ES2715834T3 - Use and agrochemical composition of dibutylamides of carboxylic acids - Google Patents

Abstract

Use of carboxylic acid amides of the formula (I) R1-CO-NR2R3 (I), wherein R1 means C16-C18 alkyl or C16-C18 alkenyl and R2 means C4 alkyl and R3 means C4 alkyl for the promotion of Protioconazole penetration in plants.

Description

DESCRIPTION

Use and agrochemical composition of dibutylamides of carboxylic acids

The invention relates to the use of dibutylamides of carboxylic acids in agrochemical formulations and plant protective agents, agrochemical formulations and plant protective agents containing such compounds, and use as a substance for addition in tank mix, in which the formulations and the plant protection agent contains protioconazole as an agrochemical active substance.

From EP-A 0453899 the use of C5-C19 alkylcarboxylic acid dimethylamides is known as crystallization inhibitors for certain azol fungicides that tend to crystallize, such as tebuconazole. The use of dibutylamides of carboxylic acids for this purpose or for the improvement of the action of agrochemical substances after application on the plant is not disclosed or suggested in this document.

From WO2005 / 104844 it is known that C5-C19 alkylcarboxylic acid dimethylamides are penetration promoters for certain active ingredients, such as protioconazole. The use of dibutylamides of carboxylic acids for this purpose or for the improvement of the action of agrochemical substances after application on the plant is not disclosed or suggested in this document.

In US2011 / 0124505, compositions with C5-C19 alkylcarboxylic acid dimethylamide are claimed as solvents for biocides and pesticides and different emulsifiers. The use of dibutylamides of carboxylic acids for this purpose or for the improvement of the action of agrochemical substances after application on the plant is not disclosed or suggested in this document.

In DE-A-4341986 and WO-A-2008/145063 dialkyl amides of alkyl or alkenyl carboxylic acid are used in agrochemical formulations, to prevent the formation of crystals in atomization broths. In DE-A-4341986 and WO-A-2008/145063 no teaching is given to use alkyl or alkenyl carboxylic acid dialkylamides as a penetration promoter.

WO-A-1988/02216 teaches the use of dialkyl amides of carboxylic acid to promote the penetration of medicinal drugs, through human or animal skin, as well as methods for the use of dialkyl amides of carboxylic acid in agrochemical applications. . However, WO-A-1988/02216 does not disclose in particular the use of the C16-C18 alkyl / alkenyl carboxylic acid dibutylamides used in accordance with the invention.

WO-A-2010/078852 teaches agrochemical formulations in the form of suspensoemulsions. However, WO-A-2010/078852 does not teach the use of C16-C18 alkyl / alkenyl carboxylic acid dibutylamides used in accordance with the invention in EC or OD formulations.

WO-A-2008/101629 describes biocidal compositions, which contain certain dialkylamides based on oleic acid or linoleic acid, as well as their use as solvents or dispersing agents for biocides.

It was now surprisingly found that the dibutylamides of carboxylic acids used in accordance with the invention, with respect to the dimethylamides of carboxylic alkyl acids, are much more bad solvents. In spite of this, they are outstanding and even better additives for the promotion of the penetration of protioconazole through the cuticle of the plants, compared with the dimethylamides of known carboxylic acids (see examples 16 and 17). With this they are suitable for increasing the biological action of protioconazole. In this regard, they are in order of magnitude, less volatile of the surface of the sheet, compared with dimethylamides of carboxylic alkyl acids. In the dibutylamides of carboxylic acids used in accordance with the invention, partial differences in the chain lengths C8-10, C12-14 (based on coconut fat) and C15- were detectable, depending on the carboxylic acid or fatty acid present. 18 (based on tallow fat) in the influence on the temporal course of active ingredient penetration. In particular, it is shown that C16-C18 alkyl / alkenyl carboxylic acid dibutylamides in EC formulations lead to a clearly improved penetration with respect to carboxylic acid dimethylamides (examples 16, 18).

Additionally, it is shown that the C16-C18 alkyl / alkenyl carboxylic acid dibutylamides, with respect to the C12-C14 alkyl / alkenyl carboxylic acid dibutylamides and in a very particular way against the analog carboxylic acid dimethylamides, exhibit a penetration behavior clearly modified. C16-C18 alkyl / alkenyl carboxylic acid dibutylamides are absorbed in the cuticle of the sheet, but no longer penetrate inside the sheet; by this they can ensure the penetration promoting effect for a longer period of time. In particular, dimethyl amides of analogous carboxylic acids exhibit a clearly stronger penetration in the sheet, whereby the penetration-promoting effect is limited to the first hours after spray application (example 22).

Another advantage of the C16-C18 alkyl / alkenyl carboxylic acid dibutylamides over the C8-C14 alkyl / alkenyl carboxylic acid dibutylamides is their wide absence of volatility.

Therefore, the use of carboxylic acid amides of the formula (I) is an object of the invention.

R1-CO-NR2R3 (I),

in which

R1 means C16-C18 alkyl or C16-C18 alkenyl and

R2 means C4 alkyl and

R3 means C4 alkyl

for the promotion of the penetration of protioconazole in plants.

In this regard, the penetration of protioconazole in plants means the penetration of protioconazole through the surface of the leaves in the plant.

R2 and R3 are preferably alkyl groups with 4 carbon atoms, the same or different, particularly preferably the same, particularly preferably n-butyl, 1-methyl-propyl or 2-methyl-propyl, very particularly preferably n- butyl.

R1 exhibits 16-18 carbon atoms (tallow carboxylic acid dibutylamide). In this regard, it can mean C16-C18 alkyl or C16-C18 alkenyl.

It is simple to prepare the dibutylamides of carboxylic acids. For example, in WO-A-1995/015685, in example 1 on page 26, for the di-n-propylamide of hexanoic acid a suitable manufacturing process is disclosed, which analogously can also be applied for dibutylamides of carboxylic acids (for example in example 16 on page 28 of WO-A-1995/015685).

Preferably a mixture of at least two carboxylic acid amides of the formula (I) is used. Preferably, a mixture based on the tallow fatty acid composition is applied. A typical source of raw material is bovine tallow fatty acids.

Particularly preferably, the mixture used according to the invention exhibits both at least one carboxylic acid amide of the formula (I), in which R 1 represents C 16 -C 18 alkyl, as well as at least one carboxylic acid amide of the formula (I), in which R 1 represents C 16 -C 18 alkenyl.

In particular, a mixture based on the fatty acid composition in bovine tallow is preferred. It contains predominantly saturated and unsaturated fatty acids with an even number of carbon atoms. Fatty acids with an odd number of carbon atoms, such as pentadecanoic acid (C15) or margaric acid (C17) are present only in small quantities.

Typically, bovine tallow contains more than 80% by weight, as a rule even more than 90% by weight, based on the sum of the weights of fatty acids, saturated and unsaturated C16-C18 fatty acids, in particular palmitic acid ( C16 saturated), palmitoleic acid (C16 partially unsaturated), margaric acid (C17 saturated), stearic acid (C18 saturated) and oleic acid (C18 partially unsaturated). In this regard, margaric acid and palmitoleic acid are present only in small amounts (typically less than 10% by weight in the sum).

The dibutylamides of carboxylic acids have a reduced volatility from the surface of the sheets in orders of magnitude, with respect to the dimethylamides of carboxylic acids used as solvents. Dibutylamides of carboxylic acids with an alkyl chain length R 1 of C 8 -C 10, however, still exhibit considerable volatility relevant in practice. Even shorter chain lengths are, due to their volatility, generally unsuitable for use as additives that increase biological efficacy, in agrochemical formulations. Also in the dibutylamides of carboxylic acids with an alkyl chain length R 1 of C 12 -C 14 a certain volatility is still present. On the other hand, due to their molecule size, dibutylamides of carboxylic acids with an alkyl chain length R1 of more than C18, that is C20, C22, or more C22 are still poorly suited to penetrate significantly in the cuticle of the plants and with them are excluded as promoters of penetration above the level of the plants. Thus, dibutylamides of carboxylic acids with an alkyl chain length R1 of C16-C18 are ideal.

The carboxylic acid amides of the formula (I) are used individually or in the form of mixtures. If the description or claims refer to carboxylic acid amides, they expressly mean individual compounds or mixtures of various carboxylic acid amides.

The amount of one or more compounds of the formula (I) for use according to the invention in plant protection agents may vary within wide limits, depending on the active ingredient and type of formulation. The compounds of the formula (I) can be used in all current agrochemical formulations, preferably in the liquid ones. It is also the object of the present invention to use the carboxylic acid amides of the formula (I) for the improvement of plant-level efficacy as a tank mixing additive, that is to say that the carboxylic acid amides are added directly. just before the application of a spray broth prepared from a concentrated formulation. However, in principle the compounds can also be applied in solid form.

The use according to the invention of the carboxylic acid amides of the formula (I) occurs for example in ready-to-use protioconazole and plant protection formulations (broths for atomization) preparations prepared therefrom by dilution (preferably with water).

The invention also relates to formulations in the form of emulsion concentrates (EC) or oil dispersions (OD) containing

• protioconazole as well as

• at least one carboxylic acid amide of the formula (I)

R1-CO-NR2R3 (I),

in which

R1 means C16-C18 alkyl or C16-C18 alkenyl and

R2 means C4 alkyl and

R3 means C4 alkyl as well as

• at least one solvent and / or oil.

Preferably the content of the at least one carboxylic acid amide of the formula (I) in the formulation is of

• 1 to 50% by weight,

• particularly preferably 2 to 40% by weight,

• very particularly preferably 5 to 25% by weight.

Due to their physical properties, such as aggregation status, viscosity, fixed point, dibutylamides of carboxylic acids are less suitable for application in solid formulations such as granules (WG, WP). Suitable types of formulation are liquid formulations. However, due to the unmarked dissolution strength present of the carboxylic acid amides, a use in suspensoemulsions (SE) containing active ingredients in liquid and solid form is not preferred.

Particularly preferred is the use in emulsion concentrates (EC), in which the dibutylamides of carboxylic acids are uniformly distributed in the homogeneous formulation and are applied with the most intimate contact with the dissolved active ingredients, by means of the Spray application on the target crop sheet. Likewise, the use in oil dispersions (OD) is particularly preferred, in which the dibutylamides of carboxylic acids in the oil phase in the formulation and after spray application remain on the sheet in direct contact with the principle. active.

The invention also relates to plant protection agents, ready for use, which contain

• protioconazole as well as

• at least one carboxylic acid amide of the formula (I)

• R1-CO-NR2R3 (I),

in which

R1 means C16-C18 alkyl or C16-C18 alkenyl and

R2 means C4 alkyl and

R3 means C4 alkyl as well as

• at least one solvent and or oil as well as

• Water.

Preferably the content of the at least one carboxylic acid amide of the formula (I) in the plant protective agent is of

• 0.01 to 10% by weight,

• particularly preferably 0.02 to 2% by weight,

• very particularly preferably 0.05 to 0.2% by weight.

If a formulation / plant protection agent contains several carboxylic acid amides of the formula (I), then the amount data is understood as the total content of all the carboxylic acid amides of the formula (I).

The definitions of radicals, ranges of values or clarifications cited in general above or cited in preferred scopes, can be combined in any way also mutually, therefore between the respective scopes and preferred scopes.

Suitable oils are in particular vegetable oils or their esters or mineral oils or other organic solvents. Particularly suitable are sunflower oil, rapeseed oil or methyl ester of rapeseed oil, as well as paraffin oil or mineral white oil and mixtures of aromatic hydrocarbons (preferably reduced Naphalin), for example SolvessoMR.

In the sense of this invention, suitable solvents are in particular also organic solvents such as N, N-dimethyldecanamide, N, N-dimethyloctanamide, N, N-dimethyldodecanamide, gamma-butyrolactone, Rhodiasolv PolarcleanMR (methyl-5- (dimethylamino) -2- methyl-5-oxopentanoate) N-methylpyrolidone or mixtures of aromatic hydrocarbons (preferably reduced naphalin), for example SolvessoMR. Other suitable solvents are for example aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene, or methylene chloride, aliphatic hydrocarbons such as cyclohexane, alcohols such as methanol, ethanol, iso -propanol, butanol or glycol as well as its ethers and esters (also fats and oils) and (poly-) ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulfoxide.

Particularly preferably, as an agrochemical active ingredient protioconazole is used. Formulations containing

• 15 - 35% by weight of protioconazole and

• 25 - 45% by weight of N, N-dimethyldecanamide and

• 10-40% by weight of one or more emulsifiers, preferably castor oil polyglycerol ester or a mixture of ethoxypropoxy-triestyryl-phenol (block copolymer) and triestirl-phenol-ethoxylate with an average of 16 units of EO or a mixture of 2-ethylhexanolpropylenenetylene glycol ether, ethoxypropoxy-triethyryl-phenol (block copolymer), alkoxylated ethylenediamine with an average of 16 units of EO and 16 units of PO and tristirl-phenol-ethoxylate with an average of 16 units of EO or a mixture of emulsifiers mentioned in another combination and

• 0.01 - 1.0% by weight of defoamer, preferably silicone antifoam emulsion and

• 5-30% by weight of C16-C18 alkyl carboxylic acid dibutylamide and C16-C18 alkenyl carboxylic acid dibutylamide (in the sum).

The mechanism of action of carboxylic acid amides as penetration promoters is essentially independent of the type of agrochemical active ingredient used. Therefore, its use in formulations and protective agents of plants, containing protioconazole, whose biological efficacy can be increased in a crop or harmful plant, through high penetration, is considered.

As examples of other fungicides are mentioned:

(1) Ergosterol synthesis inhibitors, such as Aldimorph, Azaconazole, Bitertanol, Bromuconazole, Cyproconazole, Diclobutrazol, Diphenoconazole, Diniconazole, Diniconazole-M, Dodemorph, Dodemorph acetate, Epoxiconazole, Etaconazole, Fenarimol, Fenbuconazole, Fenhexamide, Fenpropidin, Fenpropimorph, Fluquinconazole, Flurprimidol, Flusilazol, Flutriafol, Furconazole, Furconazole-Cis, Hexaconazole, Imazalil, Imazalil sulfate, Iibconaconazole, Nibconaconazole, Nibconaconazole, Nibconaconazole, Nibconaconazole, Nibconaconazole, Nibconaconazole, Nibconaconazole, Nibconaconazole, Nichconaconazole, Nibconaconazole, Nichloconazole, Nichconaconazole Oxpoconazole, Paclobutrazol, Pefurazoat, Penconazol, Piperalin, Prochlorozine, Propiconazole, Piributicarb, Pirifenox, Quinconazole, Simeconazole, Spiroxamin, Tebuconazole, Terbinafin, Tetraconazole, Triadimefon, Triadimenol, Tridemorph, Triflorzolone, Vinylonazole, Unicorone, Vinyl Voriconazole, 1 - (4-chlorophenyl) -2- (1 H-1,2,4-triazol-1-yl) cycloheptanol, methyl-1 - (2,2-dimethyl-2,3-dihydro-1 H- inden-1-yl) -1 H-imidazol-5-carboxylate, N '- {5- (difluoromethyl) -2-methyl-4- [3- (trimethylsilyl) propoxy] phenyl} -N-ethyl-N-methylimidoformamide , N-ethyl-N-methyl-N '- {2-methyl-5- (trifluoromethyl) -4- [3- (trimethylsilyl) propoxy] phenyl} imidoformamide and O- [1 - (4-methoxyphenoxy) -3, 3-dimethylbutan-2- il] -1 H-imidazol-1-carbotioate.

(2) Breathing inhibitors (respiratory chain inhibitors), such as Bixafen, Boscalid, Carboxin, Diflumetorim, Fenfuram, Fluopiram, Flutolanil, Fluxapiroxad, Furametpir, Furmeciclox, Isopyrazam racemate mixture of epimers syn 1 RS, 4SR , 9RS and 1 RS antiepimer racemate, 4SR, 9SR, Isopyrazam (antiepimer racemate), Isopyrazam (1R, 4S, 9S antiepimer enantiomer), Isopyrazam (1S, 4R, 9R antiepimer enantiomer, Isopyrazam racemate syn 1 RS, 4SR, 9RS), Isopyrazam (enantiomer of epimers syn 1 R, 4S, 9R), Isopyrazam (enantiomer of epimers syn 1S, 4R, 9S), Mepronil, Oxicarboxin, Penflufen, Pentiopirad, Sedaxane, Thifluzamide, 1- methyl-N- [2- (1,1,2,2-tetrafluoroethoxy) phenyl] -3- (trifluoromethyl) -1 H -pyrazol-4-carboxamide, 3- (difluoromethyl) -1-methyl-N- [2 - (1,1,2,2-tetrafluoroethoxy) phenyl] -1 H -pyrazol-4-carboxamide, 3- (difluoromethyl) -N- [4-fluoro-2- (1,1,2,3,3, 3-hexafluoropropoxy) phenyl] -1-methyl-1 H-pyrazol-4-carboxamide, N- [1 - (2,4-dic lorophenyl) -1-methoxypropan-2-yl] -3- (difluoromethyl) -1-methyl-1 H -pyrazol-4-carboxamide, 5,8-difluoro-N- [2- (2-fluoro-4- { [4- (trifluoromethyl) pyridin-2-yl] oxy} phenyl) ethyl] quinazolin-4-amine, N- [9- (dichloromethylene) -1,2,3,4-tetrahydro-1,4-methanophthalene-5 -yl] -3- (difluoromethyl) -1-methyl-1 H -pyrazol-4-carboxamide, N - [(1 S, 4R) -9- (dichloromethylene) -1,2,3,4-tetrahydro-1 , 4-methanonaphthalene-5-yl] -3- (difluoromethyl) -1-methyl-1 H-pyrazol-4-carboxamide and N - [(lR, 4S) -9- (dichloromethylene) -1.2.3.4- tetrahydro- 1,4-methanonaphthalene-5-yl] -3- (difluoromethyl) -1-methyl-1 H-pyrazol-4-carboxamide.

(3) Breathing inhibitors (breathing chain inhibitors) in the complex III of the breathing chain, such as Ametoctradin, Amisulbrom, Azoxistrobin, Cyazofamide, Coumetoxistrobin, Coumoxistrobin, Dimoxistrobin, Enestroburin, Famoxadon, Fenamidon, Phenoxystrobin , Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxistrobin, Piraclostrobin, Pirametostrobin, Piraoxistrobin, Piribencarb, Triclopiricarb, Trifloxistrobin, (2E) -2- (2 - {[6- (3-chloro-2-methylphenoxy) -5-fluoropyrimid 4-yl] oxy} phenyl) -2- (methoxyimino) -N-methylenamnamide, (2E) -2- (methoxyimino) -N-methyl-2- (2 - {[({(1 E) -1- [ 3- (trifluoromethyl) phenyl] ethyliden} amino) oxy] methyl} phenyl) ethanamide, (2E) -2- (methoxyimino) -N-methyl-2- {2 - [(E) - ({1- [3- (trifluoromethyl) phenyl] ethoxy} imino) methyl] phenyl} ethanamide, (2E) -2- {2 - [({[(1 E) -1 - (3 - {[(E) -1-fluoro-2- phenyletenyl] oxy} phenyl) ethylidene] amino} oxy) methyl] phenyl} -2- (methoxyimino) -N-methylethanamide, (2E) -2- {2 - [({[(2E, 3E) -4- (2 , 6-dichlorophenyl) but-3-en-2-ylidene] amino} oxy) methyl ] phenyl} -2- (methoxyimino) -N-methylethanamide, 2-chloro-N- (1,1,3-trimethyl-2,3-dihydro-1 H-inden-4-yl) pyridine-3-carboxamide, 5-methoxy-2-methyl-4- (2 - {[({(1 E) -1 - [3- (trifluoromethyl) phenyl] ethyliden} amino) oxy] methyl} phenyl) -2,4-dihydro-3H -1,2,4-triazol-3-one, methyl- (2E) -2- {2 - [({cyclopropyl [(4-methoxyphenyl) imino] methyl} sulfanyl) methyl] phenyl} -3-methoxypropy-2 -enoate, N- (3-ethyl-3,5,5-trimethylcyclohexyl) -3- (formylamino) -2-hydroxybenzamide, 2- {2 - [(2,5-dimethylphenoxy) methyl] phenyl} -2-methoxy -N-Methylacetamide and (2R) -2- {2 - [(2,5-dimethylphenoxy) methyl] phenyl} -2-methoxy-N-methylacetamide.

(4) Inhibitors of mitosis and cell division, such as Benomil, Carbendazim, Chlorophenazole, Dietofencarb, Etaboxam, Fluopicolid, Fuberidazole, Pencycuron, Thiabendazole, Thiophanat-methyl, Thiophanat, Zoxamid, 5-chloro-7- (4-methylpiperid -1-yl) -6- (2,4,6-trifluorophenyl) [1,2,4] triazolo [1,5-a] pyrimidine and 3-chloro-5- (6-chloropyridin-3-yl) - 6-methyl-4- (2,4,6-trifluorophenyl) pyridazine.

(5) Compounds with multi-site activity, such as a mixture of Bordeaux, Captafol, Captan, Chlorothalonil, copper preparations such as copper hydroxide, copper naphthenate, copper oxide, copper oxychloride, copper sulfate, Dichlofluanid, Dithianon, Dodine , Dodine free base, Ferbam, Fluorofolpet, Folpet, Guazatin, Guazatinacetate, Iminoctadin, Iminoctadinalbesilat, Iminoctadintriacetat, Mankupfer, Mancozeb, Maneb, Metiram, Zinkmetiram, copper oxine, Propamidin, sulfur propineb sulfur, example Calcium, Thiram, Tolilfluanid, Zineb and Ziram.

(6) Resistance inductors, such as Acibenzolar-S-methyl, Isothianyl, Probenazole and Thiadinyl.

(7) Inhibitors of amino acid and protein biosynthesis, such as Andoprim, Blasticidin-S, Cyprodinil, Casugamycin, Casugamycin Hydrochloride, Mepanipirim, Pyrimethanil and 3- (5-fluoro-3.3.4.4-tetramethyl-3, 4-dihydroisoquinolin-1-yl) quinoline.

(8) Inhibitors of ATP production, such as Fentin acetate, Fentin chloride, Fentin hydroxide and Siltiofam.

(9) Inhibitors of cell wall synthesis, such as Benthiavalicarb, Dimetomorph, Flumorph, Iprovalicarb, Mandipropamid, Polyoxins, Polyoxorim, Validamycin A and Valifenalat.

(10) Inhibitors of lipid and membrane synthesis, such as Biphenyl, Cloroneb, Dicloran, Edifenphos, Etridiazol, Iodocarb, Iprobenfos, Isoprotiolan, Propamocarb, Propamocarb hydrochloride, Protiocarb, Pirazophos, Quintozen, Tecnazene and Tolclofosthyl.

(11) Melanin synthesis inhibitors, such as Carpropamid, Diclocymet, Phenoxanil, Fthalid, Pyroquilon, Tricyclazole and 2,2,2-trifluoroethyl {3-methyl-1 - [(4-methylbenzoyl) amino] butan-2 -il} carbamate.

(12) Nucleic acid synthesis inhibitors, such as Benalaxil, Benalaxil-M (Kiralaxil), Bupirimat, Clozilacon, Dimetirimol, Etirimol, Furalaxil, Hymexazol, Metalaxil, Metalaxil-M (Mefenoxam), Ofurace, Oxadixil and oxolinic acid .

(13) Signal transduction inhibitors, such as Chlozolinat, Fenpiclonil, Fludioxonil, Iprodion, Procymidon, Quinoxifen and Vinclozolin.

(14) Uncouplers, such as Binapacril, Dinocap, Ferimzon, Fluazinam and Meptildinocap.

(15) Other compounds, such as, for example, Benthiazol, Betoxazin, Capsimycin, Carvon, Chinometionat, Piriofenon (Chlazafenon), Cufraneb, Cyflufenamid, Cymoxanil, Cyprosulfamide, Dazomet, Debacarb, Dichlorophen, Diclomeztil, Diphenyaminamine, Diphenyaminamine, Diphenyaminamine, Diphenyaminamine, Diphenyaminamine , flumetover, Fluoromid, flusulfamide, Flutianilo, fosetyl-aluminum, fosetyl-calcium, fosetyl-sodium, hexachlorobenzene, Irumamycin, methasulfocarb, methyl isothiocyanate, Metrafenon, Mildiomycin, natamycin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, Octhilinone, Oxamocarb, Oxifenthiin, pentachlorophenol and its salts, Phenothrin, phosphoric acid and its salts, Propamocarb-Fosetilat, Propanosin-sodium, Proquinazid, Pirimorph, (2E) -3- (4-tert-butylphenyl) -3- (2-chloropyridin-4-yl) - 1 - (morpholin-4-yl) prop-2-en-1 -one, (2Z) -3- (4-tertbutylphenyl) -3- (2-chloropyridin-4-yl) -1 - (morpholin-4- il) prop-2-en-1 -one, Pyrrolnitrin, Tebufloquin, Tecloftalam, Tolnifanid, Triazoxid, Trichlamide, Zarilamide, (3S, 6S, 7R, 8R) -8-b encyl-3 - [({3 - [(isobutyryloxy) methoxy] -4-methoxypyridin-2-yl} carbonyl) amino] -6-methyl-4,9-dioxo-1,5-dioxonan-7-yl 2- methylpropanoate, 1 - (4- {4 - [(5R) -5- (2,6-difluorophenyl) -4,5-dihydro-1,2-oxazol-3-yl] -1,3-thiazol-2- il} piperidin-1-yl) -2- [5-methyl-3- (trifluoromethyl) -1 H-pyrazol-1-yl] ethanone, 1 - (4- {4 - [(5S) -5- (2 , 6-difluorophenyl) -4,5-dihydro-1,2-oxazol-3-yl] -1,3-thiazol-2-yl} piperidin-1-yl) -2- [5-methyl-3- ( trifluoromethyl) -1 H-pyrazol-1-yl] ethanone, 1 - (4- {4- [5- (2,6-difluorophenyl) -4,5-dihydro-1,2-oxazol-3-yl] - 1,3-thiazol-2-yl} piperidin-1-yl) -2- [5-methyl-3- (trifluoromethyl) -1 H-pyrazol-1-yl] ethanone, 1 - (4-methoxyphenoxy) -3 , 3-dimethylbutan-2-yl-1 H-imidazol-1-carboxylate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,3-dibutyl-6-chlorothiene [2,3-d ] pyrimidin-4 (3H) -one, 2,6-dimethyl-1 H, 5H- [1,4] dithiino [2,3-c: 5,6-c '] dipyrrol-1,3,5,7 (2H, 6H) -tetrone, 2- [5-methyl-3- (trifluoromethyl) -1 H-pyrazol-1-yl] -1 - (4- {4 - [(5R) -5-phenyl-4, 5-dihydro-1,2-oxazol-3-yl] -1,3-thiazol-2-yl} piperidin-1-yl) ethanone, 2- [5-methyl-3- (tr ifluoromethyl) -1 H-pyrazol-1-yl] -1 - (4- {4 - [(5S) -5-phenyl-4,5-dlhydro-1,2-oxazol-3-yl] -1,3 -thiazol-2-yl} piperidin-1-yl) ethanone, 2- [5-methyl-3- (trifluoromethyl) -1 H-pyrazol-1-yl] -1 - {4- [4- (5-phenyl -4,5-dihydro-1,2-oxazol-3-yl) -1,3-thiazol-2-yl] piperidin-1-yl} ethanone, 2-butoxy-6-iodo-3-propyl-4H- chromen-4-one, 2-chloro-5- [2-chloro-1- (2,6-difluoro-4-methoxyphenyl) -4-methyl-1H-imidazol-5-yl] pyridin, 2-phenylphenol and its salts, 3- (4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) quinolin, 3,4,5-trichloropyridine-2,6-dicarbonitrile, 3- [5- (4-chlorophenyl) -2,3-dimethyl-1,2-oxazolidin-3-yl] pyridin, 3-chloro-5- (4-chlorophenyl) -4- (2,6-difluorophenyl) -6-methylpyrididazine, 4- (4-chlorophenyl) -5- (2,6-difluorophenyl) -3,6-dimethylpyridazine, 5-amino-1,3,4-thiadiazol-2-thiol, 5-chloro-N'-phenyl-N '- (prop-2-in-1-yl) thiophene-2-sulfonohydrazide, 5-fluoro-2 - [(4-fluorobenzyl) oxy] pyrimidin-4-amine, 5-fluoro-2 - [(4-methylbenzyl ) oxy] pyrimidin-4-amine, 5-methyl-6-octyl [1,2,4] triazolo [1,5-a] pyrimidin-7-amine, ethyl- (2Z) -3-amino-2-cyan -3-fen ilprop-2-enoate, N '- (4 - {[3- (4-chlorobenzyl) -1,2,4-thiadiazol-5-yl] oxy} -2,5-dimethylphenyl) -N-ethyl-N- methylimidoformamide, N- (4-chlorobenzyl) -3- [3-methoxy-4- (prop-2-in-1-yloxy) phenyl] propanamide, N - [(4-chlorophenyl) (cyan) methyl] -3- [3-Methoxy-4- (prop-2-in-1-yloxy) phenyl] propanamide, N - [(5-bromo-3-chloropyridin-2-yl) methyl] -2,4-dichloropyridin-3-carboxamide , N- [1- (5-Bromo-3-chloropyridin-2-yl) ethyl] -2,4-dichloropyridin-3-carboxamide, N- [1- (5-bromo-3-chloropyridin-2-yl) ethyl] -2-fluoro-4-iodopyridin-3-carboxamide, N - {(E) - [(cyclopropylmethoxy) imino] [6- (difluoromethoxy) -2,3-difluorophenyl] methyl} -2-phenylacetamide, N- {(Z) - [(cyclopropylmethoxy) imino] [6- (difluoromethoxy) -2,3-difluorophenyl] methyl} -2-phenylacetamide, N '- {4 - [(3-tert-butyl-4-cyano-1 , 2-thiazol-5-yl) oxyl-2-chloro-5-methylphenyl} -N-ethyl-N-methylimidoformamide, N-methyl-2- (1 - {[5-methyl-3- (trifluoromethyl) -1 H-pyrazol-1-yl] acetyl} piperidin-4-yl) -N- (1,2,3,4-tetrahydronaphthalene-1-yl) -1,3-thiazol-4-carboxamide, N-methyl-2 - (1 - {[5-methyl-3- (trifluoromethyl) -1 H-pyrazol-1-yl] ace til} piperidin-4-yl) -N - [(1 R) -1,2,3,4-tetrahydronaphthalene-1-yl] -1,3-thiazol-4-carboxamide, N-methyl-2- (1 - {[5-methyl-3- (trifluoromethyl) -1 H -pyrazol-1-yl] acetyl} piperidin-4-yl) -N - [(1 S) -1,2,3,4-tetrahydronaphthalene-1 -yl] -1,3-thiazol-4-carboxamide, pentyl- {6 - [({[(1-methyl-1 H-tetrazol-5-yl) (phenyl) methyliden] amino} oxy) methyl] pyridine- 2-yl} carbamate, phenacin-1-carboxylic acid, quinolin-8-ol, quinolin-8-ol sulfate (2: 1) and tert-butyl {6 - [({[(1-methyl-1H-tetrazol- 5-yl) (phenyl) methylene] amino} oxy) methyl] pyridin-2-yl} carbamate.

(16) Other compounds, such as 1-methyl-3- (trifluoromethyl) -N- [2 '- (trifluoromethyl) biphenyl-2-yl] -1 H -pyrazol-4-carboxamide, N- (4'-chlorobiphenyl -2-yl) -3- (difluoromethyl) -1-methyl-1 H-pyrazol-4-carboxamide, N- (2 ', 4' dichlorobiphenyl-2-yl) -3- (difluoromethyl) -1-methyl-1 H -pyrazol-4-carboxamide, 3- (difluoromethyl) -1-methyl-N- [4'- (trifluoromethyl) biphenyl-2-yl] -1 H -pyrazol-4-carboxamide, N- (2 ', 5'-difluorobiphenyl-2-yl) -1-methyl-3- (trifluoromethyl) -1 H-pyrazole- 4-carboxamide, 3- (difluoromethyl) -1-methyl-N- [4 '- (prop-1 -in-1-yl) biphenyl-2-yl] -1 H-pyrazol-4-carboxamide, 5-fluoro -1,3-dimethyl-N- [4 '- (prop-1-in-1-yl) biphenyl-2-yl] -1 H -pyrazol-4-carboxamide, 2-chloro-N- [4'- (prop-1-in-1-yl) biphenyl-2-yl] pyridin-3-carboxamide, 3- (difluoromethyl) -N- [4 '- (3,3-dimethylbut-1-in-1-yl) biphenyl-2-yl] -1-methyl-1 H -pyrazol-4-carboxamide, N- [4 '- (3,3-dimethylbut-1-in-1-yl) biphenyl-2-yl] -5- fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide, 3- (difluoromethyl) -N- (4'-ethynylbiphenyl-2-yl) -1-methyl-1 H-pyrazole-4-carboxamide, N - (4'-ethynylbiphenyl-2-yl) -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide, 2-chloro-N- (4'-ethynylbiphenyl-2-yl) pyridin-3 -carboxamide, 2-chloro-N- [4 '- (3,3-dimethylbut-1-in-1-yl) biphenyl-2-yl] pyridin-3-carboxamide, 4- (diflu oromethyl) -2-methyl-N- [4 '- (trifluoromethyl) biphenyl-2-yl] -1,3-thiazol-5-carboxamide, 5-fluoro-N- [4' - (3-hydroxy-3- methylbut-1-in-1-yl) biphenyl-2-yl] -1,3-dimethyl-1 H -pyrazol-4-carboxamide, 2-chloro-N- [4 '- (3-hydroxy-3-methylbut -1-in-1-yl) biphenyl-2-yl] pyridin-3-carboxamide, 3- (difluoromethyl) -N- [4 '- (3-methoxy-3-methylbut-1-in-1-yl) biphenyl-2-yl] -1-methyl-1 H -pyrazol-4-carboxamide, 5-fluoro-N- [4 '- (3-methoxy-3-methylbut-1-in-1-yl) biphenyl-2 -yl] -1,3-dimethyl-1 H-pyrazol-4-carboxamide, 2-chloro-N- [4 '- (3-methoxy-3-methylbut-1-in-1-yl) biphenyl-2- il] pyridin-3-carboxamide, (5-bromo-2-methoxy-4-methylpyridin-3-yl) (2,3,4-trimethoxy-6-methylphenyl) methanone, N- [2- (4 - {[ 3- (4-Chlorophenyl) prop-2-in-1-yl] oxy} -3-methoxyphenyl) ethyl] -N2- (methylsulfonyl) valinamide, 4-oxo-4 - [(2-phenylethyl) amino] butanoic acid and but-3-in-1-yl {6 - [({[(Z) - (1-methyl-1 H-tetrazol-5-yl) (phenyl) methylene] amino} oxy) methyl] pyridin-2- il} carbamate.

All the mentioned mixed associates of classes (1) to (16) can, when due to their functional groups are able to do so, if necessary form salts with suitable acids or bases.

As examples of visits are mentioned:

As combination associates for the compounds according to the invention, known active ingredients are used in mixed formulations or in tank mixing, which are based on an inhibitor of, for example, acetolactate synthetase, acetyl-CoA-carboxylase, cellulose -sintetase, enolpiruvilshikimato-3-phosphate-synthetase, glutamin-synthetase, p-hydroxyphenylpyruvate-dioxygenase, phytoenodesaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, as described for example in Weed Research 26 (1986) 441-4 The Pesticide Manual ", 15th edition, The British Crop Protection Council and the Royal Soc. Of Chemistry, 2006 and the literature cited there. As herbicides or growth regulators of known plants, which can be combined with the compounds according to the invention, the following active ingredients are mentioned for example (the compounds are referred to as the "common name" according to the International Organization for Standardization (ISO) or with the chemical name or with the code number) and always include all forms of application such as acids, salts, esters and isomers such as stereoisomers and optical isomers. in this regard, several and several forms of application are also mentioned as examples: Acetochlor, Acibencenoar, Acibencenoar-S-methyl, Acifluorofen, Acifluorophen-sodium, Aclonifen, Alachlor, Allidochlor, Alloxidim, Alloxidim-sodium, Ametryn, Amicarbazone, Amidochlor, Amidosulfuron, Aminocyclopirachlor, Aminocyclopirachlor-potassium, Aminocyclopirachlor-methyl, Aminopiralid, Amitrole, ammonium sulfamate, Ancymidol, Anilofos, Asulam, Atrazine, Aviglicin, Azafenidin, Azimsulfuron, Aziprotryn, Benabonate, Benflubate, Benflubate, Benflubate bensulide, bensulfuron, bensulfuron-methyl, bentazone, Benzfendizone, benzobicyclon, benzofenap, benzofluor, benzoylprop, Benciladenin, Biciclopirone, bifenox, bilanafos, bilanafos sodium, bispyribac, bispyribac-natrium, Bromacil, bromobutide, bromofenoxim, bromoxynil bromuron, buminafos, Busoxinone , Butachlor, Butafenacil, Butamifos, Butenachlor, Butralin, Butroxidim, Butilate, Cafenstrole, Carbaril, Carbetami of, Carfentrazone, Carfentrazone-ethyl, Carvone, chlorocholine chloride, Chlomethoxyphene, Chloramben, Chlorazifop, Chlorazifop-butyl, Chlorbromuron, Chlorbufam, Chlorfenac, Chlorfenac-sodium, Chlorfenprop, Chlorflureon, Chlorflureon, Chlorflimmon, Chlorflimmon, Chlorflimmon, Chlorflimmon, Chlorflimmon, Chlorflimmon, Chlorflimmon, Chlorflimmon, Chlorflimmon, Chlorflimmon, Chlorflimmon, Chlorflimmon, Chlorflimmon Chlornitrofen chloride, Chlornitrofen, 4-chlorophenoxyatic acid, Chlorophthalim, Chlorpropham, Chlorthal-dimethyl, Chlorotoluron, Chlorsulfuron, Cinidon, Cinidon-ethyl, Cinmetilin, Cinosulfuron, Cletodim, Clodinafop, Clodinapopropyl Clopropyl, Clodinapopropyl Clopropyl, Clodinapopropyl Clopomethylpropromate, Clodinapopropyl, Clodinapopropyl Clopropylpropyl, Clodinapopropyl Clopomapropyl, Clodinapopropyl Clopropylpropyl, Clodinapopropyl Clopropylchopropyl, Clodinapopropyl Chlornomethylchloride , Chloratram, Chloratram-methyl, Cloxifonac, Cumiluron, Cyanamide, Cyanazine, Cyclanilide, Cycloate, Cyclosulfamuron, Cycloxidim, Cycluron, Cyhalofop, Cyhalofop-butyl, Cyperquat, Cyprazine, Cyprazole-2,4, Cytokinine-2,4, Cytokinine-2,4, Cytokinine-2,4 , Daimuron / Dymron, Dalapon, Daminozide, Dazomet, n-decanol, Desmedipham, Desmetryn, Detosil-Pirazolate (DTP), Diallate, Diaminozid, Dicamba, Dichlobenyl, Dichlorprop, Dichlorprop-P, Diclofo p, Diclofop-methyl, Diclofop-P-methyl, Diclosulam, Dietathyl, Diethyl-ethyl, Diphenoxuron, Difenzoquat, Diflufenican, Diflufenzopir, Diflufenzopyr sodium, Dikegulac-sodium, Dimefuron, Dimepiperate, Dimetachlor, Dimetametn, Dimenamidimete, Dimenamidimete, Dimenamidimete, Dimenamidimete, Dimenamidimetry , dimetrasulfuron, dinitramine, dinoseb, Dinoterb, Diphenamida, diisopropilnaftalenos, dipropetryn, diquat, Diquat-dibromide, Dithiopyr, diuron, DNOC, Eglinazine-ethyl, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, etilnaftilacetato, Etephon, ethidimuron , Ethiozin, Etofumesate, Ethoxyphene, Ethoxyphene-ethyl, Ethoxy sulfuron, Etobenzanid, F-5331, that is N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5 -oxo-1H-tetrazol-1-yl] -phenyl] -etansulfonamide, F-7967, that is 3- [7-chloro-5-fluoro-2- (trifluoromethyl) -1 H-benzimidazol-4-yl] - 1-methyl-6- (trifluoromethyl) pyrimidin-2,4 (1 H, 3H) -dion, Fenoprop, Fenoxaprop, Phenoxaprop-P, Phenoxaprop-ethyl, Phenoxaprop-P-ethyl, Phenoxasulfone, Fentrazamide, Fenuron, Flamprop, Flamprop-M-isopropyl, Flamprop-M-methyl, Flazasulfuron, Florasulam, Fluazifop, Fluazifop-P, Fluazifopbutyl, Fluazifop-P-butyl, Fluazolate, Flucarbazone, Flucarbazone-sodium, Flucetosulfuron, Flufenloralin, Flufenloralin (Thiafluamide), flufenpyr, flufenpyr-ethyl, flumetralin, Flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, flupoxam, flupropacil, Flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, Flurenol, Flurenol-butyl, Fluridone, Flurochloridone, Fluroxipir, Fluroxipirmeptyl, Flurprimidol, Flurtamone, Fluthiacet, Fluthiacet-methyl, Fluthiamide, Fomesafen, Foramsulfuron, Forchlorfenuron, Fosamine, Furiloxifen-glutaphosphio, P-glyphosphonium-phosphinate, P-glyphonphosphine, P-glyphonphosphio, ammonium glycinephthinate, P-glyphino-phosphinateammonium, Pyroxyphosphine-ammonium, Pyloro-phosphonamphosphio, Phenyl-butyl , Glufosinate-P-sodium, glyphosate, glyphosate isopropylammonium, H-9201, that is O- (2,4-dimethyl-6-nitrophenyl) -O-ethyl-isopropyl phosphorus amidothioate, Halosafen, Halosulfuron, Halosulfuron-methyl, Haloxifop, Haloxifop- P, Haloxifopetoxyethyl, Haloxifop-P-ethoxyethyl, Haloxifop-methyl, Haloxifop-P-methyl, Hexazinone, HW-02, that is 1 (dimethoxyphosphoryl) -ethyl- (2,4-dichlorophenoxy) acetate, Imazametabenz, Imazametabenzmethyl, azamox, Imazamoxamonium, Imazapic, Imazapir, Imazapir-isopropylammonium, Imazaquin, Imazaquin-ammonium, Imazetapir, Imazetapylammonium, Imazosulfuron, Inabenfide, Indanofan, Indaziflam, indolacetic acid (IAA), 4-indole-3, indol-I-4-indul-acid Iodosulfuron-methyl-sodium, Iofensulfuron, Iofensulfuron-sodium, Ioxinyl, Ipfencarbazone, Isocarbamide, Isopropalin, Isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapirifop, KUH-043 [i.e. methyl-3- (trifluoromethyl) -1 H-pyrazol-4-yl] methyl} sulfonyl) -5,5-dimethyl-4,5-dihydro-1,2-oxazole, Karbutilate, Ketospiradox, Lactofen, Lenacil, Linuron, malehydrazide, MCPA, MCPB, MCPB-methyl, -ethyl and -sodium, Mecoprop, Mecopropsodium, Mecoprop-butotyl, Mecoprop-P-butotyl, Mecoprop-P-dimethylammonium, Mecoprop-P-2-ethylhexyl, Mecoprop-P-potassium Mefenacet, Mefluidide, Mepiquat chloride, Mesosulfuron, Mesosulfuron-methyl, Mesotrione, Metabenzthiazuron, Metam, Metamifop, Metamitron, Metazachlor, Metazasulfuron, M etazole, Metiopirsulfuron, Metiozolin, methoxypheone, Metildymron, 1-methylcyclopropene, methylisothiocyanate, Methobenzuron, Metobromuron, Metolachlor, S-metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron, Methyl sulfide, Mono-midamidabide, Monosulfuronide, Monosulfuronide, Monosulfuronide, Monosulfuronide, Monosulfuron monohydrogen monohydride Monosulfuron, Monosulfuron-ester, Monuron, MT-128, that is 6-chloro-N - [(2E) -3-chloroprop-2-en-1-yl] -5-methyl-N-phenylpyrididazin-3-amine, MT-5950, that is N- [3-chloro-4- (1-methyl ethyl) -phenyl] -2-methylpentanamide, NGGC-011, 1-naphthylacetic acid (NAA), naphthylacetamide (NAAm), 2-naphthoxyacetic acid, Naproanilide, Napropamide, Naptalam, NC-310, that is 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole, Neburon, Nicosulfuron, Nipiraclofen, Nitralin, Nitrofen, nitroguayacholate, nitrophenolate sodium (mixture of isomers) , Nitrofluorophen, nonanoic acid, Norflurazon, Orbencarb, Orthosulfamuron, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxifluorofen, Paclobutraz ol, Paraquat, Paraquat dichloride, pelargonic acid (nonanoic acid), Pendimetalin, Pendralin, Penoxsulam, Pentanochlor, Pentoxazone, Perfluidone, Petoxamide, Phenisopham, Phenmedipham, Phenmedipham-ethyl, Picloram, Picolinafen, Pinoxaen, Pyrophiphenyl, Pyroliphenyl, Pyroliphenyl, Pyroxyphene, Pyroxyphene, Pyroxyphene , Pretilachlor, Primisulfuron, Primisulfuron-methyl, Probenazole, Profluazol, Procyazine, Prodiamine, Prifluraline, Profoxidim, Prohexadione, Prohexadione-Calcium, Prohydrojasmone, Prometon, Prometryn, Propachlor, Propanyl, Propaxopropozone, Propaxin, Propaxate , Propirisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, Prynachlor, pyraclonil, pyraflufen, pyraflufen-ethyl, Pirasulfotole, Pirazolynate (Pirazolate), pyrazosulfuron, Pirazosulfuronetilo, pyrazoxyfen, Piribambenz, Piribambenz-isopropyl Piribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, Piridate, Piriftalid, Piriminobac, Piriminobac-methyl, Pirimisulfan, Piritiobac, Piri Thiobac-sodium, Piroxasulfone, Piroxsulam, Quinclorac, Quinmerac, Quinoclamine, Quizalofop, Quizalofop-ethyl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, Rimsulfuron, Saflufenacil, Secbimeton, Setoximine, Sidbimatine, Sidbimatine, Sebimimez, Setoximine, Sidbimin, Sidbimatine SN-106279, that is to say methyl- (2R) -2 - ({7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthyl} oxy) propanoate, Sulcotrione, Sulfallate (CDEC), Sulfentrazone, Sulfometuron, Sulfometuron-methyl, Sulfosate (Gliphosate-trimesium), Sulfosulfuron, SW-065, SYN-523, SYP-249, that is 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl-5- [ 2-Chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoate, SYP-300, ie 1- [7-fluoro-3-oxo-4- (prop-2-in-1-yl) -3.4 -dihydro-2H-1,4-benzoxazin-6-yl] -3-propyl-2-thioxoimidazolidin-4,5-dione, Tebutam, Tebuthiuron, Tecnazene, Tefuriltrione, Tembotrione, Tepraloxidim, Terbacilo, Terbucarb, Terbuchlor, Terbumeton, Terbuthilazine, Terbutryn, Thenilchlor, Thiafluamide, Thiazafluron, Thiazopir, Thidiazimin, Thidiazuron, Thiencarbazone, Thiencarbazone-methyl, Thifen Sulfuron, Thifensulfuron-methyl, Thiobencarb, Thiocarbazil, Topramezone, Tralkoxidim, Triafamone, Triallate, Triasulfuron, Triaziflam, Triazofenamide, Tribenuron, Tribenuron-methyl, Tribufos, Trichloro-trifuryloxy, TCA, Trichloroacetic acid, TCA Trifluralin, Triflusulfuron, Triflusulfuron-methyl, Trimeturon, Trinexapac, Trinexapac-ethyl, Tritosulfuron, Tsitodef,

Uniconazole, Uniconazole-P, Vernolate, ZJ-0862, that is 3,4-dichloro-N- {2 - [(4,6-dimethoxypyrimidin-2-yl) oxy] benzyl} aniline, as well as the following compounds:

Other preferred agrochemical active ingredients are triazoles and strobilurines, in particular Cyproconazole, Epoxiconazole, Metconazole, Propiconazole, Tebuconazole as well as Azoxistrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Picoxistrobin, Piraclostrobin and Trifloxistrobin. Likewise, Isopyrazam, Indaziflam, Fluopiram, Fluxapiroxad and Bixafen are preferred. Likewise, all systemic herbicides applied to the sheet or post-emergence and protectors are preferred, in particular Amidosulfuron, Bromoxynil, Cypsosulfamide, 2,4-D, Glufosinat, Gliphosat, Iodosulfuron-methyl, Isoxadifen-ethyl, Mefenpyr, Mesosulfuron, Mesotrione, Metamitron, Phenmedipham, Sulcotrione, Tembotrione and Thiencarbazone-methyl.

The present invention further relates to formulations and forms of application prepared therefrom, as plant protective agents and / or agents to combat pests such as broths for soaking, dripping and atomizing, which comprise at least one of dibutylamides of carboxylic acids according to the invention. If applicable, the application forms contain other plant protection agents and / or agents to combat pests and / or adjuvants that improve the effect as penetration promoters, for example vegetable oils such as rapeseed oil, sunflower oil, mineral oils such as paraffin oils, vegetable fatty acid alkyl esters such as rapeseed oil or soybean oil or alkanol alkoxylates and / or spreading agents such as alkylsiloxanes and / or salts for example organic or inorganic salts of ammonium or phosphonium such as for example ammonium sulfate or diammonium hydrogen phosphate and / or retention promoting agents such as dioctylsulfosuccinate or hydroxypropyl guar polymers and / or humectants such as glycerin and / or fertilizers such as fertilizers containing Ammonium, potassium or phosphorus.

If necessary, the formulations contain, apart from protioconazole, other agrochemical active ingredients.

Preferably they are formulations or application forms, which contain auxiliary substances such as extenders, solvents, spontaneity promoters, support substances, emulsifying agents, dispersing agents, antifreeze agents, biocides, thickeners and / or other auxiliary substances such as adjuvants. In this context, an adjuvant is a component that improves the biological action of the formulation, without the component having a biological effect in itself. Examples of adjuvants are agents that promote retention, spreading behavior, adhesion to leaf surfaces or penetration.

These formulations are prepared in a known manner, for example by mixing the active ingredients with auxiliary substances such as extenders, solvents and / or solid support substances and / or other auxiliary substances such as substances with surface activity. The preparation of the formulations occurs in suitable facilities or also before or during the application.

As auxiliary substances, those substances that are suitable for imparting to the formulation of the active substance or the forms of application prepared from these formulations (such as, for example, plant protection agents ready for use, such as broths for atomization or disinfectants) of seeds) appropriate properties, such as certain physical, technical and / or biological properties.

Suitable extension agents are, for example, water, polar and non-polar organic chemical liquids, for example of the aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalene, chlorobenzenes), alcohols and polyols (which may also be the case) substituted, forming ethers and / or forming esters), ketones (such as acetone, cyclohexanone), esters (also fats and oils) and (poly-) ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethylsulfoxide) as well as N, N-dimethyldecanamide, N, N-dimethyloctanamide, N, N-dimethyldodecanamide, Rhodiasolv PolarcleanMR (methyl-5 (dimethylamino) -2-methyl-5-oxopentanoate).

In the case of the use of water as an extender agent, for example organic solvents can also be used as auxiliary dissolving agents. Liquid solvents essentially include: aromatic compounds such as xylene, toluene or alkylnaphthalene, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral oils and vegetables, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide as well as water.

Basically all suitable solvents can be used. Suitable solvents are for example aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene, chlorinated aliphatic or aromatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane, paraffins, petroleum fractions, mineral and vegetable oils , alcohols such as methanol, ethanol, iso-propanol, butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulfoxide as well as water.

Basically all suitable support materials can be used. In particular, support materials include: for example, ammonium salts and natural rock flours such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or infusory lands and synthetic rock flour, such as highly dispersed silicic acid, aluminum oxide and natural or synthetic silicates, resins, waxes and / or solid fertilizers. Also, mixtures of such support materials can be used. As support materials for granulates come into consideration: for example fractured and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules of organic and inorganic flours, as well as granules of organic materials such as sawdust, paper, shells of coconut nut, corn cobs and tobacco stalk.

Liquefied gaseous extender agents or gaseous solvents can also be used. Particularly suitable are those extender agents or support materials that at normal temperature and under normal pressure are gaseous, for example aerosol propellant gases such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

Examples of emulsifying and / or foaming agents, dispersing agents or wetting agents with ionic or non-ionic properties or mixtures of these substances with surface activity, salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid , polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, with substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (preferably alkyl restaurant), phosphoric acid esters of alcohols or polyethoxylated phenols, fatty acid esters of polyols and derivatives of compounds containing sulfates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, egg protein hydrolysates, spent lignin sulphite and methyl cellulose. The presence of a substance with surface activity is advantageous when one of the active ingredients and / or one of the inert support materials is not soluble in water and when the application occurs in water.

Like other auxiliary substances, dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyanide blue and organic dyes such as alizarin, azo and metaphthalocyanine dyes and nutrients may be present in the formulation and the application forms derived therefrom. and micronutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salts.

In addition, stabilizers such as cold stabilizers, preservatives, antioxidants, lightning agents or other agents that improve chemical and / or physical stability may be present. In addition, agents that generate foam or defoamers may be present.

In addition, the formulations and application forms derived therefrom may contain as additional auxiliary substances also adhesion agents such as carboxymethyl cellulose, natural and synthetic polymers in powder, in grain or in the form of latex such as gum arabic, polyvinyl alcohol, polyvinyl acetate as well as natural phospholipids such as cephalin and lecithin and synthetic phospholipids. Other auxiliary substances may be vegetable and mineral oils.

If necessary, other auxiliary substances may still be present in the formulations and application forms derived from them. Such additives are for example odoriferous substances, protective colloids, binders, adhesives, thickeners, thixotropic substances, penetration promoters, retention promoters, stabilizers, sequestering agents, complexing agents, humectants, spreading agents. In general, the active ingredients can be combined with any solid or liquid additive, which is commonly used for formulation purposes.

As retention promoters, all substances that decrease dynamic surface tension such as dioctylsulfosuccinate or that raise viscoelasticity such as hydroxypropyl-guar polymers are considered.

In the present relationship, all substances that are commonly used to improve the penetration of agrochemical active ingredients in plants come into consideration as penetration promoters. In this relationship, the penetration promoters are defined because they penetrate the cuticle of the plants from the application broth and / or from the atomization charge (usually aqueous) and because they can increase the mobility of the substances (mobility) of the active ingredients. The methods described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used for the determination of this property. By way of example, there are mentioned the alcoholalkoxylates such as coconut fat ethoxylate (10) or isotridecyloxylate (12), fatty acid esters such as rapeseed oil or soybean oil, fatty amine alkoxylates such as ethoxylate of tallow amine (15) or ammonium and / or phosphonium salts such as, for example, ammonium sulfate or diamonium hydrogen phosphate.

The formulations preferably contain between 0.00000001 and 98% by weight of active ingredient or, in particular preferably between 0.01 and 95% by weight of active ingredient, particularly preferably between 0.5 and 90% by weight of principle. active, referring to the weight of the formulation.

The content of active ingredient of the application forms (plant protection agents) prepared from the formulations can vary over wide ranges. The concentration of active ingredient of the application forms may commonly be between 0.00000001 and 95% by weight of active ingredient, preferably between 0.00001 and 1% by weight, based on the weight of the application form. The application happens in a current mode adjusted to the application forms.

The content of the individual components may vary in the formulations according to the invention within a wide range.

The manufacture of the formulations according to the invention occurs for example so that the components are mutually mixed in the respective desired relationships. If the agrochemical active substance is a solid substance, then it is generally used in finely ground form or in the form of a solution or suspension in an organic solvent or water. If the agrochemical active substance is liquid, then the use of an organic solvent is often unnecessary. In addition, it is possible to use a solid agrochemical active ingredient in the form of a molten product.

Temperatures may vary in the execution of the procedure in a given interval. In general, it works at temperatures between 00C and 80 0C, preferably between 100C and 60 0C.

For the execution of the process according to the invention, it is generally carried out so that the dibutylamides of carboxylic acids of the formula (I) are mixed with one or more active ingredients, as well as with additives. The order in which the components are mutually mixed is any.

For the execution of the process according to the invention, current apparatuses are used which are used for the manufacture of agrochemical formulations.

As methods of application all the procedures known as conventional by the experts can be used; for example, they are mentioned: atomization, immersion, fogging, as well as a series of special procedures for the direct aerial or underground treatment of the whole plant or parts (seed, root, stolons, trunk, stem, leaf), as for example Injection in the stem for trees or bandages in the stem for perennial plants, and a series of special indirect application procedures.

The concept of "harmful organisms" includes all forms of organisms that in the corresponding field of use cause economic and / or health damage. Preferably they are organisms harmful to plants and animals, as well as organisms that cause diseases, particularly preferably they are weeds and weeds, algae, mosses, insects, mites, nematodes, rodents, fungi, bacteria and viruses, terrestrial and aquatic.

The respective application amounts referred to the surface and / or the object, of the plant protection agents of the most diverse types of formulations, to combat said harmful organisms, vary very strongly. In general, the means of application are used here in conventional amounts, known by the expert as usual for the respective field of use; such as several hundred liters of water per hectare for standard atomization procedures on a few liters of oil per hectare in the “ultra low volume” application by plane, up to a few milliliters of a physiological solution in the injection procedure. The concentrations of the plant protective agents according to the invention in the corresponding means of application therefore vary over a wide range, and depend on the respective field of use. In general, concentrations that are known to the experts as currents for the respective field of use are used. Concentrations of 0.01% by weight to 99% by weight are preferred, particularly preferably from 0.1% by weight to 90% by weight.

The plant protection agents according to the invention can be applied, for example, in common preparation forms for liquid preparations, as such or after prior dilution with water, therefore, for example, as emulsions, suspensoemulsions, suspensions or solutions. In this regard, the application occurred according to current methods, also for example by atomization, watering or injection.

The amount of application of the plant protection agent according to the invention may vary within a wide range. It is determined by the respective agrochemical active ingredients and by their content in plant protection agents.

According to the invention, all plants and parts of plants can be treated. Plants are understood here as all plants and plant populations, such as crop plants or desired and unwanted wild plants (including naturally occurring crop plants). Cultivation plants can be plants that can be obtained by conventional methods of cultivation and optimization or by biotechnological and gene technology methods or combinations of these methods, including transgenic plants and including the types of plants that can be protected or cannot. be protected by trademark rights of varieties. By parts of plants should be understood all the aerial and underground parts and organs of the plants, such as shoots, leaves, flowers and roots, in which there are mentioned for example leaves, needles, stems, trunks, flowers, fruit bodies, fruits and seeds, as well as roots, bulbs and rhizomes. To the parts of plants belong also crops as well as vegetative and generative propagation materials, for example cuttings, bulbs, rhizomes, spikes and seeds.

As already mentioned above, all plants and their parts according to the invention can be treated. In a preferred embodiment, plant species and types of plants are treated as well as their parts, of wild origin or obtained by conventional biological methods of cultivation, such as crossing or fusion of protoplasts. In another preferred embodiment, transgenic plants and types of plants are treated, which were obtained by means of genetic technology methods, if necessary in combination with conventional methods (Genetically Modified Organisms), and their parts. The concept "parts" or "parts of plants" or "parts of plants" was clarified above. Particularly preferably, plants according to the invention are treated with the types of plants that in each case are currently on the market or in use. Under plant types are understood as plants with novel properties ("traits"), which had been cultivated either by conventional culture, by mutagenesis or by recombinant DNA techniques. These can be types, races, bio- and genotypes.

Plants or types of plants according to the invention that are to be treated transgenically (obtained by genetic technology) also belong to plants, which were obtained by modification of genetic technology of the genetic material, which impart to these plants valuable properties. particularly advantageous ("features"). Examples of such properties are improved plant growth, high tolerance against high or low temperatures, high tolerance for dryness or water or salt content in the soil, high flowering power, facilitated harvesting, acceleration of the plant. maturity, high crop yield, higher quality and / or higher nutritional value of the harvested product, greater storage stability and / or ease of processing the harvested product. Other and particularly prominent examples of such properties are a high resistance of plants against animal and microbial pests, such as against insects, mites, fungi, bacteria and / or pathogenic viruses to plants as well as a high tolerance of plants against certain herbicidal active ingredients. Examples of transgenic plants are important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, sugar cane, tomatoes, peas and other types of vegetables, cotton, tobacco, rapeseed, as well as fruit plants (with apple, pear, citrus fruits and grapes), in which corn, soybeans, potatoes, cotton, tobacco and rapeseed stand out in particular. As properties ("traits"), the high resistance of plants against insects, arachnids, nematodes and snails is particularly highlighted, through the toxins that arise in plants, in particular those that are generated in plants (hereinafter "Bt plants") by the genetic material of Bacillus Thuringiensis (for example by the genes CryIA (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryI 11B2, Cry9c Cry2Ab, Cry3Bb and CryIF as well as their combinations ). The properties ("traits") also highlight in particular the high resistance of plants against fungi, bacteria and viruses, due to acquired systemic resistance (SAR), systemin, phytoalexin, generators as well as resistance genes and toxins and expressed proteins correspondingly. As properties ("traits"), in particular, high tolerance of plants against certain herbicidal active ingredients, for example imidazolinones, sulfonylureas, glyphosate or phosphinothricin (for example "PAT" gene), are particularly highlighted. The genes that impart in each case the desired properties ("traits") can also occur in mutual combinations of the transgenic plants. Examples of "Bt plants" include corn varieties, cotton varieties, soy varieties and potato varieties, which are distributed under the trade name YIELD GARD® (for example corn, cotton, soybeans), KnockOut® (for example corn), StarLink® (eg corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato) As examples of herbicide tolerant plants, corn varieties, cotton varieties and soybean varieties are mentioned , which are distributed under the trade names Roundup Ready® (tolerance against glyphosate for example from corn, cotton, soybeans), Liberty Link® (tolerance against phosphinothricin, for example rapeseed), IMI® (tolerance against imidazolinone) and STS® (tolerance against sulfonylureas for example corn) As herbicide resistant plants (conventionally grown with herbicide tolerance), varieties distributed under the designation are also mentioned Clearfield® (for example corn). Obviously you are Declarations are also valid for types of plants that will be on the market in the future or will be developed in the future, with these or genetic properties (“traits”) developed in the future.

Plants of the group of useful plants, ornamental plants, grass species, in general used trees that find application as ornamental plants in public and private areas, and forest sites are preferred. The forest site includes trees for the manufacture of wood, pulp, paper and products, which are manufactured from parts of the trees.

As used herein, the concept of useful plants called crop plants, which are used as plants for obtaining food, fodder, fuels or for technical purposes.

Among the useful plants, which can be treated according to the invention, there are, for example, the following plant species: grass, vines, cereals, for example wheat, barley, rye, rice, oats, corn and millet; beets, for example sugar beet and fodder beet; fruits, for example seed fruits, stone fruits and berries, for example apple, pear, plum, peach, almond, cherry and berries for example strawberry, raspberry, blackberry; legumes, for example beans, lentils, peas and soybeans; oil crops, for example rapeseed, mustard, poppy seeds, olives, sunflower, coconut, castor oil plants, cocoa beans and peanuts; cucumber plants, for example pumpkins, cucumbers and melons; fiber plants, for example cotton, linen, hemp and jute; citrus fruits, for example oranges and lemons, grapefruit and tangerines; types of vegetables, for example spinach, salad (lettuce), asparagus, cabbage, carrot, onion, tomato, potato and pepper; family of laurels, for example avocado, cinnamon, camphor, or likewise, plants such as tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, vine, hops, bananas, natural rubber as well as ornamental plants, for example flowers, shrubs, deciduous trees and coniferous trees like conifers. This enumeration does not represent any limitation.

The following plants are considered as particularly suitable target crops for the application of the process according to the invention: cotton, eggplant, grass, pips fruits, stone fruits, berries, corn, wheat, barley, cucumber, tobacco, vine, rice , cereals, pear, beans, soy, rapeseed, tomato, pepper, melons, cabbage, potato and apple.

Plants treated in accordance with the invention are, as long as weed killers are required, all types of weeds. As regards the protection of crop plants by application of for example fungicides and insecticides, the application is also preferred in, for example, transgenic crops of useful and ornamental plants, for example cereals, such as wheat, barley, rye , oats, millet, rice, cassava and corn, or also sugar beet, cotton, soybean, rapeseed, potato, tomato, peas and other types of vegetables, economically important.

The invention is clarified in more detail by the examples, without being limited.

Manufacturing examples

Penetration test

In this test the penetration of active ingredients was measured through apple tree leaf cuticles, enzymatically isolated. Leaves were used, which were chopped in a fully developed state of the Golden Delicious apple tree. The cuticle isolation occurred so that first on the lower side it was marked with dye and die-cut leaf disks were filled, by means of vacuum infiltration, with a solution (0.2 to 2%) of buffered pectinase buffered at pH value between 3 and 4, then sodium azide was added and the leaf disks thus treated were left until the original structure of the leaf was dissolved and until the non-cellular cuticle was removed.

After that, only the cuticles of the upper sides of the leaf, free of stomata and hair, were used again. They were washed several times alternately with water and a buffered solution of pH 7. The cuticles thus obtained were then placed on Teflon plates and smoothed and dried with a weak stream of air.

In the next stage, the cuticle membranes thus obtained were deposited on stainless steel, for membrane transport investigations in diffusion cells (= transport chambers). To do this, with a clamp the cuticles were placed in the center of the edges of the diffusion cells coated with silicone grease, and sealed with a greased ring. The arrangement was chosen so that the morphologically outer side of the cuticles was oriented outward, therefore towards the air, while the originally inner side was oriented inwardly of the diffusion cell. The diffusion cells were filled with water, or with a mixture of water and solvent.

In the case of formulated samples, the active ingredients were placed in tap water and the test additive was added. For use of non-formulated active ingredients an acetone / tap water mixture was used. In this regard, the acetone content varied between 20% (m / m) and 30% (m / m). This mixture was then added to the previously placed additive / emulsifier mixture, which resulted in a clear solution or an emulsion. In cases where a solvent or emulsifier was not used, an emulsion with application capacity had been prepared by ultrasonic homogenization.

For the determination of penetration, 10 pl of a broth for atomization of the composition mentioned in the examples were applied in each case. After the application of the atomization broth, the water was evaporated in each case, the chambers were then rotated in each case and placed in tubs at a constant temperature, in which air with a temperature was blown on the outer side of the cuticle and humidity defined. With this, the initial penetration occurred at a relative humidity of 60% and an adjusted temperature of 25 ° C. The penetration of active substance was measured by means of HPLC or radioactively labeled active ingredient.

As recognized by the examples cited in the tables, the presence of dibutylamides of carboxylic acids leads to a clear increase in the penetration of all the active ingredients tested. In this regard, the variants without dibutylamides of carboxylic acids, which was the active ingredient or the formulation alone or also, when an emulsifier was used in the mixture with carboxylic acid dibutylamide, the active ingredient or the formulation with this emulsifier were used as controls .

The dimethyl- and dibutylcarboxylic acid amides used in the examples are the respective mixtures of the corresponding carboxylic acid amides. Thus, for example, C16-18 dibutylamide means a mixture consisting essentially of dibutylamides of C16 and C18 carboxylic acids.

Table, example 1 (not according to the invention)

The active substance Bromoxynil was placed in tap water formulated as WP 20 (1 g / l of Bromoxynil) and was applied with castor ethoxylate emulsifier only (0.5 g / l) or in different broth concentrations for dibutylamide atomization of C12-14 carboxylic acids (emulsified with a castor ethoxylate emulsifier) and the penetration of Bromoxynil was measured. The table shows the penetration after 3 and 24 hours at 20 0C and 60% relative humidity.

The addition of dibutylamide of C12-14 carboxylic acids has led to a clear elevation of the penetration of Bromoxynil, little concentration dependent, above 1 g / l.

Table, example 2 (not according to the invention)

The active substance Bromoxynil-octanoate was placed in water formulated as EC225 (1.5 g / l of Bromoxyniloctanoate) and was applied with castor ethoxylate emulsifier only (0.5 g / l) or at different concentrations of dibutylamide broth for C12-14 carboxylic acid atomization (emulsified with a castor ethoxylate emulsifier) and the penetration of Bromoxynil Octanoate was measured. The table shows the penetration after 3 and 24 hours at 20 0C and 60% relative humidity.

The addition of dibutylamide of C12-14 carboxylic acids has led to a clear elevation, depending on the concentration, of the penetration of Bromoxynil-octanoate, especially immediately after application.

Table, example 3 (not according to the invention)

The active substance Bromoxynil was placed in acetone / water (1.5 g / l of Bromoxynil) and was applied with castor ethoxylate emulsifier only (0.5 g / l) or in different broth concentrations for dibutylamide atomization of carboxylic acids C12-14 (emulsified with a castor ethoxylate emulsifier) and Bromoxynil penetration was measured. The table shows the penetration after 3 and 24 hours at 20 0C and 60% relative humidity.

The addition of dibutylamide of C12-14 carboxylic acids has led to a clear elevation dependent on the concentration of the penetration of Bromoxynil.

Table, example 4 (not according to the invention)

The active substance Bromoxynil was placed in acetone / water (1.5 g / l of Bromoxynil) and was applied with castor ethoxylate emulsifier only (0.5 g / l) or in different broth concentrations for dibutylamide atomization of carboxylic acids C8-10 (emulsified with a castor ethoxylate emulsifier) and the Bromoxynil penetration. The table shows the penetration after 3 and 24 hours at 20 0C and 60% relative humidity.

The addition of dibutylamide of C12-14 carboxylic acids has led to a clear elevation, depending on the concentration, of the penetration of Bromoxynil.

Table, example 5 (not according to the invention)

The active substance Bromoxynil was placed in acetone / water (1.5 g / l of Bromoxynil) and was applied with castor ethoxylate emulsifier (0.5 g / l) alone or together with C8-10 carboxylic acid dibutylamide, dibutylamide of C12-14 carboxylic acids or C16-18 carboxylic acid dibutylamide (emulsified with a castor ethoxylate emulsifier) at a spray concentration of 3 g / l and the penetration of Bromoxynil was measured. The table shows the penetration after 3 and 24 hours at 20 0C and 60% relative humidity.

The addition of the dibutylamides of carboxylic acids has led to a clear elevation of the penetration of Bromoxynil.

Table, example 6 (not according to the invention)

The active substance Bromoxynil was placed in acetone / water (1.5 g / l of Bromoxynil) and was applied with castor ethoxylate emulsifier (0.5 g / l) alone or together with C8-10 carboxylic acid dimethylamide. according to the invention or dibutylamide of Cb-1ü carboxylic acids or dibutylamide of C12-14 carboxylic acids of according to the invention (emulsified with a castor ethoxylate emulsifier) at a concentration of atomization broth of 1 or 3 g / l and the penetration of Bromoxynil was measured. The table shows the penetration after 5 and 24 hours at 20 0C and 60% relative humidity.

Average penetration of Bromoxynil * in% (n = 4-8) Variant Bromoxynil without / with Concentration (g / l) of 5h 24h carboxylic acid dialkylamide

Bromoxynil in acetone / water with 0.5 g / l of castor ethoxylate emulsifier 4 20 Dimethylamide C8-10 ** 1 20 30 Dimethylamide C8-10 ** 3 45 57 Dibutylamide C8-10 ** 1 32 72 Dibutylamide C8 -10 ** 3 67 86 C12-14 Dibutylamide ** 1 29 70 C12-14 Dibutylamide ** 3 59 85 * 1.5 g / l Bromoxynil ** with 0.5 g / l castor ethoxylate emulsifier

The addition of the dibutylamides of carboxylic acids has led to a clear elevation, depending on the concentration, of the penetration of Bromoxynil. In all cases the effect of C8-10 carboxylic acid dimethylamide was clearly superior.

Table, example 7 (not according to the invention)

The active substance Spirotetramat was dissolved in acetone / water (0.3 g / l of Spirotetramat) and was applied alone or together with different concentrations of broth for atomization of dibutylamide of C12-14 carboxylic acids (emulsified with a castor ethoxylate emulsifier ) and Spirotetramat penetration was measured. The table shows the penetration after 3 and 24 hours at 20 0C and 60% relative humidity.

Average penetration of Spirotetramat * in% (n = 4-8) Spirotetramat without / with dibutylamide concentration 3h 24h carboxylic acid

Spiroetramat in acetone / water without - 0 1 carboxylic acid dibutylamide

Dibutylamide C12-14 ** 0.2 2 23 Dibutylamide C12-14 ** 0.5 2 25 Dibutylamide C12-14 ** 1 8 39 Dibutylamide C12-14 ** 3 13 65 Average penetration of Spirotetramat * in% (n = 4-8)

Spirotetramat without / with dibutylamide concentration 3h 24h

of carboxylic acid

* 0.3 g / l Spirotetramat; ** with 0.5 g / l castor ethoxylate as emulsifier

The addition of dibutylamide of C12-14 carboxylic acids has led to a clear concentration-dependent elevation of Spirotetramat penetration.

Table, example 8 (not according to the invention)

The active substance Spirotetramat was placed in tap water, formulated as SC240 (0.3 g / l of Spirotetramat) and applied alone or together with C8-10 carboxylic acid dibutylamide, C12-14 carboxylic acid dibutylamide or carboxylic acid dibutylamide C16-18 at a concentration of 1 g / l atomization broth (homogenized by ultrasound treatment) and Spirotetramat penetration was measured. The table shows the penetration after 3 and 24 hours at 20 0C and 60% relative humidity.

Average penetration of Spirotetramat * in% (n = 4-8)

Spirotetramat without / with Concentration (g / l) of dibutylamide 3h 24h

of carboxylic acid

Spiroetramat SC240 without dibutylamide -carboxylic acid 1 2

Dibutylamide C8-10 1 11 13

Dibutylamide C12-14 1 4 10

Dibutylamide C16-18 1 4 16

* 0.3 g / l Spirotetramat

The addition of the three dibutylamides of carboxylic acids has led to a clear increase in the penetration of Spirotetramat.

Table, example 9 (not according to the invention)

The active substance Kresoxim-methyl was placed in acetone / tap water (0.3 g / l of Kresoxim-methyl) and was applied alone or together with C8-10 carboxylic acid dibutylamide, C12-14 carboxylic acid dibutylamide or dibutylamide of C16-18 carboxylic acids at a concentration of 1 or 3 g / l atomization broth (emulsified with 0.4 g / l of triethyrylphenol-ethoxylate) and Kresoxim-methyl penetration was measured. The table shows penetration after 3 and 24 hours at 20 ° C and 60% relative humidity.

Average penetration of Kresoxim-methyl * in% (n = 4-8)

Kresoxim-methyl Concentration (g / l) of 3h 24h carboxylic acid dibutylamide

Kresoxim-methyl in acetone / water without carboxylic acid dibutyl amide 1 3 Average penetration of Kresoxim-methyl * in% (n = 4-8)

Kresoxim-methyl Concentration (g / l) of 3h 24h carboxylic acid dibutylamide

Dibutylamide C8-10 ** 3 60 66

Dibutylamide C12-14 ** 1 51 82

Dibutylamide C12-14 ** 3 68 99

Dibutylamide C16-18 ** 3 52 76

* 0.3 g / l Kresoxim-methyl, ** with 0.4 g / l of triestyrylphenol-ethoxylate

The addition of the three dibutylamides of carboxylic acid has led to a clear elevation of Kresoxim-methyl penetration.

Table, example 10 (not according to the invention)

The active substance Azoxistrobin was placed in acetone / tap water (0.3 g / l of Azoxistrobin) and was applied alone or together with C8-10 carboxylic acid dibutylamide, C12-14 carboxylic acid dibutylamide or C16 carboxylic acid dibutylamide -18 at a concentration of broth for atomization of 1 or 3 g / l (emulsified with 0.4 g / l of triestyrylphenol-ethoxylate) and Azoxistrobin penetration was measured. The table shows the penetration after 3 and 24 hours at 20 0C and 60% relative humidity.

Average penetration of Azoxistrobin * in% (n = 4-8)

Variant Azoxistrobin without / with Concentration (g / l) of dibutylamide 3h 24h of carboxylic acid

Azoxistrobin in acetone / water without carboxylic acid dibutyl amide <1 1

Dibutylamide C8-10 ** 3 34 46

Dibutylamide C12-14 ** 1 7 14

Dibutylamide C12-14 ** 3 9 37

Dibutylamide C16-18 ** 3 6 36

* 0.3 g / l of Azoxistrobin, ** with 0.4 g / l of triestyrylphenol-ethoxylate

The addition of the three dibutylamides of carboxylic acid has led to a clear increase in the penetration of Azoxistrobin.

Table, example 11 (not according to the invention)

The active substance Epoxiconazole was placed in acetone / tap water (0.3 g / l of Epoxiconazole) and was applied alone or together with C8-10 carboxylic acid dibutylamide, C12-14 carboxylic acid dibutylamide or C16 carboxylic acid dibutylamide -18 at a concentration of broth for atomization of 1 or 3 g / l (emulsified with 0.4 g / l of triestyrylphenol-ethoxylate) and the penetration of Epoxiconazole was measured. The table shows the penetration after 3 and 24 hours at 20 0C and 60% relative humidity.

Average penetration of Epoxiconazole * in% (n = 4-8)

Variant Epoxiconazole without / with Concentration (g / l) of 3h 24h carboxylic acid dibutylamide

Epoxiconazole in acetone / water without carboxylic acid dibutyl amide 1 2

Dibutylamide C8-10 ** 3 67 73

Dibutylamide C12-14 ** 1 52 96

Dibutylamide C12-14 ** 3 54 95

Dibutylamide C16-18 ** 3 17 95

* 0.3 g / l of Epoxiconazole, ** with 0.4 g / l of triestyrylphenol-ethoxylate

The addition of the three dibutylamides of carboxylic acid has led to a clear increase in the penetration of Epoxiconazole.

Table, example 12 (not according to the invention)

The active substance Propiconazole was placed in acetone / tap water (0.3 g / l of Propiconazole) and was applied alone or together with C12-14 carboxylic acid dibutylamide or C16-18 carboxylic acid dibutylamide at a broth concentration for Atomization of 1 or 3 g / l (emulsified with 0.4 g / l of triestyrylphenol-ethoxylate) and Propiconazole penetration was measured. The table shows penetration after 3 and 24 hours at 20 ° C and 60% relative humidity.

Average penetration of Propiconazole * in% (n = 4-8)

Variant Propiconazole without / with Concentration (g / l) of dibutylamide 3h 24h of carboxylic acid

Propiconazole in acetone / water without carboxylic acid dibutyl amide 4 44

Dibutylamide C12-14 ** 1 53 85

Dibutylamide C12-14 ** 3 72 89

Dibutylamide C16-18 ** 3 45 92

* 0.3 g / l Propiconazole, ** with 0.4 g / l triestyrylphenol-ethoxylate

The addition of dibutylamide of C12-14 carboxylic acids or dibutylamide of C16-18 carboxylic acids has led to a clear increase in the penetration of Propiconazole.

Table, example 13 (not according to the invention)

The active substance Isopyrazam was placed in acetone / tap water (0.3 g / l of Isopyrazam) and was applied alone or together with C8-10 carboxylic acid dibutylamide, C12-14 carboxylic acid dibutylamide or C16 carboxylic acid dibutylamide -18 at a concentration of broth for atomization of 1 or 3 g / l (emulsified with 0.4 g / l of triestyrylphenol-ethoxylate) and the penetration of Isopyrazam was measured. The table shows the penetration after 3 and 24 hours at 20 0C and 60% relative humidity.

Average penetration of Isopyrazam * in% (n = 4-8)

Isopyrazam variant without / with Concentration (g / l) of dibutylamide 3h 24h of carboxylic acid

Isopyrazam in acetone / water without carboxylic acid dibutyl amide 1 2

Dibutylamide C8-10 ** 3 37 87

Dibutylamide C12-14 ** 1 11 54

Dibutylamide C12-14 ** 3 12 49

Dibutylamide C16-18 ** 3 10 35

* 0.3 g / l Isopyrazam, ** with 0.4 g / l triestyrylphenol-ethoxylate

The addition of the three dibutylamides of carboxylic acid has led to a clear elevation of Isopyrazam penetration.

Table, example 14 (not according to the invention)

The active substance Indaziflam (formulated as SC500) was placed in tap water (0.3 g / l Indaziflam) and was applied alone or together with C8-10 carboxylic acid dibutylamide, C12-14 carboxylic acid dibutylamide or acid dibutylamide C16-18 carboxylic acids at a concentration of broth for atomization of 2.5 g / l (emulsified with castor ethoxylate or triestyrylphenol ethoxylates) and the penetration of Indaziflam was measured. The table shows penetration after 24 and 48 hours at 20 ° C and 60% relative humidity.

Average penetration of Indaziflam * in% (n = 4-8)

Variant Indaziflam without / with Concentration (g / l) of dibutylamide 24h 48h of carboxylic acid

Indaziflam SC500 in water without 3-carboxylic acid dibutyl amide

Dibutylamide C8-10 ** 2.5 26 34

Dibutylamide C12-14 ** 2.5 27 49

Dibutylamide C16-18 ** 2.5 8 17

Dibutylamide C16-18 *** 2.5 14 70

Dibutylamide C16-18 **** 2.5 40 77 * 0.3 g / l Indaziflam, ** with 0.5 g / l castor ethoxylate as emulsifier, *** with 0.5 g / triestyrylphenol ethoxylate 16 ( ***) or 29 EO (****)

The addition of the three dibutylamides of carboxylic acid has led to a clear increase in the penetration of Indaziflam.

Table, example 15

The active substance protioconazole was placed in acetone / tap water (0.3 g / l of protioconazole) and was applied alone or together with C12-14 carboxylic acid dibutylamide or C16-18 carboxylic acid dibutylamide at a broth concentration for 1 g / l atomization (emulsified by ultrasound treatment) and protioconazole penetration was measured. The table shows the penetration after 3 and 24 hours at 25 ° C and 60% relative humidity.

Average penetration of protioconazole * in% (n = 4-8) Protioconazole variant Concentration (g / l) of dibutylamide from 3h 24h without / with carboxylic acid

Protioconazole in - 1 2 acetone / water

Dibutylamide C12-14 1 1 11 Dibutylamide C16-18 1 5 18

* 0.3 g / l protioconazole

The addition of the two dibutylamides of carboxylic acids has led to a clear increase in the penetration of protioconazole.

Table, example 16

Comparison of the dibutylamides of carboxylic acids used in accordance with the invention against the carboxylic acid dimethylamide of the prior art:

The following table shows the comparison of protioconazole penetration of the market formulation or a novel composition according to the invention, where 20% of the C8-10 carboxylic acid dimethylamide solvent was replaced by C16-18 carboxylic acid dibutylamide (data in mass percentage) with 25% protioconazole.

Formulation A:

20% KS emulsifier

20% dibutylamide of C16-18 carboxylic acids

34.9% C8-10 carboxylic acid dimethylamide

0.1% antifoam

The active substance protioconazole was placed in tap water formulated as commercial standard EC250 or with the formulation according to the invention (0.3 g / l protioconazole) and the penetration of protioconazole was measured in a test in which in the first day 15 ° C and 80% relative humidity had been adjusted and on the second day 25 ° and 60%. The table shows the penetration after 12 and 24 hours at 25 0C and 60% relative humidity.

Average penetration of protioconazole * in% (n = 4-8) Variant 12 h 24 h 36 h 48 h Standard formulation EC250 3 4 6 8 EC250 formulation A according to the invention 6 10 19 23 * 0.3 g / l of protioconazole

The example shows that the dibutylamides of carboxylic acids used in accordance with the invention lead to a reinforced penetration against the carboxylic acid dimethylamide of the prior art.

Table, example 17

Comparison of the dibutylamides of carboxylic acids used according to the invention, against carboxylic acid dimethylamide of the prior art:

The active substance protioconazole was placed in acetone / tap water (0.8 g / l of protioconazole) and was applied together with C8-10 carboxylic acid dimethylamide (1.5 g / l) alone or with addition (0.5 g / l or 1 g / l in the load) of C8-10 carboxylic acid dibutylamide, C12-14 carboxylic acid dibutylamide or C16-18 carboxylic acid dibutylamide according to the invention (in each case with 0.4 g / l of triestyrylphenol-ethoxylate) and the penetration of protioconazole was measured. The table shows the penetration after 3 and 24 hours at 20 0C and 60% relative humidity.

Average penetration of protioconazole * in% (n = 4-8) Protioconazole variant without / with Concentration (g / l) of 3h 24h acid dibutylamide

carboxylic

Protioconazole in acetone / water with 1.5g / l -dimethylamide of C8-C10 carboxylic acids ** 1.3 (n = 21) 3.7 (n = 21)

C8-10 Dibutylamide ** 0.5 2.1 6.3 C8-10 Dibutylamide ** 1 2.5 9.3 C12-14 Dibutylamide ** 0.5 2.0 9.4

Dibutylamide C12-14 ** 1 4.2 16.6

Dibutylamide C16-18 ** 0.5 2.1 7.4 Dibutylamide C16-18 ** 1 3.2 17.9

* 0.8 g / l of protioconazole, ** with 0.4 g / l of triestyrylphenol-ethoxylate

The addition of the three dibutylamides of carboxylic acid to a solution of protioconazole that already contains a high amount of C8-C10 carboxylic acid dimethylamide has led to a clear, stronger and concentration-dependent elevation of protioconazole penetration.

Table, example 18

Elevation of the fungicidal effect of Proline in wheats with C16-18 carboxylic acid dibutylamide

In two field trials, the influence of dibutylamide of C16-18 carboxylic acids on the fungicidal efficacy of Proline EC250 against several harmful fungal pathogens was evaluated. Field trials were applied to winter wheat in a field in Burscheid, Germany. The trials were organized randomly with three repetitions and a test site had an area of 6m2. The planting time was October 20, 2009 or October 21, 2009. Other fertilization and plant protection measures were applied, as corresponds to agricultural practice.

The test substances were applied twice successively in the cereal growth states EC32 and EC39. The interval was 2 or 3 weeks. Protioconazole was used as formulation EC 250 (trade name Proline), dibutylamide of C16-18 carboxylic acids as EC500. Proline was used alone or with the addition of a C16-18 carboxylic acid dibutylamide tank mixture. Water consumption for spray application was 300 l / ha.

The degree of disease attack on wheat leaves and disease controls (effect) were evaluated on June 30 and July 1, 2010, that is approximately 4 weeks after the second fungicide application. The following table shows the influence of dibutylamide of C16-18 carboxylic acids on the elevation of the action of Proline:

Trial 1 Trial 2

Pathogen Leptosphaeria Puccina Pyrenephora nodorum recondita teres Variant Amount of principle Effect according to (%)

active per hectare

Untreated (attack) - 14 5 5

Proline 75 67 72 70

Proline 0.1% dibutylamide 75 85 99 91 C16-18 carboxylic acids *

* 0.2% C16-18 carboxylic acid dibutylamide EC500 is a C16-C18 carboxylic acid dibutylamide The result shows that already a concentration of 0.1% dibutylamide of C16-C18 carboxylic acids significantly increases the fungicidal effect of Proline.

Table, example 19 (not according to the invention)

Elevation of the herbicidal efficacy of Indaziflam with dibutylamide of C12-14 carboxylic acids:

Two field trials were conducted to investigate the influence of dibutylamide C12-14 on the herbicidal efficacy of the herbicide Indaziflam. Field trials were applied (1) in Fresno (California, USA) and (2) Mereville (France). Both products were applied in a mixed infestation with natural weeds. The size of the property in Test 1 was 9.3 km and that of Test 2 was 6 km. The weed plants were treated with the products, in an early stage of development (the measured height of the plant, depending on the weed species, was 2 cm to 7 cm). For this purpose, the products that were to be applied were dissolved and diluted in water and then atomized with 187 liters per hectare (Test 1) and 250 liters per hectare (Test 2) as a solution for atomization, directly on the weed plants.

In both field trials, Indaziflam SC500 was tested as a product alone, compared with Indaziflam SC500 in tank mix with 0.5 liters of C12-14 carboxylic acid dibutylamide per hectare. In Test 1 the applied amount of Indaziflam (formulated as SC500) was 50 grams of active substance per hectare and in Test 2 it was 75 grams of active substance per hectare. The mixed weed consisted of the following monocotyledonous weeds: Digitaria sanguinalis (DIGSA), Lolium multiflorum (LOLMU), Setaria glauca (PESGL) and Setaria verticillata (SETVE), and the following dicotyledonous weeds: Amaranthus retroflexus (AMARE), Abutilon theophrasti (AMARE) ), Chenopodium album (CHEAL), Fallopia convolvulus (POLCO).

The herbicidal effect of the products was visually evaluated, compared to untreated controls. In this regard, the herbicidal effect was expressed as a percentage (%): 100% herbicidal effect = weed plants are completely dead; 0% effect = as control plants). Test 1 was evaluated 7 days after application of the products and Test 2 was evaluated 28 days after application. Table 1 (field test 1) and table 2 (field test 2) show the respective results of the field tests.

Table 19a:

Weed controls in agreement Amount of active substance per AMARE CHEAL PESGL LOLMU ABUTH with Abbott (%) hectare (g / ha)

Indaziflam 50 46 28 43 53 55

Indaziflam Dibutylamide C12-14 50 88 73 82 83 85

Table 19 b:

Weed controls according to Amount of active substance per POLCO CHEAL SETVE DIGSA Abbott (%) hectare (g / ha)

Indaziflam 75 15 10 45 15

Indaziflam Dibutylamide C12-14 75 0.5 L / ha 63 86 55 80

In both field trials it could be shown that the addition of 0.5 liters of dibutylamide of C12-14 carboxylic acids per hectare, to the herbicide Indaziflam significantly increases the efficacy on weeds.

Example 20: Degree of coverage

Surprisingly it was also found that dibutylamides of non-water soluble carboxylic acids clearly raise the degree of coverage - the fraction of the plant surface covered with the liquid for atomization, in the application of atomization - after emulsion with different emulsifiers. Thus, in the spray application with an air injector nozzle (TeeJet AI11003, 200L / ha) on corn with 2 g / l of a C12-14 carboxylic acid dibutylamide emulsion or C16-18 carboxylic acid dibutylamide (emulsified with 0.5 g / l of sorbitan ester ethoxylate), the degree of coverage increased from 1.1% (fraction of the moistened surface with reference to the surface of the treated plant) for water to 18.5% (dibutylamide C12-14 carboxylic acid) or 17.9% (C16-18 carboxylic acid dibutylamide). The emulsifier value was only 7.3%.

Table, example 21 (not according to the invention)

The active substance Fluopiram was placed as an EC formulation in the laboratory: Fluopiram is dissolved in a previous mixture of solvent and emulsifier (dimethylacetamide Tanemul PS16) and diluted with water to the test solution ready for use. The test solution contains 0.5g / l of active substance, 0.5g / l of emulsifier and 2% by weight of solvent. It is applied on isolated cuticles of apple leaf, alone or together with C16-18 carboxylic acid dibutylamide or C18 carboxylic acid dimethylamide at a spray concentration of 1.5g / l (emulsified by ultrasound treatment) and measured Fluopiram penetration. The table shows the penetration after 6 and 24 hours at 25 0C and 60% relative humidity.

Average penetration of Fluopiram in% (n = 8-10)

Test solution Concentration (g / l) of acid amide 6h 24h

carboxylic

Fluopiram (0.5g / l) - 20 53

Fluopiram & dibutylamide 1.5 84 95

C16-18

Fluopiram & dimethylamide 1.5 34 51

C18

The addition of dibutylamide of C16-C18 carboxylic acids leads, in comparison with the corresponding dimethylamide, to a strong increase in the penetration of Fluopiram.

Table, example 22

Penetration of dibutylamides of carboxylic acids

C12-C14 and C16-C18 alkyl / alkenyl carboxylic acid dibutylamides and analogous dimethylamides were placed as EC formulations in the laboratory: they are dissolved in a previous mixture of solvent and emulsifier (Tanemul PS16 dimethylacetamide) and diluted with water until ready-to-use test solution (emulsified by ultrasound treatment). The test solutions contain in each case 1.5g / l of carboxylic acid amide, 0.5g / l of emulsifier and 2% by weight of solvent. They are applied on cuticles isolated from apple leaf and then the penetration of carboxylic acid amides is measured. The table shows the penetration after 6 and 24 hours at 25 ° C and 60% relative humidity.

Penetration of carboxylic acid amide in% (n = 8-10)

Concentration Solution (g / l) of acid amide 6h 24h

carboxylic test

Dibutylamide C16-18 1.5 0 0

Dimethylamide C18 1.5 22 61

Dibutylamide C12-14 1.5 2 4

Dimethylamide C16- 1.5 49 47

C12

The penetration of dimethylamides of carboxylic acids is essentially greater than that of dibutylamides. Dibutylamide C16-18 penetrates in general in a non-measurable way.

Formulation Examples

The following formulations according to the invention were prepared by mixing the individual components.

Formulation example 1 (not according to the invention)

For the proper preparation of the invention with the active substance Tebuconazole, 20 g of Tebuconazole are first mixed with

56 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 10 g of ethoxypropoxy-triestyryl-phenol (block copolymer),

4 g of water and

10 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 2 (not according to the invention)

For the proper preparation of the invention with the active substance Tebuconazole, they are first mixed

20 g of Tebuconazole with

51 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 10 g of ethoxypropoxy-triestyryl-phenol (block copolymer),

4 g of water and

15 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 3 (not according to the invention)

For the proper preparation of the invention with the active substance Tebuconazole, they are first mixed

20 g of Tebuconazole with

52 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 3 g of ethoxypropoxy-triestyryl-phenol (block copolymer),

10 g of polyglycerol of castor oil and

15 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation Example 4 (not according to the invention)

For the proper preparation of the invention with the active substance Epoxiconazole, they are first mixed

10 g of epoxiconazole with

65 g of benzylalcohol and then mixed under stirring at room temperature with

7.5 g of ethoxypropoxy-triestyryl-phenol (block copolymer),

7.5 g of polyglycerol of castor oil and

10 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 5 (not according to the invention)

For the proper preparation of the invention with the active substance Epoxiconazole, they are first mixed

10 g of epoxiconazole with

50 g of benzylalcohol and then mixed under stirring at room temperature with

10 g of 2-sec-butylphenol,

7.5 g of ethoxypropoxy-triestyryl-phenol (block copolymer),

7.5 g of polyglycerol of castor oil and

15 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 6 (not according to the invention)

For the proper preparation of the invention with the active substance Fluoxastrobin, they are first mixed

10 g of fluoxastrobin with

35 g of gamma-butyrolactone and then mixed under stirring at room temperature with

15 g of 2-ethylhexanol-propylenenetylene glycol ether,

15 g of ethoxypropoxy-triestyryl-phenol (block copolymer),

10 g of alkoxylated ethylenediamine with an average of 16 units of EO and 16 units of PO,

5 g of triestirl-phenol-ethoxylate with an average of 16 units of EO and

10 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 7 (not according to the invention)

For the proper preparation of the invention with the active substance Fluoxastrobin, they are first mixed

10 g of fluoxastrobin with

30 g of gamma-butyrolactone and then mixed under stirring at room temperature with

15 g of 2-ethylhexanol-propylenenetylene glycol ether,

15 g of ethoxypropoxy-triestyryl-phenol (block copolymer),

10 g of alkoxylated ethylenediamine with an average of 16 units of EO and 16 units of PO,

5 g of triestyryl-phenol-ethoxylate with an average of 16 units of EO and

15 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation Example 8 (not according to the invention)

For the proper preparation of the invention with the active substance Azoxistrobin, they are first mixed

10 g azoxistrobin with

35 g of gamma-butyrolactone and then mixed under stirring at room temperature with

15 g of 2-ethylhexanol-propylenenetylene glycol ether,

15 g of ethoxypropoxy-triestyryl-phenol (block copolymer),

10 g of alkoxylated ethylenediamine with an average of 16 units of EO and 16 units of PO,

5 g of triestyryl-phenol-ethoxylate with an average of 16 units of EO and

10 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation Example 9 (not according to the invention)

For the proper preparation of the invention with the active substance Azoxistrobin, they are first mixed

10 g azoxistrobin with

30 g of gamma-butyrolactone and then mixed under stirring at room temperature with

15 g of 2-ethylhexanol-propylenenetylene glycol ether,

15 g of ethoxypropoxy-triestyryl-phenol (block copolymer),

10 g of alkoxylated ethylenediamine with an average of 16 units of EO and 16 units of PO,

5 g of triestyryl-phenol-ethoxylate with an average of 16 units of EO and

15 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 10 (not according to the invention)

For the proper preparation of the invention with the active substance Trifloxistrobin, they are first mixed

10 g of trifloxistrobin with

44.97 g of N-methylpyrolidone and then mixed under stirring at room temperature with 10 g of triestyryl-phenol-ethoxylate with an average of 16 units of EO,

2.5 g of triestyryl-phenol-ethoxylate salt with an average of 16 units of EO,

12.5 g of butoxypolyethylene propylene glycol (block copolymer),

0.03 g of silicone antifoam emulsion and

20 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation Example 11

For the proper preparation of the invention with the active substance protioconazole are first mixed

25 g of protioconazole with

34.9 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 20 g of castor oil polyglycerol,

0.1 g of silicone antifoam emulsion and

20 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation Example 12

For the proper preparation of the invention with the active substance protioconazole, they are first mixed

25 g of protioconazole with

39.9 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 10 g of ethoxypropoxy-triestyryl-phenol (block copolymer),

10 g of triestyryl-phenol-ethoxylate with an average of 16 units of EO and

0.1 g of silicone antifoam emulsion and

15 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 13 (not according to the invention)

For the proper preparation of the invention with the active ingredient Bixafen, they are first mixed

10 g of bixafen with

45 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 10 g of aromatic hydrocarbon mixture, reduced Naphalin,

10 g of 2-ethylhexanol-propylenenetylene glycol ether,

10 g of polyglycerol of castor oil,

5 g of ethoxypropoxy-triestyryl-phenol (block copolymer) and

10 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 14 (not according to the invention)

For the proper preparation of the invention with the active ingredient Bixafen, they are first mixed

10 g of bixafen with

40 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 10 g of aromatic hydrocarbon mixture, reduced Naphalin,

10 g of 2-ethylhexanol-propylenenetylene glycol ether,

10 g of polyglycerol of castor oil,

5 g of ethoxypropoxy-triestyryl-phenol (block copolymer) and

15 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 15 (not according to the invention)

For the proper preparation of the invention with the active ingredient Bixafen, they are first mixed

10 g of bixafen with

40 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 5 g of aromatic hydrocarbon mixture, reduced Naphalin,

10 g of 2-ethylhexanol-propylenenetylene glycol ether,

10 g of polyglycerol of castor oil,

5 g of ethoxypropoxy-triestyryl-phenol (block copolymer) and

20 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 16 (not according to the invention)

For the proper preparation of the invention with the active substance Isopyrazam, they are first mixed

10 g of Isopyrazam with

45 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 10 g of aromatic hydrocarbon mixture, reduced Naphalin,

10 g of 2-ethylhexanol-propylenenetylene glycol ether,

10 g of polyglycerol of castor oil,

5 g of ethoxypropoxy-triestyryl-phenol (block copolymer) and

10 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 17 (not according to the invention)

For the proper preparation of the invention with the active substance Isopyrazam, they are first mixed

10 g of Isopyrazam with

40 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 10 g of aromatic hydrocarbon mixture, reduced Naphalin,

10 g of 2-ethylhexanol-propylenenetylene glycol ether,

10 g of polyglycerol of castor oil,

5 g of ethoxypropoxy-triestyryl-phenol (block copolymer) and

15 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation example 18 (not according to the invention)

For the proper preparation of the invention with the active substance Fluxapiroxad, they are first mixed

10 g of Fluxapiroxad with

45 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 10 g of aromatic hydrocarbon mixture, reduced Naphalin,

10 g of 2-ethylhexanol-propylenenetylene glycol ether,

10 g of polyglycerol of castor oil,

5 g of ethoxypropoxy-triestyryl-phenol (block copolymer) and

10 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation Example 19 (not according to the invention)

For the proper preparation of the invention with the active substance Fluxapiroxad, they are first mixed

10 g of Fluxapiroxad with

40 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 10 g of aromatic hydrocarbon mixture, reduced Naphalin,

10 g of 2-ethylhexanol-propylenenetylene glycol ether,

10 g of polyglycerol of castor oil,

5 g of ethoxypropoxy-triestyryl-phenol (block copolymer) and

15 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation Example 20

For the proper preparation of the invention as a tank mixing additive, they are first mixed

50 g of C16-C18 carboxylic acid dibutylamide with

25 g of polyglycerol of castor oil and then mixed under stirring at room temperature with

25 g of benzyl alcohol

Once the addition is finished, it is stirred for another 2 hours at room temperature. In this way a homogeneous solution is obtained.

Formulation Example 21

For the proper preparation of the invention with the active substance protioconazole, they are first mixed

20 g of protioconazole with

44.9 g of N, N-dimethyldecanamide and then mixed under stirring at room temperature with 15 g of 2-ethylhexanol-propylenenetylene glycol ether,

10 g of polyglycerol of castor oil,

5 g ethoxypropoxy triestyryl phenol (block copolymer)

0.1 g of silicone antifoam emulsion and

5 g of C16-C18 carboxylic acid dibutylamide

Once the addition is finished, it is stirred for another 4 hours at room temperature. In this way a homogeneous solution is obtained.

Claims (5)

1. Use of carboxylic acid amides of the formula (I) R1-CO-NR2R3 (I), in which R1 means C16-C18 alkyl or C16-C18 alkenyl and R2 means C4 alkyl and R3 means C4 alkyl for the promotion of the penetration of protioconazole in plants. 2. Use according to claim 1, wherein the carboxylic acid amides of the formula (I) are added to the agrochemical active ingredient protioconazole as a tank mixing additive. 3. Agrochemical formulations in the form of emulsion concentrates or oil dispersions, containing ° protioconazole as well as At least one carboxylic acid amide of the formula (I) R1-CO-NR2R3 (I), in which R1 means C16-C18 alkyl or C16-C18 alkenyl and R2 means C4 alkyl and R3 means C4 alkyl, as well as ° at least one solvent and / or oil. 4. Agrochemical formulation according to claim 3, wherein the content of the at least one carboxylic acid amide of the formula (I) in the agrochemical formulation is 1 to 50% by weight. 5. Agrochemical formulations according to claim 3 containing • 15 - 35% by weight of protioconazole and • 25 - 45% by weight of N, N-dimethyldecanamide and • 10 - 40% by weight of one or more emulsifiers and • 0.01 - 1.0% by weight of defoamers, and • 5-30% by weight of C16-C18 alkyl carboxylic acid dibutylamide and C16-C18 alkenyl carboxylic acid dibutylamide (in the sum).