HK1112811A - Fungicidal mixtures of thiophene derivative - Google Patents

Description

Fungicidal mixtures of thiophene derivatives

Technical Field

The present invention relates to fungicidal mixtures of certain thiophene derivatives and compositions comprising the mixtures and methods of using the mixtures as fungicides.

Background

Control of plant diseases caused by fungal phytopathogens is important to obtain high yield crops. Plant diseases damage ornamental, vegetable, field, cereal and fruit crops causing significant yield losses and resulting increased costs to the consumer. Many products are commercially available for this purpose, but there is also a need for new mixtures and compositions that are more effective, less costly, less toxic, environmentally safer or have different modes of action.

Growers are in constant need of fungicides that are effective in controlling plant fungi. Combinations of fungicides are often used to promote disease control and delay the development of resistance. It is desirable to combine treatment, systemic and prophylactic control of phytopathogens with a blend of active ingredients to improve the active range and efficacy of disease control. There is also a need for a mixture that provides greater residual control in view of the extended spray intervals. There is also a great need for mixed fungicides that inhibit different biochemical pathways in fungal pathogens, thereby slowing the development of resistance to any particular plant disease control agent.

It is desirable to reduce the amount of chemical agents released into the environment while ensuring that crops are effectively protected from disease caused by plant pathogens. The disease control of the fungicide mixtures is clearly better than that which can be expected on the basis of the one-component activity. This synergistic effect is referred to as "the combined action of the two components of the mixture, such that the overall effect is better or more durable than the sum of the two (or more) individual effects" (see p.m.l.tames, neth.j.planta pathlogy 1964, 70, 73-80).

There remains a need for new fungicides that are particularly advantageous for achieving one or more of the foregoing objectives.

U.S. patent 5,747,517 discloses certain thiophene derivative compounds of formula i as novel fungicidal active ingredients.

Summary of The Invention

The present invention relates to a fungicidal mixture comprising:

(a) n- [2- (1, 3-dimethylbutyl) -3-thienyl ] -1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxamide (including all stereoisomers) or an agriculturally suitable salt thereof; and

(b) at least one compound selected from the group consisting of compounds of formula III or compounds of formula IV acting on bc, the respiratory electron transfer site of the fungal mitochondria₁A complex;

wherein

W is one of the following groups

Or

W¹Is N or CH;

W²is NH, O or CH₂；

W³Is O or CH₂；

A is one of the following groups (wherein the asterisk is: (^*) Attached to the benzene ring of formula III),

or

B is 1, 2-propanedione-di (O-methyloxime) -1-yl; or phenyl, phenoxy or pyridyl, each of which groups may be optionally substituted with 1 or 2 substituents selected from Cl, CN, methyl or trifluoromethyl; or

A and B together are-CH₂O (1- [ 4-chlorophenyl)]-pyrazol-3-yl) or-CH₂O (6-trifluoromethyl-2-pyridyl,

d is one of the following groups (wherein the asterisk is: (^*) The carbon (carbon 1) pound symbol (#) attached to the benzene ring adjacent to formula IV is attached to the carbon (carbon 2) adjacent to the nitrogen atom of formula IV),

or

R⁵Is H or phenoxy; and

R⁶is O or S;

and agriculturally suitable salts thereof; and optionally

(c) At least one compound selected from the group consisting of compounds acting on demethylase of the sterol biosynthesis pathway and agriculturally useful salts thereof.

The present invention also relates to a fungicidal composition comprising a fungicidally effective amount of the mixture of the invention and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.

The present invention also relates to a method of controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof a fungicidally effective amount of a mixture of the present invention (e.g., a composition as described above).

Detailed Description

The compound N- [2- (1, 3-dimethylbutyl) -3-thienyl ] -1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxamide, which may also be named 3- (trifluoromethyl) -1-methyl-N- (2- (4-methylpent-2-yl) thiophen-3-yl) -1H-pyrazole-4-carboxamide and N- {2- (1, 3-dimethylphenyl) -3-thienyl } -3-trifluoromethyl-1-methylpyrazole-4-carboxamide, may be represented by the general formula I:

many of the compounds in the mixtures of the present invention (e.g., compounds of formula I) may exist as one or more stereoisomers. Depending on the compounds, the various stereoisomers include enantiomers, diastereomers, atropisomers (atropisomers) and geometric isomers. One skilled in the art can estimate that one stereoisomer will be more active and/or exhibit beneficial effects when enriched relative to the other stereoisomer or when separated from the other stereoisomer. Furthermore, one skilled in the art would know how to separate, enrich, and/or selectively prepare the indicated stereoisomers. The compounds in the mixtures of the invention may exist as mixtures of stereoisomers, individual stereoisomers or optically active forms.

Agriculturally suitable salts of the compounds in the mixtures of the present invention include acid addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfinic or valeric acids. Agriculturally suitable salts of the compounds of the mixtures of the present invention also include those salts formed with organic radicals (pyrimidine, ammonia or triethylamine) or inorganic radicals (hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compounds contain an acid group such as a carboxylic acid or phenol.

Embodiments of the invention include:

embodiment 1 component (b) of the mixture is pyraclostrobin (pyraclostatin).

Embodiment 2 component (b) of the mixture is triflurosensitin (trifloxystrobin).

Embodiment 3 component (b) of the mixture is famoxadone.

Embodiment 4. the mixture further comprises at least one compound selected from the group consisting of demethylases that act on sterol biosynthesis pathways and agriculturally acceptable salts thereof.

A further notable embodiment is the fungicidal composition of the present invention, comprising a fungicidally effective amount of the mixture of embodiments 1 through 4 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. Embodiments of the present invention also include methods of controlling plant diseases caused by fungal phytopathogens comprising applying a fungicidally effective amount of a mixture of embodiments 1 to 4 (a composition as described herein) to a plant or part thereof, or to a plant seed or seedling.

The compound N- [2- (1, 3-dimethylbutyl) -3-thienyl ] -1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxamide may be prepared using one or more of the methods and variations thereof as described in U.S. patent 5,747,518 (see, e.g., example 14).

Fungicidal compounds of components (b) and (c) have been described in published patent and scientific journals. Many of these compounds are commercially available as active ingredients for fungicidal products. These compounds are described in synopsis such as The Pesticide Manual, 13th edition, C.D.S.Thomlin (Ed), British Crop Protection Council, Surrey, UK, 2003. These compounds will be further described below.

bx₁Complex fungicide (component (b))

The known fungicidal strobilurin agents such as fluoroxastribin, orysastrobin, picoxystrobin, pyraclostrobin (pyraclostrobin) and trifluomin (trifloxystrobin) have a fungicidal mode of action which is the inhibition of bc in the mitochondrial respiratory chain₁Complexes (Angew. chem. int. Ed.1999, 38, 1328-. Other strobilurin fungicides suitable for component (b) include (2E) -2- (2- { [6- (3-chloro-2-methylphenoxy) -5-fluoro-4-pyrimidinyl]Oxy } phenyl) -2- (methoxyimino) -N-methylacetamide, (2E) -2- (methoxyimino) -N-methyl-2- (2- { [ ({ (1E) -1- [3- (trifluoromethyl) phenyl]Ethylene } amino) oxy]Methyl } phenyl) acetamide, (2E) -2- (methoxyimino) -N-methyl-2- {2- [ (E) - ({1- [3- (trifluoromethyl) phenyl]Ethoxy } imino) methyl]Phenyl) acetamide. Other complexes bc inhibiting mitochondrial respiratory chain₁The compounds of (a) include famoxadone (famoxadone) and fenamidone. Complex bc₁Sometimes referred to by other names in the biochemical literature, including complex III, which includes electron transport chains, and ubihydroquinone: cytochrome c oxidoreductase, which is uniquely identified by Enzyme Commission number EC1.10.12.2. Complex bc₁In the fields of the methods described in J.biol.chem.1989, 264, 14543-48; methods Enzymol.1986, 126, 253-71 and references cited therein.

Demethylase inhibitor in sterol biosynthesis (combination (c))

Sterol biosynthesis inhibitors control fungi by inhibiting enzymes in the sterol biosynthesis pathway. Inhibiting demethylase fungicides have a common site of action in the fungal sterol biosynthesis pathway; it is the inhibition of the demethylation at position 14 of lanosterol or 24-methylenelanosterol, which are precursors of sterols in fungi. Compounds acting at this site are often referred to as demethylase inhibitors, DMI fungicides, or DMIs. Demethylases are sometimes referred to by other names in the biochemical literature, including cytochrome P-450(14 DM). Demethylases are described, for example, in J.biol.chem.1992, 267, 13175-79 and references cited therein. DMI fungicides fall into a variety of chemical classes: azoles (including triazoles and imidazoles), pyrimidines, piperazines, and pyridines. Triazoles include azaconazole (azaconazole), bromuconazole (bromoconazole), cyproconazole (cyproconazole),' difenoconazole (difenoconazole), diniconazole (diniconazole) (including diniconazole-M), epoxiconazole, etaconazole (etaconazole), fenbuconazole (febuconazole), fluquinconazole (fluquinconazole), flusilazole (flusilazole), flutriafol (flutriafol), hexaconazole (hexaconazole), imibenconazole (imibenconazole), ipconazole (ipconazole), metconazole (metconazole), myclobutanil (myclobutanil), penconazole (penconazole), propiconazole (propiconazole), prothioconazole, quinconazole (quinconazole), tetraconazole (tetraconazole), triticonazole (tetraconazole). Imidazoles (imidazoles) include clotrimazole (clotrimazole), econazole (econazole), imazalil (imazalil), isoconazole (isoconazole), diflunisal (miconazole), oxyponazole (oxyponazole), prochloraz (prochloz) and triflumizole (triflumizole). Piperazine includes azinam (triforine) pyridine includes buthiosulphate (buthiobate) and pyribenzoxim (pyrifenox). Biochemical studies have shown that the fungicides mentioned above are, for example, those described by k.h. kuck, et al, in Modern selective fungicides-Properties, Applications and Mechanisms of Action, h.lyr (Ed.), Gustav Fischer Verlag: DMI fungicides described in New York, 1995, 205-258.

A description of The commercially available compounds listed above can be found in The Pesticide Manual, third Edition, c.d.s.tomlin (Ed.), British, Crop protocol Council, 2003.

The present invention provides combinations of fungicides having different biochemical modes of action. This combination is particularly advantageous for drug resistance management, especially where fungicides are incorporated to control the same or similar diseases. Examples include compounds of formula I in combination with strobilurins (Strobilurins) such as fluoxastrobin, picoxystrobin, pyraclosterobin and trifloxystrobin; and optionally in combination with DMIs such as cyproconazole (cyproconazole), epoxiconazole, fluquinconazole (fluquinconazole), flusilazole (flusilazole), hexaconazole (hexaconazole), metconazole (metconazole), propiconazole (propiconazole), prothioconazole and tebuconazole (tebuconazole).

The invention also provides combinations of fungicides that provide extended spectrum of disease control or improved efficacy, including improved control of residual, therapeutic or prophylactic. Examples include the combination of a compound of formula I with a Strobilurin (Strobilurin) such as fluoxastrobin, picoxystrobin, pyraclosterobin and trifloxystrobin; and optionally in combination with DMIs such as bromuconazole (bromuconazole), cyproconazole (cyproconazole), epoxiconazole, fluquinconazole (fluquinconazole), flusilazole (flusilazole), hexaconazole (hexaconazole), metconazole (metconazole), propiconazole (propiconazole), prothioconazole and tebuconazole (tebuconazole).

The present invention also provides combinations of fungicides that are particularly useful for controlling cereal diseases such as erysiphe graminis (Erisyphagemis), Septoria nodorum (Septoria nodorum), Septoria tritici (Septoria), Puccinia recondite (Puccinia recondite) and Pyrenophora teres (Pyrenophorates). Examples include compounds of formula I in combination with strobilurins (Strobilurins) such as fluoxastrobin, picoxystrobin, pyraclosterobin and trifloxystrobin; and, optionally, with DMIs such as bromuconazole (bromuconazole), cyproconazole (cyproconazole), epoxiconazole, fluquinconazole (fluquinconazole), flusilazole (flusilazole), hexaconazole (hexaconazole), metconazole (metconazole), propiconazole (propiconazole), prothioconazole and tebuconazole (tebuconazole).

The invention also provides a combination of fungicides that are particularly useful for controlling fruit and vegetable diseases (potato early blight (alternariolania), grape gray mold (Botrytis cinerea), potato black nevus (rhizoctoniasporani), grape powdery mildew (Uncinula nectorius) and apple scab (venturiaequalis)). Examples include compounds of formula I in combination with strobilurins (Strobilurins) such as picoxystrobin, pyraclostrobin and trifloxystrobin; and optionally in combination with DMIs such as bromuconazole (bromuconazole), cyproconazole (cyproconazole), epoxiconazole, fluquinconazole (fluquinconazole), flusilazole (flusilazole), hexaconazole (hexaconazole), metconazole (metconazole), propiconazole (propiconazole), prothioconazole and tebuconazole (tebuconazole).

The weight ratio of component (b) to component (a) in the mixtures and compositions of the invention is generally from 100: 1 to 1: 100, preferably from 25: 1 to 1: 25, more preferably from 10: 1 to 1: 10. It is noted that the weight ratio of component (b) to component (a) in the mixture and composition is from 5: 1 to 1: 5. Examples of such compositions include compositions comprising a mixture of a compound of formula I with trifloxystrobin, a mixture of a compound of formula I with fluxastrobin, a mixture of a compound of formula I with picoxystrobin or a mixture of a compound of formula I with pyraclosterobin.

Of note are compositions comprising component (b) and component (c). Examples are combinations of pyraclostrobin or trifloxystrobin, which cooperate as component (b), and at least one compound of component (c). Compositions of note are those in which the weight ratio of the total amount of components (b) and (c) to component (a) is from 100: 1 to 1: 100, and the weight ratio of component (b) to component (a) is from 25: 1 to 1: 25. Comprising a composition having a weight ratio of component (b) to component (a) of from 5: 1 to 1: 1. Examples of such compositions include compositions comprising a mixture of component (a) and trifloxystrobin and a compound selected from the group consisting of epoxiconazole and flusilazole.

Dosage form/Effect

The mixtures of the present invention are generally used in dosage forms or compositions containing at least one carrier selected from agriculturally suitable liquid diluents, solid diluents and surfactants. The ingredients of the formulation or composition are selected to be compatible with the physical properties of the active ingredient, the mode of action, and environmental factors such as soil type, moisture, and temperature. Useful dosage forms include solutions such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and also optionally gels. Useful dosage forms also include solids, such as powders (dust), dusts, granules, pills, tablets, films, and also water-dispersible (wettable) or water-soluble. The active ingredient may be in the form of a (micro) capsule and further form a suspension or solid dosage form, alternatively the entire dosage form of the active ingredient may be encapsulated (or "overcoated"). Sprayable formulations can be dispersed in a suitable vehicle at a spray volume of about 1 to several hundred liters per hectare. The high concentration of the composition is mainly used as a semi-finished product of other dosage forms.

Dosage forms typically contain an effective amount (e.g., 0.01-99.99%) of the active ingredient, with the following approximate ranges of diluents and/or surfactants to total 100%.

	Weight percent (wt.%) of
				Active ingredient	Diluent	Surface active agent
	Water dispersible and water soluble granules, tablets and powders	5-90	0-94				1-15
Suspending agent, emulsion, solution (including missible oil)				5-50	40-95	0-25
	Powder preparation	1-25	70-99				0-5
Granules and tablets				0.01-99	5-99.99	0-15
	High concentration composition	90-99	0-10				0-2

Typical solid diluents are described in Watkins, et a1., Handbook of insulation DustDiluents and Cariers, 2nd edition, Dorland Books, Caldwell, New Jersey. Typical liquid diluents are listed as surfactants and recommended use in Marsden, solutions Guide, 2 conclusion, Interscience, New York, 1950. McCutcheon's Detergents and emulsifiers annular, Allured Publ.Corp., Ridgewood.New Jersey, Wood, Encyclopedia of Surface Active Agents, chemical Publ.Co., Inc., New York, 1964. All formulations may contain small amounts of additives to reduce foaming, caking, corrosion, microbial growth, etc., or thickeners to increase viscosity.

Surfactants include, for example, polyoxyethylene alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkyl benzene sulfonates, organosilicon compounds, N-dialkyl taurates (N, N-dialkyltaurates), lignosulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starches, sugars, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, olive oil, castor oil, linseed oil, tung oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and cocoa butter, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cycloethanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the components. Dusts and powders can be prepared by mixing, usually by comminution in a hammer mill or air-flow mixer. Suspending agents are typically prepared by wet milling; see, e.g., U.S.3,060,084. Preferred suspending agent concentrates include those containing from 5% to 20% of a non-ionic surfactant (such as polyethoxylated fatty alcohol) optionally in combination with from 50 to 60% of a liquid diluent and up to 5% of an ionic surfactant in addition to the active ingredient. Granules and pellets can be prepared by spraying the active substance onto a particulate carrier prepared beforehand or by granulation techniques. See Browning, "Agglorations," Chemical engineering, Decumber 4, 167, pp147-48, Perry's Chemical engineering's handbook, 4 th edition, McGraw-Hill, New York, 1963, Page 8-57 and below, and WO 91/13546. The preparation of pellets is also described in U.S.4,172,714. the preparation of water-dispersible and water-soluble granules is described in U.S.4,144,050, U.S.3,920,442 and DE3,246,493. Tablets were made as described in U.S.5,180,587, U.S.5,232,701 and U.S.5,208,030. Film preparations can be found in GB 2,095,558 and U.S.3,299,566.

Further information on dosage forms can be found in U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S. Pat. No. 3,309,192, column 5, column 43 to column 7, column 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138, 140, 162, 164, 166, 167 and 169, 182; U.S.2,891,855, column 3, line 66 to column 5, line 17 and examples 1-4; klingman, Weed Control as a Science, john wiley and Sons, inc., New York, 1961, pp 81-96; and Hance et al, WeedControlhandbook, 8 th edition, Blackwell Scientific Publications, Oxford, 1989.

In the following examples, all percentages are by weight and all dosage forms are prepared by conventional methods. The term "active ingredient" as used in examples a to E means that a compound selected from group (a) and group (b) is mixed with any other active ingredient present, such as any compound selected from group (c). Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following examples are therefore illustrative only and in no way limit the scope of the invention. Unless otherwise indicated, percentages are by weight.

Example A

Wettable powder

65.0 percent of active ingredient

2.0 percent of dodecyl phenol polyglycol ether

Sodium lignosulfonate 4.0%

Sodium aluminosilicate 6.0%

Montmorillonite (calcined) 23.0%

Example B

Granules

Active ingredient is 10.0%

Attapulgite particles (low volatiles, 0.71/0.30 mm;

U.S.S.No.25-50 sieve) 90.0%

Example C

Extruded pellets

Active ingredient 25.0%

10.0 percent of anhydrous sodium sulfate

5.0 percent of crude calcium lignosulfonate

Sodium alkylnaphthalenesulfonate 1.0%

Calcium/magnesium Bentonite 59.0%

Example D

Emulsifiable concentrate

20.0 percent of active ingredients

10.0 percent of mixture of oil-soluble sulfonate and polyoxyethylene ether

70 percent of isophorone

Example E

Concentrated suspension concentrate

20.0 percent of active ingredients

Polyethoxylated fatty alcohol 15.0%

Ester derivatives of montan wax 3.0%

2.0 percent of crude calcium lignosulfonate

Polyethoxylated/polypropoxylated polyethylene glycols

Block copolymer 1.0%

6.4 percent of propylene glycol

0.6 percent of poly (dimethyl siloxane)

0.1 percent of antibacterial agent

51.9 percent of water

The compositions of the present invention may also include one or more other insecticides, fungicides, nematocides, bactericides, acaricides, plant growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds mixed to form a multi-component insecticide to provide a broader range of agricultural protection. Examples of such agricultural protection agents which can be formulated with the mixtures according to the invention are: insecticides such as abamectin, acephate, glutethion, bifenthrin (bifenthrin), buprofezin (buprofezin), carbofuran (carbofuran), chlorenapyr, chlorpyrifos-methyl, cyfluthrin (cyfluthrin), beta-cyfluthrin, gelonin (cyhalothrin), lambda-glanin, deltamethrin, diafenthiuron, diazinon, diflubenzuron (difluubeniron), dimethoate, S-fenvalerate (esfenvalant), ethiprole, fenoxycarb (fenoxycarb), fenpropathrin, fenvalerate, flufenvalerate, fluvalinate, cyhalothrin, cyphonophos, imidacloprid, indoxacarb, isofenphos, malathion, mechlorfenphos, methidathion, fenoxathion, fenoxaprop-p, fenofos, chlorpyrifos, metofos, metocloprid, metoclopramide, metocloprid, chlorpyrifos, chlorpyri, Tefluthrin, terbufos, carbofuran, thiodicarb, tralomethrin, trichlorfon, and triflumuron; fungicides, in addition to those listed under component (b) and component (c), are, for example, acibenzolar-S-methyl, benalaxyl (benalaxyl), including benalaxyl-M, benhiavalicarb, benomyl, blasticidin-S, poloxamine (tribasic copper sulfate), boscalid, buthiodine (buthiobate), clomipramide (carpropamide), captafol (captafol), captan (captan), carbendazim (carbendazim), chlorfenapyr (chloroneb), chlorothalonil (chlorothalonil), copperylon (copperoxyporide), copper salts, cymoxanil (cymoxazole), cyazofamid (cyofemid), cyflufenamid (cyprodin), cyprodinil (fenpropidin), fenpropidin (chlorpyrifos), chlorpyrifos, Fentin (fentin hydroxide), fluazinam (fluazinam), fludioxonil (fluxonil), fluumorph, flutolanil (flutolanil), folpet (folpet), fosetyl-aluminum (fosetyl-aluminum), furalaxyl (furalaxyl), furametpyr (furametpyr), biguanide (guazatine), hymexazol (hymexazol), biguanide (iminoctadine), iprobenfos (iprobenfos), iprodione (iprodione), iprovalicarb, isoprothiolane (isoprothiolane), kasugamycin (kasugamycin), mancozeb (mancozeb), maneb (metfenpyr), mepanzine, mepapsilamide (mepronil), mepiquat (fenpropiconazole), mepiquat (fenpyr), fluazidine (fluazidine), thifluazimide (fluazimide), mepiquat (fluazidine), thifluazimide (fluazimide), thifluazimide (metosulindazone (metoclopramide), thiuram (propiconazole), thiuram (propiconazole), thiuram (propiconazole), thiuram (propiconazole), thiuram (propiconazole, Thiram (thiram), tiadinil, tolyfluoride (tolyfluoranid), validamycin (validamycin); vinclozolin (vinclozolin) and zoxamide; nematicides such as sulfocarb (aldoxycarb) and fenamiphos (fenamiphos); bactericides such as streptomycin; acaricides such as amitraz, chlorfenapyr (chinomethionat), chlorfenapyr (chlorobenzilate) cyhexatin (cyhexatin), clorac (dicofol), dienochlor, etoxazole, fenazaquin, fenbutatin oxide (fenbutatin oxide), fenpropathrin (fenpropathrin), fenpyroximate (fenpyroximate), hexythiazox (hexythiazox), propargite (prodigite), pyridaben (pyridaben) and tebufenpyrad (tebufenpyrad); biological agents such as Bacillus thuringiensis including Bacillus thuringiensis subspecies silurus (ssp. aizawai) and Bacillus thuringiensis subspecies kurstaki (ssp. kurstaki), Bacillus thuringiensis (Bacillus thuringiensis) delta endotoxin, baculovirus and entomophagic bacteria, viruses and fungi. Various commercially available compounds listed above are described in the pesticide Manual, Twelfth Edition, c.d.s.tomlin, ed., British CropProtection Council, 2000. In embodiments where these different blending components are used, the weight ratio of these different blending components (total) to the total of component (a) and component (b) is typically between 100: 1 and 1: 3000. It is noted that the weight ratio is between 30: 1 and 1: 300 (e.g., the ratio is between 1: 1 and 1: 30). It is apparent that the inclusion of these additional components extends the control range of diseases compared to the combination of component (a), component (b) and optional component (c) used alone.

Of particular note are compositions that, in addition to component (a), component (b), and optional component (c), (d) at least one compound selected from the group consisting of:

(d1) alkylene bis (dithiocarbamate) fungicides;

(d2) cymoxanil;

(d3) phenylamide fungicides;

(d4) pyrimidinone (pyrimidinone) fungicides;

(d5) chlorothalonil;

(d6) carbamoyl of complex II acting at the site of fungal mitochondrial respiratory electron transport;

(d7) quinoxyfen (quinoxyfen);

(d8)metrafenone；

(d9)cyflufenamid；

(d10) cyprodinil (Cyprodinil);

(d11) a copper compound;

(d12) a phthalamide fungicide;

(d13) fosetyl-aluminum (fosetyl-aluminum);

(d14) a benzimidazole fungicide;

(d15) cyazofamid;

(d16) fluazinam;

(d17)iprovalicarb；

(d18) propamocarb;

(d19)validomycin；

(d20) dichlorophenyl dicarboximide fungicide;

(d21)zoxamide；

(d22) dimethomorph;

(d23) a non-DMI sterol biosynthesis inhibitor; and

salts of agriculturally suitable compounds (d1) to (d 23).

Pyrimidone fungicides (group (d4))

Pyrimidone fungicides include compounds represented by the general formula II

Wherein

G forms a fused phenyl, thiophene or pyridine ring;

R¹is C₁-C₆An alkyl group;

R²is C₁-C₆Alkyl or C₁-C₆An alkoxy group;

R³is halogen; and is

R⁴Is hydrogen or halogen.

Pyrimidinone fungicides are described in world patent application publication WO 94/26722, us patent 6,066,638, us patent 6,245,770, us patent 6,262,058 and us patent 6,277,858.

Of note are pyrimidinones selected from the group consisting of:

6-bromo-3-propyl-2-propoxy-4- (3H) -quinazolinone,

6, 8-diiodo-3-propyl-2-propoxy-4 (3H) -quinazolinone,

6-iodo-3-propyl-2-propoxy-4 (3H) -quinazolinone (proquinazid),

6-chloro-2-propoxy-3-propylthieno [2, 3-d ] pyrimidin-4 (3H) -one,

6-bromo-2-propoxy-3-propylthieno [2, 3-d ] pyrimidin-4 (3H) -one,

7-bromo-2-propoxy-3-propylthieno [2, 3-d ] pyrimidin-4 (3H) -one,

6-bromo-2-propoxy-3-propylpyrido [2, 3-d ] pyrimidin-4 (3H) -one,

6, 7-dibromo-2-propoxy-3-propylthieno [3, 2-d ] pyrimidin-4 (3H) -one, and

3- (cyclopropylmethyl) -6-iodo-2- (propylsulfanyl) pyrido [2, 3-d ] pyrimidin-4 (3H) -one.

Other fungicidal groups

Hydrocarbylene di (dithiocarbamate) fungicides (d1) include compounds such as mancozeb, maneb, propineb and zineb.

Phenylamide fungicides (d3) include compounds such as metalaxyl (metalaxyl), benalaxyl (benalaxyl), Furalaxyl (Furalaxyl) and oxadixyl (oxadixyl).

Carbamoyl (d6) includes compounds known to inhibit mitochondrial action by interrupting complex II (succinate dehydrogenase) in the respiratory electron transport chain, such as boscalid, carboxin, furamectin (fenfuram), fluoxadin, furametpyr, basidin, carboxin and fludioxonil (thifluzamide).

Copper compounds (d11) include compounds such as copper oxychloride, copper sulfate and copper hydroxide, including compositions such as bordeaux mixture (basic copper sulfate).

Phthalimide fungicides (d12) include compounds such as folpet and captan.

Benzimidazole fungicides (d14) include benomyl and carbendazim.

Dichlorophenyl dicarboximide fungicides (d20) include ethiprole (chlorzolite), sclerotinia, iprodione, isovaledione, myclozolin, pythium and vinclozolin.

non-DMI sterol biosynthesis inhibitors (d23) include morpholine and piperidine fungicides. Morpholine and piperidine are sterol biosynthesis inhibitors which have been shown to inhibit the sterol biosynthesis pathway at a later time than the inhibition obtained by MDI sterol biosynthesis (i.e. component (c)). Morpholines include aldimorph, moroxydine, fenprimorph (fenpropimorph), tridemorph and trimorphamide (trimorphamid). The piperidine includes fenpropidine.

It is notable that the total weight of components (b), (d) and, if present, (c) of this composition is from 100: 1 to 1: 100 by weight with component (a), and the weight ratio of component (b) to component (a) is from 25: 1 to 1: 25. Comprising a composition having a weight ratio of component (a) to component (b) of from 5: 1 to 1: 1.

The mixtures and compositions of the present invention are useful as plant disease control agents. The invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant to be protected or a part thereof or the seed or seedling to be protected an effective amount of a mixture according to the invention or of a fungicidal composition comprising said mixture.

The mixtures and compositions of the present invention provide control of diseases caused by a broad spectrum of fungal phytopathogens among basidiomycetes (basidiomycetes), ascomycetes (ascomycetes), Oomycetes (Oomycetes) and Deuteromycetes (Deuteromycetes). They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal and fruit crops. These pathogens include:

oomycetes (oomyces), including Phytophthora (Phytophthora) pathogens such as Phytophthora infestans (Phytophthora infestans), Phytophthora infestans (Phytophthora megaspora), Phytophthora parasitica (Phytophthora parasitica), Phytophthora cinnamomi (Phytophthora cincamoni) and Phytophthora capsici (Phytophthora capsici); pythium (Pythium) pathogens such as Pythium aphanidermatum (Pythium aphanidermatum); and Peronosporaceae (Peronosporaceae) pathogens such as Plasmopara viticola (Plasmopara viticola), Peronospora spp (Peronospora spp.) (including Peronospora tabacina (Peronospora tabacina) and Peronospora brassicae (Peronospora parasitica)), Pseudoperonospora spp (including Pseudoperonospora cubensis), and Bremia lactucae (Bremia lactucae);

ascomycetes include Alternaria alternata (Alternaria) pathogens such as Alternaria solani (Alternaria solani) and Alternaria brassicae (Alternaria brassicca); coccobacillus (Guignardia) pathogens, such as grape black rot (Guignardia bidwelli); venturia nigricans (Venturia) pathogens, such as Venturia inaequalis (Venturia inaqualis); bacterial blight (septiria), such as glume blight (Septoria nodorum) and leaf spot blight (Septoria tritici); erysiphe species, such as Erysiphe spp (including Erysiphe graminis and Erysiphe graminis), Uncaria vinifera (Uncinula necator), Sphaerotheca fuliginea (Sphaerotheca fuliginea) and Malaria necator (Podosphaera leucotricha); ocular plaque bacteria (pseudocercospora herpotrichoides) on wheat and barley; botrytis (Botrytis) such as Botrytis cinerea (Botrytis cinerea); candida fructogenes (Monilinia (corymbola), Sclerotinia sclerotiorum (Sclerotinia) such as Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), Pyricularia oryzae (Magnaporthe grisea), Phomopsis (Phomopsis viticola), Helminthosporium (Helminthosporium) such as Helminthosporium tritici (Helminthosporium tritici reptilis), Pyrenophora teres (Pyrenophora teres), Anthragma collecticum (Anthracnidium), such as Microtheca circulans (Glomerella) and Colletotrichum spinosum (Colletotrichum spp.) (such as Colletotrichum gramineum (Colletotrichum graminicum)), and Populus capsulatus (Gaeumannomyces graminis);

basidiomycetes include rust caused by Puccinia spp (such as Puccinia triticina (Pucciniarecandia), Puccinia striatum (Puccinia striatoria), Puccinia hordei (Puccinia hordei), Puccinia graminis (Puccinia graminis), and Puccinia arachidis (Puccinia arachidis)); rust of camelina (Hemileia vastatrix) and Phakopsora pachyrhizi (Phakopsora pachyrhizi);

other pathogenic bacteria include Rhizoctonia sp (e.g., Rhizoctonia solani); fusarium (Fusarium) pathogens such as Fusarium roseum (Fusarium roseum), Fusarium graminearum (Fusarium graminearum), and Fusarium oxysporum (Fusarium oxysporum); verticillium dahliae (Verticillium dahliae); sclerotium rolfsii (Sclerotium rolfsii); rynchosporium secalis; cercospora persimmoniatum, peanut tail spore (Cercospora arachidicola) and beet tail spore (Cercospora betacola);

and other species close to these pathogenic bacteria.

In addition to their fungicidal activity, the mixtures and compositions contain antibacterial active substances, such as Erwinia amylovora (Erwinia amylovora), Xanthomonas campestris (Xanthomonas campestris), Pseudomonas syringae (Pseudomonas syringae) and other related species.

It is noteworthy that the mixtures according to the invention are used for controlling erysiphe graminis (erysiphe graminis), in particular the application component (b) is a mixture of trifloxystrobin (trifloxystrobin).

It is noteworthy that the mixtures of the invention are used for controlling Septoria nodorum (Septoria nodorum) of wheat, in particular the application component (b) is a mixture of triflumsensitines (trifloxystrobin).

It is noteworthy that the mixtures according to the invention are used for controlling Pyrenophora teres (barley net blotch), in particular mixtures in which the component (b) is trifloxystrobin (trifloxystrobin) are used.

It is noteworthy that the mixtures of the invention are used for controlling pucciniae (wheat leaf rust) in wheat, in particular the mixture of the application component (b) is trifloxystrobin (trifioxytrobin).

It is also noteworthy that a prophylactically or therapeutically effective amount of a mixture or composition of the present invention is used to provide control of diseases caused by a broad spectrum of fungal phytopathogens, either before or after infection.

Control of disease in plants is generally accomplished by applying an effective amount of the mixture of the invention either pre-or post-infection, to the plant parts to be protected, such as roots, stems, leaves, fruits, seeds, tubers or bulbs, or to the medium (soil or sand) in which the plants to be protected are growing. The mixture is applied to seeds to protect the seeds and seedlings growing from the seeds. Generally, the mixture is applied in the form of a composition comprising at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.

The use ratio of these compounds is influenced by many environmental factors and should be determined according to actual use conditions. The treatment ratio which generally enables the leaves to be protected is such that the total amount of active ingredient components (a) and (b) in the mixture or composition of the invention is less than 1 to 5,000 g/ha. The seed protection is generally achieved when 1 kg of seed is treated with a total amount of active ingredient components (a) and (b) of 0.1 to 10 g.

The control of fungal phytopathogens by the mixtures of the present invention is more advantageous than the effect obtained by the individual components. It has been found that the mixtures of the invention show a synergistic effect, in particular with respect to the control of certain diseases such as barley net blotch caused by Pyrenophora teres.

The following tests may be used to demonstrate the control effect of the compositions of the present invention against specific pathogenic bacteria. However, the pathogen control protection provided by these compounds is not limited to these species.

Biological examples of the present invention

The test suspensions included spraying the active ingredients of the individual formulations to demonstrate the control effect of the individual active ingredients. To demonstrate the control effect of the composition, (a) an appropriate amount of the active ingredient is mixed into the individual test suspensions, (b) stock solutions of the individual active ingredients are prepared and then mixed in the appropriate proportions and diluted to the final desired concentration to form the test suspensions, or (c) the test suspensions including the individual active ingredients can be sprayed continuously at the desired proportions.

Composition 1

Ingredient Wt.%

A compound of the general formula I, prepared in suspension at a concentration of 20% 200g active ingredient/l

Composition 2

Ingredient Wt.%

Triflufen (TWIST fungicide) in the form of a suspension containing 125 g of active ingredient/l

Composition 3

Ingredient Wt.%

Epoxiconazole (OPUS fungicide) in the form of emulsifiable concentrate 125 g active ingredient/l

The test composition is first mixed with water. The suspension resulting from the test was then used for the field test described below. The test suspension was sprayed in a volume of 200 liters per hectare the application rates were 50, 100 and 200 grams per hectare.

Test A

When node 4 of the wheat plant is at least 2 cm above node 3, the set winter wheat (cv. 'Onvalinlis') field test area is sprayed, and the spraying is repeated when the top leaves are fully grown. With four replicates. The test area was visually assessed for the control of wheat leaf spot disease symptoms caused by Septoria tritici (Septoria tritici.) the average of four replicates was recorded as a result.

Test B

When the top leaves of the barley plants were fully grown, the set winter barley (cv. 'Esterel') field trial area was sprayed. Three replicates were used. The test area was visually assessed for symptom control of barley leaf spot caused by pyrenophoraes. The average of three replicates was recorded as the result.

Table 1 lists the results of test a and test B. In table a, a ratio of 100 indicates control of a disease of 100%, and a ratio of 0 indicates control without a disease (relative control). The column labeled "Avg" represents the average of three or four replicates.

TABLE A

Test results

Composition comprising a metal oxide and a metal oxide	Use ratio (g/ha)	Test A		Test B
						Avg	Exp	Avg	Exp
		1	50	31	-					12	-
1	100					48	-	28	-
		1	200	56	-					31	-
2	100					53	-	66	-
		3	100	63	-					31	-
1+2	100+200					73	76	86	75
		1+3	100+100	86	80					66	50
2+3	200+100					80	83	67	76

Table a shows the advantageous control of the mixtures and compositions of the invention.

In the Colby equation (see S.R.C0lby, "marketing synergy and anticancer Responses of pharmaceutical compositions" Weed, 1967, 15, 20-22): the synergistic effect between the two active ingredients is proved by the following steps:

img id="idf0011" file="A20058003258700251.GIF" wi="138" he="56" img-content="drawing" img-format="GIF"/

with the method of Colby, it was confirmed by first calculating the predicted activity p that the mixing ratio of the two active ingredients alone had a synergistic effect on the activities of the two components. If p is lower than the effect measured in the test, a synergistic effect occurs. In the above equation, A is the percent fungicidal activity of one component applied alone in the ratio x. Term B is the percent fungicidal activity of the second component applied in the ratio y. The equation estimates the fungicidal activity of mixtures of p, A in the ratio x and B in the ratio y if their effect is indeed additive and no mutual interference occurs.

As shown in Table A, the application of the Colby equation shows that the control ratio of the mixture of composition 1 and composition 2 of test B (100g/ha +200g/ha) and the mixture of composition 1 and composition 3 of test A and test B (100g/ha +100g/ha) is higher than expected.

The claims (modification according to treaty clause 19)

1. A fungicidal mixture, the mixture comprising:

(a) thiophene derivatives represented by the general formula I or agriculturally useful salts thereof;

and

(b) at least one compound selected from the group consisting of compounds of formula III or compounds of formula IV acting on bc, the respiratory electron transfer site of the fungal mitochondria₁A complex;

wherein

W is one of the following groups

Or

W¹Is N or CH;

W²is NH, O or CH₂；

W³Is O or CH₂；

A is one of the following groups (wherein the asterisk is: (^*) Attached to the benzene ring of formula III),

or

B is 1, 2-propanedione-di (O-methyloxime) -1-yl; or phenyl, phenoxy or pyridyl, each of which groups may be optionally substituted with 1 or 2 substituents selected from Cl, CN, methyl or trifluoromethyl; or

A and B together are-CH₂O (1- [ 4-chlorophenyl)]-pyrazol-3-yl) or-CH₂O (6-trifluoromethyl-2-pyridyl),

d is one of the following groups (wherein the asterisk is: (^*) Attached to the carbon (carbon 1) adjacent to the phenyl ring of formula IV, the pound symbol (#) is attached to the ring nitrogen (nitrogen 2) of formula IV),

or

R⁵Is H or phenoxy; and is

R⁶Is O or S;

and agriculturally suitable salts thereof; and optionally

(c) At least one compound selected from the group consisting of compounds acting on demethylase of the sterol biosynthesis pathway and agriculturally suitable salts thereof.

2. The mixture according to claim 1, wherein component (b) is triflurosensitin (trifloxystrobin).

3. The mixture of claim 2, wherein component (c) is present and component (c) is epoxiconazole.

4. A fungicidal composition comprising a fungicidally effective amount of the mixture of any one of claims 1 to 3 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.

5. A composition as claimed in claim 4 wherein the weight ratio of component (b) to component (a) is from 100: 1 to 1: 100.

6. A composition as claimed in claim 5 wherein the weight ratio of component (b) to component (a) is from 10: 1 to 1: 10.

7. A composition as claimed in claim 6 wherein the weight ratio of component (b) to component (a) is from 5: 1 to 1: 1.

8. A method of controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof a fungicidally effective amount of a mixture according to any one of claims 1 to 3.

9. A method as claimed in claim 8 wherein the fungal phytopathogen is Pyrenophora teres.

10. A method as claimed in claim 8 wherein the fungal phytopathogen is Septoria tritici.

Claims (10)

1. A fungicidal mixture, the mixture comprising:

(a) thiophene derivatives represented by the general formula I or agriculturally useful salts thereof;

and

(b) at least one compound selected from the group consisting of compounds of formula III or compounds of formula IV acting on bc, the respiratory electron transfer site of the fungal mitochondria₁A complex;

wherein

W is one of the following groups

W¹Is N or CH;

W²is NH, O or CH₂；

w³Is O or CH₂；

A is one of the following groups (wherein the asterisk (—) is attached to the benzene ring of formula III),

or

B is 1, 2-propanedione-di (O-methyloxime) -1-yl; or phenyl, phenoxy or pyridyl, each of which groups may be optionally substituted with 1 or 2 substituents selected from Cl, CN, methyl or trifluoromethyl; or

A and B together are-CH₂O (1- [ 4-chlorophenyl)]-pyrazol-3-yl) or-CH₂O (6-trifluoromethyl-2-pyridyl),

d is one of the following groups (wherein the asterisk (#) is attached to the carbon (carbon 1) adjacent to the phenyl ring of formula IV, the pound symbol (#) is attached to the carbon (carbon 2) adjacent to the nitrogen of formula IV),

or

R⁵Is H or phenoxy; and is

R⁶Is O or S;

and agriculturally suitable salts thereof; and optionally

(c) At least one compound selected from the group consisting of compounds acting on demethylase of the sterol biosynthesis pathway and agriculturally useful salts thereof.

2. The mixture according to claim 1, wherein component (b) is triflurosensitin (trifloxystrobin).

3. The mixture of claim 2, wherein component (c) is present and component (c) is epoxiconazole.

4. A fungicidal composition comprising a fungicidally effective amount of the mixture of any one of claims 1 to 3 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.

5. A composition as claimed in claim 4 wherein the weight ratio of component (b) to component (a) is from 100: 1 to 1: 100.

6. A composition as claimed in claim 5 wherein the weight ratio of component (b) to component (a) is from 10: 1 to 1: 10.

7. A composition as claimed in claim 6 wherein the weight ratio of component (b) to component (a) is from 5: 1 to 1: 1.

8. A method of controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof a fungicidally effective amount of a mixture according to any one of claims 1 to 3.

9. A method as claimed in claim 8 wherein the fungal phytopathogen is Pyrenophora teres.

10. A method as claimed in claim 8 wherein the fungal phytopathogen is Septoria tritici.