JP5689293B2 - Anti-anticide and anti-ant method using the same - Google Patents

Description

  The present invention relates to an ant-proofing agent and an ant-proofing method using the ant-proofing agent, and more particularly to an ant-proofing agent for protecting wood and the like from the damage caused by white ants, and an ant-proofing method using the ant-proofing agent.

  2. Description of the Related Art Conventionally, it is widely known to use an ant inhibitor to protect wood and the like used for general industrial materials and civil engineering materials from white ants.

  As such an anti-anticide, for example, E-1- (2-chloro-1,3-thiazol-5-ylmethyl) -3-methyl-2-nitroguanidine (clothianidin) (for example, see Patent Document 1) 2-methylbiphenyl-3-ylmethyl (Z)-(1RS, 3RS) -3- (2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate (Bifentrin) has been proposed (see, for example, Patent Document 2).

JP 2008-206492 A JP-A-8-225401

  However, the termite-proofing agents described in Patent Documents 1 and 2 have a complicated chemical structure, and a multi-step synthesis process is required to produce such a termite-proofing agent, resulting in an increase in production cost. There is a problem of doing.

  Then, this invention is providing the ant-proofing method which expresses the outstanding ant-proofing effect and can aim at reduction of manufacturing cost, and the ant-proofing method using the ant-proofing agent.

  In order to achieve the above object, the present inventors have intensively studied an active ingredient that can be used as an antifungal agent. As a result, a specific amide compound has a simple structure and a sufficient antifungal effect. As a result of finding knowledge and further research, the present invention has been completed.

That is, the present invention
(1) An antproofing agent characterized by containing an amide compound represented by the following general formula (1):
General formula (1):

(In the formula, any one of X ₁ and X ₂ represents a halogen atom, an alkyl group or a phenyl group which may have a substituent, and the other represents a hydrogen atom. X ₁ and X ₂ are May be bonded to each other to form a saturated or unsaturated 5- to 6-membered ring which may have a substituent, Y represents an alkylene group having 6 to 14 carbon atoms, and Z represents a methyl group , A vinyl group or a substituent represented by the following general formula (2).
General formula (2):

(Wherein, _{X 1} and _{X 2} are as defined for _{X 1} and _{X 2} in the general formula (1).)
(2) In the general formula (1), X ₁ and X ₂ are bonded to each other to form a saturated 5- to 6-membered ring,
(3) In the general formula (1), Z is represented by a vinyl group or the general formula (2), and X ₁ and X ₂ are bonded to each other to form a saturated 5- to 6-membered ring. An anti-anticide as described in (1) or (2) above,
(4) In said general formula (1), Y is a C8-C10 alkylene group, The termite-proofing agent as described in any one of said (1)-(3) characterized by the above-mentioned.
(5) An ant-proofing method characterized by using the ant-proofing agent according to any one of (1) to (4).

  The termite-proofing agent of the present invention contains an amide compound represented by the above general formula (1) as an active ingredient. The amide compound represented by the general formula (1) has a sufficient ant-repellent effect and can be synthesized from an inexpensive raw material by a simple method. Therefore, in addition to being able to express an excellent ant-proofing effect, the ant-proofing agent of the present invention can reduce the manufacturing cost.

  The termite-proofing agent of the present invention contains an amide compound represented by the following general formula (1).

  General formula (1):

(In the formula, any one of X ₁ and X ₂ represents a halogen atom, an alkyl group or a phenyl group which may have a substituent, and the other represents a hydrogen atom. X ₁ and X ₂ are May be bonded to each other to form a saturated or unsaturated 5- to 6-membered ring which may have a substituent, Y represents an alkylene group having 6 to 14 carbon atoms, and Z represents a methyl group , A vinyl group or a substituent represented by the following general formula (2).
General formula (2):

(Wherein, _{X 1} and _{X 2} are as defined for _{X 1} and _{X 2} in the general formula (1).)
In the general formulas (1) and (2), examples of the halogen atom represented by X ₁ or X ₂ include bromine, chlorine, fluorine, and iodine.

In the general formulas (1) and (2), examples of the alkyl group represented by X ₁ or X ₂ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. , Pentyl, isopentyl, sec-pentyl, hexyl, heptyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc., linear or branched Of the alkyl group.

  Among these alkyl groups, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable.

In the general formulas (1) and (2), examples of the substituent of the phenyl group represented by X ₁ or X ₂ include an alkyl group, a nitro group, and a halogen atom. Examples of the alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. . Examples of the halogen atom include bromine, chlorine, fluorine, iodine and the like.

  Among these substituents, an alkyl group and a halogen atom are preferable, and a methyl group and chlorine are more preferable.

  Examples of the phenyl group which may have such a substituent include, for example, an unsubstituted phenyl group, for example, a phenyl group in which an alkyl group having 1 to 4 carbon atoms such as a tolyl group and an ethylphenyl group is monosubstituted, for example, A phenyl group disubstituted by an alkyl group having 1 to 4 carbon atoms such as xylyl group, diethylphenyl group or methylethylphenyl group, for example, a phenyl group trisubstituted by an alkyl group having 1 to 4 carbon atoms such as a trimethylphenyl group Etc.

  Among these phenyl groups which may have a substituent, a tolyl group and a xylyl group are preferable.

In the general formulas (1) and (2), X ₁ and X ₂ may be bonded to each other to form a saturated or unsaturated 5- to 6-membered ring which may have a substituent.

The saturated or unsaturated 5- to 6-membered ring is a heterocycle containing a common nitrogen atom to which X ₁ and X ₂ are bonded, and may further contain a hetero atom (eg, nitrogen atom, oxygen atom, sulfur atom). Moreover, you may have a C1-C4 alkyl group, a nitro group, and a halogen atom as a substituent.

  Examples of the alkyl group having 1 to 4 carbon atoms include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. .

  Examples of the halogen atom include bromine, chlorine, fluorine, iodine and the like.

  Such substituents are substituted, for example 1-4, on saturated or unsaturated 5-6 membered rings.

  Examples of the saturated or unsaturated 5- to 6-membered ring which may have such a substituent include, for example, pyrrolidine ring, pyrrole ring, pyrazolidine ring, imidazolidine ring, pyrazole ring, imidazole ring, thiazolidine ring, oxazolidine ring, Examples include 2-methylpyrrolidine ring, 3-chloropyrrolidine ring, piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, 2-methylpiperazine ring, 3-chloropiperidine ring and the like.

  Of these saturated or unsaturated 5- to 6-membered rings, a piperidine ring is preferable.

Among X ₁ and X _{2 in} the above general formula (1), a phenyl group which may have a substituent and a saturated or unsaturated 5-6 formed by bonding to each other are preferable. A member ring is mentioned, More preferably, the saturated 5-6 membered ring formed by mutually bonding is mentioned.

  In the general formula (1), examples of the alkylene group represented by Y include alkylene groups having 6 to 14 carbon atoms such as hexylene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, isodecylene, dodecylene, and tetradecylene. Is mentioned.

  Among these alkylene groups, an alkylene group having 8 to 10 carbon atoms such as octylene, 2-ethylhexylene, nonylene, decylene, and isodecylene is preferable.

  In the general formula (1), Z represents a methyl group, a vinyl group, or a functional group represented by the general formula (2).

Among Z in the above general formula (1), preferably, a vinyl group and a saturated 5 represented by the above general formula (2), wherein X ₁ and X ₂ are bonded to each other. A 6-membered ring.

Examples of such an amide compound represented by the general formula (1) include 1- (piperidin-1-yl) undec-10-en-1-one (the following chemical formula (3)), 1,10-di- (Piperidin-1-yl) decane-1,10-dione (the following chemical formula (4)), Np-tolyldecanamide (the following chemical formula (5)), N- (2,6-dimethylphenyl) decanamide (the following Chemical formula (6)), N- (2,3-dimethylphenyl) decanamide (the following chemical formula (7)), and the like.
Chemical formula (3):

Chemical formula (4):

Chemical formula (5):

Chemical formula (6):

Chemical formula (7):

  Next, a method for synthesizing the amide compound represented by the general formula (1) will be described.

The amide represented by the general formula (1) is not particularly limited. For example, as shown in the following reaction formula (1), a carboxylic acid (8) and a halogenating agent are reacted to produce a carboxylic acid halide. After preparing (9), the carboxylic acid halide (9) and the amine (10) are synthesized by a condensation reaction.
Reaction formula (1):

(In the formula, R ₁ represents a methyl group, a vinyl group, or a carboxyl group, R ₂ represents a methyl group, a vinyl group, or a halogenated carbonyl group. X ₃ represents a halogen atom. X _{1, X 2,} Y and Z show the _X 1, _{X 2,} as defined and Y and Z in the general formula (1).)
In order to synthesize the amide represented by the general formula (1), first, a carboxylic acid halide (9) is prepared by reacting a carboxylic acid (8) with a halogenating agent.

  Examples of the carboxylic acid (8) include saturated monocarboxylic acids having 8 to 16 carbon atoms such as octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, etc. , 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, etc. 9 To 17 unsaturated monocarboxylic acids such as octanedioic acid, nonanedioic acid, decanedioic acid (sebacic acid), undecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, etc. Examples thereof include 8 to 16 dicarboxylic acids.

  Among these carboxylic acids (8), decanoic acid, 10-undecenoic acid, and decanedioic acid (sebacic acid) are preferable.

  Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like.

  Among these halogenating agents, preferably, thionyl chloride is used.

  The usage-amount of a halogenating agent is 1-8 mass parts with respect to 1 mass part of carboxylic acid (8), for example, Preferably, it is 2-4 mass parts.

  As the reaction conditions of the carboxylic acid (8) and the halogenating agent, the temperature is, for example, 20 to 120 ° C., preferably 60 to 80 ° C. under normal pressure, and the time is 0.5 to 5 hours, for example. Preferably, it is 1 to 3 hours.

  Moreover, you may implement reaction of carboxylic acid (8) and a halogenating agent under recirculation | reflux.

  Further, it can be carried out in either an air atmosphere or an inert gas (nitrogen gas, argon gas) atmosphere.

  Examples of the carboxylic acid halide (9) thus prepared include octanoic acid chloride, nonanoic acid chloride, decanoic acid chloride, undecanoic acid chloride, dodecanoic acid chloride, tridecanoic acid chloride, tetradecanoic acid chloride, pentadecanoic acid chloride, C8-16 saturated monocarboxylic acid chlorides such as hexadecanoic acid chloride, such as 8-nonenoic acid chloride, 9-decenoic acid chloride, 10-undecenoic acid chloride, 11-dodecenoic acid chloride, 12-tridecenoic acid chloride, C9-C17 unsaturated monocarboxylic acid chlorides such as 13-tetradecenoic acid chloride, 14-pentadecenoic acid chloride, 15-hexadecenoic acid chloride, 16-heptadecenoic acid chloride, for example, octanedioic acid dichloride, nonanedioic acid dichloride Decane Acid dichloride (sebacic acid dichloride), undecanoic diacid dichloride, tridecane diacid dichloride, tetradecane diacid dichloride, pentadecanedioic acid dichloride, etc. dicarboxylic acid dichloride of 8-16 carbon atoms such as hexadecanoic diacid dichloride and the like.

  Next, if necessary, excess halogenating agent is distilled off under reduced pressure, for example, and then the prepared carboxylic acid halide (9) and amine (10) are subjected to a condensation reaction in a reaction solvent. Thus, the amide compound represented by the general formula (1) is synthesized.

  More specifically, for example, a carboxylic acid halide (9) and an amine (10) are dissolved in a reaction solvent to prepare a carboxylic acid halide solution and an amine solution. Add the chemical solution dropwise.

  Amine (10) is a primary or secondary amine, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, aniline, toluidine, ethylaniline, xylidine. Primary amines such as pyrrolidine, pyrrole, pyrazolidine, imidazolidine, pyrazole, imidazole, thiazolidine, oxazolidine, 2-methylpyrrolidine, piperidine, piperazine, morpholine Secondary amines having 4 to 18 carbon atoms such as thiomorpholine and 2-methylpiperazine.

  Of these amines (10), toluidine, xylidine, and piperidine are preferable, and piperidine is more preferable.

  Examples of the reaction solvent include low polar solvents such as diethyl ether, chloroform, ethyl acetate, and methylene chloride, and aprotic polar solvents such as tetrahydrofuran (THF), acetonitrile, propionitrile, N, N-dimethylformamide, and dimethyl sulfoxide. Etc.

  These reaction solvents may be used alone or in combination.

  Of these reaction solvents, tetrahydrofuran (THF) is preferable.

  The usage-amount of the reaction solvent with respect to a carboxylic acid halide solution is 300-4000 mL with respect to 1 mol of carboxylic acid (8) used as the raw material of carboxylic acid halide, Preferably, it is 500-2000 mL.

  The usage-amount of the reaction solvent with respect to an amine solution is 200-4000 mL with respect to 1 mol of amine (10), Preferably, it is 300-2000 mL.

  Moreover, the density | concentration of an amine solution is 0.1-5 mmol / mL, for example, Preferably, it is 0.5-3 mmol / mL.

  The usage-amount of the reaction solvent with respect to a carboxylic acid halide solution and an amine solution is 100-4000 mass parts with respect to 100 mass parts of total of carboxylic acid (8) and amine (10), Preferably, it is 300-2000 mass. Part.

  As the reaction conditions for the carboxylic acid halide (9) and the amine (10), under normal pressure, the temperature is, for example, 20 to 120 ° C., preferably 50 to 80 ° C., and the time is, for example, 0.5 to 5 Time, preferably 1 to 4 hours.

  Further, the condensation reaction between the carboxylic acid halide (9) and the amine (10) may be carried out under reflux. Further, it can be carried out in either an air atmosphere or an inert gas (nitrogen gas, argon gas) atmosphere.

  The mixing ratio of the carboxylic acid (8) and the amine (10) is, for example, 40 to 300 parts by mass, preferably 50 to 200 parts by mass of the amine (10) with respect to 100 parts by mass of the carboxylic acid (8). It is.

  Moreover, as for the ratio of the carboxyl group and amine (10) which carboxylic acid has, amine (10) is 1-4 equivalent with respect to 1 equivalent of carboxyl groups, Preferably, it is 1-2 equivalent.

  The reaction product (crude product) obtained by the above synthesis reaction contains impurities in addition to the amide compound represented by the general formula (1), but can be used as it is, and has undergone isolation and purification. It can also be used above.

  The reaction product can be separated by known separation means such as concentration, vacuum concentration, distillation, fractional distillation, solvent extraction, liquid conversion, phase transfer, chromatography, crystallization, recrystallization (if necessary, single These can be isolated and purified by repeating the separation and purification by the separation means, or by combining the separation and purification by two or more separation means.

  The yield of the amide compound synthesized in this way is, for example, 60 to 100%, preferably 70 to 100%, based on the carboxylic acid (8) used in the reaction.

  The amide compound represented by the above general formula (1) synthesized in this way exhibits an anti-ant effect, and therefore can be used as an active ingredient of the anti-anticide of the present invention.

  When such an amide compound is used as an active ingredient of the termite-proofing agent of the present invention, it is not particularly limited, and the above-mentioned amide compound may be blended alone or in combination of two or more. Also good.

  Moreover, the termite-proofing agent of the present invention may be appropriately formulated by a known method.

  Examples of the dosage form include, for example, a solution, a wettable powder, a suspension, a dispersant, an oil formulation for emulsification, an oily formulation, a lotion, etc., such as a powder or granular carrier. Solid agents such as powders and granules, for example, microcapsules, for example, semi-solid agents such as pastes and creams, for example, sprays, aerosols and the like can be mentioned.

  For example, in order to prepare the antifungal agent of the present invention as a liquid (solution, wettable powder, suspending agent, dispersing agent, emulsifying oil preparation, oily preparation, lotion, etc.), for example, the amide compound is described below. So that it may be contained in a solvent, and if necessary, a dispersion stabilizer, an emulsifier, etc. are blended according to the form of the liquid agent, and if necessary, a thickener, an antifreezing agent, a preservative, What is necessary is just to mix | blend well-known additives, such as a mold agent and a specific gravity regulator.

  The solvent used for preparing the liquid agent is not particularly limited as long as it can dissolve or disperse the amide compound. For example, water, for example, methanol, ethanol, 1-propanol, 2-propanol Alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tripropylene glycol monomethyl Glycols such as ethers, e.g., acetone, methyl ethyl ketone and methyl isobutyl ketone, for example, 1,4-dioxane, and the like ethers such as tetrahydrofuran (THF). These solvents may be used alone or in combination.

  Of these solvents, acetone and diethylene glycol monomethyl ether are preferable.

  Examples of the solvent for preparing an anti-anticide in an oil formulation for emulsification, an oily formulation, or a lotion include, for example, dialkyl adipate (specifically, for example, dioctyl adipate, diisooctyl adipate, dinonyl adipate, Diisononyl adipate, didecyl adipate, didodecyl adipate, ditetradecyl adipate, dihexadecyl adipate, dioctadecyl adipate, decylisooctyl adipate, etc.), citrate esters (specifically, for example, acetyltributyl citrate, citrate Carboxylic acid alkyl esters such as acetyl triethyl and triethyl citrate) and alkyl acetates (specifically, for example, ethyl acetate and butyl acetate), aliphatic such as hexane, cyclohexane, octane and decane Hydrogen fluorides, for example, aromatic hydrocarbons such as benzene, toluene, xylene, alkylene glycol esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, for example, acetone, methyl ethyl ketone , Ketones such as methyl isobutyl ketone, for example, ethers such as 1,4-dioxane, tetrahydrofuran (THF), for example, alcohols such as hexanol, octanol, benzyl alcohol, furfuryl alcohol, such as ethylene glycol, diethylene glycol, Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and other glycols Halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,1,1-trichloroethane, chlorobenzene, dichlorobenzene, such as N-methylpyrrolidone, N, N-dimethylaniline, pyridine, acetonitrile, dimethyl Nitrogen-containing compounds such as formamide, for example, petroleum-based solvents such as alkylcycloparaffins, oils such as rapeseed oil, such as exon naphth No. 7. Exxon naphtha no. 6. Aliphatic organic solvents such as Exol D80, Aipa-L, Aipa-M, Aipah-H (exxon chemical), for example, Solvesso 150, Solvesso200 (exxon, chemical), Japan Aromatic organic solvents such as Stone Hyzol SAS296 ("Nisseki Hyzol" is a registered trademark), Nisseki Hyzol SAS-LH, Alkene L (Nippon Petrochemical Co., Ltd.), PAD (Nikko Oil Co., Ltd.), etc. Can be mentioned. These solvents may be used alone or in combination.

  Among these solvents, diisononyl adipate, diethylene glycol monomethyl ether, alkene L, and rapeseed oil are preferable, and diisononyl adipate, ethylene glycol monomethyl ether, and alkene L or rapeseed oil are more preferable.

  Examples of dispersion stabilizers and emulsifiers used in the preparation of suspensions, dispersants, emulsified oil preparations and the like include conventionally known surfactants such as nonionic surfactants, cationic surfactants, and anionic surfactants. Is mentioned.

  Nonionic surfactants include, for example, polyoxyethylene sorbitan fatty acid esters (for example, trade name: Leodole TW-O120V (“Reodol” is a registered trademark), manufactured by Kao Corporation), polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether. (For example, trade name: NAROACTY CL100 (“NAROACTY” is a registered trademark), manufactured by Sanyo Chemical Co., Ltd.), polyethylene oxide / polypropylene oxide copolymer (for example, trade name: NAROACTY NH100, manufactured by Sanyo Chemical Co., Ltd.), poly Oxyethylene alkyl aryl ether, polyoxyethylene phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyalkylene styryl phenyl ether (for example, trade name: New Calgen CP80 (“Calgen” Registered trademark), New Calgen CP120, Takemoto Yushi Co., Ltd.), aliphatic polyhydric alcohol ester, aliphatic polyhydric alcohol polyoxyethylene, sucrose fatty acid ester, block copolymer of ethylene oxide and propylene oxide, and the like. .

  Among these nonionic surfactants, polyoxyalkylene alkyl ethers (for example, trade name: NAROACTY CL100, manufactured by Sanyo Kasei Co., Ltd.) are preferable.

  Examples of the cationic surfactant mainly include quaternary ammonium salts. Specifically, for example, alkyls such as octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, stearyltrimethylammonium chloride (C8 to C18). ) Trimethylammonium halides such as dialkyl (C8 to C18) dimethylammonium halides such as octadecyldimethylammonium chloride, dioctyldimethylammonium chloride, octyldodecyldimethylammonium chloride, and the like.

  Also, mixtures having mixed alkyl groups derived from fats and oils, such as alkyl (C8 to C18) trimethylammonium salts, dialkyl (C8 to C18) dimethylammonium salts, alkyl (C8 to C18) dimethylbenzylammonium salts (for example, trade names) : Sanizole C ("Sanisol" is a registered trademark), manufactured by Kao Corporation).

  Examples of the anionic surfactant include metal soaps, sulfate esters such as alkyl sodium sulfate, alkyl benzene sulfonates such as sodium alkyl benzene sulfonate, alkyl naphthalene sulfonates such as sodium alkyl naphthalene sulfonate, and 2-sulfosuccinic acid. Examples include 2-sulfosuccinic acid dialkyl salts such as dialkyl sodium, polycarboxylic acid type surfactants, α-olefin sulfonates, polyoxyethylene distyrenated phenyl ether sulfate ammonium salts, sodium lignin sulfonate, potassium lignin sulfonate, and the like. It is done.

  The above surfactants may be used alone or in combination.

  The blending ratio of the surfactant is not particularly limited, but is, for example, 50 parts by mass or less, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the above-mentioned termite-proofing agent.

  Although it does not specifically limit as a thickener, For example, polyoxyethylene fatty acid ester, sodium polyacrylate, polyvinyl alcohol, xanthan gum etc. are mentioned.

  The blending ratio of the thickener is not particularly limited, but is, for example, 50 parts by mass or less, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the above-mentioned termite-proofing agent.

  Antifreezing agents, antiseptics, fungicides, specific gravity regulators and the like are not particularly limited, and include known additives used for each application.

  In order to prepare the above termicidal agent as a solid agent (powder, granule, etc.), for example, the above amide compound is stirred and mixed with a powdery or granular carrier so as to have a content ratio described later. Alternatively, the above amide compound is blended in a solvent so as to have a content ratio described later, and if necessary, a known additive such as a thickener, an antifreezing agent, a preservative, or a specific gravity regulator is blended appropriately. After preparing the suspension, the resulting suspension is dried. Further, the suspension may be powdered or granulated by spray drying.

  Examples of the powder or granular carrier include resin fine particles (for example, synthetic resin fine particles “Gantz Pearl” series (“Gantz Pearl” is a registered trademark) manufactured by Gantz Kasei Co., Ltd.), etc.), fine powder silica, perlite (obsidian and pearls). White granular foam produced by heat-treating rock at high temperature), zeolite, diatomaceous earth, clay, talc, acid clay, activated carbon, calcium carbonate, wood powder, powdered cellulose, starch, saccharides and the like.

  In addition, in order to prepare the above-mentioned termite-proofing agent as a microcapsule, the above amide compound can be prepared by, for example, interfacial polymerization method, in situ polymerization method (interfacial reaction method), coacervation method, submerged drying method, melt dispersion cooling. Microencapsulation may be performed by a method such as a coating method, a liquid-cured coating method, a coating method (in-air suspension method), a spray-drying method, an electrostatic coalescence method, or a vacuum deposition method (for example, Japanese Patent Laid-Open No. 61-249904). No. 6-92282, JP-B-6-92283, JP-A-10-114608, JP-A-2000-247821).

  Liquid dispersion or paste containing microcapsules by appropriately adding known additives such as thickeners, antifreezing agents, preservatives, specific gravity regulators, etc., to the dispersion containing the microcapsules thus obtained, if necessary. An anti-anticide can be obtained. Further, by drying the dispersant containing the microcapsules, it is possible to obtain an antifungal agent as a powder or granule composed of the microcapsules.

  In order to prepare the above-mentioned ant preventive agent as a semi-solid agent (paste agent, cream, etc.), the above amide compound is blended in an excipient for forming a paste or cream so as to have a content ratio described later. Further, if necessary, known additives such as thickeners, antifreezing agents, preservatives, and specific gravity regulators may be appropriately blended.

  In order to prepare the above-mentioned ant-preventing agent as a spray, the amide compound is blended in a solvent so as to have a content ratio described below, and if necessary, a thickener, an antifreezing agent, an antiseptic, and a specific gravity adjustment. What is necessary is just to mix | blend well-known additives, such as an agent, and to accommodate in containers, such as a sprayer and a spray container.

  In order to prepare the above-mentioned antifungal agent as an aerosol agent, the above amide compound and, if necessary, a known additive such as a thickener, an antifreezing agent, an antiseptic, or a specific gravity adjusting agent are blended in a solvent. What is necessary is just to accommodate with an aerosol container with a propellant.

  Examples of the solvent used for preparing the solid agent, microcapsule agent, aerosol agent and the like include the same solvents as those described above as the solvent used for preparing the liquid agent.

  A dispersion stabilizer, an emulsifier, a thickener, an antifreezing agent, an antiseptic, a fungicide, a specific gravity adjuster, and the like are not particularly limited, and examples thereof include known additives used for each application.

  In addition, in order to prepare the above-mentioned ant-preventing agent as a supporting agent, known amide compounds, powdered or granular carriers, and, if necessary, known thickeners, antifreezing agents, preservatives, specific gravity adjusting agents, etc. An additive may be blended so that the amide compound has a content ratio described later, and these blended components may be stirred and mixed.

  In the above termiticide, the content of the amide compound is not particularly limited. It is.

  In addition to the amide compound, other termite control components may be blended in the above-mentioned termite-proofing agent.

  Other termite control components include, for example, neonicotinoid compounds, pyrethroid compounds, organochlorine compounds, organophosphorus compounds, carbamate compounds, pyrrole compounds, phenylpyrazol compounds, oxadiazine compounds, semicarbazone compounds Examples thereof include compounds, plants, processed products or derivatives thereof.

  Among these other termite control components, neonicotinoid compounds are preferable.

Examples of neonicotinoid compounds include (E) -1- (2-chlorothiazol-5-ylmethyl) -3-methyl-2-nitroguanidine (generic name: clothianidin), N-acetyl-N- (2 -Chlorothiazol-5-yl) methyl-N'-methyl-N "-nitroguanidine, N- (2-chlorothiazol-5-yl) methyl-N-me (toxoxycarbonyl-N'-methyl-N"- Nitroguanidine, 1- (6-chloro-3-pyridylmethyl) -N-nitroimidazoline-2-ylideneamine (generic name: imidacloprid), 3- (2-chloro-thiazol-5-ylmethyl) -5- [1, 3,5] oxadiazinan-4-ylindene-N-nitroamine (generic name: thiamethoxam), (RS) -1-methyl-2-nitro-3- (tetrahydro B-3-furyl methyl) guanidine (common name: dinotefuran) and the like.
These neonicotinoid compounds may be used alone or in combination.

  Examples of the organic chlorine compound, the organic phosphorus compound, the carbamate compound, the pyrrole compound, the phenylpyrazole compound, the oxadiazine compound, and the semicarbazone compound include various compounds known as an antifungal agent.

  As a plant or its processed material, or its derivative (s), what was described in Unexamined-Japanese-Patent No. 2002-307406, Unexamined-Japanese-Patent No. 2003-252708, and Unexamined-Japanese-Patent No. 2005-74776 is mentioned, for example.

  The above-mentioned termite-proofing agent can be widely used for purposes such as extermination of termites and prevention of damage caused by termites (eg food damage).

  Although it does not specifically limit as a site | part which controls a termite, For example, soil (ground surface etc.), for example, timber, for example, a building (building; ie, a house, a warehouse, a gate, a fence, and these auxiliary equipment etc.) The base structure part, the upper structure part, and the underground structure part, for example, an underground buried object as an accessory of a building, for example, a termite inhabiting / occurrence area.

  Furthermore, it can be used as a treating agent for soil, or as a treating agent for various kinds of wood used for general industrial or civil engineering industries.

  The method of using an anti-anticide formulated as a liquid agent, solid agent, microcapsule agent, semi-solid agent, spray agent, aerosol agent or carrier is not particularly limited. For example, what is necessary is just to spray on the wood etc. which are the process target.

More specifically, for example, when the amide compound as an active ingredient is contained at a ratio of 1 to 20% by mass and prepared as a liquid agent, the surface of the wood is used by using a power sprayer or a manual sprayer. May be sprayed at 50 to 500 g / m ² .

  Even when spraying the solid agent, microcapsule agent, semi-solid agent, spray agent, aerosol agent or support agent containing the amide compound in an amount of 1 to 20% by mass as an active ingredient on the surface of wood, What is necessary is just to spray by the amount mentioned above.

When spraying the termite-proofing agent on the soil, it varies depending on the spraying conditions and the form of the preparation, but in the case of full spraying, it is about 0.5-5 L / m ² and in the case of strip-shaped spraying, it is about 3-10 L / m. ² can be applied.

  The target to be controlled by the above-mentioned termiticide is not particularly limited except that it is an insect belonging to the termite (Isoptera) order. Examples include those belonging to the family of termites, and those belonging to the family of white-tailed termites such as the American white-tailed termite and the white-tailed termite.

  Note that termite control (termite extermination and termite damage prevention) includes not only ant killing (termite killing), but also avoidance and feeding inhibition.

  The termite-proofing agent of the present invention contains an amide compound represented by the above general formula (1) as an active ingredient.

  The amide compound represented by the general formula (1) is synthesized by, for example, condensing a carboxylic acid halide and an amine without inducing isolation and purification after derivatizing the carboxylic acid into a carboxylic acid halide. The

  That is, the amide compound represented by the general formula (1) can be easily synthesized by a one-step synthesis process without isolating and purifying the intermediate product.

  Therefore, it can be easily synthesized, and the yield can be improved without causing a decrease in yield due to the isolation and purification of the intermediate product.

  The raw materials for the amide compound represented by the general formula (1) are all inexpensive carboxylic acids, halogenating agents and amines.

  Therefore, the termite-proofing agent of the present invention can exhibit an excellent termite-proofing effect and can reduce the manufacturing cost.

  Next, although a synthesis example and an Example are given and this invention is demonstrated in more detail, this invention is not limited by these synthesis examples and Examples.

Synthesis example 1
To 10-undecenoic acid (3.7 g, 0.02 mol) was added thionyl chloride (8 mL), and the mixture was refluxed on a water bath for 2 hours. Thereafter, excess thionyl chloride was distilled off under reduced pressure to obtain 10-undecenoic acid chloride.

  Subsequently, 10-undecenoic acid chloride was dissolved in tetrahydrofuran (THF) (20 mL) to prepare a carboxylic acid chloride solution.

  On the other hand, piperidine (3.4 g, 0.04 mol) was dissolved in THF (30 mL).

  And the piperidine solution was dripped at the carboxylic acid chloride solution, and it was set as the reaction liquid.

  The reaction solution was refluxed on a water bath for 3 hours, and then the THF in the reaction solution was distilled off under reduced pressure.

  Next, water and ethyl acetate were added to the reaction solution for partitioning, and the ethyl acetate layer was separated. The ethyl acetate layer was washed once with water, and then ethyl acetate was distilled off to obtain a crude product.

The crude product was purified by silica gel column chromatography (developing solvent: chloroform) to give 1- (piperidin-1-yl) undec-10-en-1-one (C ₁₆ H ₂₉ NO) (in formula 3 above). Was obtained as a light brown oil.

Molecular weight (MW): 251, Yield: 4.2 g, Yield: 84%
Electron collision mass spectrum (EIMS) m / z (%): 251 (M ⁺ , 13), 210 (8), 140 (27), 127 (100), 84 (23)
Synthesis example 2
To decanedioic acid (sebacic acid) (3 g, 0.015 mol) was added thionyl chloride (5 mL), and the mixture was refluxed for 2 hours on a water bath. Thereafter, excess thionyl chloride was distilled off under reduced pressure to obtain decanedioic acid dichloride.

  Subsequently, decanedioic acid dichloride was dissolved in tetrahydrofuran (THF) (20 mL) to prepare a carboxylic acid chloride solution.

  On the other hand, piperidine (5.1 g, 0.06 mol) was dissolved in THF (30 mL).

  And the piperidine solution was dripped at the carboxylic acid chloride solution, and it was set as the reaction liquid.

  The reaction solution was refluxed on a water bath for 3 hours, and then the THF in the reaction solution was distilled off under reduced pressure.

  Next, water and ethyl acetate were added to the reaction solution for partitioning, and the ethyl acetate layer was separated. The ethyl acetate layer was washed once with water, and then ethyl acetate was distilled off to obtain a crude product.

The crude product was purified by silica gel column chromatography (developing solvent: chloroform) to give 1,10-di (piperidin-1-yl) decane-1,10-dione _{(C 20 H 36 N 2 O} 2) ( (Corresponding to the above chemical formula 4) was obtained as colorless crystals.

Molecular weight (MW): 336, Yield: 4.1 g, Yield: 76%, Melting point: 50-53 ° C.
EIMS m / z (%): 336 (M ⁺ , 21), 252 (19), 210 (96), 140 (41), 127 (57), 84 (100)
Synthesis example 3
To decanoic acid (3.5 g, 0.02 mol) was added thionyl chloride (8 mL) and refluxed in a water bath for 2 hours. Thereafter, excess thionyl chloride was distilled off under reduced pressure to obtain decanoic acid chloride.

  Subsequently, decanoic acid chloride was dissolved in tetrahydrofuran (THF) (20 mL) to prepare a carboxylic acid chloride solution.

  On the other hand, p-toluidine (2.1 g, 0.02 mol) was dissolved in THF (30 mL).

  And p-toluidine solution was dripped at the carboxylic acid chloride solution, and it was set as the reaction liquid.

  The reaction solution was refluxed on a water bath for 3 hours, and then the THF in the reaction solution was distilled off under reduced pressure.

  Next, water and ethyl acetate were added to the reaction solution for partitioning, and the ethyl acetate layer was separated. The ethyl acetate layer was washed once with water, and then ethyl acetate was distilled off to obtain a crude product.

The crude product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain Np-tolyldecanamide (C ₁₇ H ₂₇ NO) (corresponding to the above chemical formula 5) as colorless needle crystals. .

Molecular weight (MW): 261, Yield: 4.0 g, Yield: 77%, Melting point: 74-75 ° C.
EIMS m / z (%): 261 (M ⁺ , 12), 149 (10), 107 (100)
Synthesis example 4
To decanoic acid (3.5 g, 0.02 mol) was added thionyl chloride (8 mL) and refluxed in a water bath for 2 hours. Thereafter, excess thionyl chloride was distilled off under reduced pressure to obtain decanoic acid chloride.

  Subsequently, decanoic acid chloride was dissolved in tetrahydrofuran (THF) (20 mL) to prepare a carboxylic acid chloride solution.

  On the other hand, 2,6-xylidine (3.6 g, 0.03 mol) was dissolved in THF (30 mL).

  Then, the 2,6-xylidine solution was dropped into the carboxylic acid chloride solution to obtain a reaction solution.

  The reaction solution was refluxed on a water bath for 3 hours, and then the THF in the reaction solution was distilled off under reduced pressure.

  Next, water and ethyl acetate were added to the reaction solution for partitioning, and the ethyl acetate layer was separated. The ethyl acetate layer was washed once with water, and then ethyl acetate was distilled off to obtain a crude product.

The crude product was purified by silica gel column chromatography (developing solvent: chloroform) to give N- (2,6-dimethylphenyl) decanamide (C ₁₈ H ₂₉ NO) (corresponding to the above chemical formula 6) as colorless needles. Obtained as crystals.

Molecular weight (MW): 275, Yield: 4.5 g, Yield: 82%, Melting point: 83-85 ° C.
EIMS m / z (%): 275 (M ⁺ , 11), 163 (9), 121 (100)
Synthesis example 5
To decanoic acid (3.5 g, 0.02 mol) was added thionyl chloride (8 mL) and refluxed in a water bath for 2 hours. Thereafter, excess thionyl chloride was distilled off under reduced pressure to obtain decanoic acid chloride.

  Subsequently, decanoic acid chloride was dissolved in tetrahydrofuran (THF) (20 mL) to prepare a carboxylic acid chloride solution.

  Meanwhile, 2,3-xylidine (3.6 g, 0.03 mol) was dissolved in THF (30 mL).

  Then, the 2,3-xylidine solution was dropped into the carboxylic acid chloride solution to obtain a reaction solution.

  The reaction solution was refluxed on a water bath for 3 hours, and then the THF in the reaction solution was distilled off under reduced pressure.

  Next, water and ethyl acetate were added to the reaction solution for partitioning, and the ethyl acetate layer was separated. The ethyl acetate layer was washed once with water, and then ethyl acetate was distilled off to obtain a crude product.

The crude product was purified by silica gel column chromatography (developing solvent: chloroform) to give N- (2,3-dimethylphenyl) decanamide (C ₁₈ H ₂₉ NO) (corresponding to the above chemical formula 7) as colorless needles. Obtained as crystals.

Molecular weight (MW): 275, Yield: 3.9 g, Yield: 71%, Melting point: 86-87 ° C.
EIMS m / z (%): 275 (M ⁺ , 12), 163 (9), 121 (100)
Example 1
1- (Piperidin-1-yl) undec-10-en-1-one synthesized in Synthesis Example 1 was diluted with acetone to prepare a concentration of 10 mg / mL (10000 ppm). An ant agent (liquid agent) was obtained.

Example 2
1,10-di (piperidin-1-yl) decane-1,10-dione synthesized in Synthesis Example 2 was diluted with acetone to prepare a concentration of 10 mg / mL (10000 ppm), An anti-anticide (liquid agent) was obtained.

Example 3
The Np-tolyldecanamide synthesized in Synthesis Example 3 was diluted with acetone to prepare a concentration of 10 mg / mL (10000 ppm) to obtain an antifungal agent (liquid agent).

Example 4
N- (2,6-dimethylphenyl) decanamide synthesized in Synthesis Example 4 is diluted with acetone to prepare a concentration of 10 mg / mL (10000 ppm) to obtain an anti-anticide (liquid agent). It was.

Example 5
N- (2,3-dimethylphenyl) decanamide synthesized in Synthesis Example 5 is diluted with acetone to prepare a concentration of 10 mg / mL (10000 ppm) to obtain an antifungal agent (liquid agent). It was.

Test example (ant resistance test)
The termiticide prepared in Examples 1-5, respectively, a filter paper having a diameter of 12 mm (2 kinds (No.2: _{JIS P3801 -1995))} with respect to added drop by 40 [mu] L, air-dried, the weight of the filter paper It was measured.

  Next, 50 gites of termites (Coptothermes formosanus) and filter paper soaked with each of the termite-proofing agents prepared in Examples 1 to 5 were put into a glass bottle filled with 50 g of silica sand No. 5 having a water content of 12%. Then, the ant defense resistance test was started. At that time, the glass bottle was covered so that termites did not escape to the outside.

  From the start of the ant defense test (introduction of the termites and the filter paper into the glass bottle), the test pieces were left for 21 days. After 21 days from the start of the test, the behavior of the termites in the glass bottle was observed.

Further, as a control, instead of the filter paper impregnated is termiticide, filter paper that is not impregnated with termiticide (diameter 12 mm, 2 kinds (No.2: _{JIS P3801 -1995))} except for using the above The behavior of the termites in the glass bottle was observed in the same manner as in the ant defense resistance test.

  The mortality rate after 21 days from the start of the ant defense resistance test and the feeding damage rate of the filter paper were measured, and Table 1 shows the results of the ant defense resistance test.

  The death rate is calculated based on the number of the termites before the start of the ant resistance test (50) against the number of the termites before the start of the ant resistance test. It is a percentage of the reduced value.

  Moreover, the corrosion rate of the filter paper is calculated based on the mass (g) of the filter paper before the start of the ant defense resistance test, compared to the mass (g) of the filter paper before the start of the ant defense resistance test. ) Is the percentage of the value.

Claims (4)

An ant-preventing agent comprising an amide compound represented by the following general formula (1) as an active ingredient .
General formula (1):

(Wherein one of X ₁ and X ₂ represents a phenyl group which may have a location substituent, the other is a hydrogen atom. Or, X ₁ and X ₂ are bonded to each other Te may be formed good piperidine ring which may have a substituent .Y is .Z showing an alkylene group having 6 to 14 carbon atoms, represented by a methyl group, a vinyl group or a group represented by the general formula (2) Represents a substituent.
General formula (2):

(Wherein, _{X 1} and _{X 2} are as defined for _{X 1} and _{X 2} in the general formula (1).) In the general formula (1), Z represents a vinyl group or a piperidine ring represented by the general formula (2), and X ₁ and X ₂ may be bonded to each other to have a substituent. The termite-proofing agent according to claim 1, which is a substituent to be formed. In the said General formula (1), Y is a C8-C10 alkylene group, The termite-proofing agent of Claim 1 or 2 characterized by the above-mentioned. A method for preventing ants, comprising using the ant preventive agent according to any one of claims 1 to 3 .