JP2000119263A - New 1,3-thiazine derivative, 1,3-selenazine derivative, use thereof and methd of use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject new compound capable of being obtained under a mild condition in high yield by using a raw material easily available as an industrial raw material, and useful as an insecticidal agent or a microbicidal agent for agriculture or horticulture, or antimicrobial agent for medical care. SOLUTION: This new compound is a 1,3-thiazine derivative or a 1,3- selenazine derivative of formula I (X is S or Se; R is H, an alkyl, an alkenyl, an alkynyl, an aryl, a substituted phenyl, an alkoxy, an acyl or the like; R1 is H, hydroxy, an alkoxy, an alkenyloxy or the like; and R2 to R6 are each H, an alkyl, an alkenyl an alkynyl, an aryl or the like), e.g. 4-hydroxy-4- methyl-2-(4-methylphenyl)-4H-5,6-dihydro-1,3-selenazine. The compound of formula I is obtained by reacting a thioamide or a selenoamide of formula II (e.g. 4- methylselenobenzamide) with an α,β-unsaturated ketones (e.g. methyl ethyl ketone) in the presence of a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound, 1,
The present invention relates to a 3-thiazine derivative or a 1,3-selenazine derivative, a method for producing the same, and their use as an agricultural / horticultural insecticide, an agricultural / horticultural fungicide, or a medical antibacterial agent.

[0002]

2. Description of the Related Art Conventionally, 1,3-thiazine derivatives or 1,1-thiazine derivatives
Although several methods are known as a method for producing a 3-selenazine derivative, a method for industrially easily producing the compound in a high yield has not been known. For example, the following method may be mentioned as a method for producing a 1,3-thiazine derivative. (1) 1,3 using enamine in the presence of perchloric acid
-Methods for obtaining thiazinium salts: Monats Hefts Fear Chemie (Monatsh. Chem., 1987, page 1383),
(2) Method for obtaining 1,3-thiazin-4 (3H) -one from N-phenylthiourea and ethyl propionate (Kh
im. Geterotsikl. Soedin., 1984, page 997). In addition, as a method for producing a 1,3-selenazine derivative, the following method is exemplified. (1) 4-oxide-6-oxo-1,4 from carbonyl chloride phenyl ketone and S-alkyl-N-phenylthiocarbamate
Method for Obtaining 3-Selenadinium Mesomeric Betaine:
Journal of Organic Chemistry (J.O.
rg. Chem., 1977, page 1644) (2) 2-cyano-
Method for obtaining 2,3-dihydro-1,3-selenazin-4-one from 3-hydroseleno-3- (methylthio) acrylamide and acryloyl chloride: Journal of the Chemical Society of Japan (Bull. Che
m. Soc. Jpn., 1986, page 2909).

[0003] However, in any of these methods, starting materials are very complicated compounds which are difficult to obtain or prepare easily, and are not industrially preferable methods.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a novel compound, a 1,3-thiazine derivative or a 1,3-selenazine derivative, a process for producing them, and an insecticide for agricultural and horticultural use containing the compounds. And a fungicide for agricultural and horticultural use or an antibacterial agent for medical use.

[0005]

Means for Solving the Problems The present inventors have made 1,3-
A method for producing a thiazine derivative or a 1,3-selenazine derivative in an industrially advantageous manner to find an industrially advantageous method, using raw materials that can be easily obtained as industrial raw materials, and producing them under mild conditions and in a high yield. Embarked on. As a result, a 1,3-thiazine derivative or a 1,3-selenazine derivative represented by the general formula (I) of the present invention is a novel compound not described in any literature, and a novel production method and an agricultural and horticultural insecticide. The present invention has been found to be useful as an agricultural or horticultural fungicide or a medical antibacterial agent, and has completed the present invention.

The present invention provides a compound of the general formula (I):

Embedded image (In the formula, X represents a sulfur atom or a selenium atom, and R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an alkoxy group, an acyl group, an alkylthio group, an arylthio group or an alkoxycarbonyl group. the stands, R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group,
Represents an alkenyloxy group, an alkynyloxy group, an aryloxy group, an acyloxy group or an alkoxycarbonyloxy group. R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an arylalkenyl group, an alkoxy group, an acyl group. group, an alkylthio group, an arylthio group, a substituent selected from an alkoxycarbonyl group or a hydroxyl group, can also indicate binding R ₂ and R ₃ or R ₄ and R ₅ together, R ₂
And R ₅ together represent an alkylene group having 1 to 5 carbon atoms, which may be the same or different, and may have one or more alkyl groups. 1,3) -thiazine derivative or 1,3-selenazine derivative represented by the formula (1), an agricultural and horticultural insecticide, an agricultural and horticultural fungicide or a medical antibacterial agent containing the compound as an active ingredient, and methods for using them It is.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The substituents used in the structural notation of the present invention will be described below. In the following description, n- means normal, i- means iso, sec- means secondary, and t- means tertiary. General formula of the present invention
In the definition of each substituent of the 1,3-thiazine derivative or 1,3-selenazine derivative represented by (I), "halogen atom"
Represents a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, and the `` alkyl '' portion or the `` alkyl group '' in the structure represents a linear or branched alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s
-Butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, represents an alkyl group such as n-decyl group,

[0008] The term "alkenyl group" means a linear or branched alkenyl group having 2 or more carbon atoms and having one or more double bonds, such as ethenyl, 1-propenyl and 2-alkenyl. Propenyl group, 2-butenyl group, 3-methyl-
Examples thereof include a 1-butenyl group and a 4,4-dimethylpentenyl group, and the “alkynyl group” refers to a linear or branched alkynyl group having 2 or more carbon atoms and having 1 or more triple bonds. Represents, for example, an ethynyl group, a 1-propynyl group, 2
-Propynyl group, 2-butynyl group, 3-methyl-1-butynyl group, 4,4-dimethylpentynyl group and the like, and the "aryl group" is, for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group The "substituted phenyl group" means that the hydrogen atom on the benzene ring is a substituent selected from an alkyl group, an alkynyl group, an aryl group, an alkoxy group, an acyl group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or a hydroxyl group. A phenyl group substituted with a group; these substituents may be substituted by two or more, and when substituted by two or more, they may be the same or different; Further, the substituent having 3 or more carbon atoms may be linear or branched.

The "arylalkenyl group" refers to a linear or branched alkenyl group having 2 or more carbon atoms and having at least one double bond having a phenyl group, a naphthyl group, a phenanthryl group, an anthranyl group and the like. Is shown.

An "alkoxy group" is defined as having 1 to 8 carbon atoms.
Represents a linear or branched alkoxy group of, for example, methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group, s-butyloxy group, n-octyloxy group and the like And

An "alkylthio group" refers to a group having 1 to 1 carbon atoms.
8 represents a linear or branched alkylthio group, for example, methylthio, ethylthio, isopropylthio, n
-Butylthio group, i-butylthio group, s-butylthio group, n-hexylthio group, n-octylthio group and the like. The "arylthio group" indicates, for example, a phenylthio group, a naphthylthio group, an anthrylthio group and the like.

The term "acyl group" refers to a carbonyl group having a linear or branched alkyl group having 1 to 8 carbon atoms, such as a formyl group, an acetyl group, a propionyl group, a hexanoyl group, a heptanoyl group. , 2-methylpropanoyl group, 2,3-dimethylpropanoyl group and the like, and the “alkoxycarbonyl group” is a group having 1 carbon atom.
And represents a carbonyl group having a straight-chain or branched alkoxy group of, for example, methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, s-butoxycarbonyl group, n-hexyl Examples thereof include an oxycarbonyl group and an n-octyloxycarbonyl group.

The process for producing a 1,3-thiazine derivative or a 1,3-selenazine derivative represented by the general formula (I) according to the present invention comprises the steps of preparing a thioamide or a selenoamide represented by the general formula (II) with α, β- It can be produced by reacting unsaturated ketones in the presence of a catalyst, in the presence or absence of an inert solvent. As α, β-unsaturated ketones,
When a cyclic compound, for example, 2-cyclohexen-1-one is used, a 1,3-thiazine derivative or a 1,3-selenazine derivative represented by the above general formula (I-1) can be produced. Further, after the 1,3-thiazine derivative or 1,3-selenazine derivative represented by the general formula (I) in which R ₁ is a hydroxyl group is formed, the hydroxyl group is alkylated and acylated (esterified) according to a conventional method. And the like, a derivative of the compound can be produced. At that time, various catalysts, inert solvents and the like can be used.

Further, although it varies depending on the starting compound to be reacted and the reaction conditions, after forming a 1,3-thiazine derivative or a 1,3-selenazine derivative represented by the general formula (I) wherein R ₁ is a hydroxyl group, The elimination reaction of a hydroxyl group and a hydrogen atom is allowed to proceed without isolating the resulting compound, and the compound represented by the general formula (I-2)
1,3-thiazine derivative or 1,3-selenazine derivative represented by the following formula: The 1,3-thiazine derivative or 1,3-selenazine derivative has a double bond at a portion adjacent to the ring nitrogen atom. Further, after isolating a 1,3-thiazine derivative or a 1,3-selenazine derivative in which R ₁ is a hydroxyl group represented by the general formula (I), the hydroxyl group portion of the compound is modified (for example, a methanesulfonyloxy group, a paratoluene group). After conversion to a leaving group by performing a sulfonyloxy group, a trifluoromethanesulfonyloxy group, or the like, or by halogenation, a catalyst (for example, a base catalyst such as triethylamine, pyridine, etc., bistetra-n-butylammonium oxalate, etc.) The elimination reaction is carried out in the presence or absence of an acid quaternary amine salt catalyst or a catalyst (eg, sulfuric acid, potassium hydroxide, phosphorus pentoxide, etc.) without modifying or converting the hydroxyl group. A dehydration reaction under heating conditions in the presence or absence of a catalyst or a dehydrating agent) to give a 1,3-thiazine derivative represented by the general formula (I-2) or a 1,3-thiazine derivative
A 3-selenazine derivative can be obtained. Here, it is a well-known reaction to those skilled in the art that a substitution reaction can be performed instead of the dehydration reaction. That is, for example, when the reaction is performed in an alcohol, R ₁ can be an alkyl derived from the alkyl portion of the alcohol. Further, a compound obtained by modifying or converting the above hydroxyl group (R ₁ = hydroxyl group) to a leaving group (eg, halogen, methanesulfonate, paratoluenesulfonate, etc.) can be reacted with various nucleophiles to lead to various derivatives. .

The thioamide or selenoamide used as a raw material in the production of the present invention is represented by the following general formula (II):

Embedded image (Wherein, R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an alkoxy group, an acyl group, an alkylthio group, an arylthio group or an alkoxycarbonyl group) or Selenoamide.

Some of the thioamides or selenoamides represented by the general formula (II), which are the starting materials of the present invention, are commercially available, or for example, a method for producing thioamides reviewed (Journal of the French Chemical Society: Bull. Soc. Chim. France, 1949
Year, p. 272), a method for producing selenoamide (Synthesis: Synthesis, pp. 668-669, 1978, Journal of Organic Chemistry: J. Org. Chem., 50, 384).
-386 page, 1985, Synthetic Communications: Syn. Commun., 24, 1761-1765, 1994). Selenoamide is produced by the reaction of selenium hydride with nitrile by the method of Berichte der Deutschen Hemischen Gezershaft (Ber. 7 , 1273, (1874), ibid. 37 , 551, (19
2004)), Chemical Abstracts 47, 3, 344 (1953) and the like, and can be produced according to the methods described therein.

The α, β-unsaturated ketone used as a raw material in the production of the present invention is a compound having an unsaturated bond between α-position and β-position with respect to the carbonyl group of the ketone,
Either the compound on both sides of the ketone or the compound on only one side can be used. The unsaturated bond may be a double bond or a triple bond. The α, β-unsaturated ketones may be the same or different as a substituent, and may be an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an arylalkenyl group, an alkoxy group, an acyl group, an alkylthio group. It may have a group, an arylthio group, an alkoxycarbonyl group or a hydroxyl group. Some of the α, β-unsaturated ketones used in the present invention are commercially available or may be produced according to a known method by aldol condensation of ketone and aldehyde, ketone and ketone, or the like. Can be.
(For example, Large Organic Chemistry (Asakura Shoten), Aliphatic Compound II,
Method using aluminum chloride shown on pages 82 to 83 (Chem. Zentr .; 1910, I, page 1335) (“Anhydrous
Aluminum Chloride in Organic Chemistry ”, p.752, 19
41 years).

As the catalyst for this reaction, any catalyst generally used in organic synthetic chemistry can be used without any problem. Therefore, although not particularly limited, for example, metal fluorides, metal chlorides, metal halides such as metal bromides, metal ions, alkylated metals such as alkylated aluminum, alkoxylated metals such as trialkoxyboron , A Lewis acid catalyst containing a metal hydride such as borohydride, a metal catalyst, a base catalyst, an enzyme, and the like.

As the inert solvent, any reaction solvent generally used in organic synthetic chemistry can be used without any problem.
Therefore, although not particularly limited, for example, alcohols (eg, methanol, ethanol, isopropyl alcohol, butanol, etc.), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride, etc.), ether-based Hydrocarbons (eg, diethyl ether, dimethyl ether, tetrahydrofuran, etc.),
Alkanes (e.g., hexane, cyclohexane, isooctane, etc.), esters (e.g., ethyl acetate, methyl propionate, etc.), polar solvents (e.g., dimethyl sulfoxide, dimethylformamide, etc.) and the like can be exemplified. Alcohols, halogenated hydrocarbons and alkanes are preferred. These inert solvents may be used alone or in combination of two or more.

The 1,3-thiazine derivative or 1,1 of the present invention
In the production method of the 3-selenazine derivative, the raw materials used, thioamide or selenoamide and the α, β-unsaturated ketone, may be equimolar to each other or one of them may be used in excess. It is in the range of equivalents, and preferably one of the equimolar to the larger one is in the range of about 2 equivalents. The reaction temperature can be generally in the range of -78 ° C to 200 ° C, preferably in the range of -78 ° C to room temperature.
The reaction time varies depending on the catalyst and the reaction conditions.
The time may be in the range of 4 hours, and preferably about 30 minutes to 3 hours. In the production of the 1,3-thiazine derivative or 1,3-selenazine derivative of the present invention, enantiomers (R-form, S-form) having different stereopositions of substituents with respect to the asymmetric carbon on the ring and Although diastereomers and the like can be produced by a combination of configurations at two or more different asymmetric carbon atoms on the ring, the present invention includes a mixture containing various isomers in any ratio.

The object of the agricultural and horticultural insecticide, the agricultural and horticultural fungicide and the medical antibacterial agent in the present invention is not particularly limited, and examples thereof include the following. As a target, for example, as an agricultural and horticultural insecticide, it is suitable for controlling various agriculture and forestry that harms rice, fruit trees, vegetables, other crops and flowers, horticulture, stored grain pests, sanitary pests, nematodes, etc. For example, apple oysters (Adoxophyes orana fasciata), sycamores (Adoxophyes sp.), Apple crocodile (Grapholita inopinata), pears (Grapho)
lita molesta, legume mini squirt (Leguminivora glyci)
nivorella), Kuwahamaki (Olethreutes mori), Canohosoga (Caloptilia thevivora), Apple hosoga (Calo)
ptilia zachrysa, Kimmon Hosoga (Phyllonorycter)
ringoniella), Nashihosoga (Spulerrina astaurot)
a), cabbage butterfly (Piers rapae crucivora), giant tobacco (Heliothis sp.), codling moth (Laspey)
resia pomonella) and diamondback moth (Plutella xylostella)
), Apple turtle (Argyresthia conjugell)
a), peach sink moth (Carposina niponensis), squid moth (Chilo suppressalis), cob beetle (Cnapha
locrocis medinalis, Chamodara meiga (Ephestia e)
lutella), Kwanomeiga (Glyphodes pyloalis), Sankameiga (Scirpophagaincertulas), Scutellaria parsley (Parnara guttata), and armyworm (Pseudaletia)
separata), Spodoptera litura (Sesamia inferens), Spodoptera litura (Spodoptera litura), Spodoptera exigua (Spodoptera exigua), Plutella xylostel
la) and other lepidopteran pests,

[0022] Empoasca brass
sicae), leafhopper leafhopper (Macrosteles fascifron)
s), leafhopper (Nephotettix cincticeps),
Brown planthopper (Nilaparvata lugens), white-spotted planthopper (Sogatella furcifera), orange lice (Diaphori)
na citri, whitefly (Aleurolobus taonaba)
e), whitefly (Bemisia tabaci), whitefly (Trialeurodes vaporariorum), radish aphid (Brevicoryne brassicae), cotton aphid
(Aphis gossipii), Raspalosiph
um padi), Aphid aphid (Lipaphis erysim)
i), peach aphid (Myzus persicae), horned beetle (Ceroplastes ceriferus), citrus stag beetle (Pulvinariaaurantii), citrus stalk beetle (Pseudaonidia duplex), pear stag beetle (Comstockaspis perniciosa), and half-spotted beetle Unos sis isan Winged pests,

The nematode nematode (Pratylenchus s)
p.), Japanese beetle (Anomala rufocuprea), Japanese beetle (Popillia japonica), Tobacco beetle (Lasioder)
ma serricorne, Flycatcher beetle (Lyctus brunneu)
s), Ladybird (Epilachna vigintioto)
punctata), adzuki beetle (Callosobruchus chinens)
is), weevil (Listroderes costirostris),
Weevil (Sitophilus zeamais), Cotton weevil (Anthonomus gradis gradis), Rice weevil (Li
ssorhoptrus oryzophilus, turtle beetle (Aulacophor)
a femoralis), rice beetle (Oulema oryzae)
), Beetle beetles (Phyllotreta striolata), pine bark beetles (Tomicus piniperda), colorado potato beetle (Leptinotarsa decemlineata), Mexican beetle (Epilachna varivestis), corn rootworms (Diabrotica sp.), Etc.

The fruit fly (Dacus (Zeugodacus) cucurbit
ae), Citrus fruit fly (Dacus (Bactrocera) dorsali
s), rice leaf fly (Agromyza oryzae), onion fly (Delia antiqua), and fly (Delia platura)
), Soybean flies (Asphondylia sp.), House flies (Musca domestica), and Culex pipien
s), such as dipteran pests,

Citrus red mite (Panonychus citri), red mite (Tetranychus urticae), apple spider mite (Panonych)
us ulmi), Tetranychus kanzawai, Tetranychus viennensis Zacher, Tetranychus spider mite (Brevipalpus phoenicis), Grape spider mite (Brevipalpus lewsi), and other mites (Calacarus carinas)
elekassi), pear mite (Epitrimerus pyri), rust mite (Eriophyes chibaensis) and other rust mites, Palyphagotarsonemus (Pyphagotarsonemus), and mite pests such as drug-resistant mites such as Tyrophagus putrescentiae),

The southern nematode (Pratylenchus)
coffeae), potato cyst nematode (Globodera)
rostochiensis), root-knot nematode (Meloidogyne s)
p.), Tangerine nematode (Tylenchulus semipenetra)
ns), Nepenthes nematode (Aphelenchus avena)
e), Agarene nematode (Aphelenchoides ritzemabos)
It has a strong insecticidal effect against pests of the order Nematodes such as i). The scientific names and the like are based on the 1987 Agricultural and Forestry Pest and Animal Directory, edited by the Japan Society of Applied Animal Entomology.

Examples of fungicides for agricultural and horticultural use include, for example, rice blast (Pyricularia oryzae) and rice sheath blight (Rhizoctonia soybean).
lani), powdery mildew on various host plants such as rice sesame leaf blight (Cochiobolus miyabeanus), powdery mildew on barley and wheat (Erysiphe graminis), crown rust on oats (Puccinia coronata) and other plants. Rust,
Tomato plague (Phytophthora infestans) and other plant plagues, cucumber downy mildew (Pseudoperonospora cubens)
ist), downy mildew of various plants such as downy mildew of grape (Plasmopara viticola), and apple scab (Venturia inaequalis)
), Apple leaf spot (Alternaria mali), pear black spot (Alternaria kikuchiana), citrus black spot (Di
aporthe citri), Pseudomonas species such as cucumber spot bacterial disease (Pseudomonas syringae pv. lachrymans)
), Tomato bacterial wilt (Pseudomonas solanacearum), Xanthomonas species such as cabbage black rot (Xanthomonas cam)
pestris), rice leaf blight (Xanthomonas oryzae), citrus canker (Xanthomonas citri), Erwinia species,
For example, the product of the present invention exhibits excellent effects on diseases such as bacterial diseases such as cabbage soft rot (Erwinia carotovora) and viral diseases such as tobacco mosaic virus.

Examples of medical antibacterial agents include gram-negative bacteria such as streptococci, pneumococci, and staphylococci, Escherichia coli,
For the purpose of sterilization and antibacterial of fungi such as Shigella, cholera, pestis, influenza, tubercle bacillus chancroid, gonococcus, meningococcus, etc., fungi such as ringworm, Candida, fungi, etc. Can be used. Agricultural and horticultural insecticides of the present invention,
In addition to use as an agricultural and horticultural fungicide or a medical antibacterial agent,
The 1,3-thiazine derivative or 1,3-selenazine derivative of the present invention can also be used as an industrial antibacterial / antifungal agent, wood preservative, and the like.

The 1,3-thiazine derivative or 1,1 of the present invention
Agricultural and horticultural insecticides, agricultural and horticultural fungicides, and medical antimicrobial agents containing a 3-selenazine derivative as an active ingredient are used for applications to pharmaceuticals, foods, and agricultural chemicals, and are in powder, solution, and pellet forms. It is used in any dosage form, such as a surfactant, a fixing agent, a dispersing agent, a stabilizer and the like, if necessary, to prepare a solution, a tablet (including a sugar-coated tablet, a film-coated tablet), a powder, a granule, Formulated into capsules (including soft capsules), injections, suspensions, suppositories, ointments, creams, lotions, cataplasms, emulsions, wettable powders, suspensions, granules, aerosols, microcapsules, etc. can do. These can be used in any form, and are used in the form of formulation most suitable for use according to the mode of use.

The inert carrier which can be used in the present invention includes:
Any material which may be solid or liquid and can be a solid carrier includes, for example, soybean flour, cereal flour, wood flour, bark flour, saw flour, tobacco stem flour, walnut husk flour, bran, fibrous powder Residue after extraction of plant extracts, synthetic polymers such as pulverized synthetic resins, clays (eg, kaolin, bentonite, acid clay, etc.), talcs (eg, talc, pyrophyllide, etc.), silicas (eg, diatomaceous earth, silica sand, mica, White carbon [Synthetic high-dispersion silicic acid, also known as hydrous finely divided silicon and hydrous silicic acid, some of which contain calcium silicate as a main component.]), Activated carbon, sulfur powder, pumice, calcined diatomaceous earth, crushed bricks, fly ash, Inorganic mineral powders such as sand, calcium carbonate, calcium phosphate, ammonium sulfate,
Examples include chemical fertilizers such as phosphorous, nitrate, urea, and salt, and composts, and these are used alone or in the form of a mixture of two or more.

The material which can be a liquid carrier is selected from those having a solvent function per se and those capable of dispersing the active ingredient compound with the aid of an adjuvant even without the solvent function. The following carriers can be exemplified as typical examples. These can be used alone or in the form of a mixture of two or more types. Examples thereof include water, alcohols (eg, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.), ketones (For example, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Diisobutyl ketone, cyclohexanone, etc.), ethers (eg, ethyl ether, dioxane, cellosolve,
Dipropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, kerosene, mineral oil, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, alkylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloroethane) , Chloroform, carbon tetrachloride, chlorinated benzene, etc.), esters (eg, ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, etc.), amides (eg, dimethylformamide, diethylformamide, dimethylacetamide, etc.), nitriles (For example, acetonitrile and the like), dimethyl sulfoxides and the like. Examples of the other adjuvants include the following representative adjuvants. These adjuvants are used according to the purpose, and may be used alone or in combination of two or more kinds. In some cases, it is possible to use no auxiliaries at all.

Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compounds, such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene higher fatty acid esters, Polyoxyethylene resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkyl aryl sulfonate, naphthalene sulfonic acid condensate,
Surfactants such as lignin sulfonate and higher alcohol sulfate can be exemplified. For the purpose of stabilizing the dispersion of the active ingredient compound, adhering and / or binding, the following exemplified auxiliaries can be used. For example, casein, gelatin, starch, methylcellulose, carboxymethylcellulose, acacia, polyvinyl Auxiliaries such as alcohol, pine oil, bran oil, bentonite, ligninsulfonate and the like can also be used.

The following auxiliaries can be used for improving the flowability of the solid product. For example, auxiliaries such as wax, stearate, alkyl phosphate and the like can be used. As peptizers for suspension products, auxiliary agents such as, for example, naphthalenesulfonic acid condensates, condensed phosphates and the like can also be used. As an antifoaming agent, for example, an auxiliary agent such as silicone oil can be used. The compounding ratio of the active ingredient compound can be adjusted according to need. For example, 0.01 to 50% by weight in the case of powder or granules, and 0.01 to 50% in the case of emulsion or wettable powder. % By weight is appropriate.

The agricultural or horticultural insecticide or agricultural and horticultural fungicide of the present invention containing a 1,3-thiazine derivative or a 1,3-selenazine derivative represented by the general formula (I) as an active ingredient is suitable for paddy field crops and field crops. Since it has a remarkable control effect on the diseases and pests that damage products, fruit trees, vegetables, other crops and flowers, etc., The desired effects of the present invention can be obtained by treating paddy fields, fields, fruit trees, vegetables, other crops, paddy water such as flowers, foliage or soil before or at the time of occurrence of the pest. It is.

The 1,3-thiazine derivative or 1,1 of the present invention
Agricultural and horticultural insecticides or agricultural and horticultural fungicides containing the 3-serenazine derivative can be used as such for controlling various diseases, pests and fungi, or as appropriately diluted or suspended with water or the like for control. An effective amount may be applied to crops in which the occurrence of the disease, pest, fungus or the like is predicted or a place where the occurrence is not preferable.

The amount of the agricultural or horticultural insecticide or agricultural and horticultural fungicide of the present invention depends on various factors, for example, the purpose of use, the place of use,
Target disease / pest. Bacterial species, growth status of crops, tendency to produce diseases and pests, weather, environmental conditions, dosage form, method of application, location of application, application time, etc., vary as active ingredient compound, 0.1 g to 10 kg per 10 ares, Or, 0.
What is necessary is just to select suitably from the range of 1 ppm-1000 ppm according to the objective. When the 1,3-thiazine derivative or 1,3-selenazine derivative of the present invention is used as a medical antibacterial agent, for example, the dose to humans depends on the type of disease,
Depending on the degree, dosage form of administration, administration route, patient age, sex, body weight, etc., it is usually 1 to 100 per adult per day.
Preferably, 0 mg is administered. The agricultural or horticultural insecticide, the agricultural or horticultural fungicide or the medical antibacterial agent of the present invention may further be used for other agricultural or horticultural purposes for the purpose of controlling pests to be controlled, applicable disease states, suitable control period, or reducing the amount of medicine. It can also be used in admixture with an insect pest control agent or an antibacterial agent.

[0037]

The present invention will be specifically described below with reference to Examples, Formulation Examples and Test Examples. In the following description, "TH
"F" indicates tetrahydrofuran. Example 1. 4-Hydroxy-4-methyl-2- (4-
Methylphenyl) -4H-5,6-dihydro-1,3-
Production of selenazine (Compound No. 2) 4-Methylselenobenzamide (1.64 g, 10.0)
Of methyl vinyl ketone (700 mg, 10.0 mmol) dissolved in 20 ml of chloroform and stirred well, and then titanium tetrachloride TiCl ₄ (1.90 mmol) was added.
g, 10.0 mmol) and reacted at -20 ° C for 1 hour. The reaction mixture was extracted, washed with water, and dried by a conventional method, and the solvent was distilled off to obtain 2.28 g of the desired compound. Purity is 98.7%, yield is 97.2%
Met.

[0038]

Embedded image

The obtained 4-hydroxy-4-methyl-2
-(4-methylphenyl) -4H-5,6-dihydro-
The melting point, elemental analysis value, nuclear magnetic resonance absorption spectrum and infrared absorption spectrum of 1,3-selenazine are as follows. Melting point 89.0-89.6 ° C Elemental analysis value CHN calculated value 53.74 5.64 5.22 measured value 53.49 5.61 5.03 Nuclear magnetic resonance absorption spectrum (CDCl ₃ solvent, TMS internal standard, δ value) ¹ H-NMR 1.28 (3H, s), 1.55 (1H, m), 1.88 (1H, m),
2.25 (3H, s), 3.04 (2H, m), 3.81 (1H, br s), 7.07
(2H, d), 7.54 (2H, d) ¹³ C-NMR 18.1, 21.2, 24.7, 29.9, 85.0, 126.4, 128.
8, 137.3, 140.7, 156.8 Infrared absorption spectrum (KBr tablet) 1594 (υC = N), 3160 (υ O-H)

Example 2. Preparation of 4-hydroxy-4-methyl-2-pentyl-6-phenyl-4H-5,6-dihydro-1,3-selenazine (Compound No. 13) Hexaneselenoamide (1.44 g) , 10.0 mmol), 4-phenyl-3-buten-2-one (1.46 g, 10.0 mmol) dissolved in 10 ml of THF was added, and after stirring well, aluminum trichloride AlCl ₃ (1.
33 g, 10.0 mmol) and reacted at 0 ° C. for 3 hours. The reaction mixture was extracted, washed with water, and dried by a conventional method, and the solvent was distilled off to obtain 2.99 g of the desired compound.
Purity was 97.9% and yield was 92.0%.

[0041]

Embedded image

The obtained 4-hydroxy-4-methyl-2
-Pentyl-6-phenyl-4H-5,6-dihydro-
The nuclear magnetic resonance absorption spectrum and infrared absorption spectrum of 1,3-selenazine are as follows. Nuclear magnetic resonance absorption spectrum (CDCl ₃ solvent, TMS internal standard, δ value) ⁷⁷ Se-NMR 395 Infrared absorption spectrum (KBr tablet) 1634 (υC = N), 3198 (υ O-H)

Example 3 Preparation of 4-hydroxy-4-methyl-2-phenyl-4H-5,6-dihydro-1,3-thiazine (Compound No. 1) To thiobenzamide (756 mg, 5.00 mmol) Methyl vinyl ketone dissolved in 5 ml of methylene chloride (3
50 mg, 5.00 mmol) was added, and after sufficient stirring, boron trifluoride BF ₃ (680 mg, 10.0 mmol) was added, and the mixture was reacted at -78 ° C for 8 hours. The reaction mixture was extracted, washed with water, and dried by a conventional method, and the solvent was distilled off to obtain 1.25 g of the desired compound. Purity was 96.5% and yield was 92.9%.

[0044]

Embedded image

The melting point and nuclear magnetic resonance absorption spectrum of 4-hydroxy-4-methyl-2-phenyl-4H-5,6-dihydro-1,3-thiazine are as follows. Melting point 124.2-126.8 ° C Nuclear magnetic resonance absorption spectrum (Acetone-d6 solvent, TMS internal standard) ¹ H-NMR 1.42 (3H, s), 1.77 (1H, m), 1.96 (1H, m),
3.18 (1H, m), 3.29 (1H, m), 7.42 (3H, m), 7.83 (2
(H, m) ¹³ C-NMR 24.1, 28.1, 30.9, 81.7, 127.2, 129.0, 131.
2, 140., 156.0

Example 4 5-Hydroxy-3- (4-
Production of (methylphenyl) -4-aza-2-selenobicyclo [3,3,1] non-3-ene (Compound No. 1)
6) 4-methylselenobenzamide (1.64 g, 10.0
To this solution, cyclohexenone (961 mg, 10.0 mmol) dissolved in 10 ml of carbon tetrachloride was added, and after stirring well, titanium tetrachloride TiCl ₄ (949 mg, 5.0 mmol) was added.
0 mmol) and reacted at 0 ° C. for 4 hours. The reaction mixture was not extracted, washed with water, or dried by a conventional method, and the solvent was distilled off to obtain 2.20 g of the desired compound. Purity is 95.
3%, and the yield was 84.5%.

[0047]

Embedded image

The melting point, nuclear magnetic resonance absorption spectrum and infrared absorption spectrum of 5-hydroxy-3- (4-methylphenyl) -4-aza-2-selenobicyclo [3,3,1] non-3-ene are shown below. It is as follows. Melting point 115.1-117.0 ℃ Nuclear magnetic resonance absorption spectrum (CDCl ₃ solvent, TMS internal standard) ¹ H-NMR 1.62 (2H, dd), 1.79 (2H, dd), 1.94 (1H,
d), 2.00 (2H, d), 2.06 (1H, d), 2.34 (3H, s), 3.51
(1H, d), 3.90 (1H, br s), 7.15 (2H, d), 7.64 (2H,
d) ¹³ C-NMR 19.0, 21.2, 33.3, 34.1, 36.2, 39.4, 82.9,
126.4, 128.9, 137.3, 140.6, 158.0 Infrared absorption spectrum (KBr tablet) 1596 (υC = N), 3264 (υO-H)

Example 5. 4-ethoxy-4-methyl-
Production of 2- (4-methylphenyl) -4H-5,6-dihydro-1,3-selenazine (Compound No. 14) 4-Methylselenobenzamide (1.64 g, 10.0)
Of methyl vinyl ketone (701 mg, 10.0 mmol) dissolved in 20 ml of ethanol, and after stirring well, boron trifluoride BF ₃ (678 mg, 10.0 mmol).
Mmol) and reacted at 0 ° C. for 4 hours. The reaction mixture was extracted, washed with water, and dried by a conventional method, and the solvent was distilled off to obtain 2.34 g of the target compound as a yellow oil. Purity was 97.6% and yield was 89.4%.

[0050]

Embedded image

The nuclear magnetic resonance absorption spectrum and infrared absorption spectrum of 4-ethoxy-4-methyl-2- (4-methylphenyl) -4H-5,6-dihydro-1,3-selenazine are as follows. . Nuclear magnetic resonance absorption spectrum (CDCl ₃ solvent, TMS internal standard) ¹ H-NMR 1.24 (3H, t), 1.38 (3H, s), 1.79 (1H, dt),
1.88 (1H, dt), 2.35 (3H, s), 3.19 (2H, dd), 3.71
(1H, dq), 3.84 (1H, dq), 7.16 (2H, d), 7.66 (2H, d) ¹³ C-NMR 16.0, 17.8, 21.3, 21.7, 28.7, 56.2, 88.1,
126.5, 128.9, 137.8, 140.7, 155.4 Infrared absorption spectrum (KBr tablet) 1615 (υC = N)

Embodiment 6 FIG. Production of 4-methyl-2- (4-methylphenyl) -6H-1,3-selenazine (Compound No. 19) 4-Hydroxy-4-methyl-2- obtained in Example 1
(4-methylphenyl) -4H-5,6-dihydro-
1,3-Selenazine (270 mg, 1.0 mmol) was dissolved in 3 ml of dry pyridine, and phosphorus oxychloride (80 mg,
0.52 mmol) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and then reacted at 50 ° C. for 1 hour with stirring. After completion of the reaction, the reaction mixture is extracted, washed with water and dried by a conventional method, and the solvent is distilled off to obtain the desired compound 2
35 mg were obtained. The purity is 95.2% and the yield is
93.9%.

Embedded image

Representative examples and physical properties of specific compounds produced according to the above-mentioned production methods and Examples are described below.
As shown in Tables 5 to 5, the compounds of the present invention are not limited to only these. Se in the table represents a selenium atom,
S represents a sulfur atom, Me represents methyl, Et represents ethyl, Pr represents propyl, and Ph represents phenyl. In the table, OR ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R
_6th grade does not define the stereo position, and may interchange with each other and may be a mixture.

Formula (I)

Embedded image Table 1 化合物 Compound RXR ₁ R ₂ R ₃ R ₄ R ₅ R ₆ Physical properties mp (° C) No. ──────────────────────────────── 1 Ph SH Me HHHH 124.2-126.8 2 4-MePh Se H Me HHHH 89.0-89.6 3 4-MePh Se H Et HHHH 60.6-61.3 4 4-MePh Se H Me HH Me Me 92.0-93.3 5 4-MePh Se H Me HH n-Pr H 115.1-117.0 6 4-MePh Se H Me HH i-Pr H 79.5-80.6 7 4-MePh Se H Me Me H Me H 110.0-111.8 8 4-MePh Se H Me HH Ph H 105.3-106.3 9 4-MePh Se H Me HH nC ₅ H ₁₁ H _{66.9-67.7 10 nC 5 H 11 Se H} Me HHHH oil _{11 nC 5 H 11 Se H Me} Me H Me H oil _{12 nC 5 H 11 Se H Me} HH n-Pr H oil 13 nC ₅ H ₁₁ Se H Me HH Ph H Oily paste 14 4-MePh Se Et Me HHHH Oily ────────────────────────────────

General formula (I-1)

Embedded image Table 2 ──────────────────────────────── Compound RXR ₁ Yn Physical properties mp. (° C) No. ─── _{───────────────────────────── 15 4-MePh SH -CH 2} - 3 16 4-MePh Se H -CH 2 - 3 _{115.1-117.0 17 nC 5 H 11 SH -CH} 2 - 3 18 nC 5 H 11 Se H -CH 2 - 3 oil ────────────────────── ──────────

Formula (I-2)

Embedded image Table 3 化合物 Compound RXR ₂ R ₅ R ₆ Physical properties mp. (℃) No. ─ ─────────────────────────────── 19 4-MePh Se Me HH Oil 20 4-MePh S -CH = CH- Ph Ph H 21 4-MePh Se -CH = CH-Ph Ph H 54.5-56.0 22 nC ₅ H ₁₁ S -CH = CH-Ph Ph H 23 nC ₅ H ₁₁ Se -CH = CH-Ph Ph H 24 4- MePh Se -CH ₂ -CH = CH-Ph Ph H ────────────────────────────────

Tables 4 and 5 show physical property data of the oily substances. In the table, ¹ H-NMR represents hydrogen nuclear magnetic resonance, and ¹³ C-NMR represents carbon nuclear magnetic resonance. TM
S represents tetramethylsilane. Table 4 ──────────────────────────────── Compound ¹ H-NMR δ value (CDCl ₃ solvent, TMS internal standard) ) (Ppm) No. ──────────────────────────────── 14 1.24 (3H, t), 1.38 (3H, s ), 1.79 (1H, dt), 1.88 (1H, dt), 2.35 (3H, s), 3.19 (2H, dd), 3.71 (1H, dq), 3.84 (1H, dq), 7.16 (2H, d) , 7.66 (2H, d) ────────────────────────────────

Table 5 Compound ¹³ C-NMR δ value (CDCl ₃ solvent, TMS internal standard) (ppm) No. Selena (thia) azine ring 2nd carbon ^* 4th carbon ^* ──────────────────────────── ──── 10 160.9 84.5 11 162.9 89.6 12 161.4 87.3 13 162.1 87.7 18 163.6 82.5 19 160.1 148.6 ──────────────────────────── ──── The 2-position is the carbon that R substitutes between selenium (sulfur) and the nitrogen atom. The 4-position represents a carbon atom which is adjacent to the nitrogen atom and is substituted by R ₁ O and R ₂ .

Formulation Examples Next, formulation examples of the present invention are shown below, but the present invention is not limited to these. The middle part of the formulation means parts by weight. Formulation Example 1 10 parts of the compounds described in Tables 1 to 3 10 parts Magnesium stearate 10 parts Lactose 80 parts are uniformly mixed to give a powder or fine granules to give a powder. Formulation Example 2 Compounds listed in Tables 1 to 3 20 parts Starch 10 parts Lactose 15 parts Ethyl cellulose 20 parts Polyvinyl alcohol 5 parts Water 30 parts After uniformly mixing and mixing, crushed and granulated and sieved to obtain granules. I do.

Formulation Example 3 Compounds listed in Tables 1 to 3 0.5 parts Nonionic surfactant 2.5 parts Physiological saline 97 parts After heating and mixing, sterilized to give an injection. Formulation Example 4 0.01 parts of the compounds described in Tables 1 to 3 and 99.99 parts of 0.5% carboxymethylcellulose are suspended to prepare a suspension.

Formulation Example 5 One part of the compounds shown in Tables 1 to 3 1 part polyethylene glycol 400 99 parts was mixed and dissolved to prepare a coating solution. [Formulation Example 6] After mixing and dissolving 2 parts of the compounds shown in Tables 1 to 3 with 49 parts of polyethylene glycol 400 and 49 parts of polyethylene glycol 4000 under heating, the mixture is cooled to obtain an ointment.

Formulation Example 7 Compounds listed in Tables 1 to 3 3 parts 1,2-propanediol 5 parts Glycerol stearate 5 parts Whale wax 5 parts Isopropyl myristate 10 parts Polysorbate 4 parts were heated and mixed. Thereafter, 68 parts of water is added while cooling and stirring to form a cream. Formulation Example 8 One part of the compounds described in Tables 1 to 3, 5 parts of benzyl alcohol, 30 parts of ethanol and 47 parts of propylene glycol were mixed and dissolved, and 1 part of hibiscowa 104 and 1 part of purified water were added to this solution. An aqueous solution consisting of 15 parts was added to obtain a uniform solution. Then, diisopropanolamine was added with stirring to obtain a gel.

Formulation Example 9 One part of the compounds described in Tables 1 to 3 was dissolved in 5 parts of benzyl alcohol and 5 parts of diethyl sebacate, and 5 parts of ethyl alcohol, 6 parts of stearyl alcohol, and sorbitan monostearate 1 were dissolved. And 8 parts of polyoxyethylene monostearate were added and dissolved by heating at 70 ° C. While maintaining the obtained homogeneous solution at 70 ° C,
69 parts of purified water heated to 70 ° C. was added, and the mixture was cooled with continued stirring to obtain a cream composition. [Formulation Example 10] Compounds described in Tables 1 to 3 50 parts Xylene 40 parts Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 10 parts The above are uniformly mixed and dissolved to form an emulsion.

Formulation Example 11 Compounds shown in Tables 1 to 3 3 parts Clay powder 82 parts Diatomaceous earth powder 15 parts The above are uniformly mixed and pulverized to give a powder.

Formulation Example 12 Compounds listed in Tables 1 to 3 5 parts Mixed powder of bentonite and clay 90 parts lignin sulfonate 5 parts The above components were uniformly mixed, kneaded by adding an appropriate amount of water, Granulation,
Dry to granules.

Formulation Example 13 Compounds shown in Tables 1 to 3 20 parts Kaolin and synthetic highly dispersed silicic acid 75 parts Mixture of polyoxyethylene nonyl phenyl ether and calcium alkylbenzenesulfonate 5 parts Mix and grind to make a wettable powder.

Test Example 1 Diamondback moth (Plutella xylostella)
Insecticidal effect test on Chinese cabbage seedlings was released from adult Japanese moths and laid eggs, and two days after release, Chinese cabbage seedlings with spawning eggs were used as active ingredients with the compounds shown in Tables 1 to 3 as active ingredients. Is 500pp
m for about 30 seconds and air-dried at 25 ° C.
In a constant temperature room. Six days after the immersion in the drug solution, the number of hatching insects was investigated, the mortality was calculated by the following formula, and the judgment was made according to the following criteria. 10 units in 1 ward, 3 consecutive As a result of the above test, the compounds shown in Tables 1 to 3 showed an excellent insecticidal activity of Japanese moth, and the compounds Nos. 3 and 4 showed the controlling effect of A.

Test Example 2 Anthracite (Adoxo
phyes sp.) Pesticide leaf (cultivar: Yabukita) is immersed for about 30 seconds in a drug solution prepared by diluting a drug containing the compounds listed in Tables 1 to 3 to an active ingredient of 500 ppm for about 30 seconds and air-dried. After placing in a 9 cm plastic petri dish and inoculating the second instar larvae of the Anemone brassicae, it was capped and allowed to stand in a constant temperature room at 25 ° C. and 70% humidity. 8 days after inoculation, the number of live and dead insects was investigated, and Test Example 1
The judgment was made according to the following. As a result of the test described above, the compounds shown in Tables 1 to 3 show excellent insecticidal activity of Antrodia cinnamomea, and compounds Nos. 3 and 9 show the control effect of A. Was.

Test Example 3 Brown planthopper (Nilaparvata)
Insecticidal effect test on lugens) A preparation containing the compounds shown in Tables 1 to 3 of the present invention as an active ingredient is dispersed in water and diluted into a 500 ppm drug solution.
Rice seedlings (variety: Nipponbare) were immersed in the chemical solution for 30 seconds,
After air-drying, it was put into a glass test tube, inoculated with ten third-stage larvae of the brown planthopper, each of which was plugged with cotton, and stored in a constant temperature room at 25 ° C. Eight days after the inoculation, the number of live and dead insects was investigated, and the mortality was calculated by the following equation, and the judgment was made according to the following judgment criteria.

Corrected mortality (%) = [(untreated group survival rate−
Survival rate of treated section) / (survival rate of untreated section)] × 100 Survival rate = number of surviving insects / number of inoculated insects. Criteria: A: mortality rate 100% B: mortality rate 90-99% C: mortality rate 80-89% D: mortality rate 50-79%

As a result of the above test, the compounds shown in Tables 1 to 3 showed excellent insecticidal activity to brown planthopper, and compounds Nos. 1, 3, 4, 5, 6, 7, and 9 were judged to be A. In particular, the compounds of Compound Nos. 4 and 9 are 50 p
The control effect of A is shown even at a concentration of pm.

Test Example 4 Spider mite (Tetranychus urtic)
ae) Insecticidal effect test A plastic cup with a diameter of 8 cm is filled with water, a lid with a hole of 1 cm in diameter is placed, a partially cut filter paper is placed on the lid, and the lid is suspended in water from the lid. The filter paper was kept moist by capillary action. A leaf disk having a diameter of 2 cm was prepared from the primary leaves of the kidney beans (variety: top crop), and 10 female adults were inoculated. This leaf disk was placed on the filter paper, and a drug containing the compounds shown in Tables 1 to 3 as active ingredients was placed on a turntable at 50 pp.
After uniformly spraying 50 ml of the drug solution diluted to m, the solution was allowed to stand in a constant temperature room at 25 ° C. Two days after the chemical treatment, the number of abnormal insects and the number of dead insects were investigated, and the ratio of abnormal and dead insects was calculated according to the following formula. 1 ward 2
Consolidation.

[0073] As a result of the above test, the compounds shown in Tables 1 to 3 show excellent insecticidal activity of the spider mite, Compound Nos. 1, 4,
Compounds 5, 6, 7 and 9 showed the controlling effect of A.

Test Example 5 Rice Blast Control Test A 6-leaf stage rice (cultivar: Kinnan style) cultivated in a pot was prepared by adding 200 ppm of a drug containing the compounds shown in Tables 1 to 3 as active ingredients prepared according to the examples in water. It was diluted to a concentration and sprayed with foliage. After air drying, the rice blast fungus (Pyricularia or
yzae) was spray inoculated with a spore suspension. After the inoculation, the plants were placed under a humid condition of 20 ° C. for 7 days to sufficiently develop the disease. The number of lesions on each leaf was examined, and the control value was calculated according to the following formula. The judgment was made according to the following criteria. A: Control value 100-95% B: Control value 94-85% C: Control value 84-60% D: Control value 59-0%

As a result of the above test, the compounds shown in Tables 1 to 3 show excellent blast control activity, and compounds Nos. 1, 7 and 9 are judged to be C or higher, and especially compound Nos. Compounds 5 and 7 show the controlling effect of A.

Test Example 6 Antibacterial activity test against plant pathogenic bacteria Rice paddy blight disease (Ps) of compounds listed in Tables 1 to 3
eudomonas glumae) was evaluated by the agar plate dilution method. Tables 1 to 3 created according to the examples
Drugs containing the compounds listed in the table as active ingredients were diluted with ethanol, and added to a concentration of 50 ppm in the medium. The test bacteria were cultured in a liquid medium at 30 ° C. for 1 day, and the suspension was dropped and inoculated on the medium containing the drug. After inoculation, the cells were cultured at 30 ° C. for 1 day, and the growth inhibitory concentration was visually determined according to the following criteria. A: No growth of bacteria was observed. B: Growth of bacteria was slightly observed. C: Growth of bacteria was observed but growth was smaller than that of untreated. D: Growth equivalent to that of untreated was observed. As a result, the compounds shown in Tables 1 to 3 exhibited excellent blast control activities, and Compound Nos. 3, 4, and 5
The compounds of Nos. 7 and 7 were judged to be C or higher, and in particular, the compound of compound No. 3 showed the controlling effect of A.

Test Example 7 Antimicrobial effect test Gram-negative fungi of the product of the present invention (Escherichia coli
K12), Gram-positive fungi (Staphylococci: Staphylococc
us aureus IFO14462, Micrococcus Luteus: Micr
ococcus luteus, Bacillus subtilis), fungi (Saccharomyces cerevisiae: Saccharomyces ce)
revisiae IFO0203, Candida Albicans: Cand
ida albicans IFO1061) and the like.
The test cells were cultured in a liquid medium autoclaved at 120 ° C. for 15 minutes under each condition to obtain a bacterial solution. In the test, the antibacterial activity was measured by a paper disk method.
In the paper disk method, an agar plate inoculated with each of the bacterial liquids was prepared by diluting and applying the inventive product formulation to water to a concentration of 0.25 μmol per paper disk using a paper disk having a diameter of 8 mm. After placing on a medium and culturing for 24 hours in a thermostat at 30 ° C., the growth inhibition circle was measured from the growth state of the colony around the paper disk. Streptomycin was used as a control. The results are shown in Table 6. In the table,-indicates that no inhibitory circle was shown at a predetermined concentration, and + indicates that the activity was observed but the formation of the inhibitory circle was not clear.

Table 6 Antibacterial effect test (paper disc method) Growth inhibition circle (diameter mm)化合物 Compound No. E. coli M. luteus S. aureus B. subtilis １ 1 -----Test 2 25 25 18 18 25 32 21 20 17 11 11 4 13 18 13 19 19 5-16 + 176-15 11 15 15 Test 7--11 23 8 12 15 15 14 15 911 25 11 -12 +16 section 12 11 17 16 12 12 13 13 15 15 16 16-----18-16 11 11 21 19 13 21 21 18 1824----比 ratio Strept comparison Ishin 12 15 + 18 ° ────────────────────────────────

[0079]

According to the process of the present invention, a novel 1,3-thiazine derivative or a thioamide or selenoamide, which is easily available as an industrial raw material, is reacted with an α, β-unsaturated ketone in the presence of a catalyst. 1,3-Selenazine derivatives can be prepared. Usually, many heterocycles containing a sulfur atom or a selenium atom take the form of a sterically stable 5-membered ring (thiazole, selenazole, etc.). Thiazole and selenazole, which are easy to synthesize, are
It is an important compound from a biochemical point of view and also from an engineering and chemical point of view. The 1,3-thiazine derivative or 1,3-selenazine derivative obtained by the present invention is a novel compound which has not been reported so far. According to the present invention, the compound group according to claims 1 to 3 of the present invention can be produced under mild conditions and in high yield. Moreover, they are very useful as insecticides or fungicides or antibacterials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 31/395 A61K 31/395 31/54 31/54 602 602 C07D 279/08 C07D 279/08 293/08 293/08 293/10 293/10 (72) Inventor Takayuki Senda 39-1 Haguro Nankyoya, Inuyama City, Aichi Prefecture (72) Inventor Hideharu Ishihara 5-61 Hayata Higashicho, Gifu City, Gifu Prefecture

Claims (10)

[Claims] [Claim 1] General formula (I): (In the formula, X represents a sulfur atom or a selenium atom, and R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an alkoxy group, an acyl group, an alkylthio group, an arylthio group or an alkoxycarbonyl group. the stands, R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group,
Represents an alkenyloxy group, an alkynyloxy group, an aryloxy group, an acyloxy group or an alkoxycarbonyloxy group. R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an arylalkenyl group, an alkoxy group, an acyl group. group, an alkylthio group, an arylthio group, a substituent selected from an alkoxycarbonyl group or a hydroxyl group, can also indicate binding R ₂ and R ₃ or R ₄ and R ₅ together, R ₂
And R ₅ together represent an alkylene group having 1 to 5 carbon atoms, which may be the same or different, and may have one or more alkyl groups. A) 1,3-thiazine derivative or 1,3-selenazine derivative. 2. A compound represented by the general formula (I):
-1):(Wherein, X represents a sulfur atom or a selenium atom, and R is hydrogen
Atom, alkyl, alkenyl, alkynyl, ant
Allyl group, substituted phenyl group, alkoxy group, acyl group,
Alkylthio, arylthio, or alkoxycarbo
And Y represents -CR₇R₈(R₇And R₈Is hydrogen
Indicates an atom or an alkyl group. ) And R ₁Is hydrogen field
, A hydroxyl group, an alkoxy group, an alkenyloxy group,
Quinyloxy, aryloxy, acyloxy or
Represents an alkoxycarbonyloxy group, and n represents 1 to 5
Represents an integer. 2. The 1,3-thio according to claim 1, wherein
An azine derivative or a 1,3-selenazine derivative. 3. The compound represented by the general formula (I)
-2): embedded image (In the formula, X represents a sulfur atom or a selenium atom, and R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an alkoxy group, an acyl group, an alkylthio group, an arylthio group or an alkoxycarbonyl group. R ₂ , R ₅ and R ₆ may be the same or different, and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an arylalkenyl group, an alkoxy group, an acyl group, an alkylthio group. A 1,3-thiazine derivative or a 1,3-selenazine derivative according to claim 1, which represents a substituent selected from a group, an arylthio group, an alkoxycarbonyl group and a hydroxyl group. 4. A compound of the general formula (II): (In the formula, X represents a sulfur atom or a selenium atom, and R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an alkoxy group, an acyl group, an alkylthio group, an arylthio group or an alkoxycarbonyl group. Wherein a thioamide or a selenoamide represented by the general formula (I) is reacted with an α, β-unsaturated ketone in the presence of a catalyst. (Wherein X and R are as defined above, R ₁ is a hydrogen atom,
Represents a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an acyloxy group or an alkoxycarbonyloxy group, R ₂ , R ₃ ,
R ₄ , R ₅ and R ₆ may be the same or different, and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an arylalkenyl group, an alkoxy group, an acyl group, an alkylthio group, an arylthio group. R ₂ and R ₃ or R ₄ and R ₅ may together represent a bond, and R ₂ and R ₅ together represent a carbon atom. And an alkylene group having 1 to 5 atoms. The alkylene group may be the same or different, and may have one or more alkyl groups. )), A method for producing a 1,3-thiazine derivative or a 1,3-selenazine derivative compound. 5. The compound represented by the general formula (I)
-1):(Wherein, X represents a sulfur atom or a selenium atom, and R is hydrogen
Atom, alkyl, alkenyl, alkynyl, ant
Allyl group, substituted phenyl group, alkoxy group, acyl group,
Alkylthio, arylthio, or alkoxycarbo
And Y represents -CR₇R₈(R₇And R₈Is hydrogen
Indicates an atom or an alkyl group. ) And R ₁Is hydrogen field
, A hydroxyl group, an alkoxy group, an alkenyloxy group,
Quinyloxy, aryloxy, acyloxy or
Represents an alkoxycarbonyloxy group, and n represents 1 to 5
Represents an integer. 5. The 1,3-thio according to claim 4, wherein
Method for producing azine derivative or 1,3-selenazine derivative
Law. 6. A compound represented by the general formula (I)
-2): embedded image (In the formula, X represents a sulfur atom or a selenium atom, and R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an alkoxy group, an acyl group, an alkylthio group, an arylthio group or an alkoxycarbonyl group. R ₂ , R ₅ and R ₆ may be the same or different, and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted phenyl group, an arylalkenyl group, an alkoxy group, an acyl group, an alkylthio group. A substituent selected from a group, an arylthio group, an alkoxycarbonyl group, or a hydroxyl group.) The method for producing a 1,3-thiazine derivative or a 1,3-selenazine derivative according to claim 4, wherein 7. An insecticide for agricultural and horticultural use, comprising the 1,3-thiazine derivative or the 1,3-selenazine derivative according to any one of claims 1 to 3 as an active ingredient. 8. A fungicide for agricultural and horticultural use, comprising the 1,3-thiazine derivative or the 1,3-selenazine derivative according to any one of claims 1 to 3 as an active ingredient. 9. An antibacterial agent for medical use, comprising the 1,3-thiazine derivative or the 1,3-selenazine derivative according to claim 1 as an active ingredient. 10. A method for controlling pests, comprising treating a target crop with an effective amount of the agricultural or horticultural insecticide or the agricultural or horticultural fungicide according to any one of claims 7 to 8.