JPS6052728B2 - Fungicide for agriculture and horticulture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an agricultural and horticultural fungicide containing a phenoxypyridazine derivative as an active ingredient.

JP-A-51-3256 Gin is 3-Chloro 6-[2-(
2-methylallyl)-6-methylphenoxy]pyridazine, 3-chloro6-[2-(2-methylallyl)-6
-isopropylphenoxy]viridazine and the like have herbicidal and fungicidal effects.

In addition, 3-chloro
6-(2-aryl-6-isopropylphenoxy)pyridazine, 3-chloro6-(2,6-diallylphenoxy)pyridazine, 3-chloro6-(2-aryl-6
-methoxyphenoxy)pyridazine, 3-chloro 6
-(2-aryl-4-chlorophenoxy)pyridazine,
3-chloro6-[2-(2-putenyl)-6-methylphenoxy]pyridazine, 3-chloro62[2-(2
Pyridazine derivatives such as -putenyl)-6-isopropylphenoxy]pyridazine are described as raw materials for the synthesis of xanthines. The present inventors have discovered that a phenoxypyridazine derivative having the following general formula (1) is effective in controlling diseases of various agricultural and horticultural crops. Formula R, X (I) R,! (In the formula, X represents a halogen atom, R and R2 both represent a lower alkyl group or a lower alkenyl group, or one represents a lower alkyl group and the other represents a halogen atom.

) The compound having the general formula (1) has an excellent bactericidal effect against a wide range of bacteria and fungi that parasitize and cause harm to agricultural and horticultural crops, and is particularly effective against blast and sheath blight, which are major diseases of rice. It has a high control effect against leaf blight, powdery mildew of tomatoes, powdery mildew of cucurbits, gray mold, etc., and also kills various soil pathogens and algal fungi that have a negative effect on the germination of paddy rice. Effectively suppress. In the definition of the general formula (1), a halogen atom means chlorine, bromine, fluorine or iodine, and a lower alkyl group means a linear or branched alkyl group having 1 to 4 carbon atoms, such as methyl. ,ethyl,
Indicates n-propyl, isopropyl, n-butyl, isobutyl, Sec-butyl or tert-butyl.

The lower alkenyl group refers to a linear or branched alkenyl group having 3 or 4 carbon atoms, such as propenyl, allyl, 2-butenyl, 1-methyl-2-propenyl, 2-methylallyl or 3-butenyl. The compound exhibiting an excellent bactericidal effect in the general formula (1) has the general formula (wherein x'' represents a chlorine atom, a bromine atom, or an iodine atom, and R''1 and R''2 are the same or different and are a methyl group, Indicates an ethyl group, n-propyl group or n-butyl group.

). Examples of the compound having the general formula (1) used in the agricultural and horticultural fungicide of the present invention are as follows. (The compound number is referred to in the following description.) 13-chloro6-(2,6-diallylphenoxy)pyridazine M.
p. 63-64°C 23-bromo6-(2,6-diallylphenoxy)pyridazine M. p.
64-65°C 33-Iodo6-(2,6-diallylphenoxy)pyridazine M. p. 72
~73 43-chloro6-(2,6-diisopropylphenoxy)pyridazine M. p. l8l~187
IC13-chloro6-(2,6-dipropenylphenoxy)pyridazine M. p. l32~1
0Ci3-Bromo6-(2,6-diethylphenoxy)pyridazine M. p. 69-70℃
3-Bromo6-(2,6-di-n-propylphenoxy)pyridazine M. p. 56 ~ Kano C 3-chloro6-(2-n-butyl-6-methylphenoxy)pyridazine M. p. 66-6
8°CE3-chloro6-(2-methyl-6-n-propylphenoxy)pyridazine M. p.
5O~51 03-chloro6-(2-ethyl-6-n-propylphenoxy)pyridazine M. p. 39
~41 13-chloro6-(2,6-dimethylphenoxy)pyridazine M. p. 93-94 23-chloro6-(2,6-diethylphenoxy)pyridazine M. p. 69-700C3
3-chloro6-(2,6-di-n-propylphenoxy)pyridazine M. p. 8-59°C 43-Iodo6-(2,6-dimethylphenoxy)pyridazine M. p. l29~131CC
53-Iodo6-(2,6-diethylphenoxy)pyridazine M. p. lO2~103CC
63-Iodo6-(2,6-di-n-propylphenoxy)pyridazine M. p. 88-9
00C73-chloro6-(2-chloro6-n-propylphenoxy)pyridazine M. p
．． 64-65°C The active ingredient compound according to the present invention can be easily produced, for example, by the method shown in the following formula.

(In the formula, R1, R2 and
) will be explained by giving reference examples.

Reference Example 13-Chloro-6-(2,6-diallylphenoxy)pyridazine 20 mL of dry toluene and 11.5 y of 2,6-diallylphenol were mixed with 1.5 f of metallic sodium, heated and stirred at 80°C for about 2 hours, After cooling, a solution of 9.83y of 3,6-dichloropyridazine dissolved in 20ml of toluene was added dropwise, and the mixture was stirred at room temperature for 1 hour and then at 75-80°C for 7 hours.

After stirring, pour the reaction mixture into 4 ml of sodium hydroxide solution.
Transfer it to a separation load with 0 mt and 10 ml of toluene, shake well, separate the toluene layer, wash with 40 ml each of sodium hydroxide solution and water, dry over anhydrous sodium sulfate, filter, and remove the solvent under reduced pressure. When the residue was distilled off, the desired product 15y was obtained as an oily substance. This product was dissolved in 5 ml of benzene and subjected to silica gel column chromatography (eluent: benzene ethyl diacetate 40:1) for fractional purification, yielding 12.9 y of the target compound as colorless needle-like crystals.
was gotten. Yield 68%. M. p. 63~63°C (reconsolidation solvent: n-hexane) Elemental analysis value (%) Cl6Hl5Cl
Calculated value C as N2O, 67. O3;H,5. l7;N
, 9.77 Experimental value C, 67. O5;H, 5.3l;N,
lO. O6 Reference Example 2 3-Iodo6-(2,6-dimethylphenoxy)pyridazine A mixture of 1.65y of 3,6-diiodopyridazine, 0.6y of 12,6-xylenol and 0.7y of anhydrous potassium carbonate was mixed with 5ml of dimethyl sulfoxide. , 90° C. for about 1 CBI.

After cooling, the reaction mixture was mixed with 20 ml of water and 40 ml of benzene.
The mixture was transferred to a separation load along with 1 and shaken well, and the benzene layer was separated, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was dissolved in a small amount of benzene and subjected to silica gel ◆ column chromatography (eluent: benzene) for fractional purification to obtain 0.6 fI of the target compound. Yield 37%M. p. l29~131℃ Elemental analysis value (%) Calculated value C as Cl2HlllN2O
,44. l9; H, 3.39; N, 8.58 experimental value C,
44.72; H, 3.43: N, 8.3O Reference Example 33-
Chloro 6-(2-n-butyl-6-methylphenoxy)pyridazine 3,6-dichloropyridazine 1.5y12
1.6y of -n-butyl-6-methylphenol and 0.69y of anhydrous potassium carbonate were heated and stirred on an oil bath at 160 to 170°C for 2 hours.

After cooling, add 30ml of sodium hydroxide solution to the reaction mixture.
1 was added, and the mixture was stirred for 2 hours. The precipitated crystals were collected, washed with water, and dried to obtain the target compound 1.9y. Yield 69%. M. p. 66~Seki °C (reconsolidation solvent; n-hexane) Elemental analysis value (%) Calculated value as Cl5H17CIN2O C, 65. lO; H, 6. l9; N, lO. l2;
Cl, l2.8l Experimental value C, 65.34; H, 6. l9; N, lO. 28:Cl, l2.86 The compound of the present invention can be mixed with a carrier and other adjuvants as necessary to form a formulation commonly used as an agricultural and horticultural fungicide, such as a powder, a coarse powder, a fine granule, or a granule. agent, hydrating agent,
It is prepared and used as an emulsion, aqueous solution, aqueous solution, oil suspension, etc.

The term "carrier" here refers to a synthetic compound that is mixed into agricultural and horticultural fungicides to help the active ingredient compound reach the area to be treated, and to facilitate the storage, transportation, or handling of the active ingredient compound. or any natural inorganic or organic substance. Suitable solid carriers include clays represented by ``kaolinite group, montmorillonite group, or attabulgite group, etc.'', talc, mica, phyllite, vermiyukilite, gypsum, calcium carbonate, dolomite, diatomaceous earth, and magnesium lime. , inorganic substances such as apatite, generalite, anhydrous silicic acid, synthetic calcium silicate, soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch powder,
Vegetable organic substances such as crystalline cellulose, coumaron resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, synthetic or natural polymer compounds such as ester gum, cobal gum, dammar gum, carnauba wax, beeswax, etc. Examples include waxes, urea, etc.

Suitable liquid carriers include paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene, carbon tetrachloride, chloroform, etc. , chlorinated hydrocarbons such as trichloroethylene, monochlorobenzene, and 0-chlorotoluene, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, and isoborone, ethyl acetate, amyl acetate, Ethylene glycol acetate, diethylene glycol acetate,
Esters such as dibutyl maleate and diethyl succinate, alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether,
Examples include ether alcohols such as diethylene glycol ethyl ether and diethylene glycol butyl ether, polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. emulsification, dispersion, wetting, spreading,
Surfactants used for the purposes of binding, adjusting disintegration, stabilizing active ingredients, improving fluidity, and preventing rust can be nonionic, anionic, cationic, or zwitterionic. Can be used, but usually non-ionic and/or
Anionic substances are used.

Suitable nonionic surfactants include, for example, those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol; those obtained by polymerizing and adding ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol; Products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol, products obtained by polymerizing and adding ethylene oxide to higher aliphatic acids such as palmitic acid, stearizic acid, and oleic acid, stearyl phosphoric acid, dilauryl phosphoric acid, etc. Those obtained by polymerizing and adding ethylene oxide to mono- or dialkyl phosphoric acid, those obtained by polymerizing and adding ethylene oxide to amines such as dodecylamine and stearic acid amide, and those obtained by polymerizing and adding ethylene oxide to higher aliphatic esters of polyhydric alcohols such as zorbitan. Examples include those obtained by polymerizing and adding ethylene oxide and propylene oxide. Suitable anionic surfactants include, for example, sodium lauryl sulfate, alkyl sulfate salts such as oleyl alcohol sulfate amine salts, sodium sulfosuccinate dioctyl ester, 2
- Alkyl sulfonates such as sodium ethylhexene sulfonate, sodium isopropylnaphthalene sulfonate, sodium methylene bisnaphthalene sulfonate,
Examples include arylsulfonates such as sodium ligninsulfonate and sodium dodecylbenzenesulfonate. In addition, the agricultural and horticultural fungicides of the present invention contain tin, gelatin, albumin, glue, sodium alginate, alkoxymethylcellulose, methylcellulose, hydroxyethylcellulose, polyvinyl alcohol, etc., in order to improve the properties of the preparation and increase its biological effects. Polymer compounds and other adjuvants can also be used in combination.

The above-mentioned carriers and various auxiliary agents are used individually or in combination as appropriate depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc.

For example, a powder usually contains 1 to 25 parts by weight of the active ingredient compound, with the remainder being a solid carrier.

Wettable powders, for example, usually contain 25 to 9 parts of the active ingredient compound, with the remainder being a solid carrier and a dispersing wetting agent, with protective colloid agents, thixotropic agents, antifoaming agents, etc. being added as necessary. . Granules, for example, usually contain 1 to 35 parts by weight of the active ingredient compound, with the remainder being mostly solid carrier.

Is the active ingredient compound homogeneously mixed with the solid carrier?
Alternatively, it is fixed or adsorbed uniformly on the surface of a solid carrier, and the particle size is about 0.2 to 1.5 wn. Emulsions, for example, usually contain 5 to 5 parts of the active ingredient compound, this includes about 5 to 2 parts of emulsifier, the remainder is a liquid carrier, and if necessary, a rust inhibitor is added. Added.

The agricultural and horticultural fungicides of the present invention prepared in various formulations in this way are sprayed on the leaves and foliage of crops before or after disease outbreaks in rice fields or fields, for example.
Or when treating the soil or water surface, 1 to 5000y of active ingredient per 1011, preferably 10 to 1
By casting 000y, diseases can be effectively controlled.

In addition, when the agricultural and horticultural fungicide of the present invention is used for seed treatment, for example, as a seed dressing, 0.1% to 2%, preferably 0.2 to 0.5%, of the active ingredient is added to the powder per seed weight. By covering the soil, soil or seed-borne diseases can be effectively controlled.

The agricultural and horticultural fungicide of the present invention is preferably blended with other agricultural and horticultural fungicides in order to broaden the bactericidal spectrum, and in some cases a synergistic effect can be expected.

Examples of such other agricultural and horticultural fungicides include, for example, 3,3゛-1ethylenebis(tetrahydro-4,6-dimethyl-2H-1,3,5-thiadiazine-2-thione; ethylenebisdithiocarbamate, zinc salt or manganese salt; bis(dimethyldithiocarbamoyl)disulfide; propylene bisdithiocarbamate, zinc salt;
Bis(dimethyldithiocarbamoyl)ethylenediamine; dimethyldithiocarbamate, nickel salt; methyl-1-(ω-cyanopentylcarbamoyl)-2-benzimidazole carbamate; methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate; 2-
(methoxycarbonylamino)-benzimidazole;
Carbamate fungicides such as 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene, 0,0-diisopropyl-S-benzylphosphorothioate; 0-
Phosphorous fungicides such as ethyl-S,S-diphenyldithiophosphate, N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, N-tetrachloroethylthio-4-cyclohexene-1,2-dicarboximide, etc. Dicarboximide fungicides, oxazine fungicides such as 5,6-dihythro-2-methyl-1,4-oxazine-3-carboxanilide 4,4-dioxide, 2
, 3-dichloro-1,4-naphthoquinone and other naphthoquinone fungicides, pentachloronitrobenzene; 3-hydroxy-5-methylisoxazole; 6-(3,5-dichloro-4-methylphenyl)-3(2H)pyridazinone; 6-(3-bromphenyl)-3(2H)pyridazinone; N-2,3-dichlorophenyltetrachlorophthalamic acid; 5-ethoxy-3-trichloromethyl-1,
2,4-thiadiazole; 2,4-dichloro6-(i)-chloroanilino)-1,3,5-triazine; 2,
3-dicyano-1,4-dithioanthraquinone; 8-oxyquinoline copper: polyoxine; validamycin; cycloheximide; methanarsonic acid iron salt; tetrachloroisophthalonitrile; 2-(1-methylpropyl)-4
,6-dinitrophenyl β,β-dimethylacrylate di2-(4-thiazolyl)-benzimidazole; triphenyltin hydroxide lipolyoxin lihumanycin; kasugamycin; plasticidin S; 4,
Examples include, but are not limited to, disinfectants such as 5,6,7-tetrachlorophthalide. The agricultural and horticultural fungicides of the present invention can also be used in combination with plant growth regulators, herbicides or insecticides.

The drugs that can be combined with the fungicide of the present invention as a simultaneous control agent are as described above. The amount to be blended varies depending on the target to be controlled and the formulation form, and is adjusted to contain the amount of active ingredient required for pest control. Dusts, fine granules and fine granules F are particularly suitable for rice disease damage and soil treatment. Examples of formulations of the agricultural and horticultural fungicide of the present invention are given below.

In the text, all parts simply refer to parts by weight. Formulation Example 1 Powder 5 parts of compound No. 11, talc stamped part, 4 parts of kaolin
Five parts were uniformly mixed to obtain a powder.

Formulation Example 2 Wettable powder Compound (branch) part of compound number 16, clay 2? , w parts of diatomaceous earth, 5 parts of white carbon, 3 parts of sodium ligninsulfonate, 2 parts of Nucor 1106 (trade name of Nippon Nyukazai Co., Ltd.) and 1 part of polyvinyl alcohol were mixed uniformly in a mixer, and then mixed in a hammer mill. The powder was crushed three times to obtain a wettable powder.

Formulation Example 3 Granule Compound No. 1 Compound 7 was finely ground, and 9 parts of clay were added thereto and mixed in a mixer to prepare a premix.

Part W of this premix was uniformly mixed with 6 parts clay and 3 parts bentonite in a mixer. Add an appropriate amount of water to this material, knead it in a kneader, and make a diameter of 0.8 Tfr.
The mixture was extruded through a 50° C. screen and dried in a ventilation dryer at 50°C. This product was sized using a sifter to obtain granules. Examples of the agricultural and horticultural fungicide of the present invention prepared in this way are given below. The test drug was manufactured according to Formulation Example 2, and a wettable powder containing 50% of the active ingredient compound of the present invention was used. Test Example 1 Agar dilution method Each test compound was mixed in a PDA medium to a predetermined concentration, and the mixture was poured into a shear dish with a diameter of 7 d and solidified.

Afterwards, Strawberry Botrytiscine (BOtrytiscine)
rea), CercOspOraT
icOla) or pear scab fungus (Venturiar).
lashi-COla) was inoculated and cultured under the following conditions, and then the minimum growth inhibitory concentration was investigated.

Strawberry gray mold fungus; 2rC, 5 days Heat brown spot fungus; 27℃, 7 days Pear scab fungus; 20℃, 10 days The results are shown in Table 1.

Test Example 2 Chicumber Powdery Mildew Control Test Two cucumber seedlings (variety: Sagami Hanshiro) were transplanted into pots with a diameter of 12 crn, and when the first true leaves had completely developed, cucumber powdery mildew had already developed. Sphaer Othecafull can be detected using a brush from a cucumber leaf.
ginea) was dropped and inoculated.

After storing at a temperature of 24-26° C. for 3 days, a hydrated suspension of the test compound at a concentration of 500 ppm was sprayed at 20 ml per 3 pots per treatment, and after air-drying for several hours, they were stored again in a greenhouse for 7 days. The results were calculated as the diseased area rate. There were 3 pots in each ward, and the average values are shown in Table 2.

Test Example 3 Juicy Botrytis Botrytis Disease Control Test Young cucumber fruits (variety: Sagami Hanjiro) with no disease symptoms other than Botrytis spores observed on the flowers were collected from a plastic greenhouse where Botrytis botrytis disease had occurred. The sample was then immersed in a hydrated suspension of the test compound at a concentration of 500 ppm for 5 seconds, then taken out and air-dried.

After being left in a humid room at 20°C for 10 days, the degree of disease onset on the fruit was investigated.

−: No or almost no mycelium is observed on the fruit surface +: Mycelia are spread over 10% to 30% of the fruit surface Test Example 4 Rice shingles disease control test 500 powder 1 Earl Wagner Rice (variety: Kinnanfu) cultivated in pots at the stage of flag leaf development was spray-inoculated with a suspension of XanthOmOnasOryzae, which had been cultured in advance, and placed indoors at a temperature of 26-28℃ and a relative humidity of 100%. I left it there for a day and night.

Thereafter, they were transferred to a greenhouse at 28°C. Three days after inoculation, a test drug solution having an active ingredient concentration of 100 ppm was sprayed onto each pot in an area of 20 ml. In the investigation, the lesion area ratio was determined with respect to the leaf area of the flag leaf and the next leaf 20 days after the chemical treatment. There were 3 pots in each ward, and the average values are shown in Table 4.

Test Example 5 Rice blast control test 300,10 ml was applied to 3- to 4-leaf stage rice seedlings (variety: Norin No. 20) planted in pots with a diameter of 10 cTn in 3 pots.
After spraying 0 ppm test chemical solution and air drying, the rice blast fungus (P
yricularia Oryzae) was spray inoculated and left in a room with a temperature of 20 to 27C and 100% humidity for 48 hours.

The test plants were then transferred to a greenhouse at 24 to 26°C, and the number of lesions was investigated on the top two leaves of the test plants three days later. Table 5 shows the average number of lesions per leaf with three consecutive plots.

Claims (1)

[Claims] Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X represents a halogen atom, R_1 and R_2
both represent a lower alkyl group or a lower alkenyl group, or one represents a lower alkyl group and the other represents a halogen atom. ) is an agricultural and horticultural fungicide whose active ingredient is a compound having