DE2757066C2 - - Google Patents

Description

The invention relates to phenylalkanoic acid m-phenoxybenzyl ester, a process for the preparation of these compounds and agents containing these compounds Control of insects and mites.

South American patent application No. 7 34 462 is to be regarded as the next known prior art. In this patent application tens of thousands of phenylacetic acid esters are described, including α- isopropyl-4-methoxyphenyl-acetic acid-3′-phenoxybenzyl ester, α- isopropyl-3-methoxyphenyl-acetic acid-3′-phenoxybenzyl ester, α- isopropyl-4-chlorophenyl-acetic acid- 3'-phenoxybenzyl ester, a -isopropyl-4-methylphenyl-acetic acid-3'-phenoxybenzyl ester, α- isopropyl-3-chlorophenyl-acetic acid-3'-phenoxybenzyl ester and α -isopropyl-4-fluorophenyl-acetic acid-3'-phenoxybenzyl ester. It is also stated that many of these compounds are potent pesticides and can be used to control a variety of insects and mites. In this patent application, however, neither the 2-fluoroalkoxypheny) alkanoic acid m-phenoxybenzyl esters according to the invention nor a synthetic method suitable for the preparation of these compounds are described.

It has now surprisingly been found that the inventive Compounds not just effective insecticides Represent funds, but also have a strong impact against Exercise ticks. The compounds of the invention systemic insecticidal and ixodicidal agents. They show a high safety margin and can be effective Wise used for pets, laboratory animals and agricultural animals against insect infestation and to protect ticks. Compared to known pyrethroids, like permethrin, phenothrin or allethrin show the compounds of the invention continue to be superior  residual ixodicidal and insecticidal effects and are special effective for fighting tobacco caterpillar (Heliothis virescens) and mosquitoes.

The invention relates to those characterized in claim 1 Phenylalkanoic acid m-phenoxybenzyl ester, which in Claim 5 specified method for their preparation and the acaricidal and insecticidal agent specified in claim 6.

The reaction of the α- substituted 2-fluoroalkyl- (oxy-, thio -) - phenylacetyl chloride of the general formula II defined below with an m-phenoxybenzyl alcohol which follows in the preparation of the phenylalkanoic acid m-phenoxybenzyl esters of the general formula I given in claim 1 defined general formula III is generally carried out in the presence of a solvent such as diethyl ether, benzene or toluene and at a temperature between about 10 ° C and about 30 ° C in the presence of an acid acceptor. Tertiary organic amines, trimethylamine, triethylamine and pyridine can be used as acid acceptors. This reaction can be illustrated by the following reaction scheme:

wherein

X is an oxygen atom or a sulfur atom, Pure hydrogen atom, a fluorine atom, a difluoromethyl group  or a trifluoromethyl group, R₂ is an ethyl group, an n-propyl group, an isopropyl group or a tert-butyl group and R₃ represents a hydrogen atom or a cyano group.

Preferred compounds of general formula I are those in which R is a hydrogen atom or a fluorine atom and R₂ an ethyl group, an n-propyl group or an isopropyl group mean.

It should also be noted that the above described Preparation of the general compounds of the invention Formula I various optical isomers of these Connections result.  

For example, in the preparation of the esters of the general formula I, when R₃ represents a hydrogen atom, a chiral center is present in the region of the group R₂, so that d- and l-isomer pairs are formed. Furthermore, a further chiral center is formed in the case of a cyano group as the α substituent in the region of the substituent R₃, so that a further pair of d and l isomers is possible.

For example, it has been found that when α- isopropyl-4-trifluoromethoxyphenylacetic acid is mixed with about 0.5 to 1.0 molar equivalents of (-) - α- phenethylamine in a suitable solvent such as ethanol or aqueous ethanol, the salt of (+) - acid fails. When acidified, this salt gives the acid, which is generally more than 85% in the form of the (+) isomer. An even better cleavage can be achieved by recrystallization of the (-) - α- phenethylamine salt or by repeating the cleavage process with fresh (-) - α- phenethylamine. The m-phenoxybenzyl esters or α- cyano-m-phenoxybenzyl esters of the fully split (+) - α- isopropyl-4-trifluoromethoxyphenylacetic acid are insecticidal about twice as effective as the corresponding esters formed from the racemic acid. In the case of the α- cyano-m-phenoxybenzyl ester, a further increase in activity is achieved by using the corresponding optically active α- cyano-m-phenoxybenzyl alcohol in the ester formation.

The α- substituted 2-fluoroalkyl (oxy-, thio -) - phenylacetylchloride of the general formula II, in which R₂ is an ethyl group, an n-propyl group or an isopropyl group, can be prepared using the corresponding toluene of the general formula IV as a starting material . The manufacturing process comprises five stages, the first of which involves halogenating the toluene of general formula IV with bromine, chlorine or N-bromosuccinimide (NBS). This reaction is preferably carried out in the presence of an inert organic solvent, such as carbon tetrachloride, and a radical initiator, such as light, benzoyl peroxide or azo-bis- (isobutyronitrile), to form the benzyl halide of the general formula V. The benzyl halide of the general formula V is then converted into the corresponding phenylacetonitrile of the general formula VI by reaction with sodium cyanide or potassium cyanide in the presence of dimethyl sulfoxide (DMSO), ethanol or the like. This substituted phenylacetonitrile of the general formula VI is readily alkylated by treatment with an alkyl halide in the presence of a base and an inert organic solvent; it has been shown that crown ethers are useful catalysts for this reaction. The phenylacetonitrile which is alkyl-substituted in the α- position and which is formed in the above reaction is represented in the following reaction scheme I by the general formula VII and, by hydrolysis using an alkali metal hydroxide in the presence of an alkylene glycol and water, gives the corresponding α- alkyl-substituted phenylacetic acid of the general formula VIII. The reaction of the acid of the general formula VIII with thionyl chloride, which is preferably carried out in the presence of an aromatic solvent, such as benzene or toluene, gives the α- alkyl-substituted phenylacetyl chloride of the general formula II, which is then reacted with the m-phenoxybenzyl alcohol or α- cyano-m- phenoxybenzyl alcohol of the general formula III to the desired m-phenoxybenzyl ester or the α- cyano-m-phenoxybenzyl ester of the corresponding 4-fluoroalkyl (oxy-, thio -) - phenylalkanoic acid of the general formula I is reacted. These reactions are shown in Reaction Scheme I below.

Reaction scheme I

Preparation of the 4-fluoroalkyl (oxy-, thio -) - phenylalkanoic acid-m-phenoxybenzyl ester

As an alternative to the benzyl bromide given in Reaction Scheme I the general formula V can be the corresponding Fluoroalkyl (oxy- or thio -) - benzene of the general Formula IX using a mixture of paraformaldehyde or trioxane and zinc chloride and dry hydrogen chloride to form the corresponding benzyl chloride general formula X chloromethylate, which you then instead of the benzyl bromide of the general formula V in the further Synthesis to the compounds of the general invention Formula I can use. This modification of the procedure can be reproduced as follows:

The preparation of the m-phenoxybenzyl esters and α- cyano-m-phenoxybenzyl esters of α- alkyl-4-fluoromethoxyphenyl ester acetic acid can also be achieved via a reaction sequence that begins with the alkylation of p-methoxyphenylacetonitrile, which involves an alkyl halide in the presence of a crown ether and a Base used. The a thereby obtained is alkyl-4-methoxyphenylacetonitrile then by treatment with boron tribromide, preferably being in the presence of a solvent such as methylene chloride, operates, converted 4-hydroxyphenylacetonitrile alkyl in the α. The reaction of the phenol thus formed with thiophosgene and a base in the presence of a solvent such as chloroform then gives the chlorothioester of O- [p- (l-cyano-2-methylpropyl) phenyl] formic acid. -This ester can easily be converted with molybdenum hexafluoride into the corresponding α- alkyl-4-trifluoromethoxyphenylacetonitrile, which is then hydrolyzed by reaction with ethylene glycol in the presence of an alkali metal hydroxide and water to give the corresponding α- alkyl-4-trifluoromethoxyphenylacetic acid.

Treatment of the α- alkyl-4-trifluoromethoxyphenylacetic acid with thionyl chloride in the presence of an aromatic solvent, such as benzene or toluene, gives the corresponding acid chloride, the desired α- alkyl-4-trifluoromethoxyphenylacetic acid with m-phenoxybenzyl alcohol or α- cyano-m-phenoxybenzyl alcohol -m-phenoxybenzyl ester or α- cyano-m-phenoxybenzyl ester. These reactions are illustrated by Reaction Scheme II below.

Reaction scheme II

In Reaction Scheme II above, R₂ represents an ethyl group, an n-propyl group or an isopropyl group and R₃ for a hydrogen atom or a cyano group.

Although Reaction Scheme I generally relates to preparation a variety of the compounds of the invention is applicable, it has been shown that the alkaline hydrolysis  the nitriles of those compounds in which the substituent RCF₂X- a difluoromethyloxy group (HCF₂O-) or one Difluormethylthioogruppe (HCF₂S-) represents the Difluormethylgruppe (HCF₂-) can split off. However, it has been shown that reintroduced this group can be that the corresponding phenol or thiophenol with chlorifluoromethane in a mixture of aqueous Reacts alkali and dioxane.

The actual synthesis used for those compounds which have a difluoromethyloxy group of the formula HCF₂O- can best be illustrated by Reaction Scheme III below, after which the corresponding α- alkyl-4-methoxyphenylacetonitrile (as indicated in Reaction Scheme II) is used is converted from hydrobromic acid into the corresponding α- alkyl-4-hydroxyphenylacetic acid. Treatment with chloride fluoromethane in aqueous alkali and dioxane gives the corresponding α- alkyl-4-difluoromethoxyphenylacetic acids. These acids are then converted into the desired m-phenoxybenzyl esters or α- cyano-m-phenoxybenzyl esters in the manner indicated in Reaction Scheme II.

Reaction scheme III

To prepare the compounds of the general formula I in which R₂ represents a tert-butyl group, the following Reaction sequence applied by the corresponding p-substituted aldehyde starts:

• 1. A reaction with tert-butyl magnesium chloride is effected;
• 2. One converts neopentyl alcohol using thionyl chloride to the corresponding chloride;
• 3. One forms from the chloride using magnesium the corresponding Grignard reagent in tetrahydrofuran; and
• 4. carboxylated with carbon dioxide

The reaction sequence is further illustrated by the synthesis of α- tert-butyl-4-trifluoromethoxyphenylacetic acid according to Reaction Scheme IV below. The acids can then be converted to the corresponding esters as indicated in Reaction Scheme I.

Reaction scheme IV

When forming the α- cyano-m-phenoxybenzyl ester products using the procedures illustrated by Reaction Schemes I and II above, it is not necessary to produce α- cyano-m-phenoxybenzyl alcohol. It is exactly as, or even more preferred, a mixture of m-phenoxybenzaldehyde, an alkali cyanide, such as sodium cyanide, and the corresponding α- substituted 2-haloalkyl (oxy-, thio -) - phenylacetyl halide in one step to form the desired end product α -Cyanoesters implement.

The compounds of the invention are extremely effective Contact poisons and stomach poisons for ticks and a variety of Insects, especially double-winged insects, butterflies, Beetles and equal-wingers. They stand out against pyrethroids in that they have a very long residual insecticide Effect in plant tissue, effective in the soil are and are surprisingly effective for controlling ticks and to protect animals from insect infestation and ticks if these compounds are on oral or parenteral Ways or topically in the form of insecticides or acaricidal formulations administered to the animals. You don't have to be mixed with a stabilizer be used to stabilize insecticidal and acaricidal agents Effect. You can also in combination with common insecticides such as phosphates, Carbamates, formamidines, chlorinated hydrocarbons or halogenoboylureas can be used. For fighting of insects, including soil insects that growing plants and / or harvested crops, including stored crop, infested, the insecticides according to the invention Connections to the foliage of plants, the area of life of the insects and / or the food supply the insects are applied. In general the active ingredient is in the form of a diluted spray liquid  applied, although it is also in the form of an aerosol, dust powder, granulate or wettable Can use powder.

Oil spray liquids are particularly suitable spray liquids and emulsifiable concentrates suitable for use can be further diluted. Although for the sake of easier handling and easier transport in Form of liquid concentrates are made these formulations are usually at the application site in water dispersed and then as a diluted spray liquid the foliage of the plants, the soil or the surface applied to the area to be treated.

A typical emulsifiable concentrate that is used to protect a Variety of crops, such as cereals, cabbage, pumpkin, corn, Cotton, tobacco, soybeans, ornamental plants or shrubs can be used, about 20 wt .-% of Active ingredient; 4% by weight of an emulsifier, as is customary used for the preparation of pyrethroid formulations becomes; 4% by weight of a surfactant; 25% by weight an organic solvent such as cyclohexanone; and about 47% by weight of a petroleum solvent with an aromatic content of at least about 83% by volume.

When used as a systemic insecticidal and acaricidal Agents according to the invention can be used to treat animals Compounds either on oral or on parenteral Routes can be administered to the animals to be treated. For oral administration, the active ingredients can be administered in brought into any form suitable for this route of administration are, for example in the form of a bolus, in the form of capsules, tablets or one to be administered orally Drug. The active ingredient can also be found in animal feed be incorporated, for example a nutritionally balanced one  Feed, preferably 0.0001 to 0.1% by weight 0.001 to 0.05% by weight of the active ingredient, based on the weight of the feed.

If desired, this can be systemic against insects and mites active agents by subcutaneous, intramuscular or intraperitoneal Injection into the carcass, so that it is in the animal's circulatory system distributed throughout the animal body. In practice, the systemically active ingredient in a pharmaceutically acceptable Carrier material, such as water, propylene glycol, one vegetable oil or glycerin-formal, dissolved or be dispersed.

The systemic active ingredients advantageously show one good security area and protect a variety of animals, especially cattle and pets, such as cattle, sheep, Horses, dogs or cats, against an infestation through fleas, mosquitoes, flies or ticks.

Particularly preferred insecticidal and acaricidal active compounds according to the invention are:
α- isopropyl-4-trifluoromethoxyphenyl-acetic acid-m-phenoxybenzyl ester,
α- isopropyl-4-trifluoromethoxyphenyl-acetic acid- α- cyano-m-phenoxybenzyl ester,
α- isopropyl-4- (1,1,2,2-tetrafluoroethoxy) phenylacetic acid-m-phenoxybenzyl ester,
α -isopropyl-4-pentafluoroethoxyphenyl acetic acid α- cyano-m-phenoxybenzyl ester,
α- tert-butyl-4-trifluoromethoxyphenyl acetic acid α- cyano-m-phenoxybenzyl ester,
α -isopropyl-4-difluoromethoxyphenyl-acetic acid- α- cyano-m-phenoxybenzyl ester,
α- isopropyl-4-trifluoromethylthiophenyl-acetic acid- α- cyano-m-phenoxybenzyl ester and
α- Ethyl-4-trifluoromethoxyphenyl-acetic acid- α- cyano-m-phenoxybenzyl ester.

The following examples serve to further explain the Invention.

example 1 Preparation of p- (1,1,2,2-tetrafluoroethoxy) toluene

In a mixture stirred using a magnetic stirrer  10.8 g (0.100 mol) of p-cresol, 1.67 g (1.43 g real, 0.0255 mol) Potassium hydroxide cookies and 70 ml of dried dimethylformamide, which is kept at 68 ° C is conducted for 1 hour Tetrafluoroethylene and nitrogen. After dilution the reaction mixture is extracted with 250 ml of water 100 ml ether. The ether solution is washed with 200 ml of 5% Sodium hydroxide solution and twice with 400 ml of water. Then the ether solution is dried, filtered and evaporated a rotary evaporator using 18.14 g (87%) receives p- (1,1,2,2-tetrafluoroethoxy) toluene.

Analysis C₉H₉F₄O:
calculated: C 51.93% H 3.87% F 36.51% found: C 52.06% H 3.76% F 41.52%

Example 2 Preparation of p- (1,1,2,2-tetrafluoroethoxy) benzyl bromide

A mechanically stirred mixture of 118.45 g is heated (0.569 mol) p- (1,1,2,2-tetrafluoroethoxy) toluene, 123.00 g (0.691 mol), 121 mol%) N-bromosuccinimide, 1.00 g (4.13 mol, 0.73 mol%) benzoyl peroxide and 350 ml carbon tetrachloride refluxing for 2.25 hours. After cooling if the reaction mixture is diluted with 350 ml of carbon tetrachloride, filtered to remove solids, dries over sodium sulfate, filtered and evaporated using a rotary evaporator, whereby 160.99 g (99%) of a clear, red oil. This product will as it is used in the next stage of the process. The infrared spectrum and the NMR spectrum show that it the product is p- (1,1,2,2-tetrafluoroethoxy) benzyl bromide acts.

Example 3 Preparation of p- (1,1,2,2-tetrafluoroethoxy) phenylacetonitrile

A hot solution of is given over the course of 40 minutes 75.1 g (1.15 mol) of potassium cyanide in 140 ml of water to one mechanically stirred solution of 160.99 g (0.561 mol) of p- (1,1,2,2-tetrafluoroethoxy) benzyl bromide and 500 ml of anhydrous alcohol (2B alcohol), which is kept at 75 ° C. The mixture obtained is then refluxed for 1.75 hours heated. After standing overnight, the reaction mixture is poured in 500 ml of cold water and 400 ml of ether. Man washes the combined ether solutions twice with 500 ml of water, dries over sodium sulfate, filtered and then evaporated on a rotary evaporator, with 114.95 g of a Oil. The vacuum distillation of this oil is the only one  Distillate fraction 37.10 g (28%) of the nitrile, which at 85 to 100 ° C (0.39 mbar 0.29 mm Hg) boils.

Example 4 Preparation of α- isopropyl-p- (1,1,2,2-tetrafluoroethoxy) phenylacetonitrile

A mixture of 39.85 g (0.171 mol) of p- (1,1,2,2-tetrafluoroethoxy) phenylacetonitrile is stirred, -3.71 g (9.96 mmol, 5.8 mol%) Dicyclohexyl- [18] crown-6, 22.0 ml (28.8 g, 0.234 mol) 2-bromopropane, 55 ml benzene and 55 ml 50% sodium hydroxide solution for 45 minutes with an exothermic reaction taking place which increases the temperature of 25 and 43 ° C. The reaction mixture is then heated to 45 ° C for 16.5 hours. After dilution with 200 ml of water, the reaction mixture is extracted with 200 ml ether. You wash the ether solution in 400 ml of 12% hydrochloric acid, 200 ml of 5% Hydrochloric acid and 300 ml of water. Then you dry the ether solution with sodium sulfate, filtered, evaporates and receives 47.13 g of an oil. This oil is in a vacuum distilled to give 34.83 g (74%) of an oil which 83 to 85 ° C (0.07-0.1 mbar 0.055 to 0.090 mm Hg) boiling.

Analysis C ₁₃ H ₁₃ F ₄ NO:
calculated: C 56.73% H 4.76% N 5.09% F 27.61% found: C 56.12% H 4.85% N 4.99% F 34.07%

Example 5 Preparation of 3-methyl-2- [p- (1,1,2,2-tetrafluoroethoxy) phenyl] butyric acid

A stirred mixture of 48.0 g (24.0 g, 0.60 mol) of 50% sodium hydroxide solution, 21.78 g (0.0791 mol) of α- isopropyl-p- (1,1,2,2 -tetrafluoroethoxy) -phenylacetonitrile and 240 ml of ethylene glycol over 12 hours at 135 ° C. After dilution with 600 ml of water, the reaction mixture is washed twice with 100 ml of ether. The aqueous layer is acidified with concentrated hydrochloric acid and then extracted twice with 300 ml of ether. The ether solution is washed twice with 500 ml of water, dried over sodium sulfate, filtered, evaporated and 20.74 g (89%) of a brown solid is obtained, which melts at 92 to 97 ° C. (hexane).

Analysis C ₁₃ H ₁₄ F ₄ O ₃ :
calculated: C 53.06% H 4.80% F 25.83% found: C 53.04% H 4.79% F 25.93%

Example 6 Preparation of 3-methyl-2- [p- (1,1,2,2-tetrafluoroethoxy) phenyl] butyryl chloride

A stirred mixture of 20.00 g (0.0680 mol) is heated 3-methyl-2- [p- (1,1,2,2-tetrafluoroethoxy) phenyl] butyric acid, 20.00 ml (33.2 g, 0.280 mol) of thionyl chloride and 75 ml dried benzene at reflux for 4 hours. Then you evaporate the reaction mixture, dilute the formed Residue with 50 ml of benzene, evaporate again and receives 22.46 g (106%) of a clear, dark brown liquid. This product will be as it is in the next one Process stage used. The infrared spectrum of the liquid shows that it is the title compound.  

Example 7 Preparation of α- isopropyl-4- (1,1,2,2-tetrafluoroethoxy) -phenylacetic acid-m-phenoxybenzyl ester

To a stirred mixture of 6.81 g (0.0340 mol) of m-phenoxybenzyl alcohol, 3.0 ml (2.95 g, 0.0372 mol) dried Pyridine and 20 ml of methylene chloride are added in the course of 20 minutes, a solution of 10.6 g (0.034 mol) of 3-methyl-2- [p- (1,1,2,2-tetrafluoroethoxy) phenyl] butyryl chloride in 20 ml Methylene chloride. The reaction mixture is stirred for 66 Hours at room temperature and then diluted with 200 ml ether. The ether solution is washed with 200 ml of 20% hydrochloric acid solution and 200 ml of water, dries over sodium sulfate, filtered, evaporated and obtained 16.24 g (100%) of the product. This product is made using a dry silica gel column (116 cm × 5 cm; eluent Hexane / methylene chloride mixture (1/1)) cleaned, by taking a sample between 85 cm and 63 cm (where the solvent front is at 113 cm) and preserved 12.60 g (78%) of a clear, slightly yellow colored oil.

Analysis C ₂₆ H ₂₄ F ₄ O ₄ :
calculated: C 65.54% H 5.08% F 15.95% found: C 64.99% H 4.96% F 19.10%

Example 8 Preparation of α- isopropyl-4- (1,1,2,2-tetrafluoroethoxy) -phenylacetic acid- α -cyano-m-phenoxybenzyl ester

To a stirred mixture of 8.81 g (7.49 g real, 0.0333 mol) of α- cyano-m-phenoxybenzyl alcohol, 3.0 ml (2.95 g, 0.0372 mol) of dried pyridine and 20 ml of methylene chloride a solution of 10.6 g (0.034 mol) of 3-methyl-2- [p- (1,1,2,2-tetrafluoroethoxy) phenyl] butyryl chloride in 20 ml of methylene chloride is added over the course of 20 minutes. The reaction mixture is stirred for 66 hours at room temperature, then diluted with 200 ml of ether, washed with 200 ml of 20% hydrochloric acid solution and 200 ml of water, dried over sodium sulfate, filtered and evaporated to give a dark red oil. To remove the m-phenoxybenzaldehyde present as an impurity, the oil is reacted with 0.5 g of sodium borohydride at the ice bath temperature and the oil obtained is purified using a column loaded with dry silica gel (121 cm × 5 cm, eluent = hexane / methylene chloride mixture (1/1)), collecting a sample between 77 cm and 57 cm (with the solvent front at 113 cm), and obtained 11.17 g (66%), a clear, orange oil.

Analysis C ₂₇ H ₂₃ F ₄ NO ₄ :
calculated: C 64.67% H 4.62% N 2.79% F 15.16% found: C 65.26% H 4.81% N 2.82% F 17.94%

Example 9 Preparation of α- isopropyl-4-methoxyphenylacetonitrile

To a solution of 147 g (1 mol) of p-methoxyphenylacetonitrile, 18.63 g (5 mol%) of dicyclohexyl [18] crown-6 and 320 g (2.6 mol) 2-Bromopropane in 300 ml of benzene is added to 300 ml of a 50% Sodium hydroxide solution. The reaction mixture is heated 45 ° C and it remains at this temperature for 4 days. Then you separate the organic phase, wash it well Water (three times 200 ml), dilute hydrochloric acid (once 200 ml), water (twice 200 ml) and evaporated to one Oil a. Vacuum distillation delivers 175.6 g (81%)  Product boiling at 96 to 100 ° C (0.2 mbar / 0.15 mm Hg). The NMR spectrum (CDCl₃) shows that the distilled material 12.5 mol% of the nitrile used as the starting material contains.

Example 10 Preparation of α- isopropyl-4-hydroxyphenylacetonitrile

A solution of 51.0 g (0.2 mol) of boron tribromide in 20 ml of methylene chloride is added to a solution of 37.8 g (0.2 mol) of a -isopropyl-4-methoxyphenylacetonitrile in 35 ml of methylene chloride, which is Holds 40 ° C. The red solution is then allowed to warm to room temperature and stirred for 3 days. The reaction solution is added to ice, extracted with ether (three times 100 ml), washed with water (twice 100 ml) and evaporated to an oil. Vacuum distillation gives 28.9 g (81%) of α- isopropyl-4-hydroxyphenylacetonitrile, which boils at 142 to 143 ° C (0.33 mbar / 0.25 mm Hg).

Example 11 Preparation of the chlorothio formic acid O- [p- (1-cyano-2-methylpropyl) phenyl] ester

16.43 g (0.143 mol) of thiophosgene in 50 ml of chloroform are added over 30 minutes to a solution of 25.0 g (0.143 mol) of α- isopropyl-4-hydroxyphenylacetonitrile in a 5% sodium hydroxide solution (5.72 g , 0.143 mol), occasionally using an ice bath to keep the temperature below 30 ° C. The mixture is stirred for 15 minutes, the chloroform layer is separated off, washed with water and evaporated to a yellow oil (38.2 g). The product is used as it is in the procedure of Example 12.

Example 12 Preparation of α- isopropyl-4-trifluorometoxyphenylacetonitrile

The 38.2 g of the thiocarbonate from Example 11 are treated at -25 ° C. with 15.8 g of molybdenum hexafluoride. Then the temperature of the thick reaction mass is allowed to rise to room temperature and then slowly heated to 160 ° C. using an oil bath. The mixture is cooled to room temperature, poured into water, extracted with ether (four times 50 ml), washed with water (once 50 ml) and evaporated to an oil. Vacuum distillation gives α- isopropyl-4-trifluoromethoxyphenylacetonitrile, which boils at 78 to 80 ° C (0.2 mbar / 0.15 mm Hg).

Example 13 Alternative process for the preparation of α- isopropyl-4-trifluoromethoxyphenylacetonitrile A. Preparation of 4-trifluoromethoxybenzyl chloride

A mixture of 355 mg trioxane and 340 mg zinc chloride is heated and 600 mg trifluoromethoxybenzene at 73 ° C and conducts Hydrogen chloride gas through the reaction mixture. Then the reaction mixture is cooled to room temperature and diluted with water. The organic phase is washed with a saturated sodium carbonate solution and then with water. The product is obtained by removing the solvents (1.42 g) as a colorless liquid.

B. Preparation of 4-trifluoromethoxyphenylacetonitrile

According to the procedure of Example 3, the is converted into the above step A. Chlorine compound obtained with 93% Yield to the corresponding nitrile.  

C. Preparation of a- isopropyl-4-trifluoromethoxyphenylacetonitrile

The alkylation of 4-trifluoromethoxyphenylacetonitrile following the procedure of Example 4 gives the desired one Connection with a yield of 90%.

Example 14 Preparation of α- isopropyl-4-trifluoromethoxyphenylacetic acid

A mixture of 2.0 g of α- isopropyl-4-trifluoromethoxyphenylacetonitrile, 3.0 g of potassium hydroxide, 35 ml of ethylene glycol and 3 ml of water is heated at 140 ° C. for 8 hours. Then the solution is poured into water and extracted with ether (twice 10 ml). The aqueous layer is acidified with dilute hydrochloric acid and extracted with ether (three times 10 ml), washed with water (once 25 ml), dried over sodium sulfate and evaporated to an oil (1.23 gg). IR spectrum (of the pure material) 1700 cm ^-1 .

Example 15 Preparation of α- isopropyl-4-trifluoromethoxyphenylacetyl chloride

A solution of 1.2 g of α- isopropyl-4-trifluoromethoxyphenylacetic acid and 0.6 ml of thionyl chloride in 5 ml of benzene is refluxed for 4 hours. Evaporation of the solvent and excess thionyl chloride gives the acid chloride which, as it is, is used in the esterification described in Examples 16 and 17.

Example 16 Production of α- isopropyl-4-trifluoromethoxyphenylacetic acid- α- cyano-m-phenoxybenzyl ester

A solution of 4.58 mmol of a -isopropyl-4-trifluoromethoxyphenylacetyl chloride in 5 ml of ether is added to a solution of 4.58 mmol of α- cyano-m-phenoxybenzyl alcohol and 0.5 ml of pyridine in 20 ml of ether. The mixture is stirred overnight and filtered. Then the filtrate and the washing liquid are evaporated and the remaining oil is cleaned on plates coated with silica gel (5 × 2 mm), using a methylene chloride / hexane mixture (1/1) as eluent. The band with an R _f value of 0.55 is extracted with ether, evaporated and the desired ester (0.85 g) is obtained.
IR spectrum (of the pure material): 1755 cm ^-1
NMR spectrum (CDCl₃): δ 6.8-7.6 (m, 13 H, ArH), 6.31 and

3.27 (d, J = 7 Hz, 1 H, CH-CH (CH₃) ₂), 2.0-2.6 (m, 1 H, CH (CH₃) ₂), 0.6-1.2 (four doublets, J = 7 Hz, 6 H, isopropyl-CH₃).
¹⁹F spectrum: chemical shift compared to CFCl₃ δ = 58.8.

Example 17 Preparation of α- isopropyl-4-trifluoromethoxyphenylacetic acid-m-phenoxybenzyl ester

To a solution of 1.89 g of m-phenoxybenzyl alcohol and 1 ml of pyridine in 6 ml of methylene chloride is added a solution of the α- isopropyl-4-trifluoromethoxyphenylacetyl chloride formed from 2.46 g of the corresponding acid in Example 7 in 7 ml of methylene chloride. After stirring the reaction mixture overnight, it is washed with water, with dilute hydrochloric acid solution, with dilute potassium hydroxide solution and water and evaporated to an orange oil. Chromatographic purification on silica gel gives 2.76 g of the desired ester.

IR spectrum (of the pure material): 1738 cm ^-1 NMR spectrum (CDCl₃): δ 6.73 to 7.45 (m, 13 h), 5.03 (S, 2 H), 3.20 (d , J = 10.5 Hz, 1 H), 2.26 (m, 1 H), 0.66 and 0.94 (two d, J = 6.6 Hz, 6 H).

Example 18 Production of α- ethyl and α- n-propyl-4-trifluoromethoxyphenylacetic acids and their esters.

According to the procedure of Example 9, but using ethyl bromide and 1-bromopropane instead of the 2-bromopropane used there and using the process steps described in Examples 10, 11, 12 and 14, the α- ethyl-4-trifluoromethoxyphenylacetic acid or α- n-propyl-4-trifluoromethoxyphenylacetic acid. These acids are then converted to the following esters using the appropriate procedure of Examples 15, 16 and 17:

Example 19 Production of α- bromo-4-trifluoromethylthiotoluene

A solution of 20.5 g (0.13 mol) of bromine is slowly added  20 ml carbon tetrachloride to a solution of 29 g (0.15 mol) 4-trifluoromethylthiotoluene in 90 ml carbon tetrachloride, to moderate under a 275 W sunlight lamp Boiling is heated to reflux. After the addition is complete is done, the solution is heated another Hour to reflux. Then you draw the bulk the solvent at atmospheric pressure and distilled then the residue in vacuo. The 15.5 g of the fraction with a boiling range of 64 to 77 ° C 0.8-1.06 mbar 0.6 to 0.8 mm Hg contains 92% of the monobromine compound according to gas chromatographic analysis.

Example 20 Preparation of 4-trifluoromethylthiophenylacetonitrile

3.9 g (0.08 mol) of sodium cyanide are added to 40 ml of dimethyl sulfoxide at 65 ° C. under nitrogen. The heating is then stopped and 14.3 g (0.053 mol) of α -bromo-4-trifluoromethylthiotoluene are added dropwise at such a rate that the temperature of the reaction mixture never rises above 75 ° C. as a result of the exothermic reaction. The red-colored reaction mixture is heated to 90 to 95 ° C. for about 45 minutes, then cooled to room temperature and treated with 50 to 100 ml of ice water. The aqueous suspension is extracted with several portions of ether, which are combined, washed with water and dried over sodium sulfate. Evaporation in vacuo gives 9.7 g of a dark red oil with a purity of 95% determined by gas chromatography

Example 21 Preparation of α- isopropyl-4-trifluoroethylthiophenylacetonitrile

Over the course of 30 minutes, 13.5 ml of a 50% solution are added  Sodium hydroxide solution dropwise to a suspension of 9.7 g (0.045 mol) of 4-trifluoromethylthiophenylacetonitrile, 9.5 g (0.056 mol) of 2-iodopropane and 0.61 g (0.0023 mol) of the Crown ether [18] crown-6 in 13.5 ml benzene, taking the reaction mixture a temperature as a result of the exothermic reaction of 43 ° C. After stirring for 2.5 hours at room temperature shows a gas chromatograph aliquot that none used as starting material Nitrile is present. Then the reaction mixture by adding ice water and extracting with ether, with a 10% hydrochloric acid solution and water washed and dried over sodium sulfate, worked up. Evaporation in vacuo gives 10.2 g (86.8%) of a reddish brown oil.

Comparable results are obtained using, instead of 2-iodopropane ethyl bromide and n-propyl iodide used to obtain trifluormethylthiophenylacetonitril 4-propyl-a -ethyl-4-α trifluormethylthiophenylacetonitril or -N-.

Example 22 Preparation of α- isopropyl-4-trifluoromethylthiophenylacetic acid

6.9 g (0.00265 mol) of α- isopropyl-4-trifluoromethylthiophenyl acetonitrile and 25 g (0.312 mol) of 50% sodium hydroxide solution are mixed with 53 ml of ethylene glycol and the mixture is heated under moderate reflux for 18 hours. Then the reaction mixture is poured into ice water and extracted with ether. The aqueous phase is acidified with concentrated hydrochloric acid and extracted again with ether, which is washed with water and dried over sodium sulfate. Evaporation in vacuo gives 2.05 g of an oily product.

Similar results are obtained if, for the synthesis of α- ethyl-4-trifluoromethylthiophenyl acetic acid or α -n-propyl-4-trifluoromethylthiophenyl acetic acid as starting material, α- ethyl-4-trifluoromethylthiophenyl acetonitrile or α- n- Propyl-4-trifluoromethylthiophenyl acetonitrile is used.

Example 23 Production of α- isopropyl-4-trifluoromethylthiophenyl-acetic acid- α- cyano-m-phenoxybenzyl ester

Using a-isopropyl-4-trifluoromethylthiophenyl-acetic acid and using the procedures of Examples 15 and 16 to give the title compound as an oil.

Analysis C ₂₆ H ₂₂ F ₃ NO ₃ S:
calculated: C 64.32% H 4.57% F 11.74% N 2.89% S 6.60% found: C 64.27% H 4.62% F 11.66% N 2.68% S 6.43%

Comparable results are obtained if α- ethyl-4-trifluoromethylthiophenylacetic acid or α- n-propyl-4-tri fluoromethylthiophenyl-acetic acid as starting materials in the synthesis of α- ethyl-4-trifluoromethylthiophenyl-acetic acid- α- cyano-m -phenoxybenzylesters or the α- n-propyl-4-trifluoromethylthiophenyl-acetic acid- α- cyano-n-phenoxybenzylesters used.

Example 24 Production of α- isopropyl-4-trifluoromethylthiophenyl-acetic acid-m-phenoxybenzyl ester

Using α- isopropyl-4-trifluoromethylthiophenyl acetic acid and the procedures of Examples 15 and 16, the title compound is obtained in the form of an oil.

Example 25 Production of α- isopropyl-4-mercaptophenyl-acetic acid

A solution of 15.7 g (0.065 mol) of α -isopropyl-4-difluoromethylthiophenyl acetonitrile in 42 g of a 50% strength sodium hydroxide solution and 80 ml of ethylene glycol is boiled under reflux for 18 hours. Then the reaction mixture is poured into ice water and extracted with ether. The alkaline layer is acidified at 15 to 20 ° C. using concentrated hydrochloric acid and extracted with ether. The ether extract is washed with water and a saturated sodium chloride solution and evaporated to give 11.4 g (83%) of an oil. The NMR and IR spectra show that the difluoromethyl group was split off during the reaction and that the product obtained was the thiol.

Example 26 Preparation of α -isopropyl-4-difluoromethylthiophenyl acetic acid

Combine 18.4 g (0.46 mol) of sodium hydroxide in 50 ml of water and 11 g (0.05 mol) of α- isopropyl-4-mercaptophenylacetic acid in 40 ml of dioxane and the mixture is heated to a temperature of 50 ° C. Then chlorodifluoromethane is slowly passed under the surface of the liquid, which immediately causes an exothermic reaction that raises the temperature to 75 ° C. The addition is continued until the exothermic reaction slowly begins to subside (after about ½ hour). Then the reaction mixture is cooled to room temperature and treated with 100 ml of ice water. The aqueous layer is extracted three times with 200 ml of ether and then acidified at 15 to 20 ° C. with concentrated hydrochloric acid. The oil formed is extracted with ether. The ether solution is washed with water and saturated sodium chloride solution before being dried over sodium sulfate and evaporated in vacuo, 10.2 g of a dark brown resin being obtained. This resin is used in the subsequent esterification stage without further purification.

Example 27 Production of α -isopropyl-4-difluoromethylthiophenyl-acetic acid- α- cyano-m-phenoxybenzyl ester

Using the α -isopropyl-4-difluoromethylthiophenyl-acetic acid and the procedure of Examples 15 and 16, the title compound is obtained in the form of an oil.

Analysis C ₂₆ H ₂₃ F ₂ NO ₃ S:
calculated: C 66.79% H 4.96% F 8.13% N 3.00% S 6.86% found: C 66.58% H 5.13% F 8.02% N 2.87% S 6.95%

Example 28 Production of α- isopropyl-4-hydroxyphenyl acetic acid

A mixture of 40.0 g of α- isopropyl-4-methoxyphenylacetonitrile and 200 ml of 48% hydrobromic acid is heated for 14 hours on an oil bath at a temperature of 126 to 128 ° C. to boiling under reflux. Then the reaction mixture is diluted with ice and water, extracted several times with ether, washed with water and evaporated to a solid residue. The solid is boiled with 200 ml of chloroform, cooled, filtered and dried. 23.8 g of the title compound with a melting point of 172-174 ° C. are obtained.

IR spectrum (Nujol): 3250-2900 (broad, OH), 1690 (C = O) cm ^-1 .

Comparable results are obtained if, for the synthesis of α- ethyl-4-hydroxyphenyl-acetic acid or α- n-propyl-4-hydroxyphenyl-acetic acid, α- ethyl-4-methoxyphenyl acetonitrile or α- n- Propyl-4-methoxyphenyl acetonitrile used.

Example 29 Preparation of a -isopropyl-4-difluoromethylthiophenyl acetic acid

In a mixture of 10.00 g (0.0515 mol) of α- isopropyl-4-hydroxyphenylacetic acid, 65 ml of dioxane, 19.08 g (18.56 g real, 0.464 mol) of sodium hydroxide and a mixture stirred with a magnetic stirrer at 80 ° C. 30 ml of water are passed in over the course of 4 hours, 46 g (0.532 mol) of chlorodifluoromethane. The reaction mixture is poured into 250 ml of ice water and the mixture obtained is washed with ether, acidified to pH 3 with concentrated hydrochloric acid and then extracted with 200 ml of ether. Then the ether solution is washed once with 100 ml of water, dried over sodium sulfate, filtered and evaporated to a white paste. A mixture of hexane and methylene chloride is then added and the mixture obtained is filtered to remove the starting material in the form of a solid. The filtrate is then evaporated to give 5.41 g of a clear brown oil. It can be estimated from the NMR spectrum that the product has a purity of at least 85%.

NMR spectrum (CDCl₃-d₅ pyridine): δ 7.43 (d, J = 8.2 Hz, 2 H), w 7.08 (d, J = 8.2 Hz, 2 H). δ 6.57 (t, J = 74, 3 Hz, 1 H), δ 3.63 (see imp.), δ 3.25 (d, J = 10 Hz, 1 H), δ 2.37 ( m, 1 H), δ 1.19 (d, J = 6.5 Hz, 3 H), δ 0.78 (d, J = 6.5 Hz, 3 H), δ 13.82 (s, 1 H).

Comparable results are obtained if the starting materials used are α- ethyl-4-hydroxyphenylacetic acid or α- n-propyl-4-hydroxyphenylacetic acid, whereby α- ethyl-4-difluoromethoxyphenylacetic acid or α- n-propyl-4-difluoromethoxyphenylacetic acid is obtained .

Example 30 Preparation of α -isopropyl-4-difluoromethoxyphenyl-acetic acid-m-phenoxybenzyl ester

Using α -isopropyl-4-difluoromethoxyphenyl-acetic acid and the procedures of Examples 15 and 17, the title compound is obtained in the form of a light yellow oil.

Analysis C ₂₅ H ₂₄ F ₂ O ₄ :
calculated: C 70.41% H 5.67% F 8.91% found: C 73.36% H 5.96% F 10.56%

Comparable results can be achieved if the synthesis of α- ethyl-4-difluoromethoxyphenyl-acetic acid-m-phenoxybenzyl ester or α- n-propyl-4-difluoromethoxyphenyl-acetic acid-m-phenoxybenzyl ester as starting materials α- ethyl-4-difluoromethoxphenyl-acetic acid or α- n-propyl-4-difluoromethoxyphenyl-acetic acid.

Example 31 Production of α -isopropyl-4-difluoromethoxyphenylacetic acid- α- cyano-m-phenoxybenzyl ester

Using a-isopropyl-4-difluormethoxyphenylessigsäure and the procedures of Examples 15 and 16 to give the title compound as an oil.

NMR spectrum (CDCl₃): δ 0.88 (four doublets, J = 6 Hz, 6 H CH₃),

6.33 (two singlets, 1 H, -CHCN), 6.45 (t, J = 74 Hz, 1H, CHF₂O-), 7.16 (m, 13H, ArH).

Analysis C ₂₆ H ₂₃ F ₂ NO ₄ :
calculated: C 69.17% H 5.13% F 8.42% N 3.10% found: C 69.41% H 5.20% F 10.25% N 3.70%

Comparable results are obtained if the starting materials used for the production of α- ethyl-4-di fluoromethoxyphenylacetic acid- α- cyano-m-phenoxybenzyl ester- α- ethyl-4-difluoromethoxyphenylacetic acid are used:

NMR spectrum (CDCl₃): δ 6.85-7.53 (m, 13 H, ArH), 6.46, 6.43 (two triplets, J = 74 Hz, 1 H, OCHF₂), 6.35 ( S, 1 H, -CHCN), 3.55 (triplet, J = 7.8 Hz, 1 H, CH-C₂H₅), 1.88 (m, 2 H, CH₂CH₃), 0.87 and 0.82 ( two triplets, J = 7.9 Hz, 3 H, CH₃).

Analysis C ₂₅ H ₂₁ F ₂ NO ₄ :
calculated: C 68.64% H 4.84% N 3.20% F 8.69% found: C 68.91% H 4.83% N 3.12% F 8.40%

Example 32 Preparation of 4-trifluoromethoxy- α- tert-butylbenzyl alcohol

To a solution of 1.0 mole of commercially available tert-butyl magnesium chloride in tetrahydrofuran at 38 to 40 ° C and a solution of 56 g (0.4 mol) under a nitrogen atmosphere 4-trifluoromethoxybenzaldehyde in 50 ml of tetrahydrofuran. Man the reaction solution is stirred overnight at room temperature and then acidify carefully with dilute sulfuric acid at 15 up to 20 ° C. You add ether, wash the organic phase with water, dries over sodium sulfate and evaporates to a rubbery solid. The raw material is cleaned by chromatography on silica gel, taking the alcohol obtained, which is used in Example 33.

Example 33 Preparation of p- (1-chloro-2,2-dimethylpropyl) - α, α, α -trifluoranisole

To 14.87 g (0.125 mol) of freshly distilled thionyl chloride, which is cooled with a salt-ice bath is added in portions in the course of 30 minutes, 12.4 g (0.05 mol) of the Example 32 neopentyl alcohol prepared. Then removed the ice bath and the slurry are left overnight.  Obtained by evaporating the excess thionyl chloride one a solid.

Example 34 Preparation of α- tert-butyl-4-trifluoromethoxyphenyl acetic acid

The neopentyl chloride prepared according to Example 33 is transferred into the corresponding Grignard reagent and obtained by subsequent Carbonization with carbon dioxide after the process by Weinstein and Morse (Journal of the American Chemical Society 74 (1952), 1133) the desired acid in the form of a white solid.

Example 35 Production of α- tert-butyl-4-trifluoromethoxyphenyl-acetic acid- α- cyano-m-phenoxybenzyl ester

Using α- tert-butyl-4-trifluoromethoxyphenyl acetic acid and the procedures of Examples 15 and 16, the title compound is obtained in the form of an oil.

Example 36 Insecticidal effects

The insecticidal activity of the compounds according to the invention is verified with the help of the following tests, in which the tobacco caterpillar, Heliothis virescens (Fabricius); the potato leafhopper (Western Potato Leafhopper) Empoasca abrupta (DeLong); and the bean aphid Aphis fabae (Scopoli) can be used as insect species. The applied Procedures are the following:  

Tobacco caterpillar, Heliothis virescens (Fabricius) in the first stage of development

You dip a cotton plant with two real unfolded ones Scroll for 3 seconds into the test area with stirring Solution (35% water / 65% acetone) containing 300, 100 or Contains 10 ppm of the compound to be examined. Then bring you put each leaf in a cup with a wick and put it a gauze cloth filled with 50 to 100 newly hatched larvae before you close the cup with a lid. After 3 days at a temperature of 27 ° C and one relative humidity of 50%, the cups are examined and assessed the kill of the newly hatched larvae. The numerical values obtained are as a percentage of the kill listed in Table I.

Bean aphid, Aphis fabae (Scopoli)

Five fiber pots, each containing a 5 cm tall nasturtium plant that had been populated with 100 to 150 aphids two days earlier, are placed on a rotary table that is operated at a speed of 4 min ^-1 and sprayed on Plants with a solution containing 35% water and 65% acetone containing 100, 10, 1.0 and 0.1 ppm of the compound to be tested, respectively, applying the solution for two turns using a spray device (DeVilbis Atomizer), which is operated with air at a pressure of 1.38 bar. The spray nozzle is placed approximately 15 cm from the plant and the spray is directed to completely cover the aphids and plants. The sprayed plants are then placed in white enamel bowls. Morality is determined after one day at 21 ° C and a relative humidity of 50%. The numerical values obtained are listed as a percentage of mortality in Table I below.

Potato leafhopper, Empoasca abrupta (DeLong)

A bean plant (Sieva lima) with the first leaf folded out to 7.5 to 10 cm is immersed in a solution of 35% water and 65% acetone, which contains 100, 10 or 1 ppm of the compound to be investigated. Then place the immersed plant in a hood to dry and cut a 2.5 cm piece of the tip of a leaf and place it in a 10 cm (4 inch) diameter petri dish containing a damp filter paper on the bottom . Then you transfer three to ten nymphs of the second stage of development into the petri dish, which is then covered. The mortality is then counted after storing the Petri dishes for two days at 27 ° C. and a relative humidity of 50%. The numerical values obtained are listed in Table I below. Permethrin is used as the reference standard in these studies.

Example 37 Insecticidal effects

The insecticidal activity of the compounds according to the invention will continue using the following investigation methods determined in which the action against mosquito larvae, Mexican Ladybird and caterpillars being examined.

Malaria mosquito, Anopheles quadrimaculatus (Say)

Pipette 1 ml of a solution of 35% water and 65% Acetone, which contains 300 ppm of the compound to be investigated, in a 400 ml beaker containing 250 ml of deionized water contains, mixes with the pipette and reaches a concentration of 1.2 ppm. Then you take aliquots of this Solution and further dilute to 0.4 0.04 and 0.004 ppm. To prevent the eggs on the side wall of the Float on the beaker and let it dry there the surface of the solution to be examined into the Beaker matching wax paper ring with a width of Swim 0.6 cm. A sieve spoon is used for the absorption and transfer of approximately 100 eggs (with the age of 0 up to 24 hours) in the beaker. After 2 days at 27 ° C and a relative humidity of 50% will Hatching observed. The percentage mortality is in the listed in Table II below.

Mexican ladybird, Epilachna varivestis (Mulsant)

Bean plants (Sieva lima) (two per pot) are also dipped 7.5 to 10 cm long first sheets in the 300, 100, 10 or Solution containing 1 ppm of the compound to be tested and let them dry in the hood. Then you take a sheet of the plant and put it in a 10 cm petri dish,  on the bottom a damp filter paper and 10 larvae in the last developmental stage (13 days before hatching) contains. The next day you take another leaf from the plant and feed it to the larvae after the remnants of the first sheet have been removed. 2 days after one feeds a third leaf to the larvae, this being is generally the last sheet required. The fourth Leaf is given on the third day after the start of treatment, if the larvae have not stopped feeding. Then the petri dishes are set aside and stored until the adult animals hatched, which takes about 9 days after the start of treatment. After the full Leakage of the animals will affect each petri dish killed larvae, pupae or adult animals, deformed Dolls or adult animals; Intermediate stages between the larval stage and the pupa stage and the Doll stage and the adult stage; or regarding any other effects in normal moulting, the normal development and appearance of Dolls or adult animals are examined.

The numerical values obtained are in Table II below listed.

Cotton caterpillar (Southern Armyworm), Spodoptera eridania (Cramer)

Bean plants (Sieva lima) with two folded 7.5 to 10 cm long first leaves are immersed in the treatment solution with stirring for 3 seconds and then left to dry in a hood. After the leaves are dry, they are cut out, and each cut sheet is placed in a 10 cm petri dish containing a piece of damp filter paper and 10 cotton caterpillar larvae in the third stage of development, about 1 cm in length. The petri dishes are covered and stored for 2 days at a temperature of 27 ° C and a relative humidity of 50%. Mortality is counted after 2 days. The results obtained are summarized in Table II below.

Example 38 Insecticidal effects Spotted mite, Tetranychus urticae (Koch)

Bean plants (Sieva lima) are planted, the first leaves of which 7.5 to 10 cm long, with about 100 full-grown, phosphate-resistant Mites per leaf, 4 hours before Conduct the investigation to lay eggs before to allow treatment. The infested plants will then with stirring for 3 seconds into the 1000, 300, 100 or Solution containing 10 ppm of the active substance is immersed, whereupon the plants are placed in the fume cupboard to dry. To 2 days at 27 ° C the mortality of the adult Mites on a leaf under a stereoscopic microscope estimated with 10x magnification. The other Leaf is left on the plant for another 5 days and then examined at 10x magnification to see the kill to estimate the eggs of the newly hatched nymphs, whereby the ovicidal effect or the residual effect is determined can be. The results are shown in Table III below compiled.

Tobacco caterpillar, Heliothis virescens (Fabricius) in the third stage of development

You dive three cotton plants with just unfolded Cotyledons in the 1000 or 100 ppm of the active ingredient containing solution and then transfers it to dry a deduction. After drying, each cotyledon is halved, and put 10 sheet sections in a 28 g plastic medicine cup introduced, the one 1.25 cm thick Contains dental tampon, which is saturated with water, after which to develop a tobacco caterpillar in the third stage of development  Brings in the mug. You close the cup and keep it him for 3 days at 27 ° C and a relative Humidity of 50%, after which the mortality is counted. The results obtained are shown in Table III below compiled.

Cabbage looper Trichoplusia ni (Hübner) in the third stage of development

A real leaf of a cotton plant is immersed in the solution to be examined, which contains 1000, 100 or 10 ppm of the compound to be examined, is stirred for 3 seconds, the plant is removed and it is allowed to dry in the hood. After drying, the sheet is transferred to a 9.0 cm petri dish, which contains a moist filter paper on the bottom. Then add three third stage larvae and cover the dish with the lid. Mortality is counted after 3 days at 27 ° C and a relative humidity of 50 ± 10%. The numerical values obtained are summarized in Table III below.

Example 39 Insecticidal effects on the soil Corn Rootworm, Diabrotica undecimpunctata howardi (Barber)

10 mg of the compound to be investigated are diluted with 10 ml Acetone to form a stock solution A. Then dilute 2 ml of this solution with acetone to 10 ml and receives solution B. Then you load a 28 g wide-mouth bottle with about 0.7 g Talc (Pyrax ABB) and gives 1.25 ml of the solution to be examined to the talc, resulting in the following concentrations result in:

1.25 ml of solution A corresponds to an application dose of 56 kg / ga,
1.25 ml of solution B corresponds to an application dose of 11.2 kg / ha.

The selected test solution is then mixed with the talc mixed to wet this evenly before the material for 10 to 15 minutes with the help of an air jet dryer is dried. Then 25 ml of moist, sterilized Vegetable soil and about 0.6 g millet seeds (as feed for the larvae) into the bottles, which are the ones to be examined Connection included. The bottles are closed, and the content is made using a vibration mixer mixed. Then you bring 10 corn rootworm larvae in each bottle at the age of 6 to 8 days. The bottles are covered loosely and placed in a room, where they are under constant lighting at 27 ° C and a relative humidity of 50%. The Mortality is counted after 6 days.  

In this study, α -isopropyl-4-trifluorometh oxyphenylacetic acid- a- cyano-m-phenoxybenzyl ester causes 100% killing of the corn rootworms at an application dose of 56 kg / ha and 70% killing at a dose of 11.2 kg / Ha.

Example 40 Remaining insecticidal effects after the treatment of the leaves of cotton plants

Young cotton plants with at least two folded ones are dipped real leaves drawn in 10 cm plastic pots be in a 65% acetone and 35% water containing Solution of the compound to be examined, whereby during Stir for 3 seconds and immerse one sheet at a time. The concentration the compound to be examined in the solutions is 30, 100, 300 or 900 ppm of the active ingredient.

After the leaves have dried, two leaves each cut out of two plants and placed in petri dishes (90 mm × 10 mm) placed on damp filter paper (9 mm Whatman No. 1). Five tobacco caterpillar larvae are then placed on each leaf in the third stage of development, whereupon the petri dish is covered. The petri dishes are then at constant lighting at a temperature of 27 ° C and a relative humidity of 50%. The The larvae killed are counted after 72 hours.

The remaining plants are exposed to intense light in the greenhouse, which is switched on for 14 hours a day. Then leaf samples are populated with tobacco caterpillar larvae in the third stage of development after an exposure time in the greenhouse of 3, 7, 10 or 14 days. The percentage killing of these larvae is determined again.

Example 41 Ixodicidal activity (activity against ticks)

With the help of the following investigation, the effective control of mite larvae, larvae of Boophilus microplus a landlord tick that during their three Stages of development d. H. the larval stage, the nymph stage and the full-blown stage, on one Host can be examined. In this investigation a mixture of 10% acetone and 90% water is used, the 0.025, 0.1, 0.5, 2.5 and 12.5 ppm of those to be examined Contains connection. There will be 20 larvae in one at one end pipette sealed with a gauze material, whereupon the solution containing the compound to be examined drawn through the pipette using a vacuum hose which simulates a spray system. The ticks are then kept at room temperature for 48 hours, after which mortality is determined. The results obtained are summarized in Table V below.

Table V

Percentage of tick larvae (Boophilus microplus)

The above procedure is repeated with the Difference that you have the active ingredient in a concentration of 0.1, 0.025, 0.005 or 0.001 ppm. The received Results are given in Table VI below.

Table VI

Percent mortality from tick larvae (Boophilus microplus)

Repeat the above procedure with the difference that the investigated compound in a concentration of 0.1, 0.01, 0.001, 0.0001 or 0.00001 ppm is used. The received Results are shown in Table VIa below.

Table VIa

Percent mortality from tick larvae (Boophilus microplus)

Repeat the above procedure with the difference that the compound under investigation is in a concentration of 100 ppm. The results obtained here are compiled in the following Table VIb.

Table VIb

Percent mortality from tick larvae (Boophilus microplus)

Example 42

The effectiveness of the compounds according to the invention is determined with regard to the control of adult ticks (Boophilus microplus) using the following test method, in which the connection to be tested according to the procedure of Example 41 is brought into solution with the difference that the active ingredient in such amounts used to obtain solutions that 125, 52.6, 31.2, Contain 15.6 and 7.3 ppm of the compound to be examined.

Then you dip adult, full, female ticks during 3 seconds transferred to the solutions to be examined into separate containers and keep them for 48 Hours at 27 ° C and relative humidity from 50% to. After the retention period, the Ticks are examined and the egg deposits are counted. Rich female ticks that have no eggs deposited have been assessed as dead. The results obtained are summarized in Table VII below.

Table VII

Ixodicidal activity against adult ticks (Boophilus microplus)

Example 43

The effectiveness of the compounds according to the invention is investigated to control gold fly larvae (Cochliomyia hominivorax), a very dangerous livestock pest, where five larvae of Cochliomyia hominovorax in the first stage of development with a mixture of ground Beef (8.0 g), blood (7.0 ml), water (2.1 ml) and 0.9 ml of a formulation containing 1, 5 and 25 ppm, respectively contains investigating compound, feeds.

For the evaluation, two repetitions are made 20 larvae per dose. The larvae are cared for ad libitum for 24 hours with the nutrient medium. After this Period of time is the number of larvae killed at each Treatment and each repeat treatment determined and the percentage mortality is calculated. The received Numerical values are summarized in Table VIII below.

Table VIII

Evaluation of the compound according to the invention with regard to controlling larvae of the golden fly (Cochliomyia hominivorax)

Example 44 Determination of the LC ₅₀ value of the compounds according to the invention in relation to tobacco caterpillars on cotton plants

Young cotton plants with at least two folded ones are dipped real leaves drawn in 10 cm plastic pots into a solution of the compound to be examined in a mixture of 65% acetone and 35% water, whereby you dip one sheet at a time and the liquid stirs. The active ingredient concentration of the solutions used is 1.1, 2.8, 7.5, 20, 60 and 150 ppm, respectively.

After the leaves have dried, cut two plants take two leaves each and put them in Petri dishes (90 mm × 10 mm) on damp filter paper (9 cm, Whatman No. 1) a. Then you put five on each hand Third tobacco caterpillar larvae and covered the petri dish. The shells then become permanent Lighting, a temperature of 27 ° C and a relative Keep moisture of 50%. The count the larvae take place after 72 hours. Every treatment will repeated four times. The numerical values obtained are in the The following table IX is compiled from which can be seen is that the compound of the invention in terms of Combating tobacco caterpillars is two to five times more effective than the conventional compounds examined in the same way.  

Table IX

Determination of LC ₅₀ values when using the compounds to control tobacco caterpillars in the third stage of development

Example 45 Determination of the LC ₅₀ value of the compounds used against adult mosquitoes (Anopheles quadrimaculatus (Say))

The connections to be evaluated are in the desired Concentration (in ppm) dissolved in acetone. Then 0.15 ml of insecticide solutions applied via an aerosol application to be pipetted into the top of a nozzle and passed through the atomizer nozzle. The atomized Droplets are removed using an air jet (with a speed of 6.436 km / hour (4 miles / hour) on the caged mosquitoes (each of which contains 25 adult female animals per cage) led, the treatment being carried out for 4 to 5 seconds. The mosquitoes are then covered with carbon dioxide (3 to 4 Seconds) anesthetized and transferred to storage cages. The Treated mosquitoes are then placed in these storage cages at 29.4 ± 0.55 ° C and a relative Keep humidity of 46 ± 2%. The counting of the Mortality occurs after 24 hours.

The numerical values obtained are in Table X below listed, from which it can be seen that the invention Connection related to the control of adult Mosquitoes (Anopheles quadrimaculatus) about four times as effective is as the link of the prior art.  

Table X

Determination of the LC ₅₀ values of the investigated compounds in the control of adult female mosquitoes (Anopheles quadrimaculatus)

Example 46 Remaining insecticidal activity, determined by application of the compounds to be examined in a small volume

The compounds to be examined are in such quantities dispersed in a mixture of 65% acetone and 35% water, that there is an application dose in 19.31 l of water of 0.08 kg of compound per active ingredient. Then be Cotton plants placed in a spray room and from above with the help of a stationary sprayer splashed under the sprayer.

After the leaves have dried, two leaves each cut out of two plants and placed in petri dishes (90 mm × 10 mm) on damp filter paper (9 cm, Whatman No. 1) brought in. Then put five tobacco caterpillar larvae on each leaf in the third stage of development and covers the petri dish. The Petri dishes are then under constant lighting and at a temperature of 27 ° C and a relative Keep moisture of 50%. The counting of the killed larvae occurs 72 hours later.

The remaining plants are then transferred to the greenhouse and irradiated with intense light. Then leaf samples are examined again after 3, 7, 10 or 14 days with tobacco caterpillar larvae in the third stage of development. The numerical values obtained are summarized in Table XI below.

Example 47 Ixodicidal effect

The test method described in Example 22 is used to determine the ixodicidal activity of the compounds according to the invention in active compound concentrations of 12.5, 2.5, 0.5, 0.1, 0.02 and 0.004 ppm. The results obtained are shown in Table XII below.

Example 48

The effectiveness of the compounds according to the invention is determined in the control of adult multi-host ticks (Rhipicephalus sanguineus (R. S.) and Dermacentor variabilis (D. V)) of dogs, using the following test method applies in which the test connection is prepared in the manner as described in Example 41. The active substance is used in such an amount that solutions receives the 100, 10 or 1 ppm of the investigated Connection included.

Then you dip adult, full, female ticks during 3 seconds into the solutions to be examined then put them into individual containers and keep them for 48 hours at 27 ° C and a relative humidity from 50% to. Towards the end of the retention period, the Ticks examined and the egg laying counted. Rich female Ticks that have not laid eggs are considered to be killed rated. The results obtained are shown in Table XIII below compiled.  

Table XIII

Ixodicidal activity against adult ticks, namely Rhipicephalus sanguineus (RS) and Dermacentor variabilis (DV)

Example 49 Investigation of the action of the compounds according to the invention in vitro against adult fleas of the species Ctenocephalides felis

In this investigation, 10 adult fleas of the Species Ctenocephalides felis for 30 seconds with a Sprayed acetone / water solution, the 100, 50, 10 or 1 ppm contains the compound to be examined. After this treatment the fleas are kept at room temperature for 48 hours and a relative humidity of 80%, whereupon the fleas are examined after 24 hours and after 48 hours and be counted for mortality. The numerical values obtained are compiled in the following table XIV.  

Table XIV

Effect of the compounds examined against fleas

Repeat the above investigation with the difference that the compound under investigation is in a concentration of 80, 40, 20, 10, 5 or 2.5 ppm. The received Results are taken as averages of two replicates each dose, unless otherwise stated, in the following Table XIVa compiled.

Table XIVa

Effect of the compounds examined against fleas

Example 50

The investigation of Example 48 is repeated with the Difference that one male and female multi-host ticks (Rhipicephalus sanguineus (R. S.) and Dermacentor variabilis (D.V.) used. The compounds to be examined are used in such an amount that solutions are obtained the 1.0%, 0.1%, 0.01% or 0.001% of the subjects to be examined Connections included. Mortality counts are made 24 or 48 hours after treatment.

The numerical values obtained are listed in Table XV below.

Example 51

The effectiveness of the compounds according to the invention for combating of facial flies (Musca autumnalis) is included Demonstrated the help of the following exams where 1 day old face fly larvae feed on cow dung can, the 0.13, 0.25 or 0.50 ppm of the investigated Contains connection.

Two repetitions are made per dose using 10 larvae are carried out each, and there are in the evaluation untreated controls performed.

A suitable amount of solution is given for each dose of the compound to be examined in acetone to 1 kg fresh Cow dung and mixed with an electric one for 1 minute Mixer. The one for the control tests not treated with the active ingredient Manure used is treated in the same way with the difference that only acetone was added becomes. The manure samples are placed on four paper cups divided up. At each dose (and at controls) are two cups with 1 day old face fly larvae vaccinated. The cups are kept at one for 7 days Temperature of about 27 ° C and a relative humidity saved by 50%. Then the cups are referring to examined the dolls, which were then counted, weighed and put in Plastic vessels are transferred to where they hatch and die. After the flies are killed, they become is counted and the percentage of mortality is determined. The results obtained are as follows Table XVI listed.  

Table XVI

In vitro evaluation of the activity of the compounds according to the invention as potential feed additives for controlling facial flies (Musca autumnalis) in manure (the numerical values given are mean values of two repetitions)

Claims (6)

1. Phenylalkanoic acid m-phenoxybenzyl ester of the general formula I whereinX is a sulfur atom or an oxygen atom, pure hydrogen atom, fluorine atom, a difluoromethyl group or a trifluoromethyl group, R₂ is an ethyl group, an n-propyl group, an isopropyl group or a tert-butyl group and R₃ is a hydrogen atom or a cyano group, and the optical isomers of these compounds. 2. α -isopropyl-4-difluoromethoxyphenyl-acetic acid- α- cyano-m-phenoxybenzyl ester. 3. α- isopropyl-4-trifluoromethoxyphenyl-acetic acid- α- cyano-m-phenoxybenzyl ester. 4. α- ethyl-4-difluoromethoxyphenyl-acetic acid- α- cyano-m-phenoxybenzyl ester. 5. A process for the preparation of the compounds according to claim 1, characterized in that the corresponding t position in the p-position with the substituent RCF₂X brominated or chlorinated brominated or chlorinated, the benzyl halide formed is reacted with an alkali metal cyanide, the benzyl nitrile formed with a suitable alkylating agent introducing the group R₂ alkylated, the alkylated nitrile hydrolyzed and the acid obtained with thionyl chloride to the corresponding acid chloride of the general formula in which R and R₂ have the meanings given in claim 1, and this with an m-phenoxybenzyl alcohol of the general formula in which R₃ has the meanings given in Claim 1, is implemented. 6. Acaricidal and insecticidal composition containing as active ingredient a compound according to claim 1 together with a common emulsifying, solution and surface active Medium.