DE2738873A1 - HERBICIDES AND ALGICIDES - Google Patents

Description

PFENNINO MAAS

MEtNIQ - LEMKE - Mockery

& CHLEISSHEIMEHSTR. 299

Θ000 MUNICH 40

X-4002

Eli Lilly and Company, Indianapolis, Indiana, V. St. A. Herbicides and algicides

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X-

(O

It is known (Lacefield et al., J. Med. Chem., Vol. 14, pp. (1971)) that biphenylyloxyalkylamxne is able to inhibit ADP-induced platelet aggregation in vitro. However, there is none Evidence that by modifying the biphenylyl structure valuable new compounds are obtained, nor that these compounds would be effective as water herbicides or algicides.

In U.S. Patent 3,449,418, the manufacture of some of those is in accordance with the invention described compounds used and stated that they are useful as pharmaceuticals, but is found therein there is no indication that the compounds are herbicidal or algicidal could be effective.

The invention relates to new agents for controlling aquatic weeds or algae. These remedies contain a compound the formula

—Ο -

CHa I.

R ¹ I -N - R ^s

- —η

R ¹

CH N - R '

where mean:

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both remainders R,

both leftovers

both leftovers

which are identical to one another »hydrogen, halogen or a nitro, methoxy or C ₁ -C ₄ alkyl group,

which are equal to each other. Hydrogen or a C ₁ -C ₃ alkyl group or the group -CH ₂ CH ₂ OH,

which are identical to one another, hydrogen or a C ₁ -C alkyl, benzyl or cyclohexyl group or the group -CH ₂ CH ₂ OH,

the value 0 or 1,

the value 2, 3 or 4 if η has the value 0 and the value 2 if η has the value 1,

one of the groups -CH ₃ -, - (
or S,

CH-CH

or an acid addition salt thereof.

The compounds preferred for use in the new herbicides and algicides are those in whose formula I mean:

both radicals R, which are identical to one another, halogen or

Methyl groups,

both radicals R ₁ , which are identical to one another, are hydrogen

or C ₁ -C ₂ -alkyl groups,

both radicals R ₃ , which are identical to one another, C.-C ₄ -alkyl-

groups,

the value 0 or 1,

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m has the value 2 or 3, if η has the value 0,

and the value 2, if η has the value 1,

X is the group -CH ₉ -, -CH-CH, - or CH, CH,

and their acid addition salts.

The compounds of choice are the following:

2,2'-methylenebis / 3- (p-tolyloxy) -N, N, 1-trimethyI-n-propylamine / -dihydrochloride,

2,2'-methylenebis / 3- (4-chlorophenoxy) -Ν, Ν-dimethyl-n-propylamine / dihydrochloride,

2,2'-methylenebis / 3- (4-chlorophenoxy) -N- (sec-butyl) -n-propylamine / ■ dihydrochloride,

2,2'-Ethylenebis / 3- (4-chlorophenoxy) -N, N, 1-trimethyl-n-propylamine / dihydrochloride.

In the explanation of the general formula given above, C-C ₄ alkyl refers to straight or branched chain saturated alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl , and halogen can be bromine, chlorine, or fluorine.

Further examples of compounds of the formula given above are the following:

2,2'-methylenebis / 4- (4-bromophenoxy) -Ν, Ν-diethyl-n-butylamine / dihydrobromide,

2,2'-methylenebis / 4- (4-fluorophenoxy) -N-methyl-N- (2-hydroxyethyl) -n-butylamine / -dihydrochloride,

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2,2'-thiobis / 2- (4-chlorophenoxy) -N-ethyl-N-butyl-ethylamino dihydrochloride.

The new compounds of formula I are made from known starting materials and after known. Process made.

The starting materials having a 2, 2 '-Thiobrücke be prepared by reaction of a substituted phenol with sulfur dichloride in a solvent such as carbon tetrachloride prepared. For example, by reacting 4-chlorophenol with sulfur dichloride, 2,2'-thiobis (4-chlorophenol) is obtained.

Another example of the preparation of starting materials is the synthesis of 2,2'-methylenebis (4-methoxyphenol), which is obtained by reacting a mixture of 4-methoxyphenol, concentrated aqueous hydrochloric acid and calcium chloride in a suitable solvent such as benzene with p -Formaldehyde at a temperature between room temperature and 40 ⁰ C can be produced. Other 2,2 * -methylene bis compounds with substituted phenol rings can also be prepared by this process.

Another starting material, 2,2'-ethylenebis (4-chlorophenol), is prepared in stages by the method of Pfleger et al., Chem. Ber. Vol. 90, pp. 2395-2400 (1957). Here, 4-chloroanisole is reacted with 37 percent strength aqueous formaldehyde solution in the presence of zinc chloride while saturating the mixture with anhydrous hydrogen chloride at a temperature of 70 to 80 ^° C. to form 2-methoxy-5-chlorobenzyl chloride. Part of this intermediate is reacted with magnesium turnings in ether, after which the remaining part of the substituted benzyl chloride is slowly added to the reaction mixture. When the addition is complete, the reaction mixture is refluxed for about 2 hours. After cooling, aqueous hydrochloric acid (3N) is slowly added. That

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crystalline product that precipitates is 2,2'-ethylenebis (4-chloroanisole). In the third step of the synthesis the 2, 2 '-Ethylenbis (4-chloroanisole) with a mixture of 48 percent aqueous hydrobromic acid and glacial acetic acid to the desired 2,2'-ethylenebis (4-chlorophenol) is reacted.

The above-described phenol ring substituted 2,2'-thiobis (phenol) -, 2,2 'methylenebis (phenol) - and 2, 2'-ethylene bis (phenol) compounds for the preparation of a series of intermediates for the synthesis of of the compounds of the formula I are used.

Thus, 2,2 'methylenebis example, (4-chlorophenol) was reacted with 1,3-dibromopropane in the presence of an alkali hydroxide in ethanol to give 4 hours heated to boiling under reflux. The reaction mixture obtained is filtered off and the filtrate is concentrated in vacuo to a residue which is then stripped under vacuum at 100 ⁰ C of volatile impurities. The residue thus obtained is the intermediate 3,3 '- / 2,2'-methylenebis (4-chlorophenoxy ^ / - bis (propyl bromide).

The 2,2'-methylenebis (phenoxy) bis (alkylhalogen) intermediates prepared as described above are then used to prepare the compounds of formula I with the corresponding Amine implemented.

For example, 4,4 '- / 2,2'-methylenebis (4-chlorophenoxy ) _ / - bis (butyl bromide) with an aminoalkanol, for example 2- (ethylamino) ethanol in a solvent such as ethanol, in a pressure vessel reacted at a temperature of 130 to 140 ⁰ C for a period sufficient for a practically complete conversion. The reaction product is concentrated in vacuo and the residue is made alkaline with aqueous sodium hydroxide. This mixture is extracted with a solvent such as chloroform and this solution is in turn extracted with dilute aqueous acid. The aqueous acidic extract

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is made alkaline and with a solvent such as chloroform or ether, extracted. The extracts are combined, dried and concentrated in vacuo.

The residue thus obtained is dissolved in a small amount of ethanol, and the solution is treated with anhydrous hydrogen chloride saturated and mixed with ether. The precipitate that separates out is recrystallized and gives crystalline products 2,2 · -Methylene bis / 4- (4-chlorophenoxy) -N-ethyl ~ N- (2-hydroxyethyl) -n-butylamine / -dihydrochloride. Other compounds of this group can also be prepared using the same procedure will.

Another process for the preparation of the compounds of formula I is illustrated below.

The alkali salt of a 2,2'-bisphenol or substituted phenol prepared as previously described, for example 2,2'-methylenebisphenol, is in a solvent for Example ethanol, using an alkali alkoxide, for example sodium ethoxide, or an alkali hydroxide, for Example potassium hydroxide, made in methanol and is isolated by concentrating the solution in vacuo. The salt is then suspended in a solvent such as benzene and a solution of an aminoalkyl halide, for example dimethylaminopropyl chloride, is added and the mixture is refluxed overnight. The reaction mixture is diluted with water and ether, and the organic Layer is separated. The nitrogen base formed is in the form after the acid-base work-up described above their acid additxon salt isolated. In the present case, the isolated product is 2,2'-methylenebis (N, N-dimethyl-3-phenoxy-n-propylamine) dihydrochloride.

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Compounds used as starting materials or as intermediates for the preparation of the new compounds are prepared in a manner known per se as described above, and these syntheses are carried out by the following Preparations further explained.

Preparation 1 2,2'-thiobis (4-chlorophenol)

A solution of 128 g of 4-chlorophenol in 250 ml of carbon tetrachloride is added dropwise to a solution of 51.5 g of sulfur dichloride in 250 ml of carbon tetrachloride, which takes about an hour. The reaction mixture is refluxed for 2 hours and then stirred at room temperature for 16 hours. The precipitate formed is filtered off and recrystallized from benzene, whereby 42 g of yellow flakes with a melting point of 171 to 173 ^° C. are obtained. Its elemental analysis identifies the product as 2,2 * -thiobis (4-chlorophenol).

analysis , C ₁₂ H ₈ Cl ₂ 2.2 O ₂ S: Preparation 2 calculated found • -Methylene bis (4-methoxyphenol) C. 50.18% 50.48% H 2.81 2.91

A mixture of 500 g of 4-methoxyphenol, 10 ml more concentrated aqueous hydrochloric acid, 150 g calcium chloride and 1.5 1 benzene

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is produced by stirring. Then 60 g of paraformaldehyde are added in part with stirring over the course of 5 hours. The addition rate is adjusted so that the temperature of the reaction mixture not exceeding 40 ⁰ C increases. The mixture is then stirred for a further 16 hours at room temperature. After filtering off, the material remaining on the filter is discarded and the filtrate is washed with water and dried over anhydrous sodium sulfate. The dried solution is concentrated in vacuo to a residue which is distilled under reduced pressure. 200 g of the phenol used as the starting material are obtained as first runnings. The fraction boiling 220-235 ° C / 0.05 mm solidifies on standing and is recrystallized three times from benzene / petroleum ether to give 27 g of product are obtained, m.p. = 78 to 80 ⁰ C. The product is identified as 2,2'-methylenebis (4-methoxyphenol) by its NMR spectrum and its elemental analysis.

analysis , C ₁₅ H ₁₆ O ₄ found preparation 3 calculated 69.16% C. 69.21% 6.14 H 6.20

2,2'-ethylene bis (4-chlorophenol)

This intermediate is prepared according to the procedure of R. Pfleger et al., Chem. Ber. Vol. 90, pp. 2395-2400 (1957).

step 1

A mixture of 270 g of 4-chloroanisole, 163 g of 37-percent aqueous formaldehyde and 80 g of zinc chloride is heated with stirring at 7O ⁰ C and saturated with anhydrous hydrogen chloride, wherein the temperature in the range of 70 to 80 ⁰ C. The mixture is then stirred for a further 35 minutes and poured onto a mixture of Els and water.

The mixture thus obtained is extracted with chloroform and the chloroform extract is dried over anhydrous sodium sulfate. The drying agent is filtered off, and the filtrate is distilled to obtain 199 g of colorless product are obtained having a boiling point 128-130 ° C / 10 mm and a melting point 47-49 ⁰ C. The product is identified as 2-methoxy-5-chlorobenzyl chloride by its elemental analysis and its NMR spectrum.

Analysis, CgH-Cl-O:

calculated 2 29% found C. 50, 21 50.55% H 4, 4.25 step

100 ml of a solution of 199 g of 2-methoxy-5-chlorobenzyl chloride in 750 ml of dry ethyl ether are added to 14.8 g of magnesium turnings, whereupon 1 ml of methyl iodide is added and the mixture is heated. The remainder of the ethereal solution is then added at such a rate that vigorous refluxing is maintained. After the addition is complete, the reaction mixture is refluxed for a further 2 hours. 400 ml of 3N aqueous hydrochloric acid are then added dropwise. After 10% of the acid has been added, most of the precipitated product crystallizes, which leads to vigorous boiling of the ether. The mixture is filtered and the crystals obtained are combined with the residue obtained by evaporating the filtrate in vacuo. By recrystallization from ethyl acetate, 73 g of product with a melting point of 132 to 134 ^° C. are obtained. The product is identified as 2,2'-ethylenebis (4-chloroanisole) by its elemental analysis and its NMR spectrum.

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analysis ' ^C 16 ^H 16 ^C1 2 ° 2 ^: calculated found C. 61.74% 61.90% H 5.18 5.13 level 3

A mixture of 10 g of the product from Step 2, 60 ml of 48 percent aqueous hydrobromic acid, and 100 ml of glacial acetic acid is refluxed for 24 hours. The reaction mixture is poured onto 1 l of an ice-water mixture, and the precipitate is collected by filtration. After recrystallization from benzene 1OO ml 7 g of product are obtained with Enera melting point 163-164 ⁰ C. The product is identified as 2,2'-ethylenebis (4-chlorophenol) by its elemental analysis and its NMR spectrum.

Analysis, C ₁₄ H ₁₂ Cl ₂ O ₂ :

calculated found

C. 59, 36 % 58 , 92 % 4th H 4, 24 4th r41 preparation

3,3 ' - / 2,2' -Methylene bis (4-chlorophenoxy2 / -bis (propyl bromide)

From 135 g of 2,2'-methylenebis (4-chlorophenol), 66 g of 85 percent Potassium hydroxide and 2 l of ethanol a solution is made, which is mixed with 606 g of 1,3-dibromopropane. The reaction mixture is refluxed for 4 hours and heated then filtered. The filtrate is concentrated in vacuo, and the

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The residue obtained is dissolved in ether and washed with 15 percent aqueous sodium hydroxide and then with water until neutral. After drying the organic layer over anhydrous sodium sulfate, the solvent is removed in vacuo and the residue is subjected to a vacuum of 0.02 mm at 100 ° C. This residue is identified as 3,3 ' - / 2 , 2'-methylenebis (4-chlorophenoxy2 / -bis (propyl bromide).

The syntheses of the compounds of formula 1 are illustrated by the following preparations.

Preparation 5

2,2'-methylenebis (N, N-dimethyl-3-phenoxy-n-propylamine) dihydrochloride

0.575 g of metallic sodium are dissolved in 50 ml of absolute ethanol, and 10 g of 2,2'-methylenebisphenol are added. The solution obtained is evaporated to dryness in vacuo. The residue obtained in this way is suspended in reagent-grade benzene, and a solution of 10 g of dimethylaminopropyl chloride hydrochloride in benzene is added. The reaction mixture is refluxed for 16 hours and then diluted with water and ether. The ether layer is separated off and extracted with dilute aqueous hydrochloric acid. The aqueous acidic solution is cooled, made alkaline and extracted several times with ether. The combined ether extracts are dried over anhydrous potassium hydroxide and concentrated in vacuo to an oily residue. This residue is taken up in dry ether and treated with anhydrous hydrogen chloride. The precipitate is filtered off and recrystallized from a mixture of ethanol and ethyl acetate, whereby the product with a melting point of 204 to 205 ^° C. is obtained. From its elemental analysis, this product is identified as 2,2'-methylenebis (N, N-dimethyl-3-phenoxy-n-propylamine) dihydrochloride.

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analysis * 23 ^H 34 ^N 2 29% O ₀ .2 .43% calculated 18th , 53 C. 62, 32 found , 89 H 8th, 62 N 6, 8th 5

According to the general procedure described under preparation 5, further compounds are made, for example the following:

Preparation 6

2,2'-methylenebis / 3- (4-chlorophenoxy) -N, N, 1-trimethyl-n-propylamine / dihydrochloride

Preparation 7

2,2 * -Methylene bis / 4- (4-chlorophenoxy) -N-ethyl-N- (2-hydroxyethyl) -n-

butylarain / dihydrochloride

A mixture of 15 g of 4,4 '- / 2,2'-methylenebis (4-chlorophenoxy) _ / - bis (butyl bromide) and excess 2- (ethylamino) ethanol in 100 ml of absolute ethanol is in a pressure vessel for 10 hours 140 ⁰ C heated. The mixture thus obtained is evaporated to dryness in vacuo and the residue obtained is made alkaline and extracted with chloroform. The chloroform solution is extracted successively with dilute aqueous hydrochloric acid and water. The combined extracts are made alkaline with aqueous sodium hydroxide solution and extracted several times with chloroform. The combined chloroform extracts are washed with water and dried over anhydrous sodium sulfate. It is then filtered off and the filtrate is in vacuo

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evaporated and the residue is dissolved in a small amount of absolute ethanol. The ethanolic solution is saturated with anhydrous hydrogen chloride and mixed with ether. The precipitate is filtered off and recrystallized from a mixture of ethanol and ether, whereby the product with a melting point of 154 to 157 ^° C. is obtained. Its elemental analysis identifies it as 2,2'-methylenebis / 4- (4-chlorophenoxy) -N-ethyl-N- (2-hydroxyethyl-n-butylamine / dihydrochloride.

analysis '* "29 ** 44 ^ ₂ N ₂ O ₄ .2HC calculated found C. 55.23% 55.28% H 7.67 7.26

According to the procedure described above, further compounds are established, for example the following:

Preparation 8

2,2'-methylenebis / 3- (4-chlorophenoxy) -N-methyl-n-propylamine / dihydrochloride

Preparation 9

2,2'-methylenebis / 3- (4-chlorophenoxy) -n-propylamino-dihydrochloride

Preparation 10

2.2 "-Methylene bis / 3- (4-chlorophenoxy) -N-cyclohexyl-n-propylamine / dihydrochloride

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Preparation 11

2,2'-methylenebis / 3- (4-chlorophenoxy) -N- (2-hydroxyethyl) -npropylamine / dihydrochloride

Preparation 12

2,2'-methylenebis / 3- (4-chlorophenoxy) -Ν, Ν-di- (2-hydroxyethyl) n-propylamine / dihydrochloride

Preparation 13

2,2'-methylenebis / 3- (4-chlorophenoxy) -N-ethyl-N- (2-hydroxyethyl) -n-propylamine / -dihydrochloride id

Preparation 14

2,2 * -Methylene bis / 3- (4-chlorophenoxy) -N- (η-butyl) -n-propylamine / dihydrochloride id

Preparation 15

2,2'-methylenebis / 3- (4-chlorophenoxy) -N- (t-butyl) -n-propylamine / dihydrochloride

Preparation 16

2,2'-methylenebis / 3- (4-chlorophenoxy) -N, N-diethyl-n-propylamine / -dihydrochloride,

Preparation 17

2,2'-methylenebis / 3- (4-chlorophenoxy) -N-isopropyl-n-propylamine / dihydrochloride

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Preparation 18

2,2'-methylenebis / 3- (4-chlorophenoxy) -N- (sec, -butyl) -n-propylamine / -dihydrochloride

Preparation 19

2,2'-methylenebis / 3- (4-chlorophenoxy) -N ~ isobutyl-n-propylamine / dihydrochloride

Preparation 20

2,2'-methylenebis / 3- (4-chlorophenoxy) ~ N-propyl-n-propylamine / dihydrochloride

Preparation 21

2,2'-thiobis / 3- (4-chlorophenoxy) -N-ethyl-n-propylaminy-di- * hydrochloride

Preparation 22

2,2'-thiobis / 3- (4-chlorophenoxy) -N-isopropyl-n-propylamine / dihydrochloride

Preparation 23

2,2'-thiobis / 3- (4-chlorophenoxy) -Ν, Ν-dimethyl-n-propylamine / dihydrochloride

Preparation 24

2,2'-thiobis / 3- (4-chlorophenoxy) -N-methyl-n-propylamine Z-dihydrochloride

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Preparation 25

2,2 · -Methylene bis / 3- (4-chlorophenoxy) -N-benzyl-n-propylamine / -dihydrochloride

Preparation 26

2,2 * -Methylene bis / 3- (4-chlorophenoxy) -N-ethy] -n-propylamine / -dihydrochloride

Preparation 27

2,2'-methylenebis / 3- (4-methoxyphenoxy) -N, N, 1-trimethyl-n-propylamine / dihydrochloride

Preparation 28

2,2 * -Methylene bis / 3- (p-tolyloxy) -N, N, 1-trimethyl-n-propylamine / dihydrochloride

Preparation 29

2,2'-Ethylenebis / 3- (4-chlorophenoxy) -N, N, 1-trimethyI-n-propylamine) dihydrochloride

Preparation 30

2,2 * -Methylene bis / N, N-1-trimethyl-3- (4-nitrophenoxy) -n-propylamine / -dihydr ochlor id

Preparation 31

2,2 * -Methylene bis / 3- (4-chlorophenoxy) -Ν, Ν-dimethyl-n-propylamine / dihydrochloride

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Preparation 32

2,2 * -Methylene bis / 2- (4-chlorophenoxy) -Ν, Ν-dimethylethylamine / - dihydrochloride

The compounds are used to combat water weeds and algae of formula I added to the water in which these plants grow. Since some of the aquatic weeds in the water or swim on its surface, while others are rooted in the bottom, depending on the type of weed to be controlled, It may be convenient to use the compounds in a form that floats or that sinks.

Preferably, the compounds are used in amounts corresponding to concentrations of 1 to 10 parts per million, based on lead the weight (0.0001 to 0.001%).

The optimal concentration varies with the temperature, the type of plant to be controlled and the shape of the one to be treated Body of water. When the water temperature is high, a desired level of control is generally lower Amount of the compound of the formula I required than at lower temperatures.

When treating flowing water to destroy its flora, special consideration must be given to the compounds of formula I flow over the area to be treated and that the concentration during the contact time depends on the flow rate of the water and the speed and duration of the addition of the agent.

The compounds of formula I are the water in the form of the new herbicidal and algicidal compositions according to the Invention added. The novelty of the compositions is due to their content of compounds of formula I, of which so far they were not known to be valuable pesticides.

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inert ingredients of the compositions are essentially the same as those used with other agricultural chemicals be used.

Agents according to the invention contain 0.1 to 90% active ingredient and are in the form of granules, wettable powders, emulsifiable Concentrates and solutions. Granules are applied by sprinkling on the surface of the water. Through appropriate Adjusting the density, sinking or floating granules can be prepared. They contain in the generally 0.1 to 10% active ingredient, which is distributed in dried earth stones or sand or adsorbed on it. Diatomaceous earth, Kaolin, bentonite, montmorillonite and attapulgite are examples of earths which can be used for the production of the invention Granules are suitable and make up 90 to 99.9% of the funds.

Wettable powders, emulsifiable concentrates and solutions are particularly useful when the active ingredient-containing agents should swim, but can be made with a high density, so that the active ingredient to the bottom of the water got. Usually they are made by dispersing the agent in a relatively small amount of water and spraying it the dispersion applied to the surface of the water. The concentration of the active ingredient in the initially produced Dispersion is not important.

Wettable powders are intimate mixtures of the active ingredient with an inert carrier, which is a mixture of a fine represents inert powders and surfactants. The concentration of the active ingredient is usually from 10 to 90 percent by weight. An attapulgite clay, a montmorrilonite clay, a diatomaceous earth or a purified silicate is used. Effective surfactants that make up 0.5 to 10% of the wettable powder, are sulfonated lignins, condensed naphthalene sulfonates,

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Naphthalene sulfonates, alkylbenzenesulfonates, alkyl sulfates and nonionic surfactants such as ethylene oxide adducts of alkylphenols.

Contain exemplary emulsifiable concentrates of the active ingredients about 50 to 500 g of active ingredient per liter of liquid, which is 5 to * 50% equivalent, dissolved in an inert carrier, the one Is a mixture of water-immiscible organic solvents and emulsifiers. To suitable organic Solvents include the aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling ones Naphthalene and olefin components of petroleum, for example heavy aromatic naphtha, also other organic ones Solvents can be used, for example the terpene solvents, including the natural resin derivatives and alcohol derivatives such as 2-ethoxyethanol. Emulsifiers suitable for emulsifiable concentrates are surface-active Agents of the kind used for wettable powders and are used in comparable concentrations.

Solutions of the active ingredients correspond to the emulsifiable concentrates, but do not contain any surfactants. Solutions can also be prepared in water or aqueous alcohols as many of the active ingredients are more or less water-soluble salts.

The following formulations illustrate the invention Means, whereby the active ingredients are identified by the respective preparation number.

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- 20 -

Granules

example 1

granulated limestone compound celulose gums 95% 4 1

Example 2

granulated kaolin compound 90% 10

Example 3

Silica sand compound polybutenes 98%

Example 4

granulated diatomaceous earth compound 93% 7

Wettable powders

Example 5

Compound attapulgite surfactant

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Wettable powders

Example 6

Connection 13 80%

Kaolin 16

surfactant 4

Example 7

Connection 16 50%

Diatomaceous earth 40

surfactant 10

Example 8

Connection 17 90%

purified silicates 6

surfactant 4

Emulsifiable Concentrates Example 9

Connection 25 40%

aromatic naphtha 45

surface agent 5

Example 10

Connection 20 25%

Xylene 70

surfactant 5

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Example 11 2738873 45% Connection 8 20th Emulsifiable concentrates aromatic naphtha 30th 2-methoxyethanol 5 surfactant Example 12 15% Connection 29 80 Xylene 5 surfactant

solutions Example 13

Connection 22 30%

Haters 30

Ethanol 40

Example 14 Connection 14 12%

Water 88

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it

The herbicidal action of the compositions according to the invention is illustrated by the following tests carried out in the laboratory .

Attempt 1

The plants used in this test are bear's tail, Ceratophyllum demersum L; Florida Elodea, Hydrilla verticillata (L.F.) and duckweed Lemna minor L. Cut about 10 cm long end branches from the bear's tail and Elodea, and duckweed or groats are used in such an amount that they just cover the surface of the water in a 10 ml beaker (about 30 plants). Bear's tail, Elodea and duckweed are then placed in beakers containing 750 ml of dechlorinated water and which contain active ingredients.

The active ingredients for this test are formulated as follows. 17 mg of active ingredient are weighed into a 12 ml glass and 1 ml of acetone and then 10 ml of aqueous 0.1 percent polyoxyethylene sorbitan monooleate are added. This stock solution is then pipetted into the beakers in volumes of 0.45 ml and 4.55 ml, respectively, creating a concentration of the test compound in 750 ml of water from 1 to 10 parts per million.

The effect of the active ingredients on the plants will be 7 days observed for a long time. The scale for evaluating the water herbicidal effect of the active ingredients is as follows:

1 = no effect

2 = weak effect

3 = moderate effect

4 = strong effect

5 = complete destruction

The test results are shown in Table I below. Each test compound is identified by its preparation number.

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Tabel

Connect
manure
No. Τ / Μ
(ppm) 1 aydrilla 5 Bears
tail Ducks
herb 5 10 5 5 5 4th 1 1 2 2 1 3. 1 1 4th 2 1 9 10 5 5 4th 1 3 1 1 10 10 4th 5 5 4th 1 4th 5 2 1 1 4th 1 2 5 3 14th 10 5 5 5 4th 1 3 5 2 1 3 5 1 4th 5 3 15th 10 5 5 5 4th 3 4th 5 2 1 2 5 1 1 5 4th 17th 10 5 5 5 4th 1 4th 5 2 1 2 5 1 3 5 4th 18th 10 5 5 5 4 3
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2 2 4th
2 5
5 1 5 3

T a b e 1] L e I (continued) Bears
tail 2738873 Connect
manure
No. T / M
(Ppm) Hydrilla 5 Ducks
herb 19th 10 5 2 5 4th 2 1 5 2 1 4th 5 1 1 5 2 24 10 5 2 5 1 1 5 1 25th 10 4th 2 2 1 3 5 1 28 10 5 2 5 4th 3 1 5 2 2 2 5 1 1 5 2 29 10 4th 2 5 4th 2 1 5 2 1 5 5 1 4th 1 2 30th 10 1 2 2 1 2 5 2 31 10 5 2 5 4th 2 1 5 2 1 2 5 1 3 5 2 32 10 5 3 5 4th 5 ^ 09809 ^ 1057 ^X
114 5 5
4th

The algicidal effect of the agents according to the invention is demonstrated by the following results.

Attempt 2

In this test, the active ingredients are checked against green, red and blue-green algae. The species tested belong to the Genera Chlorella, Scenedesmus and Anacyslis. The test method is the same as that in Trial

Table II

link T / M (ppm) Chlorine. "Scene. Anacy. 5 1 3 2 5 14 _. 10 5 4th 5 18th 10 5 1 5 19th 10 5 1 5 29 10 5 1 5 31 10 4th 1 5

809809/1057

Claims (14)

Claims where mean: both radicals R, which are identical to one another, hydrogen, Halogen or a nitro, methoxy or C, -C ₄ -alkyl group, both radicals R ₁ , which are identical to one another, are hydrogen or a Cj-Cj-alkyl group or the group -CH ₂ CH ₂ OH, both radicals R ₂ , which are identical to one another, are hydrogen or a C .. -C alkyl, benzyl or cyclohexy! group or the group -CH ₂ CH the value 0 or 1, the value 2, 3 or 4 if η has the value 0 and the value 2 if η has the value 1, one of the groups -CH ₃ -, -CH ₂ CH ₂ -, CH ₃ C or S, CH or an acid addition salt thereof and an inert carrier. 809809/1057 2. Means according to claim 1, characterized by the content of a compound in whose formula I mean: both radicals R, which are identical to one another, halogen or Methyl groups, both radicals R, which are identical to one another, are hydrogen or C ₁ -Cj-alkyl groups, both radicals R, which are identical to one another, Cj-C.-alkyl- groups, η the value 0 or 1, m has the value 2 or 3, if η has the value 0, and the value 2, if η has the value 1, ~ ^CH 2 ~ '~ ^CH 2 ^CH 2 ~ ^or or an acid addition salt thereof. 3. Agent according to claim 2, characterized in that it is the active ingredient 2,2'-methylenebis / 3- (p-tolyloxy) -N, N, 1-trimethyl-n-propylamine / contains dihydrochloride. 4. Composition according to claim 2, characterized in that it is the active ingredient 2,2'-methylenebis / 3- (4-chlorophenoxy) -N, N-dimethyl-n-propylamine / dihydrochloride contains. 809809/1057 5. Composition according to claim 2, characterized in that it is the active ingredient 2,2 * -Methylenbis / 3- (4-chlorophenoxy) -N- (sec-butyl) -n-propylaminy-dihydrochloride contains. 6. A composition according to claim 2, characterized in that it comprises, 'as active ingredient, 2,2'-ethylenebis / 3- (4-chlorophenoxy) -N, N, 1-trimethyl-n-propylamine / dihydrochloride. 7. Agent according to one of claims 1 to 6, characterized in that it is an emuigable concentrate is present. 8. Composition according to claim 7, characterized in that it contains the active ingredient in an amount of Contains 5 to 50%. 9. Agent according to one of claims 1 to 6, characterized in that it is in the form of a wettable powder . 1O. Agent according to Claim 9, characterized in that it contains the active ingredient in an amount of from 10 to 90%. 11. Agent according to one of claims 1 to 6, characterized in that it is present as a solution. B09809 / 1057 12. Means according to claim 11, characterized draws that it contains the active ingredient in an amount of 5 to 50%. 13. Means according to one of claims 1 to 6, thereby characterized in that it is in the form of granules. 14. Composition according to claim 13, characterized in that it contains the active ingredient in an amount of Contains 0.1 to 10%. 809809/1057