PL229317B1 - Protonic salts of diphenoconazol with organic anion, method for obtaining them and their application as fungicides - Google Patents

Abstract

The invention relates to protic salts of diphenoconazole with an organic anion of the general formula, in which A- is: an organic anion: dihydrogen citrate or salicylate, or bitartrate, or hydrogen oxalate or dichloroacetate, their preparation and use as fungicides. The method of their preparation consists in dissolving diphenoconazole in an aliphatic alcohol with a carbon chain length from one to four carbon atoms, or a mixture thereof, preferably in methanol, further mixed with a methanolic solution of citric or salicylic or tartaric or oxalic acid, or dichloroacetic acid, at a concentration of at least 1%, in a molar ratio of 1: 1 to 1: 1.05, preferably 1: 1, at a temperature below 100 ° C, preferably at 20 ° C, for at least 40 minutes, then the solvent is removed. The use of the new organic anion proton salts of difenoconazole as fungicides has also been disclosed.

Description

Description of the invention

The subject of the invention is protic salts of difenoconazole with an organic anion, a method of their preparation and use as fungicides.

Ionic liquids are multifunctional chemicals consisting of a large, unsymmetrical organic cation and an organic or inorganic anion whose melting point is less than the boiling point of water. This is a relatively new group of compounds, the first mention of which was in 1914 when Walden described ethylammonium nitrate in Bull. Acad. Imper. Sci. St. Petersbourg. 1914, 8 (8), 405-422. Currently, the subject of ionic liquids is developing very intensively and is being studied by numerous academic and industrial centers around the world.

In the course of the synthesis, it is possible to select such ions to obtain an ionic liquid with specific, desired properties (soluble in water or organic solvents, with a specific viscosity and density). Their physico-chemical properties can vary widely and strongly depend on the structure of the cation and anion. For this reason, ionic liquids can be referred to as "design solvents". Thanks to their multifunctional properties, these compounds have many applications, including wood preservatives, surfactants, disinfectants, anti-electrostatic, anti-caking or softening substances. They are also used as electrolytes and reaction media discussed by C. Wolff, S. Jeong, E. Paillard, A. Balducci, S. Passerini in Journal of Power Sources, 2015, 293, 85-70. Due to the near-zero vapor pressure above the surface of the liquid and thermal stability, as well as selective solubility, liquid membranes and sensors are produced from them, which was presented by F.J. Hernandez-Fernandez, A. Perez de los Rios, F. Mateo-Ramirez, C. Godinez, L.J. Lozano-Blanco, J.l. Moreno, F. Tomas-Alonso in ChemicalEngineering Journal, 2015, 279, 115-119). Among ionic liquids, a large group of biologically active substances can be distinguished, including fungicides, herbicides and insecticides.

In terms of production volume, fungicides constitute the second group of plant protection chemicals after herbicides. Modifications of the structure and extensive research on synergistic compositions allowed for a significant reduction in doses, which indirectly translates into lower exposure of non-target organisms.

Western Europe is the leading applicator of fungicides, and their use is increasing every year. In the 1960s, the period of synthesis of new fungicides, triazole derivatives, began. This group includes, among others highly effective, low toxic to the environment difenoconazole which has been described by Z. Zhang, W. Jiang, Q. Jian, W. Song, Z. Zheng, D. Wang, X. Liu in Food Chemistry, 2015, 168, 396-403 .

Quaternary triazole salts are of great interest due to their low cost and unique bactericidal and fungicidal properties. They owe them to their molecular structure: a positively charged nitrogen atom in a cyclic system and hydrocarbon groups, which are the hydrophilic part of the compound. The remainder of the alkyl chain is hydrophobic. Triazole fungicides include compounds such as difenoconazole, tebuconazole, propiconazole and cyproconazole. Triazole derivatives are widely used in the world due to their broad spectrum of activity. Since 1980, they have been used in pure form or as salts to protect plants and their seeds and preserve wood, as confirmed by EP2637501, R.D. Rogers, L.R. Cooke, 2013. They have protective and healing properties in relation to, inter alia, cereals, vines, and bananas, and documented in US Patent 08,765,720 by A.R.A. Valcke, M.A.J. Van Der Flaas, 1998. Triazole compounds are systemically acting fungicides which disrupt the development of plant pathogens. When used even during an infection, they guarantee the effectiveness of the therapy. As a result of the reaction of organic and inorganic acids with tebuconazole and propiconazole, salts were obtained that fight against fungi such as Fusarium culmorum or Sclerotinia sclerotiorum, as described in the publication of J. Pernak, B. Markiewicz, B. Łęgosz, R. Gwiazdowski, T. Praczyk at RSC Advances, 2015, 5, 9695-9702. They also exhibit antibacterial properties and can be used as artificial sweeteners, as discussed by W.L. Hough-Troutman, M. Smiglak, S. Griffin, W.M. Reichert, I. Mirska, J. Jodynis-Liebert, T. Adamska, J. Nawrot, M. Stasiewicz, R.D. Rogers, J. Pernak in New Journal of Chemistry, 2009, 33, 26-33). The use of fungicides in the pharmaceutical industry is also known, for example Voriconazole against Candida albicans as confirmed by Nickie D. Greer, Baylor in University Medical Center Proceedings, 2003, 16, 241-248. The action of fungicides is often selective simenoconazole fights powdery mildew, which appears on barley leaves, as confirmed by M. Tsuda, H. Itoh, S. Katów Pest Management Science, 2004, 60 (9), 875-880, and itraconazole,

PL229 317B1 is used against Aspergillus fumigatus which causes histoplasmosis, sporotrichosis or blastomycosis; described by P. Bowyer, P.W. Denning in Pest Management Science, 2014, 70 (2), 173-178).

Difenoconazole is a yellow-brown solid. Its melting point is 78-79 ° C. This compound exhibits biological activity against pathogens, penetrates into plant tissues and is spread there. It has a strong fungicidal effect alone or in a mixture, e.g. with triticonazole. To be discussed in US 8,293,680 by D.C Lindholm, H.L. Ypema, N.T. Froese, 2012. In Poland, it is a component of fungicides, for example Difo 250 EC fights apple and pear scab and apple mildew, Golden Difenoconazole 250 EC, fights apple mildew, apple scab and Score 250 EC, fights, among others, leaf spot, gooseberry mildew.

Examples of compounds from the group of the protic salts of difenoconazole with an organic anion of the general formula I can be mentioned:

• Diphenoconazole dihydrogen citrate [DFC] [CYT], • Diphenoconazole salicylate [DFC] [SAL], • Diphenoconazole hydrogen tartrate [DFC] [WIN], • Diphenoconazole hydrogen oxalate (DFC] [SZCZ], • Diphenoconazole dichloroacetate [DFC] [DFC]

The essence of the invention is the protic salts of diphenoconazole with an organic anion of the general formula I, in which A represents: an organic anion: dihydrogen citrate or salicylate, or bitartrate or hydrogen oxalate or dichloroacetate, and the method of their preparation consists in the fact that the diphenoconazole of general formula 2 is dissolved in an aliphatic alcohol with a carbon chain length of one to four carbon atoms, or a mixture thereof, preferably methanol, further mixed with a methanolic solution of citric or salicylic or tartaric or oxalic or dichloroacetic acid, at a concentration of at least 1% , in a molar ratio of from 1: 1 to 1: 1.05, preferably 1: 1, at a temperature below 100 ° C, preferably at 20 ° C. for at least 40 minutes, after which the solvent is removed.

The second method of preparation is that a quaternary diphenoconazole chloride or bromide or iodide of general formula III is dissolved in an aliphatic alcohol with a carbon chain length of one to four carbon atoms, or a mixture thereof, preferably ethanol, is further reacted exchange of the anion with a sodium or potassium or ammonium salt of citric or salicylic or tartaric or oxalic or dichloroacetic acid at a concentration of at least 1%, in a molar ratio of 1: 1 to 1: 1.05, preferably 1: 1 at a temperature below 100 ° C, preferably at 20 ° C, for at least 40 minutes, whereupon the product is isolated, and then the solvent is removed from the filtrate.

The third method of preparation consists in dissolving the diphenoconazole hydroxide of the general formula III in an aliphatic alcohol with a carbon chain length of one to four carbon atoms, or a mixture thereof, preferably in propanol, and further reacting an anion with a sodium or potassium salt. or ammonium of citric or salicylic or tartaric or oxalic or dichloroacetic acid at a concentration of at least 1%, in a molar ratio of 1: 1 to 1: 1.05, preferably 1: 1, at a temperature below 100 ° C preferably at 20 ° C for at least 40 minutes, whereupon the product is isolated and then the solvent is removed from the filtrate.

The fourth method of preparation consists in dissolving a quaternary diphenoconazole chloride or bromide or iodide of general formula III in an aliphatic alcohol with a carbon chain length of one to four carbon atoms, or a mixture thereof, preferably methanol, is further reacted neutralization with citric or salicylic or tartaric or oxalic or dichloroacetic acid at a concentration of at least 1%, in a molar ratio of 1: 1 to 1: 1.05, preferably 1: 1, at a temperature below 100 ° C, preferably at 20 ° C for at least 40 minutes, whereupon the product was isolated and then the solvent was removed from the filtrate.

A further method of preparation consists in dissolving a quaternary diphenoconazole chloride or bromide or iodide of general formula III in an aliphatic alcohol with a carbon chain length of one to four carbon atoms, or a mixture thereof, preferably in butanol, is further reacted exchange of the anion with a sodium or potassium or anionic salt of citric or salicylic or tartaric or oxalic or dichloroacetic acid at a concentration of at least 1%, in a molar ratio of 1: 1 to 1: 1.05, preferably 1: 1, at a temperature below 100 ° C, preferably at 50 ° C, for at least 50 minutes, whereupon the product is isolated and then the solvent is removed from the filtrate.

PL229 317 Β1

The use of the new proton organic anion salts of difenoconazole as defined in claims 1 as fungicides.

It is preferred that the salts are used in pure form.

It is also advantageous when the salts are used in the form of hydroalcoholic solutions.

It is also preferred that the salts are used in hydroalcoholic solutions with a concentration of at least 0.1%.

Thanks to the solution according to the invention, the following technical and economic effects were obtained:

• new protic salts containing difenoconazole have been developed, • the synthesized salts include protic ionic liquids, • the reaction yields of obtaining protic salts of difenoconazole with an organic anion are high and exceed 80%, • the obtained salts are well soluble in many organic solvents, but they dissolve to a small extent in water, • the synthesized salts are not sensitive to contact with air and water, • the obtained protic salts of difenoconazole show high effectiveness against fungi and can be used as fungicides.

The preparation of protic salts of difenoconazole with an organic anion is illustrated by the following examples:

Example I.

Method for producing diphenoconazole citrate [DFC] [CYT]:

9.81 g of citric acid with a purity of 99% dissolved in 10 cm ^{3 of} methanol (0.05 mol) were placed in the flask, to which was added in small portions, with constant stirring, 20.31 g of a 97% methanolic solution of difenoconazole (0.05 mol). ). The mixture was stirred for 40 minutes at 50 ° C. From the resulting liquid, the solvent was evaporated under reduced pressure to give a protic ionic liquid which was thoroughly dried.

The product was obtained in a 94% yield.

The structure of the compound was confirmed by proton and carbon nuclear magnetic resonance spectra:

Ή NMR (400 MHz DMSO-c / 6) δ [ppm] = 1.04 (dd, J = 6.04; 27.51Hz, 3H); 2.70 (d, J = 15.34 Hz, 2H); 2.77 (d, J = 15.34 Hz, 2H); 3.27 (m, 1H); 4.05 (m, 2H); 4.73 (m, 2H); 6.92 (m, 1H); 7.13 (m, 3H); 7.48 (m, 3H); 7.90 (d, J = 13.80Hz); 8.43 (d, J = 5.46 Hz, 1H). ¹³ C NMR (DMSO-6) δ (ppm] = 176.85; 171.39; 157.54; 154.41; 150.66; 145.41; 132.48; 132.21; 131.55; 130 , 21; 129.91; 128.44; 121.28; 120.57; 116.38; 106.73; 7234, 70.85; 53.71; 48.88; 42.80; 17.89.

Example II

Method for producing diphenoconazole salicylate [DFC] [SAL]:

50 cm ³ of ethanol was dissolved 44.27 g (0.10 mol) of difenoconazole. Then a stoichiometric amount of potassium salicylate (0.10 mol) dissolved in 30 cm ^{3 of} ethanol was added in small portions with constant stirring. Stirring was continued for 50 minutes at room temperature, then the solvent was evaporated and the reaction product was dried for 24 hours at room temperature under reduced pressure. The product was obtained in 83% yield.

The structure of the compound was confirmed by proton and carbon nuclear magnetic resonance spectra;

Ή NMR (400 MHz DMSO-c / 6) δ [ppm] = 1.04 (dd, J = 6.00; 26.51 Hz, 3H); 3.27 (m, 1H); 4.07 (m, 2H); 4.74 (m, 2H); 6.95 (m, 3H); 7.13 (m, 3H); 7.48 (m, 3H); 7.82 (dd, J = 1.56, 7.92 Hz, 1H); 7.92 (d, J = 13.08 Hz, 1 H) 8.44 (d, J = 5.04 Hz, 1 H], ¹³ C NMR (DMSO-O6) δ [ppm] = 171.98; 161, 17; 157.46; 154.35; 150.61; 145.34; 135.62; 132.41; 132.15; 131.48; 130.26; 130.13; 129.83; 128.36; 121.19; 120.51; 119.14; 117.07; 11830; 112.90; 106.67; 72.51; 70.78; 53.64; 17.60.

Example III

Method for producing difenoconazole tartrate [DFC] [WIN]:

50 cm ^{3 of} propanol was dissolved 42.42 g (0.10 mol] Difenoconazole hydroxide. Then was added in small portions with stirring, a stoichiometric amount of sodium tartrate (0.10 mol) dissolved in 30 cm ^{3 of} propanol. Stirring was continued for 40 minutes at room temperature, then the solvent was evaporated, and the reaction product was dried for 24 hours at 50 ° C under reduced pressure The product was obtained in 97% yield.

PL229 317B1

The structure of the compound was confirmed by proton and carbon nuclear magnetic resonance spectra;

Ή NMR (400 MHz DMSO-c / 6] δ [ppm] = 1.05 (dd, J = 6.02; 20.63Hz, 3H); 3.27 (m, 1H) 4.05 (m, 2H ) 4.37 (s, 2H); 4.74 (m, 2H); 6.93 (td; J = 2.56; 2.56; 2.56 Hz, 1H); 7.14 (m, 3H ); 7.47 (m, 3H); 7.91 (d, J = 10.39 Hz, 1H); 8.44 (d, J = 3.91 Hz, 1H). ¹³ C NMR (DMSO-d6 ) δ [ppm] = 173.26; 172.16; 157.58; 154.43; 150.70; 145.44; 132.52; 131.57; 130.24; 129.94; 128.49; 121.30; 120.58; 116.23; 106.72; 73.69; 72.30; 70.89; 53.75; 17.71.

Example IV

Method for producing difenoconazole oxalate [DFC] [SZCZ]:

50 cm ³ of methanol was dissolved 48.71 g (0.10 mol) of difenoconazole. They were then added in small portions with stirring, a stoichiometric amount of oxalic acid (0.10 mol) dissolved in 30 cm ³ of methanol. Stirring was continued for 50 minutes at room temperature, then the solvent was evaporated and the reaction product was dried for 24 hours at 50 ° C under reduced pressure. The product was obtained in a yield of 80%.

The structure of the compound was confirmed by proton and carbon nuclear magnetic resonance spectra;

Ή NMR (400 MHz DMSO-C6) δ [ppm] = 1.03 (dd, J = 5.94; 20.41 Hz, 3H); 3.27 (m, 1H) 4.06 (m, 2H) 4.74 (m, 2H); 6.93 (m, 1H); 7.14 (m, 3H); 7.47 (m, 3H); 7.91 (d, J = 10.13 Hz, 1H); 8.44 (d, J = 4.05 Hz, 1H). ¹³ C NMR (DMSO-d6) δ [ppm] = 161.00; 157.62; 154.39; 150.62; 145.35; 132.44; 132.18; 131.52; 130.16; 129.87; 128.40; 121.22; 120.54; 116.17; 106.66; 72.54; 70.78; 53.69; 17.64

Example V

Method for producing difenoconazole dichloroacetate:

50 cm ^{3 of} butanol was dissolved 53.42 g (0.10 mol) of iodide difenoconazole. Then a stoichiometric amount of ammonium dichloroacetate (0.10 mol) dissolved in 30 cm ^{3 of} butanol was added in small portions with constant stirring. Stirring was continued for 50 minutes at room temperature, then the solvent was evaporated and the reaction product was dried for 24 hours at 50 ° C under reduced pressure. The product was obtained in a 96% yield.

The structure of the compound was confirmed by proton and carbon nuclear magnetic resonance spectra:

Ή NMR (400 MHz DMSO-c / 6) δ [ppm] = 1.05 (dd, J = 6.06; 26.85 Hz, 3H); 3.27 (m, 1H); 4.05 (m, 2H) 4.73 (m, 2H); 6.69 (s. 1H); 6.90 (m, 1H); 7.13 (m, 3H); 7.47 (m, 3H); 7.90 (d, J = 13.34 Hz, 1H); 8.43 (d, J = 5.32 Hz, 1H). ¹³ C NMR (DMSO-d6) δ [ppm] = 165.78; 157.47; 154.34; 150.58; 145.33; 132.42; 132.14; 131.48; 130.13; 129.84; 128.37; 121.21; 120.51; 116.31; 106.67; 72.57; 70.79; 65.82; 53.65; 17.81.

The solubility in water and common solvents was established for the five synthesized salts. The results are summarized in Table 1 which shows the solubility of the synthesized salts. Table 2 shows the yields and melting points of the obtained difenoconazole salts. The synthesized salts do not dissolve in water but well in DMSO, methanol, ethanol, chloroform and acetone.

Table 1

j Salt DMSO water methanol chloroform: and ethanol acetone I [orcHWiN] ...... *. 4 . ......... 4 i | [DFCHSAL] and· 4 4 .. i and + and f * (PFCUSZCZJ 4 - 4 and i and τ .......... ... ...... and [DFCHDCA] • 4 4 i ...... 7 r * j * L. ί jpFCHCYT] 4 4- i 4 4 ............... 4 < ......................and

PL 229 317 Β1

Table 2

Name · + pFCHWSNl

[PFCnSAU

[DFCHSZa] j

[DFCHDCA] ΐ

[DFCMCYT]

Performance | the reaction of ś i% and i

LL ί 47-48 liquid

122425 = 104-106

51-52

Application example:

The use of protic ionic liquids of diphenoconazole with an organic anion as fungicides.

Determination of biological activity against pathogenic fungi

The obtained [DFC] [CYT], [DFC] [SAL] and (DFC] [WIN) liquids were tested against four fungal species: Sclerotinia sclerotiorum, Botrytis cinerea, Fusarium culmorum and Microdochium nivale (IOR-PIB collection).

The test compounds were dissolved in 4 ml of 96% ethyl alcohol and then added to a sterile medium (PDA - Potato Dextrose Agar, Difco ™), preheated to 50 ° C. The concentration of preparations in the medium was set at 10, 100 and 1000 ppm (the cation - responsible for the fungistatic effect and the active substance contained in the reference product Tebu 250 EW. The liquid medium containing difenconazole derivatives was poured onto petri dishes (0 50 mm). 4 mm was placed in the center of the plate .. On the control plates, the fungi were grown on medium supplemented with ethyl alcohol The test preparations were compared to Tebu 250 EW fungicide containing tebuconazole as active ingredient Plates were incubated at room temperature about 21% until the mycelium in the control reached the edge of the plate. Then the diameter of the mycelium was measured by subtracting from the measurement the initial diameter of the disc with the fungus 4 mm. 3 replications were performed for each object. The results were analyzed by Student-Newman-Keuls, determining a significant difference between the control and the samples with the addition of preparations.

Results:

Tables 3 and 4 summarize the results showing the effect of the tested ionic liquids on the growth of pathogenic fungi: Sclerotinia sclerotiorum, Botrytis cinerea, Fusarium culmorum and Microdochium nivale.

The degree of inhibition of mycelium growth depended on the preparation used, its concentration, as well as the species of fungus. For the fungi Sclerotinia sclerotiorum, Botrytis cinerea and Microdochium nivale, all tested liquids showed 100% fungistatic activity at the concentration of 100 and 1000 ppm.

The fungus Fusarium culmorum was the least sensitive to the tested ionic liquids, where the (slight) growth of mycelium was found at the concentrations of 10 ppm, 100 ppm, and in the case of [DFC] [CYT] and [DFC] [WIN]

PL 229 317 Β1 also at 1000 ppm. The fungus B. cinerea turned out to be the most sensitive to the tested ionic liquids - even the concentration of 10 ppm of the tested compounds in the medium caused complete growth inhibition.

Table 3

Inhibition of Botrytis cinerea and Sclerotinia sclerotiorum mycelium growth by ionic liquids

| No | Object name t i and Growth ; and 5. sderotion them 1 Increase ; 3; dnereo j I and r ................................... *। and § and! km] ....... ^: . .1 and ppm; ppm i * 'JoooTw ppm and ppn km] | 1; ppm I ppm 1 L -........ f ......... ......................... | 1 and Control ....... 77 OT aMO a: 4.60 a] 430 a Γ ^ 'ϊ ........... mSnj ..... <and ......... ĘsFiTpOT bp OT b pOT b 0.00 blOT ~ b1 and 1 ^: 1 .......... ΡαΐΛΐ 7 i ....... ^ 6'd fw b p ODO b) 0JG ' 'bjo, O0 ...... φ, οο'Κ) j ..... 4 ..... | ........... pFCjtSAlj ...... Kóo b P OT b] OT bFaoobf® ..... 5 ..... j ......... TEBulSolc ........ & 77Tjtw Bp that's a bjaóo b: OT bfó ^ J J ... j Γ ........... [.......... ............. P ot ...... Γαίχ * · · X )! 0.00 = 0.00 av

Mean values followed by the same letter do not differ significantly (P = 0.05, Student-Newman-Keuls)

T Inhibition of Fl mycelium growth by] Nr i Nażw &pbfektu]; : t <tU i —..... 4- ·· .........> .... 4 ™ ............... i 1 ^w | | ] ppm [......... 1 ..................................... ....., .. ,, 7 ,, ...., ........ and 1; 14.60 a a b e 1 a 4 isarium culmorum and Microdochium nivale ionic liquids Boost and Growth 1 and Mn & nAHcmj i 100; 10O6 10 and 100 and 10o6 ppm J ppm; ppm and ppm: ppm $ 4.00 <$ and 4x00 4; and 2 | W] [CYT] 3.25 b f 'i 031 d 1 4 j («ΗΜΙΙ 0.63 c i δ'Ί ........ TEBU ZSÓ eĆ ......... 0.00 e '1 W (IMW)" ™ ~ T0Λ4 0.23 C iO) c 0.63 bO.00 b 0.00 b 0.17 dQ33 b W ciaOO b 10.W b; (W bi OT b'OT tiOT b ϊϋ, ΟΟ b OT di OT b _: 0.0? C '0.00 b = 0.00 b. ,, "...._ ..... [035' 7 ' o ^

Mean values followed by the same letter do not differ significantly (P = 0.05, Student-Newman-Keuls)

Claims (10)

Patent claims CLAIMS 1. Proton salts of diphenoconazole with an organic anion of general formula I, wherein A is: organic anion: dihydrogen citrate or salicylate or bitartrate or hydrogen oxalate or dichloroacetate. 2. A method for the preparation of protic salts of diphenoconazole with an organic anion as defined in Claims. A process as claimed in claim 1, characterized in that the diphenoconazole of general formula II is dissolved in an aliphatic alcohol with a carbon chain length of one to four carbon atoms, or a mixture thereof, preferably methanol, further mixed with a methanolic solution of citric or salicylic or tartaric acid, or oxalic or dichloroacetic, at a concentration of at least 1%, in a molar ratio of 1: 1 to 1: 1.05, preferably 1: 1, at a temperature below 100 ° C, preferably at 20 ° C, for a period of at least 40 minutes, then the solvent is removed. 3. A method for the preparation of protic salts of diphenoconazole with an organic anion as defined in Claims. The process of claim 1, wherein the quaternary diphenoconazole chloride or bromide or iodide of general formula III is dissolved in an aliphatic alcohol with a carbon chain length of one to four carbon atoms, or a mixture thereof, preferably ethanol, is further subjected to an anion exchange reaction with a sodium or potassium or ammonium salt of citric or salicylic or tartaric or oxalic or dichloroacetic acid, at a concentration of at least 1%, in a molar ratio from 1: 1 to 1: 1.05, preferably 1: 1, in at a temperature below 100 ° C, preferably at 20 ° C, for at least 40 minutes, whereupon the product is isolated and then the solvent is removed from the filtrate. 4. A method for the preparation of protic salts of diphenoconazole with an organic anion as defined in claim 1; A process as claimed in claim 1, characterized in that diphenoconazole hydroxide of general formula 3 is dissolved in an aliphatic alcohol with a carbon chain length of one to four carbon atoms, or a mixture thereof, preferably in propanol, further reacted with an anion exchange with a sodium or potassium salt, or ammonium of citric or salicylic or tartaric or oxalic or dichloroacetic acid at a concentration of at least 1%, in a molar ratio of 1: 1 to 1: 1.05, preferably 1: 1, at a temperature below 100 ° C, preferably at 20 ° C for at least 40 minutes, whereupon the product was isolated, then the solvent was removed from the filtrate. Process for the preparation of protic salts of diphenoconazole with an organic anion of the general formula 1 as defined in claims The process of claim 1, wherein the quaternary diphenoconazole chloride or bromide or iodide of general formula III is dissolved in an aliphatic alcohol with a carbon chain length of one to four carbon atoms, or a mixture thereof, preferably methanol, is further neutralized with citric or salicylic or tartaric or oxalic or dichloroacetic acid, at a concentration of at least 1%, in a molar ratio of 1: 1 to 1: 1.05, preferably 1: 1, at a temperature below 100 ° C, preferably at 20 ° C for at least 40 minutes, whereupon the product was isolated and then the solvent was removed from the filtrate. Method for the preparation of protic salts of diphenoconazole with an organic anion as defined in claims The process of claim 1, wherein the quaternary diphenoconazole chloride or bromide or iodide of general formula III is dissolved in an aliphatic alcohol with a carbon chain length of one to four carbon atoms, or a mixture thereof, preferably in butanol, is further subjected to an anion exchange reaction with sodium or potassium or ammonium salt of citric or salicylic or tartaric or oxalic or dichloroacetic acid at a concentration of at least 1%, in a molar ratio of 1: 1 to 1: 1.05, preferably 1: 1, at a temperature of below 100 ° C, preferably at 50 ° C, for at least 50 minutes, whereupon the product is isolated and then the solvent is removed from the filtrate. Use of the novel protic organic anion salts of difenoconazole as defined in claim 1; 1 as fungicides. Use of the protic organic anion salts of diphenoconazole according to claim 1; A process as claimed in claim 7, characterized in that the salts are used in pure form. PL229 317B1 Use of the protic organic anion salts of diphenoconazole according to claim 1; 7. A method according to claim 7, characterized in that the salts are used in the form of hydroalcoholic solutions. 10. Use of the protic organic anion salt of difenoconazole according to claim 1; 7. The method according to claims 7 and 9, characterized in that the salts are used in hydroalcoholic solutions with a concentration of at least 0.1%.