FI59389C - FOER BEKAEMPNING AV INSEKTER OCH ARTER AV ORDNINGEN AKARINA LAEMLIGA DIETRAR - Google Patents

Description

I. Γβ1 .... ANNOUNCEMENT „Α Λ jgttg W (11) UTLÄGGNINGSSKRIFT 59 3 89 * r ^ plot -nylnn'Lty 10 03 11 Π 'SSZs (Sn κ ^! Να3 σ 07 σ 43/02, 43/257 , (51) 'CO? D 303/24, A 01 Ν 31/14 FINLAND — FINLAND (* 1) P »wunMmh» t 173/73 (22) H «k« nitpaM ~ Aiia64 (n <flf * d * 23.01.73 (23) ΑΜηιρβΙνλ — GlMffcttsdig 23.01.73 (41) Interpreters (ufkiMfcal — BllvK offtntNg 05.08.73 PMMItti. J «reklsterihdlltu, NlMMWp« «, ^ pvm._

Pstant · och rfIttf '' AmOkan utlifd Odi utUkrtftm puMkuratf 30. oU. 8l (32) (33) (31) hnr4 «« and «tuelkeu · -« «glrtf prloriut oU. 02.72 16.02.72, 03.01.73 Switzerland-Switzerland (CH) 1695/72, 221 + 0/72, 1 + 8/73 (71) Ciba-Geigy AG, CH-1 + 002 Basel, Switzerland-Switzerland (CH) (72) Friedrich Karrer, Basel, Switzerland-Switzerland (CH) (71+) Oy Jalo Ant-Wuorinen Ab (5I +) Dieters suitable for the control of insects and members of the sect of the Akarina - For the purposes of insecticides and arteries of the Akarina warm diet 4-alkoxy or 4-alkoxymethyldiphenyl ethers, respectively, suitable for the control of insects and members of the order Akarina. Derivatives of 1-cyclohexyloxy-4-alkoxy-benzenes, optionally substituted on the phenyl nucleus, of the formula r / XX0 / ^ - ri or O7 ° I * 3 29 (ia) R5 Ub) wherein R. | means -C 1-6 alkyl, chlorine, methoxy, ethoxy, vinyl, ethinyl or the residue 2,53839? H 3? H 3? H 3 XH 3 - C - OCH '- C - OCH 7, - CH 9 - C - OCH 1 - CH - ( V f IJJ * IJ \ / \ CH3 c2h5 c2h5 ^ CH3 / Ca3 ^ CH3 - CH - C ^ or - CH »C /; CH. N rh 3 C2H5.

R 2 is hydrogen, methyl, ethyl, chlorine or R 2 and R 2 together with their common C atom are a cyclopentyl or cyclohexyl ring, R 3 is hydrogen, methyl or methoxy, R 1 is hydrogen, methyl or chlorine, R 1 and R 3 together are carbon -carbon bond or oxygen bridge,

Rg is hydrogen or methyl, R1 is cyclohexyl or R®

Rg is hydrogen, methyl, ethyl, chloro or ethoxy, and

Rg residue (7) ΐΗ3 -CH <^ J or - CH = C - C2H5

Suitable alkyl groups R 1 are methyl, ethyl, propyl, isopropyl, n-, i-, sec- and tert-butyl.

FI patent application 2898/71 describes alkenyl or alkynyloxyphenyl ethers. Two phenoxyphenyl ether compounds are also included in the table of Example 6 of said application, but due to the lack of physicochemical characterization, these compounds cannot be considered as prepared or known on the basis of this application. In contrast, DE-A-2 114 257 and FR-A-2 086 145 describe compounds close to the invention which have been used as reference substances in the following experimental description.

The compounds of the formulas Ia and Ib are prepared in a manner known per se, for example as follows: 1) O-alkylation by condensation of the compounds of the formula Ilia resp. The halide according to Tllb of formula Ha is e.g. With a compound according to Hb, 59389 R7 ° f ^ S () ^ 2 base OH + X - (fH - <p - <f - Rx -> la R6 R5 R3 (Iia) (III *) O 'Tj ^ LcH OM + X - CH2_R9 -e-ma - ”-> lb (Hb) R6 (Illb)

In the above formulas, R 1 -R 2 and R 9 are as defined in formulas Ia and Ib; X represents chlorine, bromine and iodine, preferably chlorine or bromine; M is a metal, especially I. or II of the Periodic Table. from the main group, or hydrogen.

2) Epoxidation of a compound of formula IaA, wherein R 5 and R 3 together represent a carbon-carbon bond, to give a compound of formula IaB: R 7 '. »—-► R7 il T '1 R, R, V V Xc =» c-R. dointl V V 1 -C-R, 1 No (IaA) (IaB) wherein in formulas IaA and IB R 1, R 2, R 4, R 9 and R 7 have the same meaning as in formula Ia.

3) Hydrogen halide is attached to an olefinic double bond of a compound of formula IaA, wherein R 1 and R 2 together represent a carbon-carbon bond: r / V 1 R 6 R 2

7 '7 «V

/ '0 p

IaA + HX

> * r / V \ r6 f 2 N (laD>

7 H

X

59389 wherein in formulas IaA, IaB and IaC R1, R2 * RRg and Ry have the same meaning as in formula Ia, X represents halogen, preferably chlorine.

4) Epoxidize the unsaturated halide IV to epoxy halide V and condense this with a compound of formula II: R6? 6 CH * 4 * 2 Epoxidizer ΧΗ? 4 * 2

X NC == C-R. -► X NC — C-R

i x0 1 (IV) (V) * IIa / ° \ # / \. R6 + base 7 · A / CH * 4? 2 • Ό ur — rC-R,

Ό A

(IaB) wherein in formulas IaB, IIa, IV and V R 1, R 2 / R 2, R 9 and R 4 have the same meaning as in formula Ia, X represents halogen, in particular bromine or chlorine.

5) Hydrogenate the compound IaA: h2

IaA --► ’R7 7 I 6rJ2

The catalyst · / ch \ '5c “ri Ν · / 0 C 1 (IaE) wherein in the formulas IaA and IaE R 1, R 2, R 2 / R 8 and Ry have the same meaning as in the formula Ia.

6) An alcohol is attached to the double bond of a compound of formula IaA: 5,59538

+ R'OH

laA '——

Hg (II) salt „/ ° \ /% Rc R- R7 * * R4complex hydride \ ^. / CH \ Vr'E3 —fS-— * °, OR 'OH water

HgAn (VI) „/ ° \ /% R * R?

R? J! CH4C-R

v vcN / i 3 • 0, OR '

B

(IaF) wherein R 2, R 1, R 4 * R 5 3a R 7 have the same meaning as in formula Ia, An represents the anion of the Hg (II) salt and R 'or a C 2 alkyl residue. As the mercury (II) salt, mercury acetate or mercuric fluoroacetate is preferably used.

7) Alkylation of an alcohol of formula VII is r y R6 1) Strong base 7 K A - * -

Ν · κ \ \ »3 2) R’X

I UH

* 5 (VII) / ° \ /% R * Ro R · · 16 „12 7 HI JItt R4I o · ν · ν“ γ £> s (IaF) 6 59389 where 1 * 2 »R3 / R4 * R ^ f Rg and R7 have the same meaning as in formula Ia, X represents a halogen atom and R 'or a C2-alkyl residue.

The 4-hydroxydiphenyl ether of formula IIa described in connection with process 1) The alkylation of 4-cyclohexyloxyphenol as well as substituted benzyl alcohols of formula Hb can be carried out according to the various saturated or unsaturated formulas of formula Ilia resp. However, depending on the reactivity of the halide used in different solvents and at different temperatures, always using at least one mole of base in each case. Suitable solvents are, in particular, acetone, methyl ethyl ketone, cyclohexanone, 1,2-dimethoxyethane, tetrahydrofuran, dioxane, dialkyl ethers, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric acid triamide, sulfolane, and inert hydrocarbons such as toluene, hydrocarbons, such as. However, other solvents may be used. Alkali or alkaline earth metal hydroxides, alkali or alkaline earth metal carbonates, alkali or alkaline earth metal hydrides and alkali alkoxides can be used as the necessary bases or acid acceptors in this ether formation. Organic bases, for example triethylamine, pyridine, etc., can also be used as acid acceptors. Reaction temperatures range from -10 to 130 ° C, usually from 5 to 70 ° C (e.g. when using solvents such as dimethyl sulfoxide, dimethylformamide, dioxane, sulfolane, tetrahydrofuran, hexamethylphosphoric acid amide, 1,2-dimethoxyethane, etc.) or the solvent used. boiling point (eg when using ketones).

The conversion of the compounds of formula IaA to the corresponding epoxy derivatives according to method 2) is preferably carried out in inert solvents, suitably in a chlorinated hydrocarbon at a temperature between -25 ° C and room temperature, generally between -5 and + 5 ° C, with an epoxidizing agent such as e.g. with acid. By the term "peracid" is meant preferably lower peralkanoic acids having 1 to 6 carbon atoms, such as, for example, peracetic acid, as well as aromatic peracids, such as perbenzoic acid, monoperphthalic acid, but in particular 3-chloroperbenzoic acid. Epoxy derivatives of formula IaB can also be prepared via the corresponding halide hydrides, by cleavage of 7,539,389 hydrogen halides, conversion of the corresponding alkenyl ether of formula IaA with N-halosuccinimide, e.g. N-bromosuccinimide, in water and a solvent such as tetrahydrofuran, 1,2-dimethoxy , in a solvent of dioxane or tert-butanol in a homogeneous or heterogeneous phase at a temperature between -5 ° C and room temperature to bromohydrin and then treating the bromohydrin with an alkaline substance, e.g. alkane carbonate or alkali alkoxide, to give the desired epoxy derivative; alkali means in particular sodium or potassium.

The final products are further worked up and isolated according to known methods, e.g. by adding water or ice to the reaction mixture, then extracting as a suitable solvent, e.g. ether, washing the organic phase with e.g. dilute alkali or alkali carbonate, drying the solution over anhydrous sodium sulphate. After removal of the solvent, the remaining product can be purified, if necessary, by crystallization, vacuum distillation or chromatography on silica gel or alumina.

The coupling of a hydrogen halide, in particular hydrogen chloride or bromine, to the aliphatic double bond according to method 3) is preferably carried out by allowing the anhydrous hydrogen halide to act on the 4-alkenyloxydiphenyl ether, e.g. The 4-alkenyloxy-1-cyclohexyloxybenzene derivative in a suitable solvent such as, for example, chlorinated hydrocarbon, methanol, ethanol, another alcohol, dialkyl ether, glacial acetic acid, etc. The halogen-hydrogen coupling is carried out at -30 and + 25 ° C.

Isolation of the formed halide is carried out according to known methods, such as adding water to the reaction mixture, extracting as an organic solvent and removing excess hydrogen by neutralization with a weak base or washing with water, whereby the halide remaining after removal of the solvent can be further purified by crystallization, high pressure chromatography or chromatography.

Various reaction sequences can be used to prepare the epoxidized compounds of formula IaB, as described in Method 4) above: either etherify the hydroxyl group of 4-hydroxy-diphenyl ether or 4-cyclohexyloxy-phenol compounds according to said preparation methods first in the presence of a base of formula IV 59389 with an alkenyl halide and then converting the olefinic double bond in this alkenyl ether to an epoxide as described in method 2) and / or first epoxidizing the alkenyl halide of formula IV while protecting against moisture in a chlorinated hydrocarbon at a temperature between -25 ° C and room temperature, an epoxidizing agent such as e.g. peracid and this epoxy halide of formula V is then reacted with a 4-hydroxy diphenyl ether of formula IIa or 4-cyclohexyloxyphenol in the presence of an acid acceptor to give the final product.

According to process 5), the unsaturated araliphatic ethers of the formula IaA can be hydrogenated in a known manner to the saturated araliphatic ethers of the formula IaE, e.g. with catalytically generated hydrogen, conveniently at room temperature and at the boiling point of the reaction mixture. Suitable catalysts are preferably Raney nickel or a noble metal such as platinum or palladium. Suitable solvents are, in particular, acetic acid p-methyl and ethyl ester, dioxane or an alcohol, such as methanol, ethanol, etc.

Reactions in the above process 6) for the preparation of an active ingredient of formula IaF in which R 'represents a methoxy or ethoxy group are carried out under normal pressure and in anhydrous alcohol R'OH and optionally inert solvents and diluents, for example ethers such as tetrahydrofuran. in diethyl ether, 1,2-dimethyloxyethane, etc. As the mercury (II) salts, mercury (II) acetate and mercury (II) trifluoroacetate are preferably used. As the complex hydride, for example, MeBH 2 is used, where Me represents an alkali or alkaline earth metal atom. The reaction with the complex hydride takes place in the presence of alkali hydroxide and water. The reaction temperature is in the range of -10 to + 40 ° C, preferably in the range of 0 to + 25 ° C.

Process 7) is another process for the preparation of compounds of formula IaF in which R "represents a meoxy or ethoxy group, the etherification of the alcohol of formula VII taking place by reacting it with a halide R'X, depending on the reactivity of the halide used in different solvents and temperatures, always using at least one mole of said base.

The compounds prepared are obtained - as far as possible in principle - as mixtures of bis / trans isomers. The isomeric mixture may be separated into its isomeric forms, for example, by chromatographic separation methods, for example by adsorption with a resolving agent having selective adsorption activity, such as silica gel, alumina, followed by elution of the separated isomers with a suitable solvent such as diethyl ether or hexane.

Another chromatographic separation method is gas chromatography. In some cases, the isomer mixture may also be separated by fractional distillation or fractional crystallization.

The starting materials of the formulas IIa, lib, IIIa, mb, IV, R'OH and R'X are known compounds which can be prepared according to the methods described in the literature.

The compounds of the formulas Ia and Ib are suitable for controlling various pests. Above all, they are suitable for the control of insects and members of the Akarina sect.

The compounds of the formulas Ia and Ib are also characterized by low toxicity, in particular to warm-blooded animals, and also have considerable residual and environmental properties.

The compounds of the formula Ia and Ib are particularly suitable for controlling insects of the following families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrohocoridae, Reduviidae, Aphididae, Delphacidae, Diashacidae, Diashida , Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Mescidae, Calliphoridae, Trypetidae, Pulicidae and the following Acarides: Ixodidae, Tetracid

Significant advantages can be achieved with the compounds according to the invention against crop-destroying insects, as well as their use as storage protection.

The effect of the compounds of the formulas Ia and Ib can be considerably improved and applied, depending on the situation, by the addition of other insecticides and / or acaricides or insect attractants.

10 59389

The following active ingredients can be used, for example, as organophosphorus compounds, nitrophenols and derivatives, formamides, ureas, carbamates and chlorinated hydrocarbons.

The compounds of the formula Ia and Ib can be used as such or in combination with suitable carriers and / or additives. Suitable carriers and additives are solid or liquid and correspond to those generally used in the composition art, and are, for example, natural or regenerated substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders and / or fertilizers. The compounds of the formulas Ia and Ib can be used as dusts, emulsion concentrates, granules, dispersions, sprays, solutions or slurries using conventional compositions known per se to the person skilled in the art.

The substances according to the invention are prepared in a known manner by carefully mixing and / or grinding the active compounds of the formula I with suitable carriers, optionally with the addition of dispersants or solvents which are inert to the active compounds. The active ingredients can be and can be used in the following applications: Solid applications: Dusts, dispersants, granules, coating granules, impregnation granules and homogeneous granules. Liquid applications: (a) water-dispersible active substance concentrates: wettable powders, pastes, emulsions; (b) solutions.

For the preparation of solid applications (dusts, dispersants), the active ingredient is mixed with solid carriers. Suitable carriers are, for example, kaolin, talc, clay, loess, chalk, limestone, limestone, attapulgite, dolomite, diatomaceous earth, precipitated silicic acid, alkaline earth silicates, sodium and potassium aluminum silicates (feldspar and mica, magnesium sulphide, calcium sulphide, calcium ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products such as cereal flour, wood bark flour, wood flour, nut shell flour, cellulose flour, intermittent plant extracts, activated carbon, etc., activated carbon, etc., activated carbon, etc.

Granules can be prepared very simply by dissolving the active ingredient of formula Ia or Ib in an organic solvent and adding the solution thus obtained to a granulated mineral, e.g. attapulgite, silica, granalcium, bentonite, 11,5389, etc. and then evaporating the organic solvent.

Polymer granules can also be prepared by mixing the active ingredient of the formula I with polymerizable compounds (urea / formaldehyde; dicyandiamide / formaldehyde, melamine / formaldehyde and others), whereby a slight polymerization which does not affect the active ingredients is carried out and granulation is carried out. during gel formation. It is more preferable to impregnate ready-made, porous polymer granules (urea / formaldehyde, polyacrylonitriles, polyesters, and others) with a defined surface area and a preferred, predeterminable adsorption / desorption ratio, with active ingredients, e.g. in the form of their solutions (in low boiling point). remove the solvent. Such polymer granules can be applied in the form of microgranules with a vibration weight of preferably 300-600 g / l, also by means of sprayers. Killing can be carried out in large-use crop areas using aircraft.

Granules can also be prepared by combining the carrier with potency and additives and then reducing.

These compositions may additionally contain active ingredient stabilizing additives and / or nonionic, anionic and cationic agents which, for example, improve the adhesion of the active ingredient to plants and plant parts (adhesives and adhesives) and / or provide better wettability (wetting agents) and dispersibility ( dispersing agents). Examples are: olein / lime mixture, cellulose derivatives (methylcellulose, carboxymethylcellulose), hydroxyethylene glycol ethers of mono- and dialkylphenols with 5-15 ethylene oxide residues per molecule and 8-9 carbon atoms in the alkyl residue, lignosulphonic acid, lignosulphonic acid and alkaline earth metal salts, polyelylene glycol ethers (carboxylic waxes), fatty alcohol polyglycol ethers having 5 to 20 ethylene oxide residues in the molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, ethylene oxide, propylene oxide, formyl ethanaldehyde condensation products and latex products.

Water-dispersible active ingredient concentrates, i.e. wettable powders, pastes and emulsion concentrates, are substances which can be diluted with water to the desired concentration.

They consist of the active ingredient, carrier, possibly active ingredient stabilizing additives, surfactants 59389 12 and antifoams and possibly solvents. Wettable powders and pastes are obtained by mixing and grinding the active ingredient with dispersants and powdered carriers in a homogeneous manner. Suitable carriers are, for example, the substances mentioned above for solid uses. It is often advantageous to use mixtures of different carriers. Dispersants which can be used are, for example: condensation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde, naphthalene ore, condensation products of naphthalenesulphonic acids with phenol and formaldehyde; alcohol sulfates such as salts of sulfated hexadecanols, hepta-decanols, octadecanols and salts of sulfated fatty alcohol glycol ethers, sodium salt of oleylmethyl tauride, diterer ethylene glycols, dialkyl dilauryl alkali and fatty acid alkali chloride and fatty acid amide. Suitable antifoams are, for example, silicone oils.

The active ingredients are mixed, ground, sieved and compressed with the above-mentioned additives so that the grain size of the solids in the spray powder does not exceed 0.02-0.04 and in pastes does not exceed 0.03 mm. Dispersants, such as those mentioned in the previous paragraph, organic solvents and water are used to prepare emulsion concentrates and pastes. Examples of suitable solvents are alcohols, benzene, xylenes, toluene, dimethyl sulfoxide and mineral oil fractions boiling at 120-350 ° C. The solvents must be practically odorless and inert to the active substances.

The substances according to the invention can furthermore be used in the form of solutions. In this case, the active compound of the general formula Ia and Ib, i.e. several active compounds, is dissolved in suitable organic solvents, solvent mixtures or water. As organic solvents, aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkylnaphthalenes, mineral oil as such or as a mixture with each other can be used. The concentration of the active ingredient in the above-mentioned substances is 0.1 to 95%, in which case, when using an aircraft or some other suitable method of application, a concentration of 99.5%, i.e. almost pure active ingredient, can always be used.

13 59389

For example, the active compounds of the formula I can be formulated into the following compositions: Dusting agent: a) The following substances are used to prepare 5% and b) 2% dusting agent: a) 5 parts active ingredient 95 parts talc b) 2 parts active ingredient 1 part finely dispersed silicic acid 97 knows talc

The active ingredient is mixed and ground with carriers.

Granulate: The following substances are used to prepare 5% granulate: 5 parts active ingredient 0.25 parts epichlorohydrin 0.25 parts cetyl polyglycol ether 3.50 parts polyethylene glycol 91 parts kaolin (grain size 0.3-0.8 mm).

The active ingredient is mixed with epichlorohydrin and dissolved in 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto the kaolin, after which the acetone is evaporated off in vacuo.

Spray powder: a) 40%, b) and c) 25%, d) 10t spray powder is prepared using the following ingredients: a) 40 parts of active ingredient 5 parts of lignosulfonic acid sodium salt 54 parts of silicic acid; b) 25 parts of active ingredient 4.5 parts of calcium lignosulfonate 1.9 parts of Champagne chalk / hydroxyethylcellulose mixture (1: 1) 1.5 parts of sodium dibutyl naphthalene sulfonate 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin; c) 25 parts of active ingredient 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne chalk / hydroxyethylcellulose mixture (1: 1), 8.3 parts of sodium aluminum silicate, 16.5 parts of diatomaceous earth, 46 parts of kaolin; 14 5 9389 d) 10 parts of active ingredient 3 parts of a mixture of sodium salts of saturated fatty alcohol sulphates 5 parts of naphthalenesulphonic acid / formaldehyde condensate 82 parts of kaolin.

The active ingredients are thoroughly mixed with the additives in suitable mixers and ground using suitable mills and rollers. Spray powders are obtained which can be diluted with water to suspensions of the desired concentration.

Emulsifiable concentrates: a) The following substances are used to prepare 10% and b) 25% emulsifiable concentrate: a) 10 parts of active ingredient 3.4 parts of epoxidized vegetable oil, 13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ethers and alkylaryl -calcium salt, 40 parts of dimethylformamide, 43.2 parts of xylene; b) 25 parts of active ingredient, 2.5 parts of epoxidized vegetable oil, 10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture, 5 parts of dimethylformamide and 57.5 parts of xylene.

Emulsions of the desired concentration can be prepared from such concentrates by dilution with water.

Spray: The following ingredients are used to prepare 5% spray: 5 parts active ingredient 1 part epichlorohydrin, 94 parts petrol (boiling range 160-190 ° C);

Example 1:

To a solution of 19.2 g of 4-cyclohexyloxyphenol and 16.4 g of 1-bromo-3-methyl-2-pentene in 150 ml of 1,2-dimethoxyethane was added dropwise at room temperature with stirring within 6 hours. a solution of 6.4 g of about 90% potassium hydroxide in 90 ml abs. ethanol. After the addition of the base, stirring was continued for 15 hours at room temperature.

59389 15 Further treated by filtration off the precipitated potassium bromide, the filtrate was evaporated in vacuo, the residue was dissolved in hexane, washed three times with ice-cold 10% potassium hydroxide and then with water until neutral. After drying the organic phase over sodium sulfate, filtration and complete removal of the solvent, pure 1-cyclohexyloxy-4- (3-methyl-2,2-pentenyl-1-oxy) benzene was obtained. n ^: 1.5265.

Example 2:

To a solution of 13.7 g of 1-cyclohexyloxy-4- (3-methyl-2-pentenyl-1-oxy) -benzene in 150 ml of methylene chloride was added dropwise at -5 ° C over about 5 hours a solution of was 10.3 g of 84% 3-chloroperbenzoic acid in 100 ml of methylene chloride-diethyl ether (9: 1). The temperature was maintained at 0 overnight, then n-hexane was added to the reaction mixture, washed three times with ice-cold water. % potassium hydroxide followed by water until neutral. After drying the organic solution over sodium sulfate, the solvent was removed in vacuo and the oily residue was purified by chromatography on silica gel (eluent: ether / hexane 1: 4) to give pure 1-cyclohexyloxy-4- (2,3-epoxy-3-methyl-pentyl-1). -oxy) -benzene, n ^ 20: 1.5180.

Example 3: To a suspension cooled to -2 ° C with 12.7 g of powdered mercuric acetate in 80 ml of abs. a solution of 10.7 g of 1 - ((p-phenoxy) -phenoxy} -3-methyl-2-pentene in 50 ml of absolute methanol was added over 10 minutes with vigorous stirring, 30 minutes after the addition of the alkene was added. to the reaction mixture at -2 ° C 40 ml of 3N aqueous sodium hydroxide solution and then immediately 40 ml of 0.5 molar sodium hydride solution in 3N sodium hydroxide, the temperature rising to about 25 ° C.

It was then stirred for a further 2 hours at 15-20 ° C. The reaction mixture was further treated by decanting off the separated mercury, the supernatant solution was poured into 500 ml of saturated sodium chloride solution and extracted four times with diethyl ether. The combined ether solutions were washed with brine, dried over sodium sulfate and the solvent removed completely in vacuo, the oily residue was further purified by chromatography on silica gel (eluent: diethyl ether / hexane 1: 5) to give pure 1 - ((p-enoxy) -phenoxy) -3-methyl -methoxypentane, η ^ 20: 1.5440.

16 59389

Example 4:

To a mixture of 28 g of 4-hydroxydiphenyl ether, 150 ml of acetone, 26.6 g of anhydrous powdered potassium carbonate and 50 ml of hexamethylphosphoric triamide was added dropwise at 55 ° C over 30 minutes while stirring 22 g of 1,3-dichloropropene and the mixture was kept for a further 18 hours at reflux temperature. The reaction mixture was then poured into about 1.5 liters of ice water and extracted repeatedly with diethyl ether. The combined ether solutions were washed four times with 10% potassium hydroxide and repeatedly saturated sodium chloride solution until neutral. After drying the ether solution over sodium sulfate, the solvent was completely removed in vacuo to give pure 3 - ((p-hydroxy) -N-hydroxy-1-chloro-1-propylene, nD20: 1.5819.

i. 3.2 g of 5 - ((p-enoxy) -phenoxy} -3-methyl-3-penten-1-yne (prepared from 4-hydroxydiphenyl ether and 1-bromo-3-methyl-2-penten-1-yne potassium carbonate nD20: 1.5814) was dissolved in 140 ml of 95% ethanol and hydrogenated with 1.3 g of Lindlar catalyst with the addition of 0.5 g of quinoline under reduced pressure and at room temperature until the absorption of hydrogen was complete. by distilling off ethanol from the filtrate, dissolving the residue in ether-hexane (1: 2) and washing this solution repeatedly with ice-cold N-hydrochloric acid and then with water until neutral, and after drying the ether solution over sodium sulfate, the solvent was completely removed and the oily 5-p-phenoxy) phenoxy ) -3-methyl-1,3-pentadiene was purified by chromatography on silica gel (eluent: ether-hexane 1: 4) n-20: 1.5710.

Example 6:

To a solution of 18.6 g of 4-hydroxydiphenyl ether in 125 ml of dimethyl sulfoxide was added and dissolved portionwise at about 10 ° C, 6.3 g of 90% ground potassium hydroxide. To this solution, 17.8 g of 1-bromo-4-methyl-3-hexene was added dropwise over 3 hours while stirring at 10-15 ° C. After addition of the halide, stirring was continued for 20 hours at room temperature. Further work-up by pouring the reaction mixture into about 1 liter of ice water and repeatedly extracting the mixture with diethyl ether. The combined ether phases were washed twice with water, four times with 20% aqueous potassium hydroxide and finally with 59389 water to neutral. After drying the ether phase over sodium sulfate, the solvent was distilled off and the residual oily product was purified by chromatography on silica gel (eluent: ether-hexane 1: 5) to give pure 1 - ((p-phenoxy) -phenoxy) -4-methyl-3 -hekseeniä; n ^ 20: 1.5580.

In a manner similar to that described in Example 1-6, the following compounds were prepared: ____

Active substance Physical values

/ Vq ^ A

I I / ch3 \ / \ Z-0 “CH2-CH = Cs nD20: 1.5667 a CH, 3 t ί ^ ° Ί ^] ch5

m.p .: 40-41 ° C

0 CH, CH- I I I 3 yy ^ v> - (> - CH2-CH = C-CH2-CH3 nD2O: 1.5589 i ^ Hii λ

\ y \ y ~ {Sul.p; 50-52 ° C

0 CH2-CH3 CH, λ I I I 3 p ^^ - 0-CH2-CH2-C-CH3 nD2O: 1.5399 ch3

No N-N

x / λΑ-οη2 ^ \ vo. lf5640 -

CH3 CH3 I

··!

59389 I

Physical:

Active ingredient values. , i

• J

(rf) / 1 I

^ ^ / - O-CH2-CH == C ^ nD20: 1.5770 -k CH ^ OH- nu III 3 xCH3 k ^ / k5 ^ /> - O-CH-CH2-CH2-CH = C 1.5436 in CH 2 CH, no II! 3 / ch3 {1 H-CH 2 -CH 2 -Ct-nD 2 O: 1.5413 ^ CH ~ 3 fV | 1.5453

CH, * V

3 I1 'f <r r ^ Vaf ^ CH- I j I 3

mp-O-CH2-CH-C-CeCH m.p. 45-47 ° C

j i I - μ i 5 9389 19 -, - a.

Physical

Active substance values fYf \ ^ 9 '^ /' - O-OHg-CH2 m.p .: 31-3? 0

Cl / \ & - / \ / \

1 1 H

m.p .: 55-57 C

S \ o-S \ / \ 1 I H o

\ s ^ / CH2 ~ CH - / \ y) m.p. 82-84 ° C

/ Ychf ^ N Cl

III

1 H-O 2 -CH 2 -CH =: CH n D 2 O: 1.5887

Cl .Ί t 2o 5 9 3 8 9

Physical)

Active substance values O,

^^ - 0-0Η2-0Η = 0Η-0Η3 m.p .: 39-41 C J

CH, "II I3 / hk ^ y-O-CH-CH2-CH2-ClI = C ^ nD20: 1.5364 ch2-ch3 CH, CH, III 3 I j ^ y> ^ / - 0-0Η-0Η2 -0Η2-0Η2-σ-0σΗ3 nD20: 1.5350 ch2-cii3 59389

Physical

Active ingredient values

/ Yo ^ N

I I

O-CH2-CH2-CH2-C = CH nD20: 1> 5652 CH, II I 3 ls ^ y-OY: H2-CH2 - ^ - 0 - <! H2-CH5 n ^ PO: 1, 5444

11 I

CH

Ani λ

/? -O-O-CH2-CH = Cn m.p. 67-68 ° C

: 1 ch3

/ ky / CH 2 -CH = GH-C 1 m.p .: 35 ° C

Λ cis / trans nD20: 1.5905 (subcooled melt) CH,

Il I 3 1N, N-O-O-CH2-CH2-Clf-OCH5 nD2O: 1.5450 22 5 5389

Fysikaalisetl

Active substance values CH, I I I 3 \ / - O-CH2-CH = C-CH2-CH5 nD2O: 1.5536 y

V

.V

r * · I ^ Vo-f ^ 1 OH, III 5 CH / ^ O-CH2-CH2-O-OCH3 nD2O: 1.5385 ch2-ch3 II κ0Η5 Ο, Η Λ / ^ yO-CH2-OH ^ nD20: 1.5662 25 Cl / Vo-A CH, „III 3 / 1¾ yy-O-CH2-CH = C-CH2-CH nD2O: 1.5475 CH3 CH,„ „III 3 / oh3 ^ y-O-CH -CH 2 -CH n D 2 O: 1.5335, CH, 5 k _____1___1>; t

X

> 23 59389 "». Physical

Active substance values CH, III 5 ^ / - 0 ~ OH2-CH2-C-OCH2CH3 nD2O: 1.5569 ch3 CH3 CH -GIL, 2 ^. * »Ch III 3 h ^ / - σΗ-σ-0Η2-0Η =: \ ^ nD20: 1.5602 t CH_ CH_ III 3 I 3 '\ y ^ y-CH-O-CH2 -CH = C-CH 2 H 3 n D 2 O: 1.5468 (1-

-I

r · _ 1 '! —— ------- 1-1

V

24 59389

Physical

Active substance values ___ CH,

Il I 3 np20: 1.0360 CH2-CH3 / Y & - / N 9h3 9¾:

I l 20 I

1 ^ ^ 1-O-CH-C ^ -C-OC ^ n *; 1.5260 1 6¾ CH j 11. | 3

i C2II S ^ y-O-CH2-GH = C-CH2-CH3 Sul.p. : 55-57 ° C

GH

I I I 3 n20 · 1 5347 o2H5 (Ay ^ / - ^ 2 ^ ¾- ^ 00¾ D '' CH2-CH2

| . I C 10 -CH 2 -CH 2 CHCl Melting point: 62-64 ° C

j c2H5 <r ^ 2 j

I I

I I

fYfX R t °: 1.5760 25 59389

Active substance Physical values - 20 I H V · ^ 5558 lVLo-CH2'0H2-j \ / 10CH-.

P

CH- II J J 20

Lii-O-CH2 -Cl2-CH2 -C-OCH ^ nD: 1.5374 ch3 ch »i 20. 20., 9ft nD 1.5628 ♦ Cl3 j i I n30; 1.5774 μm {^ CH2 “CH: = CH“ C1 d CH ^ 26 59389

Example 7:

Inhibitory effect on Dysdercus fasciatus larvae 10 Dysdercus fasciatus larvae were treated topically with acetone active substance solutions 8-10 days before encapsulation. The larvae were then maintained at 28 ° C and 80-90% relative humidity. The animals were fed pre-swollen cottonseed meal. After about 10 days, i.e., as soon as the control animals were fully adult encapsulated, the experimental animals were examined against the number of normal adult animals. The compounds of Examples 1-6 had good potency in this experiment.

Example 8:

Inhibitory effect in the gas phase To Spodoptera littoralis eggs 40 mg of active substance was added to a 130 ml ground flask and to another 175 ml flask 100 Spodoptera littoralis eggs were added. Both flasks were connected with a spacer and allowed to stand at 25 ° C.

The inhibitory effect was evaluated after 5-6 days. The compounds of Examples 1-6 had a good effect in this experiment.

27 5 9 3 8 9

Comparative test I

Compounds 1-14 shown in Table 1 below were subjected to biological experimental methods A and B. Experimental methods A and B were performed as described below, while conducting parallel experiments with untreated controls with no effect.

Table 1 tested compounds / \ / \ / \ Cl 1 i !! 'Ϊ. Lei V V v v v / vvV 'according to the invention of this / \ / \ / \ Cl 2 ΐ l * T l * I .A.A / \ 3 I II I II I · v VVV \ # / vV \

4 i il i il I

v VVviv / \ / V \ | ,

5 i li i il II

v VyV \ A

28 s 93 8 9

Table 1 (cont.)

tested compounds no. J

s \ / K y \ • · · ·

6 I II I II

• · · · · ·

\ / \ / v / \ S

'·' · O · Cl • O · of this _ S \ '\ * \? C2H5 invention

7 I II I II I

\ /% e / \ 0 / \ /] \ compliant with • n · aAa • · · ·

8 I II I II

• · · · · · ^ y v ^ y / \ / ° \ y \ • · · ·

9 I I I II

X Wv

DE-OS

s \ s 2 114 257 • · 10 I II rt · compliant ^ \ / \ s \ • · · ·

l \ I II

'V \ o / \ * y \ A / \ • · · ·

11 I I I II

• · · · X v w

s \ A A

• · · ·

12 I I I II

X

29 59389

Table 1 (cont.) * Compounds tested

Well. J

/ \ / 13 * '* n

K

I / \ i n

V Wv DE- ° S

According to 2,114,257 / \ / ° \ / \ • · · ·

14 I I I II

· · · I \ ^ \ ** · coo · /

Test method

Topical effect on Tenebrio Molitor enclosures

A 0.5% solution of test compounds was prepared. Using a micropipette, 10 μm of this solution was pipetted into each Tenebrio housing, corresponding to 5 μπι of active substance per housing. For each active ingredient, 20 cases of Tenebrio, up to one day old, were treated. After treatment, the housings were placed on a filter paper in an unsupported petri dish and kept there for about 10-12 days at 27 ° C and 70% relative humidity.

After the untreated control animals had left their casings as adults, experimental animals developed from housings treated as described above were examined for the number of normally developed adults, adultoids, and special forms. Evaluation was performed by determining the percentage of normal normal cultures compared to untreated controls.

100% effect = no normal dots at all 0% effect = only normal dults.

30 59389

Test method B

Effect on Aedes aegypti larvae

An amount of 0.1% acetone solution of the active substance to be tested was added by pipette to the surface of a 150 ml volume of water in the beaker to give an active substance concentration of 1 ppm. After evaporation of the acetone, 40 two-day-old Aedes aegypti larvae were placed in each beaker filled with the active ingredient. Powdered feed was added to the goblets after which they were covered with a copper gauze lid.

Thereafter, potential mortality was regularly determined every other day, and disturbances in encapsulation, metamorphosis, and hatching were further assessed. After the untreated control animals hatched as adults, experimental animals treated as described above were examined and estimates were based on the percentage of normal cultures developed relative to the control batch.

100% effect = complete disappearance of the adult population, i.e. no mosquitoes at all.

0% effect = no reduction in the adult population. Score:

Table 2 shows the results obtained from experiments A and B, expressed as% effects of the tested compounds:

Table 2 3 '59389

Compound potency as% no. - -

test method A test method B

1 55 20 2 45 0 3 100 100 4 100 45 5 100 100 6 85 90 7 100 100 8 100 100 9 0 20 10 0 0 11 10 0 12 0 0 13 0 0 14 0 25 The compounds 1-8 of the present invention have substantially 100% effect against tested pests. In contrast, compounds 9-14 known from DE-OS 2 114 257 are completely ineffective, in fact ineffective.

32 59389

Comparative test II

Compounds 1-5 shown in Table 1 below are subjected to biological experimental methods A, B, and C. Experimental methods A, B, and C were performed as follows, with parallel experiments performed on untreated control animals that showed no effect.

Table 1 compound tested compounds no l • Cl it --------- (—- J-r--

G

•B

| 1 || * [n (N E> 1

Test methods A) Contact effect Dysdercus fasciatus larvae

An aliquot of a 0.1% acetone solution of the active substance to be tested, corresponding to 10 mg / ml of active substance, was pipetted into an aluminum dish and distributed evenly. After evaporation of the acetone, 10 Dysdercus fasciatus stage 5 larval feeds and 33 59389 moist cotton wool were placed on a treated surface. The dish was then covered with a sieve lid.

Approximately 10 days later, i.e., as soon as the untreated control animals had hatched as adults, experimental animals developed from larvae treated as described above were examined for the number of normal dulls developed.

Judgment:

Value 5 = 100% lethal special forms (dead in shells and special larvae)

Value 4 = lethal special forms and non-lethal special forms (adultoids)

Value 3 = lethal special forms, no lethal special forms and normal dults

Value 2 = no lethal special shapes and normal dults Value 1 = 100% normal dults.

B) Contact effect Tenebrio Molitor case

An aliquot of a 0.1% solution of the active substance to be tested in acetone-2, corresponding to an amount of 10 mg / ml of active substance, was pipetted into an aluminum dish and distributed evenly. After evaporation of the acetone, 10 shells of the newly formed Tenebrio Molitor were placed on the treated surface. The dish was then covered with a sieve lid.

After the untreated control animals left their enclosures as adults, experimental animals evolved from the enclosures treated as described above were determined for the number of normal cultures developed.

Judgment:

Value 5 = 100% lethal special forms (special cases and adulttoids)

Value 4 = lethal special forms and non-lethal special forms (adultoids)

Value 3 = lethal special forms, no lethal special forms and normal dults

Value 2 = no lethal special shapes and normal dults Value 1 = 100% normal dults.

C) Effect on Aädes aegypti larvae

An amount of a 0.1% solution of the active substance to be tested was added by pipette to the surface of a 150 ml volume of water in the beaker to give an active substance concentration of 5 ppm. After evaporation of the acetone, about 20 two-day-old Aedes aegypti larvae were placed in each beaker filled with the active ingredient solution. Powdered feed was added to the cups, after which 1 'I: 34 59389 they were covered with a copper gauze lid.

After the untreated control animals hatched as adults, the experimental animals treated as described above were examined and the percentage of normal normal cultures developed compared to the control animals was determined.

Judgment;

Value 5 = 100% reduction in the adult population (100% effect)

Value 4 = 75-99% reduction in the adult population

Value 3 = 50-74% reduction in the adult population

Value 1 = <50% reduction in the adult population (0% effect).

Score:

The evaluation is done by giving the values (1-5) where the value 5 means that no normal dults have been formed, i.e. the maximum effect has been reached. A value of 1 means no effect on normal development at all, i.e. the compound is ineffective.

The following Table 2 shows the results obtained:

Table 2

Compound Well test method

ABC

power rating pin Γ 5 5 w 2 5 5 5 3 4 5 3 4 5 5 5 5 14 1

Thus, each of the compounds 1-4 according to this application has a superior insecticidal activity compared to the compound 5 according to FR patent 2,086,145.

Claims (10)

35 59389