DEG0008796MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: May 7, 1952 Admitted to October 11, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 451 GROUP 3oi INTERNAT. CLASS A 01 η——

G 8796 IVa / 451

Dr. Franz Häfliger, Basel, and Dr. Emil Girod, Riehen, Basel (Switzerland)

have been named as inventors

J. R. Geigy A.-G., Basel (Switzerland)

Representative: Dr. F. Zumstein, patent attorney, Munich .2

Control of pests, especially mites

The priority of registrations in Switzerland from May 8, 19S1 and January 11, 1952 in Great Britain from November 26, 1951 is claimed

Monoether of a, a-bis (4-chloro-phenyl) -ethylene glycol of the general formula

Cl

OH

'in which R denotes a low molecular weight alkyl or alkenyl radical have not yet become known.

As has now been found, such compounds have a very good acaricidal activity and are outstandingly suitable as active ingredients for the production of pesticides, in particular those for combating mites. The new compounds are strongly superior to bis (p-chlorophenoxy) methane, 2,2-bis (p-chlorophenyl) -i, i-dichloroethane and bis (5-chloro-2-oxyphenylmethane in acaricidal activity, while et compared with the process known from USA. Patent 2,430,586, a-bis (p-chlorophenyl) -methylcarbinol have the advantage of lower volatility. from said patent it is clear that only the a, a-bis - (p-chlorophenyl) -methylcarbinol is highly effective, while the higher homologues, especially

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special also the corresponding ethyl carbinol, look much weaker. In contrast, it was surprising in the case of those produced according to the invention Compounds did not find a similar decrease in activity, e.g. B. also the ethyl ether is extremely effective.

When mixed with dichloro-diphenyl-trichloroethane, the new compounds increase the effectiveness of the the latter, namely z. B. also against flies,

ίο resistant to pure dichlorodiphenyl trichloroethane are.

The new compounds can be obtained by reacting a functional derivative, e.g. B. one Esters, halides or anhydrides, or a salt of an etherified oxyacetic acid of the general type formula

RO-CH ₂ -COOH

wherein R has the meaning given above, with 2 moles of an organometallic 4-chlorophenyl compound getting produced.

For example, an alkyl ester of an etherified oxyacetic acid according to the definition is used 4-chlorophenyl magnesium bromide or iodide the Grignard method.

In modification of the aforementioned method, you can also use a functional derivative or a Salt of an etherified oxyacetic acid of the general formula

RO-CH ₂ -COOH,

where R has the meaning given above, here in particular also the nitrile, initially by reaction with a molecule of an organometallic 4-chlorophenyl compound into a ketone of the general formula

CH ₉ -OR

Cl

> —CO

and transfer this ketone with another Reacting a molecule of an organometallic 4-chlorophenyl compound. As an organometallic compound can in both stages z. B. 4-chlorophenyl magnesium bromide Find use.

The esters preferably used as starting materials in the former process are easy to manufacture, e.g. B.; by reacting chloroacetic acid esters or bromoacetic acid esters with sodium alcoholates of the general formula

R-O-Na.

Methoxy, ethoxy, propoxy, butoxy and isobutoxy acetic acid esters as well as methoxy-, ethoxy-, propoxy- and isobutoxy-acetic acid nitrile are already in .Beilstein's handbook of organic Chemie, Vol. III, listed. Isopropoxy- and sec-butoxy-acetic acid ethyl ester were described in the USA patent 1 759 331. The allyloxy, methallyloxy, 2-butenyloxy and 3-butenyloxyacetic acid esters can in an analogous manner or by esterification of the corresponding acids, some of which are described in US Pat. No. 2,406,590 are to be produced.

Instead of one or both chlorophenyl radicals in compounds with an ether group that is already present introduce, you can also α, a-bis (4-chlorophenyl) -ethylene glycol or its functional derivatives (with respect to the ^ -hydroxyl group) with implement low molecular weight alcohols or their functional derivatives. Under functional Derivatives of the glycol mentioned are, for example, the / J-mono-alkali compounds, the inner one Ether or the ^ -halohydrins understood, under the functional derivatives of the low molecular weight Alcohols their derivatives serving as alkylating agents or also, e.g. B. to implement with the eligible glycol halohydrins, the alkali metal alcoholates.

For example, you can 'the a, a-bis (4-chlorophenyl) ethylene glycol with alkyl halides, especially alkyl iodides or bromides, in the presence of alkali-releasing agents, such as. B. sodium hydride, or a, a-bis- (4-chlorophenyl) - ethylene glycol - / J-chlorohydrin (= a, aB-is- (4-chlorophenyl) -a-oxy - /? - chloroethane) with low molecular weight sodium alcoholates implement.

The compounds required as starting materials can be, for. B. obtained from a, a-bis (4-chlorophenyl) -ethylene by this z. B. by oxidation with potassium permanganate or with hydrogen peroxide according to conventional methods in the a, a-bis (4-chlorophenyl) -ethylene glycol, or by adding hypochlorous, hypobromous or iodine acid to the ethylene bond to the a, a - Bis - (4 - chlorophenyl) -ethylene glycol-ß-halohydrins directly produces. The / J-chlorohydrin is e.g. B. also by reacting ω, 4 - dichloroacetophenone or ethyl chloroacetate with 1 or 2 moles of an organometallic 4-chlorophenyl compound, e.g. B. 4-chlorophenylmagnesium bromide accessible by Grignard, also the a, a-bis- (4-chlorophenyl) -ethylene glycol in an analogous way by reacting glycolic acid esters with at least 3 moles of 4-chlorophenylmagnesium bromide, or by reducing 4, 4'-dichlorobenzilic acid esters .

Suitable alkyl halides for the reaction are, for example, methyl iodide, methyl bromide, Ethyl iodide, ethyl bromide, propyl and isopropyl bromide, Called allyl iodide, allyl bromide, allyl chloride, η-butyl, isobutyl and sec-butyl bromide, as low molecular weight sodium alcoholates, for. B. those of methanol, ethanol, n-propanol and isopropanol as well as n-butanol, isobutanol and sec. Butanol into consideration.

For the production of the compounds mentioned, no Protection desired.

The forms of application of the new compounds depend entirely on the intended use. The active compounds can be used as such or in suitable solvents or diluents, in the form of emulsions or dispersions, on suitable solid carriers, in the usual way

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or synthetic soaps, detergents, dispersants, etc., but also together with others acaricidal, insecticidal, ovicidal, fungicidal and / or bactericidal compounds or together be used with ineffective aggregates.

As solid carriers, which are suitable for the production of powdery preparations, There are various inert porous and powdery distribution agents, inorganic or organic Nature in question, such as B. tricalcium phosphate calcium carbonate in the form of whiting chalk or ground limestone, kaolin, bolus, bentonite, talc, magnesia usta, kieselguhr, boric acid, but also cork flour, wood flour and other fine, powdery materials of vegetable origin are suitable carriers. The active component is mixed with these carriers, z. B. by grinding together; or the inert carrier is impregnated with a solution of the active component in a volatile solvent and then removes the solvent by heating or by suction under reduced pressure. By adding network and / or dispersants, such pulverulent preparations can easily be mixed with water Make wettable, so that you get suspended suspensions, which as a spray in the Plant protection are applicable.

Suitable inert solvents for the production of liquid preparations must not be highly flammable and should be as odorless as possible and, if handled properly, as non-toxic for humans and animals as possible. Furthermore, they must not change the active component and also not corrode the materials of the storage containers. Suitable solvents for this are: on the one hand high-boiling oils, ζ. Β. of vegetable, animal or mineral origin, such as castor oil, paraffin oil and the like; on the other hand, lower boiling hydrocarbons with a flash point of at least 30 ⁰ , such as. B. hydrogenated naphthalenes, alkylated naphthalenes, solvent naphtha, petroleum distillates of the kerosene type, etc. Of course, solvent mixtures can also be used. Solutions are prepared in the usual way, if appropriate with the aid of solubilizers.

.50 Other liquid forms of application consist of emulsions or suspensions of the active Component in water or suitable inert solvents, or from concentrates for preparation such emulsions that are immediately available at the point of use by diluting to the desired Concentration can be adjusted. For this purpose, the active component is mixed with a dispersing or emulsifying agent. One can also use the active component in a suitable one Dissolve or distribute inert solvents and simultaneously or subsequently with a dispersing agent or mix emulsifiers. By diluting such a concentrate, e.g. B. with Water, ready-to-use emulsions or suspensions are obtained. With a suitable concentration and mixing ratio of active component, emulsifier and water can be made clear, perfect obtain stable, aqueous solutions.

Various capillary-active substances with anionic substances are used as dispersants or emulsifiers. or cation-active or non-ionic component in question. Examples are natural ones or synthetic soaps, turkey red oil, fatty alcohol sulfonates, sulfated fats and fatty acid esters etc., also higher molecular quaternary ammonium compounds, as well as condensation products from aliphatic or araliphatic compounds and ethylene oxide, z. B. the condensation product of stearic alcohol and ethylene oxide.

The active component for its part can consist of one or more compounds of the defined formula. It can also be used in combination with other acaricidal, insecticidal, ovicidal, fungicidal or bactericidal substances. Examples include: benzyl benzoate, dimethylthianthrene, phtalonitrile, a, ct-bis (chlorophenyl) - β, β, β - trichloroethane or -ß, ß-ai chloroethane, 1, 2, 4, 5, 6, 7, 10 , 10 - Octachlor-4, 7-methylen-4, 7, 8, 9-tetrahydrohydrindene, diethyl-p-nitro-phenyl-thiophosphate, 5, 5-dimethyldihydroresorcinol - dimethylcarbamate, dinitrocresol, nitrated naphthylamines, cross-silver compounds or inorganic substances such as copper compounds, sublimate, sulfur, etc. In this way, combination preparations with a wide range of effects are obtained.

It is also possible to use the active component in the form of aerosols. j For this purpose, the active component is in a solvent such as fluorochloromethane, which is used in Boils, dissolved or dispersed, possibly below atmospheric pressure below room temperature Use of suitable inert solvents as carrier liquid. How to get printing solutions which deliver aerosols when sprayed, which are particularly useful for combating mites in in closed rooms, in greenhouses, in grain silos and other storage rooms.

As additional additives that can be added to the above-mentioned application forms, the following should be mentioned: adhesives such as casein, fatty acid salts, glue, resins, fats, protein breakdown products; Wetting agents, solubilizers, dyes, odorous substances, in the case of powdered preparations also dust binding agents etc.

It is entirely up to you, through the selection of the various distribution agents and additives, the composition of the agent and its composition to give dependent properties that make them suitable for the specific purpose. For example, dipping agents, sprays, sprays in the form of emulsions or Suspensions, generally emulsions and suspensions and concentrates for their preparation produce. The agents mentioned are mostly in the form of liquid preparations. Of solid preparations

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enumerated: dusts, dry powder, grit etc., but also solid soap preparations that can be used as fittings.

The mite control agents are used according to the usual application methods. The mites or the goods to be treated or to be protected from attack by mites, in particular Plants, but e.g. B. also roots, tubers, drugs, textiles, packaging materials, grain, dried fruits, food and feed stocks, seeds, wood, leather, hides, Paper, furs, hair, feathers, objects of all kinds, wallpaper, walls, floors, can be used with the active Component or treated with the means described, be it by dusting, sprinkling, Spraying, brushing, rubbing in, impregnating, placing in or surrounding with. one the active substance as smoke, steam or aerosol containing atmosphere, or otherwise suitable Measures.

In the further examples below, various embodiments of the mite control agents are intended and their use are described.

example 1

Up to 5 parts of a, a-bis- (4-chlorophenyl) - /? - ethoxyethanol are triturated with 99 to 95 parts of talc and ground until the active ingredient is evenly distributed on the carrier. The dust produced in this way shows a good effect against adults and larvae of red spiders, e.g. B-. Paratetranychus pilosus, Tetranychus urticae etc., but it can also be used to control ticks. If a mixture of talc, kaolin and ground limestone is used as the carrier material, products with a similar effect are obtained.

B e i s ρ i e 1 2

10 parts of et, a-bis (4-chlorophenyl) - /? - 'ethoxy-ethanol are ground homogeneously with 80 parts of carrier material and 10 parts of auxiliaries. When Carriers come into consideration: kaolin, bentonite, chalk etc. B. sulphite waste liquor, Sodium dibutylnaphthalenesulfonate and other wetting agents and adhesives are used will. Such a suspension spray is used at 0.1% to 1% strength and shows a good effect against adults and larvae of red spiders.

Example 3

Suspension sprays with insecticidal and acaricidal action are obtained if you mix 25 to 50 parts of dichlorodiphenyltrichloroethane with S to 10 parts of a, a-Bi'S- (4-chlorophenyl) - /? - methoxy-ethanol and a porous, absorbent, voluminous carrier, e.g. B. bentonite, kaolin or precipitated magnesium carbonate, intimately mixed. AIs additives in amounts of 5 to 10 parts are sulfite waste liquor, blood albumin and the sodium salt of dibutylnaphthalenesulfonic acid. Applied in a concentration of 0.05 to 0.5%, these sprays show a good effect against adults and larvae of red spiders and at the same time have an insecticidal effect.

Example 4

10 to 25 parts of α, α-bis (4-chlorophenyl) - /? - ethoxyethanol are in 85 to 65 parts of a mixture of diacetone alcohol and xylene in a ratio of 1: 2 dissolved and mixed with 5 to 10 parts of an emulsifier. As an emulsifier z. B. a high molecular weight Ethylene oxide condensation product in question.

This mixture can be emulsified in water and has an application concentration of 0.1 to ι% good effect against adults and larvae of the red spiders. Replace the solvent with 10 to 30 parts of mineral oil, one obtains a means of increased acaricidal and ovicidal action

sameness. _.

Example 5

0.1 part of a, a-bis- (4-chlorophenyl) - /? - ethoxy-ethanol is dissolved in 5 to 10 parts of mineral oil and 94.9 to 89.9 parts of petroleum with a boiling point of 180 to 220 ° and results in a spray with acaricidal effect. Example 6

Part a, a-bis (4-chlorophenyl) - /? - methoxy-ethanol is ground homogeneously with 5 parts of dichlorodiphenyl-trichloroethane and 94 parts of talc. This mixture, as well as similar combinations, e.g. B. with 5, 5-dimethyl-dihydroresorcindimethylcarbamat or other contact insecticides or fungicides are ideal for the simultaneous control of the red spider, harmful insects and fungal diseases.

Example 7

20 to 25 parts of dichlorodiphenyl trichloroethane and 4 to 6 parts of a, a-bis (4-chlorophenyl) - _/ ß-ethoxyethanol are dissolved in 71 to 59 parts of a mixture of diacetone alcohol and xylene in a ratio of 1: 2 and with 5 to 10 parts of an emulsifier of the type of ethylene oxide condensation products mixed. The solution obtained can be emulsified and, in the application concentration of 0.3 to 0.5 "/ o, has a good effect against red spiders and at the same time excellent insecticidal effectiveness.

Claims (1)

PATENT CLAIM: Pesticides, especially for combating mites, characterized by a content of compounds of the general formula CH ₂ -OR - Cl OH wherein R is a low molecular weight alkyl or Alkertyl radical means, optionally in combination with suitable carriers and distribution agents .. © 609 657 / 4.63 10.56