HUT62753A - Fungicidal compositions comprising quaternary ammonium compounds of long carbon chain - 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 having low phytotoxicity in plant protection to prevent the growth of plant-fungi.

FIELD OF THE INVENTION The present invention relates to a fungicidal composition comprising such compounds, alone or in combination with other fungicides, to a method for controlling fungal growth or to controlling fungi in plants, which method comprises applying such compositions to plants and to applying such compounds as additives.

The n-alkyltrimethylammonium salts (ATAX) of the formula I, the alkylbenzyldimethylammonium salts of the formula II (AKX) and the dialkyldimethylammonium of the formula III salts (DADAX) are well known compounds.

In the present specification, the term very long-chain quaternary ammonium compounds (VLCQAC) is used as a generic name for ATAX compounds of formula I, AKX compounds of formula II, and DADAX compounds of formula III. In the above formulas (I), (II) and (III)

R is a straight chain. or a branched alkyl or alkylene group containing more than 17 carbon atoms,

R 'and R are identical alkyl and straight or branched alkyl groups or alkylene groups having more than 11 carbon atoms, and

X is a halogen anion, acetate anion, sulfate anion or phosphate anion.

Quaternary ammonium compounds (QACs) with a shorter carbon chain than VLCQAO compounds are commonly used as disinfectants and pharmaceutical preservatives.

The antimicrobial activity of QACs is the subject of a wide range of literature, of which only some illustrative examples are provided.

The antimicrobial activity of certain ATAX-type alkyl trimethylammonium bromides has been described by Gilbert and Al-Taae in Letters in Applied Microbiology, II, 101-104 (1985), where the chain length of the n-alkyl group is 5 to 22 carbon atoms. means.

It has been found that the anti-ricrobial activity is maximal when the n-alkyl substituent chain contains 14 to 16 carbon atoms and some bacterial strains are most sensitive to compounds containing 14 carbon atoms and fungi to compounds having 16 carbon atoms. contain the above chain.

Similarly, Daoud, Dickinson, and Gilbert, Microbios 37. 73 -85. (1983) describe the dependence of the antimicrobial activity of AKC compounds on alkyl groups containing 1 to 18 carbon atoms in the length of the n-alkyl chain. It has been found that fungi are most sensitive to compounds containing 12 carbon atoms, gram-positive bacteria most sensitive to compounds having 14 carbon-hours and Gram-negative bacteria most sensitive to compounds containing 16 carbon-hours.

Hueck, Adema and Wiegmann, Applied Microbiology, 14 (3), 3 - 8 - 3 - 9. (1966)] carried out extensive comparisons of bacteriostatic, fungistatic and algistatic activity of nitrogen-containing compounds containing grease. It has been found that among the alkyl trimethyl aramonium chloride compounds having carbon numbers 12, 14, 16 and 18, the carbon number 14 showed the highest biostatic activity. Among the dialkyldimethylammonium chloride compounds in which the n-alkyl group contained from 8 to 18 carbon atoms, the di-C 10 -alkyl compound showed the best fungistatic activity.

Although QACs have excellent fungicidal and fungistatic properties, these types of substances are used very little as agricultural fungicides. In a recent monograph on pesticide chemistry [Matolcsy, Nádasy and Andriska; 32 Studies in Environmental Science, Pesticide Chenistry, Dlsevier (1388) 1 cheat: Didecyldimethylammonium bromide (DDDAB) is mentioned as an agent for the protection and prevention of apple scab (Venturia inalqualis).

QACs are probably not used because they are phytotoxic. Studies to eradicate overwintering apple powdery mildew (Podosphaera leucotricha [Ell. And Ξν. Salm]) have shown that benzalkonium chloride, a mixture of 12, 14 and 16 carbon atoms of n-alkylbenzyldimethylammonium chloride, is perfect for powdery mildew eradication. however, it is highly phytotoxic (Hislop and Clifford, 1976, Annals of Applied Biology 82, 557-568; Hislop, Clifford, Holgate and Gendle, Pesticide Science 9, 12-21 (1978).) Didecyldimethylammonium -bromide also showed phytotoxicity in the experiments and no other QACs were tested.

The phytotoxicity of QAC compounds has also been established in a study investigating the toxicity of a variety of bactericicL against Clavibacter michiganense and the tomato plant (Lycopersicon esculentum) (Thompson, Journal of Applied Bacteriology 61, 427-436 (3986)). Cetyltrimethylammonium bromide (CTAB), benzalkonium chloride and N-cetylpyridinium chloride have proved to be very effective bactericides; however, they are highly phytotoxic even at concentrations of 2 to 20 µg / ml. The assay only determined the phytotoxicity of the said compound.

Edgington observed the phytotoxic effect of QACs on tomato plants in his study of the use of QACs as a fungicide on plants as a function of chain length (Edgington: 2hytopathology, 56, 23-25 (1966)). He found that if the length of the n-alkyl group in the alkyl trimethylammonium bromide series ranged from ethyl to dodecyl, the study investigated a 6-carbon even n-alkyl compound (the test compounds. In the case of a C12 compound, a slight shoot necrosis occurs. Edgington also found that the use of QACs containing more than 8 carbon atoms in the n-alkyl chain as a fungicide for the whole plant is limited because they are not well dispersed in sand, roots and woody areas.

Offenlegungsschrift DE 2342005 discloses the use of QAO compounds, in particular cetyltrimethylammonium bromide (CTAB), in combination with an 8-hydroxyquinoline derivative and thiabenzazole, in a low phytotoxic fungicidal composition for seed, bulb or tuber. In the examples, however, only the use of CTAB on seed, tubers and fruits has been described.

In addition, Offenlegungsschrift 2408662 discloses the use of dicoco-dimethylammonium chloride (wherein the coco group is a mixture of 8 to 18 carbon atoms) to control bodosphaera leucotricha attacking overwintering subspecies; in the same specification, the phytotoxicity of a 5% aqueous solution of didecyldimethylammonium bromide (DDDAB) was mentioned. No other compound is exemplified in the study.

It is apparent from the above summarized publications that the use of QACs in plant protection, despite their fungicidal activity, is limited because they are phytotoxic. In addition, the use of VLCQACs as biocidal agents is limited.

The present invention is the first to inoculate the VLCQACS compounds all®. Converted as a fungicide to provide improved protection of plants against disease. It has been shown that in many cases the combined use of VLCQACS compounds and other fungicidal active substances results in a synergistic effect. This synergistic effect allows the other fungicide to be applied at a significantly lower dose relative to the usual dose, while at the same time achieving the same or improved activity against the fungus. Other fungicides which may be combined with the VLCQACS compounds of the invention include residual fungicidal dithiocarbarates (e.g. maneb / BASF-maneb 80, BASj?) And mancozeb / dithane LI45 / LF, Kemisk Vaerk Koge, Denmark) and regularly administered fungicidal carbamates. (e.g., propamocarb (Previcur N, Schering), metal ethyl phosphonates (Fosethyl aluminum, Rhone-Poulenc) and acylalanines (metalaxyl, Ridomil 5b / metalaxyl and manzoceb in combination = Ridomil MZ).

The diluent or carrier used in the composition of the present invention may be in solid or liquid form and may optionally contain a surfactant such as a dispersant, emulsifier or wetting agent.

Suitable surfactants include, for example, condensation products of non-ionic materials such as fatty acid esters of polyhydroxy alcohol ethers such as sorbitan fatty acid esters, ethylene oxide condensation products of such esters such as polyoxyethylene sorbitan. fatty acid esters, ethylene oxide and propylene oxide block copolymers, acetylene glycols such as 2,4,7,9-tetramethyl-5-decin-4,7-diol, or ethoxylated acetylene glycols .

When used alone or in combination with conventional fungicides in the composition of the invention, the concentration of VLCQAC compounds applied to the plants is preferably from 0.001 to greater than 1.0% by weight, most preferably from 0.01 to 0.5% by weight.

The concentration of VLCQAC compounds in a base formulation or concentrate, which will generally need to be diluted prior to use, may range from a wide range, for example from about 1 to about 100% by weight, preferably from about 5 to about 30% by weight.

The concentration of other fungicidal active compounds in the blended composition of the invention, when used in the form of the plant, is preferably from 0.001 to 10% by weight, particularly preferably from 0.01 to 5% by weight. The amount of active ingredient in a base formulation may vary within wide limits and may be, for example, 5 to 80% by weight of the formulation.

The active VLCQAC composition or compositions of the invention may be applied directly to the plant, for example in the form of a spray or powder, and may be applied at the time the fungal infection is detected and determined by the plant, thereby destroying the fungus or fungi. before the appearance of fungi as a preventive treatment. In both cases, the preferred application is spray application to the foliage. In general, it is essential that the fungi are well killed during the early growth phase of the plant, as the plants are the most vulnerable during this period. The spray or powder form may also suitably contain a pre-emergence or post-emergence herbicide if necessary.

Occasionally it is possible to treat the roots of the plant before or during planting, for example by immersing the roots of the plant in a suitable liquid or solid preparation. When the active VLCQAC composition according to the invention is applied directly to the plant, the application rate is 0.01 to 10 kg / ha, preferably 0.05 to 5 kg / ha.

Table I shows the VLCQAC compounds used in the Examples. The following abbreviations are used in the names of the compounds:

L

Μ

C s

Ei

on

DD

DL

DM

DS

T

D

K

A = ^η ~ ^ Ί 2 ^ 25 (lauryl), = (myristyl), = nC ^ H ^ (cetyl), = η-Ο ^ θΗ ^ γ (stearyl), = η- ^ θΗ ^ η (eicosyl), = ⁿ ~ ^ 22 ^ L5 (behenil), = ^ ^η " ^σ ηο ^Η 21 ^ 2 (<l ^id - ^ec il) j = (11-0 ^ 2 ^ 25) 2 {<ül ^aur iD j = (nC ^ H (g) 2 (dimyristyl), = (ii-C ^ g H - ^^ (distearyl), = (CH 3) 3 (trimethyl), = (CH) ₂ (dimethyl), = C N * (benzyldinethyl) -ammonium), = H ⁺ (ammonium) and anions B = Br, C = Cl.

TABLE I

QAC materials used in the experiments

Compound - . ^R ! ^R 2 X 10 ~ LTAC ^nC 12 ^H 25 ch ₃ ' cl MTAC ^nC 14 ^H 29 ch ₃ cl CTAC ^nC 16 ^H 33 ch ₃ cl STAC ^n_C 18 ^H 37 · ch ₃ cl 20 / 22TAC Π- ^C 20 ^H 41 7 ^s 15 1: 3 mixture ^nC 22 ^H 45 ch ₃ cl Betacam ^n_C 22 ^H 45 ch ₃ cl ^n_C 12 ^H 25 ch ₃ Br ^{n C} 14 ^H 29 ch ₃ Br ^nc i6 ^H 33 ch ₃ Br 20 ^nC 18 ^H 37 ch ₃ Br ⁿ " ^C 12 ^H 25 c ₆ h ₅ -ch ₂ cl ^{n C} 14 ^H 29 c ₆ h ₅ -ch ₂ cl ^{n C} 16 ^H 33 c ₆ h ₅ -ch ₂ cl ^nC ! 8 ^R 37 c ₆ h ₅ -ch ₂ cl 25 EiKC ^n_C 20 ^H 41 c ₆ h ₅ -ch ₂ cl LKB ⁿ " ^C 12 ^H 25 ^C 6 ^H 5 ^CH 2 Br ^nC 14 ^H 29 c ₆ h ₅ -ch ₂ Br ^n_C 16 ^H 33 c ₆ h ₅ -ch ₂ Br ^{n C} 18 ^H 37 c ₆ h ₅ -ch ₂ Br 30 ⁿ " ^C 16 ^H 33 ch ₃ so ₄ ⁿ " ^C 16 ^H 33 ch ₃ PO ₄ ^nC 16 ^H 33 ch ₃ ch ₃ co ₂ n- ^c ie ^H 37 ch ₃ so ₄ n- ^c ₁₈ H ₃ 7 ch ₃ ^R ° 4 35 ^nC 18 ^H 37 ch ₃ ch ₃ co ₂ DDAC ^nC 10 ^H 21 ^nc io ^H 2i cl DLDAB ^{n C} 12 ^H 25 ^n_C 12 ^H 25 Br DMDAB ^{n C} 14 ^H 29 ^{n C} 14 ^H 29 Br DSDAC ^nC 18 ^H 37 ^{n C} 18 ^H 37 cl 40

The invention is illustrated in detail by the following examples.

Example 1

LTAC, KITAC and CTAC were prepared by quaternizing alkyl dimethylamine methyl chloride at 3 kg / cnP in Me25% aqueous solution.

STAC, 20 / 22TAC and BeTAC were quaternized by alkyldimethylamine using methyl chloride at 3 kg / cirr in acetone and then crystallized.

LKB is prepared by reacting alkyl dimethylamine with benzyl bromide in water; A 25% aqueous solution was used.

The EIKC is prepared by reaction of alkyldimethylamine with benzyl chloride by refluxing in acetone and crystallizing the product.

Lonza used Bardac 22 commercial product, a 50% solution of DDDAC in water / isopropanol.

DLDAB and DMDAB are prepared by reaction of alkyl dimethylamine with alkyl bromide.

DSDAC material, Querton product from Berol-Nobel.

The identification and purity of the compounds is carried out and determined by high-performance liquid chromatography, N-CII analysis and standard titration analysis.

HPLC analysis by Helboe, Journal of Chromatography, 261, 117-122 (1983); A modification of the method described in U.S. Pat. Using a Mucleosil CN column and 70:30 methanol: water eluent containing 5 mM p-toluenesulfonic acid in the series of ATAX and AKC containing 12 to 22 carbon atoms in the long alkyl group, the compounds can be readily separated.

1 H-NMR analysis was performed on a 500 MHz spectrometer at 125.97 MHz with simultaneous wide band decoupling. Samples were measured in 10 mm tubes using CDCl3 solvent and chemical shifts were reported in the literature (Pairchild, 59C7). 305-330. / 1982 /) 1, with the exception that ♦ · · * * * · «that at 25 ppm is absorbed by a winter union which

Fairchild is not experienced.

Example 2

Phyt oph.t'ora in parasites on potatoes

Potato plants (variety: Sava ecology, grown for 14 days in 7 cm plastic pots. 1 plant / pot) are treated with an aqueous solution spray, which is prepared as described in Example II below. in the table

given concentration. The solutions also contain 0.1% Tween 20 and 5 µl ethanol.

After spraying the plants for 24 hours

Incubate at 20 ° C and then

The inoculum is inoculated with an aqueous suspension of Phytophthora infestans spores.

After inoculation, the potato plants are incubated in a humid chamber. The dark / light duration during the incubation period was 6 hours / 18 hours. The level of fungicide and phytotoxicity was determined 6 days after inoculation.

The fungicidal activity is denoted by a scale number of 0-9, where 9 is the total fungal activity. Phytotoxicity is evaluated on a scale of Ρθ (non-phytotoxic) - P ^ (total collapse or death).

The results

X-P y

, where X is the degree of antifungal activity and

P _y is the measure of phytotoxicity.

The results are shown in Table II. in the table below:

- 17 '* f: ···. ··. ·· • ”·. : ··. ·: ·· «·· ·« «k

P I H ti K.-J 1 u ΓΌ ω Ω you: ie I t> Φ φ 1 She She b3 you you you 1 II ( □ ie 3 1 you you you you you i ti Φ 1 you ARC) She Ω SHE Ω I - P> 1 C 4 you 1 Q ARC) 1 She P Φ Φ 1 1 <1 1 P ti < Ps p N 1 you φ 1 She P · 1 - ¹ Ω Φ 1 you σς 1 Φ eb * eb F · H 1 She 1 P SHE P dog 1 I2: 1 dog eb | ti ·· 1 H 1 4 O 1 □ you 1 Φ 1 ps kJ 1 rs i 3 SHE 1 dog 1 Ω Ρ- dog P 1 Φ 1 P- Ω l 4 dog 1 rí 1 Ancestor P- < SHE 4 1 1 eb 1 P She 1 1 px 1 1________1 P 1 1 ffl t · P 1 1 > * 1 1 5 1 1 P- 1 1 P 1 1 dog 1 1 dog 1 1 i co 1 P 1 1 1 Φ 1 V) VO <0 1 P you 03 P P P i She rr: 1 1 1 1 I 1 1 1 1 1 1 ti ti you 1 you you you you you you 1 VJ CDs Ο O She 1 N3 She ARC) you) r— -t— you 1 4 1 1 I C. · '· dog 1 you) 1 Ancestor σ> 1 1 you 1 1 Φ 5 1 1 ti • V H 1 J F Φ you 1 1 1 1 dog P- 1 1 SHE* dog í 1 *. _the 1 → i 1 P 1 ω 1 P 1 1 i φ i you Refer to 03 ARC) you CX l SHE σ ' 1 1 1 I you you you 1 _the 1 you you you 1 1 1 1 II Neither 1 ΓΟ She -THE you you you 1 1 1x3 FJ you) 1 *, <4 <3 A you P 1 1 1 ro 1 you 1 you you 1 1 you M · l 1 ω cb 1 1 dog SHE 1 1 cb 1 1 CQ SHE 1 1 CDs M 1 1 O'q Ρ- 1 i Ω l 1 you P- 1 1 She P · <rb 1 1 THE* N ps 1 -0 03 E.g P] you l \ 3 i She SHE ω 1 l 1 1 1 1 1 | VJ 1 you you you you you you l VJ S 1 -λ She She -THE -THE ARC) | cb P- 1 1 1 l νΛ C'A P P 1 -THE t \ 3 1 H cb 1 | P dog 1 i 4 1

P N

CDs eb

ws

I

H

H ti> s ti ti

ÍSi ti * * t. ·· »*. ·· '. «·· ·· ·· ♦ ·«

The results clearly show that VLCQAC materials have a good effect on STAC, and especially 2O / 22-TAC; the latter exhibits a very good fungicidal activity against Phytophthora infestans without showing a fit οι oxidative effect.

Example 3

Phytophthora infestans on potato plants

Potato plants were prepared according to Example 2 test but disperse- agent Surfynol TG3 (0.05%) was used.

The results are shown in Table III. Table ··

Ρ

II

Ρ, 1 ro ω i She 1 Η b 1 ARC) 1 Ρ Ρ ro ro 1 ο υ She rv> 1 She ο hj S I milk ω 1 milk <4 1 P ARC) -Y ro 1 · 1Ρ SHE b b 1-9 1-9 ro 1 She • Ρ 4 ARC > > c} í » GO I ro Ό Η ¹ ro ro ΙΩ ο U3 SHE Q 1 P ρχ Ρ Ν 1 P: 1 c + CDs · Η ο CD 1 H 1 4 Η Cl · Η Η I CD 1 ps Ρ c + 1 c + 1 She Ρ ARC ·· 1 J H · Ο ARC ι 1 Ancestor Ρ Ο 1 1 ro c + Ρ 1 1 0¾ 4 e {- 1 1 C_J. Ο 4 1 1 ro Η ¹ Ο 1 1 Co Η Η 1 1 'Ο ·· Η 1 I Ν ·· 1 I CDs 1 l ω ARC) <ο W 1-0 -ο vn P -She P 1 ro 1 i · Η 1 1 1 1 1 1 1 1 1 1 1 SHE c + » l v * 41 43 Μ 141 'd 43 43 43 43 1 OJ Ο Ο Ο ο C SHE -Λ SHE ro 1 1 l OJ 1 1 cl ι 1 ι 1 1 « 1 1 1 ι l 1 ι i Ινπ -ο P · -4 -0 P 1 l l l SHE 1 1 1 1 141 1 1 1 1 1 -Δ 43 43 43 43 4j 1 Ο 1 1 ο She -X SHE ro 1 1 1 1 1 1 1 I 1 1 1 1 1 1 1 1 1 1 1 1 She ΐνπ νη ARC) -She vn ΌΊ 1 · 5 1 1 She 1 1 1 1 1 1 1 1 U) 1 1 OJ 143 41 41 43 43 43 i ο Ο She SHE SHE -Δ 1

III Τ A Β L A Ζ A Τ

I i

* r-.

»· - ··· · ·· · 4 ·

The results show that inhibition of the fungal attack can be achieved without the phytotoxic effect of the ATAX, AKX and DADILIX series VLCQACs. ' However, the use of Surfynol instead of Tween 20 appears to slightly reduce the efficacy of VLCQAC agents.

Example 4

In vitro activity of QAC compounds

in various life cycles of many varieties of Oomycetes on microtiter plates. QACs are dissolved in dilute saline and the minimum inhibitory concentration (MIC) is determined. Concentrations tested were 333, 66, 13.2, 2.6, 0.5 and 0.0 µg / ml DS (= hig saline solution (Dili and Vuller, Arch. Lucicobiol. 87, 92-98). The results are shown in Table IV.

in the table: '

- 21 • · »* · '·% ··» ··

V • va • V · * • ♦ ··

C9 ο S σ 'p_ í-b Ο ρ

1- ¹

I ί3 ο: <! φ íV φ ρ. Φχ ω

ΟΧ

ΟΧ _Δ V-O

Μ

ΓΌ

-X. OJ

V »

ΓΌ σχ σχ σχ ΟΧ

ΓΌ

XV σχ

ω N Ν 09 09 Γ · a - She ο Ρ Ρ 1 P She ο S I O ^J ω τη φχ ω 1 H · hd 45 c + c + 1 1- ¹ Ox Οχ ρ Ο 1 H · 4 4 09 ί> 1 c + P ω φ Η 1 px C9 C? Ρ Η 1 ω ω Ρ Φχ Ο 1 P σ ' Ν 5 1 Φχ · Η ρ- I Μ 1- ¹ ω ο 1 · Η · Ρ φ 1 ω c + ω 1 Ρχ 1 ω 1 1 1 1 Γ 1 1 1 1 1 1 1 1 1 1 1 1 OJ OJ 1 1 σχ OJ -X OJ 1 σχ Όο OJ OJ 1 ι ΓΟ 1 1 1 1 _x σχ σχ 1 I OJ ΟΧ ΓΌ σχ 1 «· Μ 1 ΓΌ σχ 1 Γ Γ I 1 ι 1 -X σχ -X 1 OJ σχ ο OJ 1 "V XV χ » 1 Γ0 ΓΟ 1 1 1 1 1 OJ νο 1 I Oh OJ σχ OJ 1 CTX OJ σχ OJ 1 1 1 Γ 1 1 OJ 1 σχ OJ σχ 1 σχ OJ OJ σχ 1 X * I ΓΌ 1 1 1 1 1 σχ _χ 1 ΓΌ σχ Ο OJ 1 "V X * X * 1 σχ νπ ΓΌ 1

Ρ CJ.

c + P * 4

Φ

t4

1-3

Ω

1-9>

Ω

Ω

1-9>

Ω

C / 2

1-9>

Ω ro o

ΓΌ ΓΌ ö o ü> Ω

Η- ' Ν ζ- ' Ν Hd -S ο: ο ΙΌ Ο vj Ο '<! S ο Ο 3 dog ρ Η ω Ρ ω Ρ σ ' Ρ ' Ρ Οϋ Ρ Ρ Ρ · Ρ 1 θ ' ►ò Οχ +3 -pyrrole Ρ Η> 4 Η χ- ' Ο 3 Ο Ο ³ Ρ Ρ Ρ 1 Ρ ω Ρ ω RV Η ►ò [_____ ι c + · Η 1 . 1 Ρ σ ' Ρ (Ν ' σ ' ο ο: ARC) Οχ · Η ο < ο ►ò Η £ 0 ο -Ο Ν · Η Ρχ rS ^J 1 Ο% + c - CF (D C0 & Ρχ Ρχ Ρ> σ> Οχ ω ω Οχ ΐα Μ

ΓΌ OJ «* · σ> γό kJ kJ kJ kJ kJ kJ

_Λ -Λ -Λ σ> VjJ Ό-> OJ ΟΛ Μ ΓΌ ΓΌ ΓΌ

ΓΟ **

ΓΟ

Ολ kJ!

Ολ η kJ

ΙΌ

σ> σ> Ο Ο σ> σ> X » ΌΊ ΌΊ

-Λ kJ ΓΌ ΓΌ kJ > · * · «· Μ ΓΌ Ο ΓΌ

-Δ _Δ ΓΌ ο VO kJ * · \ · * · Μ σ> kn ΓΌ ΙΌ

zoosporangium pete spore formation (3 days) _Δ

L * ->

ro

-Δ

M

ΓΧ3

N '

«· Σχ

09 Μ 43 43 ζ ^ χ 09 43 Shoot ο Ρ ' j φ _Δ ω SHOOT ο j 3 <Η- C3 2 c + Ρ σ ' c + Ρ φ £ φ Ρ σ ' Ρ ' Ρ Ρ Ο Ρ ω Ρ Μ Ρ Ρ Η- hj 43 43 45 43 Ή hj 'Ρ - Ο Χ --- Οχ χ ^> Οχ the__ Ο 3 Ρ c + 4 4 Ρ Ρ P ^J Ρ Ρ Ρ Ρ Η Ο I I Η Η> 1 4 ARC ο 1 c + Ρ Ρ Φχ ω Ρ · Η ο: 43 Η- ο: 3 43 Ν 4 <1 Ρ ω Ρ Ο§ Ρχ φ 3 lk 4 · Ρ Ν 43 ω Ρ Φχ Ρχ Φ & ω ω ω · Ρ Φχ Η- Φχ ω π- ω ρ- ο

αχ σχ σχ σχ í \ 3 σχ σχ σχ σχ σχ σχ σχ σχ σχ

j Shoot <Ύ \ j SHOOT ΟΑ ao La)

-Δ

VJ (Ό

ΓΌ

Μ »

ΟΧ ex σχ σχ σχ σχ σχ

ΓΌ σχ

H <1

Pj σχ ao σχ aj σχ σχ _Δ aj

ΓΟ σχ οχ _λ aj

Μ

ΓΌ

-Δ

ÍX3 1x3 She La) | X3 * · M * · σχ σχ lh 1x3 σχ

(continued f12

1 Gq ω I-d 1 ΙΌ She > Ti P ^J 1 S She 1 P o ^J 4 Η- i P P P Ο 1 »Ü hj 4 ►ò 1 SHE G7 ARC 1 P 4 · <Rl · 1 P P TV I t— ¹ g ο 1 1 1 4 ι P She Ρ 1 She: ω I <1 · Η · Η 1 ro 4 Ρ 1 TV px Η> i Φ N Φ 1 E.G px ω 1 G> ω <+ 1 CQ Ρ 1 CDs Ρ 1 ω ω 1 1 1 1 i I. 1 1 1 i | 1 I PJ 1 pj l 1 v> i 1 1 I l σ> I σχ 1 I 1 l J I 1 1 1 1 1 ΙΌ i i σχ 1 l 1 1 1 1 1 σχ 1 1 σχ 1 1 1 l 1 I 1 1 1 ο l 1 VI 1 1 1 1 1 1 1 ΙΌ | Μ 1 σχ

Ό ~ z. Co hd 4> Φ PJ Ο P ^J στ- S £ Ο Ρ V c + Ρ ω Ρ - Ρ Ο Ή VJ hj "She Οχ X ' ο P ^J 4 Ρ c + Ρ Ρ P ^J 1 Η She ARC 1 4 CDs Ρ P ►ò ο: Ν <! CQ 0¾ φ * 0 & V CDs ω ω Ρ> PJ CDs σχ Μ She | 1 co OX VJ OJ VJ OJ Triphenylphosphine OJ ΙΌ cj V Μ cx Μ ro Ό V Μ σχ σχ σχ σχ οχ σχ _Δ _λ OJ - - ΙΌ ΙΌ ΙΌ Ό V σχ σχ

(continuation)

The IV. The data presented in Table 1A show that CTAC and DDDAC materials generally exhibit the best MIC values in the assay system, with values at which phytotoxicity is not a problem. It is interesting to note, however, that the lowest MIC for Phytophthora infestans is for 20/22-TAC.

Example 5

Plasmopara hastedii on sunflower

Small sunflower plants are spray-treated using aqueous solutions or suspensions of QAC substances; treatment is performed 2A hours before the plants are inoculated with a P. halstedii spore suspension. The results were evaluated after 7 days and reported in Table V below.

TABLE V

Concentration 0.3% 0.1% 0.033%

Compound

LTAC the ^P 4 the ^P 4 7 ^P 3 MTAC the ^P 4 the ^P 4 the - ^P 3 CTAC the ^P 4 9 - ^P 3 ° 9 ^P 3 ^C STAC 9 - ^P 3 ^C 9 - ^P 3 ' 9 ~ ^P 3 20/22-TAC 9 ^P 2 6 - ^p o 9 - ^p o EÍKC 9 ^p o 8 ^p o 5 - ^p o DDDAC 9 ^P 2 9 - ^P 1 9 ' ^P ! DLDAB the - ^P 4 9 " ^P 3 9 - ^p o DMDAB 9 ^P 3 9 ^p o 9 - ^p o DSDAC 9 - ^P 1 5 ^p o 5 - ^p o

^a and = As in Example 2. ^c = Stunt growth.

It is apparent from the data in Table V / VLCQAC that they are very potent fungicides in this test assay system. The data further indicate that phytotoxicity is a problem for short-chain QACs.

Example 6

Pseudoperenospora cubensis on cucumber

The cucumber leaf is spray-treated with aqueous solutions / suspensions of QAC compounds. Twenty-four hours after treatment, the plants are inoculated with a suspension of P. cubensis spore.

The results were evaluated 7 days after inoculation and shown below in Section VI. The following table shows:

0.33%

VI / T A B 1-A Z A Τ

Concentration

0.3%

0.1%

Compound

LTAC the ^P 4 _ ^{3 P} 3 2 ' ^P 1 MTAC the ' ^P 4 2 - P ₂ 0 ~ ^P 3 CTAC the ' ^P 4 ⁸ - ^P 2 0 ~ ^P 2 STAC 7 ^P 1 ⁹ - ^p o 5-6 - ^p o 20/22-TAC 7 ^p o 4 - P _o 2 ^P 0 EiKC 5 ^P 3 5 - P, 4 ^P 0-1 DDDAC the - ^P 4 ³ - ^P 4 DLDAB the ~ ^P 4 o - p ₃ 5 - ^P 2 DMDAB 6 ^p o ^{6 P} i DSDAB 8 ^P 5 - Ρθ 5 ^p o

= As in Example 2.

The effect of VLCQACs on the cucumber Pseudoperonospora cubensis is obvious; in this example the optimum effect is achieved by the STAC material

Synergistic effect of BeTAC and Dithane

Example 7

Potato plants were spray treated with Dithane BeTAC (5% in aqueous ethanol) and 0.1% Tween 20. After 1 day, the plants are inoculated with a suspension of Phytophthora infestans spore and incubated for 6 days at 18 ° C, 18 hours light - 13 ° C, 6 hours dark

period in a room with a relative moisture content 30%. The results are shown in Table VII below. given in table; VII SPREADSHEET

Dithane concentration

0.006 0.06 6 ml / L

BeTAC concentration,%

0 ¹ - ^p o - ^p o 2 - ^P 0 9 ^P O 0,001 ¹ - ^p o - ^p o 1 “ ^P 0 0.01 ² - ^p o 3 - ^P 0 4 ^P 0

The comments in k are as in Example 2.

Untreated control value: 9 - Ρθ.

The results of the example clearly show that the VLCQAC material is BeTAC and the conventional fungicide.

- Dithane - has a synergistic effect on each other.

Example 8

Synergistic effect of Be'TAC and Ridomil MZ

Potato plants are spray treated; treatment with a solution containing BeTAC and / or fungicide - Ridomil I'.IZ in 0.1% (w / w)

- ♦>

Baoen has 20 contents. BefAC is dissolved in 5% ethanol. Ridomil LIZ is diluted to 0.005 mg / ml (1: 1000 part of the normal dose). The test conditions are the same as those described in Example 7.

VIII. SPREADSHEET

Ridomil MZ concentration in mg / ml BeTAC concentration,% 0 0.0005 0,005 0 ¹ to ^P 0 3 - ^p o ^P - ^p o  0.01 ² - ^p o 6 - P _o s - p ₀ 0.05 3 ^P 0 ⁸ - ^p o 9 - P _o

The results show that

BeTAC, a VLCQAC substance, exerts a synergistic effect in combination with Ridomil TEN.

Example 9

Phytotoxic effects of QAC substances on certain dicotyledons

The following small plants are sprayed to full coverage with an aqueous solution of 0.1% Tween 20 QAC Compounds. Phytotoxicity was evaluated after 72 hours. The results are shown in Table IX. Table.

Total necrosis.

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It can be seen from the table that a

Among VLCQACs, STAC (18-carbon chain) is less phytotoxic than LO (12-carbon chain) and MTAC (14-carbon chain).

Claims (19)

PATENT CLAIMS A fungicidal composition having the general formula (I) ATAX, alkyl (ene) trimethylammonium salts, AKX of the formula, alkyl (ene) benzyldimethylammonium salts and / or dialkyl (ene) dimethylammonium salts of the formula (DADAX) ) having at least one of the formula wherein the formula is a alkyl or alkylene group containing more than 17 carbon atoms, R 'and R are the same or different and are linear or alkylene and characterized in that R 'and R are η-ΟηθΗ ^ γ (stearyl), 1-cosyl) or n-C ^ pH ^^ (behenyl), meaning n-C ^ 2 ^ 25 Clauryl), til), η-Οη ^ Η ^ · ^ (cetli), nC ^ H. ^ ^l - " ^G 20 ^H 41 (eicosyl) or n- ^c ₂ 2 ^H 45 means B = Br, C = C1, Ac = acetate, or P = disodium. n-C ^ H ^ (myris (stearyl), (behenyl), and 3. A composition according to claim 1 or 2 wherein R is stearyl or behenyl. X • 4 «« »4 · ·· 4. A composition according to any one of claims 1 to 3, characterized in that it comprises a mixture of compounds wherein R is eicosyl and behenyl. Composition according to any one of claims 1 to 4, characterized in that an additional fungicide is used. The composition of claim 5, a mixture of carbazoles The composition of claim 6, wherein - ¹ I ve, so a δ. A composition according to claim 1, characterized by carbamate (s), Claim 6 according to any one of claims 1 to 9, characterized in that Ov salt (s) in the preparation 0.001 strain% Greater than 1.0% by weight, preferably 0.01% by weight 0.5 wt.%) 11. Concentrate or basic preparation which is 1-9. The salt according to any one of claims 1 to 3, characterized in that the salt (s) is present in an amount of 1 to 100% by weight, preferably 5 to 30% by weight. 12. A composition according to any one of claims 5 to 10, wherein the other goracidal active ingredient is present in an amount of 0.001% to 30% by weight. 13. The concentrate of claim 11, wherein the additional fungicidal active ingredient is present in an amount of from 5% to 80% by weight. A process for controlling plant pathogenic fungi, including plant yeasts, characterized in that the method of claim 1-13. The fungicidal active composition of any one of claims 1 to 3 is applied to the plants. The method of claim 14, wherein the fungus to be controlled is of the species Kastigomycotina, 16. The method of claim 15, wherein the fungus to be controlled is of the species Oomycetes. 17. The method of claim 16, wherein the fungus to be controlled is of the Phytophthora or Pythium strain. The process according to any one of claims 14 to 17, characterized in that the plants to which the above composition is applied are in the group of dicotyledons. 19. The method of claim 18, wherein the treated plant is sunflower, tomato, cucumber and potato. 20. The method of claim 19, wherein the treated plant is potato. A · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ● · · A process characterized in that the composition is applied to the above plants prior to the onset of the fungus, at the onset of the development, preferably in the form of a cut. The method according to any one of claims 14 to 20, wherein the composition is for the above-mentioned woman. The use of one of the general formula (II) of formula (I) as an additive in a composition according to any one of claims 1 to 4, for an antifungal active preparation or compound. 25. Use of stearyl trimethyl ammonium chloride as an additive in an active fungicide or 26th The use of behenyltrimethylammonium chloride as an additive in antifungal active preparation. «* Use of a mixture of eicosyl and behenyltrimethylammonium chloride as an additive in or in combination with an antifungal active ingredient.