DE3242646A1 - FUNGICIDE COMPOSITION - Google Patents

Description

- ^: - ■ "" - "324264S

Nov 18, 1982

PATENT ADVERTISEMENT ^{24642 Dr} ' ^{K / sch}

OR. RICHARD KNEISSL Widenmayerstr. 46

D-8000 MUNICH Tel. 089/295125

Imperial Chemical Industries PLC, London / Great Britain

Fungicide composition

description

The invention relates to compositions for control of plant fungi. The invention relates in particular to mixtures of fungicidal substances that contain a first fungicide that is either an inhibitor for adenosine deaminase or an inhibitor for sterol biosynthesis is in Fungi, and contains at least one other fungicidal substance that has a different fungicidal effect.

It is known that plant fungi, especially certain Races (phyla, species) can develop resistance to fungicidal chemicals, reducing their effectiveness of the chemical in question is reduced. It is believed that there are certain fungal plant pathogens that are resistant to fungicides of this type, which fight the pathogens, for example, that they inhibit their ability to biosynthesize certain steroids that are important for their metabolism, such as z. B. the biosynthesis of ergosterol. More precisely, these fungicides block the incorporation of acetate into ergosterol, an important metabolic pathway of the fungus. The synthesis and function of cell membranes in the Fungus stopped. Are plant pathogens of the latter type in particular certain breeds of powdery mildew, such as. B. Erysiphe graminis, which infect cereal crops, such as B. barley and wheat plantations, and of such Powdery mildew that infect other crops, such as B. Wine and apples. Examples of the latter diseases are Uncinula necator, Podosphaera leucotricha and Sphaerotheca fuliginea as well as Venturia inacquatis Apples or Cercospora, which cause leaf spots on peanuts, bananas and sugar beets.

■ S-

It has now been found that certain mixtures or combinations of fungicides are not only far less than their individual components of a reduction in their effect due to the development of certain resistance Plant pathogens are subject to, but also often show a synergism, that is, the The combined antifungal effect of the mixture is greater than that which would be expected if the fungicidal Components would act separately. Such mixtures are those in which a pyrimidine fungicide or a the sterol biosynthesis inhibiting fungicide with one or more fungicides that have a different effect against the fungus pathogens to be controlled are combined.

The invention therefore relates to a fungicidal composition which has either a cofungitoxicans as the first component or a fungicide that inhibits adenosine deaminase, or a fungicide whose effect on blocking the sterol biosynthesis is based, and at least one other fungicide that is used in the fight against fungi a has another effect.

The fungicide which inhibits adenosine deaminase in fungi can be a pyrimidine fungicide. With the expression "Pyrimidine fungicide" means compounds with a single ring, such as e.g. B. ethirimol, dimethirimol and bupirimate. This term is not intended to include bicyclic and tricyclic compounds in which a central Carbon atom, a pyrimidine ring and one or more carries other aryl or heterocyclic rings.

The cofungitoxicans need not have any fungicidal activity itself. It doesn't even take one activity against such strains of pathogens,

BAD ORIGfNAL

which are resistant to triazoles.

The fungicide Ethirimol is the subject of the British Patent 11 82 584 and has the chemical structure:

HC ₄ H ₉

OH

ι r

N ^Η ^ C ₂ H ₅

The fungicide dimethirimol is also the subject of British patent 11 82 584 and has the chemical Structure:

N N

I CH ₃ ^X CH ₃

The fungicide bupirimate is the subject of the British Patent 14 00 710 and has the chemical structure

nc ₄ H ₉

N _ N

OSO ₂ N

CH.

C ₂ H ₅

As already stated, the above fungicides have a fungicidal effect due to the inhibition of adenosine deaminase in the metabolism of the fungi.

The invention accordingly further relates to a fungicidal composition which is one of the fungicides ethirimol, dimethirimol or bupirimate or a fungicidal substance whose effect is based on sterol biosynthesis, and Contains at least one other fungicide that has a different effect in combating fungi. Examples for fungicidal substances that inhibit sterol biosynthesis can, and for classes to which they belong are as follows:

CLASS AND COMMON NAME OF THE FUNGICID Imidazole Imazalil

Prochloraz fenaponil

Piperazine

Triforin P yridine

Buthiobate EL 241

Piperidines

Fenpropidin

Pyrimidines

Fenarimol Nuarimol

Triarimol TRADE NAME OF FUNGICID PRODUCTS, THAT CONTAIN THE FUNGICTD

Fungaflor, Mist-O-Matic Murbenine Plus, Mist-O-Matic Muridal Seed Treatment
Sportak

Saprol, Trifor ine LST, Nimrod

Parnon

Rubigan

Triminol, Mist-O-Matic Murox Seed Treatment

Triazoles

Bitertanol

Diclobutrazole Vigil, Vigil K, Vigil T

Fluotrimazole Persulon

Propiconazole Tilt 250 EC, Tilt mbe 4 5WP,

Triadimefon Bayleton, Bayleton 5, Bayleton BM,

Bayleton CF.

Triadimenol Baytan

Etaconazole Vanguard, Sonax PP969

Morpholines

Dodemorph BASF F238

Fenpropimorph Corbel, Mistral

Tridemorph Calixin, Bardew, Beacon, Cosmic

The chemical structures of the above chemicals are listed below.

IMIDAZOLE

egg-

Cl

CN ¹

CN HO-CH-ca -cn. / "Λ. ¹

Imazalil CH.

Fenaponll

Cl

Cl

Prochloraz

: ^ - CEj-CH ₃

PIPERAZINE CHO

CH- / \

HO

Cl.

CH CCl. Triforine

PYRIDINE

C.H-S-C-S

^{4 9} Il

OH

Buthiobate EL-241

PIPERIDINE

CH.

N-CH-CH-CH

C (CH ₃ )

Penpropidine

PYRIMIDINE

Cl

Fenarimol

Nuarimol Triarimol

TRIAZOLE

f \ -f

- CH-CHOH-C (CH.

Cl ι

Bitertanol

Propiconazole CGA 64250 R = Ii-C ₃ H ₇

Etaconazole CGA 64 R = C ₃ H ₅

B ₂ -CH -CHOH-C (CS ₃ ) ₃

Diclobutrazole

Cl

Fluotrimazole Triadimefon

C ± (/ VO — CH — CHOH-C (CH). I OH
-. CH-CH-CH

? l

L.

PP969

Triadimenol MORPHOLINS

CB ₃ . 5 ^

(CH ₃ ) ₃ C- ^ J- CH ₂ - CH. / I

CH- CH.

Dodemorph Fenpropimorph

Yh.

Tridemorph

Cl

Fluotrimazole

O \ _o — CH — CHOH-C (CR ₃ ).

Triadimephone

_t -C ₄ H _g -.CH-CH

PP9

Triadimenol MORPHOLINE / (CB ₂ J ₅

\ 2 5 '

Dodemorph

CH-

CH ₃ . J * l

CH.

Fenpropimorph

^C 13 ^H 27- \ 9

\ 9

Tridemorph

BAD ORfGINAL

Carboxamides

Mode of action carboxin, oxycarboxin, Methfuroxam, fenfuram, furmecyclox, benodanil, Pyracarbolide

interferes with respiration by blocking succinate dehydrogenase

Dicarboxamides

Mode of action iprodione, procymidone, vinclozolin, M8164 (serinal) disrupts mitotic segregation

Aromatic hydrocarbons
Mode of action 2-phenylphenol, sodium o-phenylphenolate, biphenyl, chloroneb, dichlorane, quintozene, tecnazene disrupt mitotic segregation

Dinitrophenols action Dinapacryl, dinocap
decouples the oxidative phosphorylation

Di-methyldithiocarbamate
Mode of action Thiram

Pyruvate dehydrogenation inhibitors

Guanidines Mode of action Dodine, guazatine

affects the permeability of cell membranes

Organo tin compounds Mode of action Fentin

Inhibition of oxidative phosphorylation

BATH ORIGINAL

Organic phosphates and isoprothiolane Mode of action Pyrazophos, Edinfenphos, BP Isoprothiolane

Inhibition of the conversion of phosphatidylethanolamine into phosphatidylcholine

Acetamide
Effectiveness Curzat unknown

Aminobutane
Mode of action of 2-aminobutane Inhibition of pyrovine dehydrogenase

Anthraquinones Mode of Action Dithianon Inhibits glycolysis

Isoxazolones
Mode of action Drazoxalone respiratory uncoupler

Nitroisophthalate action nitrothal-isopropyl unknown

Organic

Phosphates

How Ditalimfos works

interrupts the metabolism

Quinoxalines
Mode of action quinomethionate

Sulphamides
Mode of action Dichlofluanid, Tolyfluanid

Thiocarbamate Mode of action Prothiocarb, propanocarb causes a disruption of the function of the membrane cells

N-phenyl carbamate derivatives

Such substances are in the EU-PA DJr. 81109561.1 (Publication No. 51871) and own the general formula:

. NHCOR

wherein X and Y are alkyl, alkoxy or halogen and R is methyl or ethyl.

Thiadiazole - Etridiazole mode of action - disrupts respiration

2. Multi-site inhibitors

Dithiocarbamates - Maneb, Zineb, Mancozeb, Näbam,

Propineb etc.

Mode of action - inhibitor for thiol groups

Phthalimides - Captafol, Captan, Folpet

Mode of action - inhibitors for thiol groups

Phthalonitrile - Chlorothalonil

Mode of action - inhibitor for thiol groups

■■■■■ "■ 32426A6

Copper compounds - various modes of action -?

Mercury compounds - various compounds

Mode of action -?

sulfur

Mode of action -?

Aluminum - Fosetylaluminium compounds

Mode of action -?

Anionic agents

Sodium dodecylbenzenesulphonate Sodium dodecyl sulphate sodium Ci3 / C15 alcohol ether sulphonate Sodium cetostearyl phosphate ester, dioctyl sodium sulphosuccinate, sodium isopropyl naphthalene sulphonate Sodium methylenebisnaphthalene sulphonate

Cationic agents

Cetyl trimethyl ammonium chloride Salts of long-chain primary, secondary or tertiary amines, alkyl propyleneamines Lauryl pyridinium bromide ethoxylated quaternized fatty amines, alkyl dimethyl benzyl ammonium chloride 1-hydroxyethyl-2-alkyl-imidazoline.

The invention therefore further relates to a fungicidal composition which, as active ingredients first fungicide that either ethirimol, dimethirimol or bupirimate or an inhibitor of sterol biosynthesis in plant fungus and a special fungicidal substance selected from the list of chemical compounds above is, and contains at least one other fungicidal substance whose mode of action in combating Fungi is different from that of the first fungicide and which substance is selected from the special fungicidal substances in the list immediately above is.

The invention also relates to a method of treatment of seeds, which is carried out by treating the seeds with a composition according to the invention bites.

In another embodiment, the seed can initially with ethirimol or with a fungicide that inhibits sterol biosynthesis in plant fungi, and then pickled with another fungicide defined above. Batches of seeds separately with a first fungicide and another fungicidal substance can be treated with untreated Seeds are mixed, for example in a drum, so that a batch of treated seeds is obtained.

Finally, the invention also relates to a method for the control of plant fungi, in which on a plant, on the seeds of a plant or on the site a fungicidal composition according to any one of the preceding claims is applied to a plant or a seed will.

The invention finally also relates to a method for controlling plant fungi, in which alternating Planting with Ethirimol, Dimethirimol or Bupirimat or with a fungicide, which in plant fungi inhibits sterol biosynthesis, and then with another fungicidal substance as defined above treated, for example splashed.

The amount of the fungicidal substance that is present in the Compositions used can be easily determined through simple experimentation. In general but with regard to the ability of the compositions according to the invention to produce resistant (insensitive) It is better to control breeds of plant fungi, and because of the synergism that occurs, that is not necessary otherwise normal full rates of chemical substances to be used.

example 1

A number of preliminary tests were carried out to determine the effectiveness of a number of cofungitoxicants in the control of two isolates of E. graminis f. sp. hordei in the absence of triadimephone to be determined, whereby the following results were obtained (Table 1).

Sumisclex showed activity against only one of the two fungus isolates, whereas Sanspor and Terrazol were inactive was.

Sumisclex was also tested to more closely assess the response rates in two isolates of E.

graminis f.sp. hordei to be determined (Table 2). Based

-yt-

on this data, suboptimal rates of this compound were selected for another interaction experiment using the Triadimefon (Tables 3 and 4).

In both isolates, the addition of Sumisclex reinforced in an amount of 150 ppm to Triadimefon in an amount of 0.1 ppm the activity of Triadimefon at the disease control level. The increase in activity must be attributed to a synergistic interaction between the two compounds.

Materials and methods

1) sowing; Approximately 10 seeds / pot of Golden Promise- "spring barley were sown in John Innes No. 1 compost, which was in mini-pots.

1.1, growing conditions; Daytime temperature 21 ⁰ C, relative humidity 60%, night temperature 17 ⁰ C, relative humidity 95%, day length 16 h.

The plants were watered by an automatic system.

2) Test method for spraying the plants: the plants were sprayed at an age of 6 days; the chemicals were made up in 0.03% Tween 20; the plants were sprayed until both leaf surfaces were evenly covered, using a De Vilbiss hand spray gun at a pressure of 1 bar. After spraying, the plants were placed in a second growth chamber for 24 hours and allowed to dry.

2.1. The growing conditions in this room were: daily temperature door 24 ⁰ C, relative humidity 60%, night temperature 17 ° C, relative humidity 95%, day length 16 hours. The plants were watered by an automatic system.

3) Procedure for preparing the replica dishes; Plants were removed from the growth space and cut into lengths of 2 cm, counted from just below the tip of the propyllum. Only plants of the same size were selected. Only one piece of leaf was taken from each Prophyllum.

The cut leaf pieces were then placed in a slot in the agar in the Repli dish. The bowls contained 45 ml of 10% tap water agar. First it was with the highest rate of chemical substances worked, then the lower rates followed. For every Rate of chemicals were 5 replicate leaf pieces used.

When moving from one rate of chemicals to a lower rate, then the scissors and Tweezers wiped with a rag dipped in methanol to avoid contamination. Special Attention was drawn to the fact that the leaf pieces did not touch or get in the lid of the bowl the shell overlapped each other. The former causes namely a condensation of water, which runs down over the leaf pieces and thereby washes off some spores. The latter leads to uneven inoculation and thus to incorrect results.

4) inoculation procedure; Infected leaf pieces were cut from stock plants in growth tubes and placed in Petri dishes on moist foam squares, 48 hours before inoculation. The infected leaf pieces were kept in a room with a constant temperature of 19 ^° C., the length of the day being 16 h.

The replica pans were made using a settling tower inoculated, with the tower placed over the opened Repli dishes and sporic leaf pieces, which with tweezers were placed in the nose of the tower. An air flow of 50 mbar was used to to blow the spores from the leaf pieces into the settling tower.

The replica bowls remained in the tower for 2 minutes, after which the tower was removed and the lids back on the Kepli bowls were applied. The tower, tweezers, and air line were wiped with methanol to clean them to sterilize.

After all of the repli dishes were inoculated, they became at a day length of 16 h placed in a room with a constant temperature of 19 ° C, where they are 6 days remained until the determination.

5) Determination: The percentage of sporulating disease on the leaf pieces was determined.

-χ-
TA
TABLE 1 3242646 Disease control Erysiphe graminis f .sp.hordei Isolate

Fungitoxicans Rate ppm TABEL 1 2 2 ai. 2% disease control Sumisclex 500 99 100 (Procymidone) 250 98 100 125 65 39 100 93 56 50 98 25th 0 0 0

Erysiphe graminis f.sp. hordei

Isolate

Fungitoxicans Rate ppm
ai. 1 2 87 Sumisclex 250 99 30th (Procymidone) 200 96 69 175 97 57 150 27 27 125 22nd 0 0 0

TABLE 3 Isolate 1,% Disease Control

Triadimefon Triadimefon

Rate ■ - +, "■.

ppm ai 150 ppm Sumisclex

0.25 '. -

0.1 59 (20)

0.05 30

0.025 43

0.01 ■ - ■. '.

Sumisclex 150 0

untreated - 0

Disease 74 %

untreated

() = Activity of Triadimefon alone in the same test dish at O ₁₇ 1 ppm »

TABLE 4 Isolate 2,% Disease Control

Triadimefon Triadimefon

Rate +

ppm ai 150 ppm Sumisclex

0.5 93 (52)

0.25 0

0.1 -15 0.05

Sumisclex 150-31

untreated - 0 "

Degree of disease 61%

untreated

() Activity of Triadimefon alone in the same test dish at 0.1 ppm.

Claims (9)

Claims 1. Fungicidal composition, characterized in that the first component is either a cofungitoxicans or a fungicide, which is adenosine deaminase inhibits / or a fungicide, the effect of which is based on the blocking of sterol biosynthesis, and at least one other fungicide which is used in combating of fungi has a different effect. 2. Fungicidal composition according to claim 1, characterized in that it is used as an adenosine deaminase inhibitor a pyrimidine derivative of the structure B ~ ^C 4 ^H 9 £ " ^C 4 ^H 9 or OSO ₀ N P i N
^Xc 2 «5 contains. 3. Fungicidal composition according to claim 1, characterized in that it is used as a fungicide, the effect of which is based on the blocking of sterol biosynthesis, an imidazole, piperazine, pyridine, piperidine, Contains pyrimidine, triazole or morpholine derivative as defined below. 4. Fungicidal composition according to one of the preceding Claims, characterized in that the further fungicide is a site-specific inhibitor or a Multi-site inhibitor according to the definition below or a general, e.g. metabolic, Is an inhibitor of fungal growth. 5. Fungicidal composition according to any one of the preceding claims, characterized in that the further Fungicid consists of one of the special fungicidal substances defined below. 6. A method for treating seeds, characterized in that that the seed is pitted with a composition according to the invention. 7. A method for dressing seeds, characterized in that the seeds are first bitten with ethirimol or with a fungicide which inhibits sterol biosynthesis in plant fungi, and then with a further fungicide as defined in one of the preceding claims . 8. A method of combating Pflanzenfungi, characterized in that applying a fungicidal composition according to any one of the preceding claims to a plant, to seed of a plant or to the locus of a plant or seed. 9. A method of combating plant fungi ', characterized in that alternating plantings with ethirimol, dimethirimol or bupirimate or with a fungicide which inhibits sterol biosynthesis in plant fungi, and then treated with another fungicidal substance as defined above, for example sprayed .