DE954017C - Means applicable in agriculture and industry for combating living organisms of the plant kingdom - Google Patents

Description

Means for combating living animals useful in agriculture and industry Organisms of the Plant Kingdom This invention relates to new and useful herbicides and fungicides, because of their ability to destroy living organisms of the plant kingdom kill or prevent or inhibit their normal functions for use in agriculture and industry are their essential active component is a polyhalocyclohexenone containing 6 to 8 halogen atoms on the cyclohexenone ring. The agents are suitable for the treatment and control of undesired plant life, including killing weeds during growth or in the crop through treatment after sprouting, preventing weed seeds from germinating through treatment before sprouting and the immediate treatment of plant seeds before they are treated with the Come into contact with the ground.

It has been found that polycyclohexenones with 6 to 8 chlorine atoms in the Cyclohexenone ring almost all non-woody vegetation or everything herbaceous Plant growth to which they are applied in the short time from 24 to 48 Kill hours. This herbicidal effectiveness can be made very economical are, if you Q, Z to 5o weight percent of the polycyclohexenones in herbicides Blends mixtures made using a suitable inert and non-corrosive Carrier are produced, e.g. B. by placing them in aqueous media or in finely divided, atomized solids distributed or in suitable hydrocarbon solvents, such as petroleum, fuel oils, diesel oils and the like, or in mixtures of solvents, like acetone and petroleum, dissolves. Field tests have shown that with a single Use of such herbicidal mixtures in an amount of about 0.2 to 2 g of the active component per square meter of all vegetation with the exception of woody plants is killed in the short time of 24 to 48 hours.

It has also been found that such polyhalocyclohexenones, preferably in similar mixtures containing an inert carrier, also the killing of cause such plants that do not belong to the weeds, or such plants at least somehow inhibit or prevent them from exercising their vital functions. So are she z. B. effective against plants of the myxophyte group (slime mold) and the thallophyte group (Algae, fungi and bacteria) and can therefore be used as fungicides and bactericides can be used to prevent melt dew and mold growth in textiles, Leather, wood and other materials prevent the destruction by fungus and Exposed to bacteria. They can also be used with success as a fungicide for immunization of seeds and tubers and in the fight against fungal diseases of plants in used in the cases in which they are the germination of the seed or the growth of the plants to which they are applied do not completely prevent it.

The polyhalocyclohexenones which can be used as active ingredients for the purposes of the invention include all chlorine, bromine, iodine and fluorocyclohexenones which have 6 to 8 halogen atoms on the cyclohexenone ring, although the polychlorocyclohexenones having 6 to 8 chlorine atoms are preferred. These compounds have the general formula in which 6 to 8 free valences are bonded to halogen, while the remainder are saturated by hydrogen or alkyl or haloalkyl groups.

The preparation of the polychlorocyclohexenones, the preferred active ones Ingredients, is in the literature, e.g. B. in the reports 37, 4017 (19o4), described. In general, they can be obtained by chlorinating phenol or a chlorinated phenol being represented. The literature describes a process for the preparation of hexachlorocyclohexenone 207 parts by weight of 2, 4, 6-trichlorophenol, 2o7 parts by weight of glacial acetic acid and as follows 166 parts by weight of liquid chlorine are enclosed in a reaction vessel. This mixture is left to stand at room temperature for 30 days, but every day _ Shaken to loosen the crystals that form on the walls of the vessel. then the reaction vessel is aerated and the reaction mixture with water and aqueous Sodium bicarbonate solution washed until neutral. Then the crystalline Product obtained by filtration and drying over calcium chloride. Heptachlorocyclohexenone is prepared in a similar manner from 2, 3, 4, 6-tetrachlorophenol.

Octachlorocyclohexenone is prepared according to the literature by igo parts by weight of pentachlorophenol with 150 parts by weight of liquid chlorine in the presence of 285 parts by weight of glacial acetic acid at room temperature for 30 days in a sealed container React reaction vessel, which is shaken daily to get to the To detach the crystals forming the walls of the vessel. After draining the unreacted chlorine the mother liquor is filtered to recover the crystalline product formed. The ß- and γ-isomers of octachlorocyclohexenone can be obtained from the mother liquor while the a-isomer as a crystalline precipitate formed in the reaction accrues.

Octachlorocyclohexenone can also be made by chlorinating phenol directly at about 130 °. The chlorination is carried out until trichlorophenol has formed, then a catalyst, e.g. B. a chloride of antimony, iron or aluminum, added and the chlorination continued until octachlorocyclohexenone has formed. This process takes about 30 hours. This process also produces a mixture of the a-, ß- and y-isomers, mainly the a- and ß-isomers, while the first process mainly produces the a-isomer.

Other polyhalocyclohexenones that contain 6 to 8 halogen atoms in the nucleus, can be carried out in a similar manner by halogenating the corresponding or halogenated Phenol can be produced. So z. B. cresol or halogenated cresols be halogenated in the manner described to form hexa- and heptahalomethylcyclohexenone to obtain.

Various approaches can be used to prepare the active ingredients to be incorporated into herbicidal or fungicidal mixtures. So herbicidal dusts, containing the desired polyhalocyclohexenone by incorporating the halocyclohexenone into a finely divided, inert, powdery material such as talc, diatomaceous earth, Clay, calcium carbonate, inorganic silicates and the like by means of a ball mill or a similar mixing device. In general, the herbicidal effect of such dusts increases if the dust compositions also include one surface-active (wetting or dispersing) agent is incorporated. Such dusts can be prepared by adding a small amount of the powdery Solid with an aqueous dispersion of the polyhalocyclohexenone in an aqueous one Solution of a surfactant wetted, the mixture then dries and them with further amounts of the powdery carrier, e.g. B. in a ball mill, ground, to get the desired concentration of active ingredient. Watery, the polyhalocyclohexenones containing dispersions can be prepared by the active ingredient in a water-miscible, inert, organic Solvent dissolves and adds enough water to get the desired concentration to obtain. A concentrated solution of the active ingredient in one with water Immiscible organic solvents can also be mixed with an aqueous solution A surfactant can be combined to form an oil-in-water emulsion to obtain. In addition, solid polyhalocyclohexenones can be brought into finely powdered form and dispersed in an aqueous surfactant solution; the liquid Polyhalocyclohexenone can in an aqueous solution of a surface-active To be emulsified or dispersed by means.

Suitable surface-active (dispersing or wetting agents) that are suitable for the preparation of the mixtures described above are generally as categorize sodium and potassium salts of fatty acids, as they are used as lubricants and curd soaps are known; Salts of disproportionated abietic acid, known as resin soaps; Salts of carbohydrate derivatives found in seaweed known as Algin soaps; Alkali caseinates; water-soluble lignosulfonic acid salts; long chain, alcohols usually containing from 10 to 18 carbon atoms; water-soluble columns of fatty alcohol sulfates with 10 to 18 carbon atoms; water-soluble salts of sulfonated Fatty acid amides; water-soluble alkyl sulfonates with 10 to 18 carbon atoms in the alkyl group; water soluble aryl sulfonates; water soluble alkyl aryl sulfonates; water soluble aralkyl sulfonates; water-soluble sorbitan monolaurate, palmitate, stearate and oleate; quaternary ammonium alkyl halides; with amines and amino alcohols aminolyzed fats; Blood albumin and others. 'These substances are under different Trade names either as pure compounds or as mixtures of compounds the same group and mixtures of these compounds with fillers or diluents sold.

When the above surfactants for the preparation of the Invention explained mixtures are used, they may only in amounts of o, oi to about i percent by weight, based on the weight of the total agent, is used will.

Among the solvents that are used in the preparation of the solutions and oil-in-water emulsions Suitable include hydrocarbons, chlorinated hydrocarbons, alcohols, ketones and other neutral, inert, organic solvents and mixtures of these.

Mixtures in which the active ingredient is in a suitable carrier dissolved or dispersed have proven to be herbicides in greenhouse trials proven effective; in field trials, however, it is definitely more recommendable to spray it Use mixtures in which the polychlorocyclohexenone is in a solvent is dissolved, which consists of a liquid hydrocarbon oil with 12 to 18 carbon atoms, a specific gravity of o.7 to o.9 and a Saybolt viscosity of no persists for more than 85 seconds at 54.5 °. Such mineral oils are petroleum, light fuel oil and diesel oils. Such 0.1 to 25 or more percent by weight of polychlorocyclohexenon containing oil solutions are the preferred mode of application.

The following Examples I to VII are greenhouse experiments which explain the herbicidal activity of various polyhalocyclohexenones of the invention and illustrate various mixtures and processes. EXAMPLE I i percent by weight of a mixture of isomeric hexachlorocyclohexenones would be dissolved in a solvent mixture consisting of 10 parts by weight of ethylene glycol monoethyl ether, 10 parts by weight of acetone and 80 parts by weight of petroleum and this solution on bean, tomato,. Cabbage, pumpkin, oat and radish plants grown in a greenhouse sprinkled. The solution was splashed until the foliage was soaked. The plants treated in this way were then tended to as usual in the greenhouse. One week after this treatment, all of the treated plants had died. Example II Twenty tomato, onion, radish, lettuce and wheat seeds were placed in the hexachlorocyclohexenone solution described in Example I and left in it for 30 minutes. The seeds were then removed from the solution, placed on moist filter paper in 10 cm humidity chambers and incubated for 4 days at 20 °. Only the radish seeds sprouted, none of the others. Example III A solution of isomeric hexachlorocyclohexenones prepared by dissolving one part by weight of this active ingredient in 20 parts by weight of alcohol and then adding this solution to so parts of water containing 0.025 percent by weight sodium lauryl sulfate was grown in the greenhouse on tomato, Bean, cabbage, pumpkin =, oat and radish plants sprinkled. Twenty lettuce and twenty wheat seeds each were immersed in this solution for 30 minutes and then incubated for 4 days as described in Example II. None of the seeds germinated in 4 days. All plants had died one week after the treatment. Example IV Solutions of the a-isomer of octachlorocyclohexenone (m.p. the 1 percent by weight of this α-isomer in a solvent mixture of 20 percent by weight acetone and 80 percent by weight petroleum was sprayed onto tomato, bean, cabbage, pumpkin, oat and radish plants until the plants were completely wetted. One week after the treatment, all plants that had been sprayed next to one another with the three different solutions had died.

Example V The twenty seeds of tomato, onion, radish, lettuce and wheat were 30 minutes in a igewichtsprozentige solution of a-Octachlorcyclohexenon in a solvent suitable for insecticidal agent Petroleum, and the twenty seeds of the same plants also for 30 minutes in a igewichtsprozentige solution of a-octachlorocyclohexenone immersed in a solvent mixture of 2o percent by weight acetone and 8o percent by weight petroleum. The seeds of each species were treated only once, then placed on moist filter paper in a 10 cm humidity chamber and incubated there for 4 days at 20 ° to initiate germination. After incubation, the seeds were checked for germination. As a result, of the seeds treated with petroleum solution, only the tomato, radish and lettuce seeds germinated, while of the seeds treated with the acetone-petroleum solution, only the lettuce and radish seeds germinated. EXAMPLE VI A petroleum solution containing 0.1 percent by weight of a mixture of β-octachlorocyclohexenone (F. 89.5 to 90 °) and γ-octachlorocyclohexenone (F. 88 to 89 °) was placed on beans and tomatoes growing there in the greenhouse -, cabbage, pumpkin, oat and radish plants sprinkled until the entire foliage was covered. 7 days after the treatment, all plants had died. EXAMPLE VII The petroleum solution of the β- and γ-isomers of octachlorocyclohexenone described in Example VI was sprayed onto blue-grass, bean, tomato and radish plants which were grown in beds in the greenhouse with non-sterilized soil, ie the usual soil , contained weed seed mixture found in garden soils, were wetted. All plants on the beds, including the various weeds, were sprayed until they were completely wetted. The beds were observed daily. 2 days after the spraying, all the plants mentioned, including the weeds, with the exception of the bean plants, had died. But the bean plants were badly damaged and by the morning of the 4th day after the treatment they were also dead.

The following Examples VIII to XII are from field tests that the action of the herbicidal mixtures of the invention under natural conditions explain.

Example VIII Spinach, Eggplant, and Fingergrass in a Garden Plot were with a petroleum solution, the 0.1 percent by weight of the a-isomer of octachlorocyclohexenone contained, splattered. All plants had died 3 days after the treatment.

EXAMPLE IX Perennial rye grass was sprayed with a petroleum solution of the α-isomer of octachlorocyclohexenone, about 1/10 l of spray liquid containing 0.5 or µg of the active ingredient per square meter. 17 days after the treatment, living rye grass in the treated plots was cut off at ground level and weighed. The average weight of rye grass per about 0.1 square meter of the plot was 7.6 g for those treated with 0.5 g / m², 6.8 g for those treated with ig / m² and 103 g for the untreated controls. Example X Ripened weeds along a railway embankment were sprayed with an oil solution containing 9 kg of a mixture of the 3 isomers of octachlorocyclohexenone dissolved in about 47o 1 of a petroleum light oil diesel fuel, which was used in this amount on about 4000 square meters as a spray liquid . 3 days after the spraying, all the plants, with the exception of the woody plants, had been killed.

Example XI Mature, narrow-leaved and broad-leaved plants on an untreated pasture were sprayed with light petroleum solutions of the isomeric hexachlorocyclohexenones and octachlorocyclohexenones. Different amounts of the two active ingredients were used. 0.5 to 2.5 g of the active ingredient were used per square meter, which were dissolved in about 1 / 1o 1 of a light-colored paraffin-based oil, which had a specific gravity of 0.88, the Saybolt viscosity of 60 seconds at 54, 5 ° and had a flash point of 165 to 17o °. In the areas treated with 2 to 2.5 g of the two active ingredients per square meter, all plants, with the exception of woody plants, had died 4 hours after the treatment. In the finite 1.5 to 2 g per square meter treated areas, the plants died after 48 hours. In the areas treated with 0.5 to 1.5 g per square meter, the plants were dead 3 days after treatment. narrow-leaved plantain; broad-leaved: knotweed, melde, Jacob's ragwort, pennywort, goose foot, buttonwort, purslane, goldenrod, wild aster, dandelion, broad-leaved plantain, chickweed, clover. Example XII An area of the untreated pasture described in Example XI was plowed and prepared for sowing, but not planted in a manner suitable for harvesting. With the oil solvent described in Example XI, isomeric octachlorocyclohexenones and isomeric hexachlorocyclohexenones were dissolved and used as herbicides for treatment before the plants emerge in four concentrations, 0.25, 0.5, 1 and 2 g per square meter, on different plots same size applied. Each spraying test was carried out on four different plots; control plots located accordingly were not treated. The active ingredients were applied as oil solutions to a petroleum light oil diesel fuel. Thirteen weeks after the treatment, the plants that had emerged in each block were cut off at ground level, counted, dried for 48 hours at 40 ° and weighed. When counting, all narrow-leaved and all broad-leaved plants were counted separately. But not every single species was counted individually. The average results obtained from the four parallel tests are summarized below: Herbicider test by pre-emergence treatment Octachlorcyclohexenone Hexachlorcyclohexenone (control Applied amount, g / qm ........ 0.25 0.5 1 2 O, 25 11 0.5 1 2 - Number of broad-leaved plants per 0.4 sqm .................. 42 40 40 38 75 75 45 15 591 Number of narrow-leaved plants per 0.4 sqm .................. 275 225 200 _ 175 21 0 I 18o 120 48 664 Total weight of plants in 9 / 0.4 sqm ..................... 187 171 169 151 92 82 75 46 334 The weed species in the control plots were the same as in the field trials of Example X. The above treatment tests, ie pre-emergence treatment, indicate that the polychlorocyclohexenones display excellent herbicidal activity when applied prior to emergence of the plants.

In the above examples, relatively large amounts of spray liquid were used because a dilute solution of the active ingredient in the oil solvent was sprayed with an ordinary spray gun. However, one can use solutions that contain 25 to 50 and more percent by weight of the active ingredient, and spray them with modern fog machines, which to a certain extent also use air as a carrier. Such spray devices can evenly distribute amounts of the active ingredient in concentrations of 0.25, 0.5, 1, 1.5 g, etc. per square meter, even when fairly concentrated solutions are used.

Example XIII 100 parts by weight of wheat grains that are 15 to 16 percent by weight Containing moisture were treated with z parts by weight of a solution containing the i contained percent by weight octachlorocyclohexenone in acetone. After two weeks of storage the grains were tested for meltau at temperatures between about 21 and 24 °. Meltau was not present in the treated grains. The grains that are not treated had melted mildew.

Example XIV pea seeds of the var. Blue Bantarns were mixed with dust containing 20 percent by weight octachlorocyclohexenone on inorganic silicate as a carrier, using 0.3125 g of dust for one hundred pea seeds. In the same way, pea seeds of the same variety were treated with a dust containing 20 percent by weight of hexachlorocyclohexenone. The pea seeds so treated and untreated pea seeds were planted in a demarcated plot in moist soil known to be infected with putrefactive bacteria and fungi. Over 50% of the seeds treated with octachlorocyclohexenone and hexachlorocyclohexenone had started to germinate 10 days after planting, while a percentage of the untreated seeds had rotted over 50%.

Example XV Samples of a piece of cotton fabric approximately 3.5 cm wide and 10 cm long became. Soaked for 1 hour in an acetone solution containing 1 percent by weight of hexachlorocyclohexenone, Contained heptachlorocyclohexenone or octachlorocyclohexenone. Samples of the same size were soaked in pure acetone for comparison. All samples were marked air-dried after treatment and buried in moist humus. To After being buried for 14 days at about 27 °, the samples were dug up and placed on their Tensile strength investigated. The octachlorocyclohexenone treated samples had an average tensile strength of 70 g / mm2, that with heptachlorocyclohexenone and Hexachlorocyclohexenone treated samples such of 65 g / mm2, while the only Samples treated with the solvent are completely decomposed by the microorganisms were that they disintegrated immediately and consequently had no tensile strength. Before burying, the cotton fabric had a tensile strength of 245 g / mm2.

If, instead of the solutions, aqueous dispersions of the polychlorocyclohexenones are used for the purposes outlined in the above three examples obtained essentially the same results.

In addition to the embodiments mentioned in the examples, there are equivalent ones Carriers and equivalent types of application are also within the scope of the invention.

Claims (1)

PATENT CLAIMS: i. Applicable in agriculture and industry. Agents for combating living organisms of the plant kingdom, characterized in that they contain 0.1 to 50 percent by weight of a polyhalocyclohexenone with 6 to 8 halogen atoms on the cyclohexenone ring and also an inert carrier for the active ingredient as the essential active ingredient. z. Composition according to claim i, characterized in that the carrier is a liquid hydrocarbon oil having 12 to 18 carbon atoms, which has a specific gravity of 0.7 to 0.9 and a viscosity of not more than 85 Saybolt seconds at 54.5 °. 3.- Composition according to claim i or 2, characterized in that said polyhalocyclohexenone is a polychlorocyclohexenone. 4. Agent according to one of the preceding claims, characterized in that the active ingredient is octachlorocyclohexenone or hexachlorocyclohexenone.