an acid chloride.

Stage II

A solution of 2.1 g of triethylamine in 8.0 ml of ether is added dropwise to a solution of 4.7 g of the above acid chloride and 4.0 g of m-phenoxybenzyl alcohol in 50 ml of ether with cooling. Solids precipitate out immediately. The crude product obtained after 3 hours of reaction at room temperature is worked up in ether and then in water.

The crude product obtained is then purified by dry column chromatography using silica gel and a solvent mixture of 25% CH2C12 / hexane for development. This gives 3.9 g (49% of theory) of a pale yellow viscous liquid. A carbonyl band can be seen in the IR spectrum at 1720 cm-1. The structure of the compound is determined by the NMR spectrum

10th

15

20th

cn hi delta 2.3-2.9; - o - c - delta 6.36; aroma-li •

h table delta 6.8-7.6; IR Carbonyl 1725 cm 1. Analysis for C28H25NO3:

calculated: C 79.41 H 5.95 N 3.31 found: C 78.22 H 6.06 N 3.15

Example 7 2,2-Dimethylspiro [2,4] heptane-1-carboxylic acid m-phenoxybenzyl ester

- c-o-ch 2-

confirmed: delta = 1.1-3.2 (11H, (CH3) 2,

, Cyclo-

propane-H), 4.8-5.1 (2H, -0CH2-), 6.7-7.6 (13H, aromatic).

Analysis for 03C27H26:

calculated: C 81.42 H 6.53 found: C 81.57 H 6.97

Example 6 2,2-Dimethylspiro [2,4] hepta-4,6-diene-1-carboxylic acid alpha-cyano-m-phenoxybenzyl ester ch-

The procedure described in Example 1 is carried out using 2,2-dimethylspiro [2,4] heptane-l-carboxylic acid instead of 2,2-dimethyl-4,5-benzospiro [2,4] hepta-4,6- dien-l-carboxylic acid repeated. Chromatographic purification of the resulting crude product gives the pure ester mentioned in the title with the following properties: 30 IR spectrum (pure film) 1730 cm-1; nuclear magnetic resonance spectrum (CCI4) delta = 6.8-7.4 (m, 3H aromatic, 5.0 (s, 2H, O-CHa), 1.4-1.7 (m, 8H, cyclopentane-CH2), 1.1 (s, 3H, CHs), 1.2 (s, 3H, CH3).

35

40

Example 8 2,2-Dimethylspiro [2,4] heptane-1-carboxylic acid alpha-cyano-m-phenoxybenzyl ester ch3 o

3 O

ch3-

c-o-ch-

-o -

f

1

1

45

, -0

4.1 g of 2,2-dimethylspiro [2,4] hepta-4,6-diene-l-carboxylic acid are heated to reflux temperature in 20 ml of thionyl chloride for 1 hour and then at a temperature of 50 ° C. to remove excess thionyl chloride Stripped water jet pressure.

The acid chloride formed in this way is then taken up in 50 ml of benzene, whereupon a solution of 3.1 g of alpha-cyano-o-phenoxybenzyl alcohol and 1.5 g of pyridine in 50 ml of benzene is added. The solution is then stirred for a further 18 hours. Working up the reaction mixture while filtering off the precipitate and removing the solvent in vacuo gives a light yellow oil. Purification by dry column chromatography on silica gel using ethyl acetate: hexane (1: 9) as the eluent leads to 4.1 g of a pale yellow viscous oil.

NMR

delta 1.2-1.45;

gh3 ch3

delta 2.06; H

The procedure described in Example 2 is carried out using 2,2-dimethylspiro [2,4] heptane-l-carboxylic acid 50 instead of 2,2-dimethyl-4,5-benzospiro [2,4] hepta-4,6- dien-1-carboxylic acid repeated, whereby the compound mentioned in the title is obtained as a crude product.

Various geometric isomers and optical isomers are obtained in the above manufacturing processes. In the case of the 2,2-dimethylspiro [2,4] hepta-4,6-diene-l-carboxylic acid esters and 2,2-dimethylspiro [2,4] heptane-l-carboxylic acid esters of m-phenoxybenzyl alcohol, the d- and 1-isomer pairs. In the production of the alpha-cyano and alpha-ethynyl-m-phenoxybenzyl esters, another optically active center is created, which results in additional d, l pairs. The separation of these isomers is not practical in most cases. However, the individual isomers differ in the extent of their effectiveness and their spectrum of activity against a number of insects and 65 other economically important pests. Those of 2,2-dimethyl-4,5-benzospiro [2,4] hepta-4,6-diene-1-carboxylic acid and 2,2-dimethyl-4,5-benzospiro [2,4] hepta- Acids derived from 4-en-l-carbonic acid can also be used

616 313

still occur as ice and trans isomers. When examined separately, the esters of this type are also likely to show different levels of insecticidal activity.

Example 9

3,3'-Dimethylspiro- [cyclopropan-1, V -indenj-2-carboxylic acid alpha-ethynyl-m-phenoxybenzyl ester

The procedure described in Example 1 is repeated using alpha-ethynyl-m-phenoxybenzyl alcohol instead of m-phenoxybenzyl alcohol to give an oil of the title compound.

Example 10

3,3'-Dimethylspiro- [cyclopropan-l, l'-indan] -2-carboxylic acid alpha-ethynyl-m-phenoxybenzyl ester

The procedure described in Example 1 is carried out using 3,3'-dimethylspiro- [cyclopropan-l, l'-indanl-carboxylic acid instead of 3,3'-dimethylspiro- [cyclopropan-l, l'-indene] -2- carboxylic acid and alpha-ethynyl-m-phenoxy-benzyl alcohol instead of m-phenoxybenzyl alcohol are repeated to give an oil of the title compound.

Example 11 2,2-Dimethylspiro [2,4] hepta-4,6-diene-1-carboxylic acid alpha-ethynyl-m-phenoxybenzyl ester

The procedure described in Example 1 is carried out using 2,2-dimethylspiro [2,4] hepta-4,6-diene-1-car-bonic acid instead of 2,2-dimethyl-4,5-benzospiro [2,4 ] hep-ta-4,6-diene-l-carboxylic acid and alpha-ethynyl-m-phenoxy-benzyl alcohol instead of m-phenoxybenzyl alcohol, thereby obtaining an oil of the title compound.

10th

Example 12

2,2-dimethylspiro [2,4] heptane-l-carboxylic acid-alpha-ethynyl-m-phenoxybenzyl ester c-o-ch-

C.

m c

H

15 The procedure described in Example 1 is described in

Use of 2,2-dimethylspiro [2,4] heptane-1-carboxylic acid instead of 2,2-dimethyl-4,5-benzospiro [2,4] hepta-4,6-diene-1-carboxylic acid and of alpha Repeat ethynyl-m-phenoxybenzyl alcohol instead of m-phenoxybenzyl alcohol 20 to give an oil of the title compound.

Example 13

Determination of the insecticidal activity 25 The strong activity of the new compounds of the formula I for combating insects is demonstrated on the basis of the following studies, for which tobacco budworm, Heliothis virescens (Fabricius), cotton beetle, Anthonomus grandis (Boheman), 30 potato leaf hopper are known as insect species the western parts of the United States, Empoaesca abrupta (Soy), and bean aphid, Aphis fabae (Scopoli). The procedures used for this are carried out as follows:

35 Tobacco budworm, Heliothis virescens (Fabricius)

A cotton plant with two fully opened leaves is immersed for 3 seconds while stirring in test solutions (35% water / 65% acetone), each containing 300, 100 or 10 ppm of active ingredient. A 12.7 x 19.05 mm piece of gauze is also immersed in the test solution, on which there are about 50 to 100 0 to 24-hour-old budworm eggs, whereupon this piece of gauze is placed on a leaf of the cotton plant and then in a hood to dry. The leaf with the treated budworm eggs is then removed from the plant 45 and placed with a 5.1 cm piece of a tooth tampon in a 225 g Dixie cup, which is covered with a lid. The other leaf is placed in a similar beaker with a tampon, after which a piece of gauze infected with 50 to 100 newly hatched larvae is placed in the beaker before being closed with a lid. After leaving the whole thing for 3 days at a temperature of 26.7 ° C and a relative humidity of 50%, corresponding observations are made about the hatching out of the 55 eggs and the killing of newly hatched larvae. The values obtained are listed in the form of the percentage kill in the following table.

Cotton beetle, Anthonomus grandis (Boheman) 60 A cotton plant with spreading cotyledons is immersed for 3 seconds while stirring in a solution of 35% water and 65% acetone, which contains 1000 ppm of active ingredient. The plants are placed in a hood after drying to dry. Then remove a cotyledon from the plant and place it on a 10.2 cm Petri dish, on the bottom of which there is a moist filter paper with 10 adult cotton beetles. After 2 days at a temperature of 26.7 ° C and

616 313

8th

a relative humidity of 50%, corresponding mortality counts are made. The results obtained are shown in the table below.

Potato leaf toppers, Empoasca abrupta (Soy)

A Sieva Lima bean plant with a 7.6 to 10.2 cm primary leaf is immersed in a solution of 35% water and 65% acetone, which contains 100 ppm of active ingredient. After diving, the plant is placed in a fume cupboard to dry, after which a 2.5 cm piece is cut from the tip of a leaf and placed in a 10.2 cm Petri dish, on the bottom of which there is a moist filter paper. 3 to 10 nymphs from the second state of appearance are then placed in the Petri dish, and the Petri dish is then covered. The whole is left for 2 days at a temperature of 26.7 ° C. and a relative humidity of 50%, after which mortality counts are carried out.

Bean aphid, Aphis fabae (Scopoli)

Two 5.1 cm fiber pots, each containing a 5.1 cm high nasturtium plant which had been infected with 100 to 150 aphids two days earlier, are placed on a rotary table moving at a speed of 4 revolutions per minute and then on sprayed two revolutions with a DeVilbiss atomizer operated at an air pressure of 1.41 kg / cm 2 with a solution of 35% water and 65% acetone containing 100 ppm of active ingredient. The tip of the spray nozzle is held approximately 15.25 cm from the plants and the spray is directed so that the aphids and plants are completely covered. The sprayed plants are then placed lengthways in white enamel boats. The whole is left for one day at a temperature of 21.1 ° C. and a relative humidity of 50%, after which mortality counts are carried out.

Permethrin and phenothrin, which are known pyrethroid insecticides, are used as comparison compounds in these experiments. The test values obtained are given in the form of the percentage mortality which is obtained at the active compound concentration mentioned in each case.

It can be seen from the experimental data that the new compounds of the formula I are significantly more effective than permethrin and phenothrin against the insects listed above.

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CH.

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100 100 0

(CH3) 2C = CH ^ —-— CO-O-CHgy- ^>; - 0.

CH3'-3

II

Phenothrin

100 100 0

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70 0

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10th

Example 14 Insecticidal Activity The unique insecticidal activity of the new phenoxy-benzyl esters of spirocarboxylic acids of the formula I is demonstrated by the following tests, for which a number of pyrethroid insecticides are used as reference substances. The studies are carried out on the flour beetle, Tribo-lium confusum, and on the German cockroach, Blattella germanica.

Flour beetle, Tribolium confusum The compounds to be investigated are formulated in the form of 1 percent dusts by mixing 0.1 cm3 (0.1 ml with a liquid) with 9.9 cm3 Pyraz ABB-Talc, wetting the whole with 5 ml acetone and then grated to dryness in a mortar. 12.5 mg of this dust is blown into the head of a dust settling tower with a short jet of air at a pressure of 1.41 kg / cm2, the dust being allowed to settle on 9 cm petri dishes over a period of 2 minutes. (The amount deposited here is 0.09375 mg per cm2 of 1 percent dust.) 25 adult meal beetles are then added to each Petri dish. The whole is left at a temperature of 26.7 ° C for three days, after which mortality counts are carried out. A beetle is considered to be alive if it can move two or more appendages after being hit.

R '

German cockroach, Blattella germanica

The compounds to be investigated are formulated in the form of 1 percent dusts, just as in the case of the flour beetle. 25 mg of such dust are manually distributed over the bottom of a 6.35 cm high bowl with a diameter of 19.05 cm. A water bottle with a cotton tampon is arranged on the bowl to supply the insects to be examined with water, and 10 male adult German cockroaches are placed in the bowl. To prevent the insects from ripping out, cover the shell with a net. The whole is left at a temperature of 26.7 ° C. for 3 days, after which mortality counts are carried out.

The data obtained in the above experiment are given in the table below in the form of the percentage insect mortality. From these data it can be seen that the new compounds of the formula I are extremely effective insecticidal agents, which are superior in their action to the known non-halogenated pyrethroids or which are just as effective or better effective than the known halogenated pyrethroids, in relation to the insects mentioned above.

The term pyrethrins means a mixture of four compounds, namely pyrethrin I and II and 25 cinerin I and II. This mixture is composed as follows:

o (CH3) 2

} O-C -

CH = CCH-. -

Ri

Pyrethrin I: C2iH2803 Ri = CH3

R2 = -ch2ch = chch-ch2

Pyrethrin II: c22h28os rt = -c-och3 il

O

r2 = -ch2ch = chch = ch2

Cinner I: C2oH2803 Ri = -CH3

Cinner II: C21H28Os Rj = -C-OCH3

O

R2 = -CH2CH = CHCH3

R, = -CH2CH = CHCH3

Insecticidal effectiveness *

connection

Percentage of meal beetles 1% 0.1%

Percentage of cockroaches killed 1% 0.1%

1

Allethrin cis-trans- (±) -2,2-dimethyl-3- (2-methylpropyl) -cyclo-propanecarboxylic acid- (±) -2-allyl-4-hydroxy-3-methyl-

2-cyclopenten-1-one ester

0

100

2nd

Borthrin cis-trans- (±) -2,2-dimethyl-3- (2-methylpropenyl) -cyclo-propanecarboxylic acid-6-chloro

piperonylester

0

0

3rd

Prethrine (mixture of pyrethrin I and II and

Cinerin I and II)

4th

100 15

11

Insecticidal effectiveness * (continued)

616 313

connection

Percentage of meal beetles 1% 0.1%

Percentage of cockroaches killed 1% 0.1%

4 resmethrin cis-trans- (±) -2,2-dimethyl-

3- (2-methylpropenyl) cyclo-propane carboxylic acid (5-benzyl-3-furyl) methyl ester

5 permethrin cis-trans- (±) -3- (2,2-di-

chlorovinyl) -2,2-dimethyl-cyclopropanecarboxylic acid-m-phenoxybenzyl ester

6 phenothrin cis-trans- (±) -2,2-di-

methyl 3- (2-methyl-propenyl) -cyclopropane-carboxylic acid-m-phenoxy-benzyl ester

7 3,3'-dimethylspiro [cyclo-

propane-l, l'-inden] -2-carboxylic acid-m-phenoxy-benzyl ester

8 3,3'-dimethylspiro [cyclo-

propane-1,1 '-indenj-2-carbon-acid-alpha-cyano-m-phenoxy-benzyl ester

Known compounds 1 to 6 ** Average from two experiments

100

100

24 **

100

100

80

100

100 8 ** 100 100

100 20 ** 100 100

100 100 ** 100 100

Example 15 Insecticidal Activity The unique insecticidal activity of the new compounds of the formula I in comparison to a number of insecticides of the pyrethroid type is further demonstrated by the following tests.

The test methods used to determine the effectiveness against cotton beetle beetles, southern armyworms and tobacco budworms have been described in the preceding examples. The following methods are used to determine the effectiveness against mosquito larvae and Mexican bean beetles.

Malaria mosquito, Anopheles quodrimaculatus Say 1 ml of a solution of 35% water and 65% acetone containing 300 ppm of active ingredient is pipetted into a 400 ml beaker containing 250 ml of deionized water and stirred therein with the pipette, whereby receives a solution with a concentration of 1.2 ppm. A 6.35 mm wide ring of wax paper that fits inside the cup is floated on top of the test solution to prevent the eggs from flowing up the liquid meniscus and drying out on the side of the beaker. About 100 eggs (0 to 24 hours old) are skimmed off with a sieve spoon and transferred to the test beaker. The whole is left for 2 days at a temperature of 26.7 ° C and a relative humidity of 50%, after which observations are made about hatching.

Mexican bean beetle, Epilachna varivestis Mulsant Sieva Lima bean plants (2 per pot) with 7.6 to 10.2 cm long primary leaves are immersed in the test solution with an active ingredient content of 300 ppm and then placed in a hood to dry. Then you take a leaf from a plant and place it in a 10.2 cm Petri dish, on the bottom of which is a moist filter paper and 10 larvae from the last appearance.

35

45

50

stand (13 days before hatching). On the day following the treatment, another leaf is removed from the plant and fed to the larvae after removing the remains of the original leaf. Two days after the treatment, the larvae are fed the third leaf, which is usually the last leaf that is needed. On the third day, give the larvae a fourth leaf if they have not yet stopped feeding. Then stop the experiment and let the whole thing rest until adult beetles have developed, which is usually the case about 9 days after the start of treatment. After development has been completed, each shell is examined for dead larvae, pupae or adult beetles, deformed pupae or adult beetles, larvae-pupa intermediate stages or pupa-adult intermediary stages or other intermediate stages, as is the case with normal molting, transformation and development of pupae or adults Beetles.

The results obtained in the above tests are shown in the following table.

Southern armyworm, Spodaptera eridania (Cramer) Sieva Lima bean plants, which have been defoliated to two fully developed 7.6 x 10.2 cm primary leaves 55, are immersed in the treatment solutions for 3 seconds while being agitated and then dried in given a deduction. The leaves are cut off after drying, and each leaf is placed in a 10.2 cm petri dish containing a piece of damp filter paper and 10 larvae 60 of the Southern Army worm from the third state of appearance, which are approximately 9.5 mm long. The Petri dishes are then covered and kept in a suitable room for 3 days at a temperature of 26.1 ° C and a relative humidity of 50%.

65 After 2 days, mortality counts are carried out. Compounds that lead to larval killing are suspended for another day, after which mortality counts are carried out again.

Insecticidal effectiveness

Compound mosquito larvae capsule - Southern armyworm Mexican tobacco beetle Bean beetle budworm ppm ppm ppm ppm ppm 1.2 0.4 0.04 0.004 1000 1000 100 10 300 100 1000 100

100 100 100 100 100 100 100 100 100 100 100 '100

100 100

30 100 100 0

100 80

100 100 100 50 100 100 100 90 100 90 100 100

100 100 50 100 100 100 0 100 70 100 80

- = not examined

13

616 313

Example 16 Remaining insecticidal activity Dipping test with one leaf Young cotton plants with 2 or 3 developed real leaves are immersed in solutions of 65% acetone and 35% water while thoroughly moistening the leaves. Before removing the first leaf for the bioassay with southern armyworms, Prodenia eridania (Cramer), tobacco bud worms, Heliothis virescens (Fabricius), or cabbage larvae, Trichoplusiani (Hubner), let the leaves dry. Sheet samples are then placed in a standard glass petri dish containing wet filter paper and 10 larvae of the Southern Army worm or the cabbage strainer from the third state of appearance. For the examinations with tobacco budworms, a single leaf is cut into pieces of approximately 3.25 cm2 in size and these pieces are placed in individual medicine cups which contain a moist tooth tampon and a tobacco budworm larva. The test samples are held for 72 hours at a constant temperature of 26.7 ° C., whereupon corresponding mortality counts are carried out and the 20 percent mortality is determined.

The treatment solutions are prepared by dissolving 100 mg of active ingredient in 65 ml acetone and then supplementing it with deionized water to an active ingredient concentration of 1000 ppm. To prepare 10-fold dilutions, 10 ml of the solution with an active ingredient content of 1000 ppm are then taken and this is diluted 10 ml to 100 ml with 65% acetone and water up to an active ingredient content of 100 ppm.

Then 10 ml of the solution thus prepared with an active substance content of 100 ppm are diluted in the same way to form a solution with 10 ppm active substance.

After the leaves have dried, the plants are placed in that part of a greenhouse which is provided with poly-methyl methacrylate plates through which ultraviolet light passes, the remaining insecticidal activity of the compound in question being determined. Leaf samples are taken for a bio-test over a period of 9 to 10 days.

The data obtained from the above tests are summarized in the following table. The new compounds of the formula I therefore prove to be highly effective insecticidal agents over a relatively long period of time if they are applied to plants in the form of a liquid formulation with an active ingredient content of about 100 to 1000 ppm.

Remaining insecticidal activity

Compound Concentrated Corrected Mortality Ratio 0 days 7 days 9 days 10 days

(ppm) CB SAW TBW CB SAW TBW CB SAW TBW CB SAW TBW

3,3'-dimethylspiro- [cyclo- 1000 100 100 100 100 100 100 100 80

propane-1,1 '-inden] -2- 100 100 100 60 50 20 75 38 40

carboxylic acid m-phenoxy-benzyl ester

3,3'-dimethylspiro- [cyclo- 1000 100 100 100 100 100 80

propane-l, l'-inden] -2-carbon- 100 100 80 70 80 90 20

acid-alpha-cyano-m-phenoxy-benzyl ester

CB = cabbage tensioner SAW = southern army worm TBW = tobacco bud worm

Example 17

Remaining insecticidal activity leaf spray test

Young cotton plants with 3 to 4 developed so-so leaves and young bean plants are sprayed with an overhead spraying device which delivers about 804 liters of liquid per hectare via a flat spray nozzle. By changing the active ingredient concentration in the spray solution, different amounts of active ingredient per ha are obtained. 84 mg of active ingredient per 55 240 ml of solution gives a sprayed amount of active ingredient of 280 g in about 8041 liquid per ha, with 42 mg of active ingredient per 240 ml of solution one is sprayed Active ingredient amount of about 140 g per 8041 liquid per ha, and with 21 mg active ingredient per 240 ml solution, a sprayed active ingredient amount of about 70 g results in 8041 liquid per ha.

The respective plants are sprayed and their leaves are allowed to dry before taking the first leaf sample for the bioassay with southern armyworm and tobacco budworm. The bioassay is carried out like the leaf diving experiment 65.

The respective plants are then placed in the greenhouse, and then the remaining insecticidal activity of the individual compounds is determined in the manner described in the leaf immersion test.

Solutions are prepared by dissolving 84 mg of active ingredient in 240 ml of 65% acetone water (A) for the experiment with 280 g of active ingredient per hectare. 120 ml of solution (A) are then dissolved in 65% acetone water Diluted 240 ml, whereby the solution (B) is obtained, which is used for the test with 140 g of active ingredient per ha. Diluting 120 ml of solution (B) to 240 ml with 65% acetone water gives a solution of the type used for the test with 70 g of active ingredient per hectare. In each case 120 ml of spray solution are mixed with 0.2 ml of 3 percent Triton X-100 as a surface-active agent.

The results obtained in the present experiment are summarized in the following table. It can be seen from the test values that the new compounds of the formula I have a particularly high residual insecticidal activity compared to a number of known insecticides of the pyrethroid type. Only the known chlorine-containing compound permethrin [cyclopropanecarboxylic acid re-3- (2,2-dichlorovinyl) -2,2-dimethyl-m-phenoxybenzyl ester] of all pyrethroids examined likewise has a longer residual insecticidal activity.

616 313

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616 313

Example 18 Insecticidal Activity in Soil Corn Rootworm, Diabrotica undecimpuctata howardi (Barber)

10 mg of active ingredient are diluted to 10 ml with acetone to prepare a stock solution 5. 2 ml of this solution are then diluted again to 10 ml to produce a solution B with acetone. 1 ml of this solution B is then finally diluted again to 10 ml to produce a solution C with acetone. About 0.7 g of Pyrax ABB-Talc are then placed in a 28 g wide-necked boat, after which 1.25 ml of the respective solution is added to the talc, so that preparations of the following concentrations result:

1.25 ml of solution A result in active compound amounts of

57.5 kg / ha, 15

1.25 ml of solution B lead to active ingredient amounts of 11.5 kg / ha,

1.25 ml of solution C result in active ingredient amounts of 1.15 kg / ha.

The respective test solution is mixed with the talc to moisten it cleanly before drying the whole thing for 10 to 15 minutes under an air nozzle dryer. The 20 active substance-containing boats are then mixed with 25 ml of moist, sterilized potting soil and about 0.6 g of millet seeds (as larval feed). The containers are closed, whereupon

their contents are mixed on a vibration mixer. Ten 6 to 8 day old larvae of the 25 treated southern corn rootworm are then added to each number of the containers. The individual container mice are then covered loosely and then in one

Room with a temperature of 26.7 ° C and a relative humidity of 50%, which is constantly illuminated. After 1 6 days, mortality counts are made. 30th

The following results are obtained:

Insecticidal activity in the soil oxybenzyl esters of spirocarboxylic acids of the formula I are extremely effective soil insecticides if they are mixed with soil in amounts of 11.5 to 57.5 kg per ha.

Example 19 Systemic control of barn flies in mice alpha-cyano-m-phenoxybenzyl ester of 2,2-dimethyl-4,5-benzospiro [2,4] hepta-4,6-diene-1-carboxylic acid is in a mixture of 10% Acetone and 90% corn oil dissolved, after which the solution thus obtained is administered orally (via a gastric tube) to two 20 g white female Swiss Swiss Webster mice in an amount of 400 mg per kg. A mouse is used for comparison, and you only give it the carrier made of 10% acetone and 90% corn oil.

One hour after the treatment, 9 stable flies (Stomoxys calcitrans) are placed in a cage together with one mouse each and allowed to eat for 4.5 hours. 1.5 hours after the flies were brought together with the mouse, all flies of the treated group were on the ground. The flies are left overnight and mortality counts are taken after 24 hours.

Dose (mg / kg)

Number of flies

Number of dead flies after 24 hours

400 0

18 9

17 2

connection

Southern corn rootworm 35 57.5 kg / ha 11.5 kg / ha

3,3-Dimethylspiro- [cyclo-propane-1,1 '-indene] -2-carboxylic acid-m-phenoxy-benzyl ester

3,3-Dimethylspiro- [cyclo-propane-l, l'-inden] -2-carboxylic acid alpha-cyano-m-phenoxybenzyl ester

100

100

100

40

45

It can be seen from the percentage mortality values given in the table above that the new m-phen

Example 20

Systemic insecticidal activity on animals To determine the effectiveness of the new compounds of the formula I as systemic insecticidal agents on animals, the m-phenoxybenzyl ester of 2,2-dimethyl-4,5-benzospiro [2,4] hepta-4,6- dien-l-carboxylic acid and the alpha-cyano-m-phenoxybenzyl ester of 2,2-dimethyl-4,5-benzospiro [2,4] hepta-4,6-diene-l-carboxylic acid each in a mixture of 10% acetone and 90% sesame oil, whereupon the individual preparations in concentrations of 25, 100, 200 and 400 mg / kg body weight of the animal are administered to two mice by means of a gastric tube.

Subsequently, adult one-day-old, unlined barn flies (Stomoxys calcitrans) are brought together with the mice for 18 hours so that they can feed on them. After a test period of 24 hours, mortality counts are carried out and the following results are obtained:

connection

Number of treated

Mice

Dose mg / kg

Number of flies

Number of dead

To fly

3,3-Dimethylspiro- [cyclopropan-1,1'-inden] -2-carboxylic acid m-phenoxybenzyl ester

3,3-dimethylspiro- [cyclopropane-l, l'-

inden] -2-carboxylic acid-alpha-cyano-m-phenoxy-

benzyl ester

3,3-Dimethylspiro- [cyclopropan-l, 1 '-indan] -2-carboxylic acid-m-phenoxybenzyl ester 3,3-Dimethy Ispiro- [cyclopropan-1,1' -indanl-2-carboxylic acid-alpha-cyano-m -phenoxybenzyl ester

2nd

400

20th

20th

2nd

200

20th

20th

2nd

100

20th

10th

2nd

25th

20th

2nd

2nd

0

20th

0

2nd

400

20th

20th

2nd

200

20th

20th

2nd

100

20th

20th

2nd

25th

20th

9

2nd

0

20th

0

4th

400

38

30th

4th

400

40

39

616 313

16

Example 21 Ixodicidal Efficacy The effective control of acarinal larvae is shown by the following studies, for which larvae of Boophilus microplus are used, namely a tick living on only one host, which, during their three appearance states, namely the larval form, the nymph form and the adult form, can stay on a single host. Mixtures of 10% acetone and 90% water are used for the investigations, each containing 3.1, 12.5 or 50 ppm of active ingredient. 20 larvae are enclosed in a pipette which is closed at one end with a gauze material, after which the solution containing the active substance is drawn through the pipette with a vacuum tube. The ticks are then left at room temperature for 48 hours, after which mortality determinations are carried out. The following results are obtained:

connection

Mortality of the Boophilus 20 microplus larvae

3,3-dimethylspiro- [cyclo-

propane-1,1 '-indene] -2-carbon-

acid m-phenoxybenzyl ester

3,3-dimethylspiro- [cyclo-

propane-1,1-indene] -2-carbon-

acid-alpha-cyano-m-phenoxy-

benzyl ester

100% at 50 ppm 100% at 12.5 ppm 100% at 3.1 ppm 100% at 50 ppm 100% at 12.5 ppm 80% at 3.1 ppm

30th

Example 22 Suppression of Fertility and Chemosterilizing Activity in Ixodidae The effectiveness of the new compounds of the formula I for suppressing fertility in ticks is shown by the following tests. Fully eaten adult female Boophilus micro-plus ticks that have fallen off cattle are used for these experiments.

The compounds to be investigated are dissolved in mixtures of 35% acetone and 65% water in such an amount that active compound concentrations of 15.62, 31.25, 62.5, 125 and 250 ppm result. Will be per exam

Ticks are used, which are immersed in the respective test solutions for 3 to 5 minutes, then removed again, placed on small dishes and stored in incubators at a temperature of 28 ° C. for 2 to 3 weeks. The eggs laid by the ticks are then counted. The laid eggs are weighed, placed in containers and stored for one month to observe hatching and to determine the chemosterilizing effect. Fifteen ticks resistant to Ethion are used for each test, since these are ticks that are the most difficult to control. The results obtained in these tests are shown in the following tables.

The effectiveness of the individual compounds is given in the form of the percentage weight reduction of the egg mass compared to the comparisons and is determined at the respective active substance concentrations.

The effectiveness of the individual compounds for suppressing the fertility of Ixodidae ticks is also determined on the basis of the three highest application concentrations, namely the concentrations of 62.5, 125 and 250 ppm, for which the following assessment system is used:

Assessment system

Result

Rating number no egg laying 4

partial egg laying, no hatching 3

total egg laying, viable eggs 2

partial egg laying 1

normal egg laying and hatching 0

35

The rating system is based on the summary of rating numbers of all ticks in the above tests. With this rating system, the best possible rating would be 180, namely 45 (the total number of ticks used) x 4 (the highest rating number). The effectiveness of the individual compounds is given as the percentage from the best possible rating.

Percentage reduction in weight of egg mass compared to controls

connection

Percentage reduction in weight of egg mass

250

125

ppm

62.5

31.25

15.62

3,3-Dimethylspiro- [cyclopropan-l, l'-inden] -

95.93

97.96

92.37

50.64

50.13

2-carboxylic acid m-phenoxybenzyl ester

3,3-dimethylspiro- [cyclopropane-1,1'-

99.49

96.95

88.30

68.96

34.86

inden] -2-carboxylic acid-alpha-cyano-m-

phenoxybenzyl ester

3,3-dimethylspiro- [cyclopropane-1,1'-

89.31

49.11

28.24

18.58

0

indan] -2-carboxylic acid m-phenoxybenzyl ester

3,3-dimethylspiro- [cyclopropane-1,1'-

100

83.21

97.96

44.53

13.99

indan] -2-carboxylic acid, alpha-cyano-m-phenoxybenzyl ester

It can be seen from the above experimental values that the new spirocarboxylic acid compounds of the formula I by suppressing the fertility of Ixodidae ticks when used in concentrations of 62.5 ppm or above

65 have excellent ixodicidal activity. It can also be seen that the control of Ixodidae ticks proceeds practically completely when the active compounds according to the invention are used in a dose of 250 ppm.

17th

Chemo-sterilizing effectiveness of spirocarboxylic acids

616 313

Compound Quantity Ticks resistant to Ethion Percentage in ppm Egg laying Active

Partially total

B B sterile B B sterile

3,3'-dimethylspiro- [cyclopropane

250

0

0

0

0

0

1

0

0

90

1,1 '-inden] -2-carboxylic acid-m-phenoxy-

125

0

2nd

0

1

0

0

0

0

benzyl ester

62.5

0

2nd

0

2nd

0

1

0

0

3,3'-dimethylspiro- [cyclopropane

250

0

1

0

0

0

0

0

0

92.2

l, l'-inden] -2-carboxylic acid-alpha-cyano-

125

0

1

0

0

0

0

0

0

m-phenoxybenzyl ester

62.5

0

2nd

0

1

0

1

0

0

3,3'-dimethylspiro- [cyclopropane

250

0

3rd

0

1

0

2nd

0

0

48.3

l, l'-indan] -2-carboxylic acid-m-phenoxy-

125

0

2nd

0

0

0

2nd

0

1

benzyl ester

62.5

0

1

0

1

1

1

0

1

3,3 '-D imethy ispiro [cyclopropane

250

0

0

0

0

0

0

0

0

90.5

l, l'-indan] -2-carboxylic acid alpha-

125

0

2nd

0

1

0

3rd

0

0

cyano-m-phenoxybenzyl ester

62.5

0

1

0

1

0

0

0

0

B = rating number

From the values shown in the table above, it can be seen that the new compounds of the formula I at an application concentration of 250 ppm lead to a control of Ixodidae ticks of approximately 90 to 100%.

25th

Claims (10)

616 313 2,2-dimethylspiro- [2,4] -hepta-4,6-diene-l-carboxylic acid-m- phenoxybenzyl ester or 2,2-dimethylspiro- [2,4] -hepta-4,6-diene-l-carboxylic acid-a- cyano-m-phenoxybenzyl ester, used. 2,2-dimethylspiro- [2,4] -heptane-l-carboxylic acid-a-cyano-m-phenoxybenzyl ester, 60 2,2-dimethylspiro- [2,4] -heptane-l-carboxylic acid-a-ethynyl-m-phenoxybenzyl ester or 2,2-dimethylspiro- [2,4] -hepta-4,6-diene-l- carboxylic acid a-ethynyl-m-phenoxybenzyl ester. 2. The method according to claim 1 for the preparation of compounds of the formula: (III) (xa) and their stereoisomers. 2nd PATENT CLAIMS 1. Process for the preparation of new compounds of the formula: (I) where A is a grouping of the formula: or represents, Ra is hydrogen, cyano or ethynyl and === represents a single bond or a double bond, and the optical and geometric isomers of these compounds, characterized in that 15 approximately equimolar amounts of a spirocarboxylic acid halide of the formula: CH3 0 (II) where X is halogen, with an m-phenoxybenzyl alcohol of the formula: HIGH- k implements. 3,3'-Dimethylspiro- [cyclopropan-l, l'-inden] -2-carboxylic acid - u-ethynyl-m-phenoxybenzyl ester, used. 3,3 '-Dimethylspiro- [cyclopropan-1, V -inden] -2-carboxylic acid- a-cyano-m-phenoxybenzyl ester, 3,3'-dimethylspiro- [cyclopropan-l, l'-indan] -2-carboxylic acid io m-phenoxybenzyl ester, 3,3'-dimethylspiro- [cyclopropan-l, l'- indan] -2-carboxylic acid- a-cyano-m-phenoxybenzyl ester, 3,3'-dimethylspiro- [cyclopropan-l, l'-indanl-2-carboxylic acid] a-ät hinyl-m-phenoxybenzyl ester or 15 3rd 616 313 Acaricidal effective amount of the compound or its optical or geometric isomers in contact. 3,3'-Dimethylspiro- [cyclopropan-l, l'-inden] -2-carboxylic acid-a-ethynyl-m-phenoxybenzyl ester. 3,3'-dimethylspiro- [cyclopropan-l, l'-indan] -2-carboxylic acid - a-cyano-m-phenoxybenzyl ester, 3,3'-dimethylspiro- [cyclopropan-l, l'-indan] -2-carboxylic acid 45-a-ethynyl-m-phenoxybenzyl ester or 3. The method according to claim 2 for the preparation of 3,3'-Dimethylspiro- [cyclopropan-l, l'-inden] -2-carboxylic acid m-phenoxybenzyl ester, 3,3'-dimethylspiro- [cyclopropan-l, l'-inden] -2-carboxylic acid- a-cyano-m-phenoxybenzyl ester, 3,3'-dimethylspiro- [cyclopropan-l, l'-indan] -2-carboxylic acid m-phenoxybenzyl ester, 4. The method according to claim 1 for the preparation of compounds of the formula: (Ib) and their stereoisomers. 5. The method according to claim 4 for the preparation of 2,2-dimethylspiro- [2,4] -hepta-4,6-diene-l-carboxylic acid-m- phenoxybenzyl ester, 2,2-dimethylspiro- [2,4] -hepta-4,6-diene-l-carboxylic acid-a-cy- ano-m-phenoxybenzyl ester, 2,2-dimethylspiro- [2,4] heptane-l-carboxylic acid m-phenoxy-benzyl ester, 6. Use of new compounds of the formula I specified in claim 65 1 or their optical or geometric isomers for controlling insects and mites, characterized in that the insects or mites, their habitat or their food with an insecticidal or 7. Use according to claim 6, characterized in that a compound of formula Ia given in claim 2, preferably s 3,3'-dimethylspiro- [cyclopropane-1, r-indene] -2-carboxylic acid- m-phenoxybenzyl ester, 8. Use according to claim 6, characterized in that preferably a compound of formula Ib given in claim 4 9. Use according to claim 6 for protecting plants from infestation by insects, characterized in that an insecticidally effective amount, preferably 28 to 228 g per 0.405 ha, in particular 28, is applied to the leaves of the plants or the soil in which they grow up to 113.4 g per 0.405 ha, applying a compound of formula I or a stereoisomer thereof. 10. Use according to claim 6 for protecting plants from infestation by insects, characterized in that the compound of formula I or a stereoisomer thereof in an amount of 11.2 to 56 kg per ha on the soil in which the plants grow, apply.