IE911137A1 - Fungicidal preparations - Google Patents

Abstract

The use of certain well known very long chain quaternary n-Alkyltrimethyl ammonium salts (ATAX), alkylbenzyl-dimethyl ammonium salts (AKX) and dialkyldimethyl ammonium salts (DADAX) of general formulae (I ATAX, II AKX, and III DADAX), respectively, wherein R is straight chained or branched alkyl or alkylene with more than 17 carbon atoms, R' is straight or branched alkyl or alkylene with more than 11 carbon atoms, and X is a halogen, acetate, sulfate, or phosphate anion, of low phytotoxicity in plant protection for controlling and combating fungi, fungicidal compositions comprising such compounds either alone or in combination with other fungicidally active agents, and methods for controlling or combating fungi in plants by applying said compositions to the plants, and the use of such compounds as additives to fungicidal compositions are described.

Description

The present invention relates to the use of certain very long chain quaternary ammonium compounds of low phytotoxicity in plant protection for controlling and combating fungi. It relates to fungicidal compositions comprising such compounds either alone or in combination with other fungicidally active agents, methods for controlling or combating fungi in plants by applying said compositions to the plants, and the use of such compounds as additives to fungicidal compositions.

BACKGROUND OF THE INVENTION. n-Alkyltrimethyl ammonium salts (ATAX), alkylbenzyl-dimethyl ammonium salts (AKX) and dialkyldimethyl ammonium salts (DADAX) of the general formulae I, II, and III, respectively, are well known compounds.

ATAX (I) AKX (II) DADAX (III) For the purpose chain quaternary collective term of this invention the expression very long ammonium compound (VLCQAC) will be used as for compounds in the ATAX (formula I), AKX (formula II), and DADAX (formula III) series. In formulae I, II, and III above R is straight chained or branched alkyl or alkylene with more than 17 carbon atoms, R' and R that may be the same or different are straight or branched alkyl or alkylene with more than 11 carbon atoms, and X is a halogen, acetate, sulfate, or phosphate anion.

Quaternary ammonium compounds (QACs) with shorter chain lengths than VLCQACs are widely used as disinfectants and as pharma10 ceutical preservatives.

A vast literature on the antimicrobial activity of QACs exists and only a few representative papers are discussed here.

The antimicrobial activity of some alkyltrimethyl-ammonium bromides (the ATAX-type) with n-alkyl chain lengths between C5 and C22 has been described by Gilbert & Al-Taae [Letters in Applied Microbiology 1, 101-104 (1985)]. It is concluded that the antimicrobial activity maximizes for n-alkyl substituent chain lengths of between 14 and 16 with bacterial strains being most sensitive towards the C14-compound and the fungi toward the C16-compound.

Similarly, the effect of the n-alkyl chain length on the antimicrobial activity of AKCs with a n-alkyl chain length between C., and C1g has been described by Daoud, Dickinson and Gilbert [Microbios 37, 73-85 (1983)]. They conclude that fungi were most sensitive towards C12, Gram-positive bacteria towards C14, and the Gram-negative bacteria towards C16.

In a large comparative study of the bacteriostatic, fungistatic, and algistatic activity of fatty nitrogen compounds, Hueck, Adema, and Wiegmann [Applied Microbiology 14(3), 308319 (1966)] conclude that for the C12, C14, C16, and C18 compounds in the alkyltrimethyl ammonium chloride series, the highest biostatic activity is found for the C14 compound. In the dialkyl-dimethyl-ammoniumchloride series with n-alkyl ranging from C8 to C18, the best fungistatic effect is apparently reached for the di-C10 compound.

Despite their excellent fungicidal and fungistatic properties, QACs of the above types have found little use as agricultural fungicides. A recent monograph of pesticide chemistry [Matolcsy, Nadasy, and Andriska, eds. : Studies in Environmental Science 32, Pesticide Chemistry, Elsevier (1988)] only mentions didecyl dimethyl ammonium bromide (DDDAB) as a compound having a protective and curative effect against apple scab (Venturia inalcrualis) .

The reasons is probably to be found in the phytotoxicity of the QACs. In investigations of the eradication of overwintering apple powdery mildew (Podosphaera leucotricha (Ell. & Ev.) Salm), benzalkonium chloride, which is a mixture of C12, C14 and C16 n-alkyl benzyl dimethyl ammonium chlorides completely eradicated mildew but was very phytotoxic [Hislop & Clifford: Annals of Applied Biology 82, 557-568 (1976); Hislop, Clifford, Holgate, and Gendle: Pesticide Science 9, 12-21 (1978)].

Didecyl dimethyl ammonium bromide was also phytotoxic in this study, where no other QACs were investigated.

The phytotoxicity of QACs has also been noted in an investigation of the toxicity of a number of different bactericides to Clavibacter michiganense and to the tomato plant, Lycopersicon esculentum [Thompson: Journal of Applied Bacteriology 61, 427-436 (1986)]. Cetyl trimethyl ammonium bromide (CTAB), benzalkonium chloride and N-cetylpyrinidium chloride were very efficient bactericides but were phytotoxic even in a concen30 tration of 2-20 ug/ml. As above this study was limited to the compounds mentioned.

The phytotoxic effect of QACs on tomato plants has also been observed by Edgington in a study of the effect of chain length of QACs upon their use as systemic fungicides [Edgington: Phytopathology 56, 23-25 (1966)]. He concludes that as the alkyl group of n-alkyl QACs is lengthened from ethyl to dodecyl in the alkyl trimethyl ammonium bromide series (using the six IE 911137 compounds of an even number of C-atoms in the n-alkyl chain), the compounds become more fungitoxic, but slight necrosis of the stem is seen with the C12-compound. Edgington furthermore observes that the use of QACs, with more than 8 carbon atoms in the n-alkyl chain, as systemic fungicides, is limited by their adsorption to sand, roots, and xylem.

The use of QACs, and especially cetyl trimethyl ammonium bromide (CTAB), in combination with an 8-hydroxy-chinoline deri10 vative and a thiabenzazol in a fungicide of low phytotoxicity when applied to seed, grain, or fruits has been described in Offenlegungsschrift DE 2342005. However, only the use of CTAB for seed, grain, and fruits is exemplified.

Furthermore, the use of dicoco dimethyl ammonium chloride (coco being a mixture of C8 to C18-alkyl) for combating Podosphaera leucotricha on overwintering apple buds has been exemplified in Offenlegungsschrift 2408662. The Phytotoxicity of a 5% aqueous solution of didecyl dimethyl ammonium bromide (DDDAB) has been 0 noted in this work too. No other compounds were exemplified in this study.

DESCRIPTION OF THE INVENTION.

From the publications summarized above it appears that the use of QACs in plant protection despite their fungicidal effects, is limited by their phytotoxicity. Furthermore, the use of VLCQACs as biocidal agents has been limited.

The present invention reports for the first time the use of VLCQACs as fungicides obtaining improved disease control in plants. It has here been demonstrated that a synergistic effect of VLCQACs and another fungicidally active compound or compo35 sition is often obtained. This synergistic effect allows application of the other fungicide in considerably lower dosages than the ones usually applied while still retaining the same or improved control effect of the fungal pathogen.

IE 9A1137 Examples of other fungicides which can be combined with the VLCQACs of the invention include the residual fungicidal dithiocarbamates (e.g. maneb (BASF-maneb 80, BASF) and mancozeb (dithane M45/LF, Kemisk Vaerk Kege, Denmark)) , and the systemic fungicidal carbamates (e.g. propamocarb (Previcur® N, Schering), metal ethyl phosphonates (Fosetyl-aluminium, Rhone-Poulenc), and acylalanines (metalaxyl, Ridomil® 5b (metalaxyl and mancozeb in combination = Ridomil® MZ).

The diluent or carrier in the compositions of the invention can be a solid or a liquid optionally in association with an other surface-active ingredient, for example a dispersing agent, emulsifying agent or wetting agent. Suitable surface15 active include nonionic agents as condensation products of fatty acid esters of polyhydric alcohol ethers, e.q. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide e.q. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, ace20 tylenic glycols such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol, or ethoxylated acetylenic glycols.

The concentration of the VLCQACs in the compositions of the present invention when used alone or in combination with a conventional fungicide, as applied to plants is preferably within a range of 0,001 to above 1,0 per cent by weight, especially 0,01 to 0,5 per cent by weight.

In a primary composition or concentrate that usually should be diluted prior to application the amount of VLCQACs can vary widely and can be, for example, in the range from about 1% to about 100% by weight, preferably from about 5% to 30% by weight of the composition.

The concentration of the other fungicidally active ingredient in the mixed composition of the present invention, as applied to plants is preferably within the range of 0,001 to 10 per cent by weight , especially 0,01 to 5 per cent by weight. In a primary composition the amount of active ingredient can vary widely and can be, for example, from 5 to 80 per cent by weight of the composition.

The active VLCQAC preparation or the compositions of the invention can be applied directly to the plant by, for example, spraying or dusting either at a time when an attack of the fungus has been established and determined on the plant for combating the fungus or fungi or before the appearance of fungus as a protective measure. In both such cases the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged. The spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary.

Sometimes, it is practicable to treat the roots of a plant before or during planting, for example, by dipping the roots in a suitable liquid or solid composition. When the active VLCQAC preparation of the invention is applied directly to the plant a suitable rate of application is from 0.01 to 10 kg per hectare, preferably from 0.05 to 5 kg per hectare.

In the following Table I the VLCQACs used in the Examples of this specification is listed. For the compound names the following abbreviations are used: L=n-C,2H25 (lauryl) , M=n-C14H29 (myristyl), C=n-C16H33 (cetyl), S=n-C18H37 (stearyl) , Ei=n-C20H41 (eicosyl), Be=n-C22H45 (behenyl) , DD=(n-C,0H21)2 (didecyl), DL=(n30 c12H25)2 (dilauryl), DM=(n-C14H29)2 (dimyristyl), DS=(n-C18H37)2 (distearyl), T=(CH3)3 (trimethyl), D=(CH3)2 (dimethyl), K=C6H5CH2N+ (benzyldimethylammonium), and A=N+ (ammonium), and the anions B=Br’, C=C1’. >t 911137 Ί TABLE I: QACs used in the experiments. CH. 1 5 5 1 R. - N+ - R2 1 X' 1 CHj COMPOUNDR1 r2 X 10 LTAC n-C12H25 ch3 Cl MTACn_C14H29 ch3 Cl CTACnC16H33 ch3 Cl STACn-C18H37 ch3 Cl 20/22TACn“C20H4i and 1:3 mixture of n-C22H45 CH3 Cl BeTAC n-C22H45 ch3 Cl EiKCn-C20H41 c6h5-ch2 Cl LKB n-Ci2H25 c6h5-ch2 Br DDDACn-C10H21n-C10Ii21 Cl DLDABn_C12H25n_C12H25 Br DMDABn-C14H29n-C14H29 Br DSDAC n-Ci8H37 n-Ci8H37 Cl The invention is illustrated in the following examples: Example 1.

LTAC, MTAC and CTAC were prepared by quaternization of alkyldi30 methylamine with methyl chloride at a pressure of 3 kg/cm3 in water. A 25% aqueous solution was used.

STAC, 20/22TAC and BeTAC were prepared by quaternization of alkyldimethylamine with methyl chloride at a pressure of 3 kg/cm3 in acetone followed by crystallization.

LKB was prepared by reaction of alkyldimethylamine in water with benzyl bromide. A 25% aqueous solution was used.

EiKC was prepared by reaction of alkyldimethylamine with benzyl chloride in refluxing acetone followed by crystallization.

The commercial product from Lonza, Bardac 22, which is a 50% solution of DDDAC in water/isopropanol mixture was used.

DLDAB and DMDAB were prepared by reaction of alkyldimethylamine with alkylbromide.

DSDAC was Querton from Berol-Nobel.

The identity and purity of the compounds were determined by HPLC and 13C-NMR as well as with conventional titration techniques.

The HPLC method was a modified version of the one published by Helboe [Journal of Chromatography 261. 1983, 117-122] based on chromatography of ion pairs of the QAC with an UV absorbing counterion. By using a Nucleosil CN column with methanol:water (70:30) containing 5 mM p-toluene sulphonic acid as the eluent 0 compounds in the ATAX and the AKC series with from 12 to 22 carbons in the long alkyl chain can easily be separated. 13C-NMR was performed on a 500 MHz spectrometer at a frequency of 125.97 MHz with simultaneous broad band decoupling. Samples were run in 10 mm tubes using CDC13 as solvent and as deuterium lock. The shifts obtained were in agreement with those reported by Fairchild [Journal of the American Oil Chemist Society, 59.(7), 1982, 305-309] except for an absorption at 25 ppm, which was not observed by Fairchild.

Example 2 Phvtophthora infestans on potato.

Potato plants (Variety: Sava ecology, grown 14 days in 7 cm plastic pots. 1 plant/pot) were sprayed with aqueous solutions of the compounds shown in the following Table II, the concentration of active substance being listed in the Table. ¢911137 The solutions furthermore contained 0.1% Tween® 20 and 5% ethanol.

After spraying with the solutions the plants were incubated at 5 18-20°C for 24 hours after which they were inoculated with an aqueous suspension of Phvtophthora infestans sporangia.

Following inoculation, the potato plants were incubated in humid chambers. The dark/light interval during the incubation period was 6 hrs/18 hrs. The degree of control and phytotoxicity was assessed 6 days after the inoculation.

The score of control is expressed on a scale from 0 to 9 with 9 being complete control. The phytotoxicity is evaluated on a scale from Po (no phytotoxicity) to P4 (complete collapse or extinction) . The results will thus be given in the form X-Py where X is the degree of control and Py is the phytotoxicity. The results are shown in the following Table II: TABLE II Concentration 0.3% 0.1% 0.033% Compounds LTACa“p4 6b-L 2-p2 MTACa-p4 8-9b-P3 9-PV2 25 CTACa”p32b-P2-3 7-Pi STAC 8-P2 8-p,7-P0-1 20/22-TAC 89Λ 9-po8-p0 DDDACa-P *2-3 9-p2 7-pi 30 Untreated control 9-P0 Reference9P0 (6 ml Dithane/1) Inoculated control2P0a) Impossible to evaluate due to the phytotoxicity. b) Uncertain evaluation due to the phytotoxicity.

The results clearly show the remarkable effects of the VLCQACs STAC and especially 20/22-TAC, the latter being able to give control of Phytophthora infestans without causing phytotoxic effects.

Example 3 Phytophthora infestans on potato plants.

Potato plants were tested as in Example 2. However, Surfynol TGE (0,05%) was used as dispersing agent. The results are shown in the following Table III: Concentration Compound STAC 20/22-TAC DLDAB DMDAB DSDAC EiKC TABLE III 0.3% 0.1% 0.033% a a r2-3 P„ 7 *2 Pn Untreated control: 9 - PQ Reference : 9 - Ρθ Inoculated contr.: 2 - Ρθa) See footnote in Example 2.

The present results demonstrate that inhibition of a fungal attack can be obtained without phytotoxic effects for VLCQACs both in ATAX, AKX, and the DADMX-series. The use of Surfynol® instead of Tween® 20, however, seems to decrease the effect of VLCQACs a little.

,E 91113? Example 4 In vitro effect of QACs.

QACs’s inhibitory effect on specified stages of the life cycle of several species of Oomycetes was tested on microtiter plates. The QACs were dissolved in a dilute salts solution and the minimal inhibitory concentration (MIC) was determined. Concentrations tested were 333, 66, 13.2, 2.6, 0.5, and 0.0 /ig/ml DS (= dilute salts solution [Dill and Fuller: Arch.Microbiol. 87, 92-98, 1971]). The results are shown in the following table IV: TABLE IV Species\ \Compound LTAC Allomvces MTAC 20/22 CTAC STAC -TAC DDDAC 5 gametogenesis 333 66 13.2 333 66 13.2 Gamete stability 13.2 2.6 0.5 66 13.2 0.5 Zoosporogenesis 333 66 66 333 333 66 Zoospore 66 13.2 13.2 66 66 2.6 stability 10 Hyphal growth 66 13.2 13.2 >333 66 13.2 Pythium sp. 207-86 Hyphal growth (3 days) 333 66 13.2 66 13.2 13.2 15 Zoospore release (2 days) 333 13.2 2.6 66 2.6 13.2 Zoospore stability 13.2 13.2 <0.5 <0.5 2.6 <0.5 20 Cyst-hyphae formation (1 day) Pythium ultimum 2.6 13.2 2.6 0.5 13.2 2.6 Hyphal growth (3 days) 333 66 2.6 66 13.2 2.6 25 Oospore 333 66 66 333 66 13.2 germination (1 day) Oospore 66 13.2 formation (3 days) 2.6 66 13.2 0.5 30 Phvtophthora parasitica hyphal growth 66 66 (3 days) 2.6 66 66 2.6 Zoosporangium 13.2 13.2 oospore formation (3 days) 2.6 66 66 2.6 13 TABLE IV Continued 20/22 Species\ \Compound LTAC Phvtophthora sd. 360-86 MTAC CTAC STAC -TAC DDDAC 5 hyphal growth 333 (3 days) 13.2 2.6 66 13.2 2.6 Oospore formation 333 (4 days) 2.6 2.6 66 13.2 2.6 10 Phvtophthora infestans sporangium 333 66 2.6 66 <0.5 2.6 germination and hyphal growth (2 days) Table IV shows that CTAC and DDDAC generally have the best 15 score of MIC values in this test system where there are no problems with phytotoxicity. However, it is interesting to note that 20/22-TAC has the lowest MIC value for Phvtophthora infestans.

Example 5 Plasmopara hastedii on Sunflower.

Small Sunflower plants were sprayed with aqueous solutions or 25 suspensions of QACs approximately 24 hours before inoculation with a spore suspension of P. halstedii. The results were evaluated after 7 days, and are indicated in Table V below. •Ε 911137 TABLE V Concentration 0. 3% 0. 1% 0. I 333% Compound LTAC a -p4 a -P4 7 - P3 MTAC a -P4 a -P4 aP3 CTAC a -P4 9 -P3C 9P3C STAC 9 -Ρ3' 9 -P3 9 - P3 20/22-TAC 9 -P2 6 -P0 9 - po EiKC 9 -po 8 -po 5 - po DDDAC 9 -P2 9 -P1 9 - P1 DLDAB a -P4 9 -P3 9 - po DMDAB 9 -P3 9 -po 9 - po DSDAC 9 -P1 5 -po 5 - poa> and b) as in Example 2. c) Stunted growth.

From Table V it is apparent that VLCQACs are very efficient fungicides in this test system too. Also, it is seen that the phytotoxicity apparently poses a problem to the QACs of short chain length.

Example 6 Paeudoperenospora cubensis on Cucumber.

Leaves of cucumber were sprayed with aqueous solutions/ 25 suspensions of QACs approximately 24 hours before inoculation with a spore suspension of P. cubensis. The results were evaluated after 7 days, and are shown in Table VI below.

Concentration TABLE VI 0.3% 0. 1% 0.033% Compound LTAC8 - P4 aP32 - P1 MTAC8 - P4 2 -P2 0 - p3 CTAC8 - P4 8 -P2 0 - P2 STAC 7 - P, 9 -po 5-6 - Ρθ 20/22-TAC7 - po 4 -po2 - po EiKC5 - P3 5 -P14 “ P0-1 DDDAC8 - P4 a -P4 DLDAB θ - P4 0 -P3 5 - p2 DMDAB6 - po 6 -P1 DSDAB8 - P1 5 -po5 - po a) As in Example 2.

The effect of VLCQACs against Pseudoperonospora cubensis on Cucumber is evident, but the optimal effect is seen with the STAC in this example.

Example 7 Synergistic effect of BeTAC and Dithane®.

Potato plants were sprayed with solutions containing Dithane®, BeTAC (dissolved in 5% aqueous ethanol) and 0.1% Tween® 20. After 1 day, the plants were inoculated with sporangia suspension of Phytophthora infestans and incubated 6 days at 18°C/ 18 hrs light - 13°C/6 hrs dark and a relative humidity of 80%.

Evaluation of the results gave following Table VII: TABLE VII Concentration of Dithane® ml/1 0 0.006 Concentration of BeTAC% 1 - Ρθ 1 - Po 0.001 1 - Po 1 - Ρθ 0.01 2 - po 3 - po 0.06 6 Notation as in Example 2.

An untreated control scored 9 - Po This example shows clearly the synergistic effect between the VLCQAC BeTAC and the conventional fungicide Dithane®.

Example 8 Synergistic effect of BeTAC and Ridomil® MZ.

Potato plants were sprayed with a solution containing BeTAC and/or the fungicide Ridomil® MZ and 0.1% W/W Tween® 20. BeTAC was dissolved in 5% ethanol. Ridomil* MZ was diluted to a concentration of 0.005 mg/ml (1:1000 of normal dose). The conditions were as in Example 7. 25 TABLE VIII Concentration of Ridomil® MZ mg/ml 0 0.0005 0.005 Concentration 30 of BeTAC in% 0 1 - Po3Po7 - Po 0.012 - po6 - po 8 - Po 0.053 - po8 - po 9 - Ρθ 35 The results show that the VLCQAC BeTAC exhibits a synergistic effect in combination with Ridomil® MZ.

Example 9 QACs phytotoxicity on mono- and di-cotyledons Aqueous solutions of QACs containing 0,1% Tween 20 were sprayed 5 on small plants until run off. The evaluation of phytotoxicity after 72 hrs is listed in Table IX.

TABLE IX Age of Plants plants Barley 1 week Maize 3 weeks Sunflower 3 weeks Potato 4 weeks Tomato 4 weeks Compounds and 15 cone. in % 0,5 %p0poP1P0-1P1 STAC 0,3 %po PoP0-1poP1 0,1 %po Popopopo 20 0,5 % P2 P2 p4 P3p4 MTAC 0,3 % P, p3 p2 P3 0,1 %P1poP1P1P2 25 0,5 % P3 p, P3 p3p3 LKB 0,3 %p3 P0-1P2P3P2 0,1 %P!p0P0-1P1P0-1 Ρθ = Non Phytotoxic.

P4 = Total extinction.

As seen in the Table the VLCQAC STAC (C18-chain) was less phytotoxic than LKB (C12-chain) and MTAC (C14-chain) .

Claims (30)

1. PATENT CLAIMS

1. A fungicidal composition comprising at least one nAlkyl(ene)trimethyl ammonium salts, alkyl(ene)benzyl-dimethyl 5 ammonium salts and/or dialkyl(ene)dimethyl ammonium salts (DADAX) of the general formulae I, II, and III, respectively CHj R - N + - CH,, X' ATAX (I) I ch 3 CH, L R - N - CH 2 ch 3 R' - N + - R, X ch 3 AKX (II) DADAX (III) wherein R is straight chained or branched alkyl or alkylene 30 with more than 17 carbon atoms, R' and R which are the same or different, are straight or branched alkyl or alkylene with more than 11 carbon atoms, and X is a halogen, acetate, sulfate, or phosphate anion. 35

2. The composition of claim 1, wherein R is n-C 18 H 37 (stearyl), n-C 20 H 41 (eicosyl), or n-C 22 H 45 (behenyl) , R'=R”are nC 12 H 25 (lauryl), n-C^H^(myristyl) , n=C, 6 H 33 (cetyl) , n-C 18 H 37 (stearyl) , n-C 2Q H 41 (eicosyl) or n-C 22 H 45 (behenyl) , and X is B=Br*, C=C1’, Ac=acetate, S=sulfate, or P=phosphate.

3. The composition of claim 1 or 2, wherein R is stearyl and/or behenyl.

4. The composition of any of claims 1 to 3, comprising a 45 mixture of compounds of formula I, II, or III, especially comprising at least one of formula I wherein R is stearyl, eicosyl, or behenyl.

5. The composition of any of claims 1 to 4, comprising a 5 further fungicidally active agent.

6. The composition of claim 5, wherein said further fungicidally active agent is chosen from the group comprising residual fungicidal dithiocarbamates, systemic fungicidal 10 carbamates, metal ethyl phosphonates, and acylalanines, or mixtures thereof.

7. The composition of claim 6, wherein said dithiocarbamate (s) are chosen from maneb and mancozeb.

8. The composition of claim 6, wherein said carbamate(s) is propamocarb.

9. The composition of claim 6, wherein said acylalanine(s) 20 is metalaxyl.

10. The composition of any of the claims 1 to 9, wherein said salt(s) is present in an amount of from 0.001% by weight to above 1.0% by weight, preferably from 0.01% by weight to 25 0.5% by weight.

11. A concentrate or primary composition of any of claims 1 to 9, wherein said salt(s) is present in an amount of from 1% to 100% by weight, preferably from 5% to 30% by weight.

12. The composition of any of claims 5 to 10, wherein said further fungicidally active agent is present in an amount of from 0.001% to 30% by weight. 35

13. The concentrate of claim 11, wherein a further fungicidally active agent is present in an amount of from 5% to 80% by weight.

14. A method of controlling plant pathogenic fungi including yeast in plants, wherein a fungicidally active amount of a composition as claimed in any of claims 1 to 13 is applied to said plants.

15. The method of claim 14, wherein the fungi to be controlled belong to the Mastigomvcotina.

16. The method of claim 15, wherein the fungi to be 10 controlled belong to the Oomycetes.

17. The method of claim 16, wherein the fungus to be controlled is a Phvtophthora or Pythium. 15

18. The method of any of claims 14 to 17, wherein the plants whereto said composition is applied belong to the dicotyledons.

19. The method of claim 18, wherein said plant is chosen 20. From the group comprising sun flower, tomato, cucumber, and potato.

20. The method of claim 19, wherein said plant is potato. 25

21. The method of any of claims 14 to 20, wherein said composition is applied to said plants prior to, at the outset, or after establishment and detection of an attack by fungi by spraying or dusting, preferably by foliar spraying. 30

22. The method of any of claims 14 to 20, wherein said composition is applied to the roots of said plants prior to or during planting by dipping said roots into a liquid composition of any of the claims 1 to 13. 35

23. The method of any of the claims 14 to 22, wherein said composition is applied in an amount of from 0.01 kg/ha to 10 kg/ha, preferably in an amount of from 0.05 kg/ha to 5 kg/ha. |E 911137

24. Use of at least one compound as defined by one of the formulae I, II, and III in any of claims 1 to 4 as an additive to a fungicidally active composition or compound. 5

25. Use of stearyl trimethyl ammonium chloride as an additive to a fungicidally active composition or compound.

26. Use of behenyl trimethyl ammonium chloride as additive to a fungicidally active composition.

27. Use of a mixture of eicosyl and behenyl trimethyl ammonium chloride as an additive to a fungicidally active composition or compound. '5

28. A method of preparing a fungicidal composition as defined in claim 1, substantially as described herein by way of Example.

29. A fungicidal composition as defined in claim 1, substantially as described herein by way of Example.

30. A method of controlling plant pathogenic fungi, using a fungicidal composition as claimed in any one of claims 1 to 13 or 29.