KR900007545B1 - 5h-1,2,4-thiadiazolo(3,2-a)pyrimidine-5-ones and its agricultural and horticultural composition - Google Patents

Abstract

5H-1,3,4-thiadiazlo(3,2-a)pyrimidine-5-one derivs of formula (I) are prepd. In the formula, X is H, halogen, straight or side chain alkyl, alkoxy, acyl, trihalo-alkoxy, alkynyl, phenyl, CN, phenoxy or nitro; Y is H, halogen, straight or side chain alkyl, halo-alkyl, alkoxy, alkynyl, phenyl-alkynyl, alkyl-amino, CN; R is straight or side alkyl, cyclohexyl-alkyl, alkenyl, cyclohexyl, halo-alkenyl, alkoxycarbonyl-alkyl etc. Cpds. are useful as argricultural and horticultural herbicides.

Description

5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivatives and fungicide compositions containing the same

The present invention relates to a novel agricultural horticultural fungicide.

More specifically, the present invention relates to novel 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivatives and fungicide compositions containing them.

In the specification of Japanese Patent Laid-Open No. 52-118494 (1977), thiadiazolo [3,2-a] pyrimidine represented by the following general formula is described as having an activity that inhibits the proliferation of cancer cells and is useful as an anticancer agent. have.

In which R ¹ represents an alkyl group or an aryl group; R ² represents a hydrogen atom, a halogen atom, a nitro group, a carboalkoxy group or an alkyl group; R ³ represents an alkyl group or an aralkyl group; And Y represents -SO- or -SO _2- .

In the specification of Japanese Patent Laid-Open No. 58-177997 (1983), it is described that thiadiazolopyrimidinone derivatives represented by the following general formula and physiologically acceptable salts thereof have excellent antiallergic activity.

In which R ¹ represents a 1 or 2H-tetrazol-5-yl group, a carboxyl group or a lower alkoxy carbonyl group; R ² represents an aryl group or heteroaryl group which may be substituted with an alkyl group, an alkoxy group, a hydroxyl group or a halogen atom; X represents an alkylene group, an alkenylene group, an alkynylene group or any of the above groups in which an oxygen atom, a sulfur atom or SO ₂ is attached to the terminal; Each group represented by X may be substituted with one or more types of straight or cyclic alkyl groups or substituents R ² .

As described above, various thiadiazolopyridinone derivatives are known which have a chemical structure similar to that of the compounds of the present invention.

But these are medicinal and do not clearly show activity as pesticides.

The present inventors have synthesized various derivatives thereof and studied their biological activities by paying attention to the structure of 5H-1,3,4-thiadiazolo [3,2-a] pyrimidine, which is a skeleton of many substances used as medicines.

As a result, the present inventors have found that some specific compounds having a 5H-1,3,4-thiadiazolo [3,2-a] pyrimidine structure exhibit excellent properties as agrohorticultural fungicides and have completed the present invention.

That is, an object of the present invention is to provide a novel 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivative, a useful agrohorticultural fungicide composition containing the derivative, and preparation of the derivative. It is to provide a method for preparing the derivatives as well as novel compounds for the starting material.

The present invention provides a 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivative represented by the following general formula (I).

으로 표시되는 기(여기서 Z는 할로겐원자, 저급 알킬기, 저급 알콕시기, 트리할로-저급-알킬기 또는 니트로기를 표시하며, n은 1 또는 2의 정수임)를 표시하며, 상기 식에서 두개의 치환기는 같거나 다를 수 있으며 ; X가 수소원자, 할로겐원자, 니트로기 또는 알킬기이고 Y가 알킬기인 조건일때, R은 알킬기도, 페닐-저급-알킬기도 아니다.Wherein X represents a hydrogen atom, a halogen atom, a straight or branched lower alkyl group, a lower alkoxy group, a lower acyl group, a trihalo-lower-alkoxy group, a lower alkynyl group, a phenyl group, a cyan group, a phenoxy group or a nitro group ; Y represents a hydrogen atom, a halogen atom, a linear or branched lower alkyl group, a halo-lower-alkyl group, a lower alkoxy group, a lower alkynyl group, a phenyl-lower-alkynyl group, a lower-alkyl-amino group or a cyan group; And R is a linear or branched alkyl group, cyclohexyl-lower-alkyl group, lower alkenyl group, cyclohexyl group, phenoxy-lower-alkyl group, halo-alkyl group, halo-alkenyl group, lower-alkoxycarbonyl-lower-alkyl group A phenyl group which may be substituted with a tri-lower-alkyl-silyl-lower-alkyl group, a phenyl-lower-alkyl group, an alkoxy-lower-alkyl group, one or more halogen atoms, a lower alkyl group or a nitro group or a lower alkoxy group; Formula -CH ₂

Wherein Z represents a halogen atom, a lower alkyl group, a lower alkoxy group, a trihalo-lower-alkyl group or a nitro group, n is an integer of 1 or 2, wherein two substituents are the same Or may be different; When X is a hydrogen atom, a halogen atom, a nitro group or an alkyl group and Y is an alkyl group, R is not an alkyl group or a phenyl-lower-alkyl group.

The present invention furthermore provides a 5H-1,3,4-thiadia represented by the following general formula (I) which comprises oxidizing the compound represented by the following general formula (II) by essentially known procedures. Provided are methods for preparing a solo [3,2-a] pyrimidin-5-one derivative.

으로 표시되는 기(여기에서 Z는 할로겐원자, 저급 알킬기, 저급 알콕시기, 트리할로-저급-알킬기 또는 니트로기를 표시하며, n은 1또는 2의 정수임)를 표시하며, 상기 식에서 두개의 치환기는 같거나 다를 수 있으며 ; X가 수소원자, 할로겐원자, 니트로기 또는 알킬기이고 Y가 알킬기인 조건일때, R은 알킬기도 페닐-저급-알킬기도 아니다.In the formula (I), X is a hydrogen atom, a halogen atom, a linear or branched lower alkyl group, a lower alkoxy group, a lower acyl group, a trihalo-lower-alkoxy group, a lower alkynyl group, a phenyl group, a cyan group, a phenoxy group or Nitro group; Y represents a hydrogen atom, a halogen atom, a linear or branched lower alkyl group, a halo-lower-alkyl group, a lower alkoxy group, a lower alkynyl group, a phenyl-lower-alkynyl group, a lower-alkyl-amino group or a cyan group; And R is a linear or branched alkyl group, cyclohexyl-lower-alkyl group, lower alkenyl group, cyclohexyl group, phenoxy-lower-alkyl group, halo-alkyl group, halo-alkenyl group, lower-alkoxycarbonyl-lower-alkyl group A phenyl group which may be substituted with a tri-lower-alkyl-silyl-lower-alkyl group, a phenyl-lower-alkyl group, an alkoxy-lower-alkyl group, one or more halogen atoms, a lower alkyl group or a nitro group or a lower alkoxy group; Formula -CH ₂

Wherein Z represents a halogen atom, a lower alkyl group, a lower alkoxy group, a trihalo-lower-alkyl group or a nitro group, n is an integer of 1 or 2, wherein two substituents May be the same or different; When X is a hydrogen atom, a halogen atom, a nitro group or an alkyl group and Y is an alkyl group, R is not an alkyl group or a phenyl-lower-alkyl group.

In formula (II), X, Y and R are as defined above.

Furthermore, the present invention provides a 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivative represented by the following general formula (II).

으로 표시되는 기(여기서 Z는 할로겐원자, 저급 알킬기, 저급 알콕시기, 트리할로-저급-알킬기 또는 니트로기를 표시하며, n은 1 또는 2의 정수임)를 표시하며, 상기 식에서 두개의 치환기는 같거나 다를 수 있으며 ; X가 수소원자, 할로겐원자, 니트로기 또는 알킬기이고 Y가 알킬기인 조건일때, R은 알킬기도 페닐-저급-알킬기도 아니다.Wherein X represents a hydrogen atom, a halogen atom, a straight or branched lower alkyl group, a lower alkoxy group, a lower acyl group, a trihalo-lower-alkoxy group, a lower alkynyl group, a phenyl group, a cyan group, a phenoxy group or a nitro group ; Y represents a hydrogen atom, a halogen atom, a linear or branched lower alkyl group, a halo-lower-alkyl group, a lower alkoxy group, a lower alkynyl group, a phenyl-lower-alkynyl group, a lower-alkyl-amino group or a cyan group; And R is a linear or branched alkyl group, cyclohexyl-lower-alkyl group, lower alkenyl group, cyclohexyl group, phenoxy-lower-alkyl group, halo-alkyl group, halo-alkenyl group, lower-alkoxycarbonyl-lower-alkyl group A phenyl group which may be substituted with a tri-lower-alkyl-silyl-lower-alkyl group, a phenyl-lower-alkyl group, an alkoxy-lower-alkyl group, one or more halogen atoms, a lower alkyl group or a nitro group or a lower alkoxy group; Formula -CH ₂

Wherein Z represents a halogen atom, a lower alkyl group, a lower alkoxy group, a trihalo-lower-alkyl group or a nitro group, n is an integer of 1 or 2, wherein two substituents are the same Or may be different; When X is a hydrogen atom, a halogen atom, a nitro group or an alkyl group and Y is an alkyl group, R is not an alkyl group or a phenyl-lower-alkyl group.

Furthermore, the present invention provides an agricultural and horticultural fungicide composition containing 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivative represented by the following general formula (I), and Provide agronomically acceptable carrier.

으로 표시되는 기(여기서 Z는 할로겐원자, 저급 알킬기, 저급 알콕시기, 트리할로-저급-알킬기 또는 니트로기를 표시하며, n은 1 또는 2의 정수임)를 표시하며, 상기 식에서 두개의 치환기는 같거나 다를 수 있으며 ; X가 수소원자, 할로겐원자, 니트로기 또는 알킬기이고 Y가 알킬기인 조건일때, R은 알킬기도 페닐-저급-알킬기도 아니다.Wherein X represents a hydrogen atom, a halogen atom, a straight or branched lower alkyl group, a lower alkoxy group, a lower acyl group, a trihalo-lower-alkoxy group, a lower alkynyl group, a phenyl group, a cyan group, a phenoxy group or a nitro group ; Y represents a hydrogen atom, a halogen atom, a linear or branched lower alkyl group, a halo-lower-alkyl group, a lower alkoxy group, a lower alkynyl group, a phenyl-lower-alkynyl group, a lower-alkyl-amino group or a cyan group; And R is a linear or branched alkyl group, cyclohexyl-lower-alkyl group, lower alkenyl group, cyclohexyl group, phenoxy-lower-alkyl group, halo-alkyl group, halo-alkenyl group, lower-alkoxycarbonyl-lower-alkyl group A phenyl group which may be substituted with a tri-lower-alkyl-silyl-lower-alkyl group, a phenyl-lower-alkyl group, an alkoxy-lower-alkyl group, one or more halogen atoms, a lower alkyl group or a nitro group or a lower alkoxy group; Formula -CH ₂

Wherein Z represents a halogen atom, a lower alkyl group, a lower alkoxy group, a trihalo-lower-alkyl group or a nitro group, n is an integer of 1 or 2, wherein two substituents are the same Or may be different; When X is a hydrogen atom, a halogen atom, a nitro group or an alkyl group and Y is an alkyl group, R is not an alkyl group or a phenyl-lower-alkyl group.

으로 표시되는 기(여기서 Z는 할로겐원자, C_1-4-알킬기, C_1-3-알콕시기, 트리플루오로메틸기 또는 니트로기를 표시함)를 표시하는 화합물들이다.Preferred among the compounds of the general formula (I) are compounds in which X, Y and R are represented as follows. That is, X represents a hydrogen atom, a halogen atom, a C _1-4 -alkyl group, C _1-3 -alkoxy, ethynyl group, acetyl group, trifluoroethoxy group, phenyl group, phenoxy group, nitro group or cyan group; Y represents a hydrogen atom, a halogen atom, a C _1-3 -alkyl group, a C _1-2 -alkoxy group, a C _2-3 alkynyl group, a chloromethyl group, a phenyl-ethynyl group, a C _2-3 -alkylamino group or a cyan group ; And R is a C _{1-9 -alkyl} group, cyclohexylmethyl group, allyl group, cyclohexyl group, phenoxyalkyl group, haloalkyl group, dichloroalkenyl group, ethoxycarbonylbutyl group, alkoxyalkyl group, phenyl-C _1-4 -alkyl group A phenyl group which may be substituted with a trimethylsilylpropyl group, a halogen atom or a C _1-4 -alkyl group, a C _1-3 -alkoxy group, a nitro group; Formula -CH ₂

And compounds represented by the formula (wherein Z represents a halogen atom, a C _{1-4 -alkyl} group, a C _1-3 -alkoxy group, a trifluoromethyl group or a nitro group).

Examples of compounds of the present invention represented by general formula (I) are shown in Table 1.

Each compound is referred to by a compound number given in the table below.

TABLE 1

Preferred among these compounds, in general formula (I), X represents a hydrogen atom, a chlorine atom, a fluorine atom C _1-4 -alkyl group, a C _1-3 -alkoxy group, an ethynyl group, an acetyl group or a cyan group; Y represents a hydrogen atom, a chlorine atom, a fluorine atom, a C _{1-3 -alkyl} group, a C _2-3 alkynyl group or a cyan group; And R is C _1-9 -alkyl group, trimethylsilylpropyl group, phenethyl group, phenyl group or one or two chlorine or fluorine atoms or one which may be substituted with one or two chlorine or fluorine atoms or C _1-4 -alkyl groups Or benzyl groups substituted with two C _1-4 -alkyl groups.

As more preferable compounds, in general formula (I), X represents a hydrogen atom, a chlorine or fluorine atom, a methyl group, a methoxy group, an ethynyl group, a cyan group or an acetyl group; Y represents a hydrogen atom, a chlorine or fluorine atom, an ethynyl group, a propynyl group or a cyan group; And R is a C _4-9 -alkyl group, a trimethylsilylpropyl group, a phenyl group which may be substituted with a chlorine or fluorine atom or a methyl group or a compound which represents a benzyl group substituted with one or two chlorine or fluorine atoms or one or two methyl groups .

One class of most preferred compounds is that in formula (I) X represents a hydrogen atom, a chlorine or fluorine atom or a methyl group; Y represents a hydrogen atom, an ethynyl group or a propynyl group; And R is a compound representing a C _{4-8 -alkyl} group or methylbenzyl group.

Another class of most preferred compounds is that in formula (I) X represents a chlorine or fluorine atom, a methyl group, an ethynyl group or a cyan group; Y represents a hydrogen atom or a chlorine or fluorine atom; And R are compounds representing a C _{4-8 -alkyl} group.

Yet another class of most preferred compounds is that in formula (I) X represents a chlorine or fluorine atom, a methoxy group or an acetyl group; Y represents a hydrogen atom; And R is a compound representing a C _4-9 -alkyl group or a benzyl group substituted with one or two chlorine or fluorine atoms or one or two methyl groups.

Another class of most preferred compounds is that in formula (I), X represents a hydrogen atom or a chlorine or fluorine atom; Y represents a cyan group, an ethynyl group or a propynyl group; And R is an associative group representing a C _{4-8 -alkyl} group.

Yet another class of most preferred compounds is that in formula (I) X represents a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group or a methoxy group; Y represents a hydrogen atom; And R is a compound representing a benzyl group substituted with one or two chlorine or fluorine atoms or one or two methyl groups.

Another class of most preferred compounds is that X represents a chlorine atom in formula (I); Y represents a hydrogen atom or a chlorine or fluorine atom; And R are compounds representing a C _{4-8 -alkyl} group.

Another class of most preferred compounds is that in the formula (I) X represents a chlorine atom; Y represents a hydrogen atom; And R are compounds representing a C _{5-6 -alkyl} group.

Most preferred compounds are as follows.

6-chloro-2-hexanesulfonyl-5H-1,3,4-thiadiazolo- [3,2-a] pyridinin-5-one

2-hexanesulfonyl-7- (1-propynyl) -5H-1,3,4-thiadiazolo- [3,2-a] pyrimidin-5-one

7-ethynyl-2-hexanesulfonyl-5H-1,3,4-thiadiazolo- [3,2-a] pyrimidin-5-one

6-chloro-7-fluoro-2-hexanesulfonyl-5H-1,3,4-thiadiazolo- [3,2-a] pyrimidin-5-one

7-ethynyl-6-chloro-2-hexanesulfonyl-5H-1,3,4-thiadiazolo- [3,2-a] pyrimidin-5-one

6-methoxy-2-octanesulfonyl-5H-1,3,4-thiadiazolo- [3,2-a] pyrimidin-5-one

6-cyano-2-heptansulfonyl-5H-1,3,4-thiadiazolo- [3,2-a] pyrimidin-5-one

6-acetyl-2-heptansulfonyl-5H-1,3,4-thiadiazolo- [3,2-a] pyrimidin-5-one

6-chloro-7-fluoro-2-pentanesulfonyl-5H-1,3,4-thiadiazolo- [3,2-a] pyrimidin-5-one

The compound of the present invention can be prepared by oxidizing the compound represented by the following general formula (II).

Wherein X, Y and R are as defined for formula (I).

Oxidation of the compound of formula (II) can be carried out by any method used for the oxidation of organosulfurized compounds. Examples of oxidizing agents that can be used are hydrogen peroxide, organic peracids such as metachloro perbenzoic acid, "oxone" (the "OXONE" trade name, a reagent containing potassium hydrogen peroxide commercially available from DuPont).

In addition to oxidation reagents, for example acid catalysts such as acetic acid and metal catalysts such as sodium tungstate can be used to promote the oxidation reaction.

Examples of the solvent used for the oxidation reaction include water; Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene and the like; Fatty acids such as acetic acid and propionic acid; Ketones such as acetone and methyl ethyl ketone; Amides such as dimethylformamide and dimethylacetamide; Alcohols such as methyl alcohol and ethyl alcohol; Hydrocarbons such as hexane, petroleum ether and benzene.

Oxidation is carried out in the temperature range from -20 ° C to the boiling point of the solvent used. The amount of oxidant used is usually twice or more than a substantial amount of the compound used in the general formula (II), but there is no strict limit.

Compounds of formula (II) are novel materials and can be prepared from compounds of formula (III) by four methods depending on the type of substituents described below.

In which R is as defined above.

The compound of formula (III) can be prepared by a known method for preparing 1,3,4-thiadiazole which is used as a general formula according to the following reaction overview.

Wherein R is as defined above and U ¹ represents a halogen atom, a benzenesulfonyloxy group, a substituted benzenesulfonyloxy group; And U ² represents a halogen atom.

Four methods for preparing the compound of formula (II) are as follows.

Method A

In general formula (II), R is as defined above, X is a hydrogen atom, a halogen atom or an alkyl group (designated X ¹ ); And Y is an alkyl group or a haloalkyl group (designated as Y ¹ ) can be prepared by reacting a compound of formula (III) with a beta ketoester derivative of formula (IV).

Wherein R is as defined above, X ¹ and Y ¹ are as defined above under Method A, and R ¹ represents an alkyl group.

The reaction is carried out in a nonvolatile solvent or in the presence of a condensation reagent such as polyphosphoric acid, boron trifluoride etherate, sulfuric acid and the like with or without a relatively nonvolatile solvent such as xylene.

Compounds of general formula (IV) are known or otherwise can be prepared by conventional methods. Some of them are commercially available.

Among the compounds of formula (V), compounds in which X ¹ is a halogen atom can be prepared by halogenating a corresponding compound in which X ¹ is a hydrogen atom. As the halogenating agent, for example, chlorine, bromine, sulfuryl chloride, iodine monochloride and the like can be used. If desired, metal halides such as zinc chloride, iron halides and the like and pyridine may be used as catalyst.

In addition, pyridine, zinc chloride and the like can be used as the hydrogen halide remover.

In the general formula (V), the halogen atom as the substituent X ¹ , preferably iodine, may be converted into a cyan group. As preferred cyanating agents, sodium cyanide and cuprous cyanide are used simultaneously in the presence of a dimethylformamide solvent.

Method B

X in general formula (II) is a hydrogen atom, a halogen atom, a linear or branched alkyl group, a phenyl group, an alkoxy group, a phenoxy group or a trifluoroalkoxy group (designated as X ² ); And Y is a hydrogen atom can be prepared by reacting a compound of formula III with a betaformyl ester derivative or 2-propenoate ester derivative (VI).

Wherein R is as defined above, X ² is as defined above under Method B, R ² represents an alkyl group and R ³ represents a hydroxyl group or an alkoxy group. The reaction can be carried out in the same manner as in method A described above.

The compound in which X ² is a halogen atom in formula (VII) can be prepared by halogenating the compound of formula (X) in which X ² is hydrogen atom.

Furthermore, the halogen atom, preferably iodine atom, as the substituent X ² can be converted into a cyan group or an alkynyl group. Halogenation and cyanation can be carried out as described above with respect to Method A.

The X ² in the general formula (Ⅶ) alkynyl group compounds chloride bis (triphenylphosphine) palladium (II), the X ² halogen in the presence of a hydrogen halide scavenger, such as the catalyst and triethylamine as such as iodide, cuprous A compound of general formula, which is an atom, preferably an iodine atom, can be prepared by reacting an alkyne compound such as alkylacetylene, ethynyltrimethylsilane, or the like.

If necessary, a protecting group such as trimethylsilyl group bonded to an alkynyl group is removed with a base such as potassium carbonate, tetraalkylammonium fluoride or the like.

Compounds of formula (VI) are known or can be prepared by any of the conventional methods commonly used. Some of them are commercially available.

Method C

In formula (II), R is as defined above, X is a hydrogen atom or an alkyl group (designated X ⁴ ), Y is a halogen atom (designated Y ² ) or an alkynyl group or cyan group (designated Y ³ ) Can be prepared by the following steps.

Wherein R is as defined above, X ⁴ , Y ² and Y ³ are as defined above under Method C, and R ⁴ represents a phenyl group or a substituted phenyl group. The reaction of the compound of formula III with the compound of formula III is carried out in a relatively nonvolatile solvent according to the procedure described in the following literature (Pharmacie 33, H11-13 (1978)).

The compound of formula (VII) can be converted to the corresponding compound of formula (X). If desired, the compound of formula (X) is halogen exchanged. Halogen atoms, preferably iodine atoms, may be converted to alkynyl groups or cyan groups.

Examples of halogenating agents that can be used are phosphorus oxychloride, phosphorus pentachloride and the like. If desired, a solvent such as toluene, a hydrogen halide remover such as N, N-dimethylaniline, or the like may be used. Halogen exchange can be carried out using hydroiodic acid, potassium fluoride and the like.

Compound of formula (XI) wherein Y ³ is an alkynyl group or cyan group is a halogen atom of the compound of formula (X) Y ² , preferably according to the alkynylation procedure described in Method B or the cyanation procedure described in Method A It can be prepared by converting an iodine atom into an alkynyl group or a cyan group.

The hydrogen atom as the substituent X ⁴ of the compound of formula (X), (X) or (XI) may be replaced with a halogen atom.

Wherein R is as defined above, X ⁵ represents a halogen atom and Y ⁴ represents a hydroxyl group, a halogen atom, an alkynyl group or a cyan group. The halogen atom, preferably the iodine atom, as the substituent X ⁵ may be converted to a cyan group.

Halogenation or cyanation can be carried out by a procedure such as halogenation or cyanation at the 6-position described in Method A.

Compounds of formula (XIII) wherein Y ⁴ is a hydroxyl group can be halogenated by a procedure such as halogenation of the 7-position of the compound of formula (IX).

Compounds of formula (IX) wherein X ⁴ is a hydrogen atom may be nitrided, and then the hydroxyl group at the 7-position may be substituted with a halogen atom, and furthermore the halogen atom may be substituted with an alkoxy group or an alkylamino group. have.

In which R is as defined above.

Y ^2b represents a halogen atom, and Y ⁵ represents an alkoxy group or an alkylamino group.

Compounds of formula (XIV) may be prepared by treating compounds of formula (IXb) with fuming nitric acid, if desired, in the presence of a solvent such as acetic acid.

The compound of formula (XV) can be prepared by the same method as the preparation of the compound of formula (X). Compounds of formula (XVI) may be prepared by reacting compounds of formula (XV) with alcohols or alkylamines, if desired, in the presence of a halogenating agent such as pyridine and a solvent.

Compounds of formula (XIII) are known or can be prepared by any conventional method.

Method D

The compound of formula (II) wherein X is an acetyl group can be prepared by the following method.

Wherein R is as defined above with respect to general formula (I) and R ⁵ and R ⁶ represent an alkyl group.

That is, the compound of formula (III) and the dialkylformamidodialkylacetal of formula (XVII) react to form a compound of formula (XVIII), and the latter compound reacts with diketene to form To form a compound of (XIX).

The compounds of the present invention can be used by themselves as agricultural and horticultural fungicides. However, these are usually prepared in the form of powders, emulsifiable concentrates, granules or pellets by the addition of carriers, surfactants, dispersants or auxiliaries by conventional methods.

Preferred carriers include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, hydrated lime, siliceous sand, ammonium sulfate, urea and isopropyl alcohol, xylene, cyclohexane Liquid carriers such as warmth are included.

Examples of surfactants and dispersants that can be used are alcohol sulfates, alkylsulfonates, lignosulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan monoalkylates and the like. As the adjuvant, for example, carboxymethyl cellulose, polyethylene glycol, gum arabic and the like can be used. The formulation is diluted and sprayed to an appropriate concentration. Or otherwise use them directly.

The concentration of the active ingredient may vary as necessary. Generally, however, 0.5 to 20% by weight is suitable for powder or granule formulations and 5 to 80% by weight for emulsions or wetting agents.

The amount of the agricultural or horticultural fungicide of the present invention may vary depending on the type of compound used, the type of the disease, the condition and extent of the disease, environmental conditions, the type of the preparation used, and the like. In the case of powder or granule preparations, they are used as is and the concentration of the active ingredient may be selected in the range of 10 to 500 g per 10 ares. In the case of emulsions or wetting agents it is used in the form of a liquid and the concentration is selected in the range of 10 to 2000 ppm.

The compound of the present invention is not only a disease damage spread through soil or seeds, but also a sooty pattern disease of Chinese rasp (Brassica rapa var. Pervidis) caused by Alternaria brassicicola, spot deciduous and black on apple trees. It has a remarkable effect against star pattern disease, black pattern disease of pear tree, gray mold disease of cucumber, germ disease of cucumber, rice disease of rice, plague of tomato and potato, and gray mold disease of eggplant and vine. The effect is both prophylactic and therapeutic, and it is durable. Moreover, the compounds of the present invention are very nontoxic to antiosmotic animals and aquatic animals.

The present invention will now be described in detail with reference to the preparation of the compound and the preparation of the agricultural and horticultural fungicide composition through working examples. The percentages mentioned in these examples are all by weight.

Preparation Example 1

Synthesis of 2- (4-chlorobenzylsulfonyl) -7-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (Compound No. 2)

16.4 g of 2- (4-chlorobenzylthio) -7-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one and 26.2 g of metachloro and benzoic acid were added to 500 ml of chloroform. Was dissolved and the mixture was stirred at -10? 5 占 폚 for 10 hours. An aqueous sodium hydrogen carbonate solution was added to the mixture to stop the reaction. Chloroform was added to extract and the organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was ethyl acetate as eluent; Purification by column chromatography on silica gel with toluene (1: 9) mixture. The solvent was distilled off and 9.5 g of 2- (4-chlorobenzylsulfonyl) -7-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was obtained. Melting point 192-194 degreeC, yield 53%.

Preparation Example 2

Synthesis of 2-benzenesulfonyl-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (Compound No. 40)

40.3g의 분산액을 메탄올 용액에 가하고 결과 생긴 혼합물을 60℃까지 데우고 2시간 동안 교반하였다. 냉각시킨후에 추출하기 위해 클로로포름을 첨가하고 유기층을 각각 티오황산 나트륨수용액, 탄산수소나트륨 수용액과 물로 세척하였다. 유기층을 무수황산나트륨상에서 건조시킨후, 용매를 증류제거하였다. 잔여물을 톨루엔/에탄올(1 : 1) 혼합물로부터 재결정하여 2-벤젠술포닐-6-메틸-5H-1,3,4-티아디아졸로[3,2-a]피리미딘-5-온 1.2g을 얻었다. 융점 198 내지 200℃. 수율 26%.4.1 g of 2-phenylthio-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was dissolved in 165 ml of methanol. Oxone suspended in 165 ml of water

40.3 g of the dispersion was added to the methanol solution and the resulting mixture was warmed to 60 ° C. and stirred for 2 hours. After cooling, chloroform was added to extract and the organic layer was washed with aqueous sodium thiosulfate solution, aqueous sodium bicarbonate solution and water, respectively. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off. The residue was recrystallized from a toluene / ethanol (1: 1) mixture to give 2-benzenesulfonyl-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one 1.2 g was obtained. Melting point 198 to 200 ° C. Yield 26%.

Preparation Example 3

Synthesis of 7-fluoro-2-heptansulfonyl-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (Compound No. 33)

7-fluoro-2-heptylthio-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was dissolved in 270 ml of methanol.

77.8g의 분산액을 메탄올 용액에 가하였다. 실시예 2와 같은 절차에 의해서 얻은 잔여물을 용출제로서 아세트산 에틸/노르말헥산(2 : 3) 혼합물로 실리카겔상에서 칼럼크로마토그래피에 의해 정제하였다. 용매를 증류제거시키고 잔여물을 에탄올로부터 재결정하여 7-플루오로-2-헵탄술포닐-6-메틸-5H-1,3,4-티아디아졸로[3,2-a]피리미딘-5-온 2.7g을 얻었다. 융점 143 내지 146℃. 수율 57%.Oxone in 270 ml of water

77.8 g of the dispersion was added to the methanol solution. The residue obtained by the same procedure as in Example 2 was purified by column chromatography on silica gel with a mixture of ethyl acetate / normal hexane (2: 3) as eluent. The solvent was distilled off and the residue was recrystallized from ethanol to 7-fluoro-2-heptanesulfonyl-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidine-5- 2.7 g was obtained. Melting point 143-146 캜. Yield 57%.

Preparation Example 4

Synthesis of 2- (4-chlorobenzylthio) -7-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (intermediate)

12.8 g of 2-amino-5-mercapto-1,3,4-thiadiazole and 43 g of sodium hydroxide were added to 35 ml of water and 70 ml of ethanol. 14.8 g of 4-chlorobenzyl chloride was added to the mixture, and the mixture was stirred at room temperature for 1 hour. Water was added and the reaction mixture was filtered. The residue was washed with a mixture of water and ethanol / normal hexane (1: 1) and then dried under reduced pressure to give 23.1 g of 2-amino-5- (4-chlorobenzylthio) -1,3,4-thiadiazole. Got it. Melting point 162-164 캜. Yield 93%.

20.2 g of 2-amino-5- (4-chlorobenzylthio) -1,3,4-thiadiazole and 12.2 g of ethyl aceto acetate were mixed together with 24 g of polyphosphoric acid and the mixture was stirred at 130 to 150 ° C for 45 Stir for minutes. After cooling, water was added to the mixture, the mixture was extracted with chloroform and the organic layer was washed with aqueous sodium bicarbonate solution and water, respectively. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off. The residue was recrystallized from ethanol to give 21.3 g of 2- (4-chlorobenzylthio) -7-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. Melting point 138.5 to 139.5 ° C. Yield 84%.

Preparation Example 5

Synthesis of 2-phenylthio-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (intermediate)

To a mixture of 20 ml of water and 30 ml of ethanol, 7.3 g of thiophenol and 4.5 g of potassium hydroxide were added. To this solution was added 11.7 g of 2-amino-5-bromo-1,3,4-thiadiazole and the mixture was heated to 82 ° C. and stirred for 2 hours. After cooling, water was added and the mixture was filtered. The residue was washed with water and normal hexane respectively and dried under reduced pressure to give 10.8 g of 2-amino-5-phenylthio-1,3,4-thiadiazole. Melting point 202-203 캜. Yield 77%.

7.2 g of 2-amino-5-phenylthio-1,3,4-thiadiazole and 4.9 g of ethyl 3-hydroxy-2-methyl-2-propenoate were mixed together with 13 g of polyphosphoric acid. 5.9 g of 2-phenylthio-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was obtained by the same procedure as in Preparation Example 4. Melting point 141-143 캜; Yield 58%.

Preparation Example 6

Synthesis of 7-fluoro-2-heptylthio-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (intermediate)

To 32 ml of water and 32 ml of ethanol, 27.2 g of 2-amino-5-mercapto-1,3,4-thiadiazole and 9.0 g of sodium hydroxide were added. To this solution was added 45.2 g of 1-iodine heptane and the mixture was stirred at 60 ° C. for 2 hours. After cooling, water was added to the mixture and the mixture was filtered. The residue was washed, dried under reduced pressure and recrystallized from ethanol / normal hexane (1: 1) mixture. Thus, 36.1 g of 2-amino-5-heptylthio-1,3,4-thiadiazole was obtained. Melting point 112-113 ° C. Yield 78%.

Thus obtained mixture of 19.7 g of 2-amino-5-heptylthio-1,3,4-thiadiazole, 40.9 g of 2-methyl-malonic acid bis (2,4,6-trichlorophenyl) and 55 ml of chlorobenzene was obtained. It stirred at 140-144 degreeC for 45 minutes. After cooling, normal hexane was added thereto and the precipitate was collected by filtration.

Again normal hexane was added to the filtrate to collect the precipitate.

The collected precipitates were combined.

The combined precipitate was washed with normal hexane to give 21.2 g of 2-heptylthio-7-hydroxy-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one . Melting point 141-143 캜; Yield 78%.

19.5 g of 2-heptylthio-7-hydroxy-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one thus obtained, 38 g of phosphorus oxychloride and phosphorus pentachloride 13.6 g of the mixture was warmed to 77-88 ° C. and stirred for 2 hours. The reaction solution was concentrated under reduced pressure, and the residue was dissolved in toluene and the solution was washed with aqueous potassium carbonate solution and water, respectively.

After the solution was dried over anhydrous sodium sulfate, the solvent was distilled off and the residue was purified by column chromatography on silica gel with a mixture of ethyl acetate / normal hexane (2: 3) as eluent.

After distilling off the solvent, 19.0 g of 7-chloro-2-heptylthio-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was obtained. Melting point 79-81 ° C. Yield 92%.

8.6 g of 7-chloro-2-heptylthio-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one thus obtained, 3.0 g of spray-dried potassium fluoride, and A solution of 32 ml of sulfolane was heated at 205-225 [deg.] C. for 1 hour 30 minutes under a nitrogen stream.

After cooling, water was added to the mixture and the mixture was extracted with toluene.

The toluene layer was collected and washed with water.

The toluene phase was dried over anhydrous sodium sulfate and the solvent was distilled off.

The residue was purified by column chromatography on silica gel with a mixture of ethyl acetate / normal hexane (1: 3) as eluent.

After distilling off the solvent, 5.2 g of 7-fluoro-2-heptylthio-6-methyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was obtained. Melting point 78 to 91 ° C. Yield 63%.

Preparation Example 7

Synthesis of 2-hexanesulfonyl-7- (1-propynyl) -5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (Compound No. 115)

6.6 g of 2-hexylthio-7- (1-propynyl) -5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was dissolved in 225 ml of methanol.

51.2g의 분산액을 메탄올 용액에 가하고 결과생긴 혼합물을 60 내지 65℃까지 데우고 50분간 교반하였다.Oxone suspended in 180 ml of water

51.2 g of the dispersion was added to the methanol solution and the resulting mixture was warmed to 60-65 ° C. and stirred for 50 minutes.

After cooling, the mixture was extracted with chloroform and the organic layer was washed with aqueous sodium thiosulfate solution and water, respectively, and dried over anhydrous sodium sulfate.

The solvent was distilled off and the residue was purified by silica gel column chromatography using ethyl acetate / toluene mixture as eluent and recrystallized from ethanol.

Thus 2.6 g of 2-hexanesulfonyl-7- (1-propynyl) -5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one were obtained. Melting point 122 to 125 ° C. Yield 41%.

Preparation Example 8

Synthesis of 6-chloro-7-fluoro-2-hexanesulfonyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (Compound No. 121)

In 20 ml of acetic acid 2.8 g of 6-chloro-7-fluoro-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one and sodium tungstate hydrate 0.14 g was dissolved.

8.9 g of 20% hydrogen peroxide solution was added dropwise to the acetic acid solution over 20 minutes.

The solution was warmed to 60-65 ° C. and stirred for 45 minutes. After cooling, the solution was diluted with water and extracted with chloroform.

The organic layer was washed once with water and treated in the same manner as in Preparation Example 7.

The residue thus obtained was recrystallized from ethanol to give 2.0 g of 6-chloro-7-fluoro-2-hexanesulfonyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. Got. Melting point 185-188 ° C. Yield 65%.

Preparation Example

Synthesis of 2-heptansulfonyl-6-methoxy-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (Compound No. 94)

3.3 g of 2-heptylthio-6-methoxy-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one were dissolved in 55 ml of methanol.

19.4g의 분산액을 메탄올 용액에 가하고 결과생긴 혼합물을 65℃까지 데우고 1시간 동안 교반하였다.Oxone suspended in 70 ml of water

19.4 g of the dispersion was added to the methanol solution and the resulting mixture was warmed to 65 ° C. and stirred for 1 hour.

The residue obtained by the same procedure as in Preparation Example 7 was recrystallized from ethanol to give 2-heptanesulfonyl-6-methoxy-5H-1,3,4-thiadiazolo [3,2-a] pyrimidine- 5-one 1. 8 g was obtained. Melting point 106 to 109 ° C. Yield 51%.

Preparation Example 10

Synthesis of 6-ethynyl-2-heptansulfonyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (Compound No. 87)

2.8 g of 6-ethynyl-2-heptylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was dissolved in 180 ml of methanol.

20g의 분산액을 메탄올 용액에 가하고 결과생긴 혼합물을 실온에서 24시간 동안 교반하였다. 제조실시예 7에서와 같은 절차에 의해 얻은 잔여물을 용출제로서 아세트산에틸/톨루엔 혼합물을 이용하여 실리카겔 칼럼크로마토그래피에 의해서 분리하고 에탄올/클로로포름 혼합물로부터 재결정하여 6-에티닐-2-헵탄술포닐-5H-1,3,4-티아디아졸로[3,2-a]피리미딘-5-온 1.3g을 얻었다. 융점 180 내지 182℃. 수율 39%.Oxon in 66 ml of water

20 g of the dispersion was added to the methanol solution and the resulting mixture was stirred at room temperature for 24 hours. The residue obtained by the same procedure as in Preparation Example 7 was separated by silica gel column chromatography using ethyl acetate / toluene mixture as eluent and recrystallized from ethanol / chloroform mixture to give 6-ethynyl-2-heptanesulfonyl. 1.3 g of -5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was obtained. Melting point 180 to 182 ° C. Yield 39%.

Preparation Example 11

Synthesis of 2-hexylthio-7- (1-propynyl) -5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (intermediate)

81.5 g of 2-amino-5-mercapto-1,3,4-thiadiazole and 190% of sodium hydroxide were added to 190 ml of ethanol and 240 ml of water.

99 g of 1-bromohexane was added to this solution and the resulting compound was warmed to 60-70 ° C. and stirred for 2 hours. After cooling, water was added to the reaction mixture and the resulting solution was filtered.

The residue was washed with water and dried under reduced pressure. The dried residue was recrystallized from an ethanol / hexane mixture to give 100.5 g of 2-amino-5-hexylthio-1,3,4-thiadiazole. Melting point 113 to 115 ° C. Yield 77%.

A mixture of 65.2 g of 2-amino-5-hexylthio-1,3,4-thiadiazole, 141.7 g of malonic bis (2,4,6-trichlorophenyl) and 240 ml of chlorobenzene was thus obtained at 137 to 140 ° C. Heated to and stirred for 1 h.

After cooling, hexane is added to the mixture and the precipitate formed is separated by filtration and the residue is washed with hexane to give 2-hexylthio-7-hydroxy-5H-1,3,4-thiadiazolo [3,2-a ] 74.7 g of pyrimidin-5-one. Melting point 187 to 192 캜. Yield 87%.

23.5 g of 2-hexylthio-7-hydroxy-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one thus obtained, 17.8 g of phosphorus pentachloride and 50.4 g of phosphorus oxychloride The mixture was heated to 65-90 ° C. and stirred for 2 hours. The reaction mixture was concentrated under reduced pressure. The residue was dissolved in toluene. The solution was washed with aqueous potassium carbonate solution and water, respectively, and dried over anhydrous sodium sulfate.

The solvent was distilled off and the residue was separated by silica gel column chromatography using ethyl acetate / toluene mixture as eluent to prepare 7-chloro-2-hexylthio-5H-1,3,4-thiadiazolo [3, 2-a] 10.2 g of pyrimidin-5-one was obtained. Melting point 95 to 96 ° C. Yield 41%.

A solution of 8.4 g of 7-chloro-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one and 88.2 g of a 57% aqueous solution of iodide hydrochloric acid was thus prepared. Heat to 110 ° C. and stir for 2 hours.

After cooling, the solution was filtered.

The residue was washed with water and dissolved in toluene.

The toluene solution was washed with an aqueous sodium bicarbonate solution, an aqueous sodium thiosulfate solution and water, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 9.8 g of 80% pure 7-iodo-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. Yield 72%.

8.6 g of 7-iodine-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one thus obtained, 11 g of triethylamine, bis (triphenylphosphine) Into a solution of 0.15 g of palladium (II), 0.04 g of cuprous iodide and 33 ml of tetrahydrofuran, 2.6 g of 1-propine was introduced through a bubble glass tube while stirring was continued for 1 hour under cooling with ice-cold water.

Thereafter, the solution was further stirred at room temperature for 30 minutes, and 0.23 g of bis (triphenylphosphine) palladium (II) chloride and 0.06 g of cuprous iodide were added.

The solution was further stirred for 4 hours.

Then toluene was added and the solution was filtered to concentrate the filtrate under reduced pressure.

The residue was dissolved in toluene and the solution was washed with water and dried over anhydrous sodium sulfate.

The solvent was distilled off and the residue was recrystallized from an ethanol / hexane mixture to give 7- (1-propynyl) -2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidine- 3.9 g of 5-on was obtained. Melting point 94-97 ° C. Yield 72%.

Preparation Example 12

Synthesis of 6-chloro-7-fluoro-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-one (intermediate)

30 g of 2-hexylthio-7-hydroxy-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one, 21.3 g of sulfuryl chloride, 0.85 g of ferric chloride and phosphorus oxychloride 113 g of the mixture was heated to 110 ° C. and stirred for 1.5 h.

After cooling, the reaction solution was concentrated under reduced pressure.

Toluene and water were added to this residue and extraction was performed. The organic layer was washed with water, aqueous sodium hydrogen carbonate solution and water, respectively, and dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was purified by silica gel column chromatography using ethyl acetate / toluene mixture as eluent.

Thus 18.8 g of 6,7-dichloro-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one were obtained. Yield 75%.

4.4 g of 6,7-dichloro-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one thus obtained, 2.2 g of spray-dried potassium fluoride and sulfolane 20 ml of the solution was heated to 185-200 ° C. and stirred for 45 minutes.

After cooling, toluene and water were added to the reaction solution and extraction was performed. The organic layer was washed with water and dried over anhydrous sodium sulfate.

The solvent was distilled off and the residue was separated by silica gel column chromatography using an ethyl acetate / toluene mixture as eluent.

Thus 3.0 g of 6-chloro-7-fluoro-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one were obtained. Melting point 105 to 111 ° C. Yield 71%.

Preparation Example 13

Synthesis of 2-heptylthio-6-methoxy-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (intermediate)

68.0 g of 2-amino-5-mercapto-1,3,4-thiadiazole and 22.4 g of sodium hydroxide were added to 185 ml of ethanol and 185 ml of water.

To this mixture was added 84.6 g of 1-bromoheptane and the resulting mixture was warmed to 60 ° C. and stirred for 2 hours. After cooling, water was added and the mixture was filtered.

The residue was washed with water, dried under reduced pressure and recrystallized from ethanol / hexane mixtures.

Thus, 90.2 g of 2-amino-5-heptylthio-1,3,4-thiadiazole was obtained. Melting point 112-113 ° C. Yield 78%.

A mixture of 4.7 g of 2-amino-5-heptylthio-1,3,4, -thiadiazole, 3.3 g of 3-hydroxy-2-methoxy-2-propenic acid propyl and 12 g of polyphosphoric acid was added to a mixture of 130 to 135 Heat to C and stir for 30 minutes.

After cooling, water and chloroform were added to the mixture and extraction was performed. The organic layers were washed with aqueous sodium bicarbonate solution and water, respectively, and dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was separated by silica gel column chromatography using an ethyl acetate / toluene mixture as eluent.

Thus 4.0 g of 2-heptylthio-6-methoxy-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one were obtained. Melting point 68 to 71 ° C. Yield 64%.

Preparation Example 14

Synthesis of 6-ethynyl-2-heptylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (intermediate)

A mixture of 20.1 g of 2-amino-5-heptylthio-1,3,4-thiadiazole, 20.0 g of ethyl 3-ethoxypropenoic acid and 23 g of polyphosphoric acid was heated to 130-140 ° C. and stirred for 30 minutes. The residue obtained by the same procedure as in Preparation Example 13 was purified by silica gel column chromatography using an ethyl acetate / toluene mixture as eluent.

Thus, 12.6 g of 2-heptylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one were obtained. Yield 51%.

The resulting 2-heptylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was dissolved in 65 ml of acetic acid.

10.5 g of zinc chloride was added to this solution, and a solution of 10.5 g of iodine monochloride in 20 ml of acetic acid was added dropwise to the solution.

The solution was then warmed to 70-80 ° C. and stirred for 1.5 h. After cooling, chloroform and water were added and extraction was performed.

The organic layer was washed with an aqueous sodium bicarbonate solution, an aqueous sodium thiosulfate solution and water, and dried over anhydrous sodium sulfate.

The solvent was distilled off and the residue was purified by silica gel column chromatography using ethyl acetate / toluene mixture as eluent.

Thus, 9.4 g of 2-heptylthio-6-iodo-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one were obtained. Yield 52%.

8.0 g of 2-heptylthio-6-iodine-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one thus obtained was added to a mixture of 50 ml of triethylamine and 100 ml of tetrahydrofuran. Dissolved.

0.68 g of bis (triphenylphosphine) palladium (II) chloride and 0.2 g of cuprous iodide were added to this solution as a catalyst. To this solution was added dropwise a solution of 3.9 g of ethynyltrimethylsilane in 20 ml of triethylamine.

The mixture was warmed to 60-70 ° C. and stirred for 1 hour. Then again the same amount of catalyst and ethynyltrimethylsilane were added as above and the mixture was stirred at 60-70 ° C. for 3 hours.

After cooling, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography using ethyl acetate / toluene mixture as eluent to give 2-heptylthio-6-trimethylsilylethynyl-5H-1,3,4-thiadiazolo [3,2 -a] 5.9 g of pyrimidin-5-one was obtained. Yield 80%.

Thus, 5.4 g of 2-heptylthio-6-trimethylsilethynyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was dissolved in 100 ml of tetrahydrofuran, and The solution was cooled to -65 ° C in an acetone-dry ice bath. To the cooled solution was added dropwise a solution of 0.93 g of tetrabutylammonium fluoride in 200 ml of tetrahydrofuran.

The solution was stirred at -70 to -65 ° C for 1 hour.

The solution was allowed to reach room temperature and filtered and the filtrate was concentrated under reduced pressure.

The residue was purified by silica gel column chromatography using ethyl acetate / toluene mixture as eluent to give 6-ethynyl-2-heptylthio-5H-1,3,4-thiadiazolo [3,2-a]. 3.0 g of pyrimidin-5-one was obtained. Melting point 140 to 142 ° C. Yield 70%.

Preparation Example 15

Synthesis of 2-hexanesulfonyl-7-methoxy-6-nitro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one

1.9 g of 2-hexylthio-7-methoxy-6-nitro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one in 50 ml of acetic acid and sodium tungstate dihydrate 0.1 g was dissolved.

The solution was warmed up to 50 ° C., 3.1 g of 30% hydrogen peroxide solution was added dropwise, and the solution was stirred at 52 ° C. for 1 hour. The reaction mixture was poured into 500 ml of water, and the formed precipitate was collected by filtration.

The precipitate was washed with aqueous sodium hydrogen sulfite solution and water and recrystallized from ethanol.

Thus, 1.5 g of 2-hexanesulfonyl-7-methoxy-6-nitro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was obtained as colorless tetragonal crystals. . Melting point 150-152 ° C. Yield 71%.

Preparation Example 16

Synthesis of 6-acetyl-2-hexanesulfonyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one

1.8 g of 6-acetyl-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was dissolved in 30 ml of acetic acid. To this solution was added 2.0 g of a 30% hydrogen peroxide solution and 0.1 g of sodium tungstate dihydrate, and the solution was stirred at 55 to 60 ° C. for 2 hours. The reaction mixture was extracted with chloroform, and the organic layer was washed with water, aqueous sodium thiosulfate solution, and then water.

The solvent was distilled off and the residue was recrystallized from ethanol / benzene mixture.

Thus, 1.0 g of 6-acetyl-2-hexanesulfonyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was obtained. Melting point 124 to 125 ° C. Yield 50%.

Preparation Example 17

Synthesis of 6-cyano-2-heptansulfonyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one

To 50 ml of acetic acid was added 2.1 g of 6-cyano-2-heptylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one and 0.1 g of sodium tungstate dihydrate.

2.3 g of 30% hydrogen peroxide solution was added dropwise to this solution to prevent the temperature of the solution from exceeding 50 ° C.

The solution was then stirred at 50 ° C. for 3 hours.

After the reaction was completed, water was added to the reaction mixture, and the precipitated crystals were collected by filtration.

This crude crystal was recrystallized from ethanol to obtain 2 g of 6-cyano-2-heptylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. Melting point 130 to 132 ° C. Yield 85%.

Preparation Example 18

Synthesis of 7-cyano-2-hexanesulfonyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one

Dissolve 2.2 g of 7-cyano-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one in 40 ml of acetic acid, and 0.12 g of sodium tungstate dihydrate. To this solution was added dropwise 4.3 g of 30% hydrogen peroxide mixed with 20 ml of acetic acid.

The solution was then stirred at 45-50 ° C. for 2 hours. After cooling to room temperature, the solution was extracted with chloroform and water. The organic layer was washed with aqueous sodium thiosulfate solution and water, respectively.

The solvent was distilled off after drying over anhydrous sodium sulfate.

The residue was recrystallized from ethanol to give 1.6 g of 7-cyano-2-hexanesulfonyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. Melting point 144-146 캜. Yield 65%.

Preparation Example 19

Synthesis of 2-hexylthio-7-methoxy-6-nitro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (intermediate)

76 g of 2-amino-5-hexylthio-1,3,4-thiadiazole and 170 g of malonic acid bis (2,4,6-trichlorophenyl) ester were mixed in 200 ml of chlorobenzene, and the mixture was refluxed to 1 Stir for hours.

After the reaction was over, the reaction mixture was cooled and the precipitate formed was collected by filtration and washed with ether.

Thus, 82 g of 2-hexylthio-7-hydroxy-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one as a white powder was obtained. Melting point 193-197 캜. Yield 82%.

78 g of 2-hexylthio-7-hydroxy-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one were suspended in 800 ml of acetic acid.

120 ml of fuming nitric acid was added dropwise to this suspension at room temperature.

After stirring for 3 hours, the reaction mixture was cooled and the precipitate formed was collected by filtration and washed with ether. Thus, 84.5 g of 2-hexylthio-7-hydroxy-6-nitro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was obtained as colorless filament-like crystals. Melting point 139 to 141 ° C. Yield 94%.

In 240 ml of phosphorus oxychloride, 66 g of 2-hexylthio-7-hydroxy-6-nitro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one are suspended and this suspension 24 g of N, N-dimethylaniline was added dropwise at room temperature.

The mixture was stirred at reflux for 2 hours.

Phosphorus oxychloride in the reaction mixture was distilled off under reduced pressure at 50 占 폚.

에 주가하고, 석출된 결정체를 여과에 의해 모았다.Residue on ice water 1

Was added to the solution, and the precipitated crystals were collected by filtration.

Crystals were recrystallized from ethanol and scaled pale yellow crystals of 7-chloro-2-hexylthio-6-nitro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one 58.4 g was obtained. Melting point 84.5 to 86 ° C. Yield 83%.

To 50 ml of methanol was added 3.0 g of 7-chloro-2-hexylthio-6-nitro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one and 1.0 g of pyridine. The mixture was stirred at reflux for 30 minutes.

Water was added to the reaction mixture, and the organic layer was extracted with ethyl acetate.

The ethyl acetate solution was dried over anhydrous magnesium sulfate and the solvent was distilled off.

The residue was purified by silica gel column chromatography using ethyl acetate / hexane mixtures as eluent. Thus, 1.9 g of 2-hexylthio-7-methoxy-6-nitro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one as a brown transparent viscous liquid was obtained. Yield 63%.

Preparation Example 20

Synthesis of 6-acetyl-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (intermediate)

In 60 ml of ethanol, 4.4 g of 2-amino-5-hexylthio-1,3,4-thiadiazole and 2.4 g of N, N-dimethylformamido dimethylacetal were dissolved, and the solution was refluxed for 2 hours. After cooling the reaction mixture to room temperature, the crystals formed were collected by filtration, washed with ethanol and dried.

Thus, 4.4 g of N'-2- (5-hexylthio-1,3,4-thiadiazolyl) -N, N-dimethylformamidine was obtained.

Melting point 89 to 91 캜; Yield 81%

Then a mixture of 70 ml of dry benzene, N'-2- (5-hexylthio-1,3,4-thiadiazolyl) -N, 4.4 g of N-dimethylformamidine and 2.7 g of diketene was added for 6 hours. It was refluxed. The reaction mixture was concentrated and the residue was purified by silica gel column chromatography using ethyl acetate / normal hexane (1: 3) mixture as eluent. The eluent was distilled off to obtain 1.8 g of 6-acetyl-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. Yield 36%.

Preparation Example 21

Synthesis of 6-cyano-2-heptylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (intermediate)

8 g of 2-amino-5-heptylthio-1,3,4-thiadiazole, 5 g of ethyl 3-ethoxy-2-propenoic acid, 10 g of polyphosphoric acid and 10 ml of xylene were mixed, and the mixture was mixed at 125 DEG C. Stir vigorously for a minute.

After the reaction was completed, the reaction mixture was extracted with water and toluene. The organic layer was washed with aqueous sodium hydrogen carbonate solution and then again with water.

The solvent was distilled off and the residue was recrystallized from the normal hexane / ethanol mixture to give 7.4 g of 2-heptylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. Yield 75%.

In 50 ml of acetic acid, 7.4 g of 2-heptylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one and 5.3 g of zinc chloride were dissolved. 6.3 g of iodine monochloride was added to the solution and the mixture was stirred at 70 to 80 ° C. for 1 hour.

After the reaction was completed, water and brine were added, and the precipitated crystals were collected by filtration. The collected crystals were washed with water and isopropyl ether to give 7.7 g of 2-heptylthio-6-iodo-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. Yield 72%.

Dissolve 7.7 g of 2-heptylthio-6-iodo-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one in 70 ml of dimethyl formamide, and 3.4 g of cuprous cyanide. And 1.8 g sodium cyanide were added to this solution. The mixture was stirred at 130 ° C. for 3 hours.

After the reaction was completed, the reaction mixture was injected into water. Toluene was added to the mixture and the mixture was stirred well. Insoluble material was collected by filtration with filtration aid. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off and the remaining crude crystals were recrystallized from ethanol.

Thus, 2.1 g of 2-heptylthio-6-cyano-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was obtained. Yield 37%.

Preparation Example 22

Synthesis of 2-hexylthio-7-cyano-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one (intermediate)

6 g of 2-hepsylthio-7-iodo-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was dissolved in 100 ml of dimethyl formamide.

1.77 g of cuprous cyanide and 0.97 g of sodium cyanide were added to the solution, and the solution was stirred at 100 ° C for 1 hour. The reaction mixture was cooled to room temperature and extracted with chloroform and water.

(Florisil

)을 유기층에 첨가하고 흔들어주었다.The organic layer was washed with water and dried over anhydrous sodium sulfate. Florisil

(Florisil

) Was added to the organic layer and shaken.

The solvent was distilled off and 2.3g of 7-cyano-2-hexylthio-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one was obtained. Yield 51%.

Preparation Example 1

Powder

2% compound 1, 5% diatomaceous earth and 93% clay were homogeneously mixed and ground to produce a powder.

Preparation Example 2

Hydrating agent

Compound No. 2, 45% diatomaceous earth, 2% sodium dinaphthylmethanesulfonate and 3% sodium lignosulfonate were homogeneously mixed and separated to produce a wetting agent.

Preparation Example 3

Emulsifier

30% compound No. 33, 20% cyclohexanone, 11% polyoxyethylene alkylaryl ether, 4% alkylbenzenesulfonate calcium and 35% methylnaphthalene were homogeneously mixed and emulsified.

Preparation Example 4

Granules

5% compound 40, 2% sodium salt of lauryl alcohol sulfate ester, 5% sodium lignosulfonate, 2% carboxymethylcellulose and 86% clay were mixed and ground homogeneously. 20% of water was added to the mixture and the mixture was prepared into granules of 14 to 32 mesh by an extruder. The granules were dried to complete the granules.

The bactericidal activity of the compounds of the present invention will now be described by the test examples.

Test Example 1

Protective Effect of Chinese Gat (Brassica rapa var. Pervidis) on Singe Patterns

Twelve Chinese fresh seeds were placed in plastic pots of 9cm × 9cm size, each of which was grown from greenhouse to cotyledon for 7 days.

On the grown seedlings, the hydrating agent prepared according to Preparation Example 2 was diluted to 50 ppm with water and sprinkled with about 10 ml in each pot.

After the sprinkled preparations were air dried, the plants were sprayed with a spore suspension of soot rot pathogen (Alternaria brassicicola) and the pots were stored in a 30 ° C. room. After 3 days, the disease numbers were calculated and the average number of flies was recorded. Control activity was calculated according to the following definition.

The results are shown in Table 2.

TABLE 2

* [N- (trichloromethylthio) -4-cyclohexane-1,2-dicarboxyimide]

Test Example 2

Control of Apple Spot Larch

Six to seven leafy young twigs removed from the apple tree (variety: India) were placed in a glass cylinder.

The hydrating agent prepared according to Preparation Example 2 was diluted to 1500 ppm with water and sprinkled thereon.

After air drying, the plants were inoculated with a spore suspension of Alternaria mali spores and inoculated and stored in a 28 ° C. chamber. Four days later, damage was calculated and control activity was calculated according to the following criteria.

N is the total number of leaf flies examined.

n ₁ is the number of infected leaf flies whose area is less than 5%.

n ₂ is the number of infected leaf flies with 5-10% disease area.

n ₃ is the number of infected leaf flies with 11-25% disease area.

n ₄ is the number of infected leaf flies with 26-50% disease area.

n ₅ is the number of infected leaves with 51% or more diseased area.

The results are shown in Table 3.

TABLE 3

Test Example 3

Prevention of gray mold disease in cucumber

12 seeds of cucumber (variety: Sagami-hanjiro) were sprinkled in a plastic pot of 9 cm x 9 cm square, and grown in a greenhouse for 7 days. On the young seedlings grown up to the cotyledon stage, the hydrating agent prepared according to Preparation Example 2 was diluted to 500ppm of the active ingredient concentration with water and sprinkled at about 10 ml in each pot. After the sprinkled preparations were air dried, the plants were inoculated with a homogenous suspension of mycelia of Botrytis cinearea, and the pollen was stored in a 20-23 ° C. room. After 4 days all pollen was examined for pest status.

Bite Index

0: non-ill

1: The area of disease is 25% or less.

2: the diseased area is 26-50%.

3: the diseased area is 51 to 75%.

4: The area of disease is 75%.

The results are shown in Table 4.

TABLE 4

Other compounds were also effective against cucumber's gray mold disease.

Test Example 4

Protective effect against rice fever

Twenty seeds of rice (variety: Aichiasahi) were sprinkled with 20 white porcelain pots, each 9 cm in diameter, and grown in a greenhouse for 3 to 4 weeks. At the four-leaf stage, seedlings prepared according to Preparation Example 2 were diluted to 500 ppm of active ingredient concentration with water and sprinkled with about 10 ml in each pot.

After the sprinkled preparations were air dried, seedlings were inoculated with spores of Pyricularia oryzae suspended in water and stored in a 25 ° C wet room. The outbreak was allowed for five days in the greenhouse. Control activity was calculated by counting pest numbers.

The results are shown in Table 5.

TABLE 5

Other compounds were also effective against rice fever.

Test Example 5

Control of Tomato Plague (Local Test)

Tomato seedlings (variety: Ohgata-Fukuju) were transferred on August 20, 1986. Plants having grown from 12 to 13 leaves were used for testing. Each five plants were designated as one plot and three compartments received the same treatment.

The use of the fungicide was carried out three times over September 30, October 7 and 14. The fungicide was sprayed at about 2 liters per 3 zones. Infestation was examined on October 21 for the fourth to ninth leaves. Damage and control activity were calculated according to the following definition.

Rating

Index Percentage of Area

0 0

1 1/3 or less

2 1/3 to 2/3

3 2/3 or more

(지수1의 잎숫자)×1+(지수2의 잎숫자)×2+(지수3의 잎숫자) ×3}/(잎의 총숫자) ×3]×100Damage = [{

(Leaf number of index 1) × 1 + (leaf number of index 2) × 2+ (leaf number of index 3) × 3} / (total number of leaves) × 3] × 100

The results are shown in Table 6.

TABLE 6

* TPN (tetrachloro-isophthalnitrile)

Claims (21)

5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5one derivative represented by the following general formula (I).

Wherein X is a hydrogen atom, a halogen atom, a straight or branched lower alkyl group, a lower alkoxy group, a lower acyl group, a trihalo-lower-alkoxy group, a lower alkynyl group, a phenyl group, a cyan group, a phenoxy group, or a nitro group Display; Y represents a hydrogen atom, a halogen atom, a linear or branched lower alkyl group, a halo-lower-alkyl group, a lower alkoxy group, a lower alkynyl group, a phenyl-lower-alkynyl group, a lower-alkyl-amino group, or a cyan group; And R is a linear or branched alkyl group, cyclohelical-lower-alkyl group, lower alkenyl group, cyclohexyl group, phenoxy-lower-alkyl group, halo-alkyl group, halo-alkenyl group, lower-alkoxy carbonyl-lower-alkyl group A phenyl group which may be substituted with a tri-lower-alkyl-silyl-lower-alkyl group, a phenyl-lower-alkyl group, an alkoxy-lower-alkyl group, one or more halogen atoms, a lower alkyl group or a nitro group or a lower alkoxy group; Formula -CH ₂

Wherein Z represents a halogen atom, a lower alkyl group, a lower alkoxy group, a trihalo-lower-alkyl group or a nitro group, n is an integer of 1 or 2, wherein two substituents are the same Or may be different; When X is a hydrogen atom, a halogen atom, a nitro group or an alkyl group and Y is an alkyl group, R is not an alkyl group or a phenyl-lower-alkyl group. The compound of claim 1, wherein X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, an ethynyl group, an acetyl group, a trifluoroepoxy group, a phenyl group, a phenoxy group, a nitro group or a cyan group; Y represents a hydrogen atom, a halogen atom, a lower alkyl group, a chloromethyl group, a C _1-2 -alkoxy group, an alkynyl group, a phenylethynyl group, a C _2-3 -alkylamino group or a cyan group; And R is an alkyl group, cyclohexylmethyl group, allyl group, cyclohexyl group, phenoxyalkyl group, haloalkyl group, dichloro alkenyl group, epoxycarbonylbutyl group, alkoxyalkyl group, phenyl-lower-alkyl group, trimethyl-silyl-propyl group, halogen Atom, lower alkyl group, lower alkoxy group, phenyl group which may be substituted by nitro group, general formula-CH ₂

5H-1,3,4, characterized in that it represents a group represented by (wherein Z represents a halogen atom, lower alkyl group, lower alkoxy group, trifluoromethyl or nitro group, n is an integer of 1 or 2) -Thiadiazolo [3,2-a] pyrimidin-5-one derivatives. The compound of claim 2, wherein X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, an ethynyl group, an acetyl group or a cyan group; Y represents a hydrogen atom, a halogen atom, a lower alkyl group, an alkynyl group or a cyan group; And R represents an alkyl group, trimethylsilylpropyl group, phenethyl group, one or two halogen atoms, a phenyl group which may be substituted with a lower alkyl group, or a benzyl group substituted with one or two halogen atoms or one or two lower alkyl groups 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivative, characterized in that the. The method according to claim 3, wherein X represents a hydrogen atom, a halogen atom, a methyl group, a methoxy group, an ethynyl group, a cyan group, an acetyl group; Y represents a hydrogen atom, a halogen atom, an ethynyl group, a propynyl group or a cyan group; R represents a phenyl group which may be substituted with an alkyl group, trimethylsilylpropyl group, a halogen atom or a methyl group, or a benzyl group substituted with one or two halogen atoms or one or two methyl groups, 4-thiadiazolo [3,2-a] pyrimidin-5-one derivative. 5H-1,3, according to claim 1, which is 2-hexanesulfonyl-6-chloro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. 4-thiadiazolo [3,2-a] pyrimidin-5-one derivative 5H according to claim 1, which is 2-hexanesulfonyl-7- (1-propynyl) -5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. -1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivatives. 5H-1,3 according to claim 1, which is 2-hexanesulfonyl-7-ethynyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. , 4-thiadiazolo [3,2-a] pyrimidin-5-one derivative. 5H according to claim 1, which is 2-hexanesulfonyl-6-chloro-7-fluoro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. -1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivatives. 5H according to claim 1, which is 2-hexanesulfonyl-6-chloro-7-ethynyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. -1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivatives. 5H-1,3 according to claim 1, which is 2-octanesulfonyl-6-methoxy-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. , 4-thiadiazolo [3,2-a] pyrimidin-5-one derivative. 5H-1,3 according to claim 1, which is 2-heptansulfonyl-6-cyano-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. , 4-thiadiazolo [3,2-a] pyrimidin-5-one derivative. 5H-1,3, according to claim 1, characterized in that 2-heptanesulfonyl-6-acetyl-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. 4-thiadiazolo [3,2-a] pyrimidin-5-one derivative. 5H according to claim 1, which is 2-pentanesulfonyl-6-chloro-7-fluoro-5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one. -1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivatives. 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivative represented by general formula (II).

Wherein X is a hydrogen atom, a halogen atom, a straight or branched lower alkyl group, a lower alkoxy group, a lower acyl group, a trihalo-lower-alkoxy group, a lower alkynyl group, a phenyl group, a cyan group, a phenoxy group, or a nitro group Display; Y represents a hydrogen atom, a halogen atom, a linear or branched lower alkyl group, a halo-lower-alkyl group, a lower alkoxy group, a lower alkynyl group, a phenyl-lower-alkynyl group, a lower-alkyl-amino group, or a cyan group; And R is a linear or branched alkyl group, cyclohelical-lower-alkyl group, lower alkenyl group, cyclohexyl group, phenoxy-lower-alkyl group, halo-alkyl group, halo-alkenyl group, lower-alkoxy carbonyl-lower-alkyl group A phenyl group which may be substituted with a tri-lower-alkyl-silyl-lower-alkyl group, a phenyl-lower-alkyl group, an alkoxy-lower-alkyl group, one or more halogen atoms, a lower alkyl group or a nitro group or a lower alkoxy group; Formula -CH ₂

Wherein Z represents a halogen atom, a lower alkyl group, a lower alkoxy group, a trihalo-lower-alkyl group or a nitro group, n is an integer of 1 or 2, wherein two substituents are the same Or may be different; When X is a hydrogen atom, a halogen atom, a nitro group or an alkyl group and Y is an alkyl group, R is not an alkyl group or a phenyl-lower-alkyl group. X is a hydrogen atom, a halogen atom, a C _1-4 alkyl group, a C _1-3 -alkoxy group, an ethynyl group, an acetyl group, a trifluoroethoxy group, a phenyl group, a phenoxy group, a nitro group or a cyan Group; Y represents a hydrogen atom, a halogen atom, a C _1-3 -alkyl group, a chloromethyl group, a C _1-2 -alkoxy group, a C _2-3 alkynyl group, a phenylethynyl group, a C _2-3 -alkylamino group or a cyan group ; And R is C _{1-9 -alkyl} group, cyclohexylmethyl group, allyl group, cyclohexyl group, phenoxy alkyl group, dichloroalkenyl group, ethoxycarbonylbutyl group, alkoxyalkyl group, phenyl-lower-alkyl group, trimethyl-silyl-propyl Group, halogen atom, C _1-4 -alkyl group, C _1-3 -alkoxy group, phenyl group which may be substituted by nitro group, general formula -CH ₂

5H-1,3,4 characterized by displaying a group represented by: wherein Z represents a halogen atom, C _{1-4 -alkyl} group, C _1-3 -alkoxy group, trifluoromethyl or nitro group -Thiadiazolo [3,2-a] pyrimidin-5-one derivatives. The compound of claim 15, wherein X represents a hydrogen atom, a halogen atom, a C _1-4 -alkyl group, a C _1-3 -alkoxy group, an ethynyl group, an acetyl group, or a cyan group; Y represents a hydrogen atom, a halogen atom, a C _{1-3 -alkyl} group, a C _2-3 alkynyl group or a cyan group; And R is a C _1-9 -alkyl group, trimethylsilylpropyl group, phenethyl group, one or two halogen atoms, a phenyl group which may be substituted with a C _1-4 -alkyl group, or one or two halogen atoms or one or two 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivative characterized by displaying a benzyl group substituted with a C _1-4 -alkyl group. The compound of claim 16, wherein X represents a hydrogen atom, a halogen atom, a methyl group, a methoxy group, an ethynyl group, a cyan group, an acetyl group; Y represents a hydrogen atom, a halogen atom, an ethynyl group, a propynyl group or a cyan group; R represents a C _4-9 -alkyl group, a trimethylsilylpropyl group, a phenyl group which may be substituted with a halogen atom or a methyl group, or 5H, characterized by benzyl group substituted with one or two halogen atoms or one or two methyl groups -1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivatives. Agrohorticultural germicide composition comprising a 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivative represented by Formula (I) and an agronomically acceptable carrier.

Wherein X is a hydrogen atom, a halogen atom, a straight or branched lower alkyl group, a lower alkoxy group, a lower acyl group, a trihalo-lower-alkoxy group, a lower alkynyl group, a phenyl group, a cyan group, a phenoxy group, or a nitro group Display; Y represents a hydrogen atom, a halogen atom, a linear or branched lower alkyl group, a halo-lower-alkyl group, a lower alkoxy group, a lower alkynyl group, a phenyl-lower-alkynyl group, a lower-alkyl-amino group, or a cyan group; And R is a linear or branched alkyl group, cyclohexyl-lower-alkyl group, lower alkenyl group, cyclohexyl group, phenoxy-lower-alkyl group, halo-alkyl group, halo-alkenyl group, lower-alkoxy carbonyl-lower-alkyl group A phenyl group which may be substituted with a tri-lower-alkyl-silyl-lower-alkyl group, a phenyl-lower-alkyl group, an alkoxy-lower-alkyl group, one or more halogen atoms, a lower alkyl group or a nitro group or a lower alkoxy group; Formula -CH ₂

Wherein Z represents a halogen atom, a lower alkyl group, a lower alkoxy group, a trihalo-lower-alkyl group or a nitro group, n is an integer of 1 or 2, wherein two substituents are the same Or may be different; When X is a hydrogen atom, a halogen atom, a nitro group or an alkyl group and Y is an alkyl group, R is not an alkyl group or a phenyl-lower-alkyl group. The 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivative of claim 18, wherein X is a hydrogen atom, a halogen atom, C _{1 -4} -alkyl group, C _1-3 -alkoxy group, ethynyl group, acetyl group, trifluoroethoxy group, phenyl group, phenoxy group, nitro group or cyan group; Y is hydrogen atom, halogen atom, C _1-3 -alkyl group, chloromethyl group, C _1-2 -alkoxy group, C _2-3 -alkynyl group, phenylethynyl group, C _2-3 -alkylamino group or cyan group , R is C _{1-9 -alkyl} group, cyclohexylmethyl group, alkyl group, cyclohexyl group, phenoxy alkyl group, haloalkyl group, dichloroalkenyl group, ethoxycarbonylbutyl group, alkoxyalkyl group, phenyl-lower-alkyl group, trimethyl-silyl -Propyl group, halogen atom, C _1-4 -alkyl group, C _1-3 -alkoxy group, phenyl group which may be substituted by nitro group, general formula

Agricultural horticultural germicide composition, characterized in that the compound represented by the group (where Z represents a halogen atom, C _{1-4 -alkyl} group, C _1-3 -alkoxy group, trifluoromethyl or nitro group). 20. The 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivative of claim 19, wherein X is a hydrogen atom, a halogen atom, C _{1 -4} -alkyl group, C _1-3 -alkoxy group, ethynyl group, acetyl group or cyan group, Y is hydrogen atom, halogen atom, C _{1-3 -alkyl} group, C _2-3 -alkynyl group or cyan group, R is a C _1-9 -alkyl group, trimethylsilylpropyl group, phenethyl group, one or two halogen atoms, a phenyl group which may be substituted with a C _1-4 -alkyl group, or one or two halogen atoms or one or two C _A fungicide composition for agrohorticulture, characterized in that the compound is a benzyl group substituted with a _1-4 -alkyl group. The 5H-1,3,4-thiadiazolo [3,2-a] pyrimidin-5-one derivative represented by general formula (I) is a hydrogen atom, a halogen atom, a methyl group, Methoxy group, ethynyl group, cyan group and acetyl group; Y is a hydrogen atom, a halogen atom, an ethynyl group, a propynyl group or a cyan group; R is a C _4-9 -alkyl group, trimethylsilylpropyl group, a phenyl group which may be substituted with a halogen atom or a methyl group, or a benzyl group substituted with one or two halogen atoms or one or two methyl groups Composition.