DE3817343A1 - HERBICIDES WITH INCREASED SELECTIVITY AND METHOD FOR PRODUCING THE BOTH ACTIVE SUBSTANCE COMPONENTS IN A REACTION STEP - Google Patents

Abstract

A herbicidal composition comprising a mixture of a compound of Formula I <IMAGE> and a compound of Formula II <IMAGE> (wherein X stands for chlorine or hydrogen) is prepared in one reaction step by reacting a compound of Formula III. <IMAGE> with acetic anhydride and a nitrating acid.

Description

The invention relates to herbicidal compositions increased selectivity and process for the preparation of the two active ingredient components in one process step (a potting process).

The herbicidal compositions according to the invention contain as an active ingredient in a ratio of 50: 1-1: 50 a 5- (substituted phenoxy) -2-nitro-benzaldehyde general formula I.

and a 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetate of the general formula II  

(in which formulas X means hydrogen or chlorine).

The invention furthermore relates to herbicides Agents which have a 5- (substituted Phenoxy) -2-nitro-benzaldehyde diacetate of the general Contain formula II (in which X denotes hydrogen or chlorine), and the use of the above mixture to control weeds. The active ingredients of the general formulas I and II and those in the manufacture of the same as a starting material used 3- (substituted phenoxy) benzaldehydes of the general formula III

(where X is hydrogen or chlorine) are in the  Known compounds described in technical literature, but their mixtures are new.

The compounds of general formula I and their preparation and herbicidal activity are such. B. in U.S. Patent No. 43 06 900. The Manufacturing process is the classic Ullmann ether synthesis, where 2-chloro-4-trifluoromethylphenol in Presence of potassium carbonate in dimethyl sulfoxide with 2-nitro-5-fluoro-benzaldehyde is linked.

DOS No. 30 44 810 describes new substituted phenoxycinnamic acid derivatives having a herbicidal action described, which from the 5- (substituted Phenoxy) -2-nitro-benzaldehydes of the general formula I - as new intermediates - are synthesized. The 5- (substituted phenoxy) -2-nitro-benzaldehyde However, they are not based on Ullmann synthesis e.g. B. by hydrolysis of 3- (substituted phenoxy) -2- nitro-benzaldehyde diacetates of the general formula II produced. The hydrolysis is carried out in a mixture of Methanol and water, using a dilute aqueous Sodium hydroxide solution performed. According to the quoted Laid-open patent are the 5- (substituted phenoxy) - 2-nitro-benzaldehyde-2-nitro-benzaldehyde diacetates new compounds about their herbicidal activity however, nothing is revealed. According to DOS No. 30 44 810 these new 5- (substituted phenoxy) -2-nitro- benzaldehyde diacetates of the general formula II the 3- (substituted phenoxy) benzaldehydes of of the general formula III prepared (nitriding) that said compound in the first step in Presence of a solvent (e.g. methylene chloride) at a temperature of 10-80 ° C with acetic anhydride  implemented, then in the second process step a temperature between -10 ° C and + 20 ° C with Nitric acid is nitrated, after which the obtained 5- (substituted phenoxy) -2-nitro-benzaldehyde diacetate is isolated. According to the teaching of the published patent application are also the 3- (substituted phenoxy) benzaldehydes new compounds which are produced by the reaction of 3-hydroxy benzaldehyde and 3, 4, 5-trichlorobenzotrifluoride produced will. The reaction is in a solvent (e.g. dimethylformamide or toluene) in the presence an acid binder (e.g. potassium methylate) carried out.

In DOS No. 30 17 795 the 5- (substituted Phenoxy) -2-nitro-benzaldehydes of the general Formula I also as new, not yet described intermediates mentioned. The making of these connections is carried out by reacting 4-chloro-benzotrifluoride and 3-hydroxy-benzaldehydes.

According to DOS No. 31 18 371, the 5- (2-chloro or 2,6-dichlorophenoxy) -2-nitro-benzaldehyde Nitration of 3- (2-chloro- or 2,6-dichlorophenoxy) - benzaldehyde diacetals. The nitriding is in a solvent, optionally in In the presence of a catalyst so that 1-3 moles - advantageously 1.2-1.5 moles - nitric acid phenoxy-benzaldehyde diacetal substituted on 1 mole be used. The nitrided product is made from the Reaction mixture in a known manner, for. B. so isolated that the reaction mixture is practical with water immiscible solvent added, the organic Phase separated, washed anhydrous and concentrated becomes. In the DOS quoted, the manufacturer  5- (substituted phenoxy) -2-nitro-benzaldehyde diacetate of the general formula III disclosed.

The 3- (2-substituted phenoxy) benzaldehydes of general formula III are in a solvent (e.g. methylene chloride) in a temperature range of 10-80 ° C implemented with acetic anhydride, after which the 3- (substituted phenoxy) benzaldehyde obtained diacetate at a temperature between -10 ° C and + 20 ° C be nitrided with nitric acid. The reaction mixture is diluted with water, the immiscible with water Phase is separated or distilled and the 5- (substituted phenoxy) -2-nitro-benzaldehyde-di acetate are isolated. The 3- (substituted phenoxy) - Benzaldehyde diacetates can also be obtained by reacting 3- (substituted phenoxy) benzaldehyde diacetals with a molar equivalent amount of acetic acid [Houben-Weyl, Volume VII / 1, page 443 (1958)].

According to DOS No. 31 00 387, the potassium salt of 3-hydroxy-benzaldehyde dimethylacetal in the presence of potassium carbonate and dimethyl sulfoxide with 3,4-dichloro- implemented benzotrifluoride, the obtained 3- (2-chloro 4-trifluoromethylphenoxy) benzaldehyde dimethylacetal recovered in a known manner and dissolved in dioxane. The solution is concentrated sulfuric acid in portions admitted. After half an hour, carried out at 30 ° C Hydrolysis, the reaction mixture is poured onto ice and the 3- (2-chloro-4-trifluoromethyl-phenoxy) - benzaldehyde isolated in a known manner. The 5- (2.5- Dichloro-4-trifluoromethylphenoxy) nitrobenzaldehyde is made in an analogous way, with the difference that the 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2- nitro-benzaldehyde diacetate in sulfuric acid as a medium  is hydrolyzed.

It was made according to ours, on the manufacture of the 5- (substituted phenoxy) -2-nitro-benzaldehyde-directed Attempted to find that when nitrating the compounds the general III - among the below defined molar ratios - not the desired 5- (substituted phenoxy) -2-nitro-benzaldehyde instead whose diacetate is formed. According to our detailed Experiments have shown that by appropriate Selection of molar ratios the following compounds can be produced:

• - 5- (Substituted phenoxy) -2-nitro-benzaldehyde general formula I; or
• - 5- (substituted phenoxy) -2-nitro-benzaldehyde diacetate of the general formula II; or a surprising one wise
• - Any mixture of the compounds of the general Formulas I and II.

Our further biological tests have shown that

• - The mixture of compounds of general formulas I and II - compared to the individually tested compounds of the general formula I or II - one herbicidal effect of increased selectivity. This is all the more unexpected and surprising than after the Technical literature the 5- (substituted phenoxy) -2-nitro- benzaldehyde diacetates of general formula II only can be mentioned as intermediates, the herbicidal Effectiveness of these compounds not at all is described.  
• - The increased selectivity stands with that in the root cells the energy-producing plant that took place Process and - immediately - with the inhibition of Adenosine triphosphatase (also called ATP-ase) in Context.
• - The 5- (substituted phenoxy) -2-nitro-benzaldehyde diacetates are also herbicidal.

The invention relates to a herbicidal composition with increased selectivity, characterized in that this as an active ingredient a 5- (substituted phenoxy) -2- nitro-benzaldehyde of the general formula I and a 5- (substituted phenoxy) -2-nitro-benzaldehyde diacetate of the general formula II (in which X is hydrogen or chlorine is) in a ratio of 50: 1-1: 50.

The invention further relates to a herbicidal Agent, characterized in that it is an active ingredient a 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetate of the general formula II (in which X is hydrogen or means chlorine) contains.

The invention further relates to a method to make a 50: 1-1: 50 mixture (Weight ratio) of a 5- (substituted phenoxy) -2- nitro-benzaldehyde of the general formula I and one 5- (substituted phenoxy) -2-nitro benzaldehyde diacetate of the general formula II (wherein X is hydrogen or Chlorine) in one reaction step, characterized in that that 1 mol of 3- (substituted phenoxy) benz aldehyde of the general formula III (in which X is hydrogen or chlorine) in the presence of a solvent - preferably dichloromethane - at room temperature or a lower temperature with 4-11 moles of acetic acid  anhydride and one from a mixture of 1.2-2.6 moles Nitric acid and 0.1-2.8 moles of existing sulfuric acid Nitrating acid, the resulting mixture of compounds of the general formulas I and II from the Isolated reaction mixture in a known manner and cleans if desired.

The according to the inventive method Starting material used 3- (substituted phenoxy) - benzaldehydes of the general formula III can by Linking the potassium salt of 3-hydroxy-benzaldehyde be prepared with 3, 4, 5-trichlorobenzotrifluoride.

Through a suitable selection of the molar ratios of the reactants used in the nitration can two active ingredients of the herbicides according to the invention Compositions of increased selectivity - namely the 5- (Substituted phenoxy) -2-nitro-benzaldehyde of the general Formula I and the 5- (substituted phenoxy) -2- nitrobenzaldehyde diacetate of the general formula II - be produced in any proportions.

According to the method of the invention Starting material of the general formula III first in one Solvent dissolved. Any, inert solvents which do not affect nitration (like chlorinated hydrocarbons e.g. dichloromethane) Find use. A mixture of dichloromethane and Acetic anhydride can also serve as a solvent. When choosing the amount of acetic anhydride must however care should be taken to ensure that this reagent Influence on the ratio of the compounds of the also exercises general formulas I and II if the molar ratio of sulfuric acid and nitric acid is constant. After the dissolution, the homogeneous  Solution added a further amount of acetic anhydride, whereupon the mixture is cooled and the addition nitrating acid - advantageous at one temperature between -20 ° C and + 5 ° C - slowly started. The Nitrating acid is concentrated by mixing Nitric acid (65%) and concentrated sulfuric acid (98%). The nitriding and binding of the water formed in the reaction is highly exothermic Process so that cooling is taken care of must become. It is convenient to nitrate to be carried out at a temperature between 0 ° C and + 5 ° C. The addition of nitrating acid decreases among the conditions according to the invention about an hour Claim. The system is allowed to warm up, after which it is Reaction mixture at 20-40 ° C - advantageously at 25-35 ° C - warmed and left for a few more hours (2- 4 hours) react. The reaction mixture is on Poured ice, the two phases are separated and the aqueous layer is used with that used in dissolving Solvent extracted. The organic phases are combined, one after the other with a diluted aqueous (2-5% by weight) sodium carbonate solution and Water washed neutral, dried (e.g. over magnesium sulfate), filtered and under reduced pressure evaporated. The product obtained - which mainly from a mixture of the compounds of the general Formulas I and II exist - can be cleaned if necessary be treated (e.g. by treatment with an organic Solvent or solvent mixture - such as. B. Dichloromethane, toluene, etc. - or recrystallization).

That on the starting material of the general Formula III related molar ratio of the at  reactants used according to the method of the invention (Sulfuric acid, nitric acid, acetic anhydride) have a significant influence on the ratio of the formed compounds of general formula I and II out. Increasing the amount of sulfuric acid [(0.1-2.3 moles) 1 mole of compound of the general Formula III] favors the formation of the compound of general formula I. In contrast, the increase in Amount of acetic anhydride [(4-11 moles) 1 mole of compound of the general formula III] the increase in Amount of compound of general formula II formed result. Increasing the amount of nitric acid [(1.4-1.7 moles) 1 mole compound of the general Formula III] increases the content of the product obtained on the component of general formula I, although in to a lesser extent.

Our test series will continue to be one very valuable conclusion. In case you have the molar Ratio of acetic anhydride to the value of 5 moles / mole of compound of general formula III and the total molar ratio of nitric acid and Sulfuric acid to 2.9 moles / 1 mole compound of the general Formula III sets and only the molar ratio from nitric acid to sulfuric acid in the range of 1.2 / 2.7-1.55 / 2.35 changes, the content of the obtained Mixture with the connection of the general Formula I increased from 30% by weight to 100% by weight and subsequently after a molar ratio of 2.0 / 1.9 again reduced. This way, among the molars Ratios of 1.2 / 2.7-1.55 / 2.35 or 2.2 / 1.8- 2.6 / 1.3 herbicidal combinations of any composition getting produced.  

The compounds of the general formulas I and II are first tested separately from the herbological point of view. It was found that these compounds in a dose of 0.5 kg · ha ^-1 are not phytotoxic to the following crop plants:
Of the monocots: tobacco, cotton, cabbage, flax, lettuce, carrot, sugar melon, pumpkin and plants belonging to the order of the legumes.
From the dicot: barley, winter wheat, onions, corn, rice and oats.

In contrast, the compounds of the general formulas I and II in the same can (0.5 kg · ha ^-1 ) are active against numerous dicotyledonous and several monocotyledonous weed species which emerge from seeds.

The compounds of the general formulas I and II, in a can of 2.0-3.0 kg · ha ^-1 , have a total herbicidal action against the following difficult-to-eat one- or two-seeded weeds (practically against most weed species):

From the dicotyledons:
Abutilon theophrasti Medic. (Velvet poplar)
Calystegia sepium L. (fence winch)
Datura stramonium L. (thorn apple)
Galium aparine L. (Chain bedstraw)
Xanthium strumarium L. (burdock).

From the monocots:
Alopecurus myosuroides Huds. (Field Foxtail)
Apera spica-venti L. (wind stalk)
Poa trivalis L. (panicle grass)
Sorghum halepense L. (black millet)
Panicum capillare L.

In contrast, the compounds of the general formulas I and II, when used in the same can (2.0-3.0 g kg · ha ^-1 ), destroy all of the above crop plants with the exception of soybeans and sometimes winter wheat.

The compounds of general formulas I and II are used to control particularly resistant weed species only in soybean crops and in certain cases in Winter wheat crops suitable. That on a tight Applicable acifluorene - sodium 5- (2-chloro-4-trifluoromethyl-phenoxy) benzoate - shows one similar spectrum of activity. Acifluorene takes place in the Practice only for weed control in soybean crops Use.

On the other hand, it was found that the mixture according to the invention of the two compounds of the general formulas I and II in a can of 2.0-3.0 kg · ha ^-1 destroys the above weeds (practically most of the weed species) and at the same time against a large number of crop species - in particular against pods (papilionazees) - are not phytotoxic within certain proportions of active ingredient (Examples 45-46). According to our test experiments, the mixtures according to the invention of the compounds of the general formulas I and II for selective weed control can be used not only in soybean and winter wheat crops, but also, for. B. in bean, pea, glue clover, lupine, peanut, chickpea, lentils, horse bean, alfalfa, red clover - generally used in legume crops - successfully.

In addition to the herbological experiments (Examples 45 and 46), the biological experiments (Example 47) also show that the mode of action of the compounds of the general formulas I and II and in particular the mixtures thereof according to the invention indirectly or indirectly with the energy-producing processes which took place in the plant root cells - is associated with the inhibition of ATP-ase. Our experiments are aimed at whether mixtures of these compounds of different compositions cause a change in the ATPase activity and the phytotoxicity. It was found that, in contrast to the four compounds when used alone, the 16: 1-1: 16 mixtures of the compounds of the general formulas I and II already in a dose of 1 kg · ha ^-1 cause a substantial inhibition of the activity. Excellent inhibition is found using mixtures of the compounds of general formulas I and II in a weight ratio of about 8: 1.

The agents according to the invention can be used both as pre-emergence and as post-emergence herbicides. The dose of active ingredient is - depending on the structure of the soil and the meteorological conditions, etc. - about 0.2-9.0 kg · ha ^-1 , preferably about 0.5-3.0 kg · ha ^-1 . The water can be used for spraying in an amount of 200-500 l · ha ^-1 .

The mixtures of the compounds according to the invention of the general formulas I and II can in itself formulated in a known manner to pesticides will. The herbicidal compositions according to the invention can e.g. B. as crosslinkable powder (WP), suspension concentrates (SC), water-miscible solution concentrates (SL), emulsifiable concentrates (EC) without water Granules (S), dusting agents (DP) or oily suspensions  concentrates (FO) to be completed. The active ingredient mixtures can also be used in ULV form. The The above herbicidal compositions can be obtained by mixing the Mixture of active ingredients with various solid or liquid Carriers or solvents and, if necessary, with others Auxiliaries are produced. Coming as auxiliaries surface-active substances, wetting, suspension, Dispersing agents, emulsifying agents, anti-aggregating agents, an anti-caking agent agent), adhesive, an anti-burn agent (spreader), the penetration promoting agent or the maintaining or increasing biological effect Agents or foaming agents.

As a suitable solid carrier or diluent can e.g. B. inactive minerals, such as various clay and types of clay, kaolin, china clay, attapulgite, Montmorillonite, mica schist, pyrophillite, bentonite, Diatomaceous earth etc. or highly disperse synthetic silicas, Calcium carbonate, calcined magnesium oxide, Dolomite, gypsum, tricalcium phosphate, fuller's earth, etc. serve. The ground one is also suitable for this purpose Tobacco stalks, the wood flour, etc.

The following compounds can be mentioned as suitable liquid diluents and solvents: methanol, ethanol, n-propanol, isopropanol, diacetone alcohol, benzyl alcohol; Esters of the above alcohols e.g. B. methyl cell sol; Ketones such as dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc .; Ethyl acetate, n-butyl acetate, isobutyl acetate, amil acetate, isopropyl miristate, dioctyl phthalate, dihexyl phthalate, etc .; aromatic, aliphatic and araliphatic hydrocarbons such as paraffin hydrocarbons, cyclohexane, kerosene, gasoline, benzene, toluene, xylenes, tetralin, decalin; Alkylbenzene mixtures; chlorinated hydrocarbons such as trichloroethane, dichloromethane, perchlorethylene, dichloropropane, chlorobenzene, etc .; Lactones e.g. B. γ- butyrolactone; Lactams e.g. B. N-methyl-pyrrolidone, N-cyclohexyl-pyrrolidone, etc .: acid amides such as dimethylformamide; vegetable or animal oils, e.g. B. sunflower oil, flax oil, rapeseed oil, olive oil, soybean oil, castor oil, etc.

The suitable wetting, dispersing, emulsifying and adhesives, anti-aggregation agents and burning preventive agents can be ionic or nonionic be. Suitable ionic surfactants are e.g. B. the following compounds: salts of various aliphatic, aromatic or araliphatic carboxylic acids; Aliphatic, aromatic or sulfonates araliphatic hydrocarbons; Sulfates of alkyl, Aryl or aralkyl alcohols; Sulfonates of alkyl, aryl or aralkyl acids, esters or ethers; Sulfonates of Condensation products of phenol, crezole or naphthalene; sulfated vegetable and animal oils; Alkyl, aryl or aralkyl phosphate esters or those with alkali and alkaline earth metals or organic bases (e.g. with various amines, alkanolamines) salts formed of the above connections. Particularly advantageous representatives of the ionic surfactants are as follows Products: sodium lauryl sulfate, sodium 2-ethyl hexyl sulfate; the sodium, ethanolamine, diethanolamine, Triethanolamine or isopropylamine salt of dodecylbenzenesulfonic acid; Sodium mono- and diisopropylnaphthalenesulfonate; Sodium salt of naphthalene sulfonic acid; Sodium diisooctyl sulfosuccinate, sodium xylene sulfonate; Sodium-  or calcium salt of petroleum sulfonic acid; Soft soaps; Potassium, sodium, calcium, aluminum, magnesium stearate etc. As phosphate esters come formed with polyglycol Ether of phosphated alkylphenols or fatty alcohols and those with the above cations or organic Bases partially or completely neutralized Forms of it into consideration. As another suitable anionic surfactants come that Disodium N-octadecyl sulfosuccinate, sodium N-oleyl N-methyl-tauride and various lignin sulfonates in Consider.

The following compounds can be used as suitable nonionic wetting, dispersing and emulsifying agents: ethers of ethylene oxide formed with C _10-20 alcohols, e.g. B. stearyl polyoxyethylene, oleyl polyoxyethylene, etc .; ether formed with alkylphenols, which with tert. Butyl alcohol, octyl alcohol or nonylphenol formed polyglycol ether: esters formed with various organic acids z. B. formed with polyethylene glycol ester of stearic acid or miristic acid, polyethylene glycol oleate, etc .; Ethylene oxide or propylene oxide block polymers; partial esters of fatty acids and oleic acids formed with hexitan hydrides; Esters of sorbitol and oleic acid or stearic acid, etc .; condensation products of the above compounds formed with ethylene glycol, etc .; tertiary glycols such as 3,6-dimethyl-4-octyne-3,6-diol or 4,7-dimethyl-5-decyne-4,7-diol, etc .; Polyethylene glycol thioether z. B. the ether of dodecyl mercaptan formed with polyethylene glycol, etc.

Suitable adhesives are e.g. B. the alkaline earth metal soaps, Sulfosuccinic acid ester salts, natural  or synthetic water-soluble macromolecules e.g. B. Kazein, starch, gum arabic, cellulose ether, methyl cellulose, Hydroxy cellulose, polyvinyl pyrrolidone, Polyvinyl alcohol, etc.

Suitable foaming agents are e.g. B. the low Polyoxyethylene and polyoxypropylene block polymers (number the octyl, nonyl, phenyl polyoxyethylene / ethylene oxide units is <5); long chain alcohols e.g. B. Octyl alcohol, special silicone oils.

By using suitable auxiliaries the compositions according to the invention with different Artificial fertilizers are made colloidally chemically compatible.

The herbicidal compositions according to the invention can, if desired, known pesticidal active ingredients and / or contain nutrients.

Wetting powders (WP) can e.g. B. manufactured in this way that the mixture of active ingredients, the (or the) Excipient (s) and the surface-active substance (s) mixed with the carriers, the resulting mixture is ground and finally homogenized. Liquid surface active Substances can be found on the solid organic or inorganic carrier or on the first Powder mixture containing active ingredient z. B. by pulverization or atomization. in the Case of liquid surfactants can one also proceeds in such a way that the previously ground solid components in such an organic Suspended solvent, which is liquid surface-active Contains substance (s). The suspension thus obtained can e.g. B. can be dried by atomization. The surfactant is made in the above way on the surface of the solid mixture of active ingredients or  of the solid support applied.

For the production of dispersed in an aqueous medium Emulsions suitable self-emulsifying Liquids - s. G. emulsifiable concentrates (EC) - can be obtained so that the active ingredient or Mixtures of these together with one of the above surface active substances in one with water not miscible solvent dissolves. The so obtained emulsifiable concentrate forms spontaneously with water or an emulsion spray liquor under slight physical influence, which is even after long storage does not change.

For the production of the suspension concentrates (SC) are the wetting and dispersing agents in one Mixture of water (advantageously an ion exchange subject water) and an antifreeze component (preferably ethylene glycol or glycerin) if necessary solved under heating. The surviving With constant stirring, the mixture of solid (powder or crystalline) active substances admitted, after which - if necessary - an anti-aggregation agent (anti-caking agent) is added (e.g. Aerosil 200). The suspension thus obtained (mixture of granules and liquid) in a wet grinder (e.g. in a closed Dyno mill) ground to the desired particle size, this is a maximum of 5 µm to ensure adequate storage stability to grant. After grinding, if necessary Foaming agents or compaction components (e.g. Kelzan S) incorporated by homogenization. The Order of adding the individual components can if necessary, can be changed or desired  if additional components (e.g. dyes, etc.) are added will. In addition to the solid active ingredients, as Combination partners also liquid, immiscible with water or mixable active ingredients used will. Solid active ingredients with a low melting point can be in the form of a melt in the presence or absence an emulsifying agent can be added.

The ULV compositions can be done in an analogous manner to the EC funds (or the SC funds) will.

Ready-to-use granules (G) can be produced in this way be that a granular carrier used by extrusion or coating or a liquid component in a carrier with suitable Sorbent capacity adsorbed.

Granules that can be used for atomization (WG) can be composed of WP and / or SC compositions with the help of a Agglomeration technology, e.g. B. in a drag boiler made using binders will.

The spray liquors that can be used in agriculture or powdered powder can be made from the above compositions by dilution with water or an inert solid diluent prepared in a known manner will. The active ingredient content of the ready-to-use Spray liquors or powdered powder are generally present less than 5% by weight and is advantageously 0.01-3% by weight. You can also proceed in such a way that you have several, each from one Active substance-containing compositions produced Spray liquors mixed together before use.

Further details of the invention Procedures and compositions are the following  Take examples without changing the scope of protection limit these examples.

In the examples, the following abbreviations used:

CHO compound of the general formula III; Ac₂O acetic anhydride; (I) compound of general formula I; (II) compound of the general formula II; (I / a) 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzaldehyde; (II / a) 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzaldehyde diacetate; (I / b) 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-benzaldehyde; (II / b) 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-benzaldehyde diacetate; aiAktivstoff (active ingredient); ATP-ase adenosine triphosphatase; %Weight-%

Examples 1-9

In one with thermometer, stirrer and pot funnel provided 50 ml round-bottom flask, 6.0 g (0.02 mol) of 3- (2- Weighed in chloro-4-trifluoromethyl-phenoxy) -benzaldehyde and dissolved in dichloromethane, the volume of which to the calculated Amount of acetic anhydride is identical. The homogeneous solution the acetic anhydride is added. The one in the appropriate Molar ratio (65% nitric acid and 96% sulfuric acid) The nitrating acid produced is cooled to 5 ° C. The The nitrating acid is added with vigorous stirring and cooling began. The reaction is highly exothermic and the temperature increases by a few ° C after the first drops have been added. The outside temperature is kept at -20 ° C, the addition takes about 45 minutes. After the addition is complete the cooling is switched off and the reaction mixture for 3 hours long at 30 ° C and poured onto 75 g of ice. The organic Phase is separated and the aqueous layer twice extracted with 20 ml dichloromethane each. The united organic Phases are carried out twice with 75 ml of a 3% sodium bicarbonate solution and water washed and over magnesium sulfate dried. The composition of the solution is determined by gas chromatography certainly. GLC: SE-30; 10 m capillary column; 150-300 ° C; 10 ° C / min, FIO.

After evaluating the chromatograms, the composition with those obtained by using standards Area factors modified. The qualitative analysis of the raw The mixture is mixed using a combined gas chromatograph mass spectrum measurement performed.

According to the above procedure, one mol  ratio of CHO / HNO₃ / Ac₂O = 1/1, 6/5 by change the amount of sulfuric acid given in Table 1 Obtain product compositions.

Table 1

Effect of the amount of sulfuric acid

Molar ratio CHO / HNO₃ / Ac₂O = 1 / 1.6 / 5

Examples 10-18

The procedure is as in Examples 1-9, with the Difference that the molar ratio CHO / HNO₃ / Ac₂O changes from 1 / 1.6 / 5 to 1 / 1.6 / 7. The so obtained Product compositions are shown in Table 2 specified.  

Table 2

Effect of the amount of sulfuric acid

Molar ratio CHO / HNO₃ / Ac₂O = 1 / 1.6 / 7

Examples 19-24

The procedure is as in Examples 1-9, with the Difference that with a molar ratio of CHO / HNO₃ / H₂SO₄ = 1 / 1.6 / 0.2 the Ac₂O / CHO molar ratio changes. The product compositions thus obtained are given in Table 3.  

Table 3

Effect of the amount of acetic anhydride

Molar ratio CHO / HNO₃ / H₂SO₄ = 1 / 1.6 / 0.2

Examples 25-28

The procedure is as in Examples 1-9, with the Difference that with a molar ratio of CHO / H₂SO₄ / Ac₂O = 1 / 0.2 / 5 the HNO₃ / CHO molar ratio changes. The product compositions thus obtained are summarized in Table 4.  

Table 4

Effect of the amount of nitric acid

Molar ratio CHO / H₂SO₄ / Ac₂O = 1 / 0.2 / 5

Examples 29-37

The procedure is as in Examples 1-9, with the Difference that with a molar ratio of CHO / Ac₂O = 1/5 the HNO₃ / H₂SO₄ molar ratio changes. The product compositions thus obtained are given in Table 5.  

Table 5

Effect of the HNO₃ / H₂SO₄ molar ratio

Molar ratio: CHO / Ac₂O = 1/5

Example 38 Wetting powder concentrate (WP)

Component Quantity,% by weight

8: 1 mixture of active ingredients (I / a) and (II / a) 96 Cab-O-Sil M5 1 Dispersant 1494 3

240 g one in a rotating knife Mill be pre-ground mixture of active ingredients in a grater with 2.5 g Cab-O-Sil M5 carrier (Silicon dioxide) and 7.5 g of dispersant 1494  (Sodium salt of the condensation product of sulfonated Cresol and formaldehyde) mixed. The powdery obtained Mixing is done in a fluid bed mill (Alpine JMRS-80) at an injector air pressure of 5 bar and a grinding air pressure of 4.5 bar at a feed rate ground from 250 g / hour. Although the wettable powder thus obtained is not a wetting agent contains, it is well wettable and has a maximum Partial pressure gauge of 20 µm.

The suspension is in a spray mixture with a concentration of 10 g / l, at 30 ° C after 30 minutes

• - in CIPAC Standard D water 84%; and
• - in CIPAC Standard A water 91%.

According to this example, using all of the products described in Examples 1-37 (Mixtures of active ingredients) produced a wettable powder will.

Example 39 Emulsifiable concentrates (20 EC)

Component Quantity,% by weight

Active ingredient (II / a) 20 2-ethoxyethane 10 Cyclohexanone 35 Emulsogen EL 360 7 Tensiofix CD 5 3 Xylene25

In an enamelled, equipped with agitator 500 ml autoclave in a mixture of 37 g 2-ethoxyethanol, 137 g cyclohexanone and 91 g xylene  (Solvent) 26 g Emulsogen EL 360 (ethoxylated Castor oil) and 11 g Tensiofix CD 5 (ethoxylated Coconut oil) (emulsifying agent). The emulsifiers are added in the melt (at 60-70 ° C.) The final stage in the process is 75.5 g of the active ingredient (II / a) added and stirring is 2 hours long continued. It will be a clear see-through Get solution.

According to this example, using all of those described in Examples 1-37 Products (active ingredient mixtures) an emulsifiable Concentrate.

Example 40 Emulsifiable concentrate (35 EC)

Component Quantity,% by weight

Active ingredient (II / b) 35.0 Cyclohexanone 10.0 Tensiofix CG 21 2.0 Tensiofix B 7453 8.0 Xylene 45.0

In a mixture of 30 g cyclohexanone and 133 g 6 g of Tensiofix CG 21 (a mixture of ethoxylated fatty alcohol, ethoxylated nonylphenol and their phosphates) and 24 g Tensiofix B 7453 (a solution of calcium dodecylbenzenesulfonate formed with n-butanol, ethoxylated nonylphenol and ethoxylated propoxylated nonylphenol) dissolved. After that 104 g of the active ingredient (II / b) are added and in the dissolved surfactant solution.

According to this example, using  all of those described in Examples 1-37 Products (mixtures of active ingredients) an emulsifiable Concentrate (35 EC) can be produced.

Example 41 Aqueous suspension concentrate (SC)

Component Quantity,% by weight

Active ingredient mixture (1) 40.0 Propylene glycol 7.0 Tensiofix XN6 (2) 2.0 Tensiofix B 7425 (3) 4.0 Rhodopol B 23 (4) 0.05 Silicon SRE (5) 0.5 Water (ion exchanged) 46.45

(1) According to the invention, a mixture of active substances can be used manufactured active ingredient mixture of any composition be used. (2) Ethoxylated nonylphenol and ethoxylated nonyl phenolphosphate ester. (3) A solution of calcium formed with n-butanol dodecylbenzenesulfonate, ethoxylated nonylphenol and ethoxylated-propoxylated nonylphenol. (4) Xanthangumi (thickener) (5) A 30% aqueous emulsion of dimethyl silicone oil.

In a 20 l with dissolver disc agitator 5 l of the vessel are subjected to an ion exchange Weighed in water, whereupon 800 g with stirring Propylene glycol and a mixture of  240 g of Tensiofix XN6 and 480 g of Tensiofix B 7425 were added the temperature should not exceed 35 ° C may. Stirring is continued for 20 minutes after which the suspension is an emulsion of 30 g Silicone SRE and 30 g of water are added with stirring becomes.

The wet grinding is carried out in two stages. In the first stage, the suspension is replaced by a colloid mill with corundum disc (type Fryma MK 95) until the particle size is below 90 µm is reduced. The fine grinding is done in a pearl mill (Type Dyno KD 5) up to a particle size <8 µm performed. After the grinding is over, 20 g Xanthangumi (Rhodopol B 23), 400 g propylene glycol and Distributed gel containing 500 g of water.

Example 42 Oily suspension concentrate (FO)

Component Quantity,% by weight

1: 1 mixture of active ingredients (I / b) and (II / b) 32.7 Vaseline cosmetic oil 48.8 Tensiofix AS 4 Sapogenat T-080 4.5 Ethylene glycol 10 Silicon SRE 0.5

13.5 g Sapogenat T-080 melted at 80 ° C Emulsifying agent (ethoxylated tributylphenol) and 12 g, at a temperature not exceeding 60 ° C melted homogenized Tensiofix AS emulsifier (Solution of calcium formed with n-butanol  dodecylbenzenesulfonate and ethoxylated nonylphenol) are in a Molinex 075 laboratory bead mill 145 g cosmetic vaseline heated to 60% added. 30 g of ethylene glycol are added to the surfactant oil mixture added, whereupon the mixture by 10 minutes Stirring is homogenized. The liquid so obtained Mix 98.1 g of the finely ground in a grater Active ingredient mixture added. The mixture is stirred for 5 minutes and then at a Speed of 1500 revolutions per minute using of glass beads with a diameter of 1 mm (350 g grinding media) ground for 2 hours. In the obtained oily suspension, 1.5 g of silicone SRE Foaming agent (a 30% emulsion of dimethyl silicone oil) distributed with stirring for three minutes.

According to this example, using any, prepared according to Examples 1-37 Products (active ingredient mixtures) an oily suspension concentrate getting produced.

Example 43 ULV preparation

Component Quantity,% by weight

Active ingredient (II / a) 27.5 Isophorone 30.0 2-ethoxyethane 10.0 Soybean oil (or sunflower oil) 32.5

In an anhydrous enameled autoclave 7500 g of isophorone and 2500 g of 2-ethoxyethanol weighed in. 6875 g of the solvent mixture  Active ingredient pre-ground in a hammer mill (II / a) admitted. Stirring is started and simultaneously the temperature by switching on the jacket heating of the Autoclaves increased to 45-50 ° C. After an hour - if the entire amount of active ingredient has gone into solution - 8125 g soybean oil (or sunflower oil) are placed in the autoclave weighed in. The mixture is further 20 minutes stirred further, the temperature by cooling 20 ° C is lowered. The ULV average thus obtained becomes Discharged in undiluted form without the addition of water.

Example 44 Dust powder with an active ingredient content of 1% by weight (DP)

Component Quantity,% by weight

Active ingredient (Ib) 1.0 Ultrasil VN 3 3.0 Kaolin 16.0 Talk80.0

9510 g are placed in a 50 l ribbon stirrer (ribbon type) Kaolin with 1800 g Ultrasil VN 3 (synthetic aluminum silicate) mixed, after which 600 g of the, in one Hammer mill pre-ground, active ingredient (I / b) added and stirring is continued for 30 minutes. The active ingredient premix is in a mill (type Ultraplex 250) with an addition rate of 20 kg / hour stirred until the fraction of the fraction with a Particle diameter over 44 µm the limit of 0.5% by weight falls below. After grinding, the active ingredient premix in a fluidized bed mill (type Loedige 300) with talc in a ratio of 1: 4 with stirring  mixed within 10 minutes.

This example can be used to manufacture the Dust powder of any inventive product be used.

Example 45

According to this example, the herbicidal activity and increased selectivity of the active ingredient mixtures according to the invention [(I / a) + (IIa) or (I / b) + (II / b) proven.

An identical number of seeds (20-50 seeds) - depending on the plant species - are sown in Petri dishes at a depth of 0.5 cm. After sowing, the soil is poured on. A pre-emergent (pre-emergence) treatment is carried out with an active ingredient dose of 3 kg (ai) · ha ^-1 . The floor is poured on daily. The evaluation takes place on the 10th day after the casserole. The results are expressed as% of extinction and are given in Tables 6 and 7.

The numbers in the tables (1-6) the following weeds mean:

1 = Abutilon theophrasti 2 = Amarantus retroflexus 3 = Calystegia sepium 4 = Datura stramonium 5 = Galium aparine 6 = Xanthium strumarium

Example 46

In this example (comparative example) the herbicidal activity of the compounds (Ia), (IIa), (Ib) and (IIb) as a function of the can used.

The tests are carried out in the manner described in Example 45, with the difference that the herbicidal activity of the compounds is determined in three doses (1.0, 3.0 and 9.0 kg / ai / · ha ^-1 ). Acifluorene sodium is used as standard.

The results obtained are shown in Table 8 summarized.  

Table 8

It follows from the results of the 45- 46 described biological test trials, that the selectivity of the active ingredient mixtures according to the invention (I / a) + (II / a) or (I / b) + (II / b) significant is increased, the herbicidal activity at all not reduced but even increased if the active ingredients in a ratio of 25: 1-1: 1 be used. The above mixtures of the two herbicidal effective compound types practice on pod crops an antagonistic effect, they antidote mutual the effect of the other component, being on Weeds have a synergistic effect. In contrast the active ingredient mixtures can be added to the individual components (I / a) + (II / a) or (I / b) + (II / b) [and / or (I / a) + (II / b) or (I / b) + (II / a)] not only in soybean crops but also in crops other than Pre-emergence weed control agents are used.

The size of the occurring between the active ingredients Anti-doping effects can be derived from the information in the Tables A and B are taken.

In Table A, the information of the columns Bean, Pea, Horse Bean, Table 6 and in Lupine Table B the corresponding information in the table 7 worked up so that between the connections occurring interaction is easier to see.

The designations used in Tables A and B are as follows:

Total absolute effect (%)
Calculation method:
Difference between the percentages of the damage caused by the individual active substances or the active substance mixtures. Tr: relative multiple effect (%)
Calculation method:
the Ta value is divided by the percentage damage value obtained with an agent containing an active ingredient and multiplied by 100.

Table A

(based on the information in table 6)

Table B

(based on the information in table 7)

Example 47

In this example, the treatment with the active ingredient mixtures according to the invention (I / a) + (II / a) and (I / b) + (II / b) induced change in adenosine triphosphatase activity and the phytotoxicity determined.

2-3 leaf oat plants (Avena sativa) are treated in a can of 1 kg (ai) · ha ^-1 with mixtures of active substances of different compositions (ie with different proportions). The change in adenosine phosphatase activity and the phytotoxicity are determined on the 3rd and 5th day after the post-emergence treatment.

The adenosine phosphatase enzyme is derived from the Roots of the oat using the method of W. Weltrup extracted [1]. The enzyme activity is measured according to the photometric Method by S. A. Solim and co-workers [2] certainly.

The results obtained are shown in Tables 9 and 10 summarized. The results show that if you have oats with the four compounds [(I / a), (II / a), (I / b), (II / b)] and with 1-16: 16-1 mixtures of two active substances [(I / a) + (II / a) or (I / b) + (II / b)] treats the greatest inhibition of adenosines phosphatase activity or the highest phytotoxicity with Mixtures of (I / a) + (II / a) or (I / b) + (II / b), which correspond to a weight ratio of 8: 1 becomes.

Literature:

• 1. W. Wletrup: The in vivo and in vitro effects of Ca ²⁺ and Al ³⁺ upon ATP-ases from barley roots.
  Journal of Plant Nutrition 6 (5), 349-361 (1983).
• 2nd SA Soliman, AKA El Refaie, AH El-Sebae and MI.
  Toxicity of some insecticides to dry Wood fermites Cryptotermes brevis [Walker] in relation to ATP-ase and AChE inhibition.
  International Pest Control 1981. Jan./feb.

Table 9

Table 10

There is not just one between the active ingredients common anti-doping occurring in the legumes Effect, but also a synergistic increase observe the herbicidal effect.

The amount of the synergistic additional effect is over Tables C and D can be seen, which due to the Measurement results in Tables 9 and 10 are compiled were. The Ta and Tr values are calculated in the same way as in Example 46.  

Table C.

(based on the information in Table 9)

Table D

(based on the information in table 10)

Example 48

This example uses the synergistic herbicide Effect of the mixture of the compounds according to the invention (I / a) + (II / a) and (I / b) + (II / b) shown.

The tests were carried out on 250 m² parcelles on an earth with 2.44% organic material content repeated four times.

On April 5, Pioneer 3976 maize was added to the good prepared soil at a depth of 5-6 cm, in one Seeded amount of 800,000 pieces / hectare.

The active ingredients I / a, II / a, I / b and II / b and the Mixtures of active ingredients I / a + II / a and I / b + II / b were in a ratio of 9: 1 on April 6th using a Halbinger spray apparatus in a dose of 0.25 and 0.50 kg / ha sprayed.

The tests were evaluated on June 5 determining the percentage of damage to the various Weed species on four 1 m² areas for every treatment.

The following weed species are on the test field occurred:

7 Echinochloa crus-galli 8 Setaria viridis 9Capsella bures / pastoris 10Thlaspi arvense 11 Portulaca olexaceae 12 Polygonum aviculare 13 Amaranthus retroflexus 14 Stellaria media.

The test results are summarized in Table 11. In the last column of the table, the percentage of damage to all weeds is given, from which information it can be calculated that the relative additional action of the compositions containing an active ingredient mixture compared to the compositions containing only one active ingredient at a dose of 0.5 kg · ha ^-1 25-35% and at a dose of 0.25 kg · ha ^-1 50-65%.

Table 11

Claims (15)

1. Herbicidal agent with increased selectivity, characterized in that it is a 5- (substituted phenoxy) -2-nitro-benzaldehyde of the general formula I as active ingredient and a 5- (substituted phenoxy) -2-nitro-benzaldehyde diacetate of the general formula II (wherein X is hydrogen or chlorine) in a ratio of 50: 1-1: 50. 2. Herbicidal composition according to claim 1, characterized characterized that it is the connections of the general formulas I and II in a ratio of 20: 1-1: 1 (parts by weight) contains. 3. Herbicidal composition according to claim 1 or 2, characterized in that it is a connection of the general formula I 5- (2-chloro-4-trifluoro methyl-phenoxy) -2-nitro-benzaldehyde and as a compound of the general formula II 5- (2-chloro-4-trifluoromethyl- phenoxy) -2-nitro-benzaldehyde diacetate contains. 4. Herbicidal composition according to claim 1 or 2, characterized in that it is a connection of the general formula I 5- (2,6-dichloro-4-tri fluoromethyl-phenoxy) -2-nitro-benzaldehyde and as a compound of the general formula II 5- (2,6-dichloro-4-trifluoro contains methyl-phenoxy) -2-nitro-benzaldehyde diacetate. 5. Process for the preparation of a 50: 1-1: 50 mixture (weight ratio) of a 5- (substituted phenoxy) -2-nitro-benzaldehyde of the general formula I and a 5- (substituted phenoxy (-2-nitro-benzaldehyde diacetate) of the general formula II (in which X is hydrogen or chlorine, with the restriction that X in the formulas I and II has the same meaning) in one reaction step, characterized in that 1 mol of 3- (substituted phenoxy) benzaldehyde general formula III (where X is hydrogen or chlorine) in the presence of a solvent - preferably dichloromethane - at room temperature or a lower temperature with 4-11 moles of acetic anhydride and one of a mixture of 1.2-2.6 moles of nitric acid and 0.1-2, 8 moles of sulfuric acid existing nitrating acid is implemented, the resulting mixture of compounds of general formulas I and II isolated from the reaction mixture in a known manner and, if desired, purified. 6. The method according to claim 5 for producing a 50: 1-1: 6 mixture (weight ratio) of a compound of general formula I and a compound of the general formula II in one reaction step, characterized in that 1 mol of a Compound of general formula III (wherein X is hydrogen or chlorine) in the presence of a solution using - preferably dichloromethane - with 5-6 moles Acetic anhydride and one of a mixture of 1.5-1.7 moles of nitric acid and 0.1-1.8 moles of sulfur  acid existing nitrating acid. 7. The method according to claim 5 for the production of a 1: 2-1: 25 mixture (weight ratio) of one Compound of general formula I and one Compound of the general formula II in one reaction step, characterized in that one 1 mole of a compound of general formula III (where X is hydrogen or chlorine) in the presence a solvent - preferably dichloromethane - with 6-7 moles of acetic anhydride and one from a mixture of 1.5-1.7 moles of nitric acid and 0.1-2.8 moles Sulfuric acid existing nitrating acid. 8. Herbicidal agent, characterized in that it is a 5- (substituted Phenoxy) -2-nitro-benzaldehyde diacetate of the general Formula II (where X is hydrogen or chlorine), contains. 9. Herbicidal composition according to claim 8, characterized characterized as an active ingredient 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzaldehyde contains diacetate. 10. A 50: 1-1: 50 mixture of a 5- (substituted phenoxy) -2-nitro-benzaldehyde of the general formula I and a 5- (substituted phenoxy) -2-nitro-benz aldehyde diacetate of the general formula II (where X is hydrogen or chlorine). 11. A 20: 1-1: 1 mixture of the compounds of the general formulas I and II according to claim 10. 12. Use of the mixture according to claim 1 for the selective control of weeds. 13. Use of the mixture according to claim 3 for the selective control of weeds. 14. Use of the mixture according to claim 8 for the selective control of weeds. 15. Use of the mixture according to claim 9 for the selective control of weeds.