JPWO2019031384A1 - 1,3,5,6-Tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compounds and agricultural and horticultural fungicides - Google Patents

Abstract

The present invention provides a compound of formula (I) (wherein R1 is a substituted or unsubstituted C1-6 alkyl group, R2 is a hydrogen atom or the like, and R3 is a substituted or unsubstituted C1-6 alkoxycarbonyl group). A group or the like, R4 and R4' are hydrogen atoms or the like, Z is an oxygen atom, R5 is a substituted or unsubstituted C1-6 alkyl group or the like, and X is a halogeno group or the like. , N is an integer from 0 to 5) or a salt thereof. [Chemical 1]

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 industrially advantageously synthesized. 1H,3H) dione compound, and an agricultural and horticultural fungicide containing the same as an active ingredient.
This application claims priority based on Japanese Patent Application No. 2017-152327 filed in Japan on August 7, 2017 and Japanese Patent Application No. 2018-058857 filed on March 26, 2018 in Japan, and the contents thereof Is used here.

When cultivating agricultural and horticultural crops, many control agents have been proposed for the diseases of the crops. Most of the proposed control agents have inadequate control efficacy, their use is restricted by the emergence of drug-resistant pathogens, they cause phytotoxicity and pollution to plants, or toxicity to humans and fishes. The impact on the environment is large, etc., and it is not completely satisfactory. Therefore, there is a strong demand for the emergence of a control agent that can be used safely with few such defects.

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 the use of a fungicide for agricultural and horticultural use such as a compound represented by the formula (F).

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

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 synthesized industrially advantageously. 3H) A dione 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 the formula (I) or a salt thereof.

式(I)中、
Ｒ¹は、置換若しくは無置換のＣ１〜６アルキル基である。
Ｒ²は、水素原子、ハロゲノ基、置換若しくは無置換のＣ１〜６アルキル基、置換若しくは無置換のＣ２〜６アルケニル基、置換若しくは無置換のＣ２〜６アルキニル基、置換若しくは無置換のＣ１〜６アルコキシカルボニル基、置換若しくは無置換のアミノカルボニル基、置換若しくは無置換のアミノ基、置換若しくは無置換のＣ３〜８シクロアルキル基、置換若しくは無置換の５〜６員ヘテロアリール基、またはシアノ基である。
Ｒ³は、置換若しくは無置換のＣ１〜６アルコキシカルボニル基、または置換若しくは無置換のアミノカルボニル基である。
Ｒ⁴およびＲ^4’は、それぞれ独立して、水素原子、または置換若しくは無置換のＣ１〜６アルキル基である。
Ｚは、酸素原子である。
Ｒ⁵は、水素原子、置換若しくは無置換のＣ１〜６アルキル基、置換若しくは無置換のＣ３〜８シクロアルキル基、または５〜６員環飽和ヘテロシクリル基である。
Ｘは、ハロゲノ基、または置換若しくは無置換のＣ１〜６アルコキシ基である。
ｎは、化学的に許容されるＸの個数を示し、かつ０〜５のいずれかの整数である。
ｎが２以上のときＸは互いに同じでも異なってもよい。

In formula (I),
R ¹ is a substituted or unsubstituted C1-6 alkyl group.
R ² is a hydrogen atom, a halogeno group, a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C2-6 alkenyl group, a substituted or unsubstituted C2-6 alkynyl group, a substituted or unsubstituted C1 6 alkoxycarbonyl group, substituted or unsubstituted aminocarbonyl group, substituted or unsubstituted amino group, substituted or unsubstituted C3-8 cycloalkyl group, substituted or unsubstituted 5 to 6 membered heteroaryl group, or cyano group Is.
R ³ is a substituted or unsubstituted C1-6 alkoxycarbonyl group or a substituted or unsubstituted aminocarbonyl group.
R ⁴ and R ^4′ are each independently a hydrogen atom or a substituted or unsubstituted C1-6 alkyl group.
Z is an oxygen atom.
R ⁵ is a hydrogen atom, a substituted or unsubstituted C1~6 alkyl group, a substituted or unsubstituted C3~8 cycloalkyl group or 5-6 membered ring saturated heterocyclyl group.
X is a halogeno group or a substituted or unsubstituted C1-6 alkoxy group.
n represents the number of chemically acceptable Xs, and is an integer of 0-5.
When n is 2 or more, Xs may be the same or different.

[2] the substituents on substituted Cl to 6 alkyl group in R ⁵ is a halogeno group, hydroxyl group, Cl to 6 alkoxy, Cl to 6 alkylthio, Cl to 6 alkylsulfinyl group, Cl to 6 alkylsulfonyl group, C3 A compound represented by formula (I) according to claim 1, which is a cycloalkyl group, a cyano group, or an aminothiocarbonyl group, or a salt thereof.

[3] 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] or [2] above and salts thereof.

The 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound of the present invention has excellent bactericidal activity, certain effects, and excellent safety. In addition, it can be synthesized industrially advantageously.
INDUSTRIAL APPLICABILITY The agricultural and horticultural fungicide of the present invention has an excellent control effect, does not cause phytotoxicity on plants, and has little toxicity to humans and fishes and environmental influences.

[Compound represented by formula (I)]
The 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound of the present invention is a compound represented by the formula (I) (hereinafter, compound (I ), or a salt of compound (I).

In the present invention, the term “unsubstituted” means only a group serving as a nucleus. When there is no description of “substituted” and 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 (substituent) 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 two or more. Two or more substituents may be the same or different.
Terms such as "C1-6" indicate that the group serving as a 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, a butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group.

The “substituent” is chemically acceptable and is not particularly limited as long as it has the effects of the present invention. Examples of groups that can be "substituents" are shown below.
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 (allyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, etc. A C2-6 alkenyl group;
A C2-6 alkynyl group such as ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group;

A C3-8 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cubanyl group;
C6-10 aryl group such as phenyl group and naphthyl group;
C6-10 aryl C1-6 alkyl group such as benzyl group and phenethyl group;
A 3- to 6-membered heterocyclyl group;
3- to 6-membered heterocyclyl C1-6 alkyl group;

Hydroxyl group;
A C1-6 alkoxy group 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;
C6-10 aryl C1-6 alkoxy groups such as benzyloxy group and phenethyloxy group;
5- to 6-membered heteroaryloxy groups such as thiazolyloxy group and pyridyloxy group;
5- to 6-membered heteroaryl C1-6 alkyloxy group such as thiazolylmethyloxy group and pyridylmethyloxy 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 C6-10 arylcarbonyl group such as a benzoyl 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 alkoxycarbonyloxy groups such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group;
Carboxyl group;

Fluoro, chloro, bromo, iodo and other halogeno groups;
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 C1-6 haloalkoxy group such as a trifluoromethoxy group, a 2-chloro-n-propoxy group, a 2,3-dichlorobutoxy group;
A C2-6 haloalkenyloxy group such as a 2-chloropropenyloxy group or a 3-bromobutenyloxy group;
A C1-6 haloalkylcarbonyl group such as a chloroacetyl group, a trifluoroacetyl group, a trichloroacetyl group;

Amino group;
C1-6 alkyl-substituted amino groups such as methylamino group, dimethylamino group, and diethylamino group;
C6-10 arylamino groups such as anilino group and naphthylamino group;
A C6-10 aryl C1-6 alkylamino group such as a benzylamino group or a phenethylamino group;
Formylamino group;
C1-6 alkylcarbonylamino groups 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;
An aminocarbonyl group having an unsubstituted or substituted group such as an aminocarbonyl group, a dimethylaminocarbonyl group, a phenylaminocarbonyl group, and an N-phenyl-N-methylaminocarbonyl group;
Imino C1-6 alkyl groups such as iminomethyl group, (1-imino)ethyl group, (1-imino)-n-propyl group;
N-hydroxy-iminomethyl group, (1-(N-hydroxy)-imino)ethyl group, (1-(N-hydroxy)-imino)propyl group, N-methoxy-iminomethyl group, (1-(N-methoxy)) A substituted or unsubstituted N-hydroxyimino C1-6 alkyl group such as -imino)ethyl group;
Aminocarbonyloxy group;
C1-6 alkyl-substituted aminocarbonyloxy groups such as ethylaminocarbonyloxy group and dimethylaminocarbonyloxy group;

Mercapto group;
A C1-6 alkylthio group such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group;
A C1-6 haloalkylthio group such as a trifluoromethylthio group or a 2,2,2-trifluoroethylthio group;
C6-10 arylthio groups such as phenylthio group and naphthylthio group;
5- to 6-membered heteroarylthio groups such as thiazolylthio group and pyridylthio group;

A C1-6 alkylsulfinyl group such as a methylsulfinyl group, an ethylsulfinyl group and a t-butylsulfinyl group;
A C1-6 haloalkylsulfinyl group such as a trifluoromethylsulfinyl group or a 2,2,2-trifluoroethylsulfinyl group;
A C6-10 arylsulfinyl group such as a phenylsulfinyl group;
5- to 6-membered heteroarylsulfinyl group such as thiazolylsulfinyl group and pyridylsulfinyl group;

A C1-6 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, and a t-butylsulfonyl group;
A C1-6 haloalkylsulfonyl group such as a trifluoromethylsulfonyl group or a 2,2,2-trifluoroethylsulfonyl group;
C6-10 arylsulfonyl group such as phenylsulfonyl group;
5- to 6-membered heteroarylsulfonyl groups such as thiazolylsulfonyl group and pyridylsulfonyl group;
A C1-6 alkylsulfonyloxy group such as a methylsulfonyloxy group, an ethylsulfonyloxy group or a t-butylsulfonyloxy group;
A C1-6 haloalkylsulfonyloxy group such as a trifluoromethylsulfonyloxy group or a 2,2,2-trifluoroethylsulfonyloxy group;

Tri-C1-6 alkyl-substituted silyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group;
A tri-C6-10 aryl-substituted silyl group such as a triphenylsilyl group;
Cyano group; nitro group; aminothiocarbonyl group;

Further, in these “substituents”, any hydrogen atom in the substituent may be substituted with a group having a different structure. In that case, examples of the "substituent" include a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a halogeno group, a cyano group and a nitro group.

In addition, the above-mentioned “3- to 6-membered heterocyclyl group” is a group containing 1 to 4 heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom as ring-constituting atoms. The heterocyclyl group may be either monocyclic or polycyclic. In the polycyclic heterocyclyl group, if at least one ring is a hetero ring, the remaining ring may be a saturated alicyclic ring, an unsaturated alicyclic ring or an aromatic ring. Examples of the "3 to 6 membered heterocyclyl group" include a 3 to 6 membered saturated heterocyclyl group, a 5 to 6 membered heteroaryl group, a 5 to 6 membered partially unsaturated heterocyclyl group and the like.

Examples of the 3- to 6-membered saturated heterocyclyl group include an aziridinyl group, an epoxy group, a pyrrolidinyl group, a tetrahydrofuranyl group, a thiazolidinyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, a dioxolanyl group and a dioxanyl group.

Examples of the 5-membered heteroaryl group include pyrrolyl group, furyl group, thienyl group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, triazolyl group, oxadiazolyl group, thiadiazolyl group, tetrazolyl group and the like. You can
Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group and a triazinyl 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.

Specific examples of the “C1-6 alkyl group having a substituent” in R ¹ include
Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 1-chloroethyl group, 2,2,2-trifluoro Ethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 3,3,3-trifluoropropyl group, 2,2,2-trifluoro-1 A C1-6 haloalkyl group such as a trifluoromethylethyl group, a perfluoropropan-2-yl group, a perfluorohexyl group, a perchlorohexyl group, a 2,4,6-trichlorohexyl group;

A hydroxyC1-6 alkyl group such as a hydroxymethyl group and a hydroxyethyl group;
C1 such as methoxymethyl group, ethoxymethyl group, methoxyethyl group, ethoxyethyl group, methoxy-n-propyl group, n-propoxymethyl group, i-propoxyethyl group, s-butoxymethyl group, t-butoxyethyl group. 6 alkoxy C1-6 alkyl group;
C6-10 aryl C1-6 alkyl group such as benzyl group and phenethyl group;
C3-8 cycloalkyl C1-6 alkyl groups such as cyclopropylmethyl group, 2-cyclopropylethyl group, cyclopentylmethyl group, 2-cyclohexylethyl group, 2-cyclooctylethyl group; and the like.

The substituent on the "C1-6 alkyl group" for R ¹ is preferably a halogeno group such as a fluoro group, a chloro group, a bromo group or an iodo group; a methoxy group, an ethoxy group, an n-propoxy group or an i-propoxy group. , A 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, etc. C1-6 haloalkoxy group of cyano group;

R ¹ is preferably a methyl group.

{R ² }
In formula (I), R ² is a hydrogen atom, a halogeno group, a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C2-6 alkenyl group, a substituted or unsubstituted C2-6 alkynyl group, a substituted Or an unsubstituted C1-6 alkoxycarbonyl group, a substituted or unsubstituted aminocarbonyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted C3-8 cycloalkyl group, a substituted or unsubstituted 5 to 6 membered hetero group It is an aryl group or a cyano group.

Examples of the "halogeno group" for R ² include a fluoro group, a chloro group, a bromo group, an iodo group and the like.

Examples of the “C1-6 alkyl group” for R ² include the same groups as those exemplified for R ¹ .

Examples of the "C2-6 alkenyl group" for R ² include 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-hexenyl group, 5-hexenyl group and the like.

The “C2-6 alkynyl group” for R ² is an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 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 Group, a 1,1-dimethyl-2-butynyl group, and the like.

Examples of the "C1-6 alkoxycarbonyl group" for R ² include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group and the like. it can.
Among these, a methoxycarbonyl group and an ethoxycarbonyl group are preferable.

Preferable substituents on the "C1-6 alkyl group" and "C1-6 alkoxycarbonyl group" for R ² include halogeno groups such as fluoro group, chloro group, bromo group and iodo group.

The “substituted or unsubstituted aminocarbonyl group” for R ² is a group represented by the formula (a).

In formula (a), * is a bonding position, and R ^a and R ^b are each independently a hydrogen atom or a C1-6 alkyl group.

Examples of the “C1-6 alkyl group” for R ^a and R ^b include the same groups as those exemplified for R ¹ .

The “substituted or unsubstituted aminocarbonyl group” for R ² is preferably a methylaminocarbonyl group or a dimethylaminocarbonyl group.

The “substituted or unsubstituted amino group” for R ² is a group represented by “—NR ^c R ^d ”. In the formula, R ^c and R ^d are each independently a hydrogen atom or a C1-6 alkylcarbonyl group.

Examples of the “C1-6 alkylcarbonyl group” for R ^c and R ^d include an acetyl group and a propionyl group.

The “substituted or unsubstituted amino group” for R ² is preferably an acetylamino group.

Examples of the “C3-8 cycloalkyl group” for R ² include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cubanyl group and the like.

The "5- or 6-membered heteroaryl group" for R ² is a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group. A 5-membered heteroaryl group such as tetrazolyl group; and a 6-membered heteroaryl group such as pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group and triazinyl group.
Among these, a 5-membered heteroaryl group is preferable, and a triazolyl group or a pyrazolyl group is particularly preferable.

Preferred substituents on the "C3-8 cycloalkyl group" and "5- to 6-membered heteroaryl group" for R ² are methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group. , N-hexyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, i-hexyl group Mention may be made of C1-6 alkyl groups such as groups.

R ² is preferably a halogeno group, a C 2-6 alkenyl group, a C 1-6 alkoxycarbonyl group, a substituted or unsubstituted amino group, a 5-membered heteroaryl group, or a cyano group, and a halogeno group, C 1-6 alkoxy group. A carbonyl group or a 5-membered heteroaryl group is particularly preferable.

{R ³ }
In formula (I), R ³ is a substituted or unsubstituted C1-6 alkoxycarbonyl group, or a substituted or unsubstituted aminocarbonyl group.

"C1~6 alkoxycarbonyl group" in R ^3, and "substituted or unsubstituted aminocarbonyl group" is the same thing can be mentioned those exemplified in the R ^2.

The substituent on the "C1-6 alkoxycarbonyl group" for R ³ is preferably a halogeno group such as a fluoro group, a chloro group, a bromo group or an iodo group.

R ³ is preferably a substituted or unsubstituted aminocarbonyl group, and more preferably an isopropylaminocarbonyl group.

{R ⁴ , R ^4' }
In formula (I), R ⁴ and R ^4′ 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 ⁴ and R ^4′ include the same as those specifically exemplified for R ¹ .

R ⁴ and R ^4′ are preferably methyl groups.

{Z}
In formula (I), Z is an oxygen atom.

{R ⁵ }
In formula (I), R ⁵ is a hydrogen atom, a substituted or unsubstituted C1~6 alkyl group, a substituted or unsubstituted C3~8 cycloalkyl group or 5-6 membered ring saturated heterocyclyl group.

Examples of the “C1-6 alkyl group” for R ⁵ include the same groups as those exemplified for R ¹ .

Preferred substituents on the "C1-6 alkyl group" for R ⁵ include a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C1-6 alkylthio group, a C1-6 alkylsulfinyl group, a C1-6 alkylsulfonyl group, and C3. ~8 cycloalkyl groups, cyano groups, or aminothiocarbonyl groups.

Specifically, a halogeno group such as a fluoro group, a chloro group, a bromo group and an iodo group; a hydroxyl group; a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an s-butoxy group, i -C1-6 alkoxy group such as butoxy group and t-butoxy group; methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group C1-6 alkylthio group such as group; C1-6 alkylsulfinyl group such as methylsulfinyl group, ethylsulfinyl group, t-butylsulfinyl group; C1-6 alkyl such as methylsulfonyl group, ethylsulfonyl group, t-butylsulfonyl group A sulfonyl group; a C3-8 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cubanyl group; a cyano group; and an aminothiocarbonyl group.

Examples of the “substituted or unsubstituted C3-8 cycloalkyl group” for R ⁵ include the same groups as those exemplified for R ² .

Examples of the “5- to 6-membered saturated heterocyclyl group” for R ⁵ include a pyrrolidinyl group, a tetrahydrofuranyl group, a thiazolidinyl group, a piperidyl group, a piperazinyl group, a tetrahydropyranyl group, a morpholinyl group, a dioxolanyl group, and a dioxanyl group. it can.
Among these, a tetrahydropyranyl group is preferable.

R ⁵ is preferably a hydrogen atom or a substituted or unsubstituted C1-6 alkyl group.

{X}
In formula (I), X is a halogeno group or a substituted or unsubstituted C1-6 alkoxy group.

As the “halogeno group” for X, the same groups as those exemplified for R ² can be mentioned.

As the "C1-6 alkoxy group" in X, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an i-propoxy group, an i-butoxy group, Examples thereof include s-butoxy group, t-butoxy group and i-hexyloxy group.

The substituent on the "C1-6 alkoxy group" for X is preferably a halogeno group such as a fluoro group, a chloro group, a bromo group or an iodo group.

{N}
n represents the number of chemically acceptable Xs, and is an integer of 0-5. When n is 2 or more, Xs may be the same or different.

The wavy line showing the bond (NO undefined stero bond) between N (nitrogen atom) and Z (oxygen atom) in the formula (I) is an E-form or Z-form or a mixture thereof due to a nitrogen-carbon double bond. Indicates that there is.

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; ammonia, triethylamine, tributylamine, pyridine, salts of organic bases such as hydrazine, and the like.

The compound (I) or the salt of the compound (I) is not particularly limited depending on its production method. The salt of compound (I) can be obtained from compound (I) by a known method. For example, the compound (I) or the salt of the compound (I) of the present invention can be obtained by the known production method described in Examples and the like.

[Compound represented by Formula (II)]
The 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound of the present invention is preferably a compound of formula (II).

式(II)中、Ｒ²およびＲ⁵は、式(I)中のそれらと同じ意味である。

In formula (II), R ² and R ⁵ have the same meanings as those in formula (I).

The wavy line indicating the bond (NO undefined stero bond) between N (nitrogen atom) and O (oxygen atom) in the formula (II) is an E-form or Z-form or a mixture thereof due to a nitrogen-carbon double bond. Indicates that there is.

[Fungicide for agriculture and horticulture]
The agricultural and horticultural fungicide of the present invention contains at least one compound (I) or a salt thereof as an active ingredient. The amount of the compound (I) or its salt 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), etc. Peanut: brown spot (Mycosphaerella arachidis), leaf spot (Ascochyta sp. ), rust disease (Puccinia arachidis), wilt disease (Pythium debaryanum), rust spot disease (Alternaria alternata), white silkworm disease (Sclerotium rolfsii), black rot (Mycosphaerella berkeleyi) cucumber: powdery mildew (Sphaerotheca fuliginea), Downy mildew (Pseudoperonospora cubensis), wilt blight (Mycosphaerella melonis), wilt disease (Fusarium oxysporum), sclerotinia (Sclerotinia sclerotiorum), gray mold (Botrytis cinerea), anthracnose (Colletotrichum orbiculare), scab (Cladosporium cucumerinum), brown spot (Corynespora cassiicola), seedling blight (Pythium debaryanum, Rhizoctonia solani Kuhn), Phomopsis root rot (Phomopsis sp.) Spot fungus (Pseudomonas syringae pv. Lechrymans), etc. Disease (Botrytis cinerea), leaf mold (Cladosporium fulvum), plague (Phytophthora infestans), half body wilt (Verticillium albo-atrum, Verticillium dahliae), powdery mildew (Oidium neolycopersici), ring spot disease (Alternaria solani), Mold (Pseudocercospora fuligena), etc. Eggplant: Gray mold (Botrytis cinerea), Black spot (Corynespora melongenae), Powdery mildew (Erysiphe cichoracearum), Botrytis rust (My) Strawberry: Botrytis cinerea, powdery mildew (Sphaerotheca humuli), and anthracnose (covellosiella nattrassii), sclerotinia sclerotiorum, half body wilt (Verticillium dahliae), brown leaf spot (Phomopsis vexans), etc. Colletotrichum acutatum, Colletotrichum fragariae), plague (Phytophthora cactorum), soft rot (Rhizopus stolonifer), yellow rot (Fusarium oxysporum), wilt (Verticillium dahliae), etc. Onions: gray rot (Botrytis cine alli), gray rot (Botrytis allii). ), white spot blight (Botrytis squamosa), downy mildew (Peronospora destructor), white plague (Phytophthora porri), etc. Cabbage: root-knot disease (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 Diseases (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 (Monilinia mali), black spot (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), etc. Japanese plum: Cladosporium carpophilum, gray mold (Botrytis cinerea), sterility (Monilinia mumecola), etc. Oyster: powdery mildew (Phyllactinia kakicola), anthracnose Diseases (Gloeosporium kaki), leaf spot disease (Cercospora kaki), etc. Peach: Monilinia fructicola, scab (Cladosporium carpophilum), Phomopsis rot (Phomopsis sp.), perforation bacterial disease (Xanthomonas campestris pv. pruni) ) Etc. Almonds: Monilinia laxa, Spot disease (Stigmina carpophila), Black spot disease (Cladosporium carpophilum), Leaf blight (Polystigma rubrum), Leaf spot disease (Alternaria alternata), Anthrax (Colletotrichum gloeospoides), etc. Sweet cherry: Monilinia fructicola, Anthracnose (Colletotrichum acutatum), Black spot (Alternaria sp.), Sclerotial disease (Monilinia kusanoi), etc. Grape: Gray mold (Botrytis cinerea), powdery mildew (Uncinula necato r), late rot (Glomerella cingulata, Colletotrichum acutatum), downy mildew (Plasmopara viticola), black rot (Elsinoe ampelina), brown spot (Pseudocercospora vitis), black rot (Guignardia bidwellii), white rot ( Coniella castaneicola), rust (Phakopsora ampelopsidis), etc. Pear: scab (Venturia nashicola), scab (Gymnosporangium asiaticum), black spot (Alternaria kikuchiana), ring spot (Botryosphaeria berengeriana), powdery mildew (Phyllactinia). , Blight (Phomopsis fukushii), brown leaf spot (Stemphylium vesicarium), anthracnose (Glomerella cingulata), etc. Cha: leaf spot (Pestalotiopsis longiseta, P. theae), anthracnose (Colletotrichum theae-sinensis), net Rice blast (Exobasidium reticulatum) etc. Citrus: Scab (Elsinoe fawcettii), Blue mold (Penicillium italicum), Green mold (Penicillium digitatum), Gray mold (Botrytis cinerea), Black spot disease (Diaporthe citri), Canker disease (Cal canker). Xanthomonas campestris pv.Citri), powdery mildew (Oidium sp.), etc.

Wheat: Powdery mildew (Blumeria graminis f.sp. tritici), Fusarium head blight (Gibberella zeae), Leaf rust (Puccinia recondita), Brown snow rot (Pythium iwayamai), Red snow rot (Monographella nivalis), Eye print Disease (Pseudocercosporella herpotrichoides), leaf blight (Septoria tritici), bacterial wilt (Leptosphaeria nodorum), snow rot small grain sclerot (Typhula incarnata), snow rot large grain sclerotia (Myriosclerotinia borealis), blight (Gaeumannomyces graminis). ), ergot (Claviceps purpurea), linseed scab (Tilletia caries), naked scab (Ustilago nuda), etc. Barley: leaf spot (Pyrenophora graminea), net blotch (Pyrenophora teres), cloudy leaf disease (Rhynchosporium secalis), Naked smut (Ustilago tritici, U.nuda), etc. Rice: blast (Pyricularia oryzae), blight (Rhizoctonia solani), scabbard (Gibberella fujikuroi), sesame leaf blight (Cochliobolus miyabeanus), shoot blight (Pythium graminicola), white leaf blight (Xanthomonas oryzae), bacterial bacterial blight (Burkholderia plantarii), brown streak (Acidovorax avenae), rice bacterial blight (Burkholderia glumae), streak leaf blight (Cercospora oryzae), rice Koji disease (Ustilaginoidea virens), brown rice (Alternaria alternata, Curvularia intermedia), black rice (Alternaria padwickii), red rice (Epicoccum purpurascens), etc. Tobacco: Sclerotinia sclerotiorum, powdery mildew (Erysiphe cichoracearum), Plague (Phytophthora nicotianae ), etc. Tulip: Gray mold (Botrytis cinerea) etc. Sunflower: Downy mildew (Plasmopara halstedii), Sclerotinia sclerotiorum etc. Bentgrass: Snow rot large sclerotinia borealis (Sclerotinia borealis), Large patch (Rhizoctonia solani) , Brown patch (Rhizoctonia solani), dollar spot (Sclerotinia homoeocarpa), blast (Pyricularia sp.), red burn (Pythium aphanidermatum), anthracnose (Colletotrichum graminicola), etc. Orchardgrass: powdery mildew (Erysiphe graminis), etc. Soybean: Purpura (Cercospora kikuchii), downy mildew (Peronospora manshurica), stem sickness (Phytophthora sojae), rust (Phakopsora pachyrhizi), sclerotinia sclerotiorum, anthracnose (Colletotrichum truncatum), gray mold (Botrytis cinerea), black scab (Elsinoe glycines), black spot (Diaporthe phaseolorum var. sojae), etc. Potato: Phytophthora infestans, summer blight (Alternaria solani), black blight (Thanatephorus cucumeris), wilt wilt. Verticillium albo-atrum, V. dahliae, V. nigrescens, etc. Banana: Panama disease (Fusarium oxysporum), Sigatoka disease (Mycosphaerella fijiensis, M. musicola), etc. Rape: Sclerotinia sclerotiorum, root rot (Phoma lingam) ), Black spot (Alternaria brassicae), etc. Coffee: Rust (Hemileia vastatrix), Anthrax (Colletotrichum coffeanum), Brown eye (Cercospora coffeicola), etc. Sugarcane: Brown rust ( Puccinia melanocephala, etc. Maize: Hail blotch (Gloeocercospora sorghi), rust (Puccinia sorghi), southern rust (Puccinia polysora), smut (Ustilago maydis), sesame leaf blight (Cochliobolus heterostrophus), scabbard (Setosphaeria). turcica) Cotton: Seedling blight (Pythium sp.), rust (Phakopsora gossypii), mildew (Mycosphaerella areola), anthrax (Glomerella gossypii), etc.

The agricultural and 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; turf; 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 agricultural/horticultural fungicide of the present invention is used for seed treatment, foliar spraying, soil application, water surface application, etc. performed for controlling various diseases occurring in agricultural and horticultural crops including flowers, turf, and grass. You can

The fungicide for agricultural and horticultural use of the present invention contains components other than the 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound of the present invention. Good. Other components include known carriers used for formulation. Further, as other components, conventionally known fungicides, insecticides and acaricides, nematicides, soil pesticides, plant regulators, synergists, fertilizers, soil improvers, animal feeds and the like can be mentioned. 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), benalaxyl-M (benalaxyl-M), furalaxyl (furalaxyl), metalaxyl (metalaxyl), metalaxyl-M (metalaxyl-M), oxadixyl (oxadixyl), blackzillacon (clozylacon) ), offurace;
(b) Adenosine deaminase inhibitor: bupirimate, dimethirimol, ethirimol;
(c) DNA/RNA synthesis inhibitor: hymexazol, octhilinone;
(d) DNA topoisomerase II inhibitor: oxolinic acid.

(2) Antimitotic agent and antimitotic agent:
(a) β-tubulin polymerization inhibitor: benomyl, carbendazim, carbfenazim, chlorfenazole, fuberidazole, thiabendazole, thiophanate, thiophanate-methyl , Diethofencarb, zoxamide, ethaboxam;
(b) anti-mitotic agent: pencycuron;
(c) Delocalization inhibitor of spectrin-like protein: fluopicolide.

(3) Respiratory inhibitor:
(a) Complex I NADH oxidoreductase inhibitor: diflumetorim, tolfenpyrad;
(b) Complex II succinate dehydrogenase inhibitor: benodanil, flutolanil, mepronil, isofetamid, fluopyram, fenfuram, flumecyclox , Carboxin, oxycarboxin, thifluzamide, benzovindiflupyr, bixafen, fluxapyroxad, furametpyr, isopyrazam, isopyrazam, Penflufen, penthiopyrad, sedaxane, boscalid, pyraziflumid;
(c) Complex III Ubiquinol Oxidase Qo Inhibitor: Azoxystrobin (azoxystrobin), Cumoxystrobin (Coumoxystrobin), Cummethoxystrobin, Enoxastrobin, Flufenoxystrobin , Picoxystrobin, pyraoxystrobin, pyraclostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, trifloxist Robin (trifloxystrobin), dimoxystrobin (dimoxystrobin), phenaminestrobin (fenaminstrobin), metominostrobin (metominostrobin), orysastrobin (orysastrobin), famoxadone (flumastrodone), fluoxastrobin (fluoxastrobin), fenamidone (fenamidone) , Pyribencarb, mandestrobin;
(d) Complex III ubiquinol reductase Qi inhibitor: cyazofamid, amisulbrom;
(e) Uncoupler for oxidative phosphorylation: binapacryl, meptyldinocap, dinocap, fluazinam, ferimzone;
(f) Oxidative phosphorylation inhibitors (inhibitors of ATP synthase): fentin acetate, fentin chloride, fentin hydroxide;
(g) ATP production inhibitor: silthiofam;
(h) Complex III: Qx (unknown) inhibitor of cytochrome bc1 (ubiquinone reductase): ametoctradin.

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

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

(6) Lipid and cell membrane synthesis inhibitor:
(a) Phospholipid biosynthesis, methyltransferase inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane.
(b) Lipid peroxides: biphenyl, chloroneb, dichloran, dichloran, quintozene, tecnazene, tolclofos-methyl, etridiazole;
(c) Agents that act on cell membranes: iodocarb, idiocarb, propamocarb, propamocarb-hydrochloride, propamocarb-fosetylate, prothiocarb;
(d) Microbes that disrupt the cell membrane of pathogenic bacteria: Bacillus subtilis (bacillus subtilis), Bacillus subtilis strain QST713 (bacillus subtilis strain QST713), Bacillus subtilis strain FZB24, Bacillus subtilis MBI600 strain (bacillus subtilis) , Bacillus subtilis strain D747 strain, Bacillus amyloliquefaciens;
(e) An agent that disturbs cell membranes: melaleuca alternifolia (tea tree) extract.

(7) Cell membrane sterol biosynthesis inhibitor:
(a) Demethylation inhibitor at the C14 position in sterol biosynthesis: triforine (triforine), pyrifenox (pyrifenox), pyrisoxazole (pyrisoxazole), fenarimol (fenarimol), flurprimidol (flurprimidol), nuarimol (nuarimol), Imazalil, imazalil-sulphate, oxpoconazole fumarate, pefurazoate, prochloraz, triflumizole, viniconazole, azaconazole azaconazole), bitertanol (bitertanol), bromconazole (bromuconazole), cyproconazole (cyproconazole), diclobutrazol (diclobutrazol), difenoconazole (difenoconazole) (diniconazole), diniconazole-M (diniconazole-M), epoxy Conazole (epoxiconazole), etaconazole (etaconazole), fenbuconazole (fenbuconazole) (fluquinconazole) (fluquinconazole), flusilazole (flusilazole), flutriafol (flutriafol), fluconazole (furconazole), fluconazole-cis (furconazole-cis) , Hexaconazole, imibenconazole, imibenconazole, ipconazole, metconazole, microbutanil, myclobutanil, penconazole, propiconazole, propiconazole, fluquinconazole, simeconazole (Simeconazole), tebuconazole (tebuconazole), tetraconazole (tetraconazole), triadimefon (triadimefon), triadimenol (triadimenol), triticonazole (trit) iconazole), prothioconazole (prothioconazole), voriconazole (voriconazole), mefentrifluconazole (mefentrifluconazole);
(b) Δ14 reductase and Δ8→Δ7-isomerase inhibitors in sterol biosynthesis:
Aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
(c) 3-keto reductase inhibitors in C4 demethylation of sterol biosynthesis system: fenhexamid, fenpyrazamine;
(d) Sterol biosynthesis squalene epoxidase inhibitors: pyributicarb, naphthifine, terbinafine.

(8) Cell wall synthesis inhibition
(a) Trehalase inhibitor: validamycin;
(b) Chitin synthase inhibitor: polyoxins, polyoxorim;
(c) Cellulose synthase inhibitor: dimethomorph, flumorph, pyrimorph, benchavaricarb-isopropyl, iprovalicarb, tolprocarb, valifenalate ), mandipropamid.

(9) Melanin biosynthesis inhibitor
(a) Reductase inhibitors of melanin biosynthesis: fthalide, pyroquilon, tricyclazole;
(b) Dehydrase inhibitors of melanin biosynthesis: carpropamid, diclocymet, fenoxanil.

(10) Host plant resistance inducer:
(a) Agents that act on the salicylic acid synthesis pathway: acibenzolar-S-methyl;
(b) Others: probenazole (probenazole), thiazinyl (tiadinil), isothianil (isotianil), laminarin (laminarin), oyster knotweed extract (reynoutria sachalinensis extract).

(11) Agents of unknown action: cymoxanil, fosetyl-aluminium, phosphoric acid (phosphate), tecloftalam, triazoxide, fursulfamide (flusulfamide) flusulfamide), diclomedine (diclomezine), metasulfocarb (methasulfocarb), cyflufenamid (cyflufenamid), metrafenone (metrafenone), pyriophenone (pyriofenone), dodine (dodine), dozine free base (dodine free base), flutianil (flutianil).

(12) Agents having multiple points of action: copper (copper salt), bordeaux mixture, copper hydroxide, copper naphthalate, copper oxide , Copper oxychloride, copper sulfate, sulfur, sulfur product, calcium polysulfide, ferbam, mancozeb, maneb , Mancopper, metiram, polycarbamate, propineb, thiram, zineb, ziram, captan, captafol, folpet (Folpet), chlorothalonil, dichlofluanid, tolylfluanid, tolylfluanid, guazatine, iminoctadine triacetate, iminoctadine trialbesilate, anilazine. , Dithianon, quinomethionate, fluoroimide.

(13) Other agents: DBEDC, fluorofolpet, guazatine acetate, bis(8-quinolinolato) copper(II), propamidine ( propamidine), chloropicrin, cyprofuram, agrobacterium, bethoxazin, diphenylamine, diphenylamine, methyl isothiocyanate, mildeomycin, Capsaicin, cufraneb, cyprosulfamide, cyprosulfamide, dazomet, debacarb, dichlorophen, flumetover, fosetyl-calcium, fosetyl sodium fosetyl-sodium), irumamycin, natamycin, nitrothal isopropyl, oxamocarb, pyrrolnitrin, tebufloquin, tornifanide, tolnifanide, zaliramide. , Algophase, amicalthiazol, oxathiapiprolin, metiram zinc, benthiazole, trichlamide, uniconazole, oxyfenthiin ), picarbutrazox, fenpicoxamid, fenpicoxamid, dichlobentiazox, quinofumelin thiuram, ambam, Agrobacterium aradiba. cterium radiobacter), Coniothyrium minitans, Pseudomonas fluorescens, Pseudomonas rhodesiae, Tararomyces sp. carotovora), Bacillus simplex (bacillus simplex), Variovorax paradoxus, Lactobacillus plantarum (lactobacillus plantarum).

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) Acetylcholinesterase inhibitor:
(a) Carbamate type: alanicarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbofuran, Carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomil, methomyl, oxamyl, pirimicarb. ), propoxur, thiodicarb, thiofanox, thiofanox, triazamate, trimethacarb, XMC, xylylcarb, phenothiocarb, fenothiocarb, MIPC, MPMC, MTMC, aldoxicarb (Aldoxycarb), alixycarb (allyxycarb), aminocarb (aminocarb), bufencarb (clofenthocarb), cloethocarb, metam sodium (metam-sodium), promecarb (promecarb);

(b) Organophosphorus: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenbin Phos (chlorfenvinphos), chlormephos, chlorpyrifos, chlorpyrifos-methyl, chlorphorifos-methyl, coumaphos, cyanophos, demeton-S-methyl (demeton-S-methyl), diazinon (diazinon) ), dichlorvos/DDVP, dicrotophos, dimethoate, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, femfur, fenamiphos. fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isocarbophos, isocarbophos, isoxathion, malathion, malathion. mecarbam), methamidophos, methidathion, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydimethone-oxydemeton-methyl, parathion, parathion. -Methyl (parathion-methyl), phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl (p) irimiphos-methyl), profenofos (profenofos), propetamphos (propetamphos), prothiophos (prothiofos), pyraclofos (pyraclofos), pyridaphenthion (pyridaphenthion), quinalphos (quinalphos), sulfotep (sulfotep), tebupirinphos (tebupirimfos), tebupirimfos (tebupirimfos) Terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion, bromophos-ethyl, BRP, carbophenothion , Cyanofenphos, CYAP, demeton-S-methyl sulfone, dialifos, diclolofenthion, dioxabenzophos, etrimfos, phensulfothion fensulfothion), flupyrazofos (flupyrazofos), honophos (fonofos), formothion (formothion), fosmethilan (fosmethilan), isazophos (isazofos), iodofenphos (jodfenphos), methacrifos (methacrifos), pirimiphos-ethyl (pirimiphos-bu). (Phosphocarb), propaphos, protoate, sulprofos.

(2) GABA-agonist chloride ion channel antagonists: acetoprole (acetoprole), chlordane, endosulfan, ethiprole, fipronil, pyrafluprole, pyriprole, pyriprole, Camphechlor, heptachlor, dienochlor.
(3) Sodium channel modulators: acrinathrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bio Allethrin s-cyclopentyl isomer, bioresmethrin, biopromethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin. -cyhalothrin), gamma-cyhalothrin (γ-cyhalothrin), cypermethrin (cypermethrin), alpha-cypermethrin (α-cypermethrin), beta-cypermethrin (β-cypermethrin), theta-cypermethrin (θ-cypermethrin), zeta -Cypermethrin (ζ-cypermethrin), cyphenothrin [(1R)-trans isomer] (cyphenothrin [(1R)-trans isomer]), deltamethrin, empentryn [(EZ)-(1R)-isomer] (Empenthrin[(EZ)-(1R)-Isomer]), esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin (Flumethrin), tau-fluvalinate (τ-fluvalinate), halfenprox (halfenprox), imiprothrin, cadprothrin, kadethrin, permethrin, phenothrin [(1R)-trans isomer] (phenothrin [(phenothrin [( 1R)-trans isomer]), prallethrin, pyrethrum, resmethrin, silafluoff (Silafluofen), tefluthrin (tefluthrin), tetramethrin [(1R)-isomer] (tetramethrin [(1R)-isomer]), tralomethrin (translothrin), transfluthrin (allethrin), pyrethrin ( pyrethrins), pyrethrin I, pyrethrin II, profluthrin, dimefluthrin, bioethanomethrin, bioperanothrin, biopermethrin, transpermethrin, transpermethrin (Fenfluthrin), fenpirithrin (fenpirithrin), flubrocythrinate (flubrocythrinate), flufenprox (flufenprox), metofluthrin (metofluthrin), protrifenbute (protrifenbute), pyrethmethrin (pyresmethrin), terrarethrin (terallethrin).

(4) Nicotinic acetylcholine receptor agonists: acetamiprid, clothianidin, clothianidin, dinotefuran, imidacloprid, imidacloprid, nitenpyram, nithiazine, niiaazine, thiacloprid, thiamethoxia, thiamethoprith. Sulfoxaflor (nicotine), flupyradifurone (flupyradifurone), flupyrimine (flupyrimine).
(5) Nicotinic acetylcholine receptor allosteric modulators: spinetoram and spinosad.
(6) Chloride channel activators: abamectin, emamectin-benzoate, lepimectin, milbemectin, ivermectin, seramectin, doramectin, doramectin, eprinomectin. (Eprinomectin), moxidectin (moxidectin), milbemycin (milbemycin), milbemycin oxime (milbemycin oxime), nemadectin (nemadectin).
(7) juvenile hormone-like substances: hydroprene, kinoprene, kinoprene, methoprene, phenoxycarb, pyriproxyfen, diofenolan, epophenonane, triprene ).
(8) Other non-specific inhibitors: methyl bromide, chloropicrin, sulfuryl fluoride, borax, tartar emetic.
(9) Homoptera selective feeding inhibitors: flonicamid, pymetrozine, and pyrifluquinazon.

(10) Mite growth inhibitor: clofentezine, diflovidazin, hexythiazox, etoxazole.
(11) Insect mid-intestinal membrane disrupting agent derived from microorganisms: Bacillus thuringiensis subsp. israelensis (bacillus thuringiensis subsp. Israelensis), Bacillus thuringiensis subsp. aizawai (bacillus thuringiensis subsp. aizawai) , Bacillus thuringiensis subspecies kurstaki (bacillus thuringiensis subsp kurstaki.), Bacillus thuringiensis subsp. tenebrionis (bacillus thuringiensis subsp tenebrionis.), Bt crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A , Cry3Ab, Cry3Bb, Cry34Ab1/Cry35Ab1.
(12) Mitochondrial ATP biosynthesis enzyme inhibitor: diafenthiuron, azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon.
(13) Oxidative phosphorylation uncoupler: chlorfenapyr, sulfluramid, DNOC, binapacryl, dinobuton, dinocap.
(14) Nicotinic acetylcholine receptor channel blocker: bensultap, cartap hydrochloride, nereistoxin, thiosultap-sodium, thiocyclam.
(15) Chitin synthesis inhibitor: Bistrifluron (bistrifluron), chlorfluazuron (chlorfluazuron), diflubenzuron (diflubenzuron), flucycloxuron (flucycloxuron), flufenoxuron (flufenoxuron), hexaflumuron (hexaflumuron), Lufenuron (lufenuron), novaluron (novaluron), noviflumuron (noviflumuron), teflubenzuron (teflubenzuron), triflumuron (triflumuron), buprofezin (fluprofezin), fluazuron (fluazuron).
(16) Diptera molting agent: cyromazine.
(17) Molting hormone receptor agonist: Chromafenozide, halofenozide, methoxyfenozide, tebufenozide.
(18) Octopamine receptor agonists: amitraz, demiditraz, chlordimeform.
(19) Mitochondrial electron transport complex III inhibitor: acequinocyl, fluacrypyrim, hydramethylnon.
(20) Mitochondrial electron transport system complex I inhibitor: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, rotenone.

(21) Voltage-dependent sodium channel blocker: indoxacarb, metaflumizone.
(22) Acetyl CoA carboxylase inhibitor: spirodiclofen, spiromesifen, spirotetramat.
(23) Mitochondrial electron transfer system complex IV inhibitors: aluminum phosphide (aluminium phosphide), calcium phosphide (calcium phosphide), phosphine (phosphine), zinc phosphide (zinc phosphide), cyanide (cyanide).
(24) Mitochondrial electron transport system complex II inhibitor: Cienopyrafen, cyflumetofen, pyflubumide.
(25) Ryanodine receptor modulators: chlorantraniliprole, cyantraniliprole, flubendiamide, cyclaniliprole, tetraniliprole.
(26) Mixed function oxidase inhibitor compound: piperonyl butoxide.
(27) Latrophilin receptor agonists: depsipeptide, cyclic depsipeptide, 24-membered cyclodepsipeptide, emodepside.
(28) Other agents (unknown mechanism of action): Azadirachtin, benzoximate, bifenazate, bromopropylate, quinomethionate, cryolite, dicofol. dicofol), pyridalyl, benclothiaz, sulfur, amidoflumet, 1,3-dichloropropene (1,3-dichloropropene), DCIP, phenisobromolate, benzomate benzomate), metaldehyde, chlorobenzilate, clothiazoben, dicyclanil, phenoxacrim, fentrifanil, flubenzimine, fluphenazine. , Gossyplure, japonilure, metoxadiazone, petroleum, oil, potassium oleate, tetrasul, triarathene, aphidopyropene, aphidopyropen, flomethokine, flometoquin, flometoquin, (flufiprole), fluensulfone, meperfluthrin (meperfluthrin), tetramethylfluthrin (tetramethylfluthrin), tralopyril (dimefluthrin), methylneodecanamide (methylneodecanamide), fluralaner (afluolaner), afoxoranel Fluxametamide, 5-[5-(3,5-dichlorophenyl)-5-trifluoromethyl-4,5-dihydroisoxazol-3-yl]-2-(1H-1,2,4-triazole- 1-yl)benzonite Ril (CAS:943137-49-3) (5-[5-(3,5-dichlorophenyl)-5-trifluoromethyl-4,5-dihydroisoxazole-3-yl]-2-(1H-1,2,4- triazole-1-yl)benzonitrile (CAS:943137-49-3)), broflanilide, other metadiamides, Steinanema carpocapsae, Steinanema glaseri, pasteuria penetrans, Pekiromyces Tenuipes (paecilomyces tenuipes), pekiromyces fumosoroseus (paecilomyces fumosoroseus), beauveria bassiana (beauveria bassiana), beauveria brongniartii, metalridium anisoprie re.

(29) Antiparasitic agent:
(a) Benzimidazoles: fenbendazole, albendazole, triclabendazole, triclabendazole, oxibendazole, mebendazole, oxfendazole, oxfendazole, perbendazole parbendazole), flubendazole (flubendazole), febantel (febantel), netobimin (netobimin), thiophanate (thiophanate), thiabendazole (thiabendazole), cambendazole (cambendazole);
(b) Salicylanilide series: closantel, oxyclozanide, rafoxanide, niclosamide;
(c) Substituted phenol system: nitroxinil, nitroscanate;
(d) Pyrimidines: pyrantel, morantel;
(e) Imidazothiazole system: levamisole, tetramisole;
(f) Tetrahydropyrimidines: praziquantel, epsiprantel;
(g) Other anthelmintic agents: cyclodiene, ryania, clorsulon, metronidazole, demiditraz, piperazine, diethylcarbamazine, dichlorocarb, dichlorophen. , Monepantel, tribendimidine, amidantel, thiacetarsamide, melarsomine, arsenamide.

Specific examples of the plant regulator which can be mixed or used together with the pest control agent of the present invention are shown below.
Abscisic acid, kinetin, benzylaminopurine, 1,3-diphenylurea, 1,3-diphenylurea, forchlorfenuron, thidiazuron, chlorfenuron chlorfenuron), dihydrozeatin, gibberellin A, gibberellin A4, gibberellin A7, gibberellin A3, gibberellin A3, 1-methylcyclopropane, N -Acetylaminoethoxy vinyl glycine (also known as abiglycine) (N-acetyl aminoethoxyvinyl glycine (aviglycine)), aminooxyacetate (aminooxyacetate), silver nitrate, cobalt chloride, IAA, 4-CPA, cloprop (Cloprop), 2,4-D, MCPB, indole-3-butyrate, indole-3-butyrate, dichlorprop, phenothiol, 1-naphthyl acetamide, ethiclozet (Ethychlozate), cloxyfonac (cloxyfonac), maleic acid hydrazide (2,3,5-triiodobenzoic acid), salicylic acid (salicylic acid), methyl salicylate (methyl) salicylate), (-)-jasmonic acid ((-)-jasmonic acid), methyl jasmonate (methyl jasmonate), (+)-strigol ((+)-strigol), (+)-deoxystrigol ((+ )-deoxystrigol), (+)-Orobancol ((+)-orobanchol), (+)-Sorgolactone ((+)-sorgolactone), 4-oxo-4-(2-phenylethyl)aminobutyric acid (4-oxo -4-(2-phen ylethyl)aminobutyric acid), ethephon, chlormequat, mepiquat chloride, benzyladenine, 5-aminolevulinic acid, daminozide.

[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 method for preparing 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 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound of the present invention, 53 parts of diatomaceous earth, 4 parts of higher alcohol sulfate ester, and alkylnaphthalene 3 parts of sulfonate are uniformly mixed and finely ground to obtain a wettable powder with 40% of active ingredient.

(Formulation Example 2: Emulsion)
1,3,5,6-Tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound of the present invention 30 parts, xylene 33 parts, dimethylformamide 30 parts, and polyoxyethylene alkyl 7 parts of allyl ether are mixed and dissolved to obtain an emulsion containing 30% of active ingredient.

(Formulation Example 3: Granule)
1,3,5,6-Tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound of the present invention 5 parts, talc 40 parts, clay 38 parts, bentonite 10 parts, and alkyl 7 parts of sodium sulfate are uniformly mixed and finely ground, and then granulated to a particle diameter of 0.5 to 1.0 mm to obtain a granule containing 5% of the active ingredient.

(Formulation Example 4: Granules)
1,3,5,6-Tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound of the present invention 5 parts, clay 73 parts, bentonite 20 parts, dioctyl sulfosuccinate sodium salt 1 part 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)
1,3,5,6-Tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound of the present invention 10 parts, polyoxyethylene alkyl allyl ether 4 parts, polycarboxylic acid sodium salt 2 parts, 10 parts of glycerin, 0.2 part of xanthan gum, and 73.8 parts of water are mixed and wet-milled until the particle size becomes 3 microns or less to obtain a suspension containing 10% of the active ingredient.

(Formulation Example 6: Granule wettable powder)
1,3,5,6-Tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound of the present invention 40 parts, clay 36 parts, potassium chloride 10 parts, alkylbenzene sulfonic acid sodium salt 1 part, 8 parts of sodium salt of lignin sulfonate and 5 parts of formaldehyde condensate of sodium salt of alkylbenzene sulfonate are uniformly mixed and finely pulverized, and then an appropriate amount of water is added and kneaded to form 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-(5-fluoro-2-methoxyphenyl)-2-(methoxyimino)ethyl)-5-methyl-2,4-dioxo-6-(2H-1,2,3- Synthesis of triazol-2-yl)-1,4-dihydrothieno[2,3-d]pyrimidin-3(2H)-yl)-N-isopropyl-2-methylpropanamide (Compound No. 1)

(Step 1) 2-(1-(2-(5-fluoro-2-methoxyphenyl)-2-oxoethyl)-5-methyl-2,4-dioxo-6-(2H-1,2,3-triazole 2-yl)-1,4-dihydrothieno[2,3-d]pyrimidin-3(2H)-yl)-N-isopropyl-2-methylpropanamide

Ｎ−イソプロピル−２−メチル−２−（５−メチル−２，４−ジオキソ−６−（２Ｈ−１，２，３−トリアゾール−２−イル）−１，４−ジヒドロチエノ［２，３−ｄ］ピリミジン−３（２Ｈ）−イル）プロパンアミド（０．５６ｇ）をＮ，Ｎ−ジメチルホルムアミド（１０ｍｌ）に溶解させた。これに、氷冷下、炭酸カリウム（０．６２ｇ）および２−ブロモ−５’−フルオロ−２’−メトキシアセトフェノン（０．４４ｇ）を加え、室温にて一晩撹拌した。得られた液を氷水に注加し、酢酸エチルで抽出し、抽出相を水で洗浄し、次いで飽和食塩水で洗浄した。その後、無水硫酸マグネシウムで乾燥させた。溶媒を減圧留去し、得られた残渣をシリカゲルカラムクロマトグラフィー（展開溶媒：ｎ−ヘキサン／酢酸エチル）で精製し、目的化合物０．６２ｇ（収率７７％）を得た。
得られた目的物の¹Ｈ−ＮＭＲを以下に示す。
¹H-NMR (CDCl₃,δppm): 1.14(d,6H), 1.82(s,6H), 2.65(s,3H), 3.99(s,3H), 5.22(s,2H), 6.98-7.02(m,1H), 7.24-7.31(m,1H), 7.58-7.63(m,1H), 7.76(s,2H)

N-isopropyl-2-methyl-2-(5-methyl-2,4-dioxo-6-(2H-1,2,3-triazol-2-yl)-1,4-dihydrothieno[2,3-d ] Pyrimidin-3(2H)-yl)propanamide (0.56 g) was dissolved in N,N-dimethylformamide (10 ml). Potassium carbonate (0.62 g) and 2-bromo-5′-fluoro-2′-methoxyacetophenone (0.44 g) were added to this under ice cooling, and the mixture was stirred overnight at room temperature. The obtained solution was poured into ice water and extracted with ethyl acetate, and the extract phase was washed with water and then with saturated saline. Then, it was dried with anhydrous magnesium 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 0.62 g of the desired compound (yield 77%).
¹ H-NMR of the obtained target product is shown below.
¹ H-NMR (CDCl ₃ , δppm): 1.14(d,6H), 1.82(s,6H), 2.65(s,3H), 3.99(s,3H), 5.22(s,2H), 6.98-7.02( m,1H), 7.24-7.31(m,1H), 7.58-7.63(m,1H), 7.76(s,2H)

(Step 2) 2-(1-(2-(5-fluoro-2-methoxyphenyl)-2-(methoxyimino)ethyl)-5-methyl-2,4-dioxo-6-(2H-1,2 ,3-Triazol-2-yl)-1,4-dihydrothieno[2,3-d]pyrimidin-3(2H)-yl)-N-isopropyl-2-methylpropanamide

２−（１−（２−（５−フルオロ−２−メトキシフェニル）−２−オキソエチル）−５−メチル−２，４−ジオキソ−６−（２Ｈ−１，２，３−トリアゾール−２−イル）−１，４−ジヒドロチエノ［２，３−ｄ］ピリミジン−３（２Ｈ）−イル）−Ｎ−イソプロピル−２−メチルプロパンアミド（０．２ｇ）をエタノール（５ｍｌ）に懸濁させた。これに、メトキシアミン塩酸塩（０．０５９ｇ）およびピリジン（０．０６２ｇ）を加え、一晩加熱還流した。得られた液を減圧濃縮し、濃縮液を氷水に注加し、酢酸エチルで抽出し、抽出相を水で洗浄し、次いで飽和食塩水で洗浄した。その後、無水硫酸マグネシウムで乾燥させた。溶媒を減圧留去し、得られた残渣をシリカゲルカラムクロマトグラフィー（展開溶媒：ｎ−ヘキサン／酢酸エチル）で精製し、目的化合物０．１４ｇ（収率６６％）を得た。
得られた目的物の¹Ｈ−ＮＭＲを以下に示す。
¹H-NMR (CDCl₃,δppm): 1.11(d,6H), 1.69(s,6H), 2.59(s,3H), 3.77(s,3H), 3.81(s,3H), 4.02-4.11(m,1H), 4.89(s,2H), 6.83-7.06(m,3H), 7.82(s,2H)

2-(1-(2-(5-Fluoro-2-methoxyphenyl)-2-oxoethyl)-5-methyl-2,4-dioxo-6-(2H-1,2,3-triazol-2-yl )-1,4-Dihydrothieno[2,3-d]pyrimidin-3(2H)-yl)-N-isopropyl-2-methylpropanamide (0.2 g) was suspended in ethanol (5 ml). Methoxyamine hydrochloride (0.059 g) and pyridine (0.062 g) were added thereto, and the mixture was heated under reflux overnight. The obtained liquid was concentrated under reduced pressure, the concentrated liquid was poured into ice water, and the mixture was extracted with ethyl acetate. The extract phase was washed with water and then with saturated saline. Then, it was dried with anhydrous magnesium 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 0.14 g of the desired compound (yield 66%).
¹ H-NMR of the obtained target product is shown below.
¹ H-NMR (CDCl ₃ , δppm): 1.11(d,6H), 1.69(s,6H), 2.59(s,3H), 3.77(s,3H), 3.81(s,3H), 4.02-4.11( m,1H), 4.89(s,2H), 6.83-7.06(m,3H), 7.82(s,2H)

Table 1 shows some of the compounds of the present invention produced in the same manner as in the above-mentioned Examples. In the table, the physical properties, melting point (mp) or refractive index (n _D ) of each compound are also shown. The configuration E or Z in the table indicates the geometric isomer of oxime. "E" indicates E configuration, "Z" indicates Z configuration, "E/Z" indicates that the compound is a mixture of compounds in both configurations, and "E or Z" indicates , E configuration compounds and Z configuration compounds are shown.

Of the compounds shown in Table ^{1, 1} H-NMR (CDCl ₃ ) was measured for the compounds having viscous oil or amorphous physical properties. Table 2 shows the measured values.

[Biological test]
It is shown below that the 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound of the present invention is useful as an active ingredient of an agricultural and horticultural fungicide. The test example will be shown.

(Preparation of test emulsion)
1,3,5,6-Tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound 5 parts by weight, dimethylformamide 93.5 parts by weight, and polyoxyethylene sorbitan monolaurate (Twin 20) 1.5 parts by weight were mixed and dissolved to obtain an emulsion (I) containing 5% of the active ingredient.

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

Test Example 1 Apple Scab Control Control Emulsion (I) has a 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound concentration of 125 ppm. Thus, water was added and dissolved to obtain a drug solution. Subsequently, the above-mentioned drug solution was sprayed on apple seedlings (cultivar "Ohrin", 3-4 leaf stage) grown in a pot for raising seedlings. After air-drying, conidia of apple scab (Venturia inaequalis) were inoculated (treatment group). As a control, apple seedlings that had not been 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 to determine the lesion area ratio, and the control value was calculated.

For the compounds having the compound numbers shown in Table 3, a test for controlling apple scab was carried out. All compounds showed a control value of 75% or more.

(Test Example 2) Cucumber gray mold control test Emulsion (I) had a 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound concentration of 125 ppm. Water was added so as to be 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 that had not been sprayed with the drug solution 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.

The compounds of Compound Nos. 1, 2, 6 and 11 were subjected to a cucumber gray mold control test. All compounds showed a control value of 75% or more.

(Test Example 3) Wheat powdery mildew control test Emulsion (I) had 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound concentration of 125 ppm. Water was added so as to be 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 above-mentioned 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 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 6 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 compounds having the compound numbers shown in Table 4, a wheat powdery mildew control test was conducted. All compounds showed a control value of 75% or more.

(Test Example 4) Wheat leaf rust control test Emulsion (I) had a 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound concentration of 125 ppm. Thus, water was added 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, wheat seedlings sprayed with the drug solution were inoculated by sprinkling the summer spores of wheat leaf rust (Puccinia recondita) (treatment group). 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 leaf of the wheat seedling was visually observed, the lesion area ratio was calculated, and the control value was calculated.

Compounds having the compound numbers shown in Table 5 were subjected to a wheat leaf rust control test. All compounds showed a control value of 75% or more.

(Test Example 5) Acute toxicity test of Daphnia magna 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound was used as N,N-dimethyl. Dissolved in formamide. This was added to water and mixed to obtain aquatic harmful adhering organism control compositions having final concentrations of 0.001 μg/L, 0.01 μg/L, 0.1 μg/L, and 1 μg/L.
Ten Daphnia magna were exposed to the aquatic pesticidal organism control composition at about 20° C. for 48 hours. Next, the immobilization rate of 10 Daphnia magna was measured. The half-effect concentration (EC50 value) was calculated from the measured values by a drawing method.

An acute toxicity test of Daphnia magna was conducted on the compound of Compound No. 1. The half-effect concentration (EC50 value) of the compound was >100 μg/L.

(Test Example 6) Acute toxicity test of zebrafish (Danio rario) 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound was added to N,N- It was dissolved in dimethylformamide. This was added to water and mixed to obtain aquatic harmful adhering organism control compositions having final concentrations of 0.001 μg/L, 0.01 μg/L, 0.1 μg/L, and 1 μg/L.
Twelve fertilized zebrafish eggs were exposed to the test solution at about 25° C. for 96 hours, and the mortality rate was measured. The half-maximal lethal concentration (LD50) was calculated from the measured values by a drawing method.

A compound of Compound No. 1 was subjected to an acute zebrafish toxicity test. The median lethal concentration (LD50) of the compound was >100 μg/L.

(Test Example 7) Acute toxicity test of Oryzias latipes 1,3,5,6-tetra-substituted thieno[2,3-d]pyrimidine-2,4(1H,3H)dione compound was N,N-dimethyl. Dissolved in formamide. This was added to water and mixed to obtain aquatic harmful adhering organism control compositions having final concentrations of 0.001 μg/L, 0.01 μg/L, 0.1 μg/L, and 1 μg/L.
Five adult Japanese killifish were exposed to the test solution at about 23° C. for 96 hours, and the mortality rate was measured. The half-maximal lethal concentration (LD50) was calculated from the measured values by a drawing method.

The compound of Compound No. 1 was subjected to an acute toxicity test of Japanese killifish. The median lethal concentration (LD50) of the compound was >100 μg/L.

Randomly selected from the compounds of the present invention, since the above-mentioned effects are exhibited, the compounds of the present invention have a bactericidal effect, including compounds that could not be exemplified, and cause phytotoxicity on plants. It can be understood that the compound has no toxicity and has little effect on the environment and humans and fishes.

Claims (3)

A compound represented by formula (I) or a salt thereof.

(In formula (I),
R ¹ is a substituted or unsubstituted C 1-6 alkyl group,
R ² is a hydrogen atom, a halogeno group, a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C2-6 alkenyl group, a substituted or unsubstituted C2-6 alkynyl group, a substituted or unsubstituted C1 6 alkoxycarbonyl group, substituted or unsubstituted aminocarbonyl group, substituted or unsubstituted amino group, substituted or unsubstituted C3-8 cycloalkyl group, substituted or unsubstituted 5 to 6 membered heteroaryl group, or cyano group And
R ³ is a substituted or unsubstituted C1-6 alkoxycarbonyl group, or a substituted or unsubstituted aminocarbonyl group,
R ⁴ and R ^4′ are each independently a hydrogen atom, or a substituted or unsubstituted C1-6 alkyl group,
Z is an oxygen atom,
R ⁵ is a hydrogen atom, a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 3-8 cycloalkyl group, or a 5-6 membered saturated heterocyclyl group,
X is a halogeno group, or a substituted or unsubstituted C1-6 alkoxy group,
n represents the number of chemically acceptable X, and is an integer from 0 to 5,
When n is 2 or more, Xs may be the same or different. ) The substituent on the substituted C1-6 alkyl group for R ⁵ is a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C1-6 alkylthio group, a C1-6 alkylsulfinyl group, a C1-6 alkylsulfonyl group, a C3-8 cyclo group. The compound represented by formula (I) according to claim 1, which is an alkyl group, a cyano group, or an aminothiocarbonyl group, or a salt thereof. 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 or 2 and a salt thereof.