CA2079998A1

CA2079998A1 - Fungicidal preparations

Info

Publication number: CA2079998A1
Application number: CA002079998A
Authority: CA
Inventors: Soeren Damtoft; Nannette Svendsen; Lene Lange
Original assignee: Individual
Current assignee: Novo Nordisk AS; Novo Nordisk Pharmatech AS
Priority date: 1990-04-06
Filing date: 1991-04-05
Publication date: 1991-10-07
Also published as: AU662292B2; HUT62753A; AU7652691A; WO1991015120A1; IE911137A1; DK86290D0; HU9203167D0; JPH05505614A; EP0523158A1

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

WO91/15120 PCT/DK91/0~96 ~ 3 ~ ~
Title: Fungicidal Preparations Field of the invention:

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.

lS BACRGROUND 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.
fH3 R - N~ - CH3, X ATAX (I) R - N+ - CH ~ ,X AKX (II) fH3 R' - N' - R", X~ DADAX (III) For the purpose of this invention the expression very long chain quaternary ammonium compound (VLCQAC) will be used as collective term for compounds in the ATAX (formula I), AKX

~. ;..,..,.j, (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 ll carbon atoms, and X is a halogen, acetate, sulfate, or phosphate anion.

Quaternary ammonium compounds ~QACs) with shorter chain lenyths than VLCQACs are widely used as disinfectants and as pharma-ceutical preservative~.

A vast literature on the antimicrobial activity of QACs e~istsand 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 Cs 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 betwe~n C1 and C18 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, fungista-tic, and algistatic activity of fatty nitrogen compounds, Hueck, Adema, and Wiegmann [Applied Microbiology 14(3), 308-319 (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 ~r~ r~ ~3 for the di-Clo 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 [Ma-tolcsy, Nadasy, and Andriska, eds. : Studies in Environmental Science 32, Pesticide Chemistry, Elsevier (1988)] only mentions didecyldimethyl ammonium bromide (DDDAB) as a compound having a protective and curative effect against apple scab (Venturia inaloualis).

The reasons is probably to be found ln the phytotoxicity of the QACs. In investigations of the eradication of overwin-tering 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 investi-gation of the toxicity of a number of different bactericides to Clavibacter michiaanense and to the tomato plant, Lvcoper-sicon esculentum [Thompson: Journal of Applied Bacteriology 61, 427-436 (1986)]. Cetyltrimethyl ammonium bromide (CTAB), benzalkonium chloride and N-cetylpyrinidium chloride were very efficient bactericides but were phytotoxic even in a concen-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 compounds of an even number of C-atoms in the n-alkyl chain), the compounds become more fungito~ic, 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 cetyltrimethyl ammonium bro-mide (CTAB), in combination with an 8-hydroxy-chinoline deri-vative and a thiabenzazol in a fungicide of low phytotoxicitywhen 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 dicocodimethyl ammonium chloride (coco being a mixture of C8 to C18-alkyl) for combating Podos~haera 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 noted in this work too. No other compounds were exemplified in this study.

DESC~IPTION OE T~E 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 compo-sition is often obtained. This synergistic effect allowsapplication 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.

U()91~1;12() ~CT/DK91/OnO96 Examples of other fungicides which can be combined with the VLCQACs of the invention include the residual fungicidal di-thiocarbamates (e.g. maneb (BAS~-maneb 80, BAsF) and mancozeb S (dithane M45/LF, Kemisk Vzrk K~ge, 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 = RidomilX 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 surface-active include nonionic agents as condensation products offatty 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, ace-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,OOl to above l,0 per cent by weight, especially 0,Ol 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 i 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,OOl to lO per cent by weight , especially 0,Ol to 5 per cent by weight. In w~ 91/1~120 ,~ 3~, ~ PCT/DK91/00~96 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 examp-le, 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 prefer-red 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 O.Ol to lO 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-C1zH2s (lauryl), M=n-C~4H29 (mYristyl)~ C=n-C16H33 (cetyl), S=n-C~8H37 (stearyl), Ei=n-C20H41 (eicosyl), Be=n-C22H4s (behenyl), DD=(n-C~OH2~) 2 (didecyl)~ DL=(n-c12H25)2 (dilauryl), DM=(n-C14H29)2 (dimyristyl), DS=(n-C18H37)2 (distearyl), T=(CH3)3 (trimethyl), D=(CH3)2 (dimethyl), K=C6H5-CH2N~ (benzyldimethylammonium), and A=N~ (ammonium), and the anions B=Br , C=Cl .

WO9~ 120 PCT/DK91/0009~

2~ 3r ~
TABLE I: QACs used in the experiments.
r IC~i3 R N~ R X

LTAC n_C12H2s CH3 Cl MTAC n C14Hz9 CH3 Cl CTAC n_Cl6H33 CH3 Cl STAC n ClBH37 CH3 Cl 20/22TAC n-C20H4l and 1:3 mixture of n CzH4s CH3 Cl BeTAC n_C22H45 CH3 Cl n ClzH25 CH3 Br n C~4H2s CH3 Br n_C16H33 CH3 Br n Cl8H37 CH3 Br n C12H25 C6H5 CH2 Cl n C~4Hzs C6Hs-CH2 Cl n C16H33 C6Hs~CH Cl n C~8H37 C6Hs-CH Cl EiKC n C20H41 C6Hs~CH Cl LKB n C12H25 C6H5 CH2 Br n C14H29 C6H5 CH2 Br n C16H33 C6H5 CH2 Br n C18H37 C6H5 CH2 Br -~ 30 n-C1 H CH3 S04 n-C16H33 CH3 P4 n C16H33 CH3 CH3CO2 n_C1sH37 CH3 S04 n C18H37 CH3 P4 n-C18H37 CH3 CH3CO2 DDAC n C10H21 n C10H21 Cl DLDAB n C12HZ5 n c1ZH25 Br DMDAB n Cl4H29 n Cl4Hzg Br DSDAC n Cl8H37 n-C18H37 Cl WO91/15120 ~ c~ PCT/DK91/00096 The inVentiQn is illustrated in the following examples:

Example 1.

LTAC, MTAC and CTAC were prepared by quaternisation of alkyldi-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 quaternisation of alkyldimethylamine with methyl chloride at a pressure of 3 kg/cm3 in acetone followed by crystallization.

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

EiKC was prepared by reaction of alkyl-dimethylamine with benzyl ~hloride 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 alkyldime-; 25 thy~amine 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 W absorbing counterion. By using a Nucleosil CN column with methanol:water (70:30) containing 5 mM p-toluene sulphonic acid as the eluent compounds in the ATAX and the AKC series with from 12 to 22 wos~ 20 PCT/~K91/00096 9 ~ 3~
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 CDCl3 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.

E~ample 2 Phytophthora infestans on pota~o.

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.
The solutions furthermore contained 0.1% Tween~ 20 and 5%
ethanol.

After spraying with the solutions the plants were incubated at 18-20C for 24 hours after which they were inoculated with an aqueous suspension of Phytophthora 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 phytotoxici-ty 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 P0 (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:

WOslJIsl20 PCT/DK91/00096 - J ~

TABLE II
Concentration 0.3% 0.1% 0.033%
Compounds LTAC a--p4 6 b_p3 2--P2 5MTAC a--p4 8--gb-P3 9 Pl-2 CTAC a-p3 2b-P23 7-P

20/22-TAC 8-9-Po 9~ Po 8-Po DDDAC P23 P2 7~

Untreated control : g-P0 Reference : 9-P0 (6 ml Dithane/l) Inoculated control : 2-Po 15 a~ 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 Phvtophthora infe~tan~ 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:

W(~91/15l20 PCT/DK91/00096 1 1 2 . , ~3 ~
TABLE III
Concentration. 0.3% 0.1~ 0.033 Compound STAC a _ P2 3 Pz 5 ~ P1 52 0/ 2 2 -TAC 7 - pO 7 - pO 5 _ pO
DLDAB ~ Pl 7 - Pl 7 - PO
DMDAB 5 ~ PO 4 ~ PO 2 ~ PO

- EiKC 7 - pO 5 _ p 5 _ p Untreated control: 9 - P0 Reference : 9 - P0 Inoculated contr.: 2 - PO

15 a) 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.

Example 4 In ~itro effect of OACC.

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 ~g/ml DS (= dilute salts solution [Dill and Fuller:
Arch.Microbiol. 87, 92-98, 1971]). The results are shown in the following table IV:

WOgl/l5l20 PCT/DK91/00096 TABLE IV

Species\ \Compound LTAC MTAC CTAC STAC -TAC DDDAC
Allomyces 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 lO Hyphal growth 66 13.2 13.2 ~333 66 13.2 Pythium sP. 207-86 Hyphal growth 333 66 13.2 66 13.2 13.2 (3 days) 15 Zoospore release 333 13.2 2.6 66 2.6 13.2 (2 days) Zoospore 13.2 13.2 <0.5 <0.5 2.6 <0.5 stability Cyst-hyphae 2.6 13.2 2.6 0.513.2 2.6 formation (1 day) PYthium ultimum Hyphal growth 333 66 2.6 66 13.2 2.6 (3 days) 25 Oospore 333 66 66 333 66 13.2 germination (1 day) :, Oospore 66 13.2 2.6 66 13.2 0.5 formation (3 days) 30 Phytophthora ~arasitica hyphal growth 6666 2.6 66 66 2.6 (3 days) Zoosporangium 13.2 13.2 2.6 66 66 2.6 oospore formation (3 days) WO91/15120 PCT/DK9i/00096 13 2C ~.'~
TABLE IV Continued Species\ \Compound LTAC MTAC CTAC STAC -TAC DDDAC
PhYtophthora s~. 360-86 hyphal growth 333 13.2 2.6 66 13.2 2.6 (3 days) Oospore formation 333 2.6 2.6 66 13.2 2.6 (4 days) : l0 Phvtophthora infe~tzn~
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 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 Phytophthora infestans.

` 20 Example 5 Plasmopara hastedii on Sunflower.

Small Sunflower plants were sprayed with aqueous solutions or 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.

WO91/1~120 PCT/D~91/00096 --f ~3 TABLE V
Concentration 0.3~ 0.1% 0.033%
Compound LTAC a _ p - P4 7 - P3 5MTAC a _ p a _ p a _ p CTAC - p4 9 _ p3~ 9 _ p3C
STAC 9 - P3' 9 ~ P3 9 ~ P3 20/22-TAC 9 - Pz 6 - P0 9 - P0 EiKC 9 - P0 8 - P0 5 ~ Po lODDDAC 9 - Pz 9 - P1 9 ~ P
DLDAB a _ p4 9 _ p 9 _ p DMDAB 9 - P3 9 ~ Po 9 ~ Po DSDAC g - P~ 5 - P0 5 - P0 ~) and b) as in Example 2. " 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 pseudoDerenospora cubensis on Cucu~ber.
:
Leaves of cucumber were sprayed with aqueous solutions/
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.

WO91/15120 PCT/DK91/~096 2~
TABLE VI
Concentration0.3~ 0.1% 0.033%
Compound LTAC a _ p a _ p 2 - P1 5MTAC a _ p 2 - P2 ~ P3 CTAC a _ p 8 ~ P2 ~ P
STAC 7 - P1 9 ~ Po 5-6 - P0 EiXC 5 ~ P3 5 ~ P 4 ~ P
lODDDAC a _ p a _ p~
DLDAB a _ p4 0 _ p3 5 - P

DSDAB 8 Pl 5 ~ PO 5 - P0 15 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.

ExamDle 7 - 8ynergistic effe~t of BeTAC and Dithane~.

25 Potato plants were sprayed with solutions containing Dithane0, BeTAC (dissolved in 5% aqueous ethanol) and 0.1% Tween0 20.
After l day, the plants were inoculated with sporangia suspen-sion of Phytophthora infestans and incubated 6 days at 18~C/
18 hrs light - 13C/6 hrs dark and a relative humidity of 80%.
Evaluation of the results gave following Table VII:

U'O91/1~120 PCT/DK91/00096 2- ,~3.

TABLE VII
Concentration of DithaneX mi/l o 0.006 0.06 6 Concentration of BeTAC%
0 1 - P 1 - P 2 - P~ 9 P0 O. 001 1 - P 1 - P 1 - P
0.01 2 - P0 3 ~ Po 4 ~ Po Notation as in Example 2.
An untreated control scored 9 - P0 This example shows clearly the synergistic effect between the VLCQAC BeTAC and the conventional fungicide Dithane~.

Example 8 ~; sYnergictic 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 Tween9 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 ~ Pu 3 ~ Po 7 0.01 2 - P0 6 - P0 8 - P0 The results show that the VLCQAC BeTAC exhibits a synergistic effect in combination with Ridomil~ MZ.

WOsl/l5120 PCT/DK91/00096 , , ~3"~

Example 9 o~Cs phytotoxicitY on mono- and di-cotYledons Aqueous solutions of QACs containing 0,1% Tween 20 were sprayed on small plants until "run off". The evaluation of phytotoxi-city after 72 hrs is listed in Table IX.

TABLE IX
Plants Barley Maize Sunflower Potato Tomato Age of plants 1 week 3 weeks 3 weeks 4 weeks 4 weeks Compounds and conc. in %
0,5 % Po Po P1 Pol P1 20STAC O,l % Po Po Po Po Po MTAC 0,3 % P1 p1 p3 P~ P2 .

0,5 % P3 P~ P3 P3 P3 LKB 0,1 % P1 Po Po1 P1 Po-P0 = Non Phy~otoxic.
P4 = Total extinction.

As seen in the Table the VLCQAC STAC (C18-chaln) was less phytotoxic than LKB (C12-chain) and MTAC (C~4-chain).

Claims

PATENT CLAIMS

1. A fungicidal composition comprising at least one n-Alkyl(ene)trimethyl ammonium salts, alkyl(ene)benzyl-dimethyl ammonium salts and/or dialkyl(ene)dimethyl ammonium salts (DADAX) of the general formulae I, II, and III, respectively , X ATAX (I) , X AKX (II) , X DADAX (III) wherein R is straight chained or branched alkyl or alkylene 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.

2. The composition of claim 1, wherein R is n-C18H37 (stearyl), n-C20H41 (eicosyl), or n-C22H45 (behenyl), R'=R"are n-C12H25 (lauryl), n-C14H29(myristyl), n=C16H33(cetyl), n-C18H37 (stearyl), n-C20H41 (eicosyl) or n-C22H45 (behenyl), and X is B=Br, C=Cl, 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 mixture of compounds wherein R is eicosyl and behenyl.

5. The composition of any of claims 1 to 4, comprising a 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 carbamates, metal ethyl phosphonates, and acylalanines, or mixtures thereof.

7. The composition of claim 6, wherein said dithiocarba-mate(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) 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 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.

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 Mastiqomycotina.

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

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

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 from the group comprising sun flower, tomato, cucumber, and potato.

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

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.

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.

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.

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.

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.