DE4331416A1 - Use of phenylcarboxylic acid amides as crystallization inhibitors - Google Patents

Description

The present invention relates to the novel use of certain phenyl carboxylic acid derivatives to prevent crystallization during application of aqueous spray mixtures based on certain fungicidal agents.

In sprayers, usually for the application of aqueous formulations of Plant treatment products used are several filters and nozzles available. For example, there are suction filters between intake and Tank pump and further pressure filter, which after the pump in the pressure range are arranged. In addition, nozzle filters can be included directly located in front of the spray nozzles. All these filters as well as the nozzles can at the application of aqueous spray mixtures based on solid active substances more or less easily blocked by crystallizing agent.

It is already known that the azole derivatives mentioned below are fungicidal are effective and in the form of aqueous spray liquors on plants and / or their Habitat can be applied:

1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentan - 3-ol,
1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-one,
1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol,
1- (4-phenyl-phenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-ol,
1- (2-chlorophenyl) -2- (1-chloro-cycloprop-1-yl) -3- (1,2,4-triazol-1-yl) - propan-2-ol,
1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- (1,2,4-triazol-1-yl) ethane-1-ol,
1- (1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) hexan-2-ol,
1 - ([bis (4-fluorophenyl) methyl-silyl] methyl) -1H- (1,2,4-triazole),
1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethyl-pent-1-en-3-ol,
1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimdhyl-pent-1-en-3 - ol,
1- (4-chlorophenyl) -1- (1-cyclopropyl-ethyl) -2- (1,2,4-triazol-1-yl) eth-an-1-ol,
1- (4-chlorophenyl) -3-phenyl-3-cyano-4- (1,2,4-triazol-1-yl) -butane and
1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) -oxiran-2-yl-methyl] -1H- (1,2,4 - triazol)
(cf., EP-OS 0 040 345, DE-PS 22 01 063, DE-PS 23 24 010, EP-OS 0 297 345, EP-OS 0 015 756, US-PS 4 551 469, EP-OS 0 068 813, DE-OS 28 38 847, DE-OS 30 10 560, DE-OS 34 06 993, DE-OS 28 21 971 and EP-OS 0 196 038).

Furthermore, it is known that in the production and application of spray brew the said active ingredients N-alkyl lactams and alkylcarboxylic acid dime thylamides can be used as crystallization inhibitors (see. EP-OS 0 391168, EP-OS 0 453 915 and EP-OS 0 453 899). So can be N-octyl pyrrolidone and / or a mixture containing on average 5% hexanoic acid dimethylamide, 50% octanoic acid dimethylamide, 40% decanoic acid dimethylamide and to 5% dodecanoic acid dimethylamide, use to at Aus aqueous spray mixtures containing 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4- Triazol-1-yl-methyl) -pentan-3-ol as an active ingredient, a crystallization to prevent this active ingredient in the sprayers. For longer application such spray liquors is the effectiveness of said crystallization inhibitors but not always satisfying.

Finally, phenylcarboxylic acid amides and their use for various purposes known (see J. Serb. Chem. Soc 57 (1992), 549-554).

It has now been found that phenylcarboxamides of the formula

in which
R¹ is hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, benzyl, phenethyl, alkoxy of 1 to 6 carbon atoms, phenoxy or a radical of the formula

stands in which
R⁵ is hydrogen, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl or benzyl, and
R⁶ is hydrogen, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, cycloalkyl of 5 to 7 Kohlenstoffato men, phenyl or benzyl or
R⁵ and R⁶ together represent an alkylene chain having 3 to 6 carbon atoms or a group of the formula

stand,
R 2 is hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, benzyl, phenethyl, alkoxy of 1 to 6 carbon atoms or phenoxy,
R³ is hydrogen, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl or benzyl, and
R⁴ represents alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, cycloalkyl having 5 to 7 carbon atoms, phenyl or benzyl or
R³ and R⁴ together represent an alkylene chain having 3 to 6 carbon atoms or a group of the formula

stand,
to use when spreading aqueous spray liquors, the

• A) at least one azole derivative of the formula in which
  • a) R⁷ for stands,
    R⁸ is tert-butyl and
    R⁹ is hydroxy, or
  • b) R⁷ is 4-fluorophenyl,
    R⁸ is 2-fluorophenyl and
    R⁹ is hydroxy, or
  • c) R⁷ is 2,4-dichlorophenyl,
    R⁸ is n-butyl and R⁹ is hydroxy, or
  • d) R⁷ for stands,
    R⁸ is phenyl and
    R⁹ is cyano, or
  • e) R⁷ is 2-chloro-benzyl,
    R⁸ is 1-chloro-cycloprop-1-yl and
    R⁹ is hydroxy, or
  • f) R⁷ is 4-chlorophenyl,
    R⁸ for stands and
    R⁹ is hydroxy,
• and or
  at least one azole derivative of the formula in which
  • a) Y is -CH (OH) and
    R¹⁰ is chlorine or phenyl, or
  • b) Y is CO and
    R¹⁰ is chlorine,
• and or
  at least one azole derivative of the formula in which
  R¹¹ is hydrogen or chlorine,
  and or
  1 - ([bis (4-fluorophenyl) methylsilyl] methyl) -1H- (1,2,4-triazole) of the formula and or
  1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1H- (1,2,4-triazole) of the formula and
• B) optionally one or more further active ingredients and additives

a crystallization of the active compounds of the formulas (II) to (VI) in the Prevent sprayers.

It is extremely surprising to note that the crystallization tendency of Azole derivatives of the formulas (II) to (VI) by the use according to the invention of phenylcarboxylic acid amides of the formula (I) is greatly reduced. Especially It was not to be expected that phenylcarboxylic acid amides of the formula (I) were essential better than N-alkyl lactams and alkylcarboxylic acid dimethylamides for the given purpose are suitable.

The use of phenylcarboxamides of the formula (I) in aqueous Formulations based on fungicidally active azole derivatives of the formulas (II) to (VI) has a number of advantages. So it is with the Phenylcarboxylic acid amides of the formula (I) to substances that handle easily and are also available in larger quantities. Furthermore, by using the Substances of the formula (I) prevent the spraying of aqueous Formulierun which contain active substances of the formulas (II) to (VI), both the filters and clog nozzles of sprayers. It is also advantageous that phenylcarboxylic acid amides of the formula (I) in crop protection no undesirable side effects exercise.

The phenylcarboxylic acid amides which can be used according to the invention are represented by the formula mel (I) generally defined.  

R 1 is preferably hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, phenyl, benzyl, phen-2-ethyl, phen-1-ethyl, straight-chain or branched alkoxy having 1 to 4 carbon atoms, Phenoxy or a radical of the formula

R⁵ is preferably hydrogen, straight-chain or branched Alkyl of 1 to 6 carbon atoms, straight or branched alkenyl having 2 to 6 carbon atoms, cyclopentyl, cyclo hexyl, cycloheptyl, phenyl or benzyl.

R⁶ is preferably hydrogen, straight-chain or branched Alkyl of 1 to 6 carbon atoms, straight or branched alkenyl having 2 to 6 carbon atoms, cyclopentyl, cyclo hexyl, cycloheptyl, phenyl or benzyl.

R⁵ and R⁶ together are also preferably an alkylene chain 3 to 6 carbon atoms or a group of the formula

R 2 is preferably hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, phenyl, benzyl, phen-2-ethyl, phen-1-ethyl, straight-chain or branched alkoxy having 1 to 4 carbon atoms or Phenoxy.

R³ is preferably hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight or branched alkenyl having 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl or benzyl.  

R⁴ preferably represents straight-chain or branched alkyl with 1 to 6 carbon atoms, straight-chain or branched alkenyl with 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl or Benzyl.

R³ and R⁴ together are also preferably an alkylene chain with 3 bis 6 carbon atoms or a group of the formula

R¹ is particularly preferably hydrogen, methyl, ethyl, n-propyl, iso propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, phenyl, benzyl, phen-2 ethyl, phen-1-ethyl, methoxy, ethoxy, phenoxy or a radical of the formula

R⁵ particularly preferably represents hydrogen, straight-chain or branched alkyl of 1 to 4 carbon atoms, straight-chain or branched alkenyl of 2 to 4 carbon atoms, cyclo pentyl, cyclohexyl, cycloheptyl, phenyl or benzyl.

R⁶ particularly preferably represents hydrogen, straight-chain or ver branched alkyl having 1 to 4 carbon atoms, straight or branched alkenyl of 2 to 4 carbon atoms, cyclopentyl, Cyclohexyl, cycloheptyl, phenyl or benzyl.

R⁵ and R⁶ together are also particularly preferred for one Alkylene chain of 3 to 6 carbon atoms or a group the formula  

R 2 particularly preferably represents hydrogen, methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, benzyl, phen 2-ethyl, phen-1-ethyl, methoxy, ethoxy or phenoxy.

R³ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, Isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, vinyl, allyl, But-2-en-yl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl or benzyl.

R⁴ particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, vinyl, allyl, but-2-en-yl, cyclo pentyl, cyclohexyl, cycloheptyl, phenyl or benzyl.

R³ and R⁴ together are also particularly preferred for an alkylene chain 3 to 6 carbon atoms or a group of the formula

Examples of substances which can be used according to the invention are those shown below Table 1 listed phenylcarboxylic acid amides.  

Table 1

The Phenylcarbonsäureamide of formula (I) are known or can be after Known methods in a simple manner (see Houben-Weyl "Methods of Organic Chemistry ", Georg Thieme Verlag, Stuttgart 1985, Volume E5, page 934 ff.).

The present in the aqueous spray mixtures used in the invention Azole derivatives are defined by formulas (II) to (VI). It can be individual or also contain several or the following azole derivatives:

1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentan-3-ol of For mel  

1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- (1,2,4-triazol-1-yl) ethane-1-o-1 of the formula

1- (1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -hexan-2-ol of the formula

1- (4-chlorophenyl) -3-phenyl-3-cyano-4- (1,2,4-triazol-1-yl) -butane of the formula  

1- (2-chlorophenyl) -2- (1-chloro-1-cycloprop-1-yl) -3- (1,2,4-triazol-1-yl) -propan-2-ol formula

1- (4-chlorophenyl) -1- (1-cyclopropyl-ethyl) -2- (1,2,4-triazol-1-yl) -eth-an-1-ol of For mel

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-ol of the formula  

1- (4-phenyl-phenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-ol of the formula

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-one of the formula

1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethyl-pent-1-en-3-ol of the formula

1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethyl-pent-1-en-3-ol of the formula  

1 - ([bis (4-fluorophenyl) methylsilyl] methyl) -1H- (1,2,4-triazole) of the formula

1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1H- (1,2,4-triazole) of formula

The active compounds of the formulas (II) to (VI) and their use for Fighting phytopathogenic fungi are known (see EP-OS 0 040 345, US Pat. No. 4,551,469, EP-PS 0 015 756, EP-OS 0 068 813, EP-OS 0 297 345, US Pat. DE-OS 34 06 993, DE-PS 23 24 010, DE-PS 22 01 063, DE-OS 28 38 847, DE-OS 30 10 560, DE-OS 28 21 971 and EP-OS 0 196 038).

The active compounds of the formulas (II) to (VI) can be prepared in customary formulations use. Preferably, the application takes place in the form of aqueous spray blanch.  

In the spray mixtures which can be used according to the invention, besides the active substance of the formulas (II) to (VI) also contain one or more further active ingredients his. Preferably in question come compounds with fungicidal properties companies. As examples of such additional useful agents ge mentioned are:

N, N-dimethyl-N'-phenyl- (N'-fluorodichloromethylthio) sulfamide (dichlorofluidide),
N, N-dimethyl- (N'-fluorodichloromethylthio) -N '- (4-methyl-phenyl) -sulfame-id (tolylfluanid),
N-trichloromethylmercapto-4-cyclohexene-1,2-dicarboxamide (Captan),
N- (1,1,2,2-tetrachloro-sulfenyl) -cis-4-cyclohexene-1,2-dicarboxam-id (captafol),
N-trichloromethylthio-phthalimide (folpet),
N-dodecylguanidine acetate (Dodine),
Tetrachloroisophthalonitrile (chlorothalonil),
4,5,6,7-tetrachlorophthalide,
Zinc ethylene bis-dithiocarbamate (zineb),
Manganese ethylene bis-dithiocarbamate (Maneb),
Zinc ethylene bis-dithiocarbamate / manganese ethylene bis-dithiocarbamate (Mancozeb),
Zinc-propylene-1,2-bis-dithiocarbamate (Propineb),
1- [3- (4- (1,1-dimethylethyl) -phenyl) -2-methylpropyl] -piperidine (fenpropidine),
N-tridecyl-2,6-dimethyl-morpholine (tridemorph),
N-dodecyl-2,6-dimethyl-morpholine (aldimorph)
cis-4- [3- (4-tert-butylphenyl) -2-methyl-propyl] -2,6-dimethylmorpholene-n (fenpropimorph)
2- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] imidazole (imazalil),
N- [2- (2,4,6-trichlorophenoxy) ethyl] -N-propyl-1H-imidazole (prochloraz),
1,2-dimethylcyclopropane-1,2-dicarboxylic acid 3,5-dichloro-phenylimide (procymidone),
2-methoxycarbamoylbenzimidazole (carbendazim),
1- (butylcarbamoyl) -2-benzimidazole methylcarbamate (benomyl),
1- [2- (2,4-dichlorophenyl) -4-propyl- (1,3-dioxolan-2-yl) methyl] -1H- (1, -2,4-triazole) (propiconazole),
2,4-dichloro-6- (2'-chlorophenyl-amino) -1,3,4-triazine (anilazine),
Bis (8-guanidine-O-octyl) -amine-triacetate (guazatine),
1- (4-chlorobenzyl) -1-cyclopentyl-3-phenyl-urea (pencycuron).

As additives which are present in the spray mixtures which can be used according to the invention may come from surface-active substances, organic dilution medium, acids, cold stabilizers and adhesives in question.

In this case come as surface-active substances non-ionic, anionic, cationic and zwitterionic emulsifiers. These substances include Umset tion products of fatty acids, fatty acid esters, fatty alcohols, fatty amines, alkyl phenols or alkylarylphenols with ethylene oxide and / or propylene oxide, and their sulfuric acid esters, phosphoric monoesters and phosphoric diesters, furthermore reaction products of ethylene oxide with propylene oxide, furthermore alkyl sulfonates, alkyl sulfates, aryl sulfates, tetra-alkyl-ammonium halides, trialkyl aryl ammonium halides and alkyl amine sulfonates. The emulsifiers can or be used in mixture. Preferably called Um castor oil with ethylene oxide in a molar ratio of 1: 20 to 1:60, Reaction products of C₆-C₂₀ fatty alcohols with ethylene oxide in a molar ratio 1: 5 to 1: 50, reaction products of fatty amines with ethylene oxide in Molver 1: 2 to 1:20, reaction products of 1 mole of phenol with 2 to 3 moles Styrene and 10 to 50 moles of ethylene oxide, reaction products of 1 mole of phenol with 2 to 3 moles of vinyltoluene and 10 to 50 moles of ethylene oxide, reaction products of C₈-C₁₂-alkylphenols with ethylene oxide in a molar ratio of 1: 5 to 1: 30, alkylglycol side, C₈-C₁ ₆-alkylbenzene sulfonic acid salts, such as. B. calcium, monoethanolammo ammonium, di-ethanolammonium and tri-ethanolammonium salts.

The emulsifiers used in practice from the group of alkylaryl-poly Glycol ethers are often mixtures of several compounds. In particular han These are mixtures of substances that are affected by the degree of substitution at the connected to the oxyethylene unit phenyl ring and the number Oxyethylene units differ. This will calculate for the number of sub substituents on the phenyl ring also broken numbers as averages. For example Mention may be made of substances for which the following average composition tongues result:  

As organic diluents may be used in the invention Spray mixtures all commonly used for such purposes polar and un be present polar organic solvents. Preferably come into consideration Ketones, such as methyl isobutyl ketone and cyclohexanone; furthermore, amides, such as dime methylformamide furthermore cyclic compounds, such as N-methylpyrrolidone,  N-octyl-pyrrolidone, N-dodecyl-pyrrolidone, N-octyl-caprolactam, N-dodecyl-capro lactam and γ-butyrolactone, in addition strongly polar solvents, such as dime thylsulfoxide, furthermore aromatic hydrocarbons, such as xylene, also esters, such as propylene glycol monomethyl ether acetate, adipic acid dibutyl ester, acetic acid hexyl ester, heptyl acetate, tri-n-butyl citric acid ester and phthalic acid di-n-butyl ester, and further alcohols such as ethanol, n- and i-propanol, n- and i-butanol, n- and i-amyl alcohol, benzyl alcohol and 1-methoxy-2-propanol.

As acids, all übli in the spray mixtures which can be used according to the invention cherweise suitable for such purposes inorganic and organic acid be present. Preferably suitable are aliphatic and aromatic Hydroxycarboxylic acids such as citric acid, salicylic acid, tartaric acid and ascorbic acid acid.

As cold stabilizers can be used in the invention according to spray liquors all substances normally suitable for this purpose may be included. Vorzugswei in question are urea, glycerol and propylene glycol.

As adhesives, all can be used in the spray mixtures which can be used according to the invention Usually suitable for this purpose substances are used. virtue Wise as adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, Polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and also synthetic phospholipids. Other additives can be mineral and vegetable oils.

Incidentally, water is in each case in the spray mixtures usable according to the invention contain.

The active ingredient concentrations can be used in the invention Spray mixtures can be varied within a certain range. In general my drug concentrations are between 0.0001 and 5 Gewichtspro cent, preferably between 0.001 and 3 weight percent.  

Also the ratio of active ingredient of formulas (II) to (VI) to phenylcarbon Acid amide of the formula (I) can be varied within a certain range become. In general, the weight ratio of active ingredient from the group pe (A) to phenylcarboxylic acid amide of formula (I) between 1: 0.2 and 1: 5, before preferably between 1: 0.6 and 1: 2.

The amounts of other active ingredients or additives may in the inventions spray mixtures which can be used in accordance with the invention within a relatively wide range, in particular be riiert. They are of the order of magnitude as is customary in such cases aqueous spray mixtures is the case.

The preparation of the spray mixtures according to the invention is carried out according to üb methods. In general, one proceeds in such a way that one first a Kon produced at temperatures between 10 ° C and 30 ° C the required components in any order and homogeneous mixed and the resulting mixture optionally filtered. For the production the ready-to-use spray liquor is given the concentrated formulation optionally with stirring and / or pumps with the respective desired amount Water so mixed that the formulation in water evenly and finely dispersed is distributed.

It is also possible to then add phenylcarboxylic acid amides of the formula (I) if the concentrate is diluted with water to the ready-to-use spray mixture becomes.

Both for the preparation of the concentrated formulations as well as the manufacture ment and application of the invention can be used spray mixtures all commonly used for this purpose mixing apparatus and Spritzge insert devices.

By the use of phenylcarboxamides of the formula (I) in aqueous Spray mixtures based on active compounds of the formulas (II) to (VI) is the Crystallization of active ingredient in both the concentrated, commercial Formulation as well as the application of the aqueous spray produced therefrom brew in the filters and outlets of the sprayers either completely below  tied or so far prevented that the application of the spray liquors not be is impaired.

The preparation of the inventively used phenylcarboxylic acid amides so how the production and the crystallization behavior of the invention ver reversible spray mixtures are illustrated by the following examples.

Preparation Examples example 1

In a mixture of 387.8 g (3 mol) of di-n-butyl-amine and 100 ml of water are allowed at temperatures between 20 and 30 ° C with cooling and intensive stirring two separate dropping funnels simultaneously 281.1 g (2 mol) of benzoyl chloride and Run in 200 g of 45 wt .-% aqueous sodium hydroxide solution within one hour. The reaction mixture is added at the end of addition 3 hours Temperatures between 40 and 50 ° C stirred. Thereafter, the aqueous phase separated and the remaining organic phase of a fractional distillation subjected to reduced pressure. This gives 456.5 g (97.8% of theory) of benzoic acid di-n-butylamide in the form of a colorless oil with the boiling point Kp = 115 ° C / 0.3 Torr.

After the method given in Example 1 are also in the following Table 2 listed substances.  

Table 2

Preparation of formulations Example I

To prepare a formulation

25.0 parts by weight of 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-ylmethyl) pentan-3-ol of the formula

35.0 parts by weight of benzoic acid di-n-butylamide,
6.5 parts by weight of the emulsifier of the average composition of the formula

6.5 parts by weight of 4- (n-dodecyl) benzene-sulfonic acid (2-hydroxyethyl) ammonium salt
25.0 parts by weight of N-methyl-pyrrolidone and
2.0 parts by weight of water

mixed at room temperature and stirred to a homogeneous liquid. Out The concentrate thus obtained is defined by mixing with water of defined hardness  (CIPAC-C water) prepared a spray mixture in which the concentrate in a Concentration of 0.5 wt .-% is included.

CIPAC-C water = water containing 4 mmol of calcium chloride per liter and 1 mmol magnesium chloride

Example II

To prepare a formulation

25.0 parts by weight of 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-ylmethyl) pentan-3-ol of the formula

35.0 parts by weight of (2-methyl-phenyl) -carboxylic acid di-n-butyl-amide of the formula

6.5 parts by weight of the emulsifier of the average composition of formula

6.5 parts by weight of 4- (n-dodecyl) -benzenesulfonic acid (2-hydroxyethyl) ammonium salt,
25.0 parts by weight of N-methyl-pyrrolidone and
2.0 parts by weight of water

mixed at room temperature and stirred to a homogeneous liquid. Out The concentrate thus obtained is defined by mixing with water of defined hardness (CIPAC-C water, see Example I) prepared a spray mixture in which the Concentrate is contained in a concentration of 0.5 wt .-%.

Comparative Example A

To prepare a formulation

25.0 parts by weight of 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-ylmethyl) pentan-3-ol of the formula

35.0 parts by weight of a mixture of average

5% hexanoic acid dimethylamide,
50% octanoic acid dimethylamide,
40% decanoic acid dimethylamide and
5% dodecanoic acid dimethylamide,
6.5 parts by weight of the emulsifier of the average composition of the formula

25.0 parts by weight of N-methyl-pyrrolidone,
6.5 parts by weight of 4- (n-dodecyl) -benzenesulfonic acid (2-hydroxyethyl) -ammonium salt and
2.0 parts by weight of water

mixed at room temperature and stirred to a homogeneous liquid. Out The concentrate thus obtained is defined by mixing with water of defined hardness (CIPAC-C water, see Example I) prepared a spray mixture in which the Concentrate is contained in a concentration of 0.5 wt .-%.

usage example

For checking the crystallization properties, in each case 250 ml of an aqueous spray mixture, which has a concentrate content of 0.5 wt .-%, in one Durchflußapparatur at a temperature of 5 ° C permanently through a fine pumped mesh screen, wherein after every 30 minutes, the spray mixture removed and is replaced by a newly prepared spray mixture of the same composition. The crystal separation on the screen is determined by the difference in pressure is measured on the sieve. A strong increase in pressure indicates that the stitches of the Sieves are largely blocked by crystal deposition.

The formulations used and the test results are from fol table.  

Formulation according to example Crystal deposition on the sieve of the flow-through apparatus I (according to the invention) After more than 20 hours still no crystal deposition II (according to the invention) After more than 20 hours still no crystal deposition Comparative Example A (known) After 2.8 hours, almost complete coverage of the sieve by crystals

Claims (9)

1. Use of Phenylcarbonsäureamiden of the formula in which
R¹ is hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, benzyl, phenethyl, alkoxy of 1 to 6 carbon atoms, phenoxy or a radical of the formula stands,
wherein
R⁵ is hydrogen, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl or benzyl, and
R⁶ is hydrogen, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl or benzyl, or
R⁵ and R⁶ together for an alkylene chain having 3 to 6 carbon atoms or for a group of the formula stand,
R² is hydrogen, alkyl having 1 to 6 carbon atoms, phenyl, benzyl, phenethyl, alkoxy having 1 to 6 carbon atoms or phenoxy,
R³ is hydrogen, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl or benzyl, and
R⁴ is alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, cycloalkyl having 5 to 7 carbon atoms, phenyl or benzyl or
R³ and R⁴ together represent an alkylene chain having 3 to 6 carbon atoms or a group of the formula stand,
when applying aqueous spray mixtures, the

• A) at least one azole derivative of the formula in which
  • a) R⁷ for stands,
    R⁸ is tert-butyl and
    R⁹ is hydroxy, or
  • b) R⁷ is 4-fluorophenyl,
    R⁸ is 2-fluorophenyl and
    R⁹ is hydroxy, or
  • c) R⁷ is 2,4-dichlorophenyl,
    R⁸ is n-butyl and
    R⁹ is hydroxy, or
  • d) R⁷ for stands,
    R⁸ is phenyl and
    R⁹ is cyano, or
  • e) R⁷ is 2-chloro-benzyl,
    R⁸ is 1-chloro-cycloprop-1-yl and R⁹ is hydroxy, or
  • f) R⁷ is 4-chlorophenyl,
    R⁸ for stands and
    R⁹ is hydroxy,
• and or
  at least one azole derivative of the formula in which
  • a) Y is -CH (OH) and
    R¹⁰ is chlorine or phenyl, or
  • b) Y is CO and
    R¹⁰ is chlorine,
• and or
  at least one azole derivative of the formula in which
  R¹¹ is hydrogen or chlorine,
  and or
  1 - ([bis (4-fluorophenyl) methylsilyl] methyl) -1H- (1,2,4-triazole) of the formula and or
  1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1H- (1,2,4-triazole) of the formula and
• B) optionally one or more further active ingredients and additives

a crystallization of the active compounds of the formulas (II) to (VI) in to prevent the sprayers. 2. Use according to claim 1, characterized in that one uses phenylcarboxylic acid amides of the formula (I), in which
R¹ is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, phenyl, benzyl, phen-2-ethyl, phen-1-ethyl, straight-chain or branched alkoxy having 1 to 4 carbon atoms phenoxy or a radical of the formula stands in which
R⁵ is hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkenyl having 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl or benzyl,
R⁶ is hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkenyl having 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl or benzyl or
R⁵ and R⁶ together represent an alkylene chain having 3 to 6 carbon atoms or a group of the formula stand,
R 2 is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, phenyl, benzyl, phen-2-ethyl, phen-1-ethyl, straight-chain or branched alkoxy having 1 to 4 carbon atoms or phenoxy,
R³ is hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkenyl having 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl or benzyl,
R⁴ represents straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkenyl having 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl or benzyl or
R³ and R⁴ together for an alkylene chain having 3 to 6 carbon atoms or for a group of the formula stand. 3. Use according to claim 1, characterized in that phenylcarboxamides of the formula (I) are used, in which
R¹ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, benzyl, phen-2-ethyl, phen-1-ethyl, methoxy, Ethoxy, phenoxy or a radical of the formula stands in which
R⁵ is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkenyl having 2 to 4 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl or benzyl,
R⁶ is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkenyl having 2 to 4 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl or benzyl or
R⁵ and R⁶ together represent an alkylene chain having 3 to 6 carbon atoms or a group of the formula stand,
R 2 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, benzyl, phen-2-ethyl, phen-1-ethyl, methoxy, Ethoxy or phenoxy,
R³ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, vinyl, allyl, but-2-en-yl, cyclopentyl, Cyclohexyl, cycloheptyl, phenyl or benzyl,
R⁴ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, vinyl, allyl, but-2-en-yl, cyclopentyl, cyclohexyl, Cycloheptyl, phenyl or benzyl is or
R³ and R⁴ together for an alkylene chain having 3 to 6 carbon atoms or for a group of the formula stand. 4. Use according to claim 1, characterized in that Ben zoesäure- (di-n-butyl) -amide is used.   5. Use according to claim 1, characterized in that one uses Ben zoesäure- (di-n-butyl) -amide in spray mixtures, the 1- (4-chlorophenyl) - 4,4-dimethyl-3- (1,2, 4-triazol-1-ylmethyl) pentan-3-ol of the formula contain. 6. Process for preventing the crystallization of active ingredients of For Meln (II) to (VI) according to claim 1 when applying aqueous Spray mixtures containing at least one active ingredient of the formulas (II) to (VI) ent hold, characterized in that the spray mixtures at least one A phenylcarboxylic acid amide of the formula (I) according to claim 1 added. 7. Fungicidal agent, characterized by a content of at least one Phenylcarbonsäureamid of the formula in which
R¹ is hydrogen, alkyl of 1 to 6 carbon atoms, phenyl, benzyl, phenethyl, alkoxy of 1 to 6 carbon atoms, phenoxy or a radical of the formula stands,
wherein
R⁵ is hydrogen, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl or benzyl, and
R⁶ is hydrogen, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl or benzyl, or
R⁵ and R⁶ together for an alkylene chain having 3 to 6 carbon atoms or for a group of the formula stand,
R² is hydrogen, alkyl having 1 to 6 carbon atoms, phenyl, benzyl, phenethyl, alkoxy having 1 to 6 carbon atoms or phenoxy,
R³ is hydrogen, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl or benzyl, and
R⁴ is alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, cycloalkyl having 5 to 7 carbon atoms, phenyl or benzyl or
R³ and R⁴ together represent an alkylene chain having 3 to 6 carbon atoms or a group of the formula stand,

• A) at least one azole derivative of the formula in which
  • a) R⁷ for stands,
    R⁸ is tert-butyl and
    R⁹ is hydroxy, or
  • b) R⁷ is 4-fluorophenyl,
    R⁸ is 2-fluorophenyl and
    R⁹ is hydroxy, or
  • c) R⁷ is 2,4-dichlorophenyl,
    R⁸ is n-butyl and
    R⁹ is hydroxy, or
  • d) R⁷ for stands,
    R⁸ is phenyl and
    R⁹ is cyano, or
  • e) R⁷ is 2-chloro-benzyl,
    R⁸ is 1-chloro-cycloprop-1-yl and
    R⁹ is hydroxy, or
  • f) R⁷ is 4-chlorophenyl,
    R⁸ for stands and
    R⁹ is hydroxy,
• and or
  at least one azole derivative of the formula in which
  • a) Y is -CH (OH) and
    R¹⁰ is chlorine or phenyl, or
  • b) Y is CO and
    R¹⁰ is chlorine,
• and or
  at least one azole derivative of the formula in which
  R¹¹ is hydrogen or chlorine,
  and or
  1 - ([bis (4-fluorophenyl) methylsilyl] methyl) -1H- (1,2,4-triazole) of the formula and or
  1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1H- (1,2,4-triazole) of the formula and
• B) optionally one or more further active ingredients and additives.

8. Composition according to claim 7, characterized by a content of - benzoic acid (di-n-butyl) -amide of the formula and
- 1- (4- (Chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentan-3-ol of the formula