HU200538B - Herbicidal compositons with improves selectivity and process for producing the two active ingredients in one reaction step - Google Patents

Abstract

The invention relates to herbicidal agents of increased selectivity. They contain as active ingredient a 5- (substituted phenoxy) -2-nitro-benzaldehyde diacetate of the general formula II. It is particularly advantageous if it additionally a 5- (substituted phenoxy) -2-nitro-benzaldehyde of the general formula I, So contain two active ingredients. The mixing ratio between the active compounds of the general formulas I and II is 50: 1 to 1:50, preferably 20: 1 to 1: 1. In formulas I and II, X is hydrogen or chlorine. Preferred active compounds are 5- (2-chloro-4-trifluoro-methyl-phenoxy) -2-nitro-benzaldehyde (formula I) and 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzaldehyde diacetate (Formula II). The funds are characterized by a high selectivity. The invention further relates to a method for the selective control of weeds. Formulas (I) and (II)

Description

BACKGROUND OF THE INVENTION The present invention relates to highly selective herbicidal compositions and to a process for their preparation in a single step.

The compositions of the present invention are present in an amount of from 0.05 to 96% by weight of the active ingredient, and 5- (substituted phenoxy) -2-nitrobenzaldehyde of formula (I) and 5- (substituted phenoxy) of formula (II) Containing 2-nitrobenzaldehyde diacetate

- in which formulas

X is hydrogen or chlorine.

The present invention also relates to the 5-substituted phenoxy-2-nitrobenzaldehyde diacetate compound of formula II

- in which formula

X is also a herbicidal composition containing hydrogen or chlorine alone.

The active compounds of formula (I) and (II) and the 3- (substituted phenoxy) benzaldehydes of formula (III) used in their preparation

- in which formulas

X is a hydrogen atom known in the art.

5- (substituted phenoxy) -2-nitrobenzaldehydes of formula (I), their preparation and herbicidal activity are described, for example, in U.S. Patent No. 4,306,900. U.S. Pat. The procedure involves coupling Ullmann's classical ether synthesis with 2-nitro-5-fluorobenzaldehyde in the presence of 2-chloro-4- (trifluoromethyl) phenol in the presence of potassium carbonate and DMSO.

No. 30,444,810. Disclosure in the Federal Republic of Germany discloses new substituted phenoxycinnamic acid derivatives having novel intermediates from 5- (substituted phenoxy) -2-nitrobenzaldehydes of the general formula (I)

- synthesize. However, the 5- (substituted phenoxy) -2-nitrobenzaldehydes are not obtained by Ullmann synthesis, but, for example, by the hydrolysis of the 3- (substituted phenoxy) benzaldehyde diacetates which we have represented by formula (II). The hydrolysis is carried out in a methanol-water mixture with an aqueous solution of sodium hydroxide. According to the description, 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetates are new compounds, but their herbicidal activity is not mentioned. It is described that these new 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetates are prepared (by nitration) from 3 (substituted phenoxy) benzaldehydes of the formula (III) by first reacting a compound such as methylene is reacted with acetic anhydride at 10-80 ° C in the presence of chloride and then nitrated with nitric acid in a second step at -10 + 20 ° C, whereupon the resulting 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetate is recovered. - (Substituted phenoxy) benzaldehydes are also novel compounds which are produced by the reaction of 3-hydroxybenzaldehyde with 3,4,5-trichlorobenzotrifluoride in the presence of, for example, DMSO, a toluene solvent and an acid acceptor such as potassium methylate.

No. 30,17,795. The disclosure document of the Federal Republic of Germany also mentions the 5- (substituted) -2-nitrobenzaldehydes of the general formula (I) as novel intermediates which have not yet been described. They are prepared by reaction of substituted 4-chlorobenzotrifluoride with 3-hydroxybenzaldehydes.

No. 31,183,371. According to the disclosure document of the Federal Republic of Germany, 5- (2-chloro, or 2,6-dichlorophenoxy) -2-nitrobenzaldehyde is obtained from 3- (2-chloro, or 2,6-dichlorophenoxy) - is prepared by nitration of benzaldehyde diacetals. The nitration is carried out in the presence of a solvent and, optionally, a catalyst, using 1-3 moles, preferably 1.2-1.5 moles, of nitric acid per mole of substituted phenoxybenzaldehyde diacetal. The nitro product is recovered from the reaction mixture in a known manner, for example by the addition of a solvent which is substantially immiscible with water, the organic phase is separated off, washed with acid and evaporated. This disclosure is characterized by our formula (II)

It also discloses the preparation of 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetates.

The 3- (2-substituted phenoxy-benzaldehydes) of our formula (III) is reacted with acetic anhydride at a temperature of 10-80 ° C in the presence of a solvent such as methylene chloride and the resulting 3- (substituted-phenoxy) -benzaldehyde diacetates are reacted with -10 - + After nitration with nitric acid at 20 ° C, the reaction mixture is diluted with water, the water-immiscible phase is separated off or distilled off, and the 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetates are recovered to give the 3- (substituted phenoxy) benzaldehyde. diacetates may also be prepared by reacting the 3- (substituted phenoxy) benzaldehyde diacetals with a molar equivalent of acetic acid (Houben-Weyl, Vol. VII / 1, p. 443 (1958)).

According to DE 31 00 387, the potassium salt of 3-hydroxybenzaldehyde dimethylacetal is reacted with 3,4-dichlorobenzotrifluoride in the presence of potassium carbonate and DMSO and the resulting 3 - [(2-chloro-4- / Trifluoromethyl (phenoxy) -benzaldehyde dimethylacetal is recovered in known manner, then dissolved in dioxane, and concentrated sulfuric acid is added in portions, after hydrolysis for 30 minutes at 30 ° C, the reaction mixture is poured onto ice and the resulting 3 - [(2- Chloro-4- (trifluoromethyl / phenoxy) -benzaldehyde is obtained in a known manner and 5 - [(2,5-dichloro-4- (trifluoromethyl) phenoxy] -nitrobenzaldehyde is prepared analogously. with the change that 5- (2,6-dichloro-4- / trifluoromethyl-23) in a sulfuric acid medium

EN 200538 (ethyl) phenoxy] -2-nitrobenzaldehyde diacetate is hydrolysed.

In our attempts to prepare 5- (substituted phenoxy) -2-nitrobenzaldehydes of formula (I), it has been found that nitration of compounds of formula (III), at the molar ratios described in more detail below, does not result in the expected 5- (substituted phenoxy) ) -2-nitrobenzaldehyde but its diacetate is formed. According to our detailed studies, with the proper choice of molar ratios we can produce:

- 5- (substituted phenoxy) -2-nitrobenzaldehyde of formula (I), or

- 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetate (II) or, surprisingly,

any mixture of the compounds of the formulas I and II.

Furthermore, in our biological studies it has also been found that the mixture of the compounds of the formulas I and II has a highly selective herbicidal activity compared to the compounds of the formulas I and II, respectively. it is neither surprising nor surprising, since the literature discloses 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetates of formula (II) only as intermediates and does not mention their herbicidal activity.

increased selectivity for 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetates of formula (II) related to the energy production process in plant root cells and, indirectly, to the inhibition of the function of adonesine triphosphatases (hereinafter ATPase) are also herbicidal.

The present invention is a highly selective herbicidal composition characterized in that the active ingredient is present in an amount of 0.05 to 96% by weight and 30: 1 to 1:30 by weight of 5- (substituted phenoxy) -2-nitrobenzaldehyde and (II). containing 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetate

- in which formulas

X is hydrogen or chlorine, one or more solid and / or liquid carriers, preferably ground minerals, or an inert solvent, preferably xylene or cyclohexanone, optionally surfactant (s), preferably anionic and / or nonionic emulsifier (s). ) and / or dispersing agent (s).

The present invention further provides a herbicidal composition, characterized in that it contains from 0.05 to 96% by weight of the active ingredient 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetate (II).

- in which formula

X is hydrogen or chlorine 4 one or more solid and / or liquid carriers, preferably ground natural minerals, or an inert solvent, preferably xylene or cyclohexanone, optionally surfactant (s), preferably anionic and / or nonionic emulsifier (s). ) and / or dispersant (s).

Finally, the invention provides a process for the preparation of 5- (substituted phenoxy) -2-nitrobenzaldehyde of formula (I) and of formula (II):

5- (substituted phenoxy) -2-nitrobenzaldehyde diacetate

- in which formulas

X is prepared in a reaction step for the preparation of a mixture of hydrogen atoms in a ratio of 30: 1 to 1:30 by weight, characterized in that one mole of 3- (substituted phenoxy) benzaldehyde of formula (III)

- in which formula

X is reacted with 4 to 11 moles of acetic anhydride and 1.2 to 2.6 moles of nitric acid and 0.1 to 2.8 moles of sulfuric acid in the presence of a solvent, preferably dichloromethane, at room temperature or lower, followed by the reaction mixture. the mixture of compounds of formula (I) and (II) is recovered in a known manner and, if desired, purified.

The process of the present invention is based on 3- (substituted phenoxylbenzaldehyde) of formula (III) which is coupled with the potassium salt of 3-hydroxybenzaldehyde and 3,4-dichloro and 3,4,5-trichlorobenzotrifluoride. produced.

By appropriately selecting the molar ratios of the reactants used in the nitration, the two highly active compounds of the present invention - 5- (substituted phenoxy) -2-nitrobenzaldehyde (I) and 5- (substituted phenoxy) - (II) 2-nitrobenzaldehyde diacetate may be prepared in any proportion.

According to the present invention, the compound of formula (III) is dissolved in a first step. The solvent may be any nitration-indifferent solvent, preferably a chlorinated hydrocarbon such as dichloromethane. A mixture of dichloromethane and acetic anhydride may also be used as a solvent. However, the amount of acetic anhydride should be chosen because it significantly influences the weight ratio of the compounds of formulas I and II, even at a given molar ratio of sulfuric acid and nitric acid. After dissolution, additional acetic anhydride is added to the homogeneous solution, cooled, and nitric acid prepared by mixing concentrated nitric acid (65%) and concentrated sulfuric acid (98%) is added slowly, preferably at -20 to + 5 ° C. The binding of the water formed during the nitration and the reaction is a highly exothermic process

Note that nitration is preferably carried out at a temperature of about 0 ° C to + 5 ° C. Addition of nitric acid requires about one hour under the circumstances. The system is then allowed to warm and the reaction mixture is heated to 20-40 ° C, preferably 25-35 ° C, and the reaction is carried out for a few hours (2-4 hours). The reaction mixture is poured onto ice, the two phases are separated, the aqueous phase is extracted with the solvent used for solubilization, the organic phases are combined, washed first with a dilute aqueous solution of sodium carbonate (2-5% by volume), then with water. dried over anhydrous magnesium sulfate. After removal of the desiccant (e.g., by filtration), the solvent is evaporated under reduced pressure. The resulting product, which is essentially a mixture of the compounds of formula (I) and (II), is purified, if desired, for example by treatment or recrystallization with an organic solvent or a mixture of organic solvents (dichloromethane, toluene, etc.).

The molar ratio of sulfuric acid, nitric acid and acetic anhydride calculated for the starting compound (III) in the process of the present invention greatly influences the relative weight ratio of the compounds (I) and (II) formed. For example, increasing amounts of sulfuric acid ((0.1 to 2.3) moles / mole of compound (III)) favor the formation of compound (I), whereas excess acetic anhydride (4 to 11) moles / mole ( Compound III] increases the ratio of compound II. Increasing the amount of nitric acid ((1.4-1.7) moles / mole of the compound of formula (III)) increases the content of the compound of the formula (I), if to a lesser extent. A very valuable finding can be made in our series of experiments in which acetic anhydride [5 mol / mol (III)] and the combined molar ratio of nitric acid and sulfuric acid / mol [III] are kept at 2.9, and within this only nitric acid changing the molar ratio of sulfuric acid from 1.2 / 2.7 to 1.55 / 2.35, the product of the compound of formula (I) is increased from 30 tX to 100 tX, then again from 2.0 / 1.9 molar ratio decrease. In this way, a herbicidal combination with increased selectivity at a ratio of 1.2 / 2.7 to 1.55 / 2.35 and 2.2 / 1.8 to 2.6- / 1.3 can be prepared in any composition.

The compounds of formulas (I) and (II) were first tested individually for herbology and found to be non-phytotoxic to the following crop plants at doses of 0.5 kg.ha ¹ :

of monocots: tobacco, cotton, cabbage, flax, lettuce, carrots, melons, pumpkins and leguminous plants, of dicot: barley, winter wheat, onion, corn, rice and oats, in the same dose (0, 5 kg.ha * ¹ ) effective against a number of dicotyledonous and several monocotyledonous weeds.

Compounds of formula (I) and (II), respectively, exhibit total activity at doses of 2.0 - 3.0 kg.ha * ¹ , each of which is difficult to eradicate monocotyledonous or dicotyledonous weed species (practically most weed species). against:

Of the dicotyledons: Abutilon theophrasti Medic. (Silkworm), Calystegia sepium L. (Hedgehogs), Datura stramonium L. (Hookworm), Galium aparine L. (Sticky mite) and Xanthium strumarium L. (Serpent), among the monocots Alopecurus myosuroides Huds. (Peregrine Brush Lawn), Apera spica-venti L. (Great Warbler), Poa trivalis L. (Lean Meadow), Sorghum halepense L. (Gentian sorghum) and Panicum capillare L. (Hairy Thistle), but at the same dose (2.0 3.0 gkg.ha * ¹ ) Cultivated plants are killed with the exception of soy and possibly winter wheat.

The compounds of formula (I) and (II) can only be used in soybean and possibly winter wheat crops to control particularly resistant weed species. The narrow spectrum acifluorphene, sodium tri-5 - {[2-chloro-4- (trifluoromethyl) / phenoxy) -benzoate, which is used exclusively for the chemical control of soybean, has a similar spectrum of action.

In contrast, it has been found that the mixture of the compounds of Formulas I and II according to the present invention destroys said hard-to-control weed species (practically most weed species) in a dose of 2.0-3.0 kg.ha * ¹ , is not phytotoxic in certain crops (Examples 45-46), especially in legumes (butterflies, plants), according to the present invention. other than wheat selectively used for example in beans, peas, whitetail, lupines, peanuts, leds, lentils, broad beans, alfalfa, red clover, that is to say, in the pods.

In addition to our biological experiments (Examples 45 and 46), our biological experiments (Example 47) have also shown that compounds of Formulas I and II,

The mode of action of the mixtures according to the invention with the energy producing process and / or in the plant root cell cells. indirectly related to inhibition of ATPase function. Our studies focused on whether mixtures of these compounds in varying proportions cause changes in ATPase activity and symptomatic death. In contrast to these four compounds, it has been found that the 16: 1-1: 16 mixtures of the present invention cause greater inhibition of activity at doses of 1 kg.ha / ¹ . Outstanding inhibition was observed with and around the 8: 1 weight ratio of the compounds of formula (1) :( 11).

The compositions of the present invention may be administered in either a pre-emergence or a post-emergence manner. The dose of the active ingredient may vary from 0.2 to 9.0 kg.ha ^1, preferably from 0.5 to 3.0 kg.ha ¹ , depending on soil quality, meteorological conditions, etc. Depending on. Preferably 200-500 l.ha- ¹ water is used for spraying.

Mixtures of the active compounds of formulas I and II according to the invention are formulated in known manner, for example, wettable spray powders (WP), suspension concentrates (SC), water-miscible solution concentrates (SL), emulsion-forming concentrates (EC), water-free granules. (S), dusting agents (DP), or oily suspension concentrates (FO). The active compound mixtures may also be used in the ULV form. In these formulations, the active ingredient mixtures are admixed with solid or liquid inert carriers, diluents and, optionally, other excipients. Excipients may be, for example, surfactants, wetting agents, suspending, dispersing, emulsifying, anti-caking, anti-caking, anti-caking, anti-caking, anti-caking or anti-caking agents, enhancers, antifoams. Suitable solid carriers and diluents include inactive minerals such as various kaolins, porcelain soils, attapulgite, montmorillonite, mica, pyrophyllite, bentonite, diatomaceous earth or highly dispersed synthetic silica, calcium carbonate, oxide, dolomite, gypsum, tricalcium phosphate, Fuller earth. Suitable solid diluents and carriers include tobacco leaf sticks, wood flour, and the like.

Suitable liquid carriers, diluents and solvents include water, organic and / or aqueous organic solvent mixtures, such as methanol, ethanol, n- and i-propanol, diacetone alcohol, benzyl alcohol; their esters, such as methylcellulose; ketones, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc .; ethyl acetate, n- and i-butyl acetate, amyl acetate, isopropyl myristate, dioctyl phthalate, dihexyl phthalate, etc .; aromatic, aliphatic, alicyclic hydrocarbons, paraffinic hydrocarbons, cyclohexane, kerosene, gasoline, benzene, toluene, xylenes, tetralin, decalin; mixtures of alkylbenzenes; chlorinated hydrocarbons include trichloroethane, dichloromethane, perchlorethylene, dichloropropane, chlorobenzene, etc .; lactones include χ-butyrolactone, etc .; lactams are N-methylpyrrolidone, N-cyclohexylpyrrolidone; acid amides include dimethylformamide, etc .; vegetable and animal oils include sunflower seed, linseed, rapeseed, olive, soybean, castor and spermaceti oils, etc.

Suitable wetting, dispersing and emulsifying agents, adhesion enhancing agents, anti-aggregation inhibitors, may be ionic or nonionic. They may be: salts of various saturated and unsaturated carboxylic acids; sulfonates of aliphatic, aromatic, aliphatic-aromatic hydrocarbons; sulfates of alkyl, aryl, aralkyl alcohols; sulfonates of alkyl, aryl, aralkyl acids, esters, ethers; sulfonates of the condensation products of phenol, cresol, naphthalene; sulfated vegetable and animal oils; alkyl, aryl, aralkyl phosphate ethers and the compounds listed above with alkali and alkaline earth metals or organic bases, e.g. salts with various amines, alkanolamines. Sodium lauryl sulfate, sodium 2-ethylhexyl sulfate, dodecylbenzenesulfonic acid sodium, ethanolamine, diethanolamine, triethanolamine, isopropylamine salt; sodium mono- and diisopropylnaphthalenesulfonate; sodium salt of naphthalenesulfonic acid; sodium or calcium salts of sodium diisoctylsulfosuccinate, sodium xylene sulfonate, petroleum sulfonic acid; potash soaps; potassium, sodium, calcium, aluminum, magnesium stearate, etc. The phosphate esters may be polyglycol ethers of phosphated alkyl phenols or fatty alcohols, and their partial or total neutralization with the aforementioned cations or organic bases. Similarly, anionic surfactants include disodium N-octadecyl sulfosuccinate, sodium N-oleyl N-methyl tauride, and various lignin sulfonates.

Nonionic wetting, dispersing and emulsifying agents include ethers of ethylene oxide with C10-C20 alcohols such as stearyl polyoxyethylene, oleyl polyoxyethylene, etc .; ethers with alkyl phenols are polyglycol ethers with t-butyl, octyl, nonyl phenols; esters of various organic acids are esters of stearic acid and myristic acid with polyethylene glycol or polyethylene glycol oleate, etc .; ethylene oxide, propylene oxide block polymers; partial esters of fatty acids with oleic acids or with esters of sorbitol with oleic or stearic acids

EN 200538 Β etc. and condensation products of this type with ethylene oxide; tertiary glycols are 3,6-dimethyl-4-octin-3,6-diol or 4,7-dimethyl-5-decin-4,7-diol; polyethylene glycol thioethers such as dodecyl mercaptan ether with polyethylene glycol and the like.

Suitable tackifiers include alkaline earth metal soaps, sulfobenzoic acid ester salts, natural and artificial water-soluble macromolecules, e.g. casein, starch, arabic gum, cellulose ethers, methyl cellulose, hydroxycellulose, polyvinylpyrrolidone, polyvinyl alcohol, and the like.

Suitable antifoams include low molecular weight polyoxyethylene, polyoxypropylene block polymers, octyl, nonyl, phenyl polyoxyethylene / ethylene oxide units> 5 /, long chain alcohols such as octyl alcohol, special silicone oils.

By using a suitable additive, the formulated compositions are colloid chemically compatible with various fertilizer compositions.

If necessary, known pesticides and / or nutrients are used as ingredients in the formulation.

Wettable sprayable powders (WPs) may be prepared, for example, by mixing the active ingredient mixture, excipient (s), surfactant (s) with carrier materials, and then milling and finally homogenizing. In the case of a liquid surfactant, it is also possible to apply the liquid surfactant to the solid organic or inorganic diluent (s), or to a powder mixture containing the solid, for example by spraying. In the case of a liquid surfactant, it is also possible to suspend the pre-ground solid components in an organic solvent containing a liquid surfactant. This suspension is dried, for example, by spraying. In this way, the surfactant is applied to the surface of the solid active compound mixture and the solid diluent.

A self-emulsifying liquid, a so-called emulsion-forming concentrate (EC), suitable for the preparation of an aqueous dispersion medium emulsion, may be prepared by dissolving the active ingredient or mixture thereof in one of the surfactants described above in a water immiscible solvent. The resulting emulsion-forming concentrate, with water or volumetric mechanical action, forms a spray emulsion that does not change even after standing.

For preparing a suspension concentrate (SC), the wetting and dispersing agents are dissolved in a mixture of water (preferably deionized) and an antifreeze component (preferably ethylene glycol or glycerol), if necessary by heating. To this solution is added a mixture of solid (powder or crystalline) active ingredients while maintaining constant agitation and then, if necessary, an anti-caking component (e.g. Aerosil 200) is added. The resulting granular liquid phase (slurry) is wet milled with wet grinders (e.g., in a closed Dyno mill) to the desired particle size, which is generally max. It is 5 micrometres of grain diameter, and after grinding, antifoam component or thickening component (e.g., Kelzan S) is mixed as needed during homogenization. Alternatively, the order of mixing of the components may be changed and other components (e.g., dye, etc.) may be added as needed. In addition to solids, liquid, water-immiscible or water-miscible agents may also be used as combination partners. Low melting point solids may also be incorporated in the form of a melt without an emulsifier or in admixture with an emulsifier.

ULV formulations can be formulated with EC agents (sometimes similar to SC agents).

Granules (G) for direct use can be prepared by extrusion, layering using a particulate carrier (e.g. limestone), or by absorbing a liquid component with a sorption capacity carrier.

Spray granules (WG) can be prepared from WP and / or SC using some agglomeration technology, for example using a binder in a dragee pan.

Dilution with water or an inert solid diluent, known in the art, results in an agricultural spray or dusting agent having an active ingredient content of generally less than 5% by weight, preferably 3-0.01% by weight. Alternatively, the spray broths of the various single-ingredient formulations may be combined prior to use.

The process of the present invention, the preparation of the compositions, and the biological activity are illustrated in detail by way of example, without limiting the scope of the invention to the examples.

In our examples, we use the following abbreviations:

CHO is a compound of formula III,

Ac2O acetic anhydride, (I) Compound (I), (II) Compound (II), (I / a) 5 - {[2-chloro-4- (trifluoromethyl) phenoxy} -2- nitrobenzaldehyde,

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(II / a) 5 - {[2-chloro-4- (trifluoro-methyl)] phenoxy} - -2-nitro-benzaldehyde; (I / b) 5 - {[2,6-dichloro-4- (trifluoromethyl me- methyl)] phenoxy} -2-nitrobenzaldehyde; (II / b) 5 - {[2,6-dichloro-4- (trifluoromethyl me- methyl)] phenoxy} -2-nitro-benzaldehyde-di- acetate, the. i. active ingredient, ATPase adenosine triphosphatase and % crowd%.

1-9. example

To a 50 ml round-bottomed flask fitted with a stirrer, a thermometer, was added 3 - [(2-chloro-4-trifluoromethyl) phenoxy] -benzaldehyde (6.0 g, 0.02 mol) and an equal volume of dichloroacetate calculated. dissolved in methane. Acetic anhydride is then added to the homogeneous solution. The nitric acid (65% HNO3 and 96% H2SO4) in the appropriate molar ratio was cooled to 5 ° C. After vigorous stirring and cooling of the reaction mixture, the addition of nitric acid is started. The reaction is highly exothermic and the temperature rises several degrees with the addition of a few drops. Keeping the outside temperature at -20 ° C, the addition takes ~ 45 minutes. After the addition was complete, the cooling was stopped and the reaction mixture was stirred for 3 hours at 30 ° C. The mixture was poured onto ice (75 g), the organic layer was separated and the aqueous layer was extracted with dichloromethane (2 x 20 mL). The combined organic layers were washed with 3% NaHCO3 solution (2 x 75 mL) and water, dried over MgSCH. The composition of the solution was determined by gas chromatography. GLC: SE-30, 10m capillary column, 150-300 ° C, 10 ° C / min, FID.

During the evaluation of the chromatograms, the composition was modified using area factors obtained using the standards. The quality analysis of the crude mixture was performed by combined gas chromatography-mass spectrometry.

Using the above procedure, the molar ratio of sulfuric acid to CHO / -HNO3 / AC2O = 1 / 1.6 / 5 can be obtained to give the product composition shown in Table 1.

Table 1

Effect of sulfuric acid content Mole ratio: CH0 / HNO3 / AC2O = 1 / 1.6 / 5

Example number H2SO4 / CHO molar ratio Product composition (%) (I / a) (Π / a) First 0.2 22 78 Second 0.3 28 72 Third 0.4 49 51 4th 0.5 46 54 5th 0.6 51 49 6th 1.0 63 37 7th 1.4 96 4 8th 1.8 98 2 9th 2.3 100 0

10-18. example

1-9. The procedure of Examples 1 to 6 is followed by changing the molar ratio CHO / HNO3 / AC2O = 1 / 1.6 / 5 to 1 / 1.6 / 7. The product composition thus obtained is summarized in Table 2.

Table 2

Effect of sulfuric acid content Mole ratio: CHO / HNO3 / AC2O = 1 / 1.6 / 7

Example number H2SO4 / CHO molar ratio Product composition (%) (I / a) (Π / a) 10th 0.1 5 95 11th 0.2 5 95 12th 0.4 4 96 13th 0.8 4 96 14th 1.2 5 95 15th 1.6 5 95 16th 2.0 6 94 17th 2.4 10 90 18th 2.8 23 77

19-24. example

1-9. The procedure of Examples 1 to 6 is followed by changing the molar ratio AC2O / CHO at a molar ratio of CHO / HNO3 / H2SO4 = 1 / 1.6 / 0.2. The product composition thus obtained is summarized in Table 3.

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Table 3

Effect of the amount of acetic anhydride Mole ratio: CHO / HNCl2 / HzSCU = 1 / 1.6 / 0.2

Table 5

Effect of HNO3 / H2SO4 molar ratio Molar ratio: CHO / AC2O = 1/5

Example number AC2O / CHO molar ratio Product composition (%) II / a) (II / a) 19th 4 19 81 20th 5 15 85 21st 6 8 92 22nd 7 5 95 23rd 9 5 95 24th 11 3 97

25-28. example

1-9. The procedure of Examples 1 to 5 is followed by changing the molar ratio HNO3 / CHO at a molar ratio of CHO / H2SO4 / AC2O = 1 / 0.2 / 5. The product composition thus obtained is summarized in Table 4.

Table 4

Effect of nitric acid content Mole ratio: CHO / H2SO4 / AC2O = 1 / 0.2 / 5

Example HNO3 / CHO Product

number molar ratio composition (%) (I / a) (II / a) 25th 1.4 16 84 26th 1.5 17 83 27th 1.6 22 78 28th 1.7 25 75 29-37. example 1-9. examples according to using a niche away with that changed- with that CHO / AcOO = 1/5 molar ratio-

The HNO3 / H2SO4 molar ratio was changed. The product composition thus obtained is summarized in Table 5.

Example number HNO3 / H2SO4 molar ratio Product composition (%) (I / a) (II / a) 29th 1.2 / 2.7 30 70 30th 1.4 / 2.5 58 42 31st 1.5 / 2.4 87 13 32nd 1.55 / 2.35 100 0 33rd 1.60 / 2.30 100 0 34th 1.8 / 2.1 100 0 35th 2.0 / 1.9 100 0 36th 2.4 / 1.5 42 58 37th 2.6 / 1.3 26 74

Example 38

Wettable Powder Concentrate (NP) (I / a) and (Π / a), 8: 1 by weight, 96% by weight

Cab-O-Sil M5 1%

Dispersion Rate 1494 3%

240 g of the active ingredient mixture, previously milled in a rotary mill, are mixed in a mortar with 2.5 g of Cab-O-Sil M5 silica carrier and 7.5 g of Dispergiermitt 1494 dispersant (sodium salt of sulfonated cresol and formaldehyde condensate). Feed the powder mixture in a vortex mill (Alpine JMRS-80) with a feed pressure of 5 bar and a grinding air pressure of 4.5 bar at 250 g / h. at speed. The resulting sprayable powder, even though it does not contain a separate wetting agent, is well wetted with a maximum particle diameter of 20 micrometres and a floating rate of 10 g / l at 30 ° C after 30 minutes:

84% CIPAC standard D in water and 91% CIPAC standard A in water.

According to this example, any one of the examples 1-37.

from the compound of Example 1 (a mixture of active ingredients) to form a sprayable powder.

Example 39

Emulsion-forming concentrate (20 EC) (II / a) 20% 2-ethoxyethanol 10% cyclohexanone 35% Emulsogen EL 360 7% Tensiofix CD 5 3 tX xylene 25 tX

Weigh 37 g of 2-ethoxyethanol into a 500 ml enameled autoclave with stirring,

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137 g of cyclohexanone and 91 g of xylene were dissolved in a mixture of 26 g of Emulsogen EL 360 (ethoxylated castor oil) emulsifier and 11 g of Tensiofix CD 5 (ethoxylated coconut alcohol) emulsifier. The eraulge was added in a melted state (60-70 ° C). As a final step, 75.5 g (ΙΙ / a) of the active ingredient are weighed and stirring is continued for 2 hours to give a clear clear solution.

According to this example, any one of the examples 1-37. from the product (mixture of active ingredients) obtained in Example 1 to 2 to form an emulsion concentrate.

Example 40

Emulsion-forming concentrate (35 EC) (II / b) 35.0% by weight

Cyclohexanone 10%

Tensiofix CG 21 2% by volume

Tensiofix B 7453 8%

Xylene In a mixture of 45% by weight of cyclohexanone and 133 g of xylene, 6 g of Tensiofix CG 21 (ethoxylated fatty alcohol plus a mixture of ethoxylated nonylphenol and their phosphates) and 24 g of Tensiofix B 7453 emulsifier (calcium dodecylbenzoxyl propoxylated solution of nonylphenol in n-butanol), followed by the final addition of 104 g of the active ingredient (II / b) and dissolution in a liquid containing the surfactants.

According to this example, any one of the examples 1-37. From the product obtained from Example 1 (active ingredient mixture), an emulsion-forming concentrate (35 EC) can be prepared.

Example 41

Aqueous Suspension Concentrate (SC)

active ingredient (s) (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 (deionized) 46.45% (1) the (I / a) and (I / a) and (I / b) and (II / b) active ingredients 23: 1, 16: 1, 11: 1, 8: 1, 5: 1, 4: 1, 2: 1, 1: 1, 1: 2, 1: 4, 1: 5, 1: 8, 1:11,

Mixtures of 1:16 and 1:23 by weight and the active substances (I / a), (I / b), (ΙΙ / a) and (II / b) alone, (2) ethoxylated nonylphenol and ethoxylated nonylphenol -phosphate ester, (3) n-butanolic solution of calcium dodecylbenzenesulfonated, ethoxylated nonylphenol and ethoxylated - propoxylated nonylphenol, (4) xanthan gum (thickening component), (5) dimethylsilicone oil 30 % aqueous emulsion.

5 liters of deionized water were added to a 1 liter dish equipped with a discolor mixer, and 800 g of propylene glycol and 240 g of Tensiofix XN6, 480 g of Tensiofix B 7425, heated to 50 ° C were added under stirring, rise above 35 ° C. Stirring is continued for 20 minutes and then 30 g of Silicon SRE and 30 g of water are added to the slurry.

The wet milling is carried out in two steps. First, in a circulating mode, the suspension is passed through a Fryma MK 95 type corundum colloidal mill until the particle size falls below 90 µm. Fine grinding with Dyno KD 5 tip. in a bead mill until a particle size of <8 µm is achieved. After milling, 20 g of xanthan tuber Rhodopol B 23, 400 g of propylene glycol and 500 g of water were dispersed.

Example 42

Oily suspension concentrate (FO) (I / b) and (II / b) active ingredients 1: 1

by weight 32.7 t% Vaseline oil for cosmetic purposes 48.8 t% Tensiofix AS 4 t% Sapogenat T-080 4.5 t% ethylene glycol 10 t% Silicon SRE 0.5 t%

13.5 g of Sapogenat T-080 emulsifier (ethoxylated tributylphenol) melted at 80 ° C and max. Homogenized 12 g of Tensiofix AS emulsifier (calcium dodecylbenzene sulfonate and ethoxylated nonylphenol in n-butanol solution) pre-melted at 60 ° C is added to 145 g of 60 ° C heated petrolatum oil in a Molinex 075 laboratory bead mill. To the surfactant oil mixture was added 30 g of ethylene glycol and the components were homogenized with stirring for 10 minutes. Subsequently, 98.1 g of the pre-finely powdered active compound mixture is added to the liquid mixture in a mortar. After stirring for 5 minutes at 1,500 rpm with a 1 mm diameter glass bead (350 g clock face), grinding is continued for 2 hours followed by 1.5 g Silicon SRE (30% emulsion of dimethylsilicone oil) for 3 minutes. ) an antifoam agent is distributed in the oily suspension.

In this example, any of the active compound mixtures can be formulated as an oily suspension concentrate.

-917

HU 200538 Β

Example 43

ULV preparation (ΙΙ / a) active ingredient isophorone 2-ethoxyethanol Soya Oil (or Sunflower Oil) 27.5% 30% 10% 32.5% 5 Anhydrous, enamelled autoclave 10

7500 g of isophorone and 2500 g of 2-ethoxyethanol are weighed. In a hammer mill, 6875 g of the pre-comminuted active ingredient (ΙΙ / a) are added to the solvent mixture and stirring is started simultaneously, raising the temperature to 45-50 ° C by switching on the autoclave jacket heater. After 1 hour, after confirming that the active ingredient was dissolved, 8125 g of soybean oil (or sunflower oil) was added to the autoclave for 20 additional minutes while the temperature was cooled to 20 ° C. The ULV formulation is applied in the undiluted form without the addition of water.

. In this example, any of the active ingredients, or mixtures of active ingredients, can be made into ULV forms.

Example 44 Dusting agent (DP) (I / b) containing 30% by weight of active ingredient 1.0% by weight

Ultrasil VN 3 3.0 t% 35

Kaolin 16.0%

Talc 80.0%

9510 g of kaolin is mixed with 1800 g of Ultrasil VN 3 40 synthetic sodium silicate in a ribbon-type belt mixer, 600 g of the active ingredient (I / b) pre-fried in a hammer mill are added and stirring is continued for 30 minutes. Subsequently, in an Ultraplex 250 mill at a feed rate of 20 kg / h, the active compound premix is milled so that the fraction with a particle diameter coarser than 44 micrometers does not exceed 0.5% by weight. After grinding, this active ingredient premix is mixed with talc in a 1: 4 ratio in a Lódige 300 vortex mixer using a 10 minute mixing.

According to this example, any active compound mixture may be formulated as a powder.

Example 45

This example demonstrates the herbicidal efficacy and enhanced selectivity of a mixture of the compounds of the invention / (I / a) and (Π / a) as well as (I / b) and (ΙΙ / b).

Depending on the plant species, the same number (20-50 pieces) of seeds are planted into petri dishes at a depth of 0.5 cm and the soil is watered after sowing. The compositions of Example 41 were diluted with water to form 0.2% spray broths, which were pre-emulsified at 3 kg (ai). when treating with * ¹ dose. The soil is watered daily. Evaluation is performed on the 10th day after emergence and the percentage of damage is expressed. The results are shown in Tables 6 and 7.

The numbers (1-6) in the table refer to the following weeds:

= Abutilon theophrasti = Amarantus retroflexus = Calystegia sepium = Datura stramonium = Galium aparine = Xanthium strumarium

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Example 46

In this example (counterexample), the herbicidal efficacy of (I / a), (Π / a), (I / b) and (Π / b) (active ingredient components) is shown as a function of the doses used.

The experiments were performed as described in Example 45, with the difference that the effectiveness of the herbicidal compound 10 was examined in three dose [1.0-, 3.0- and 9.0 kg (ai) .if ^_1]. Acifluorfen sodium was used as a standard.

The results of the evaluation are summarized in Table 8. 15

Table -1325

% Damage soybean pea pea bean star - 1 2 3 4 5 6 cluster o © o ω ο o © © © CO O O Ο Ο O oo © © r - t τ'-t o © © σ> © © i-H t — 1 o © o co o o τ-H p-4 © o © τρ m © © © © τρ in © Ο O © © C-00 o © © r-i CM Tp © © © o © i-1 0 50 10 60 35 75 85 85 85 85 90 0 65 25 75 45 90 95 95 100 100 100 10 75 45 85 55 100 100 100 100 100 100 o m o t- © © 1-1 o © o C- © © t — 1 T-H in in o t φ © ^ 4 o in © «> © © o o o C * © O r-t © © © C- © © T-H © © © Tp © © in © c * in © o ι-H C * 5 © in © CO Tp © © © o r-i 0 25 10 60 30 70 70 70 80 80 85 0 40 20 70 40 80 80 85 95 100 95 10 60 40 80 50 100 100 100 100 100 100 0 50 10 65 50 80 90 85 85 85 90 0 70 30 70 60 100 100 95 95 100 100 10 75 50 85 80 100 100 100 100 100 100 © © She © She She She She © She She Active substance (s) • s * -ο ώ Ό M i— <CO © η ω o 1-1 CO © r- ili) rt Π CD sign <Ö 4-r co ►— »l — l I / b Λ 1-t acifluorfen- -sodium (standard) untreated control

-1 427

HU 200538 Β

45-46. From the results of the biological assays described in Examples 1 to 8 (Tables 6-8), it can be concluded that the selectivity of the mixture of compounds (I / a) and (II / a) and (I / b) and (II / b) according to the invention is significantly improved. however, the herbicidal activity is not reduced or even increased when the active compounds are used in a 25: 1 to 1: 1 weight ratio. Mixtures of these two mixtures of the two types of herbicides have an antagonistic, antidoting effect on leguminous crops, while showing a synergistic effect on weeds. Mixtures of (I / a) and (II / a) and (I / b) and (II / b) [and / or (I / a) and (II / b) and (I / b) ) and (II / a)] may thus be used, in contrast to the individual components, for the preemergent weed control of cultivated plants.

Example 47

In this example, plant ATPase (adenosine triphosphatase) resulting from treatment with a mixture of the compounds of the invention ((I / a) and (II / a) and (I / b) and (II / b)) change in activity and symptomatic death (phytotoxicity).

2-3-leaf oat plants (Avena sativa) were treated with 0.2% (w / w) of 1% (ai) .ha ' ¹ sprayed water diluted with water of various formulations of Example 41, followed by post-emergent treatment. On days 5 and 5, changes in ATPase activity and symptomatic damage were determined.

The ATPase enzyme was extracted from oat root by W.Weltrup and the enzyme activity was determined by the photometric method of S.A. Solim et al. (2).

The results are summarized in Tables 9 and 10 showing that the four compounds / (I / a), (Π / a), (I / b) and (II / b) and the two compounds / (I / a) + (II / a), respectively. (I / b) + (II / b) / 1:16 - 16: 1 by weight, oats have the highest ATPase activity inhibition or death rate (I / a) + (Π / a) and ( 8/1 (I / b) and (II / b).

Literature:

1. W.Weltrup: The in vivo and in vitro effects of Ca ² 'and Al ³ * upon ATP in barley roots.

Journal of Plant Nutrition 6/5 /, 349-361 / 1983.

2. S.A. Soliman, A.K.A.ElRefaie, A.H.El-Sebae, and M.I.Zeid: Toxicity of somatic insecticides to dry wood cerebellum Cryptotermes brevis (Walker) in relation to ATPase and AChE inhibition.

International Pest Control 1981. Jan / -Feb.

Table 9

weight ratio symptomatic damage ATPase in activity inhibition (I / a): (II / a) control in X 3. 5. on the sun 3. Day 5 1 - 38 51 10 15 16 1 60 63 26 40 8 1 85 100 35 70 4 1 81 95 28 40 2 1 64 90 22 35 1 1 56 65 16 29 1 2 45 60 10 20 1 4 40 55 + 15 1 8 36 50 + 10 1 16 32 40 + 10 - 1 '30 38 + 8

+ indicates a slight inhibition

Table 10

symptomatic damage Inhibition of ATPase activity a control %-in (I / b): (II / b) 3. Day 5 3. Day 5 1 - 40 55 15 20 16 1 85 75 31 43 8 1 90 100 40 78 4 1 83 98 32 45 2 1 65 95 25 40 1 1 55 76 20 30 1 2 52 62 13 25 1 4 45 58 5 18 1 8 45 52 + 10 1 16 41 45 + 10 - 1 32 40 + 10

+ indicates a slight inhibition

-15HU 200538'Β

Claims (10)

PATENT CLAIMS CLAIMS 1. A highly selective herbicidal composition, characterized in that the active ingredient is present in an amount of 0.05 to 96% by weight and 30: 1 to 1:30 by weight, containing 5- (substituted phenoxy) -2-nitrobenzaldehyde (I) and 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetate (II) 10 - in which formulas X is hydrogen or chlorine, one or more solid and / or liquid excipients, preferably ground minerals, or an inert solvent, preferably xylene and / or cyclohexanone, optionally surfactant (s), preferably anionic and / or non-ionic emulsifier (s) and / or dispersant (s). Composition according to claim 1, characterized in that the weight ratio of the compounds of the formulas I and II, in which X is as defined in claim 1, is from 20: 1 to 1: 1. 3. The composition according to claim 1 or 2, wherein the 5- (substituted phenoxy) -2-nitrobenzaldehyde of formula (I) is 5 - {[2-chloro-4- (trifluoromethyl)]. ) / phenoxy} -2-nitrobenzaldehyde, 5 - {[2-chloro-4- (trifluoromethyl) / phenoxy} as 5- (substituted phenoxy) -2-nitro-benzaldehyde diacetate of formula II Contains -2-nitrobenzaldehyde diacetate. Composition according to claim 1 or 2, characterized in that the 5- (substituted phenoxy) -2-nitrobenzaldehyde of formula (I) 35 is 5 - {[2,6-dichloro-4- (trifluoromethyl)]. ) / phenoxy} -2-nitrobenzaldehyde, 5 - ((2,6-dichloro-4- 40 - (trifluoromethyl)) as 5- (substituted phenoxy) -2-nitrobenzaldehyde diacetate of formula (II) / containing phenoxy} -2-nitrobenzaldehyde diacetate. 5. A process for preparing 5- (substituted phenoxy) -2-nitrobenzaldehyde (I) and 5- (substituted phenoxy) -2-nitrobenzaldehyde (diacetate) (II) - in which formulas X is a hydrogen atom for the preparation of a mixture of 30: 1 to 1:30 by weight in a single step, characterized in that one mole of 3- (substituted phenoxy) benzaldehyde of formula (III) - in which formula X is a hydrogen atom in a solvent, preferably dichloromethane, at a temperature of -30 to + 50 ° C, with 4 to 11 moles of acetic anhydride and 1.2 to 2.6 moles of nitric acid and 0.1 to 2.8 moles of sulfuric acid. The mixture of compounds of formula (I) and (II) is recovered from the reaction mixture in a known manner and, if desired, purified. 6. A process according to claim 5 for the preparation of a compound of formula I and II in which X is a mixture of from 30: 1 to 1: 6 by volume in a single step, characterized in that The 3- (substituted phenoxy) benzaldehyde of formula (III) wherein X is hydrogen is a solvent, preferably in the presence of dichloromethane, with 5 to 6 moles of acetic anhydride, and 1.5 to 1.7 moles of nitric acid and 0.1 to 1.8 moles. of a mole of sulfuric acid. A process according to claim 5 for the preparation of a mixture of compounds of formula I and II in which X is as defined in claim 5 in a weight ratio of from 25: 1 to 1: 2, characterized in that The 3- (substituted phenoxy) benzaldehyde of formula (III) wherein X is hydrogen is a solvent, preferably in the presence of dichloromethane, with 6 to 7 moles of acetic anhydride, and 1.5 to 1.7 moles of nitric acid and 0.1 to 2.8 moles. of a mole of sulfuric acid. A process according to claim 5 for the preparation of a compound of general formula (I) and (II) wherein X is a weight ratio of from 30: 1 to 1: 4 as claimed in claim 5, characterized in that The 3- (substituted phenoxy) benzaldehyde of formula III wherein X is hydrogen is a solvent, preferably in the presence of dichloromethane, with 5 molar acetic anhydride and 1.2-1.6 molar nitric acid and Reaction is carried out with nitric acid, a mixture of 2.3 to 2.7 moles of sulfuric acid. 9. A process according to claim 5 for the preparation of a mixture of compounds of formula I and II in which X is a weight ratio of from 30: 1 to 1: 4 as claimed in claim 5, characterized in that 3- (substituted phenoxy) benzaldehyde of formula (III) wherein X is hydrogen, in the presence of a solvent, preferably dichloromethane, with 5 moles of acetic anhydride and 2.2-2.6 moles of nitric acid and Reaction is carried out with nitrating acid consisting of a mixture of 1.3 to 1.7 moles of sulfuric acid. 10. A herbicidal composition comprising from 0.05 to 96% by weight of the active ingredient 5 (substituted phenoxy) -2-nitrobenzaldehyde diacetate (II). - in which formula X is hydrogen or chlorine, one or more solid and / or liquid carriers, preferably ground minerals, or inert solvent, preferably xylene or cyclohexanone, optionally surfactant (s), preferably anionic and / or nonionic emulsifier (s) and / or dispersant (s).