JPH02250874A - Thiazole derivative - Google Patents

Abstract

NEW MATERIAL:Thiazole derivatives expressed by formula I (A is -NHR or -R1-OR; R is lower alkyl, cycloalkyl, aryl, substituted aryl or halogenated alkyl; B is lower alkyl, alkenyl, alkyloxycarbonyl, alkyloxycarbonylalkyl, benzyl, substituted benzyl or substituted benzoyl). EXAMPLE:3-Benzyl-2-(4-chlorobenzoyliminothiazole). USE:Useful as an agricultural and horticultural germicide, capable of exhibiting growth inhibition to various molds, having the ability to inhibit crops from onset and capable of providing yield increase without any disease injury. PREPARATION:2-Aminothiazole expressed by formula II is reacted with the corresponding alkyl halide to provide 3-substituted-2-iminothiazoles expressed by formula III, which are then reacted with the respective corresponding isocyanates, acid halides, etc., to afford the compounds expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to the provision of a novel compound effective as a fungicide for agriculture and horticulture, and to a method for utilizing the same.

(Problems to be Solved by the Present Invention) Today's agriculture ensures high productivity through fertilizers, pesticides, and various cage agricultural materials. On the other hand, the emergence of drug-resistant bacteria due to the continuous application of pesticides and diseases caused by the repeated cultivation of a single crop in an area are becoming major problems. Under these circumstances, there is a strong demand for the development of novel and highly safe drugs, and the present invention provides a means to solve this problem.

(Means for solving the problem) The first aspect of the present invention is a thiazole derivative represented by the following formula),
The second invention is an agricultural and horticultural fungicide containing these compounds as active ingredients.

Liao (in the formula, people represent -NHI'L, -R, and OR, where 几 represents lower alkyl, cycloalkyl, aryl-substituted aryl, or halogenated alkyl. B represents lower alkyl, alkenyl, alkyloxy Indicates carbonylalkyl, benzyl, substituted hensyl, and substituted benzoyl groups.

) The compound of the present invention can be prepared by first reacting 2-aminothiazole represented by formula (1) with a corresponding alkylnolide,
-Substituted-2-iminothiazoles [厘] (B represents the same meaning as @ symbol) Next, the compounds [㽽] are converted to the corresponding incyanates, acid nitrides, and enoformic acid esters, respectively. It can be synthesized by reacting with the like in an appropriate solvent.

Examples of organic solvents used in the reaction of isocyanates include dioxane, tetrahydrofuran, acetone,
Methyl ethyl ketone, benzene, toluene, xylene,
Examples include monochlorobenzene, dichlorobenzene, dichloromethane, chloroform, dimethylformamide, and acetonitrile. At this time, organic metal compounds such as dibutyltin silacrylate and tertiary amines such as triethylamine are effective as catalysts.

In the reaction of acid halides and halogenoformates, the same solvents as in the case of incyanates are used. At this time, effective deoxidizers include tertiary amines such as triethylamine, carbonates of alkali metals and alkaline earth metals such as sodium hydrogen carbonate, potassium carbonate, and calclum carbonate.

Further, the reaction temperature is preferably 0 to 100°C.

Typical synthesis examples of compounds related to the present invention are shown below, and the synthesized compounds are listed below! l! Shown below.

Synthesis Example 1 Synthesis of 3-benzyl-2-(4-chlorobenzoyliminothiazole 15) 3-benzyl-2-iminothiazole 1.81.

Compounds represented by the first table formula -NH No Be 〇 top - NH costume Be H Be D - NH costume Be Kanarina 116-118 100-105 1241-125 102-106 i1 0 direct weight 124-126 Triethylamine 2-01.Dichloromethane 3〇- 1.8 I of 4-chlorobenzoyl chloride was added into the solution at room temperature while stirring. After reacting for 5 hours, the reaction solution was poured into a Hontsuri 200-, the dichloromethane layer was separated, and after washing with water, The solvent was distilled off to obtain 2.8f of crude crystals, which were recrystallized from ethyl acetate to obtain the target compound 1.6I as colorless crystals.

m+p, 172-174°C IR (ffi") 1600 Synthesis Example 2 Synthesis of 5-74I-2-propylcarbamoyliminothiazole (/I65 B") 3-allyl-2-iminothiazole 1.21, catalytic amount of dibutyltin Propyl isocyanate α7t was added dropwise into the dilaurate and acetone 30-solution. After 6 hours, the reaction product was poured into about 200 ml of water, and the precipitated oil was extracted with dichloromethane.
After drying, the solvent was distilled off to obtain the desired product 1.2f as a yellow oil.

IR (z-''), 5500 1620 compound shoulder human melting point (C) IR spectrum (all-') -NH2-NH-C) -NH110H (J H・Rihiki・Shitsu-CHmC00CsHs -cHs小H3 -COOCHs -CH,C)I胛-CHrich-CHbeD -CHbeD -CYamano-CHbeD -cH3peD -cH!no121 〜124 92〜94 172〜174 154.8〜15翫5 140〜141 126〜127 140〜142 9a sea99.9 55S 55B -C)-ct-CH＊C每HI-NHTSHEH3c毫H寞-NHC(CHm), -cH*CH=Cut105
~106 76~79 81~82 S25 -NHCH CHtCHm -CHICH=CH3 [CHs -CHIC)I2cH3 78~81 NHCHs CHRD 127~129.5 5qtj When using the compound according to the present invention as a fungicide, the general Using agricultural formulation techniques, the compound can be mixed with various carriers and used in various forms such as water concentrators, emulsions, powders, granules, or suspension preparations.

Among the carriers, a usual organic solvent is used as a liquid carrier, and a usual clay mineral, pumice, etc. is used as a solid carrier. In addition, a surfactant can be added to impart emulsifying properties, dispersibility, spreading properties, etc. during formulation.

Furthermore, it can also be used in combination with agricultural products such as fertilizers, other insecticides, and monobicides.

In order to use it as a disinfectant, it is necessary to apply the active ingredient compound sufficiently to achieve the desired effect. The application rate is within the range of 50 to 20,000 f/ha, but generally 200 to 1,000 f/ha is appropriate. It is used in the form of a cloudy preparation.

To form an emulsion, the active ingredient is dissolved in an agriculturally acceptable organic solvent and a solvent-soluble emulsifier is added. Suitable solvents include xylene, 0-chlorotoluene, cyclohexanone, isophorone, dimethylformand, dimethylsulfoxide, or mixtures thereof. Particularly suitable solvents are aromatic hydrocarbons or mixed solvents of aromatic hydrocarbons, ketones and polar solvents.

The surfactant used as an emulsifier is used in an amount of 1 to 20 parts by weight of the emulsion, and may be anionic, cationic, or nonionic.

Ceramic ionic surfactants include alkyl sulfate esters, alkyldiphenyl ether disulfonates, naphthyl methanesulfonates, lignosulfonates, alkyl sulfobuccinates, alkylbenzene sulfonates, and alkyl phosphates. It will be done. Cationic surfactants are
Examples include alkylamine salts and quaternary ammonium salts.

As a nonionic surfactant, polyoxyete V 77
k $ k

The concentration of the active ingredient is between 15 and 201 parts by weight, preferably
A range of 1 to 101 parts by weight is suitable.

Wettable powders are formulated by adding the active ingredient to the active finely divided solid carrier and a surfactant. Generally, the active ingredient F is mixed within a range of 12 to 50 parts by weight, and the surfactant is mixed in an amount of 1 to 20 parts by weight.

Solid carriers commonly used for formulating the active ingredients are naturally occurring clays, silicates, silicas, and alkaline earth metal carbonates. Representative examples of these include kaolin, gicrite, talc, diatomaceous earth, magnesium carbonate, calcium carbonate, and dolomite.

Generally used emulsifiers, spreading agents, and dispersants are anionic surfactants, nonionic surfactants, or a mixture of these, and the same type of surfactants as those used in the emulsions listed for bait are used. Can be used.

Powders are made from inert active ingredients that are commonly used in the production of powders.

It is made by blending with a specific carrier such as Merck, micronized clay, pyrophyllite, diatomaceous earth, magnesium carbonate, etc.

The concentration of the active ingredient is α1 to 20% by weight, especially α5 to 5 parts by weight.
A range of 1 part by weight is suitable.

Granules are made in a granulator by mixing the active ingredient with an inert finely divided carrier, such as bentonite, kaolin clay diatomaceous earth or talc, and kneading with water. Alternatively, the active ingredient may be dissolved in a granular carrier that has been granulated in advance to have a particle size range of, for example, 15 to 30 meshes, or a granular mineral that has been crushed from natural pumice, acid clay, or zeolite and has an adjusted particle size range, along with a spreading agent. Create by attaching. The active ingredient in each granule is 0.2 to 20 parts by weight, especially 1 part by weight.
A range of 10L4 parts by weight is suitable.

Suspended formulations are made by pulverizing the active ingredient and mixing it with a surfactant and water.The surfactants used here include the anionic surfactants and cationic surfactants listed for emulsions. Both surfactants and nonionic surfactants can be used alone or in combination. The fecal amount is generally 1 to 201 parts by weight.

The amount of the active ingredient is suitably in the range of 1 to 50 parts by weight, preferably 2 to 201 parts by weight.

(Example) The present invention will be illustrated in more detail with reference to Examples below.

Formulation example 1 (emulsion) Compound number 7 10 fs orthochlorotoluene 50 parts cyclohexanone
36th part full hall”900B
4al (*trademark of IL Hokkaido Kagaku Co., Ltd.) The above components were uniformly mixed and dissolved to obtain an emulsion of the present invention.

Formulation Example 2 (Irrigation agent) Compound number 38 50 parts Kaolin clay 63s7 # Hall 503
9 5 al crane pole 5040
281 or more were mixed and pulverized to obtain an irrigation agent of the present invention.

Formulation Example 3 (Powder) Compound number 39 28 kaolin clay 988 or more were mixed and ground to obtain a powder of the present invention.

Formulation example 4 (granules) Compound number 51 5N bentonite 458 talc
45fIA lignin sulfonic acid/
More than 51 ml of the mixture was uniformly mixed and pulverized, water was added, kneaded, and granulated and dried to obtain granules of the present invention.

Formulation example 5 (suspending agent) Compound No. 38 10fs ethylene glycol 5s Tsurupol 17B
5 #7h Hall 7512
(15cm water
Uniformly mix and grind 79.5 tl or more,
A suspended preparation of the present invention was obtained.

The effect of inhibiting mycelial growth and preventing the onset of disease of the drug of the present invention against typical filamentous fungi will be shown below using test examples.

Test example 1 (ability to inhibit mycelial growth on petri dish) Diameter 9
Potato dextrose agar medium (PDA) in a petri dish.
A plate was prepared by mixing a dimethyl sulfoxide solution of the compound (medium) and a dimethyl sulfoxide solution to a predetermined concentration. On this agar, two mycelial masses grown in PDA medium were punched out to a diameter of 4 cm, and Pythium graminicola (Pythium graminicola)
ium grami-nicola) on the 2nd, and Fusarium oxysporum (Fusarium oxysporum) on the 2nd.
orum) on the 5th, Rhizoctonia solani (Rh1io
ctonia 5olanl) was cultured at 25° C. for 3 days, and the growth inhibition rate was calculated by comparing the needle side with the colony diameter without the addition of the drug. The average of the results is shown in 2nd R.

Table 2 Type M Pythium Fusarium Rhizoctonia Compound Bacterial Species Bicillum Fusarium Rhizoctonia Species Bicillum 7 Zalium Rhizoctonia Concentration (ppm) Concentration (ppm) Compound Genus Compound Species Concentration (ppm) Compound Bicillum Fusarium Rhizoctonia Test Example 2 Cucumber and Disease prevention effect test: Cultivate cucumbers (variety: Natsuaki-No.) in clay pots with a diameter of 9 mm. When they reach the 5-leaf stage, each test compound formulated based on Formulation Example 1 was adjusted to 100 ppm. , Test compound chemical solution 10- was sprayed using a spray gun. Treatments were carried out on three plants for each test compound.

After drying for 4 hours, each plant was treated with cucumber and Pseudoperonosvora cubenziis, a disease-causing cause.
The cells were inoculated by spraying with a spore suspension (2×10′ cells/−1) of S. operonospora cubensis. After this inoculation, the cucumber plants were cultured at 20° C. under water-saturated conditions for 4 hours, and then cultured at 20° C. and 70 to 80°C for 6 days. The percentage of lesions on the first and second leaves of the inoculated bales was investigated 7 days after inoculation, and the control value was determined as follows, and the results shown in Table 3 were obtained.

Table 3 Compound rot prevention value Table 4 Compound rot prevention value Test example 4 Wheat powder mildew preventive effect test Wheat (variety: Norin No. 61) was grown in a 9 m diameter warm pot, and when it reached the 2-leaf stage, the formulation Each test compound formulated based on Example 1 was adjusted to 100 ppm, and test compound chemical solution 2
0- was sprayed using a spray gun. For each test compound, 13 plants per plot were treated in duplicate.

One day after the chemical treatment, each plant was infected with ErysJ-phe g, which causes wheat powdery mildew.
raminis) conidia were spray inoculated. After this inoculation, the wheat plants were cultured at 20° C. in the dark under water-saturated conditions for 12 hours, and then cultured at 20° C. and a 12-hour photoperiod for 6 days. Seven days after inoculation, the percentage of lesions on the first and second leaves was investigated, and the control value was determined in the same manner as in Test Example 2, and the results shown in Table 4 were obtained.

(Effects of the Invention) As described above, the present invention provides an effective means for inhibiting the growth of various filamentous fungi, having the ability to suppress the onset of disease in crops, without causing chemical damage, and improving yields. Ai.

Hodogaya Chemical Industry Co., Ltd. hand Continued Supplementary Positive book (spontaneous) March 1st, 2nd year)

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. Aryl, halogenated alkyl.B is lower alkyl, alkenyl, alkyloxycarbonylalkyl,
Indicates benzyl, substituted benzyl, and substituted benzoyl groups. )
A thiazole derivative represented by 2. An agricultural and horticultural fungicide containing the compound of claim 1 as an active ingredient.