JP2020097575A - 1,3,5,6-TETRA SUBSTITUTED THIENO[2,3-d]PYRIMIDINE-2,4(1H,3H)DIONE COMPOUND AND HORTICULTURAL BACTERICIDE - Google Patents

Abstract

To provide a 1,3,5,6-tetra substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound excellent in antibacterial activity, excellent in safety, and capable of being industrially advantageously synthesized, and a horticultural bactericide containing the same as an active ingredient.SOLUTION: There is provided a compound represented by formula (I) or a salt thereof. Ris C1 to 6 alkyl, Rand Rare H or the like, Ris C1 to 6 alkoxycarbonyl or the like, Ris H or the like, Rand Rare H or the like, X is halogen or the like, n is an integer of 0 to 5, and X may be different each other.SELECTED DRAWING: None

Description

The present invention relates to a 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound and an agricultural/horticultural fungicide. More specifically, the present invention provides 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4( which has excellent bactericidal activity, excellent safety and can be synthesized industrially advantageously. 1H,3H) dione compound, and an agricultural and horticultural fungicide containing the same as an active ingredient.

Various compounds having a control activity against diseases of crops during cultivation of agricultural and horticultural crops have been proposed. In order to practically use such a compound as an agricultural and horticultural fungicide, it is not only highly effective, but also resistant to drug resistance, does not cause phytotoxicity to plants and soil pollution, against livestock and fish, etc. Low toxicity is required.

By the way, Patent Document 1 discloses a compound represented by the formula (A) and the like.

Patent Document 2 discloses a compound represented by the formula (B) and the like.

Patent Document 3 discloses a compound represented by the formula (C) and the like.

Patent Document 4 discloses a compound represented by the formula (D) and the like.

Patent Document 5 discloses a compound represented by the formula (E) and the like.

Patent Document 6 discloses a compound represented by the formula (F) and the like. Further, Patent Document 7 discloses use of a fungicide for agricultural and horticultural use, such as a compound represented by the formula (F).

Patent Document 8 discloses a compound represented by the formula (G) and the like.

Patent Document 9 discloses a compound represented by the formula (H) and the like.

WO 2013/071169 A WO 2015/007451 A WO 2017/075056 A WO 2017/091600 A WO 2017/091602 A WO 2017/091617 A WO 2017/091627 A WO 2018/171698 A WO 2018/171699 A

An object of the present invention is to provide 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H, which has excellent bactericidal activity, excellent safety, and can be industrially advantageously synthesized. 3H) dione compound (hereinafter, may be simply referred to as “thienopyrimidine compound”), and an agricultural and horticultural fungicide containing the same as an active ingredient.

As a result of intensive studies to solve the above problems, the present invention including the following modes has been completed.

[1] A compound represented by formula (I) or a salt thereof.
(In formula (I),
R ¹ is a substituted or unsubstituted C1-6 alkyl group.
R ² and R ³ are each independently a hydrogen atom or a substituted or unsubstituted C1-6 alkyl group.
R ⁴ is a substituted or unsubstituted C1-6 alkoxycarbonyl group, or a substituted or unsubstituted C1-6 alkylaminocarbonyl group.
R ⁷ is a hydrogen atom, a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C3-8 cycloalkyl group or a tri-C1-6 alkylsilyl group.
R ⁵ and R ⁶ are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C ^1-6 alkoxy group, an oxo group formed by combining R ⁵ and R ⁶ or a substituted or unsubstituted C ¹ to R ⁶ group. 6 is an alkoxyimino group.
X is a halogeno group or a substituted or unsubstituted C1-6 alkoxy group.
n is an integer of 0 to 5, and when n is 2 or more, X may be the same or different. )

[2] A fungicide for agricultural and horticultural use containing as an active ingredient at least one selected from the group consisting of the compound described in [1] above and a salt thereof.

INDUSTRIAL APPLICABILITY The thienopyrimidine compound of the present invention has excellent bactericidal activity, certain effects, excellent safety, and can be synthesized industrially advantageously.
INDUSTRIAL APPLICABILITY The agricultural and horticultural germicide of the present invention has an excellent control effect, does not cause phytotoxicity to plants, and has little toxicity to humans and fishes and environmental influence.

[Thienopyrimidine compound]
The thienopyrimidine compound of the present invention is a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)) or a salt of compound (I).

In the present invention, the term “unsubstituted” means only a group serving as a nucleus. When only the name of the group serving as a mother nucleus is described, it means “unsubstituted” unless otherwise specified.
On the other hand, the term “substituted” means that any hydrogen atom of the group serving as the nucleus is substituted with a group having the same or different structure as the nucleus. Therefore, the "substituent" is another group bonded to the group serving as the nucleus. The number of substituents may be one, or may be two or more. Two or more substituents may be the same or different.

The “substituent” is chemically acceptable and is not particularly limited as long as it has the effects of the present invention.
The following groups can be mentioned as specific examples of the group that can be a “substituent”.
Fluoro, chloro, bromo, iodo and other halogeno groups;
C1-6 such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group and n-hexyl group. Alkyl group;
Vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group , 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4 -C2-6 alkenyl group such as hexenyl group, 5-hexenyl group;

Ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 2-methyl-3-butynyl group, 1-pentynyl group , 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1-hexynyl group, 1,1-dimethyl-2-butynyl group, etc. A C2-6 alkynyl group;
A C3-8 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cubanyl group;
A C3-8 cycloalkenyl group such as a 2-cyclopropenyl group, a 2-cyclopentenyl group, a 3-cyclohexenyl group, a 4-cyclooctenyl group;
C6-10 aryl group such as phenyl group and naphthyl group;
5-membered heteroaryl group such as pyrrolyl group, furyl group, thienyl group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, triazolyl group, oxadiazolyl group, thiadiazolyl group and tetrazolyl group;
6-membered heteroaryl group such as pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, triazinyl group;
Condensed ring heteroaryl groups such as indolyl group, benzofuryl group, benzothienyl group, benzimidazolyl group, benzoxazolyl group, benzothiazolyl group, quinolyl group, isoquinolyl group, quinoxalinyl group;
Cyclic ether groups such as oxiranyl group, tetrahydrofuryl group, dioxolanyl group, dioxanyl group;
Cyclic amino groups such as aziridinyl group, pyrrolidinyl group, piperidyl group, piperazinyl group and morpholinyl group;

Hydroxyl group;
Oxo group;
C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group;
C2-6 alkenyloxy groups such as vinyloxy group, allyloxy group, propenyloxy group, butenyloxy group;
C2-6 alkynyloxy groups such as ethynyloxy group and propargyloxy group;
C6-10 aryloxy groups such as phenoxy group and naphthoxy group;
5- to 6-membered heteroaryloxy groups such as thiazolyloxy group and pyridyloxy group;

Carboxy group;
Formyl group;
C1-6 alkylcarbonyl groups such as acetyl group and propionyl group;
Formyloxy group;
C1-6 alkylcarbonyloxy groups such as acetyloxy group and propionyloxy group;
A C1-6 alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group;

C1-6 haloalkyl group such as chloromethyl group, chloroethyl group, trifluoromethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, perfluoro-n-pentyl group;
A C2-6 haloalkenyl group such as a 2-chloro-1-propenyl group or a 2-fluoro-1-butenyl group;
A C2-6 haloalkynyl group such as a 4,4-dichloro-1-butynyl group, a 4-fluoro-1-pentynyl group, a 5-bromo-2-pentynyl group;
A C3-6 halocycloalkyl group such as a 3,3-difluorocyclobutyl group;
A C1-6 haloalkoxy group such as a 2-chloro-n-propoxy group, a 2,3-dichlorobutoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group;
A C2-6 haloalkenyloxy group such as a 2-chloropropenyloxy group or a 3-bromobutenyloxy group;
C1-6 haloalkylcarbonyl groups such as chloroacetyl group, trifluoroacetyl group, trichloroacetyl group;

Cyano group;
Nitro group;
Amino group;
C1-6 alkylamino groups such as methylamino group, dimethylamino group and diethylamino group;
C6-10 arylamino groups such as anilino group and naphthylamino group;
Formylamino group; C1-6 alkylcarbonylamino group such as acetylamino group, propanoylamino group, butyrylamino group, i-propylcarbonylamino group;
A C1-6 alkoxycarbonylamino group such as a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, an i-propoxycarbonylamino group;
A C1-6 alkylsulfoxyimino group such as an S,S-dimethylsulfoxyimino group;

Aminocarbonyl group;
A C1-6 alkylaminocarbonyl group such as a methylaminocarbonyl group, a dimethylaminocarbonyl group, an ethylaminocarbonyl group, an i-propylaminocarbonyl group;
Imino C1-6 alkyl groups such as iminomethyl group, (1-imino)ethyl group, (1-imino)-n-propyl group;
Hydroxyimino C1-6 alkyl groups such as hydroxyiminomethyl group, (1-hydroxyimino)ethyl group, (1-hydroxyimino)propyl group;
C1-6 alkoxyimino C1-6 alkyl groups such as methoxyiminomethyl group and (1-methoxyimino)ethyl group;

Mercapto group;
C1-6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group;
C1-6 haloalkylthio groups such as trifluoromethylthio group and 2,2,2-trifluoroethylthio group;
C2-6 alkenylthio groups such as vinylthio group and allylthio group;
C2-6 alkynylthio groups such as ethynylthio group and propargylthio group;
A C1-6 alkylsulfinyl group such as a methylsulfinyl group, an ethylsulfinyl group, a t-butylsulfinyl group;
A C1-6 haloalkylsulfinyl group such as a trifluoromethylsulfinyl group or a 2,2,2-trifluoroethylsulfinyl group;
A C2-6 alkenylsulfinyl group such as an allylsulfinyl group;
A C2-6 alkynylsulfinyl group such as a propargylsulfinyl group;
A C1-6 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a t-butylsulfonyl group;
A C1-6 haloalkylsulfonyl group such as a trifluoromethylsulfonyl group or a 2,2,2-trifluoroethylsulfonyl group;
C2-6 alkenylsulfonyl group such as allylsulfonyl group;
A C2-6 alkynylsulfonyl group such as a propargylsulfonyl group;
Aminothiocarbonyl group;

A tri-C1-6 alkylsilyl group such as a trimethylsilyl group, a triethylsilyl group or a t-butyldimethylsilyl group;
Tri-C6-10 arylsilyl group such as triphenylsilyl group

In these "substituents", any hydrogen atom in the substituent may be substituted with a group having a different structure.

Terms such as "C1-6" indicate that the group serving as the nucleus has 1 to 6 carbon atoms. This number of carbon atoms does not include the number of carbon atoms present in the substituent. For example, the ethoxybutyl group is classified as a C2 alkoxy C4 alkyl group because the mother nucleus group is a butyl group and the substituent is an ethoxy group.

[R ¹ ]
In formula (I), R ¹ is a substituted or unsubstituted C1-6 alkyl group.

The “C1-6 alkyl group” for R ¹ may be linear or branched. As the alkyl group, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group. , I-pentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, i-hexyl group and the like.

As a substituent on the "C1-6 alkyl group" for R ¹ , preferably a halogeno group such as a fluoro group, a chloro group, a bromo group, an iodo group; a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, C1-6 alkoxy group such as n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group; 2-chloro-n-propoxy group, 2,3-dichlorobutoxy group, trifluoromethoxy group and the like C1-6 haloalkoxy group; a cyano group can be mentioned.

[R ² , R ³ ]
In formula (I), R ² and R ³ are each independently a hydrogen atom or a substituted or unsubstituted C1-6 alkyl group.

Examples of the “substituted or unsubstituted C1-6 alkyl group” for R ² and R ³ include the same groups as those specifically exemplified for R ¹ .

[R ⁴ ]
In formula (I), R ⁴ is a substituted or unsubstituted C1-6 alkoxycarbonyl group or a substituted or unsubstituted C1-6 alkylaminocarbonyl group.

Examples of the "C1-6 alkoxycarbonyl group" for R ⁴ include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group and the like. it can.

Examples of the “C1-6 alkylaminocarbonyl group” for R ⁴ include mono C1-6 alkylaminocarbonyl groups and diC1-6 alkylaminocarbonyl groups.
Examples of the mono C1-6 alkylaminocarbonyl group include a methylaminocarbonyl group, an ethylaminocarbonyl group, an i-propylaminocarbonyl group and the like.
Examples of the diC1-6 alkylaminocarbonyl group include a dimethylaminocarbonyl group and a diethylaminocarbonyl group.

As the substituents on the "C1-6 alkoxycarbonyl group" and "C1-6 alkylaminocarbonyl group" of R ⁴ , halogeno groups such as fluoro group, chloro group, bromo group, and iodo group can be preferably exemplified.

[R ⁷ ]
Wherein (I), ^{R 7} is a hydrogen atom, substituted or non-substituted C1~6 alkyl group, a substituted or non-substituted C3~8 cycloalkyl group or tri C1~6 alkyl silyl group.

Examples of the “substituted or unsubstituted C1-6 alkyl group” for R ⁷ include the same groups as those specifically exemplified for R ¹ .

Examples of the "C3-8 cycloalkyl group" for R ⁷ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cubanyl group and the like.

As the substituent on the “C3-8 cycloalkyl group” for R ^7, a halogeno group such as a fluoro group, a chloro group, a bromo group or an iodo group can be preferably exemplified.

Examples of the “tri-C1-6 alkylsilyl group” for R ⁷ include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group and the like.

[R ⁵ , R ⁶ ]
In formula (I), R ⁵ and R ⁶ are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1-6 alkoxy group, or an oxo group formed by combining R ⁵ and R ⁶ or a substituted group. Alternatively, it is an unsubstituted C1-6 alkoxyimino group.

The "C1-6 alkoxy group" for R ⁵ and R ⁶ is, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group. A group etc. can be mentioned.

As a substituent on the "C1-6 alkoxy group" for R ⁵ and R ⁶ , preferably a halogeno group such as a fluoro group, a chloro group, a bromo group and an iodo group; a cyano group; a vinyl group; an aminothiocarbonyl group. You can

Examples of the "C1-6 alkoxyimino group" formed by R ⁵ and R ⁶ together include a methoxyimino group, an ethoxyimino group, an i-propoxyimino group and the like.

The substituent on the "C1-6 alkoxyimino group" formed by R ⁵ and R ^{6 taken} together is preferably a hydroxyl group.

[X]
In formula (I), X is a halogeno group or a substituted or unsubstituted C1-6 alkoxy group.
Examples of the "halogeno group" for X include a fluoro group, a chloro group, a bromo group, an iodo group and the like.

As the “C1-6 alkoxy group” for X, the same groups as those specifically exemplified for R ⁵ and R ⁶ can be mentioned.

As the substituent on the "C1-6 alkoxy group" in X, preferably, a halogeno group such as a fluoro group, a chloro group, a bromo group or an iodo group can be mentioned.

〔salt〕
The salt of compound (I) is not particularly limited as long as it is an agro-horticulturally acceptable salt. For example, salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid; salts of alkali metals such as lithium, sodium and potassium; salts of alkaline earth metals such as calcium and magnesium; iron, copper, etc. Salts of transition metals; salts of organic bases such as triethylamine, tributylamine, pyridine and hydrazine; ammonia and the like.

〔Production method〕
The method for producing the compound (I) or the salt of the compound (I) is not limited. For example, the compound (I) or the salt of the compound (I) of the present invention can be obtained by a known method as described in Examples and the like. Further, the salt of compound (I) can be obtained from compound (I) by a known method.

[Fungicide for agriculture and horticulture]
The fungicide for agricultural and horticultural use of the present invention contains at least one selected from the compound (I) and salts thereof as an active ingredient. The amount of the compound (I) or salt thereof contained in the agricultural/horticultural germicide of the present invention is not particularly limited as long as it exhibits a germicidal effect.

The fungicide for agricultural and horticultural use of the present invention is a wide variety of filamentous fungi, for example, algae fungi (Oomycetes), ascomycetes (Ascomycetes), imperfect fungi (Deuteromycetes), basidiomycetes (Basidiomycetes), conjugation It can be used for controlling plant diseases derived from fungi belonging to fungi (Zygomycetes).

Examples of plant diseases (pathogens) to be controlled are shown below.
Sugar beet: brown spot (Cercospora beticola), black root (Aphanomyces cochlioides), root rot (Thanatephorus cucumeris), leaf rot (Thanatephorus cucumeris), rust (Uromyces betae), powdery mildew (Oidium sp.), spots Diseases (Ramularia beticola), seedling blight (Aphanomyces cochlioides, Pythium ultimum), etc. Peanut: brown spot (Mycosphaerella arachidis), spot blotch (Ascochyta sp.), rust (Puccinia arachidis), blight (Pythium debaryanum). ), rust spot disease (Alternaria alternata), white silkworm disease (Sclerotium rolfsii) black astringent disease (Mycosphaerella berkeleyi), etc. Cucumber: powdery mildew (Sphaerotheca fuliginea), downy mildew (Pseudoperonospora cubensis), wilt disease (Mycosphaerella melonis). , Fusarium oxysporum, Sclerotinia sclerotiorum, Botrytis cinerea, Anthracnose (Colletotrichum orbiculare), Black scab (Cladosporium cucumerinum), Brown spot (Corynespora cassiicola), Seedling Blight (Pythium debaryanum, Rhizoctonia solani Kuhn), Phomopsis root rot (Phomopsis sp.) Spot bacterial disease (Pseudomonas syringae pv. Lechrymans), etc. Tomato: Gray mold (Botrytis cinerea), leaf mold (Cladosporium fulvum), plague (Phytophthora infestans), half body wilt (Verticillium albo-atrum, Verticillium dahliae), powdery mildew (Oidium neolycopersici), ring spot (Alternaria solani), scab (Pseudocercospor) Eggplant: Gray mold (Botrytis cinerea), black spot (Corynespora melongenae), powdery mildew (Erysiphe cichoracearum), scab (Mycovellosiella nattrassii), sclerotinia sclerotiorum, wilt wilt Strawberry: Gray mold (Botrytis cinerea), powdery mildew (Sphaerotheca humuli), anthracnose (Colletotrichum acutatum, Colletotrichum fragariae), plague (Phytophthora cactorum), soft rot, and soft rot (Verticillium dahliae), brown rot (Phomopsis vexans) Rhizopus stolonifer), chlorosis (Fusarium oxysporum), wilt (Verticillium dahliae), etc. Onions: Gray rot (Botrytis allii), Gray mold (Botrytis cinerea), White spot blight (Botrytis squamosa), Downy mildew (Peronospora). Destructor), White plague (Phytophthora porri), Small sclerotia (Ciborinia allii), etc. Leek: Soft rot (Pectobacterium carotovorum), downy mildew (Peronospora destructor), leaf blight (Pleospora allii), black rot (Sclerotium) Sclerotium cepivorum), rust (Puccinia allii), leaf spot blight (Botrytis squamosa), etc. Cabbage: Plasmodiophora brassicae, soft rot (Erwinia carotovora), black rot (Xanthomonas campesrtis pv. campestris), black spot Bacterial disease (Pseudomonas syringae pv. maculicola, P. s. pv. alisalensis), downy mildew (Peronospora parasitica), sclerotinia sclerotiorum, black scab (Alternaria brassicicola), gray mold disease (Botrytis cinerea), etc. Green beans: Sclerotinia sclerotiorum, Gray mold (Botrytis cinerea), Anthrax (Colletotrichum lindemuthianum), Horn spot (Phaeoisariopsis griseola), etc.

Apples: powdery mildew (Podosphaera leucotricha), scab (Venturia inaequalis), monilia disease (Monilinia mali), sunspot (Mycosphaerella pomi), rot (Valsa mali), leaf spot (Alternaria mali), red scab (Gymnosporang). yamadae), leaf spot (Botryosphaeria berengeriana), anthracnose (Glomerella cingulata, Colletotrichum acutatum), brown spot (Diplocarpon mali), soot spot (Zygophiala jamaicensis), spot blotch (Gloeodes pomigena), purple leaf spot disease (Helicobasidium mompa), gray mold (Botrytis cinerea), burn injury (Erwinia amylovora), etc. Ume: scab (Cladosporium carpophilum), gray mold (Botrytis cinerea), sterility disease (Monilinia mumecola), soot spot (Peltaster). sp.) Oysters: powdery mildew (Phyllactinia kakicola), anthracnose (Gloeosporium kaki), leaf spot leaf spot (Cercospora kaki), star-leaved leaf disease (Mycosphaerella nawae), etc. Peach: Monilinia fructicola, Scab (Cladosporium carpophilum), Phomopsis rot (Phomopsis sp.), Bacterial bacterial disease (Xanthomonas campestris pv. pruni), Leaf blight (Taphrina deformans), Anthracnose (Colletotrichum gloeosporioides), etc. laxa), leaf spot (Stigmina carpophila), scab (Cladosporium carpophilum), leaf blight (Polystigma rubrum), leaf spot (Alternaria alternata), anthracnose (Colletotrichum gloeospoides), etc. Sweet cherry: ash blight (Monilinia fructi) cola), anthracnose (Colletotrichum acutatum), black spot (Alternaria sp.), sclerotial disease (Monilinia kusanoi), brown scab (Mycosphaerella cerasella), etc. Grape: Gray mold (Botrytis cinerea), powdery mildew Disease (Uncinula necator), late rot (Glomerella cingulata, Colletotrichum acutatum), downy mildew (Plasmopara viticola), black scab (Elsinoe ampelina), brown spot (Pseudocercospora vitis), black rot (Guignardia bidwellii), white Rot (Coniella castaneicola), rust (Phakopsora ampelopsidis), white cotton snow disease (pathogen unidentified), etc. Pear: scab (Venturia nashicola), scab (Gymnosporangium asiaticum), black spot (Alternaria kikuchiana), ring spot disease (Botryosphaeria berengeriana), powdery mildew (Phyllactinia mali), blight (Phomopsis fukushii), brown spot (Stemphylium vesicarium), anthracnose (Glomerella cingulata), etc. Cha: leaf spot (Pestalotiopsis longiseta, P. theae) , Anthracnose (Colletotrichum theae-sinensis), net blast (Exobasidium reticulatum), etc. Citrus: Scab (Elsinoe fawcettii), Blue mold (Penicillium italicum), Green mold (Penicillium digitatum), Gray mold (Botrytis cinerea) ), black spot (Diaporthe citri), canker (Xanthomonas campestris pv.Citri), powdery mildew (Oidium sp.), plague (Phytophthora citrophthora), anthracnose (Colletotrichum fioriniae), etc.

Wheat: Powdery mildew (Blumeria graminisf.sp. tritici), Fusarium head blight (Gibberella zeae), Leaf rust (Puccinia recondita), Yellow rust (Puccinia striiformis), Brown snow rot (Pythium iwayamai), Red snow rot (Monographella nivalis), eye blight (Pseudocercosporella herpotrichoides), leaf blight (Septoria tritici), blight (Leptosphaeria nodorum), snow rot small grain sclerot (Typhula incarnata), snow rot large grain sclerot (Myriosclerotinia borealis) Barley: Leaf blight (Pyrenophora graminea), nets, such as, blight (Gaeumannomyces graminis), ergot (Claviceps purpurea), linseed smut (Tilletia caries), naked smut (Ustilago nuda), blast (Pyricularia grisea), etc. Spot disease (Pyrenophora teres), cloud disease (Rhynchosporium secalis), naked smut (Ustilago tritici, U.nuda), etc. Rice: rice blast (Pyricularia oryzae), blight (Rhizoctonia solani), sickle seedling disease (Gibberella fujikuroi) , Sesame leaf blight (Cochliobolus miyabeanus), seedling blight (Pythium graminicola), white leaf blight (Xanthomonas oryzae), seed blight (Burkholderia plantarii), brown streak (Acidovorax avenae), rice bacterial blight ( Burkholderia glumae), streak leaf blight (Cercospora oryzae), rice scab (Ustilaginoidea virens), brown rice (Alternaria alternata, Curvularia intermedia), black rice (Alternaria padwickii), red rice (Epicoccum purpurascens), etc. Tobacco: sclerotium Disease (Sclerotinia sclerotiorum), powdery mildew (Erysiphe cichoracearum), plague (Phytophthora nicotianae), etc. Tulip: Gray mold (Botrytis cinerea), etc. Sunflower: downy mildew (Plasmopara halstedii), sclerotinia sclerotiorum, gray mold (Botrytis cinerea), etc. Bent Snow rot large grain sclerotia (Sclerotinia borealis), large patch (Rhizoctonia solani), brown patch (Rhizoctonia solani), dollar spot (Sclerotinia homoeocarpa), blast (Pyricularia sp.), red blight (Pythium aphanidermatum), anthracnose Diseases (Colletotrichum graminicola) Orchardgrass: Powdery mildew (Erysiphe graminis) Soybean: Purpura (Cercospora kikuchii), downy mildew (Peronospora manshurica), stem blight (Phytophthora sojae), rust (Phakopsora pachyrhizi) Diseases (Sclerotinia sclerotiorum), anthracnose (Colletotrichum truncatum), gray mold (Botrytis cinerea), black scab (Elsinoe glycines), black spot (Diaporthe phaseolorum var. sojae), etc. Potato: epidemic (Phytophthora infestans) (Alternaria solani), Black blight (Thanatephorus cucumeris), Half body wilt (Verticillium albo-atrum, V. dahliae, V. nigrescens), Black rot (Pectobacterium atrosepticum), Soft rot (Pectobacterium carotovorum), etc. Banana: Panama disease (Fusarium oxysporum), Sigatoka (Mycosphaerella fijiensis, M. musicola), etc. Mango: Anthracnose (Colletotrichum aenigma)
Rape: Sclerotinia sclerotiorum, root rot (Phoma lingam), black spot (Alternaria brassicae), etc. Coffee: rust (Hemileia vastatrix), anthrax (Colletotrichum coffeanum), brown eye (Cercospora coffeicola), sugarcane, etc. : Brown rust (Puccinia melanocephala), etc. Maize: Hail blotch (Gloeocercospora sorghi), Rust (Puccinia sorghi), Southern rust (Puccinia polysora), Black scab (Ustilago maydis), Leaf blight (Cochliobolus heterostrophus), Soot blotch (Setosphaeria turcica), etc. Cotton: Seedling blight (Pythium sp.), rust (Phakopsora gossypii), mildew (Mycosphaerella areola), anthrax (Glomerella gossypii), etc.

The agricultural/horticultural fungicide of the present invention is used for plants such as cereals; vegetables; root vegetables; potatoes; trees such as fruit trees, tea, coffee, cacao; grasses; grasses; cotton and the like. Is preferred.

The agricultural and horticultural fungicide of the present invention can be applied to each part of plants, for example, leaves, stems, stalks, flowers, buds, fruits, seeds, sprouts, roots, tubers, tubers, shoots, cuttings and the like. .. Further, improved varieties and varieties of these plants, cultivated varieties, mutants, hybrids and gene recombinants (GMO) can also be targeted.

The fungicide for agricultural and horticultural use of the present invention is used for seed treatment, foliar application, soil application, water application, etc., which is carried out for controlling various diseases occurring in agricultural and horticultural crops including flowers, turf, and grass. You can

The agricultural/horticultural fungicide of the present invention may contain components other than the thienopyrimidine compound of the present invention. Other components include known carriers used for formulation. Further, as other components, conventionally known fungicides, insecticides/miticides, nematicides, soil pesticides, plant regulators, synergists, fertilizers, soil conditioners, animal feeds, etc. be able to. By containing such other components, a synergistic effect may be exhibited.

Specific examples of the bactericide which can be mixed or used together with the agricultural/horticultural bactericide of the present invention are shown below.
(1) Nucleic acid biosynthesis inhibitor:
(a) RNA polymerase I inhibitor: benalaxyl, benalaxyl-M, furalaxyl, metalaxyl, metalaxyl-M; oxadixyl; clozilacon, offlace;
(b) Adenosine deaminase inhibitor: bupirimate, dimethirimol, etirimol;
(c) DNA/RNA synthesis inhibitor: hymexazole, octirinone;
(d) DNA topoisomerase II inhibitor: oxophosphate.

(2) Antimitotic agent and antimitotic agent:
(a) β-tubulin polymerization inhibitor: benomyl, carbendazim, chlorphenazole, fuveridazole, thiabendazole; thiophanate, thiophanate methyl; dietofencarb; zoxamide; etaboxam;
(b) anti-mitotic agent: pencyclone;
(c) Delocalization inhibitor of spectrin-like protein: Fluopicolide.

(3) Respiratory inhibitor:
(a) Complex I NADH oxidoreductase inhibitor: diflumetrim; tolfenpyrad;
(b) Complex II succinate dehydrogenase inhibitor: benodanyl, flutolanil, mepronil;
Isofetamide; Fluopyram; Fenfram, Flumecyclox; Carboxin, Oxycarboxin; Thifluzamide; Benzobindiflupyr, Bixaphene, Fluxapyroxad, Furametopyr, Isopyrazam, Penflufen, Penthiopyrad, Sedaxane; Boscalid, Pidiflumethofen, Isoflusifram, Pyraziflumid, inpyrfluxam;
(c) Complex III ubiquinol oxidase Qo inhibitor: azoxystrobin, cumoxystrobin, cumetoxystrobin, enoxastrobin, fluphenoxystrobin, picoxystrobin, pyraoxystrobin; pyraclostrobin, Pyrametostrobin, triclopyricarb; Klesoxime-methyl, trifloxystrobin; dimoxistrobin, phenaminestrobin, metaminostrobin, orysastrobin; famoxadone; fluoxastrobin; fenamidon; pyribencarb; methyltetraprole; mandest Robin;
(d) Complex III Ubiquinol reductase Qi inhibitor: Cyazofamide; Amisulbrom; Fenpicoxamide
(e) Uncoupling agent for oxidative phosphorylation: binapacryl, meptyldinocap, dinocap;
Fluazinam; Felimzone;
(f) Oxidative phosphorylation inhibitors (ATP synthase inhibitors): fentin acetate, fentin chloride, fentin hydroxide;
(g) ATP production inhibitor: silthiofam;
(h) Complex III: Qx (unknown) inhibitor of cytochrome bc1 (ubiquinone reductase): Amethoctrazine.

(4) Amino acid and protein synthesis inhibitors
(a) Methionine biosynthesis inhibitors: andprim, cyprodinil, mepanipyrim, pyrimethanil;
(b) Protein synthesis inhibitor: blasticidin-S; kasugamycin, kasugamycin hydrochloride; streptomycin; oxytetracycline.

(5) Signal transduction inhibitor:
(a) Signal transduction inhibitors: quinoxyphene, proquinazide;
(b) MAP/histidine kinase inhibitors in osmotic signal transduction: fenpiclonil, fludioxonil; clozolinate, iprodione, procymidone, vinclozolin.

(6) Lipid and cell membrane synthesis inhibitor:
(a) Phospholipid biosynthesis, methyltransferase inhibitor: edifenphos, iprobenphos, pyrazophos; isoprothiolane;
(b) Lipid peroxides: biphenyl, chloroneb, dichlorane, kindozen, technazene, tolclofos-methyl; etridiazole;
(c) Agents acting on cell membranes: iodocarb, propamocarb, propamocarb hydrochloride, propamocarb fosetylate, prothiocarb;
(d) Microbes that disrupt the cell membrane of pathogenic bacteria: Bacillus subtilis, Bacillus subtilis QST713, Bacillus subtilis FZB24, Bacillus subtilis MBI600, Bacillus subtilis D747;
(e) An agent that disturbs cell membranes: an extract of Goseika yupte (tea tree).

(7) Cell membrane sterol biosynthesis inhibitor:
(a) Demethylation inhibitor at the C14 position in sterol biosynthesis: triforin; pyrifenox, pyrisoxazole; fenarimol, flurprimidol, nuarimol; imazalil, imazalyl sulfate, oxpoconazole, pefurazoate, prochloraz, triflumizole , Viniconazole; azaconazole, bitertanol, bromconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, epoxyconazole, etaconazole, fenbuconazole, fluquinconazole, flucirazole, frutriahol, fluconazole, Fluconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole, microbutanyl, penconazole, propiconazole, fluquinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triazimenol, triticonazole; prothioconazole, Voriconazole, mefentrifluconazole;
(b) Inhibitors of Δ14 reductase and Δ8→Δ7-isomerase in sterol biosynthesis:
Aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph; phenpropidine, piperaline; spiroxamine;
(c) 3-Ketoreductase inhibitor in C4 demethylation of sterol biosynthesis system: fenhexamide; fenpyrazamine;
(d) Sterol biosynthesis squalene epoxidase inhibitors: pyributycarb; naphthifin, terbinafine.

(8) Cell wall synthesis inhibition
(a) Trehalase inhibitor: validamycin;
(b) Chitin synthase inhibitor: polyoxine, polyoxolim;
(c) Cellulose synthase inhibitors: dimethomorph, fulmorph, pyrimorph; benchavaricarb, iprovaricarb, valifenalate; mandipropamide.

(9) Melanin biosynthesis inhibitor
(a) Reductase inhibitor of melanin biosynthesis: Fthalide; Pyroquilon; Tricyclazole;
(b) Dehydrase inhibitors of melanin biosynthesis: carpropamide; diclocymet; phenoxanil.
(c) Polyketide synthesis inhibitor of melanin biosynthesis: Torprocarb

(10) Host plant resistance inducer:
(a) Agents that act on the salicylic acid synthesis pathway: acibenzolar-S-methyl;
(b) Others: probenazole; thiazinyl; isotianil; diclobenazox;
Laminarin; Pterus pudum extract.

(11) Agents of unknown action: cimoxanil, fosetylaluminum, phosphoric acid (phosphate), teclophthalam, triazoxide, fursulfamide, diclomedine, metasulfocarb, cyflufenamide, metraphenone, pyriophenone, dozine, dozine free base, furtianil.

(12) Agents having multiple points of action: copper (copper salt), Bordeaux solution, copper hydroxide, copper naphthalate, copper oxide, copper oxychloride, copper sulfate, sulfur, sulfur products, calcium polysulfide; farbum, mancozeb, maneb, Mankappa, methylam, polycarbamate, propineb, tiram, zineb, diram; captan, captahol, folpet; chlorothalonil; diclofluanid, tolylfluanid; guazatine, iminoctadine triacetate, iminoctadine albesylate. trialbesilate); Anilazine; Dithianon; Quinomethionate; Fluorimide.

(13) Other agents: DBEDC, fluorofolpet, guazatine acetate, bis(8-quinolinolato)copper(II), propamidine, chloropicrin, cyproflam, Agrobacterium, betoxazine, diphenylamine, methylisothianate (MITC) ), mildeomycin, capsaicin, cufraneb, cyprosulfamide, dazomet, devacarb, dichlorophen, diphenzoquat, difenzoquat methyl sulfonate, flumethobelle, fosetyl calcium, fosetyl sodium, ilmamycin, natamycin, nitrotal isopropyl , Oxamocarb, pyrrolenitrin, tebuflokine, tornifanid, zalilamide, algophase, amicalthiazol, oxathiapiprolin, metiramzinc, ventilazole, trichlamide, uniconazole, mildeomycin, oxyphene Oxyfenthiin, Picarbutrazox, Quinofumelin, Florylpicoxamid, Pyrapropoyne, Fluindapyr, Aminopyrifen, Pyridaclomethyl , Ipflufenoquin.

Specific examples of insecticides/miticides, nematicides, soil-killing insecticides, anthelmintics, etc., which can be mixed or used together with the agricultural/horticultural germicide of the present invention, are shown below.

(1) Acetylcholinesterase inhibitor:
(a) Carbamate series: Alanikalb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxyme, Butoxycarbome, Carbaryl, Carbofuran, Carbosulfan, Ethiophenecarb, Fenobucarb, Formethanate, Fratiocarb, Isoprocarb, Methiocarb, Mesomil, Oxamil, Pirimicarb, Propoxur, Thiodicarb, thiophanox, triazamate, trimetacarb, XMC, xylylcarb, phenothiocarb, MIPC, MPMC, MTMC, aldoxicarb, alixicarb, aminocarb, bufencarb, chloetcarb, metam sodium, promecarb;

(b) Organophosphorus: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cassaphos, chlorethoxyphos, chlorfenbinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethyl bottle phosphite, disulfoton, EPN, ethion, ethoprophos, Famufuru, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, Imishiahosu, isofenphos, Isokarubohosu, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, Monocrotophos, naredo, omethoate, oxydimethone-methyl, parathion, parathion-methyl, fentoate, folates, hosalon, phosmet, phosphamidon, oxime, pirimiphos-methyl, propenofos, propetamphos, prothiophos, pyraclofos, pyridafenthion, quinalfos, sulfotep, tebupyrinphosphine. Temephos, terbufos, tetrachlorbinphos, thiomethone, triazophos, trichlorfon, bamidthione; bromophos ethyl, BRP, carbophenothione, cyanophenphos, CYAP, demeton-S-methyl sulfone, dialyphos, diclofenthion, dioxabenzophos, etrimphos , Phensulfothion, flupyrazophos, honophos, formothion, phosmethylan, isazophos, iodofenphos, methacrifos, pirimiphos-ethyl, phosphocarb, propaphos, protoate, sulprophos.

(2) GABA-agonist chloride channel antagonists: acetoprol, chlordane, endosulfan, ethiprole, fipronil, pyrafluprol, piriprole; camfechlor, heptachlor, dienochlor.
(3) Sodium channel modulators: acrinathrin, d-cis-transallethrin, d-transallethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda- Cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(1R)-trans isomer], deltamethrin, empentrin [(EZ)-( 1R)-Isomer], esfenvalerate, etofenprox, fenpropatorin, fenvalerate, flucitrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, cadesrin, permethrin, phenothrin [(1R)-trans Isomer], pralethrin, pyrethrum, resmethrin, silafluofen, tefluthrin, tetramethrin [(1R)-isomer], tralomethrin, transfluthrin, allethrin, pyrethrin, pyrethrin I, pyrethrin II, profluthrin, dimefluthrin, bioethanomethrin, Permethrin, transpermethrin, fenfluthrin, fenpyritrin, flubrocitrinate, flufenprox, methfluthrin, protrifenbuto, pyrethmethrin, terraretrin.

(4) Nicotinic acetylcholine receptor agonists: acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam, sulfoxaflor, nicotine, flupyrazifron.
(5) Nicotinic acetylcholine receptor allosteric modulators: spinetoram and spinosad.
(6) Chloride channel activator: Abamectin, Emamectin benzoate, Lepimectin, Milbemectin; Ivermectin, Selamectin, Doramectin, Eprinomectin, Moxidectin, Milbemycin, Milbemycin oxime, Nemadectin.
(7) Juvenile hormone-like substances: hydroprene, quinoprene, mesoprene, phenoxycarb, pyriproxyfen; diophenolane, epophenonane, triprene.
(8) Other non-specific inhibitors: methyl bromide, chloropicrin, sulfuryl fluoride, borax, tartar.
(9) Homoptera selective feeding inhibitors: flonicamid, pymetrozine, and pyrifluquinazone.

(10) Mite growth inhibitor: Clofentedine, difrovidazine, hexithiazox, etoxazole.
(11) Microbial-derived insect midgut endometrial disruption agents: Bacillus thuringiensis subsp. isla ellensis, Bacillus sphaericus, Bacillus thuringiensis subsp. Isawai, Bacillus thuringiensis subsp. kurusutaki, Bacillus thuringiensis subsp. tenebrionis, Bt Crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Ab1/Cry35Ab1.
(12) Mitochondrial ATP biosynthetic enzyme inhibitor: diafenthiuron, azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradiphone.
(13) Oxidative phosphorylation uncoupling agent: chlorfenapyr, sulframide, DNOC; vinapacryl, ginobton, dinocap.
(14) Nicotinic acetylcholine receptor channel blocker: bensultap, cartap hydrochloride; nereistoxin; thiosultap monosodium salt, thiocyclam.
(15) Chitin synthesis inhibitor: bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, buprofezin, fluazuron.
(16) Diptera molting disruptor: cyromazine.
(17) Molting hormone receptor agonist: Chromafenozide, halofenozide, methoxyphenozide, tebufenozide.
(18) Octopamine receptor agonist: amitraz, demiditraz, chlordimeform.
(19) Mitochondrial electron transfer system complex III inhibitor: acequinocyl, fluacrypirim, hydramethylnon.
(20) Mitochondrial electron transport system complex I inhibitor: phenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, rotenone.

(21) Voltage-gated sodium channel blockers: indoxacarb, metaflumizone.
(22) Acetyl CoA carboxylase inhibitor: spirodiclofen, spiromesifen, spirotetramat.
(23) Mitochondrial electron transport complex IV inhibitor: aluminum phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide.
(24) Mitochondrial electron transport complex II inhibitor: cienopyraphen, cyflumethofen, pifluvmid.
(25) Ryanodine receptor modulator: chlorantraniliprole, cyantraniprol, flubendiamide, cyclaniliprole, tetraniliprole.
(26) Mixed function oxidase inhibitor compound: piperonyl butoxide.
(27) Latrophilin receptor agonist: Depsipeptide, cyclic depsipeptide, 24-membered cyclic depsipeptide, emodepside.
(28) Other agents (unknown mechanism of action): azadirachtin, benzoximate, biphenate, bromopropylate, quinomethionate, cryolite, dicofol, pyridalyl, benclothiaz, sulfur, amidoflumet, 1,3-dichloropropene, DCIP, Phenisobromolate, Benzomate, Methaldehyde, Chlorbenzilate, Crothiazoben, Dicyclanil, Phenoxacrime, Fentriphanyl, Flubendimine, Fluphenazine, Gossip Rua, Japonilla, Metoxadiazone, Petroleum, Potassium Oleate, Tetrasul, Triracene, Afidopyropen (afidopyropen ), flomethquine, flufiprole, flufiprole, fluene sulfone, meperfluthrin, tetramethylfluthrin, tralopyril, dimefluthrin, methylneodecanamide, fluralaner, afoxolanel, fluxamethamide, 5-[5-(3,5-dichlorophenyl)-5-trifluoro Methyl-4,5-dihydroisooxazol-3-yl]-2-(1H-1,2,4-triazol-1-yl)benzonitrile (CAS:943137-49-3), burofuranilide, acinonapyr, other Metadiamides.

(29) Antiparasitic agent:
(a) Benzimidazole type: fenbendazole, albendazole, triclabendazole, oxybendazole, mebendazole, oxfendazole, perbendazole, flubendazole; fevantel, netobimin, thiophanate; thiabendazole, cambendazole;
(b) Salicylanilide series: closantel, oxyclozanide, lafoxanide, niclosamide;
(c) Substituted phenol system: nitroxynil, nitroscanate;
(d) Pyrimidine type: Pyrantel, Morantel;
(e) Imidazothiazole system: levamisole, tetramisole;
(f) Tetrahydropyrimidines: praziquantel, epsiprantel;
(g) Other anthelmintic drugs: cyclodiene, ryania, chlorthuron, metronidazole, demiditraz; piperazine, diethylcarbamazine, dichlorophen, monepantel, tribendimidine, amidantel; thiacetarsamide, melorsamine, arsenamide.

Specific examples of the plant regulator which can be mixed or used together with the agricultural/horticultural germicide of the present invention are shown below.
Abscisic acid, kinetin, benzylaminopurine, 1,3-diphenylurea, forchlorfenuron, thidiazuron, chlorfenuron, dihydrozeatin, gibberellin A, gibberellin A4, gibberellin A7, gibberellin A3, 1-methylcyclopropane, N-acetyl. Aminoethoxyvinylglycine (also known as abiglycine), aminooxyacetic acid, silver nitrate, cobalt chloride, IAA, 4-CPA, cloprop, 2,4-D, MCPB, indole-3-butyric acid, dichlorprop, phenothiol, 1 -Naphthylacetamide, ethiclozet, cloxyfonac, maleic hydrazide, 2,3,5-triiodobenzoic acid, salicylic acid, methyl salicylate, (-)-jasmonic acid, methyl jasmonate, (+)-strigol, (+) -Deoxystrigor, (+)-Orobancol, (+)-Sorgolactone, 4-oxo-4-(2-phenylethyl)aminobutyric acid; Ethephon, Chlormequat, Mepiquat chloride, Benzyladenine, 5-Aminolevulinic acid.

[Pharmaceutical formulation]
The agricultural/horticultural germicide of the present invention is not particularly limited depending on the dosage form. Examples include dosage forms such as wettable powders, emulsions, powders, granules, water solutions, suspensions, wettable granules and tablets. The preparation method for the preparation is not particularly limited, and a known preparation method can be adopted depending on the dosage form.

The following are some formulation examples. The pharmaceutical formulations shown below are merely examples, and can be modified within the scope not departing from the gist of the present invention, and the present invention is not limited to the following formulation examples. "Parts" means "parts by weight" unless otherwise specified.

(Formulation Example 1: wettable powder)
40 parts of the thienopyrimidine compound of the present invention, 53 parts of diatomaceous earth, 4 parts of higher alcohol sulfate ester, and 3 parts of alkylnaphthalene sulfonate are uniformly mixed and finely ground to obtain a wettable powder of 40% of active ingredient. ..

(Formulation Example 2: Emulsion)
30 parts of the thienopyrimidine compound of the present invention, 33 parts of xylene, 30 parts of dimethylformamide, and 7 parts of polyoxyethylene alkylallyl ether are mixed and dissolved to obtain an emulsion containing 30% of the active ingredient.

(Formulation Example 3: Granules)
5 parts of the thienopyrimidine compound of the present invention, 40 parts of talc, 38 parts of clay, 10 parts of bentonite, and 7 parts of sodium alkyl sulfate are uniformly mixed and finely pulverized, and then the particle diameter is adjusted to 0.5 to 1.0 mm. Granulate to give granules with 5% active ingredient.

(Formulation Example 4: Granules)
5 parts of the thienopyrimidine compound of the present invention, 73 parts of clay, 20 parts of bentonite, 1 part of dioctyl sulfosuccinate sodium salt, and 1 part of potassium phosphate were uniformly mixed and ground. Water is added to this and kneaded well, then granulated and dried to obtain granules containing 5% of the active ingredient.

(Formulation Example 5: Suspension)
10 parts of the thienopyrimidine compound of the present invention, 4 parts of polyoxyethylene alkyl allyl ether, 2 parts of sodium salt of polycarboxylic acid, 10 parts of glycerin, 0.2 part of xanthan gum, and 73.8 parts of water are mixed, and the particle size is 3 microns. Wet pulverize until the following amount to obtain a suspension containing 10% of active ingredient.

(Formulation Example 6: Granule wettable powder)
The thienopyrimidine compound of the present invention 40 parts, clay 36 parts, potassium chloride 10 parts, alkylbenzene sulfonic acid sodium salt 1 part, lignin sulfonic acid sodium salt 8 parts, and alkylbenzene sulfonic acid sodium salt formaldehyde condensate 5 parts are uniformly mixed. After pulverizing finely, add an appropriate amount of water and knead to make a clay. The clay is granulated and then dried to give a granule wettable powder with 40% of active ingredient.

Next, the present invention will be described more specifically by showing synthetic examples. However, the present invention is not limited to the following synthetic examples.

[Example 1]
2-(1-(2-(2-cyanoethoxy)-2-(5-fluoro-2-methoxyphenyl)ethyl)-6-ethynyl-5-methyl-2,4-dioxo-1,4-dihydrothieno[2, Synthesis of 3-d]pyrimidin-3(2H)-yl)-N-isopropyl-2-methylpropanamide (Compound No. 1)

(Process 1)
Synthesis of ethyl 2-(3-(2-(tert-butoxy)-2-methylpropanoyl)ureido)-5-iodo-4-methylthiophene-3-carboxylate
25 g of ethyl2-(3-(2-(tert-butoxy)-2-methylpropanoyl)ureido)-4-methylthiophene-3-carboxylate was dissolved in 676 mL of methylene chloride, and 16.3 g of N-iodosuccinimide was added under ice cooling. Subsequently, 12.8 mL of acetic acid was added dropwise, and the mixture was stirred at room temperature for 30 minutes. Saturated aqueous sodium hydrogen carbonate was added to the reaction solution under ice cooling, the mixture was extracted with chloroform, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 33.16 g of the objective compound. Yield 99%
¹ H-NMR (CDCl _3, δppm) 1.39 (t, 3H), 1.47 (s, 9H), 1.59 (s, 6H), 2.34 (s, 3H), 4.33 (q, 2H), 5.69 (s, 1H ), 10.1 (s, 1H).

(Process 2)
Synthesis of tert-butyl 2-(6-iodo-5-methyl-2,4-dioxo-1,4-dihydrothieno[2,3-d]pyrimidin-3(2H)-yl)-2-methylpropanoate
Ethyl 2-(3-(2-(tert-butoxy)-2-methylpropanoyl)ureido)-5-iodo-4-methylthiophene-3-carboxylate (7.84 g) was dissolved in 199 mL of 1,4-dioxane, and the mixture was cooled with ice. 8.88 g of potassium tert-butoxide was added, and the mixture was stirred for 1 hour at 50°C. A saturated aqueous ammonium chloride solution was added to the reaction solution under ice cooling, the mixture was extracted with ethyl acetate, washed with saturated saline, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 5.11 g of the objective compound. Yield 71% ¹ H-NMR (CDCl _3, δppm) 1.45 (s, 9H), 1.78 (s, 6H), 2.43 (s, 3H).

(Process 3)
tert-butyl 2-(1-(2-(5-fluoro-2-methoxyphenyl)-2-oxoethyl)-6-iodo-5-methyl-2,4-dioxo-1,4-dihydrothieno[2,3-d ]pyrimidin-3(2H)-yl)-2-methylpropanoate synthesis
tert-butyl 2-(6-iodo-5-methyl-2,4-dioxo-1,4-dihydrothieno[2,3-d]pyrimidin-3(2H)-yl)-2-methylpropanoate 19.82 g of N was added to 275 mL of N. , N-dimethylformamide, and under ice-cooling, 13.04 g of 2-bromo-1-(5-fluoro-2-methoxyphenyl)ethan-1-one and 12.1 g of potassium carbonate were added, and the mixture was stirred at room temperature for 1 hour. .. Water was added to the reaction solution under ice-cooling, the mixture was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate) to obtain 21.13 g of the target compound. Yield 78%
¹ H -NMR (CDCl _3, δppm) 1.43 (s, 9H), 1.77 (s, 6H), 2.44 (s, 3H), 4.00 (s, 3H), 5.18 (s, 2H), 7.01 (dd, 1H ), 7.26-7.31 (m, 1H), 7.62 (dd, 1H).

(Process 4)
2-(1-(2-(5-fluoro-2-methoxyphenyl)-2-oxoethyl)-6-iodo-5-methyl-2,4-dioxo-1,4-dihydrothieno[2,3-d]pyrimidin Synthesis of -3(2H)-yl)-N-isopropyl-2-methylpropanamide
tert-butyl 2-(1-(2-(5-fluoro-2-methoxyphenyl)-2-oxoethyl)-6-iodo-5-methyl-2,4-dioxo-1,4-dihydrothieno[2,3-d ] 0.88 g of pyrimidin-3(2H)-yl)-2-methylpropanoate was dissolved in 24 mL of methylene chloride, 2.4 mL of trifluoroacetic acid was added under ice cooling, and the mixture was stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure, and 27 mL of methylene chloride, 319 μL of isopropylamine, 535 μL of N,N-diisopropylethylamine, 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]. 0.54 g of pyridinium 3-oxide hexafluorophosphate was added, and the mixture was stirred overnight at room temperature. The reaction solution was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate) to obtain 0.52 g of the desired compound. 60% yield
¹ H-NMR (CDCl _3, δppm) 1.14 (d, 6H), 1.81 (s, 6H), 2.42 (s, 3H), 4.00 (s, 3H), 4.03-4.08 (m, 1H) 5.18 (s, 2H), 5.29 (d, 1H), 7.01 (dd, 1H), 7.27-7.31 (m, 1H), 7.61 (dd, 1H).

(Process 5)
2-(1-(2-(5-fluoro-2-methoxyphenyl)-2-oxoethyl)-5-methyl-2,4-dioxo-6-((trimethylsilyl)ethynyl)-1,4-dihydrothieno[2, Synthesis of 3-d]pyrimidin-3(2H)-yl)-N-isopropyl-2-methylpropanamide
2-(1-(2-(5-fluoro-2-methoxyphenyl)-2-oxoethyl)-6-iodo-5-methyl-2,4-dioxo-1,4-dihydrothieno[2,3-d]pyrimidin -3(2H)-yl)-N-isopropyl-2-methylpropanamide (430 mg) was dissolved in toluene (2.4 mL) and N,N-diisopropylamine (7.2 mL), and bis(triphenylphosphine)palladium(II) dichloride was added under argon atmosphere. 15 mg, copper(I) iodide 20 mg and trimethylsilylacetylene 128 μL were added, and the mixture was stirred at 70° C. overnight. A 1N aqueous hydrochloric acid solution was added to the reaction solution under ice cooling, extracted with chloroform, washed with water, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate) to obtain 310 mg of the target compound. Yield 76%
¹ H-NMR (CDCl _3, δppm) 0.21 (s, 9H), 1.14 (d, 6H), 1.81 (s, 6H), 2.50 (s, 3H), 3.99 (s, 3H), 4.02-4.08 (m , 1H) 5.20 (s, 2H), 5.29(d, 1H) 7.00 (dd, 1H), 7.28-7.31
(m, 1H), 7.60 (dd, 1H).

(Process 6)
2-(6-ethynyl-1-(2-(5-fluoro-2-methoxyphenyl)-2-oxoethyl)-5-methyl-2,4-dioxo-1,4-dihydrothieno[2,3-d]pyrimidin Synthesis of -3(2H)-yl)-N-isopropyl-2-methylpropanamide
2-(1-(2-(5-fluoro-2-methoxyphenyl)-2-oxoethyl)-5-methyl-2,4-dioxo-6-((trimethylsilyl)ethynyl)-1,4-dihydrothieno[2, 310 mg of 3-d]pyrimidin-3(2H)-yl)-N-isopropyl-2-methylpropanamide was dissolved in 2.8 mL of tetrahydrofuran and 2.8 mL of methanol, 225 mg of potassium carbonate was added, and the mixture was stirred at room temperature for 10 minutes. Water was added to the reaction solution, extracted with chloroform, washed with saturated saline, and then dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate) to obtain 240 mg of the target compound. Yield 99%
¹ H-NMR (CDCl _3, δppm) 1.12 (d, 6H), 1.81 (s, 6H), 2.53 (s, 3H), 3.45 (s, 1H), 4.00 (s, 3H) 4.03-4.15 (m, 1H) 5.20 (s, 2H), 5.31(d, 1H) 7.01 (dd, 1H), 7.26-7.31 (m, 1H), 7.58-7.62 (m, 1H).

(Process 7)
2-(6-ethynyl-1-(2-(5-fluoro-2-methoxyphenyl)-2-hydroxyethyl)-5-methyl-2,4-dioxo-1,4-dihydrothieno[2,3-d]pyrimidin Synthesis of -3(2H)-yl)-N-isopropyl-2-methylpropanamide (Compound No. 2)
2-(6-ethynyl-1-(2-(5-fluoro-2-methoxyphenyl)-2-oxoethyl)-5-methyl-2,4-dioxo-1,4-dihydrothieno[2,3-d]pyrimidin 240 mg of -3(2H)-yl)-N-isopropyl-2-methylpropanamide was dissolved in 1.5 mL of methanol and 1.5 mL of tetrahydrofuran, 30 mg of sodium borohydride was added under ice cooling, and the mixture was stirred at room temperature for 10 minutes. A saturated aqueous ammonium chloride solution was added to the reaction solution, the mixture was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate) to obtain 207 mg of the target compound. Yield 86%
¹ H-NMR (CDCl _3, δppm) 1.19 (d, 6H), 1.82 (d, 6H), 2.50 (s, 3H), 3.50 (s, 1H) 3.91 (s, 3H), 4.02-4.22 (m, 1H), 4.02-4.22 (m, 2H) 5.28-5.33 (m, 1H), 5.28-5.33 (m, 1H) 6.81 (dd, 1H), 6.95-7.00 (m, 1H), 7.25-7.28 (m, 1H).

(Process 8)
2-(1-(2-(2-cyanoethoxy)-2-(5-fluoro-2-methoxyphenyl)ethyl)-6-ethynyl-5-methyl-2,4-dioxo-1,4-dihydrothieno[2, Synthesis of 3-d]pyrimidin-3(2H)-yl)-N-isopropyl-2-methylpropanamide (Compound No. 1)
2-(6-ethynyl-1-(2-(5-fluoro-2-methoxyphenyl)-2-hydroxyethyl)-5-methyl-2,4-dioxo-1,4-dihydrothieno[2,3-d]pyrimidin -3(2H)-yl)-N-isopropyl-2-methylpropanamide (157 mg) was dissolved in tetrahydrofuran (2.5 mL), 252 μL of 50% potassium hydroxide aqueous solution and acrylonitrile (500 μL) were added under ice cooling, and the mixture was stirred at -5°C overnight. did. Water was added to the reaction solution, which was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate) to obtain 137 mg of the target compound. Yield 79%
¹ H-NMR (CDCl _3, δppm) 1.12 (dd, 6H), 1.79 (d, 6H), 2.51 (s, 3H), 2.55-2.59 (m, 2H) 3.39-3.43 (m, 1H) 3.50 (s , 1H), 3.75-3.80 (m, 1H), 3.87 (s, 3H) 3.94-4.00 (m, 1H) 4.07-4.13 (m, 1H), 5.29 (dd, 1H) 5.92 (dd, 1H) 6.84 ( dd, 1H), 7.02 (dt, 1H), 7.22 (dd, 1H).

Table 1 shows some of the compounds of the present invention produced in the same manner as in the above Examples. In the table, the melting point (m.p.) is also shown as the physical property of each compound. The configuration E or Z in the table indicates the geometric isomer of oxime. "E" indicates the E configuration, "Z" indicates the Z configuration, and "E/Z" indicates that the compound is a mixture of compounds in both configurations.

[Biological test]
The following test examples show that the thienopyrimidine compound of the present invention is useful as an active ingredient of a fungicide for agricultural and horticultural use.

(Preparation of test emulsion)
5 parts by weight of a thienopyrimidine compound, 93.5 parts by weight of dimethylformamide, and 1.5 parts by weight of polyoxyethylenesorbitan monolaurate (Twin 20) were mixed and dissolved to obtain an emulsion (I) containing 5% of the active ingredient. Obtained.

The control value was calculated by the following formula.
Control value (%) =
100-{lesion area ratio in treated area/lesion area ratio in untreated area}×100

(Test Example 1) Apple scab control test Water was added to Emulsion (I) so that the concentration of the thienopyrimidine compound was 125 ppm, and dissolved to obtain a drug solution. Subsequently, the above-mentioned drug solution was sprayed on apple seedlings (cultivar "Ohrin", 3-4 leaf stage) cultivated in a pot for raising seedlings. After air-drying, conidia of apple scab (Venturia inaequalis) were inoculated (treatment group). As a control, apple seedlings not sprayed with the drug solution were similarly inoculated (untreated section). They were allowed to stand in a moist chamber at 20° C., where light and dark were repeated every 12 hours.
On the day 2 weeks after the inoculation, the leaves of apple seedlings were visually observed, the lesion area ratio was calculated, and the control value was calculated.

The thienopyrimidine compounds of compound numbers 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 were subjected to apple scab control test. All compounds showed a control value of 75% or more.

(Test Example 2) Cucumber Gray Mold Control Test Water was added to the emulsion (I) so that the concentration of the thienopyrimidine compound was 125 ppm, and dissolved to obtain a drug solution. Subsequently, the above-mentioned drug solution was sprayed on cucumber seedlings (cultivar "Crawling" system, cotyledon stage) cultivated in pots for raising seedlings. After air drying, a conidial suspension of cucumber gray mold (Botrytis cinerea) was inoculated dropwise (treatment group). As a control, cucumber seedlings to which the drug solution had not been sprayed were inoculated dropwise by the same method as above (untreated section). They were left to stand in a humid chamber at 20°C.
On the day 4 days after the inoculation, the leaves of the cucumber seedlings were visually observed, the lesion area ratio was calculated, and the control value was calculated.

A cucumber gray mold control test was performed on the thienopyrimidine compounds of Compound Nos. 1, 2, 5, 6, 7, 8, 12, 13, 14 and 15. All compounds showed a control value of 75% or more.

Test Example 3 Wheat Powdery Mildew Control Test Water was added to the emulsion (I) so that the concentration of the thienopyrimidine compound would be 125 ppm, and dissolved to obtain a drug solution. Then, the wheat seedlings (cultivar "Chihoku", 1-2 leaf stage) cultivated in a pot for raising seedlings were sprayed with the drug solution. After air-drying, conidia of wheat powdery mildew (Erysiphe graminis f.sp.tritici) were sprinkled and inoculated (treated). As a control, wheat seedlings not sprayed with the drug solution were inoculated by the same method as above (untreated plot). They were placed in a greenhouse at 20°C.
On the day 6 days after the inoculation, the leaves of wheat seedlings were visually observed, the lesion area ratio was calculated, and the control value was calculated.

A wheat powdery mildew control test was carried out on the thienopyrimidine compounds of Compound Nos. 1, 2, 3, 5, 6, 7, 8, 9, 10, 12, 13, 14, and 15. All compounds showed a control value of 75% or more.

(Test Example 4) Wheat leaf rust control test Water was added to the emulsion (I) so that the concentration of the thienopyrimidine compound was 125 ppm, and dissolved to obtain a drug solution. Then, the wheat seedlings (cultivar "Norin 61", 1-2 leaf stage) cultivated in a pot for raising seedlings were sprayed with the drug solution. After air-drying, the wheat seedlings sprayed with the drug solution were sprinkled with the summer spores of wheat leaf rust (Puccinia recondita) and inoculated (treated). As a control, wheat seedlings to which the drug solution was not sprayed were inoculated in the same manner as above (untreated plot). They were placed in a greenhouse at 20°C.
On the day 12 days after the inoculation, the leaves of wheat seedlings were visually observed to determine the lesion area ratio, and the control value was calculated.

With respect to the thienopyrimidine compounds of Compound Nos. 1, 2, 3, 5, 6, 7, 8, 9, 10, 12, 13, 14, and 15, wheat leaf rust control test was conducted. All compounds showed a control value of 75% or more.

Those randomly selected from the thienopyrimidine compounds of the present invention have the effects as described above, and thus the thienopyrimidine compounds of the present invention include bactericidal effects, including compounds that could not be exemplified, It can be understood that the compound does not cause phytotoxicity to plants and has little toxicity to human livestock and fish and little influence on environment.

Claims (2)

A compound represented by formula (I) or a salt thereof.
(In formula (I),
R ¹ is a substituted or unsubstituted C1-6 alkyl group.
R ² and R ³ are each independently a hydrogen atom or a substituted or unsubstituted C1-6 alkyl group.
R ⁴ is a substituted or unsubstituted C1-6 alkoxycarbonyl group, or a substituted or unsubstituted C1-6 alkylaminocarbonyl group.
R ⁷ is a hydrogen atom, a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C3-8 cycloalkyl group or a tri-C1-6 alkylsilyl group.
R ⁵ and R ⁶ are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C ^1-6 alkoxy group, an oxo group formed by combining R ⁵ and R ⁶ or a substituted or unsubstituted C ¹ to R ⁶ group. 6 is an alkoxyimino group.
X is a halogeno group or a substituted or unsubstituted C1-6 alkoxy group.
n is an integer of 0 to 5, and when n is 2 or more, X may be the same or different. ) An agricultural and horticultural fungicide containing as an active ingredient at least one selected from the group consisting of the compound according to claim 1 and a salt thereof.