JPS60100581A - Pyrazolo(1,5-a)pyrimidine derivative, agricultural and horticultural fungicide containing the same, and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formula 1 (R1 is H or 1-4C alkyl; R2 and R3 are H, 1-4C alkyl, aralkyl, cycloalkyl, phenyl, etc. or R2 and R3 together form a carbon ring or an O-containing carbon ring; X is H, Cl or Br). EXAMPLE:7-Amino-2-t-butyl-6-ethoxycarbonylpyrazolo[1,5-a]pyrimidine. USE:Fungicide for agricultural and horticultural use. It exhibits fungicidal effect specifically to the powdery mildew of cereal, vegetable, fruit tree and flower, etc. PREPARATION:The compound of formula 4 can be produced by reacting 3- amino-4-t-butylpyrazole of formula 2 with the cyanoacetic acid ester derivative of formula 3 (R4 is methyl or ethyl) in a solvent such as methanol or in the absence of solvent, under acidic condition at room temperature -150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized by novel pyrazolo(1,5-a)pyrimidine derivatives represented by the following general formula (1), methods for producing them, and containing them as active ingredients. This article relates to agricultural fungicides.

λ (1) [In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. , aralkyl group, sialkylaminoalkyl group,
In addition, I/'J represents a phenyl group (11' may be substituted with a chlorine atom, a methoxy group, or a methyl group), and in some cases, rc2 and R3 represent a carbon ring or a carbon ring containing an oxygen atom. It may form a ring. Furthermore, X represents a hydrogen atom, a chlorine atom, or a bromine atom.] In addition, when at least one of R2 or R3, for example, R2, is a hydrogen atom, the present compound can also be used as a tautomer as shown below. Can be displayed.

[In the formula, R1e R5e X is as above] Conventionally, 6-alkoxycarginyl-7-amino- or 6-
Alkoxycarbonyl-7-substituted 7 minobirazolo (1
, 5-a) Pyrimidine derivatives are known as medicines or synthetic intermediates.

For example, Special Publication No. 37-7982, Special Publication No. 8-8 Sho.
No. 556 describes it as a pharmaceutical, a 777 agent, an n-forming intermediate, and a stabilizer for photographic emulsifiers. The effect on &J posboesterase enzyme and the ability to induce positive muscle inotropic effect are described in the Japanese Patent Publication No. 48-64097. However, in these documents, there is no mention of agricultural fungicides in TV1, and moreover, there is no mention of agricultural fungicides, and moreover, there is no mention of agricultural fungicides, and moreover, there is no mention of a chemical compound in which a butyl group (L-butyl) is inserted at the 2nd position (19). There is no j.

Recognizing that protecting crops from diseases is an important issue in terms of yield stabilization, quality maintenance, and yield increase, the 111 people (111) have set their sights on developing new agricultural and horticultural fungicides. , pyrazolo L l+5-+t ]pyrimidine derivatives were synthesized and extensively screened.As a result, the compound represented by the general formula (1) was found to be a new substance, and moreover, it was found that the compound represented by the above-mentioned general formula (1) was a novel substance, and was also used as a farm J' bifurcated fungicide. As a result, the present inventors have discovered that the kernels contain bactericidal activity and act specifically against powdery mildew of grains, vegetables, fruit trees, flowers, and moths, and have accomplished the present invention.

The general method for preparing compounds according to the invention is illustrated in connection with the following scheme.

Reaction scheme I (2) (3) (4) [In the formula, X is as described above, R1 represents an alkyl group having 1 to 4 carbon atoms, and R4 represents a methyl group or an ethyl group] [Formula Medium %R1#i represents an alkyl group having 1 to 4 carbon atoms, R2e R5# R4 and X are as defined above] Reaction Scheme 3 [In the formula, R1 represents an alkyl group having 1 to 4 carbon atoms, R2z R5 and X are as above)] reacted 1
Formula 4 X a [In the formula, or represents a chlorine atom or a bromine atom, R-1
represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 are 6! Reaction Scheme 5 (9) [In the formula, X represents a hydrogen atom, a chlorine atom, or a bromine atom, R1 represents an alkyl group having 1 to 4 carbon atoms, and R
2 and R5 are as described above] In reaction scheme 1, the target product (4) is obtained by heating the raw materials (2) and (3) in a solvent or in the absence of a solvent. This reaction is preferably carried out under acidic conditions, but under mild conditions, especially in a neutral medium, the intermediate 01 (wherein R1 represents an argyl group having 1 to 4 carbon atoms) is After fermentation, it may be heated under heavy conditions, or it may be carried out in the presence of an alkali such as sodium alkoxide.The reaction medium is preferably a lower alcohol M such as methanol or ethanol, or a tip acid. etc., but other organic non-reactive solvents may be appropriately selected and used.

In addition, in order to make the reaction system acidic, mineral acids such as hydrochloric acid and sulfuric acid, and right-wall (':T) such as acetic acid are used.

The reaction temperature is from room temperature to 150°C, preferably 70°C.
℃ to 120℃. (3) for raw material (2)
The molar ratio used is from 0.5 to 2, preferably from 0.9 to 1.1. The molar ratio of the acid or alkali added to the raw material (2) is from 0.1 to 10, preferably from 0.5 to 2.

In reaction scheme 2, the synthetic intermediate (6) is produced by heating the raw materials (2) and (5) in a solvent or without a solvent.
) is obtained. The reaction solvent used herein is preferably methanol, lower alcohols such as ethanol, acetic acid, etc., but may be appropriately selected from other organic non-reactive solvents.

The reaction is accelerated by adding an acid such as a mineral acid such as hydrochloric acid or sulfuric acid, an organic acid such as acetic acid, or an alkali such as thorium alkoxide. The reaction temperature ranges from room temperature to 1
The temperature is 50°C, preferably 70°C to 120°C. The molar ratio of (5) to raw material (2) is from 0.05 to 2, preferably from 0.09 to 1.1. The molar ratio of the acid or alkali added to the raw material (2) is from 0.1 to 10, preferably from 0.5 to 2.

Synthetic intermediate (6) is heated to reflux with excess phosphorus chloride in the presence of a tertiary amine such as N,N-dimethylaniline to form synthetic intermediate (7). The amount of the tertiary amine used in this reaction is from equimolar to 10 times the mole of (6), preferably from equimolar to twice mole.

Synthetic intermediate (7) can be easily nuclear-substituted with various amines (8) in a solvent or in the presence of a base without dissolving Q'5, to obtain the target product (9). As the base used in this nuclear substitution reaction, a primary:S class amine such as J-ethylamine, pyridino, N,N-noethylaniline, or the reaction reagent (8) itself can be used. The reaction temperature is from -1°C to 150°C, preferably from 0°C to 12'OC.
It is. As the reaction solvent, lower alcohols such as methanol, ethanol, J chloromethane, chloroform, carbon tetrachloride, etc. are preferably used, but other organic non-reactive solvents may be appropriately selected and used. good.

In reaction scheme 3, the target product Qt) can be easily obtained by hydrolyzing (9) with an acid or an alkali. As the acid, 10% to 25% hydrochloric acid or an aqueous solution of a mineral acid having a similar acidity is used. As the alkali, 5% to 25% sodium hydroxide aqueous solution,
Or the same amount of salt 2! An alkaline aqueous solution with a specific temperature is used. In some cases, lower alcohols such as methanol and ethanol can be used as a solvent together with an acid or alkali aqueous solution. The temperature is preferably up to the reflux temperature of the solvent.

By reacting reaction scheme 4 (01) with a halocane-forming agent in a solvent, the target product (1→) can be obtained. As a logging agent, chlorine and sulfuryl chloride are used for the chlorination reaction. , N-chlorosuccinimide, etc. In addition, bromine, N-bromosuccinimide, etc. can be used for the bromination reaction.

The reaction solvent can be appropriately selected from solvents commonly used in halodanization reactions, and preference is given to non-alkanes such as carbon tetrachloride. The reaction temperature is -10
C to 150 C, preferably from 0 C to the reflux temperature of the solvent used.

In reaction scheme 5, (II is reacted with the alcohol (R, -oH) to be esterified in the presence of a suitable acid catalyst or dehydration condensation agent to obtain c10-like product (9).

As the acid catalyst, anhydrous hydrogen chloride, trifluoroboron ethyla-1, etc. are used, and dehydration condensing agents such as cyclohexylcal, lζneumit' (occ), etc. are used. Reaction temperature &: J: 0°C to 100°C, preferably t; 1 chamber i'! lagara 1201:
That's it.

Typical examples of the compounds of the present invention are listed in Tables 1 and 2, for example. In addition, the compound jrf-"i in the table is also referred to in the following synthesis examples, examples, and test examples. In the table, the properties indicate the properties at room temperature, and the melting point (mp) is
The value was determined to be 1lllJ using the rt Kofler hot vent, but it is an uncorrected value. The infrared absorption spectrum (IR) is
It + j was determined using a single spectrometer A-102 type infrared spectrophotometer,
This shows the characteristic absorption value due to the stretching vibration of the carbonyl group.

The refractive index (no) is a value determined by in+1 at Atago ABC #Ii folding. Further, the nuclear magnetic resonance spectrum (NMR) was measured using a JASCO JMN-FX200 model nuclear magnetic resonance spectrophotometer, using butramethylsilane as an internal standard, and expressed as a ppm value. The number within 0 is the solvent.

S.

d, t, q Jm and br indicate - doublet, doublet, triplet, quadruplet, multiplet, and broad line, respectively, and J
indicates the Cunnoling constant.

Next, a specific example of the method of manufacturing j'+r p=k in the present invention will be shown.

Synthesis Example 1 7-amino-2-t-butyl-(j-ethquinylbenylbi2)[L5a]bipyrimidine compound 1]3-
Amino-5-tert-butylpyrazole 50.69 was dissolved in ice vinegar in 200 mVCWj' and room iiu'h''C
i-i',c Stir'-F Ethyl ethquine methylene/anoacetic acid ti 2.3 y is added in portions. After addition,
Heating under reflux? 11,141 questions were performed, and the solvent was distilled off under reduced pressure. Pour out water to collect the precipitated crude crystals and wash thoroughly with water. Recrystallization of this t'LL product from aqueous ethanol yields Compound 1 (82.39%).

Synthesis Example 2 2, -t-Butyl-7-dimethylamino-6-ethoxycarponylpyrazooCl+5'']pi') Methane (Compound 2) 3-Amino-5-t-butylbidisole 65.09 Dissolve in 200 ml of glacial acetic acid and add dropwise at room temperature to 100 g of ethyl ethoxymethylene malonate over a total of 20 minutes. Stir at room temperature for 30 minutes after the dropwise addition, then heat to reflux. Do this for 2 hours. From now on, collect the precipitated crude crystals and wash them with water and cyclohexane in that order. Heat and dry under reduced pressure to obtain 2-t-gyl-
6-ethoxycarbonyl-7-hydroxypyrazolo[1
,5-a]pyrimidine 9 (3,4g v, q4). 500 ml of phosphorus oxychloride and 55 ml of N,N-diethylaniline were added to 52.79 ml of the obtained 7-hydroxy compound.
Add m1 and heat to reflux with stirring at a temperature of 1/11, 1:1]. Excess phosphorus oxychloride is distilled off under reduced pressure, 70. Add 200r++6 dichloromethane to the sticky residue and pour into 800g of crushed ice while stirring thoroughly. The dichloromethane layer is separated and the aqueous layer is extracted with nochloromethane 1c) Ornl. The obtained dichloromethane layer is washed with cold water, a saturated aqueous solution of sodium bicarbonate, and cold water in this order. After drying with calcium chloride (anhydrous), the solvent was distilled off under reduced pressure to give 2-t-butyl-7-chloro-6-ethoxycarginylbisizolo (
1,5-a) 75 g of syrup containing pyrivadine as the main component are obtained. This 7-chloro compound is subjected to the next reaction without being purified. Shi IJ containing 10 mmol of 7-chloro form, 8 liquids of 7° absolute ethanol 20 mef:
The mixture was added to a solution of 10 ml of anhydrous ethanol containing 1,0 g of anhydrous dimethylamine in a room temperature, and stirred for 2 hours. After the reaction, ethanol is distilled off under reduced pressure, dichloromethane is added, and the mixture is washed with water, o, 5N hydrochloric acid, and water in this order. After removing the solvent 1)'1, the crude compound 2 obtained was purified by silica gel column chromatography using a solvent system of toluene/ethyl acetate (3:1) to give a viscous oil. Target compound 2
is obtained as 2.4I.

Synthesis Example 3 7-Amino-2-L-butyl-6-carpoquinpiragro C1,,5-a) Pyrimidine (Compound 3) Synthesis 1 In Example 1? 4) Sodium hydroxide 0 to the compound l 2.69
．． Contains 5g/Water 211I/! Add a solution of 10 me of ethanol and add it for 2 hours.
I'x come on. When ethanol is distilled off from the reaction solution under reduced pressure in a pot and acidified with acetic acid, crystals precipitate out. When this crystal is separated from F and recrystallized from aqueous ethanol, the target compound 3 is obtained with 2.1. ．． 9 obtained.

Synthesis example 4! 1* l 4 ) In Synthesis Example 2? 2-t-butyl-7-chloro-6
-Ethoxycarpa? Nil e lagro [knee 1.5-a]
Anhydrous ethanol containing 10 mmol of pyrimidine (20 ml of combined solution, 0.939 ml of aniline, 1.19 K of triethylamine) was added, stirred at room temperature for 1 hour, and then heated under reflux for 2 hours. After the reaction, the solvent was distilled off under reduced pressure and Chloroform and water are added to the resulting residue, the chloroform layer is separated, and the chloroform layer is washed in this order with water, 0.5N hydrochloric acid, IN aqueous sodium carbonate solution, and water.After drying with Glauber's salt, the solvent is distilled off. The resulting residue is purified by florinol column chromatography using dichloromethane as a solvent to obtain 3.5!9 of the target compound 14 as crystals.

Synthesis Example 5 2-t-butyl-7-methylamino-6-ethoxy/cardanylvirazolo[1,5-+I J li' liminone (
7) Synthesis Example 2 4tc)
,] 20 ml of 6 solutions of 5-chloromethane containing 1 () mmol of pyrimidine was cooled in an ice-water bath, and the mixture was cooled in an ice water bath.
IS1. Gara, 10th grade methylamine suiseki (iri, 2(
) After addition, the reaction LQt is 1:11' and the room temperature is 811.'H.
＋ l'd j'; - After leaving it overnight,
Add λ to water, add 1] I] Separate the mekun layer, and wash with water 7? cormorant. C', :jlI'I'+'4 dry (il,)
Purification is carried out in the order of U-lysolnonomchroma 1'' roughy and silica gel chromatography to yield the target compound 7 as white crystals.

Synthesis Example 6 n-Butyl 7-amino-Q-1-pf nobi-pyrazolo[-1,5-a)pyrimidine-6-cal,+4xylene±(chemical-combination-40) 3-amino-5 -t-butyl bisizole in 20 m glacial acetic acid
52 g of n-butylethoxymethylenecyanoacetic acid was added to the solution under stirring at room temperature. After the instruction, the mixture was heated under reflux for 3 hours, and the solvent was distilled off under reduced pressure. Pour ice water over the residue, collect the precipitated crude crystals, and wash thoroughly with water. The crude crystals are recrystallized from aqueous ethanol to obtain 6.8 g of the target compound 20.

Synthesis Example 7 E1-Xical+1? Nilhilasoro C 115---
-a]-e. IJ amine (compound 23) 7-amino-2-t-phthyl-6-nitoquinocarbonylpyrasolo[1.5-a]biIJ obtained by Synthesis Example 1
6.6 g of methane (compound 1) was mixed with 60 m of carbon tetrachloride.
1, and stir a solution of sulfuryl chloride 349 in 10 ml of carbon tetrachloride for 15 minutes while stirring at room temperature, and after stirring, continue stirring at room temperature for 2 hours.

゛After the reaction, add an aqueous sodium hydrogen carbonate solution to neutralize. After extraction with dichloromethane, wash with water and remove the solvent.

Synthesis Example 8 7-ami2:3-bromo 2-L-dityl-6-ethyl d? Nilpyrazoo C1.5-a:]
Pipyrimidine compound 24): 3-amino-5-t-butylbisizole 13.9g
was dissolved in 3Qm6 of acetic acid, and bromine]. 6. Add acetic acid 2Qme G solution containing 3 and 9/1:☆ over 2 hours. After the lesson, 611,'j
Stir for 1 minute to complete the reaction.
Add dichloromethane to the removed P solution, wash with water, 10% carbonic acid aqueous solution, and water in that order. After drying with Glauber's salt,
When treated with linolcadim chromatography,
J67g as 3-amino-4-bromo-5-t-butylvirazolka crystalline material? 4) Rari, ru. Nuclear magnetism of this material +11, spectrum (weight I: I horno・
solvent, tetramethyl 7 run internal standard) was 0 11 pm
From 9 ppm''i., there is only a singlet at 1.358 ppm.

When 2.29 of the above 3-'amitsu-4-butylbidizole and 1.7 g of ethyl ethoxymethylene cyanoacetic acid were reacted in the same manner as in Synthesis Example 1, the target compound 24 was obtained. 2.2g is obtained.

Synthesis Example 9 7-Amino-2-obtained in Synthesis Example 3 was converted into -butyl-
6-Cal? A mixture of xypyrazolo[1,5-a:] biviridinone 4.8 and n-70 lonoyanor 3.09nitrifluoro? 11.3.9 was added little by little, stirred at room temperature for 1 hour, and then heated under reflux for 3 hours. The reaction mixture was basified with 10% aqueous sodium carbonate while cooling in a water bath. After drying, extract with dichloromethane, wash with dichloromethane and water in that order, and dry with sodium sulfate.

The solvent was distilled off under reduced pressure, and the resulting crude crystals were mixed with cyclohexane.
When recrystallized from ethanol, the target compound 19 was obtained as white crystals as 1. 8,9 can be obtained.

Synthesis Example 10 Rubonylpyrazolo[1,5-a:]pyrimidine (Compound 1) While stirring a solution of 3.2 g of ethylmethoxymethylenecyanoacetic acid in 10 ml of ethanol at room temperature, 2.8 g of 3-amino-5-t-butylpyrazole was added. .9 ethanol 5
Instruct me solution. After instruction, continue stirring at room temperature for 3 hours. - After leaving the room for a long time, the precipitated crystals were collected, washed with cold ethanol, and then dried to give α-(5-E-butylpyrazol-3-yl)amino 3.0.9 ethyl methylene-cyanoacetate is obtained.

NMR (CDCt5 solvent, 'l'Ms internal standard'-)p
pm1.34 (9H, s): 1. :36(:eye 1.L
, J=7Hz);4.3Q(2H,q,J=7H
z);5. ! 1(i(LH,s):8.28(IH
,d,J=,1.51. Iy, ) ; l −
IJ 1. (L H, brs); 11.75 (11-
1, d, J = 1511z); 2.0 g of the above α-(5-L-butylbisizol-3-yl)aminomethyl/-/anoacetate was heated under reflux in 10 me of acetic acid for 15 minutes.
The procedure was repeated in the same manner as in Synthesis Example 1 to obtain 1.5.9% of Compound 1.

As mentioned above, the compound of the present invention represented by the general formula (1) has a good bactericidal effect, does not cause damage to host plants,
Shows therapeutic and protective effects against plant diseases.

The applicable crops and diseases are shown in Table 3, for example.

Table 3: The compounds of 411-411 and, if necessary, mixed with other adjuvants, can be prepared in the formulations commonly used as agricultural fungicides, such as powders, coarse powders, etc. It is prepared and used in powders, fine granules, granules, wettable powders, emulsions, aqueous solutions, aqueous solutions, oil suspensions, etc.The J-type used here is:
Synthetic or natural inorganic or organic compounds mixed into agricultural and horticultural fungicides to aid in the access of the active ingredient to the area to be treated and to facilitate storage, transport or handling of the active ingredient. means substance.

Suitable solid carriers include clays represented by kaolinite group, montmorillonite group, or Akparnoite group, etc., talc, cloud 1, phyllite, pumice, burmy chirite, gypsum, calcium carbonate, and dolomite. , diatomite, magnesium lime, alamite, zeolite,
Inorganic substances such as silicic anhydride, synthetic calcium/umium silicate, soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch,
Vegetable organic substances such as crystalline cellulose, tamaron resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, copal g
synthetic or natural polymeric compounds such as gum, dammargum, etc.
Examples include waxes such as carnauba wax and beeswax, and urea.

Suitable liquid carriers include paraffinic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene, and carbon tetrachloride. , chlorinated hydrocarbons such as chloroform, trichloroethylene, monochlorobenzene, 0-chlorotoluene, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, soybutyl ketone, cyclohexanone, acetophenone, isophorone, ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate,
esters such as dibutyl maleate and diethyl phosphate; a) L/N-al such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, and benzyl alcohol;
x Ether alcohols such as tylendarylcol ethyl ether, ethylene glycol phenylconisol glycol ethyl ether, noethylene glycol phthyl ether, polar solvents such as trimethylformamide and tunotyl sulfoxide, or water.ノ'Lru.

Surfactants used for the purposes of emulsification, dispersion, wetting, spreading, adjusting bond disintegration, stabilizing active ingredients, improving fluidity, preventing A'7, etc. are nonionic, anionic, and cationic. Although both polar and zwitterionic gold can be used, nonionic and/or anionic golds are usually used. Suitable Jl ionic surfactants include, for example, lauryl alcohol, stearyl alcohol,
Products obtained by polymerizing and adding ethylene oxy 1'' to higher alcohols such as oleyl alcohol, products obtained by polymerizing and adding ethylene oxide to alkylphenols such as inoctylphenol, and products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as gutylnaphthol and octylnaphthol.・・Products obtained by polymerizing and adding ethylene oxide to higher fatty acids such as glumitic acid, stearic acid, and oleic acid; products obtained by polymerizing and adding ethylene oxide to mono- or dialkyl succinic acids such as stearic acid, nolauryl succinic acid, etc.; Products obtained by polymerizing and adding ethylene oxide to amines such as dodecylamine and stearic acid amide, products obtained by polymerizing and adding ethylene oxide to higher fatty acid esters of polyhydric alcohols such as Nrubikun, and products obtained by polymerizing and adding ethylene oxide and propylene oxide. Examples of suitable anionic surfactants include alkyl sulfate ester salts such as Rau IJ/strium sulfate, oleyl alcohol amine salt, sodium sulfosuccinate nooctyl ester, and 2-ethylhexene sulfone. Examples include sodium alkyl sulfonate such as sodium acid, sodium methylene bisnaphthalene sulfonate, sodium lignin sulfonate, sodium dodecylbenzene sulfonate, and the like.

Furthermore, for the purpose of improving the properties of the agricultural and horticultural fungicide formulation of the present invention and increasing its biological effect, casein, gelatin,
albumin/, glue, sodium alginate, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose N'I? ) Polymer compounds such as vinyl alcohol and other adjuvants can also be used in combination.

The above-mentioned carrier and various adjuvants are in the dosage form of IIj'j agent,
"Application" Considering the hot water level etc., depending on the purpose
'jUse alone or in combination as appropriate.

For example, is the powder the active ingredient compound? c, i+1 usually contains 1 to 25 parts by weight, and the remainder is a solid carrier.

Hydrating agents usually contain 25 to 30% of the active ingredient compound, for example.
Contains parts by weight, remaining fS1 liquid solid carrier, dispersion wetting agent, protection = loid agent, chicken trope agent, antifoaming agent may be added as required.

Granules, for example, usually contain 1 to 35 parts by weight of the active ingredient compound, with the remainder being mostly solid carrier. The active ingredient compound is uniformly mixed with the solid carrier, or is uniformly fixed or adsorbed on the surface of the solid body.9
The diameter of the particles is approximately 0.2 to 1.5 mm.

Emulsions, for example, usually contain 5 to 50 parts by weight of the active ingredient compound, including approximately 5 to 20 parts by weight of an emulsifier, the remainder being a liquid carrier, and optionally a rust preventive agent. agent is added.

The agricultural and horticultural fungicides of the present invention prepared in various dosage forms in this way are sprayed on the leaves and foliage of crops before or after disease outbreaks in rice fields or fields, for example.
When applied to the soil or water surface, diseases can be effectively controlled by applying 10 to 5000 g, preferably 100 to 2000 g, of the active ingredient per 10 acres.

In addition, when the agricultural and horticultural fungicide of the present invention is used as a seed treatment or seed dressing, the active ingredient in the seed form should be 0.1% to 2%, preferably 0.2% to 2%. ~0,
By applying 5% powder, soil or seed-borne diseases can be effectively controlled.

It is preferable that the agricultural and horticultural fungicide of the present invention be blended with other agricultural and horticultural fungicides in order to spread the germicidal spray, and in some cases, mutual effects can be expected.

The agricultural and horticultural fungicides of the present invention can be used in combination with plant growth regulators, herbicides, insecticides, or fertilizers.

Examples of formulations of the agricultural and horticultural fungicide of the present invention are listed below.

In the sentence, -'li is all in the middle: 11th part -lx
;7:3, Taste.

Formulation example 1. Powder Compound No. 2 compound 5 parts, talc 50 parts, Kaori 74
Mix 5 parts evenly and make a powder! It was.

Formulation example 2. Wettable powder compound number 7 compound 5 () parts, clay 29 parts, diatomaceous earth 10 parts, white car +1? 5 parts of sodium lignin sulfonate, 3 parts of sodium ligninsulfonate, 2 parts of Ni=+-L 110G (trade name of Nippon Nyukazai Co., Ltd.) and 1? 1 part of ribinyl alcohol was mixed uniformly in a mixer and ground three times in a hummer mill to obtain a water 7+1 agent.

Formulation Example 39 Granules 70 parts of Compound No. 14 was finely ground, and 30 parts of clay was added thereto and mixed in a mixer to obtain a premix. 10 parts of this premix were homogeneously mixed in a mixer with 60 parts of clay and 30 parts of bentonite. Add an appropriate amount of water to this mixture, knead it in a nigu,
It was extruded through a goo clean with a diameter of 0.8 mm and dried in a ventilation dryer at 50°C. This product was sized using a sifter to obtain granules.

Formulation example 4. 5 parts of emulsion compound number 21, month? 10 parts of polyethylene glycol ether surfactant, 4 parts of n-79 tanol
5 parts and 40 parts of xylene were thoroughly mixed to obtain an emulsion.

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.

The following compounds were used as known comparatively effective substances for the following tests.

S,S -6-Methylquinoxaline-2,3-diylcysothiocasenate (Molestan) C5,6,7-titrachlorophthalide (Rubside) Twinzolopyl 1,3-sothiolane-23-ylidene-malonate ( 7 no one) Also, Japanese patents (Special Publication No. 182, No. 182, No. 182)
In order to compare the bactericidal effect between the known compound described in No. 0-8556) and the compound of the present invention, all of the following compounds were used.

7-amino-6-ethoxycala IS nilpyrazolo[1
,,5-a]pyrimidine (compound A) 7-amine-6-
Ethical+l! Nyl-2-methylpyrazolo[1,5
-a) Pyrimidine (Compound B) Test Example 1 Rice blast control effect test <Method> Raw in a clay pot with a diameter of 15 crn (-r Sazeda: 3,!'l
°・, season rice (variety: Jukoku) with szorecan, 5
(2001/1. Oa equivalent of a chemical solution diluted to 10 ppm) was sprayed and air-dried in a greenhouse. After air-drying, the blast fungus was adjusted to have 50 conidia per field of view under a 100x microscope ( Pyricularia ory
zae) was inoculated by spraying with a spore suspension. Immediately after inoculation, the plants were kept under greenhouse conditions at a temperature of 23° C. and a humidity of 100 cm for 2 days, and then left in a greenhouse for 8 days, and the degree of disease onset on the third leaves of 940 leaves per pot was investigated according to the following investigation criteria. However, the number of rows was set to 3, and 120 leaves were investigated.

Test Example 2 Test method for controlling efficacy of canine root chlorosis
porumf, raphani) was packed in a clay pot with a diameter of 15 Crn, and radish seeds (variety:
15 seeds of Aokubi Miyashige) were sown per pot, and the soil was covered with field soil that had been contaminated with the radish yellowing fungus. After lightly and evenly applying water to the surface, apply 3 of the chemical solution adjusted to 500 Ppm.
An amount equivalent to 1/η was uniformly irrigated over the surface. After rinsing,
After being left undisturbed for a while, it was placed in a greenhouse. After leaf development, the plants were thinned to 10 plants per pot. During the test period, the number of trees withered and browned ducts was examined after 60 days of treatment. However, the number of series was 5 and 50 stocks were investigated.

Test Example 3 Powdery Mildew Control Efficacy Test (1) <Method> Five seeds of Kiyuushi (variety: Sagami Hanshiro) that had sprouted in advance were sown in clay pots with a diameter of 15 mm (5 seeds per pot). 200% of the chemical solution diluted to 125 ppm with a spray gun at the first leaf stage.
An amount equivalent to 1 J/10 a was sprayed. After air drying, cucumber powdery mildew fungus (Spbaerothecafulig)
inea) conidia were uniformly inoculated. After inoculation, the plants were left in a greenhouse, and 12 days after inoculation, the number of lesions that appeared on the first leaves was investigated.

However, the number of rows was 3 and 15 leaves were investigated.

<Results> Test Example 4 Powdery Mildew Control Efficacy Test (2) <Method> Five pre-sprouted cucumber seeds (variety: Kumikaku Hanshiro) were sown in a clay pot with a diameter of 15 cIn. 2 of the chemical solution diluted to 62.5 ppm with a spray gun at the first leaf stage.
001/10a A considerable amount was sprayed. After air drying, cucumber udon and disease bacteria (Sphaerothecafuligi)
nea ) conidia were lightly inoculated evenly. After inoculation, the plants were left indoors, and the number of lesions that appeared on the first leaf was investigated 12 days after inoculation. However, the number of rows was 3 and 15 leaves were investigated.

Results〉 Test Example 5 Kyusha powdery mildew control effect test (Blade <Method> Kyusha seeds (variety: Kumkei Hanshiro) that had sprouted in advance in a clay pot with a diameter of 15 crn (5 seeds per L-pot were sown) When the first true leaves are developing, spray powdery mildew fungus (5phaerotheca fuliginea) evenly with a spray gun.
Conidia were spray inoculated. After inoculation, the plants were kept indoors until lesions were formed, and then a sufficient amount of a drug solution diluted to 125 ppm was sprayed using a spray gun. After air-drying, the plants were left in a greenhouse, and 10 days after the chemical solution was applied, the lesions on the first true leaves were examined for species. However, the number of rows was 3 and 15 leaves were investigated.

<Results> Continued from page 1 0 Inventor Hidetsugu Yokoyo Tamagawa, Ota-ku, Tokyo
Niss Bioterra 2-24-25 Niss Dik Tokyo Research Institute

Claims (1)

[Claims] l) Formula [In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 and lζ5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. represents a group, a cycloalkyl group, an aralkyl group, a noalkylaminoalkyl group, or a phenyl group (which may be substituted with a chlorine atom, a methoxy group, or a methyl group), and in some cases R2 and R5 represent carbon X represents a hydrogen atom, a chlorine atom, or a bromine atom. ] Pyrazolo [1,5-a
] Pyrimidine conductor 2) Formula [wherein, X represents a hydrogen atom, a chlorine atom, or a bromine atom]. ] 3-Amino-4-t-gutylpyrazole represented by the formula (wherein R1 represents an alkyl group having 1 to 4 carbon atoms, R4 represents a methyl group or an ethyl group, and or a bromine atom] is reacted with a cyanoacetic acid ester derivative represented by a represents a chlorine atom or a bromine atom.] pyrazolo[1,5-a)pyrimidine Mi represented by
? Manufacturing method for conductors. 3) Formula [wherein, X represents a hydrogen atom, a chlorine atom, or a bromine atom]. ] 3-amino-4-t-butylpyrazole represented by [%] where R1 represents an alkyl group having 1 to 4 carbon atoms, and R4 represents a methyl group or an ethyl group. [In the formula, R1 represents an alkyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom, a chlorine atom, or a bromine atom. ] A 7-chloropyrazolo(1,5-a) virimison derivative obtained by reacting a 7-hydroxypyrazolo[1,5-a]pyrimidine derivative represented by the formula with phosphorus oxychloride is converted to a 7-chloropyrazolo(1,5-a) virimison derivative represented by the formula and R5 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aralkyl group, a dialkylaminoalkyl group, or a phenyl group (substituted with a salt window atom, a methoxy group, or a methyl group). R2 and R5 may optionally form a carbocycle or a carbocycle containing an oxygen atom. ]
'I' means to react with the compound represented by 'I'! 1″
The formula [wherein R1 represents an alkyl group having 1 to 4 carbon atoms,
Each of R2 and R3 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aralkyl group, a dialkylaminoalkyl group, or a phenyl group (
It represents chlorine (which may be substituted with a methoxy group or a methyl group), and in some cases, R2 and R3 may form a carbocycle or a carbocycle containing an oxygen atom. X represents a hydrogen atom, a chlorine atom, or a bromine atom. ] A method for producing a pyrazolo(1,5-8) virimidun derivative represented by: 4) Formula [In the formula, %R1 represents an alkyl group having 1 to 4 carbon atoms, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aralkyl group, or a dialkylamino group. Alkyl group or phenyl group (
(which may be substituted with a chlorine atom, a methoxy group, or a methyl group), and in some cases, R2 and 83 may form a carbocycle or a carbocycle containing an oxygen atom. X represents a hydrogen atom, a chlorine atom, or a bromine atom. ] 6-alkoxycarbonylpyrazolo (1,
5-a) Characterized by subjecting a pyrimidine derivative to a hydrolysis reaction, the formula [wherein R2 and R3 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group,
represents an acylkyl group, a dialkylaminoalkyl group, or a phenyl group (which may be substituted with a chlorine atom, a methoxy group, or a methyl group), and in some cases, R2 and R3
and may form a carbocycle or a carbocycle containing an oxygen atom. X represents a hydrogen atom, a chlorine atom, or a bromine atom. ] Pyrazolo[1,5-a:lpyrimidine-
6-Production method of calganic acid rust conductor. 5) Formula [wherein R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, Aralkyl group, dialkylaminoalkyl group,
or phenyl group (which may be substituted with a chlorine atom, methoxy group, or methyl group), and in some cases R
2 and R3 may form a carbocycle or a carbocycle containing an e atom. [In the formula,
R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 and R5 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group,
represents an aralkyl group, a dialkylaminoalkyl group, or an enyl group (which may be substituted with a chlorine atom, a methoxy group, or a methyl group), and in some cases, R2 and R3 represent a carbon ring or a carbon ring containing an oxygen atom. A ring may be formed. Each independently of the other is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group,
represents an aralkyl group, a dialkylaminoalkyl group, or a phenyl group (which may be substituted with a chlorine atom, a methoxy group, or a methyl group), and in some cases, R2 and R3
and may form a carbocycle or a carbocycle containing an oxygen atom. X represents a hydrogen atom, a chlorine atom, or a bromine atom. ] Pyrazolo(1,5-a)pyrimidine-6 represented by
-carboxylic acid and 2 R1-OH [In the formula, Rj represents an alkyl group having 1 to 4 carbon atoms] +ra:+From 11 years old A 21- Kai --1-L
Jinkomushi^, M+ Fu Lfu Edict X 5. A compound of the formula [wherein R1 represents an alkyl group having 1 to 4 carbon atoms, and R2 and R3 each independently represent a hydrogen atom, an argyl group having 1 to 4 carbon atoms], and is characterized by reacting with an agent. group, a cycloalkyl group, an aralkyl group, a dialkylaminoalkyl group, or a phenyl group (which may be substituted with a chlorine atom, a methoxy group, or a methyl group), and in some cases R2 and xt5 represent a carbocyclic group, or A carbon ring containing an oxygen atom may be formed. X represents a hydrogen atom, a chlorine atom, or a bromine atom. ] 6-alkoxycarbonyl♂razolo (1,
5-a) Method for producing pyrimidine derivatives. 7) Formula [wherein R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, Aralkyl group, dialkylaminoalkyl group,
or a phenyl group (which may be substituted with a chlorine atom, a methoxy group, or a methyl group), and in some cases R
2 and R3 may form a carbocycle or a carbocycle containing an oxygen atom. X represents a hydrogen atom, a chlorine atom, or a bromine atom. ] t! An agricultural and horticultural fungicide characterized by containing a lazolo(1,5-a) pyrimidine derivative as an active ingredient.