JP2017001998A - 1,4-Benzothiazine-1,3-dione or -1,1,3-trione derivative and fungicide containing the same as an active ingredient - Google Patents

Abstract

（ＲはＨ又はアルキル；XはＨ、ハロゲン原子、シアノ基、アミノ、アルキル、アルケニル、アルキニル、アルコキシ、アルキルチオ、アルキルスルホニル、アリール等；ＹはＨ、ハロゲン、アルキル等；ｍは０〜４；ｎは０〜６；ｐは１又は２）
【選択図】なしProvided is a bactericidal agent that has a high control effect on various fungi exhibiting resistance to conventional bactericides and reduces problems such as residual toxicity and environmental pollution.
A 1,4-benzothiazine-1,3-dione or -1,1,3-trione derivative represented by the following formula:

(R is H or alkyl; X is H, halogen atom, cyano group, amino, alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylsulfonyl, aryl, etc .; Y is H, halogen, alkyl, etc .; m is 0-4; n is 0-6; p is 1 or 2)
[Selection figure] None

Description

  The present invention relates to a 1,4-benzothiazine-1,3-dione or -1,1,3-trione derivative and a fungicide containing this as an active ingredient.

  In the field of agriculture and horticulture, various fungicides for the purpose of controlling various pathogenic bacteria have been developed and put into practical use.

  However, pesticides that have been widely used in the past do not necessarily satisfy the requirements such as the effect, spectrum, residual effect, etc., and further, the number of applications and the reduction of the applied dose. In addition, the emergence of pathogenic bacteria that have developed resistance to conventional general agricultural chemicals is also a problem. For example, in the cultivation of vegetables, fruit trees, flower buds, tea, wheat and rice, for example, various triazole, imidazole, pyrimidine, benzimidazole, dicarboximide, phenylamide, strobilurin, etc. Various pathogens that have developed resistance to mold-type disinfectants and the like have appeared in various places, and the control of these resistant pathogens has become difficult year by year. Therefore, the emergence of new pesticides that show sufficient control effects at low doses and have little negative impact on the environment against various pathogens that have developed resistance to conventional agricultural and horticultural fungicides is always desired. It is rare.

  Various new disinfectants have been proposed to meet these demands, but they do not necessarily meet the above demands.

(特許文献１、化合物２−５) Patent Document 1 discloses a benzothiazine derivative having the following structure having bactericidal activity. However, the compound (2-5) described in Patent Document 1 has a benzothiazin-3-one ring, and has a 1,4-benzothiazine-1,3-dione or -1,1,3-trione ring. I do not have.

(Patent Document 1, Compound 2-5)

(特許文献２、殺虫活性) Patent Document 2 discloses a compound having a substituted benzene at the 2-position of the benzothiazine ring as represented by the following structural formula. Patent Document 2 does not describe a compound in which a heterocycle is directly bonded to the 4-position of a benzothiazine ring. Furthermore, Patent Document 2 does not describe that these compounds have bactericidal activity.

(Patent Document 2, insecticidal activity)

(非特許文献１、医薬) Non-Patent Document 1 discloses a compound having a 1,4-benzothiazine-1,3-dione or -1,1,3-trione ring, but describes a derivative having a heterocycle bonded to the 4-position. Not. In addition, Non-Patent Document 1 describes a pharmaceutical activity but does not describe a bactericidal activity.

(Non-Patent Document 1, Medicine)

JP 2014-221747 International Publication No. 1999/50257

Bioorganic & Medicinal Chemistry 8 (2000) 393-404

  The present invention provides a new substance useful for the control of various fungi, and in particular, exhibits a high control effect against various fungi that are resistant to conventional fungicides, and is effective at a low dose. Accordingly, an object of the present invention is to provide a highly safe substance in which problems such as residual toxicity and environmental pollution are reduced.

（式中、Ｒは水素原子またはＣ₁〜Ｃ₆のアルキル基を示し、Xは、水素原子、ハロゲン原子、シアノ基、Ｃ₁〜Ｃ₄のアルキル基、Ｃ₂〜Ｃ₆のアルケニル基、Ｃ₂〜Ｃ₆のアルキニル基、Ｃ₁〜Ｃ₆のアルコキシ基、Ｃ₁〜Ｃ₆のアルキルチオ基、Ｃ₁〜Ｃ₆のアルキルスルフィニル基、Ｃ₁〜Ｃ₆のアルキルスルホニル基、アリール基、ヘテロアリール基、アミノ基、アシル基、カルボキシル基（等）を示し、Yは、水素原子、ハロゲン原子、Ｃ₁〜Ｃ₄のアルキル基、Ｃ₁〜Ｃ₄のアルコキシ基（等）を示し、ｍは０〜４の整数を示し、ｎは０〜６の整数を示し、ｐは１又は２を示す。）で表される１，４−ベンゾチアジン−ベンゾチアジン−１, ３−ジオン又は−１，１, 3−トリオン誘導体（以下、「本発明の化合物」とも言う）およびこれを有効成分として含有する殺菌剤に関するものである。 As a result of intensive studies to solve the above problems, the present inventors have found that the 1,4-benzothiazine-1,3-dione or -1,1,3-trione derivatives defined by the following formula are As a result, the present invention was completed.
That is, the present invention provides the following formula [I],

(Wherein, R represents a hydrogen atom or an alkyl group of C ₁ -C _6, X is a hydrogen atom, a halogen atom, a cyano group, an alkyl group of C ₁ -C _4, an alkenyl group of C ₂ -C _6, C ₂ -C ₆ alkynyl group, C ₁ -C alkoxyl group _6, C ₁ -C ₆ alkylthio, alkylsulfinyl groups of C ₁ -C _6, an alkylsulfonyl group having C ₁ -C _6, an aryl group, heteroaryl group, an amino group, an acyl group, a carboxyl group (equal), Y represents a hydrogen atom, a halogen atom, an alkyl group of C ₁ -C _4, alkoxy group of C ₁ -C ₄ (equal), m represents an integer of 0 to 4, n represents an integer of 0 to 6, and p represents 1 or 2.) 1,4-benzothiazine-benzothiazine-1,3-dione or -1, 1,3-trione derivatives (hereinafter also referred to as “compounds of the present invention”) and the It relates fungicide which comprises, as an active ingredient.

  The compound of the present invention exhibits excellent effects against various fungi.

で表される１，４−ベンゾチアジン−ベンゾチアジン−１，３−ジオン又は−１，１, 3−トリオン誘導体があり、式中、
Ｒは水素原子またはＣ1〜Ｃ6アルキル基を表し、
Ｘは、同一又は異なっていてもよく、水素原子；ハロゲン原子；水酸基；Ｃ1〜Ｃ6アルコキシ基；アシル基；カルボキシル基；シアノ基；アシルオキシ基；ニトロ基；Ｃ1〜Ｃ6アルキルチオ基；Ｃ1〜Ｃ6アルキルスルフィニル基；Ｃ1〜Ｃ6アルキルスルホニル基；ハロゲン原子、水酸基、Ｃ1〜Ｃ6アルコキシ基、Ｃ1〜Ｃ6アルキルチオ基、Ｃ1〜Ｃ6アルキルスルフィニル基、Ｃ1〜Ｃ6アルキルスルホニル基及びフェノキシ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ1〜Ｃ6アルキル基；ハロゲン原子、水酸基、Ｃ1〜Ｃ6アルコキシ基、Ｃ1〜Ｃ6アルキルチオ基、Ｃ1〜Ｃ6アルキルスルフィニル基、Ｃ1〜Ｃ6アルキルスルホニル基、フェニル基及びフェノキシ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ2〜Ｃ6アルケニル基；ハロゲン原子、水酸基、Ｃ1〜Ｃ6アルコキシ基、Ｃ1〜Ｃ6アルキルチオ基、Ｃ1〜Ｃ6アルキルスルフィニル基、Ｃ1〜Ｃ6アルキルスルホニル基、フェニル基及びフェノキシ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ2〜Ｃ6アルキニル基；ハロゲン原子、同一若しくは異なった１〜３個のハロゲン原子で置換されてよいＣ1〜Ｃ6アルキル基、Ｃ1〜Ｃ6アルコキシ基、ニトロ基、シアノ基、水酸基及び同一若しくは異なった１〜２個のＣ1〜Ｃ6アルキル基又はアシル基で置換されてよいアミノ基からなる群から選ばれる同一若しくは異なった１〜５個の置換基で置換されてよいアリール基；ハロゲン原子、同一若しくは異なった１〜３個のハロゲン原子で置換されてよいＣ1〜Ｃ6アルキル基及びＣ1〜Ｃ6アルコキシ基からなる群から選ばれる同一若しくは異なった１〜６個の置換基で置換されてよいヘテロアリール基；又は同一若しくは異なった１〜２個のＣ1〜Ｃ6アルキル基若しくはアシル基で置換されてよいアミノ基を表し、
Ｙは、同一、もしくは異なっていてもよく、水素原子、ハロゲン原子、Ｃ1〜Ｃ6アルキル基、Ｃ1〜Ｃ6アルコキシ基及び水酸基からなる群から選ばれる置換基を表し、
ｍは、０〜４の整数を表し、
ｎは、０〜６の整数を表し、
ｐは、１あるいは２を表す
で表される化合物である。 As another aspect of the present invention, the following formula [I]

1,4-benzothiazine-benzothiazine-1,3-dione or -1,1,3-trione derivatives represented by the formula:
R represents a hydrogen atom or a C1-C6 alkyl group,
X may be the same or different, and are a hydrogen atom; a halogen atom; a hydroxyl group; a C1 to C6 alkoxy group; an acyl group; a carboxyl group; a cyano group; an acyloxy group; a nitro group; a C1 to C6 alkylthio group; A sulfinyl group; a C1-C6 alkylsulfonyl group; the same selected from the group consisting of a halogen atom, a hydroxyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, and a phenoxy group Or a C1 to C6 alkyl group which may be substituted by 1 to 3 different substituents; a halogen atom, a hydroxyl group, a C1 to C6 alkoxy group, a C1 to C6 alkylthio group, a C1 to C6 alkylsulfinyl group, a C1 to C6 alkylsulfonyl The same or different 1 selected from the group consisting of a group, a phenyl group and a phenoxy group A C2-C6 alkenyl group which may be substituted with three substituents; a halogen atom, a hydroxyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a phenyl group, and A C2-C6 alkynyl group which may be substituted by the same or different 1 to 3 substituents selected from the group consisting of phenoxy groups; a halogen atom, a C1 which may be substituted by the same or different 1 to 3 halogen atoms -C6 alkyl group, C1-C6 alkoxy group, nitro group, cyano group, hydroxyl group, and the same selected from the group consisting of the same or different C1 -C6 alkyl groups or amino groups which may be substituted with acyl groups Or an aryl group which may be substituted by 1 to 5 different substituents; a halogen atom, the same or different 1 to 3 halogen atoms Or a heteroaryl group optionally substituted with 1 to 6 substituents selected from the group consisting of a C1 to C6 alkyl group and a C1 to C6 alkoxy group optionally substituted with 1 or 2; Represents an amino group which may be substituted with a C1-C6 alkyl group or an acyl group,
Y may be the same or different and each represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group and a hydroxyl group;
m represents an integer of 0 to 4,
n represents an integer of 0 to 6,
p is a compound represented by 1 or 2.

  In the present invention, the “halogen atom” is a fluorine atom, chlorine atom, bromine atom or iodine atom, preferably a fluorine atom, chlorine atom or bromine atom, more preferably a fluorine atom or chlorine atom. And most preferably a fluorine atom.

  In the present invention, the “C 1 -C 6 alkyl group” means, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, an isopentyl group, 2 -Methylbutyl group, neopentyl group, 1-ethylpropyl group, hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2 , 2-dimethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group and the like. 6 straight-chain or branched alkyl groups, preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms (C1-C5 alkyl group), more preferably carbon number 3 -4 linear or branched alkyl groups (C3 to C4 alkyl groups), more preferably a propyl group, an isobutyl group or a t-butyl group.

  In the present invention, the “C 2 -C 6 alkenyl group” may be either linear or branched and may contain any number of one or more double bonds. For example, vinyl group, prop-1-en-1-yl group, allyl group, isopropenyl group, but-1-en-1-yl group, but-2-en-1-yl group, but-3-ene -1-yl group, 2-methylprop-2-en-1-yl group, 1-methylprop-2-en-1-yl group, penta-1-en-1-yl group, penta-2-ene-1 -Yl group, penta-3-en-1-yl group, penta-4-en-1-yl group, 3-methylbut-2-en-1-yl group, 3-methylbut-3-en-1-yl Group, hexa-1-en-1-yl group, hexa-2-en-1-yl group, hexa-3-en-1-yl group, hexa-4-en-1-yl group, hexa-5- Examples thereof include an en-1-yl group and a 4-methylpent-3-en-1-yl group.

  In the present invention, the “C 2 -C 6 alkynyl group” may be linear or branched and may contain any number of one or more triple bonds. For example, ethynyl group, prop-1-in-1-yl group, prop-2-yn-1-yl group, but-1-in-1-yl group, but-3-in-1-yl group, -Methylprop-2-yn-1-yl group, penta-1-in-1-yl group, penta-4-in-1-yl group, hexa-1-in-1-yl group, hexa-5-in A -1-yl group etc. can be illustrated.

  In the present invention, the “C1-C6 alkoxy group” means, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, a pentyloxy group, an isopentyl group. Oxy group, 2-methylbutoxy group, neopentyloxy group, 1-ethylpropoxy group, hexyloxy group, (4-methylpentyl) oxy group, (3-methylpentyl) oxy group, (2-methylpentyl) oxy group (1-methylpentyl) oxy group, 3,3-dimethylbutoxy group, 2,2-dimethylbutoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, A linear or branched alkoxy group having 1 to 6 carbon atoms such as 2,3-dimethylbutoxy group and 2-ethylbutoxy group; Preferred is a linear or branched alkoxy group having 1 to 4 carbon atoms (C1 to C4 alkoxy group), more preferred is a methoxy group, an ethoxy group or an isopropoxy group, and even more preferred. Is a methoxy group or an ethoxy group, and most preferably a methoxy group.

  In the present invention, the “C1-C6 alkylthio group” means, for example, a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isopentylthio group, a neopentylthio group, a 3,3-dimethylbutylthio group, 2 A straight-chain or branched alkylthio group having 1 to 6 carbon atoms such as an ethylbutylthio group, preferably a straight-chain or branched alkylthio group having 1 to 4 carbon atoms, and more preferably Is a methylthio group.

  In the present invention, the “C 1 -C 6 alkylsulfinyl group” means, for example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, an isopentylsulfinyl group, a neopentylsulfinyl group, 3, 3 A straight-chain or branched alkylsulfinyl group having 1 to 6 carbon atoms such as a dimethylbutylsulfinyl group or 2-ethylbutylsulfinyl group, preferably a straight-chain or branched chain having 1 to 4 carbon atoms A chain alkylsulfinyl group, and more preferably a methylsulfinyl group.

  In the present invention, the “C 1 -C 6 alkylsulfonyl group” means, for example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, an isopentylsulfonyl group, a neopentylsulfonyl group, 3, 3 A straight-chain or branched alkylsulfonyl group having 1 to 6 carbon atoms such as a dimethylbutylsulfonyl group or a 2-ethylbutylsulfonyl group, preferably a straight-chain or branched chain having 1 to 4 carbon atoms A chain alkylsulfonyl group, and more preferably a methylsulfonyl group.

  In the present invention, when the C1-C6 alkyl group is substituted with a C1-C6 alkoxy group, the “C1-C6 alkyl group substituted with a C1-C6 alkoxy group” is, for example, a methoxymethyl group, a methoxyethyl group, 2 -C1-C6 linear or branched C1-C6 such as methoxy-2-methylpropyl group, 2-methoxy-1-methylethyl group, 2-methoxy-2-methylethyl, ethoxymethyl group A C1-C6 alkyl group substituted with an alkoxy group, preferably a C1-C4 alkyl group substituted with a linear or branched C1-C4 alkoxy group having 1 to 4 carbon atoms, and more preferably Is a methoxymethyl group. The “C1-C6 alkyl group substituted with a C1-C6 alkoxy group” may be optionally substituted with a halogen.

  In the present invention, when the C1-C6 alkyl group is substituted with a C1-C6 alkylthio group, the “C1-C6 alkyl group substituted with a C1-C6 alkylthio group” is, for example, a methylthiomethyl group, a methylthioethyl group, 2 -Substituted with a linear or branched C1-C6 alkylthio group having 1 to 6 carbon atoms such as methylthio-2-methylpropyl group, 2-methylthio-1-methylethyl group, ethylthio-2-methylethyl A C1-C6 alkyl group, preferably a C1-C4 alkyl group substituted with a linear or branched C1-C4 alkylthio group having 1 to 4 carbon atoms, and more preferably a methylthiomethyl group It is.

  In the present invention, when the C1-C6 alkyl group is substituted with a C1-C6 alkylsulfinyl group, “C1-C6 alkyl group substituted with a C1-C6 alkylsulfinyl group”, for example, methylsulfinylmethyl group, methylsulfinylethyl Straight chain or branched C1-C6 having 1 to 6 carbon atoms such as 2-methylsulfinyl-2-methylpropyl group, 2-methylsulfinyl-1-methylethyl group, and ethylsulfinyl-2-methylethyl group A C1-C6 alkyl group substituted with an alkylsulfinyl group, preferably a C1-C4 alkyl group substituted with a linear or branched C1-C4 alkylsulfinyl group having 1 to 4 carbon atoms. More preferably, it is a methylsulfinylmethyl group.

  In the present invention, when a C1-C6 alkyl group is substituted with a C1-C6 alkylsulfonyl group, a “C1-C6 alkyl group substituted with a C1-C6 alkylsulfonyl group”, for example, a methylsulfonylmethyl group, methylsulfonylethyl Group, 2-methylsulfonyl-2-methylpropyl group, 2-methylsulfonyl-1-methylethyl group, straight or branched C1-C6 having 1 to 6 carbon atoms such as ethylsulfonyl-2-methylethyl A C1-C6 alkyl group substituted with an alkylsulfonyl group, preferably a C1-C4 alkyl group substituted with a linear or branched C1-C4 alkylsulfonyl group having 1 to 4 carbon atoms, More preferably, it is a methylsulfonylmethyl group.

  In the present invention, examples of the “aryl group” include phenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, phenanthrenyl group, acenaphthylenyl group and the like.

  In the present invention, the “heteroaryl group” may be monocyclic or polycyclic, and a heteroaryl group containing one or two or more of the same or different ring-constituting heteroatoms can be used. . Although the kind of hetero atom is not specifically limited, For example, a nitrogen atom, an oxygen atom, a sulfur atom etc. can be illustrated. Examples of heteroaryl groups include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, dihydroisoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, thiadiazolyl, triazolyl , Tetrazolyl group, pyridyl group, azepinyl group, oxazepinyl group and the like, 5-7 membered monocyclic heteroaryl group. The polycyclic heteroaryl group constituting the heteroarylalkyl group includes benzofuranyl group, isobenzofuranyl group, benzothienyl group, indolyl group, isoindolyl group, indazolyl group, benzoxazolyl group, benzoisoxazolyl group , Benzothiazolyl group, benzoisothiazolyl group, benzoxiadiazolyl group, benzothiadiazolyl group, benzotriazolyl group, quinolyl group, isoquinolyl group, cinnolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, naphthyridinyl group, purinyl 8-14 members such as a group, pteridinyl group, carbazolyl group, carbolinyl group, acridinyl group, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl, phenoxazinyl group, phenothiazinyl group, phenazinyl group Polycyclic heteroaryl groups.

  In the present invention, examples of the “aralkyl group” include a group in which one or two or more hydrogen atoms of the “C1-C6 alkyl group” are substituted with the “aryl group”. For example, benzyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, anthracenylmethyl group, phenanthrenylmethyl group, acenaphthylenylmethyl group, diphenylmethyl group, 1-phenethyl group, 2-phenethyl group 1- (1-naphthyl) ethyl group, 1- (2-naphthyl) ethyl group, 2- (1-naphthyl) ethyl group, 2- (2-naphthyl) ethyl group, 3-phenylpropyl group, 3- ( 1-naphthyl) propyl group, 3- (2-naphthyl) propyl group, 4-phenylbutyl group, 4- (1-naphthyl) butyl group, 4- (2-naphthyl) butyl group, 5-phenylpentyl group, 5 Examples include-(1-naphthyl) pentyl group, 5- (2-naphthyl) pentyl group, 6-phenylhexyl group, 6- (1-naphthyl) hexyl group, 6- (2-naphthyl) hexyl and the like. It can be.

  In the present invention, when the C1-C6 alkyl group is substituted with a halogen atom, the "C1-C6 alkyl group substituted with a halogen atom" includes, for example, a trifluoromethyl group, a trichloromethyl group, a difluoromethyl group, a dichloromethyl. Group, dibromomethyl group, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, 2-bromoethyl group, 2- Chloroethyl group, 2-fluoroethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 4-fluorobutyl group, 3-fluoro-2-methylpropyl group, 3,3,3-trifluoro 1-3 same or different “halogen atoms” such as 2-methylpropyl group and 6,6,6-trichlorohexyl group The “C1-C6 alkyl group” substituted by “1”, preferably the “C1-C4 alkyl group” substituted by 1 to 3 “halogen atoms” which are the same or different, and more Preferred is the above-mentioned “C1-C3 alkyl group” substituted by 1 to 3 “fluorine or chlorine atoms” which are the same or different, and even more preferred is a chloromethyl group or a trifluoromethyl group. And particularly preferred is a trifluoromethyl group.

  In the present invention, “an amino group which may be substituted with the same or different 1-2 C1-C6 alkyl group” means, in addition to the amino group, the same or different 1-2 “C1-C6 alkyl group”. The “group” is a substituted amino group, and examples thereof include a dimethylamino group and a diethylamino group.

  In the present invention, the “acyl group” is, for example, a formyl group, a carbonyl group to which the “C1 to C6 alkyl group” is bonded (C2 to C7 alkylcarbonyl group), or a carbonyl group to which the “C2 to C6 alkenyl group” is bonded. (C3 to C7 alkenylcarbonyl group), a carbonyl group to which the “aryl group” is bonded (“arylcarbonyl group”), a carbonyl group to which the “C1 to C6 alkoxy group” is bonded (C2 to C7 alkoxycarbonyl group) or the above A carbonyl group (C2 to C7 alkylaminocarbonyl group) to which “an amino group which may be substituted with the same or different 1 to 2 C1 to C6 alkyl groups” is bonded, preferably 2 to 5 carbon atoms. A linear or branched alkylcarbonyl group (C2-C5 alkylcarbonyloxy group), an alkoxycarbonyl group having 2 to 7 carbon atoms (C2-C 7 alkoxycarbonyl group), more preferably an acetyl group, a methoxycarbonyl group or an ethoxycarbonyl group.

  In the present invention, the “acyloxy group” is, for example, a formyloxy group, a carbonyloxy group to which the “C1 to C6 alkyl group” is bonded (C2 to C7 alkylcarbonyloxy group), or the “C2 to C6 alkenyl group”. Carbonyloxy group (C3 to C7 alkenylcarbonyloxy group), carbonyloxy group to which the “aryl group” is bonded (“arylcarbonyloxy group”), carbonyloxy group to which the “C1 to C6 alkoxyoxy group” is bonded ( C2-C7 alkoxycarbonyloxy group) or a carbonyloxy group (aminocarbonyloxy group, C2-C7 alkylamino) to which the above-mentioned “amino group which may be substituted with the same or different 1-2 C1-C6 alkyl group” is bonded. Carbonyloxy group, di (C2-C7 alkyl) aminocarbonyloxy group) Preferably, it is a linear or branched alkylcarbonyloxy group having 2 to 5 carbon atoms (C2 to C5 alkylcarbonyloxy group) or an alkylaminocarbonyloxy group having 2 to 7 carbon atoms (C2 to C7 alkyl). Eraminocarbonyloxy group), more preferably an acetoxy group.

  In the present invention, “the same or different 1 to 5 selected from the group consisting of a halogen atom, a hydroxyl group, a C1 to C6 alkoxy group, a C1 to C6 alkylthio group, a C1 to C6 alkylsulfinyl group, a C1 to C6 alkylsulfonyl group and a phenoxy group. “C1-C6 alkyl group which may be substituted with three substituents” includes, in addition to the above-mentioned C1-C6 alkyl group, for example, C1-C6 alkyl substituted with a hydroxyl group such as hydroxymethyl group and hydroxyethyl group. Group, a C1-C6 alkyl group substituted by a phenoxy group such as a phenoxymethyl group, a phenoxyethyl group, etc., and a 2-methoxy-1-chloromethyl group, a 3-phenoxy-2-bromo-2-methoxypropyl group, etc. Groups such as halogen atoms, hydroxyl groups, C1-C6 alkoxy groups, C1-C6 alkylthio groups, C1-C6 alkyls Also included are C1-C6 alkyl groups substituted by two or more substituents selected from the group consisting of a rufinyl group, a C1-C6 alkylsulfonyl group and a phenoxy group.

  In the present invention, “the same or different selected from the group consisting of a halogen atom, a hydroxyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a phenyl group and a phenoxy group. “C2-C6 alkenyl group which may be substituted with 1 to 3 substituents” is the same as or different from the above-mentioned C2-C6 alkenyl group, 3-chloroallyl group, 4-bromo-2-butenyl group, etc. 1-3 identical or different C1-C6 alkoxy groups such as C2-C6 alkenyl group, 3-methoxy-2-propenyl group, 4-ethoxy-3-butenyl group substituted with 1 to 3 halogen atoms C2-C6 alkenyl group substituted by a phenyl group such as 1-phenylvinyl group, styryl group, cinnamyl group, etc. C6 alkenyl group, C2-C6 alkenyl group substituted by phenoxy group such as 3-phenoxy-2-butenyl group, and 4-methoxy-3-chloro-2-butenyl group, halogen atom, hydroxyl group, C1-C6 alkoxy A C2-C6 alkenyl group substituted with two or more substituents selected from the group consisting of a group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a phenyl group and a phenoxy group .

  In the present invention, “the same or different selected from the group consisting of a halogen atom, a hydroxyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a phenyl group and a phenoxy group. "C2-C6 alkynyl group optionally substituted by 1 to 3 substituents" includes 3-chloro-2-propynyl group, 4-bromo-2-butynyl group, etc. in addition to the aforementioned C2-C6 alkynyl group. 1 to 3 identical or different C1 groups such as C2-C6 alkynyl, 3-methoxy-2-propynyl, 4-ethoxy-3-butynyl, etc. substituted with 1 to 3 halogen atoms C2-C6 substituted with a phenoxy group such as a C2-C6 alkynyl group or 3-phenoxy-2-butynyl group substituted with a -C6 alkoxy group Such as alkynyl group and 4-methoxy-4-chloro-2-butynyl group, halogen atom, hydroxyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 alkylsulfinyl group, C1-C6 alkylsulfonyl group, phenyl Also included are C2 to C6 alkynyl groups substituted with two or more substituents selected from the group consisting of a group and a phenoxy group.

  In the present invention, “a halogen atom, a C1 to C6 alkyl group, a C1 to C6 alkoxy group, a nitro group, a cyano group, a hydroxyl group and the same or different 1 to 1 which may be substituted with the same or different 1 to 3 halogen atoms. The aryl group which may be substituted with the same or different 1 to 5 substituents selected from the group consisting of two C1-C6 alkyl groups or an amino group which may be substituted with an acyl group refers to the above-mentioned aryl group. Aryl group substituted with 1 to 5 halogen atoms which are the same or different, C1 to C6 alkyl which may be substituted with 1 to 5 identical or different 1 to 3 halogen atoms which are the same or different An aryl group substituted with 1 to 5 nitro groups, an aryl group substituted with 1 to 5 identical or different C1 to C6 alkoxy groups, and an aryl group substituted with 1 to 5 nitro groups Group, an aryl group substituted with 1 to 5 cyano groups, an aryl group substituted with 1 to 5 hydroxyl groups, a halogen atom, or 1 to 3 halogen atoms which are the same or different. Selected from the group consisting of a good C1 to C6 alkyl group, a C1 to C6 alkoxy group, a nitro group, a cyano group, a hydroxyl group and an amino group which may be substituted with one or two identical or different C1 to C6 alkyl groups or an acyl group An aryl group substituted by two or more kinds of substituents is also included.

  In the present invention, “a halogen atom, a C1 to C6 alkyl group, a C1 to C6 alkoxy group, a nitro group, a cyano group, a hydroxyl group and the same or different 1 to 1 which may be substituted with the same or different 1 to 3 halogen atoms. The aralkyl group which may be substituted with the same or different 1 to 6 substituents selected from the group consisting of two C1 to C6 alkyl groups or an amino group which may be substituted with an acyl group is the above-mentioned aralkyl group. In addition, an aralkyl group substituted with the same or different 1 to 6 halogen atoms, C1 to C6 alkyl optionally substituted with 1 to 6 identical or different 1 to 3 halogen atoms Substituted with 1 to 6 nitro groups, aralkyl groups substituted with 1 to 6 C1 to C6 alkoxy groups, the same or different Substituted with 1 to 6 cyano groups, an aralkyl group substituted with 1 to 6 hydroxyl groups, a halogen atom, the same or different 1 to 3 halogen atoms From the group consisting of C1-C6 alkyl groups, C1-C6 alkoxy groups, nitro groups, cyano groups, hydroxyl groups and amino groups which may be substituted with one or two identical or different C1-C6 alkyl groups or acyl groups. It also includes an aralkyl group substituted with two or more selected substituents. When the aralkyl group has a substituent, the substituent may be substituted on either or both of the aryl ring and the alkyl group constituting the aralkyl group.

R preferably represents a hydrogen atom or an alkyl group of C ₁ -C _6.

X may be substituted at any substitutable position on the benzothiazine ring, and when two or more X are present, they may be the same or different.
X is preferably a hydrogen atom, a halogen atom; a hydroxyl group; a C1-C6 alkoxy group; an acyl group; a carboxyl group; a cyano group; an acyloxy group; a nitro group; a C1-C6 alkylthio group; a halogen atom, a hydroxyl group, and a C1-C6 alkylthio group. A C1 to C6 alkyl group which may be substituted with the same or different 1 to 3 substituents selected from the group consisting of groups; the same or different 1 selected from the group consisting of halogen atoms, hydroxyl groups and C1 to C6 alkylthio groups C2 -C6 alkenyl group which may be substituted with 3 substituents; C2 which may be substituted with 1 to 3 identical or different substituents selected from the group consisting of halogen atoms, hydroxyl groups and C1 -C6 alkylthio groups -C6 alkynyl group; halogen atom, C1-C6 alkyl group optionally substituted by 1 to 3 different halogen atoms The same or different 1 to 6 selected from the group consisting of a C1 to C6 alkoxy group, a nitro group, a cyano group, a hydroxyl group and an amino group which may be substituted with the same or different 1 to 2 C1 to C6 alkyl groups or an acyl group; An aryl group which may be substituted with 6 substituents; or a halogen atom, a C1-C6 alkyl group and a C1-C6 alkoxy group which may be substituted with the same or different 1 to 3 halogen atoms. A heteroaryl group which may be substituted with the same or different 1 to 6 substituents; and an amino group which may be substituted with the same or different 1 to 2 C1 to C6 alkyl groups or acyl groups.

  Y can be substituted at 1 to 6 substitutable positions on the quinoline ring, and when two or more Y are present, they may be the same or different.

  p represents 1 or 2.

In the compound [I] of the present invention, in one embodiment,
(1) R is hydrogen atom or an alkyl group of C ₁ -C _6, even more preferably more, a propyl group, an isobutyl group, or t- butyl group,
(2) (X) m is preferably a group in which X is a hydrogen atom, a halogen atom, a C1-C6 alkyl group which may be substituted with the same or different 1-3 halogen atoms, or a C1-C6 alkoxy group M is 0 to 2, more preferably X is a hydrogen atom or a fluorine atom, m is 0, 1 or 2;
(3) (Y) n is preferably a group in which Y is a hydrogen atom, a halogen atom, a C1-C6 alkyl group which may be substituted with the same or different 1 to 3 halogen atoms, or a C1-C6 alkoxy group N is 0 to 2, more preferably Y is a hydrogen atom or a fluorine atom, n is 0, 1 or 2;
(4) p represents 1 or 2.

  The compound (I) of the present invention can be converted to a salt such as sulfate, hydrochloride, nitrate and phosphate. Those salts are included in the present invention as long as they can be used as agricultural and horticultural fungicides.

  The compound (I) of the present invention and a salt thereof can be solvated, and these solvates are also encompassed in the present invention. Such solvates are preferably hydrates.

  Among the compounds (I) of the present invention, there are also compounds having asymmetric carbon and asymmetric sulfur. In this case, the present invention is a mixture of one kind of optically active substance and several kinds of optically active substances in any proportion. Is also included.

The 1,4-benzothiazine-1,3-dione or -1,1,3-trione can be produced as follows.

  In the above formula, R, X, m, Y, n, and p are as defined above.

Step A is a step for producing the compound [I] of the present invention by converting the functional group of the compound [II].
For the oxidation reaction in this step A, a method known as an oxidation reaction can be used. For example, a halogen atom to a cyano group, a halogen atom to an amino group, a halogen atom to an alkoxy group, a halogen atom to an alkylthio group, a hydroxyl group Group to acyloxy group, amino group to acylamide group, amino group to diazonium salt to halogen atom, amino group to diazonium salt to cyano group, amino group to diazonium salt to hydroxyl group, nitro group to amino group, carboxyl group to Alkoxycarbonyl group, alkoxycarbonyl group to carboxyl group, cyano group to carboxyl group, cyano group to carbamoyl group, carbamoyl group to cyano group, chloroalkyl group or bromoalkyl group to alkoxyalkyl group, chloroalkyl Group or bromoalkyl group to alkylthioalkyl group, alkylthio group to alkylsulfinyl group or alkylsulfonyl group, acyl group to hydroxyalkyl group, hydroxyalkyl group to acyl group or carboxyl group, halogen atom to alkenyl group, halogen atom to alkynyl group, A halogen atom can be an aryl group, a halogen atom can be a heteroaryl group, and the like.
This step can be performed according to, for example, the Chemical Society of Japan, Experimental Chemistry Course Vols. 15 to 26, Organic Synthesis (1976), Maruzen, Tokyo.
Compound [II], which is the starting material of Step A, can be produced in Step B below.

  After completion of each of the above reactions, the target compound of each reaction can be collected from the reaction mixture according to a conventional method. For example, the reaction mixture is appropriately neutralized, and if insoluble matter is present, it is removed by filtration, water and an immiscible organic solvent such as ethyl acetate are added, and after washing with water, the organic layer containing the target compound is removed. After separating and drying over anhydrous magnesium sulfate or the like, the solvent is distilled off.

  If necessary, the obtained target compound can be further purified by a conventional method such as recrystallization, reprecipitation or chromatography.

  Examples of the oxidizing agent used in the reaction include an aqueous hydrogen peroxide solution, m-chloroperbenzoic acid, peracetic acid, perbenzoic acid, magnesium monoperoxyphthalate, and potassium peroxymonosulfate. More preferred is m-chloroperbenzoic acid.

  The oxidant is usually used in an amount of 1 equivalent to 10 equivalents, preferably 1 equivalent to 2 equivalents.

  The solvent used in the reaction is not particularly limited as long as it does not inhibit this reaction. For example, water, formic acid, acetic acid and other protic polar solvents, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene And halogen halogenated hydrocarbons. More preferred is dichloromethane or 1,2-dichloroethane.

  The amount of the oxidizing agent used is usually 1 to 10 mol, and preferably 1 to 3 mol, per 1 mol of compound [II].

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually −20 ° C. to 100 ° C., and preferably −10 ° C. to 30 ° C.

  Although reaction time changes with a raw material compound, a reaction reagent, a solvent, reaction temperature, etc., it is 1 to 24 hours normally, Preferably it is 1 to 8 hours.

  The target compound can be easily isolated from the reaction system containing it by a conventional method. For example, the target compound can be prepared by recrystallization, purification by column chromatography, or the like.

  Benzothiazin-2-one (compound [II]), which is the starting material of Step A, is included in the claims of JP-A No. 2014-221747, but not in the examples. Moreover, it can manufacture according to a well-known method, for example, the method described in Bioorganic & Medicinal Chemistry 8 (2000) 393-404 or IL Farmaco 53 (1998) 752-757.

  In the above formula, R, X, m, Y, and n are as defined above.

Step B is a method for producing a synthetic intermediate [II] by reacting a 1,4-benzothiazin-3-one represented by the general formula [III] with a quinoline derivative represented by the general formula [IV].

In the formula, R represents the above definition, and L ₁ represents a chlorine atom, a bromine atom, an iodine atom, an OSO ₂ CF ₃ group, or B (OH).

In step B, intermediate [II] is produced by reacting compound [III] with compound [IV] in a solvent or non-solvent in the presence of a metal catalyst, in the presence or absence of a base. It is a process.
When a solvent is used in this step, the solvent used is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene; dichloromethane, dichloroethane, chloroform, Halogenated hydrocarbons such as carbon tetrachloride; Ethers such as dioxane, diethyl ether, tetrahydrofuran (THF) and dibutyl ether; Nitriles such as acetonitrile and propionitrile; Dimethylformamide (DMF), Dimethylacetamide (DMA), It may be an aprotic polar solvent such as N-methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO) or a mixed solvent thereof, preferably dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone ( MP), aprotic polar 溶類 dimethyl sulfoxide (DMSO) or the like, more preferably a N- methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO).

  The metal catalyst used in this step is not particularly limited as long as it is used in a normal coupling reaction. For example, the metal catalyst may be a metal salt such as nickel, palladium, copper, or chromium, or a metal complex. Is tetrakistriphenylphosphine palladium or copper iodide.

  The amount of the metal catalyst used in this step is usually 0.001 to 2 mol, preferably 0.1 to 0.5 mol, per 1 mol of compound [III].

  When a base is used in this step, the base to be used is not particularly limited as long as it is used as a base in a normal reaction. For example, alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate Alkali metal hydrogen carbonates such as potassium hydrogen carbonate; alkali metal hydroxides or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, barium hydroxide; sodium methoxide, sodium ethoxide, potassium Alkali metal alkoxides such as t-butoxide; triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, pyridine, 4- (N, N-dimethylamino) pyridine, N, N-dimethylaniline, N, N-diethyl Aniline, 1,5-diazabicyclo 4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) Organic bases, preferably alkali metal carbonates, organic bases, or alkali metal hydroxides, more preferably sodium carbonate, potassium carbonate, pyridine, triethylamine, or sodium hydroxide. .

  The amount of the base to be used is usually 1 to 6 mol, preferably 1.1 to 3 mol, per 1 mol of compound [III].

  The reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, but is usually 50 ° C to 300 ° C, and preferably 80 ° C to 250 ° C.

  While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 15 minutes to 120 hours, preferably 30 minutes to 10 hours.

  The target compound can be easily isolated from the reaction system containing it by a conventional method. For example, the target compound can be prepared by recrystallization, purification by column chromatography, or the like.

（ここで、Ｒ₁，Ｒ₂，Ｒ₃およびＲ₄は水素原子、ハロゲン原子、Ｃ₁〜₃アルキル基、ＸおよびＹは水素原子、フッ素原子、塩素原子、メチル基を表す。）
下式で示される化合物

（ここで、Ｒ₁とＲ₂は水素原子、ハロゲン原子、メチル基、ＸおよびＹは水素原子、ハロゲン原子、メチル基を表す。）
例えば、下式

などが挙げられる。 The 1,4-benzothiazine-1,3-dione or -1,1,3-trione derivative of the present invention can be mixed or used in combination with at least one compound having other bactericidal activity. The mixture thus obtained has a broad activity spectrum.
Examples of fungicides (generic names) that can be mixed or used together with the 1,4-benzothiazine-1,3-dione or -1,1,3-trione derivatives of the present invention are shown below. It is not necessarily limited to this.
That is, as a compound having specific bactericidal activity,
Bactericides that inhibit nucleic acid synthesis include, for example, benalaxyl, benalaxyl M, furalaxyl, metalaxyl, metalaxyl M, oxadixyl oxaxyl (Bupirimate), dimethylirimol, ethirimol, hydroxyisoxazole, hymexazole, octylinone, oxolinic acid as mitotic inhibitor and mitotic cell such as mitotic mitotic cell (Benomyl), carbendazim (car endazim, fuberidazole, thiabendazole, thiophanate, thiophanate methyl, thiophanate methyl, deoxyfencarb, Examples of bactericides that inhibit respiration such as fluopicolide include diflumetrim, tolfenpyrad, tebufenpyrad, fenazaquin, and pyridabe. (Pyridaben), fenpyroximate, pyrimidifene, rotenone benodanil, flutolanil, mepronil, mefenil, iofetram (isoflutam) (Carboxin), oxycarboxin, thifluzamide, benzovindiflupyr, bixafen, flixapiroxad, flumethypyr Isopyrazam, penflufen, pentiopyrad, sedaxane, boscalid, pyraziflumid, azoxystrobin, mostrostrobin enoxastrobin, fluphenoxystrobin, picoxystrobin, pyraoxystrobin, pyraclostrobin, pyramethostrobin, pyramethostrobin, pyramethostrobin, pyramethostrobin lopyricarb, cresoxime-methyl, trifloxystrobin, dimoxystrobin, phenamine strobin, methinostrobin, oxadofnordon, oxamofludon fenamidone, pyribencarb, cyazofamid, amisulfrom, binapacryl, meptyldinocup, zinocapd, dinopap am), amethoctradin, tebufloquin, and the like, and bactericides that inhibit protein synthesis include, for example, andoprim, cyprodinil, mepanipyrim, pymemethystyl (Blasticidin S), kasugamycin, streptomycin, oxytetracycline, mildiomycin, and the like. d), fenpiclonil, fludioxonil, clozolinate, iprodione, procymidone, phosphine that inhibits lipid and cell membrane synthesis, such as f Iprobenfos, pyrazophos, isoprothiolane, biphenyl, chloroneb, quintozene, technazen, tolclofos-metholezol Examples of fungicides that inhibit cell membrane sterol biosynthesis, such as lomezole, iodocarb, propamocarb, and prothiocarb, are trifoline, pyrifenox, pyrisoxazole, fenarimol, nalmol, (Imazalil), oxpoconazole, pefurazoate, prochloraz, triflumizole, azaconazole, zitronol, and benzoterol. cy roconazole), difenoconazole, dinicoazole, epoxiconazole, fluconol, flubuconazole, flubuconazole, flubuconazole, flubuconazole. , Fluconazole, flutriazole, hexacazole, imibenconazole, ipconazole, metconazole le), microbutanil, penconazole, propiconazole, dimeconazole, tebuconazole, tetraconazole, tetraconazole, tetraconazole, tetraconazole, tetraconazole. Ticonazole, prothioconazole, Uniconazole-P, butiobate, diclobutrazol, aldimorph, demolmorph h), fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine, fenhexamid, fenpyrazamine, fenraminine Examples of bactericides that inhibit cell wall biosynthesis include, for example, validamycin, polyoxin, dimethomorph, flumorph, pyrimorph, benthiavalicalb, iprobalb Examples of bactericides that inhibit cell wall melanin synthesis such as alicalb, valifenalate, mandipropamide, etc. include, but are not limited to, fusaride, pyroquilon, tricyclamide, arpromid, carpropidoc, Examples of fungicides for inducing resistance of host plants such as phenoxanil include probenazole, thiadinil, isothianil, laminarin, extract from mint guanentk, Examples of fungicides that inhibit multiple action points such as cibenzolar-S-methyl are copper (copper), DBEDC (complex of bis (ethylenediamine) copper-bis- (dodecylbenzensulfonic acid)) (Copper hydroxide), copper nonylphenol sulfonate, basic copper chloride, basic copper sulfate, organic copper (sulfur), sulfur (lime), sulfur Agent (calcium polysulfide), silver (silver), DD ( , 3-dichloropropene, dazomet, methyl bromide, methylisothiocyanate, carbam (mantamez), manneb (man), manneb (man) propineb, thiuram, zinc sulfate, zineb, ziram, captan, captafol, holpet, dichlorothalofil, chlorothalonil ), Tolylfluanide (tolylflu) nid, guazatine, iminoctadate acetate, iminoctaine albecate-DBS, triazine, dithianon, chinomethionite Other fungicides such as dithane-stainless include, for example, simoxanil, fosetyl, phosphorous acid, phosphite, teclophthalam, triazoxide, triazolsulfide f lusulfamide, diclomezine, metasulfocarb, cyflufenamid, metraphenone, pyriophenone, thiophene, thiophene oxathiapiprolin, tolprocarb, picarbutrazox, WO2005081174, WO201111742, machine oil (petrolium oil), organic oil (potassium hydrogen), potassium hydrogen (potassium hydrogen) carbonate, sodium hydrogen carbonate, sodium hypochlorite, calcium carbonate, benthiazole, diclobutrazole, diclobutrazole Thiadiazin, dichlone, organic tin (organo-tin), shiitake mycelium extract (extract from musthrome), a compound represented by the following formula:

_{(Wherein, R 1, R 2, R} 3 and R ₄ are a hydrogen atom, a halogen atom, C ₁ ~ ₃ alkyl group, X and Y are hydrogen atom, a fluorine atom, a chlorine atom, a methyl group.)
Compound represented by the following formula

(Here, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, and a methyl group, and X and Y represent a hydrogen atom, a halogen atom, and a methyl group.)
For example, the following formula

Etc.

  The present invention relates to agricultural crops such as food crops (rice, barley, wheat, rye, oats and other wheat, potatoes, sweet potatoes, potatoes, potatoes, potatoes, soybeans, red beans, broad beans, peas, and beans. Peas such as peanuts, corn, persimmons, buckwheat, etc., vegetables (cabbage, Chinese cabbage, radish, persimmon, broccoli, cauliflower, pineapples, etc.), pumpkin, cucumber, watermelon, melon, zucchini, Cucurbitaceae crops such as yugao, nigari, eggplants, tomatoes, peppers, eggplants such as shrimp, mushrooms such as shrimp, mushrooms such as ladle, red crustacean crops such as spinach, fusanso, carrot, mitsuba, parsley, celery Aceraceae crops such as udon, Asteraceae crops such as lettuce and burdock, garlic, onion, leek, leek, Japanese leek, etc., asparaga , Shiso, lotus root, etc.), mushrooms (shiitake, mushrooms, etc.), fruit trees (fruits, citrus fruits, apples, pears, peaches, plums, cherry peaches, Yi, apricots, strawberries, persimmons, persimmons, no fruit fruits, Akibi, blueberries, raspberries , Pineapple, mango, kiwi fruit, banana, strawberry, olive, walnut, chestnut, almond, etc.), perfume and other crops (lavender, rosemary, thyme, sage, pepper, ginger, etc.), special crops (cigarette, tea) , Sugar beet, sugar cane, rush, sesame, konjac, hop, cotton, hemp, olive, rubber, coffee, rapeseed, sunflower, mulberry, etc., forage and forage crops (timothy, clover, alfalfa and other legumes, corn Grasses such as sorghum, orchardgrass, etc.), turf (Korean turf, bentgrass, etc.), forest trees (Todomatsu, ezoma) Pine, pine, hiba, cedar, camellia, etc. and ornamental plants (flowers, roses, carnations, lilies, eustoma, perennials), herbs / flowers such as orchids, orchids, ginkgo, sakura, and aoki Etc.).

The target diseases include plant parasitic filamentous fungi, bacteria, and actinomycetes. Specifically, rice blast (Piculararia oryzae), sesame leaf blight (Cochliobolus miyabeanus), and blight (Rhizoctonia) solani), Pantoea ananatis, idiot seedling disease (Gibberella fujikurooi), seedling blight (Pythium graminicolum), brown leaf disease (Acidovorax aveneus abunae leaf disease) Disease (Xanthomonas oryzae pv. Oryzae), bacterial disease (Burkholderia plantarii), etc .; Erysiphe graminis, Red mold disease (Gibberella zeae), Red rust disease (Puccinia striformis, P. graminis, P. recondita, P. hordei), Snow rot (Typhella sp. (Ustilago tritici, U. nuda), Tillettia caries, eye spot disease (Pseudocercosporella herpotrichoides), cloud disease (Rhynchosporum secitalis), leaf blight Disease (Pyrenophora tere s), Helminthosporum zonatum Ikata, black node disease (Pseudomonas syringae pv. japonica), etc .; citrus black spot disease (Diaporethe citri), common septic disease (Elsinoeti) italicum), brown rot (Phytophthora citrophthora, P. nicotianaae), black scab (Phyllostictina citricarpa), etc .; apple Monilia mary, diplocal disease, Dipocari Disease (Podophaera leukotr) cha), spotted leaf disease (Alternaria mali), black spot disease (Venturia inaequalis), black spot disease (Mycospherarumia pomaii), anthracnose (Colletotrichum aeratumum), Glomerella cingulata disease, ring crest disease. , Soot spot disease (Zygophiala jamaicensis), soot spot disease (Gloodes pomigena), etc .; none black spot disease (Venturia nashicola, V. pirina), powdery mildew (Phyllactinia mary), black spot disease (Alternaria kikuchiana), erythematosis (Gimnosporium haraenum), erythema disease (monilia fructigena) Monilinia fracticola, anthrax (Glomerella cingula), larvae of larvae (Monilinia fukuticola), black scab (Cladosporium carposis) Disease (Xanthomonas camp) estris pv. pruni) et al; Grapes black rot (Elsinoe ampelina), late rot (Colletotrichum acutatum), Glomerella cinulata, powdery mildew (Uncinula necator), rust pso , Downy mildew (Plasmopara viticola), black scab (Cladosporium viticolum), root bacilli (Agrobacterium vitis), etc .; oyster anthracnose (Gloeosporium kaki), powdery mildew (Phila leaf disease) Cercospora kaki, My Oshaerella nawae), Kiwi fruit horn spot disease (Phomopsis sp.), Anthracnose (Colletotrichum gloeosporioides), White leaf blight (Rosellinia necatrix leaf spot) eriobotryae), etc .; Colletotrichum lagenarium, powdery mildew (Sphaerotheca furiginea, Oidiopsis taurium), vine blight (Didymella brilliae), operonospora cubensis), late blight (Phytophthora sp. ), Seedling blight (Phythium sp., Rhizoctonia solani), etc .; cucumber spot bacterial disease (Pseudomonas syringae pv. Melon brown spot bacterial disease (Xanthomonas campestris pv. Cucurbitae), hair root disease (Agrobacterium rhizogens), scab (Septopmyces sp.), Etc .; Bacterial disease of vegetables (Ralstonia solanacerum) ) Etc .; Tomato ring-rot (Alternaria solani),
Leaf blight (Cladosporium fulvum), late blight (Phytophthora infestans), Susukabi disease (Pseudocercospora fuligena), powdery mildew (Erysiphe cichoracearum), canker (Clavibacter michiganense subsp. Michiganense), stems pixel disease (Pseudomonas corrugata), soft rot Diseases (Pectobacterium carotovorum subsp. Carotovorum) and the like; eggplant brown rot (Phomopsis vexans), powdery mildew (Erysiphe cichoracerarum), subtilis disease (Mycovellosirus cerevisiae disease) rynespora melongenae), brown circle rot (Paracerocospora genula), brown rot (Phytophthora capsici), half body wilt (Verticillium dapalonia), black spot disease (Peranospora) White spot disease (Cercosporella brassicae) soft rot disease (Pectobacterium carotovorum subsp. Carotovorum), yellowing disease (Verticillium dahaliason sampin smp.) stris pv. campestris), etc .; Bremia lactucae disease, Rhizoctonia schiriti, Pseudomonas viridae disease, Pseudomonas viridae disease, Pseudomonas viridae disease. (Peronospora destructor), black spot disease (Alternaria porri), rust disease (Puccinia alli), white silkworm (Sclerotium rulfsiii), etc .; red purple leaf spot (Cercospora kiruchiol citrum) Glomerella glycines, Gloeosporium sp. ), Downy mildew (Peronospora manshurica), stem rot (Phytophthora sojae), black scab (Elsinoe glycines), black spot (Diaporthephaeorum var. Sojae), spot blight. Xanthomonas campestris pv. Glycines) and others; Colletotrichum lindemthianum, leaf blight (Pseudomonas savastonia pv. Phasolicola) ani), etc .; Cercospora personata, brown spot (Cercospora arachidicola), etc .; Pea powdery mildew (Erysiphe pisii), etc .; Summer epidemic of potato (Alternaria insolia solato) ), Leaf rot fungi (Rhizoctonia solani), soft rot (Pectobacterium carotovorum subsp. Carotovorum), etc .; strawberry powdery mildew (Sphaerothecoleumumuli), anthrax Disease (Phytophthora nicotianae), ring spot disease (Dendrophoma obscurans), bud bacterial disease (Pseudomonas marginalis pv. Marginalis disease, etc.); (Pestarothiosis theae, Pestarothiosis longigeta), net blast (Exobasidium reticulatum), rice blast (Exobasidium vexans), white scab (Elsinoe leucospira eu pym eu peu eu v eu peu eu peu eu v eu d eu peu eu peu eu v eu peu eu peu eu v eu peu pu theae, scab (Xanthomonas campestris pv. theicola), etc .; tobacco red rot (Alternaria longipes), powdery mildew (Erysiphaticobacter's disease) Nicotianae, Blight disease (Ralstonia solaacearum), Cavity disease (Pectobacterium carotovorum subsp. carotovorum) and the like; Cercospora beticola, root rot (Rhiston rot) erys), seedling blight (Aphanomyces cochliodes), etc .; rose black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosain), etc .; Agrobacterium tumefaciens, etc .; Gray mold disease of various crops such as eggplant, cucumber and lettuce; Botrytis cinerotiarum; Sclerotidia scylotiorum; incarnate, Fusarium nivale, Sclerotinia boreali s), powdery mildew (Erysiphe graminis), Faringling disease (Lycoperdon perlatum, Lepista subnudo, Marasmius orades), pseudoleaf rot (Ceratobasidium spp.), dead leaf disease (Ceratobasidium spp.) ), Leaf rot (Rhizoctonia solani), Pysium disease (Pythium periplocum, Pythium vanterpoolii), rust disease (Puccinia spp.), Dall spot disease (Sclerotinia humoa peat); The disease (Colletotrichum sp. ),
Acacia shark skin blight (Botryosphaeria sp.), Anthrax (Glomerella singulata), hydrangea ring rot (Phoma exigua), spot disease (Phylosticta hydrangeaaeol, sarcosis) (Rhizoctonia solani), powdery mildew (Oidium sp.), Anthracnose (Glomerella singulata), ring rot (Cercospora hydrangea), Ginkgo biloba urticum red rickets (Gonatobotryum apiculosis) Red star disease (Gymnosporium yamadae), white crest feather disease (R sellinia necatrix, maple leaf blight (Rhytisma acerinum), ring-leaf blight (Cristulariella moricola), blight (Diaporthe sp.), leaf spot (Cercospora sp. ol p , Red rot (Erythricium salmonicor), powdery mildew (Uncinula sp., Sawadaea sp., Oidium sp.), White spot disease of scabies (Phomatospora albomaculans), powdery mildew (Usula aspirulis ulculans). ), Karakana Taratake disease (Ar) Millialia mellea, rot heart disease (Phaeolus schweinitzii), brown leaf disease of citrus (Septoria chinensis), diapothesis melanoculus (Diaporthe melanisul) okinawaensis), spot disease (Phaeosphaerella gardeniae), brown spot disease of zelkova (Pseudocercospora zelkova), mushroom disease (Armilaria mellea pal) rica), cherry cancer (Nectria galligena), root cancer (Agrobacterium tumefaciens), powdery mildew (Podosphaera longiseta), larvae, wisdom disease (Monilinia kasanoi), Armillaria mellea, blight disease (Valsa ambiens), pomegranate scab (Sphaceroma punicae), leafy mildew (Uncinuliella spruce disease) Herring Blight (Cristulariella m) ricola), Pseudocercospora crataegi, white mushroom white spot disease (Bagcheea albo-maculans), leaf blight (Taphrina kusanoi), anthracnose leaflet (Coletoe morbidity). (Pseudocercospora handelii), white blight (Rosellinia necatrix), shoot blight (Sclerotium sp.). ), Red blight (Cercospora sequoiae), microphage nuclear disease (Macrophopha phaseolina), red leaf blight (Ascochyta sp.), Azalea powdery mildew (Microsphaera izuensis), brown spot disease (S) , White leaf blight (Rosellinia necatrix), seedling blight (Rhizoctonia solani), leaf spot (Pseudocercospora handelii), spot disease (Phylostatica maxima), flower rot fungus nuclei ), Tsubaki root rot (Phytophthora cinnamomi), Anthracnose (Glome) ella cingula, mushroom symptom (Armillariella mellea), rose powdery mildew (Sphaerotheca pannosa, Oidium sp.), downy mildew (Peronospora spasa), spot disease (Cerocosor sero) megasperma), black scab (Marssonina rosae, Diplocarpon rosae), rot (Cryptosporella umbrina), white rot (Rosellinia necatria), cypress mushroom (Armilillo tilapia) s sp.), Erwinia herbicola pv. milletiae, poinsettia root rot (Rythium sp.), bedworm plague (Phytophathora cactorum), powdery mildew (Erysiperot disease) ), Anthracnose (Gloeosporium sp.), Brown spot (Pseudocercospora variicolor), mycorrhizal disease (Sclerotinia sclerotiorum), blight (Botrytis paeoniae), white rot (Resellid) euonymi-japonici), brown spot (Pseudocercospora destr) ctiva), pine of kelp disease (Cronartium quercuum), seedling blight (Rhizoctonia solani, Fusarium sp. , Phythium sp ,,), leaf blight (Pseudocercospora pini-densiflorae), brilliant backspot disease (Coccoidea querricola), citrus powdery mildew (Microsphaera pulcola or ol p Marsonaina brunea, eucalyptus horn spot disease (Cercospora epicoccoides), snow fluffy scab (Pseudocercospora spiraeporia), mildew Withering Nuclear disease (Sclerotinia sclerotiorum), Asagao vine split disease (Fusarium oxysporum f. Sp. Batatas), carnation powdery mildew (Oidium dianthi), gerbera powdery mildew (Sphaerothecium fouling) Sclerotinia sclerotiorum, Fusarium oxysporum, powdery mildew (Erysiphe cichoracerum), Sclerotiria sclerotium (Vertihilus lily) Goldfish grass anthracnose ( Colletotrichum gloeosporioides), powdery mildew (Oidium subgenus Reticuloidium), sclerotinia rot (Sclerotinia sclerotiorum), and cosmos of anthracnose (Colletotrichum acutatum, Gloeosporium sp.), Powdery mildew (Sphaerotheca fusca), sclerotinia rot (Sclerotinia sclerotiorum), and Periwinkle powdery mildew (Oidium sp.), Fusarium moniliforme, mycorrhizal disease (Sclerotinia sclerotiorum), sweet pea powdery mildew (Oidium sp.), Wilt disease (Fusarium sp.) ), Verticillium dahliae, Glomerella singulata, Colletotrichum gleosporioids, Glomerella singulata, powdery mildew (Oidium spider). sp. conglutinans, sclerotia sclerotia, anthracnose (Colletotrichum gleosporioids), Colletotrichum higginsianum, Fusarium avenicum wilt (Vesarium averium) m dahliae, Eustoma anthracnose (Colletotrichum acutatum), stem rot (Fusarium avenaceum), powdery mildew (Oidium sp.), mycorrhizal cerophylceae (Sclerotinia cerophyllum) , Sclerotia sclerotiorum, brown spot disease (Septoria helianthii), half body wilt disease (Verticillium dahllia), petunia powdery mildew (Sphaerothecium stigma incium, Oidro sp.) Half Examples include, but are not limited to, the fungi described here.

  The compounds of the present invention can be used in various dosage forms. In order to obtain these dosage forms, various agricultural chemical adjuvants conventionally used in the technical field of agricultural and horticultural fungicides can be appropriately used. Examples of dosage forms of agricultural and horticultural fungicides include emulsions, wettable powders, granular wettable powders, aqueous solvents, liquids, powders, flowables, dry flowables, fine granules, granules, tablets, oils, Sprays, fumes, etc. Of course, the compound of this invention can also be mix | blended as an active ingredient by combining 1 type (s) or 2 or more types.

  Such agrochemical adjuvants can be used for the purpose of, for example, improving the effects, stabilizing, and improving dispersibility of agricultural and horticultural fungicides. Examples of the agricultural chemical adjuvant include a carrier (diluent), a spreading agent, an emulsifier, a wetting agent, a dispersing agent, a disintegrating agent, and the like. Liquid carriers include water, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methyl Mention may be made of naphthalene, cyclohexane, animal and vegetable oils, fatty acids and the like. As the solid carrier, clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose, starch, gum arabic and the like can be used.

As the emulsifier and the dispersant, a normal surfactant can be used. For example, anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, etc. Cationic surfactants, nonionic surfactants, amphoteric surfactants, and the like can be used. Further, spreading agents; wetting agents such as dialkyl sulfosuccinate; fixing agents such as carboxymethyl cellulose and polyvinyl alcohol; disintegrating agents such as sodium lignin sulfonate and sodium lauryl sulfate can be used.
The content of the compound of the present invention as an active ingredient in an agricultural and horticultural fungicide is, for example, 0.01 to 99.5% by mass, preferably selected from the range of 0.5 to 90% by mass, such as formulation form, application method, etc. It may be appropriately determined according to various conditions. For example, about 0.5 to 20% by weight, preferably 1 to 10% by weight for powders, about 1 to 90% by weight for wettable powders, preferably about 10 to 10% by weight. In the case of an emulsion, it can be produced so as to contain an active ingredient in an amount of about 1 to 90% by weight, preferably 10 to 40% by weight.

  For example, in the case of an emulsion, the compound of the present invention, which is an active ingredient, can be mixed with a solvent and a surfactant to produce a stock emulsion, and this stock solution is diluted with water to a predetermined concentration when used. Can be applied. In the case of a wettable powder, the compound of the present invention as an active ingredient, a solid carrier, and a surfactant are mixed to produce a stock solution, which can be further diluted with water to a predetermined concentration before use. . In the case of powders, the compound of the present invention, which is an active ingredient, and a solid carrier can be mixed and applied as it is. In the case of granules, the compound of the present invention as an active ingredient, a solid carrier, and a surfactant It can be produced by mixing and granulating an agent and applied as it is. However, the manufacturing method of each of the above-mentioned preparation forms is not limited to the above-mentioned ones, and can be appropriately selected by those skilled in the art according to the type of active ingredient, application purpose, and the like.

For agricultural and horticultural fungicides, in addition to the compounds of the present invention which are active ingredients, other active ingredients such as other fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc. May be blended. The application method of the disinfectant comprising the compound of the present invention is not particularly limited, and can be applied by any method such as foliage spraying, soil treatment, in-house smoke, or stalk. For example, in the case of foliage spraying, for example, a solution having a concentration range of 5 to 1000 ppm, preferably 10 to 500 ppm can be used at an application rate of about 50 to 700 liters per 10 ares. In the case of soil treatment, a solution having a concentration range of 5 to 1000 ppm can be used at an application rate of about 0.1 to 1 liter per 1 m ² .

  Hereinafter, the present invention is further described in detail using Examples, Formulation Examples, and Test Examples, but the scope of the present invention is not limited by these Examples, Formulation Examples, and Test Examples.

US6417399の方法を参考に合成した。
イソロイシン（１０．６g、８０．３mmol）を６Nの臭化水素酸８０ mLに溶解し、氷冷下で亜硝酸ナトリウム５．５８ｇを水１６ mLに溶解した水溶液を７℃以下で滴下した。室温で一夜撹拌した後酢酸エチルで３回抽出した。合わせた酢酸エチル層を１０％亜硫酸水素ナトリウム水溶液、水、さらに飽和食塩水で洗浄した。無水硫酸マグネシウムで乾燥後、減圧下で溶媒を留去し無色の液体１０．１g（７０％）を得た。生成物は生成せずに次の反応に用いた。得た２-ブロモ−３−メチルペンタ酸（１１．１g、５５．４mmol）をエタノール６０mLに溶解し、濃硫酸０．７ mLを加えて８時間加熱還流した。放冷後、減圧下で約２０ mLまで濃縮し、氷水を加えた。飽和炭酸水素ナトリウム水溶液、水、さらに飽和食塩水で洗浄した。無水硫酸マグネシウムで乾燥後、減圧下で溶媒を留去し無色の液体１０．０g（８１％）を得た。生成物は生成せずに次の反応に用いた。 <Example 1> 2- (butan-2-yl) -3,4-dihydro-2H-1,4-benzothiazine-1λ ⁴ , 4- (quinolin-3-yl) -2H-1,4-benzothiazine- 1,3-dione (Compound No. A-153) and 2- (butan-2-yl) -3,4-dihydro-2H-1λ ⁶ , 4- (quinolin-3-yl) -2H-1,4 -Synthesis of benzothiazine-1,1,3-trione (Compound No. A-154) <Step 1> Synthesis of ethyl 2-bromo-3-methylpentanoate

The compound was synthesized with reference to the method of US6417399.
Isoleucine (10.6 g, 80.3 mmol) was dissolved in 80 mL of 6N hydrobromic acid, and an aqueous solution in which 5.58 g of sodium nitrite was dissolved in 16 mL of water was added dropwise at 7 ° C. or lower under ice cooling. The mixture was stirred overnight at room temperature and extracted three times with ethyl acetate. The combined ethyl acetate layers were washed with 10% aqueous sodium bisulfite solution, water, and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 10.1 g (70%) of a colorless liquid. The product was not produced and used for the next reaction. The obtained 2-bromo-3-methylpentanoic acid (11.1 g, 55.4 mmol) was dissolved in 60 mL of ethanol, 0.7 mL of concentrated sulfuric acid was added, and the mixture was heated to reflux for 8 hours. After allowing to cool, the mixture was concentrated to about 20 mL under reduced pressure, and ice water was added. The extract was washed with a saturated aqueous sodium hydrogen carbonate solution, water, and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 10.0 g (81%) of a colorless liquid. The product was not produced and used for the next reaction.

Bioorganic & Medic inal Chemistry 8 (2000), p. 393-404の方法を参考に合成した。
アルゴン雰囲気下, ２−アミノベンゼンチオール（２．５０g、２０．０ mmol）、 ２-ブロモ−３−メチルペンタ酸 エチルの合成(４．９１g、２２．０ mmol）および微粉末の炭酸カリウム（３．５９ｇ、２６ mmol）をDMF（２０ mL）中、室温で１時間、１２０℃で６時間撹拌した。反応液を氷水に注ぎ、 酢酸エチルで抽出した。有機層を水、 飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥後、減圧下で溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィー(ヘキサン：酢酸エチル＝９：１から４：１の濃度勾配）により精製し,２．３０ｇの固体（収率５２％）、mp 1０４〜１０５．５℃を得た。
¹H-NMR(CDCl₃)δppm: 8.01(br, 1H) ; 7.33-7.31(m, 2H) ; 7.17-7.14(m, 1H) ; 7.02-6.98(m, 1H), 3.31(d, 0.8H) ; 3.19(d, 0.2H) ; 1.92-1.60(m, 1H) ; 1.57-1.21(m, 2H) ; 1.02 (d, 3H) ; 0.90(t, 2.4H) ; 0.86(t, 0.6H) <Step 2> Synthesis of 2- (butan-2-yl) -3,4-dihydro-2H-1,4-benzothiazin-3-one

Synthesis was performed with reference to the method of Bioorganic & Medic inal Chemistry 8 (2000), p. 393-404.
Synthesis of 2-aminobenzenethiol (2.50 g, 20.0 mmol), ethyl 2-bromo-3-methylpentanoate (4.91 g, 22.0 mmol) and fine powder of potassium carbonate (3. 59 g, 26 mmol) was stirred in DMF (20 mL) for 1 hour at room temperature and 6 hours at 120 ° C. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1 to 4: 1 concentration gradient) to obtain 2.30 g of a solid (yield 52%), mp 104-105.5 ° C.
¹ H-NMR (CDCl ₃ ) δppm: 8.01 (br, 1H); 7.33-7.31 (m, 2H); 7.17-7.14 (m, 1H); 7.02-6.98 (m, 1H), 3.31 (d, 0.8H ); 3.19 (d, 0.2H); 1.92-1.60 (m, 1H); 1.57-1.21 (m, 2H); 1.02 (d, 3H); 0.90 (t, 2.4H); 0.86 (t, 0.6H)

US5998400の方法に従い合成した。
３，４−ジヒドロ−２, ２−ジメチル−２H−１，４−ベンゾチアジン−３−オン（０．５８ｇ）と3−ブロモキノリン（０．９４ｇ、３．００ mmol）をDMSO(３ mL)に溶解し、ヨウ化銅(1) (0.0６g, ０.３ mmol）および微粉末の炭酸カリウム（０．２５ｇ, ３．００ mmol）を加え、１７５℃で７．５時間加熱撹拌した。放冷後, アセトンを加えた後、不溶物をろ別し、減圧下で溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝９：１から３：２の濃度勾配）により精製し, ０．６７ｇの固体（収率７０％）、mp １２３〜１２６℃を得た。
¹H-NMR(CDCl₃)δppm： 8.78(S, 1H) ; 8.20(d, 1H) ; 8.14(S, 1H) ; 7.86-7.80(3H) ; 7.64-7.61(m, 1H) ; 7.42-7.25(m, 2H) ; 6.66(d, 1H), 4.12(d, 1H) ; 1.74-1.26(m, 3H) ; 1.39(d, 0.4H) ; 1.17(d, 1.2H) ; 1.12(d, 1.2H) ; 1.09-0.94(m, 3H) <Step 3> Synthesis of 2- (butan-2-yl) -3,4-dihydro-2H-1,4-benzothiazin-3-one (Compound No. B-79) (Step B)

Synthesized according to the method of US5998400.
3,4-Dihydro-2,2-dimethyl-2H-1,4-benzothiazin-3-one (0.58 g) and 3-bromoquinoline (0.94 g, 3.00 mmol) in DMSO (3 mL). After dissolution, copper iodide (1) (0.06 g, 0.3 mmol) and fine powder of potassium carbonate (0.25 g, 3.00 mmol) were added, and the mixture was heated and stirred at 175 ° C. for 7.5 hours. After allowing to cool, acetone was added, the insoluble material was filtered off, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1 to 3: 2 concentration gradient) to obtain 0.67 g of a solid (yield 70%), mp 123-126 ° C.
¹ H-NMR (CDCl ₃ ) δppm: 8.78 (S, 1H); 8.20 (d, 1H); 8.14 (S, 1H); 7.86-7.80 (3H); 7.64-7.61 (m, 1H); 7.42-7.25 (m, 2H); 6.66 (d, 1H), 4.12 (d, 1H); 1.74-1.26 (m, 3H); 1.39 (d, 0.4H); 1.17 (d, 1.2H); 1.12 (d, 1.2 H); 1.09-0.94 (m, 3H)

２−（ブタン−２−イル）−３，４−ジヒドロ−２H−１，４−ベンゾチアジン−３−オン (０．４０ｇ、１．１５mmol)をジクロロメタン(30 mL)に溶解し、氷冷撹拌下m-CPBA (０．４３ｇ、２．５４ mmol)を加えた。反応液を氷冷下で１時間, さらに室温で４時間撹拌した後, 冷やした１０％チオ硫酸水素ナトリウム水溶液、炭酸水素ナトリウムで２回洗浄し、無水硫酸マグネシウムで乾燥した。減圧下で溶媒を留去した後、残渣をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝４：１から０：１の濃度勾配）により精製し、ジオン体として０．２０g(収率9％) mp８５〜９７℃の アモルファス及びトリオン体として０．０４ｇの固体（収率４８％）mp ７９〜９１℃を得た。
Ａ−１５３：¹H-NMR(CDCl₃)δppm： 8.78(S, 1H), 8.18(d, 1H), 8.14(S, 1H), 7.88-7.78(m, 3H), 7.62(t, 1H), 7.40(t, 1H), 7.30-7.25(m, 1H), 6.66(d, 1H), 4.15-4.11(m, 1H), 2.19-1.71(m, 1H), 1.67-1.26(m, 2H), 1.21(d, 0.5H), 1.12(d, 0.5H), 1.04-0.93(m, 3H)。
Ａ−１５４：¹H-NMR(CDCl₃)δppm：8.77(S, 1H), 8.23(d, 1H), 8.14(S, 1H), 8.06-8.03(m, iH), 7.81-7.89(m, 2H), 7.75(t, 1H), 7.53(t, 1H), 7.47(t, 1H), 4.18(d, 1H), 2.34-2.22(m, 1H), 1.94-1.84(m, 0.5H), 1.78-1.32(d, 1.5H), 1.13(d, 1.5H), 0.99-0.96(m, 3H)。 <Step 4> 2- (Butane-2-yl) -3,4-dihydro-2H-1,4-benzothiazine-1λ ⁴ , 4- (quinolin-3-yl) -2H-1,4-benzothiazine-1 , 3-dione (Compound No. A-153) and 2- (butan-2-yl) -3,4-dihydro-2H-1λ ⁶ , 4- (quinolin-3-yl) -2H-1,4- Synthesis of benzothiazine-1,1,3-trione (Compound No. A-154) (Step A)

2- (butan-2-yl) -3,4-dihydro-2H-1,4-benzothiazin-3-one (0.40 g, 1.15 mmol) was dissolved in dichloromethane (30 mL) and stirred with ice cooling. m-CPBA (0.43 g, 2.54 mmol) was added. The reaction mixture was stirred for 1 hour under ice-cooling and further for 4 hours at room temperature, then washed twice with a cooled 10% aqueous sodium thiosulfate solution and sodium bicarbonate, and dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1 to 0: 1 concentration gradient) to give 0.20 g (yield 9%) as a dione mp85 0.04 g of a solid (yield 48%) mp 79-91 ° C. was obtained as an amorphous and trion body at ˜97 ° C.
A-153: ¹ H-NMR (CDCl ₃ ) δ ppm: 8.78 (S, 1H), 8.18 (d, 1H), 8.14 (S, 1H), 7.88-7.78 (m, 3H), 7.62 (t, 1H) , 7.40 (t, 1H), 7.30-7.25 (m, 1H), 6.66 (d, 1H), 4.15-4.11 (m, 1H), 2.19-1.71 (m, 1H), 1.67-1.26 (m, 2H) , 1.21 (d, 0.5H), 1.12 (d, 0.5H), 1.04-0.93 (m, 3H).
A-154: ¹ H-NMR (CDCl ₃ ) δ ppm: 8.77 (S, 1H), 8.23 (d, 1H), 8.14 (S, 1H), 8.06-8.03 (m, iH), 7.81-7.89 (m, 2H), 7.75 (t, 1H), 7.53 (t, 1H), 7.47 (t, 1H), 4.18 (d, 1H), 2.34-2.22 (m, 1H), 1.94-1.84 (m, 0.5H), 1.78-1.32 (d, 1.5H), 1.13 (d, 1.5H), 0.99-0.96 (m, 3H).

  Representative compounds of the present invention are exemplified in Table 1 below, but the present invention is not limited to these compounds.

  In the formulas shown in Table 1 and below, No. represents compound No., “Me” represents a methyl group, “Et” represents an ethyl group, “Pr” represents a propyl group, and “i-Pr” represents isopropyl. “Bu” is a butyl group, “i-Bu” is an isobutyl group, “s-Bu” is a sbutyl group, “t-Bu” is a t-butyl group, and “Pen” is a pentyl group. And “Hex” represents a hexyl group.

  In Table 1, the numerical values shown as physical properties are melting points (° C.). These compounds can be synthesized based on the production method of the synthesis example.

表１

Formula [I]

Table 1

表２

Formula [II]

Table 2

¹ H-NMR (400 MHz, CDCl ₃ ) δ was measured for the compounds indicated as oil or amorphous in the physical property column. The measurement results are shown below.

A-26: ¹ H-NMR (CDCl ₃ ) δ ppm: 8.76 (s, 1H), 8.17 (d, 1H), 8.09 (s, 1H), 7.95-7.85 (m, 1H), 7.64 (s, 1H) , 7.46-7.35 (m, 1H), 6.61 (d, 1H), 4.08-4.17 (m, 1H), 2.35-2.25 (m, 1H), 2.16-2.02 (m, 1H), 1.36 (t, 3H) .
A-102: ¹ H-NMR (CDCl ₃ ) δppm: 8.82 (s, 0.5H, 8.77 (s, 0.5H), 8.12-8.16 (m, 2H), 7.86-7.81 (m, 2H), 6.72-6.66 (m, 1H), 7.50 (t, 1H), 7.35 (t, 1H), 6.72-6.62 (m, 1H), 4.32-4.28 (m, 0.5H), 3.93-3.82 (m, 0.5H)), 2.96-2.75 (m, 0.5H), 1.67-1.42 (m, 1H), 1.10-0.97 (m, 6H).
A-157: ¹ H-NMR (CDCl ₃ ) δppm: 8.82 (S, 1H), 9.19 (S, 1H), 7.83-7.80 (1H, d), 7.90-7.04 m, (6H), 6.66 (d, 1H), 4.18-4.10 (m, 1H), 2.05-1.89 (m, 0.5H), 1.21 (d, 1.5H), 1.23 (d, 1.5H), 1.08-0.82 (m, 3H).
A-171: ¹ H-NMR (CDCl ₃ ) δ ppm: 8.83 (S, 0.2H), 8,76 (S, 0.8H), 8.22-8.13 (m, 2H), 8.88-7.81 (m, 2H), 7.44-7.36 (m, 1H), 7.10-6.94 (m, 1H), 6.49-6.40 (m, 1H), 3.91-3.83 (m, 1H), 2.79-2.67 (m, 0.9H), 2.10-1.87 ( m, 0.1H), 1.87-0.84 (m, 8H).
A-179: ¹ H-NMR (CDCl ₃ ) δ ppm: 8.79 (S, 0.25H), 8.75 (S, 0.75), 8.26-8.12 (m, 2H), 8.09-8.80 (m, 3H), 7.75-7.57 (m, 1H), 7.37-7.11 (m, 1H), 6.66 (d, 1H), 4.12 (S, 1H), 1.26 (S, 1.85H), 1.21 (S, 7.15H).
A-180: ¹ H-NMR (CDCl ₃ ) δ ppm: 8.80 (S, 1H), 8.23-8.17 (m, 2H), 7.90-7.74 (m, 3H), 7.67-7.60 (m, 1H), 7.42- 7.35 (m, 1H), 7.32-7.21 (m, 1H), 6.62 (S, 1H), 4.10 (S, 1H), 1.10 (S, 9H).
A-183: ¹ H-NMR (CDCl ₃ ) δ ppm: 8.80 (S, 1H), 8.15 (S, 1H), 7.92 (d, 1H), 7.61-7.27 (m, 5H), 6.63 (d, 1H) , 4.10 (S, 1H), 1.17 (S, 9H).
A-231: ¹ H-NMR (CDCl ₃ ) δ ppm: 8.78 (S, 1H), 8.21 (d, 1H), 8.19-8.14 (m, 1H), 7.83-7.79 (m, 3H), 7.68 (t, 1H)), 7.40 (t, 1H), 6.67 (m, 1H), 4.16-4.10 (m, 1H), 1.93-1.75 (m, 1H), 1.61-1.40 (m, 4H), 1.24 (d, 0.39 H), 1.22 (d, 0.35H), 1.23 (d, 0.26H), 0.88-0.82 (m, 3H).
A-283: ¹ H-NMR (CDCl ₃ ) δppm: 8.82 (S, 0.5H), 8.78 (S, 0.5H), 8.22-8.16 (m, 3H), 7.86-7.80 (m, 3H), 7.42- 7.38 (m, 1H), 7.32-7.25 (m, 1H), 6.69-6.64 (m, 1H), 4.28-4.24 (m, 0.5H), 8.82-3.80 (m, 0.5H), 2.42-2.35 (m , 0.5H), 2.25-2.15 (m, 0.5H), 2.05-1.77 (m, 1H), 1.75-1.57 (m, 4H), 1.44-1.35 (m, 4H), 0.92-0.87 (m, 1H) .
A-284: ¹ H-NMR (CDCl ₃ ) δppm: 8.75 (S, 1H), 8.19 (d, 1H), 8.11 (S, 1H), 7.84-7.67 (m, 2H), 7.64 (t, 1H) , 7.40 (t, 1H), 7.32 (t, 1H), 6.70 (d, 1H), 4.35-4.05 (m, 1H), 2.29-2.18 (m, 1H), 2.17-1.98 (m, 1H), 1.86 (t, 3H).
B-14: ¹ H-NMR (CDCl ₃ ) δppm: 8.70 (s, 1H), 8.17 (d, 1H), 8.08 (s, 1H), 8.78-7.73 (m, 2H), 7.60 (t, 1H) , 7.46 (t, 1H), 7.06-7.01 (2H, m), 6.50-6.47 (m, 1H), 3.56-3.53 (m, 1H), 2.13-2.08 (m, 2H), 1.80-1.69 (m, 2H), 1.15 (t, 3H). .
B-66: ¹ H-NMR (CDCl ₃ ) δppm: 8.70 (s, 1H), 8.21 (d, 1H), 8.14 (s, 1H), 7.84-7.73 (m, 2H), 7.60 (t, 1H) , 7.46-7.41 (m, 1H), 7.07-7.03 (m, 2H), 6.65-6.45 (m, 1H, 3.70-3.66 (m, 1H), 1.98-1.84 (m, 2H), 1.64-1.59 (m , 2H), 0.98 (t, 3H).
B-68: ¹ H-NMR (CDCl ₃ ) δppm: 8.74 (s, 1H), 8.10 (, 1H), 7.62-7.45 (m, 3H), 7.0607.04 (m, 2H), 6.48-6.46 (m , 1H), 3.45 (d, 0.5H), 3.38 (d, 0.5H), 2.49-1.63 (m, 2H), 1.54-1.33 (m, 1H), 1.17 (d, 1.5H), 1.10 (d, 1.5H), 1.05-0.98 (m, 1.5H), 0.92-0.84 (m, 1.5H).
B-88: ¹ H-NMR (CDCl ₃ ) δppm: 8.69 (s, 1H), 8.17 (d, 1H), 8.07 (s, 1H), 7.86-7.80 (m, 2H), 7.66-7.56 (m, 1H), 6.97-6.86 (m, 1H), 6.80-6.63 (m, 1H), 3.48 (d, 0.5H), 3.42 (d, 0.5H), 1.95-1.71 (m, 1H), 1.59-1.31 ( m, 1H), 1.17 (d, 1.5H), 1.12 (d, 1.5H), 1.05-0.97 (m, 1.5H), 0.93-0.85 (m, 1.5H).
B-118: ¹ H-NMR (CDCl ₃ ) δppm: 8.93 (s, 1H), 8.80 (d, 1H), 8.04 (s, 1H), 7.82-7.72 (m, 2H), 7.60-7.52 (m, 1H), 4.47-4.40 (m, 1H), 7.07-7.00 (m, 2H), 6.46-6.51 (m, 1H), 3.41 (d, 0.5H), 3.36 (d, 0.5H), 2.05-1.74 ( m, 1H), 1.59-1.26 (m, 4H), 1.17 (d, 1.5H), 1.17 (d, 1.5H), 0.87 (t, 1.5H), 0.87 (t, 0.5H).
B-144: ¹ H-NMR (CDCl ₃ ) δppm: 8.70 (s, 1H), 8.17 (d, 1H), 8.13 (s, 1H), 7.84-7.72 (m, 2H), 7.76-7.54 (m, 1H), 7.46-7.43 (m, 1H), 7.26-7.02 (m, 2H), 6.50-6.47 (m, 1H), 3.61-3.59 (m, 1H), 1.74-1.58 (m, 2H), 1.53- 1.46 (m, 1H), 1.44-1.24 (m, 4H), 0.88 (t, 3H).

  Next, formulation examples are shown. In addition, a part represents a mass part.

Formulation Example 1 Emulsion Compound of the present invention (10 parts), xylene (60 parts), N-methyl-2-pyrrolidone (20 parts) and Solpol 3005X (mixture of nonionic surfactant and anionic surfactant, Toho Chemical Industry Co., Ltd. (trade name) (10 parts) was uniformly mixed and dissolved to obtain an emulsion.

Formulation Example 2 Wetting Agent-1
Compound of the present invention (20 parts), Nipsil NS-K (white carbon, Tosoh Silica Co., Ltd., trade name) (20 parts), Kaolin clay (Kaolinite, Takehara Chemical Co., Ltd., trade name) (50 parts) Sun extract P-252 (sodium lignin sulfonate, Nippon Paper Chemical Co., Ltd., trade name) (5 parts) and Lunox P-65L (alkyl allyl sulfonate, Toho Chemical Co., Ltd., trade name) (5 parts) Was uniformly mixed and ground with an air mill to obtain a wettable powder.

Formulation Example 3 Wetting Agent-2
Compound of the present invention (20 parts), nip seal NS-K (20 parts), kaolin clay (50 parts), LUNOX 1000C (naphthalene sulfonate condensate, Toho Chemical Co., Ltd., trade name) (5 parts) and Solpol 5276 (nonionic surfactant, Toho Chemical Co., Ltd., trade name) (5 parts) was uniformly mixed and pulverized with an air mill to obtain a wettable powder.

Formulation Example 4 Flowable Agent-1
Premixed propylene glycol (5 parts), Solpol 7933 (anionic surfactant, Toho Chemical Co., Ltd., trade name) (5 parts), compound of the present invention (20 parts) in water (50 parts) Was dispersed into a slurry mixture, and then this slurry mixture was wet pulverized with Dynomill (Shinmaru Enterprises Co., Ltd.), and then xanthan gum (0.2 parts) was mixed and dispersed in water (19.8 parts) in advance. Was added to obtain a flowable agent.

Formulation Example 5 Flowable Agent-2
Compound of the present invention (20 parts), Newkalgen FS-26 (mixture of dioctyl sulfosuccinate and polyoxyethylene tristyryl phenyl ether, Takemoto Yushi Co., Ltd., trade name) (5 parts), propylene glycol (8 parts), Water (50 parts) was mixed in advance, and this slurry-like mixture was wet-pulverized with a Dynomill (Shinmaru Enterprises). Next, xanthan gum (0.2 parts) was thoroughly mixed and dispersed in water (16.8 parts) to prepare a gel-like material, which was thoroughly mixed with the pulverized slurry to obtain a flowable agent.

Next, it is shown by test examples that the compound of the present invention is useful as an active ingredient of a fungicide. The compounds of the present invention are indicated by the compound numbers shown in Table 1, and the compounds used for comparison are indicated by the following compound symbols.

Test Example 1: Test for cucumber gray mold disease The cotyledon part was cut out while leaving about 2 cm of the hypocotyl of a cucumber seedling (variety: Sagami Hanjiro node) 8 days after sowing. A paper towel sufficiently moistened with water was laid on the bottom of a 32 cm × 24 cm × 4.5 cm (vertical × width × height) plastic case, and a net was placed on the paper towel. On this net, the cut cotyledons were arranged so as to adhere to the lead paper wetted with the ash shaft cut surface. 50 μl of a spore suspension (spore concentration: 1.0 × 10 ⁶ / ml) was dropped into the center of the cotyledon, and a paper disk having a diameter of 8 mm was placed. 50 μl of the chemical solution prepared to the predetermined concentration by the method described above was dropped from the top of the paper disk. The plastic case was covered and sealed with vinyl tape, and then kept at room temperature of 20 ° C. for 72 hours. Thereafter, the severity of the disease was investigated according to the following criteria, and the control value was calculated based on the following formula.
Disease severity 0 (no disease), disease severity 6.25 (slight intrusion traces are observed), disease severity 12.5 (paper disc diameter about 5-8 mm lesion extension), disease severity 25 (around paper disc) Lesion spread up to about 2 mm), disease severity 50 (sickness extension around 5 mm to less than 10 mm around the paper disk), disease severity 100 (sickness extension around 10 mm or more around the paper disk)
Control value (%) = [1- (treatment group disease severity / no treatment group disease severity)] × 100
Compound Nos. A-25, A-26, A-51, A-52, A-75, A-76, A-101, A-102, A-127, A-128, A-153, A-154, The compounds of A-157, A-158, A-171, A-179, A-180, A-183, A-197, and A-231 exhibited a control value of 90% or more at a treatment concentration of 100 ppm. Comparative compound B remained at a control value of 63% at the same concentration.

Test Example 2: Preventive effect against cucumber gray mold disease A chemical solution of a predetermined concentration was sprayed onto the leaf surface and the leaf back of a cucumber cotyledon seedling (variety: Sagami Hanjiro kana) using a spray gun at a rate of 2 ml / pot. The day after the spraying, the spore suspension (1.0 × 10 ⁶ spores / ml) at a predetermined concentration was spray-inoculated on the back of the leaves. After inoculation, the temperature was maintained at 20 ° C. and humidity of 100%, and after 2 days, the disease severity was investigated based on the following lesion area ratio. Based on the following formula, the control value was calculated from the severity of the untreated group and the severity of the treated group.
Disease severity 0 (sickness area rate: 0%), disease severity 6.25 (sickness area rate: 0 to less than 6.3%), disease severity 12.5 (sickness area rate: 6.3-12. Less than 5%), disease severity 25 (sickness area rate: less than 12.5-25%), disease severity 50 (sickness area rate: less than 25-50%), disease severity 100 (sickness area rate: 50%) that's all)
Control value (%) = [1- (treatment group disease severity / no treatment group disease severity)] × 100

上記表３に示した通り、本発明化合物のA−１５３は化合物Ａに比べ高い予防効果を示した。 Table 3

As shown in Table 3 above, A-153 of the compound of the present invention showed a higher preventive effect than Compound A.

Claims (2)

The following formula [I]

(Wherein, R represents a hydrogen atom or an alkyl group of C ₁ -C _6, X is a hydrogen atom, a halogen atom, a cyano group, an alkyl group of C ₁ -C _4, an alkenyl group of C ₂ -C _6, C ₂ -C ₆ alkynyl group, C ₁ -C alkoxy group _6, C ₁ -C ₆ alkylthio, alkylsulfinyl groups of C ₁ -C _6, an alkylsulfonyl group having C ₁ -C _6, an aryl group, heteroaryl group, an amino group, an acyl group or a carboxyl group, Y is a hydrogen atom, a halogen atom, an alkyl group or a C ₁ -C ₄ alkoxy group C ₁ -C _4, m is from 0 to 4 1, 4-benzothiazine-1,3-dione or -1,1,3-trione derivative represented by the following formula: n represents an integer, n represents an integer of 0 to 6, and p represents 1 or 2.   A bactericide comprising the 1,4-benzothiazine-1,3-dione or -1,1,3-trione derivative according to claim 1 as an active ingredient.