WO1998031228A1 - Industrial antimicrobial/mildew-proofing agents, algicides and antifouling agents containing n-quinoxalylanilines - Google Patents

Industrial antimicrobial/mildew-proofing agents, algicides and antifouling agents containing n-quinoxalylanilines Download PDF

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Publication number
WO1998031228A1
WO1998031228A1 PCT/JP1998/000208 JP9800208W WO9831228A1 WO 1998031228 A1 WO1998031228 A1 WO 1998031228A1 JP 9800208 W JP9800208 W JP 9800208W WO 9831228 A1 WO9831228 A1 WO 9831228A1
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WIPO (PCT)
Prior art keywords
cfs
quinoxalyl
group
quinoxalylaniline
atom
Prior art date
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PCT/JP1998/000208
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French (fr)
Japanese (ja)
Inventor
Shinichi Igarashi
Mitsugu Futagawa
Original Assignee
Nissan Chemical Industries, Ltd.
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Publication date
Application filed by Nissan Chemical Industries, Ltd. filed Critical Nissan Chemical Industries, Ltd.
Priority to AU55747/98A priority Critical patent/AU5574798A/en
Priority to NZ336826A priority patent/NZ336826A/en
Priority to CA002278244A priority patent/CA2278244A1/en
Publication of WO1998031228A1 publication Critical patent/WO1998031228A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/50—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to ring nitrogen atoms
    • C07D241/52—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring

Definitions

  • the present invention relates to an antibacterial and antifungal agent and an algicidal agent for a product, and an antibacterial and antifungal agent used in the manufacturing process of the product and water for preventing harmful aquatic organisms such as shellfish from adhering. It relates to a biofouling inhibitor. Background technology ''
  • Industrial antibacterial and antifungal agents and algicides are used to eliminate various adverse effects caused by the growth and proliferation of bacteria, fungi, and fungi in various industrial products and facilities.
  • organic nitrogen compounds, organic nitrogen compounds, organic halogen compounds, nitrogen-containing aliphatic polymers and heavy metal coordination compounds have been used. I have.
  • Biofouling prevention il ⁇ is used for equipment installed in the sea, such as fishing nets, ship bottoms, buoys, etc., marine structures, thermal or nuclear power generation cooling water systems, chemical industry heat exchanger glue water paths, underwater It is used to prevent harmful aquatic organisms such as shellfish from attaching to structures or reservoirs.
  • Japanese Patent Application Laid-Open No. 60-97764 discloses an N-quinoxalylaniline-based compound, a method for producing the compound, a disinfectant for agricultural and horticultural use, and a use as an acaricide.
  • the compounds described as industrial antibacterials, anti-capi, algicides, and biofouling inhibitors are irritating agents and pose problems in the Labor Safety Act.
  • organotin compounds as an anti-fouling agent are effective in preventing the adhesion of aquatic organisms, they are highly toxic, and especially remarkably accumulate in fish and shellfish in the body. It has become.
  • Triphenyltin compounds and triptyltin compounds are classified as Class 1 substances. ⁇ Specified as a substance and its use is prohibited for fishing nets.
  • ⁇ ⁇ copper is widely used for anti-fouling for 3 ⁇ 47 road and ship bottom, but tinned ⁇ ! As it contains copper, which is a heavy pot, it is not a preferred agent for controlling the adhesion of underwater organisms due to concerns about ⁇ staining.
  • f ⁇ is an industrial antibacterial / anti-capi, a ⁇ agent and a biofouling preventive for N-quinoxalylaniline. ⁇ There is no mention that it is valid as ⁇ . Disclosure of the invention
  • the present inventors have conducted intensive studies to solve the above problem, and as a result, have found that ⁇ -quinoxalyl diamines have a high level of safety and a low dose of a wide range of drugs due to their ability to prevent dyeing.
  • the present invention has been found to be ih ⁇ J, which is a highly practical industrial antibacterial, anti-capi, ⁇ agent and biofouling inhibitor which expresses a tram.
  • the present invention provides (1):
  • R 1 and R 2 are each a hydrogen atom, a halogen atom, a trifluoro ⁇ -methyl atom «[an alkyl group of 1-5, an alkoxy group of an atom 1-5 Or a nitro group
  • R 3 represents a hydrogen atom, a halogen atom or an alkyl group of Linbara 1-5
  • R 4 represents a hydrogen atom, an alkyl group 1-5, an alkenyl group 2-6
  • An alkylsulfenyl group of the formula H-2 which may be substituted with an alkynyl group of the formulas 2-6, an alkylcarbonyl group of the formula 2-6, an alkylsulfonyl group of the formula 15 or a halogen atom
  • Y are each independently substituted with a nitro group, a trifluoromethylol group or a halogen atom
  • Z is substituted with a hydrogen atom, a ⁇ -gen atom, an alkoxy
  • m and n each independently represent 0 or 1, but m and n do not represent 1 at the same time.
  • J and k each independently represent 0, 1, 2 or 3, and j + k always represents 3 or less.
  • Halogen atoms include fluorine, chlorine, bromine and iodine.
  • the alkyl groups of the original 1-5 include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, S-butyl, t-butyl, 1-pentyl, 2-pentyl, 3-pentyl Pentyl, i-pentyl, neo-pentyl, t-pentyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 'cyclobutyl, cyclopipentyl and the like.
  • alkenyl group of Regen 2-6 examples include ethenyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl.
  • Phenyl 1-methyl-2-propyl succinyl, 2-methyl-2-butanol, 1-ethyl-2-vinyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 , 2-Dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propyl pidinyl, 1-ethyl-2- Pi ⁇ nil, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-1-butenyl, 1-i-propylbutyl, 2,4-pentagenenyl, 1-hexenyl, 2-to Examples include xenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 2,4-hexenyl, 1-methyl-1-pentenyl, and the like.
  • the alkynyl group of the sake brewer 2-6 includes ethynyl, 1-propyl, 2-propynyl, 1-butynyl, 2-butul, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl and the like.
  • Examples of the original alkoxy group include methoxy, ethoxy, II-propoxy, i-propoxy, II-butoxy, i-butoxy, s-butoxy, t-butoxy and pentoxy.
  • Alkylcarbonyl groups having 2 to 6 atoms include methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, i- ⁇ -pyrcarbonyl, ⁇ -butylcarbonyl, i-butylcarbonyl, S-butylcarbonyl, t-butylcarbonyl Butylcarbonyl, 1-pentylcarbonyl, 2-pentylcarbonyl, 3-pentylcarbonyl, i-pentylcarbonyl, neo-pentylcarbonyl, t-pentylcarbonyl, cyclopropyl ⁇ -pill force luponyl, 1-methylcyclopropylcarbonyl, 2-methyl Cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl and the like can be mentioned.
  • alkylsulfonyl group having 1 to 5 atoms examples include methylsulfonyl, ethylsulfonyl, ⁇ -propylsulfonyl, i-propylsulfonyl, n-butylsulfonyl, i-butylsulfonyl, s-butylsulfonyl, t-butylsulfonyl, 1-pentylsulfonyl, 2-pentylsulfonyl, 3-pentylsulfonyl, i-pentylsulfonyl, neo-pentylsulfonyl, t-pentylsulfonyl, cyclopropylsulfonyl, 1-methylcycl ⁇ -propylsulfonyl, 2-methylcyclopropylsulfonyl , Cyclobutylsulfonyl,
  • alkylsulfenyl group having 1 to 5 atoms examples include methylsulfenyl, ethylsulfenyl, n-propylsulfenyl, i-pipisulfulfenyl, n-butylsulfenyl, and i-butylsulfur Benzyl, s-butylsulfurenyl, t-butylsulfur: Lnil, 1-pentylsulfuryl, 2-pentylsulfuryl, 3-pentylsulfuryl, i-pentylsulfuryl, neo-pentylsulfur Examples include phenyl, t-pentyl sulfenyl, cyclopropylsulfenyl, 1-methylcyclopropyl sulfenyl, 2-methylcyclopropylsulfenyl, cyclobutyls
  • Preferred compounds contained in the industrial antibacterial and antifungal agents, agents and biofouling-preventing active ingredients of the present invention are listed in Tables 1 to 3 below, and the compounds used in the present invention Is not limited to these.
  • Me methyl group
  • E t Echiru group
  • CO e Asechiru group
  • COE t Echiru carbonyl group
  • S0 2 Me methanesulfonyl group
  • Me_ ⁇ methoxy
  • EiO Etokishi group
  • n-Pr 0 normal propoxy Group
  • m-HO-PhO metahydroxyx X-noxy 3 ⁇ 4o
  • HH CH 2 CHCH 2 NO 2 H N0 2 H CFs
  • HH CH 2 CHCH 2 HH NO 2 H CFs
  • H Me CH 2 CHCH 2 NO 2 CI CFs H NO 2
  • Me Me CH 2 CHCH 2 NO 2 CI CFs H NO;
  • MeO Me CH 2 CHCH 2 NO 2 CI CFa H NO
  • N-quinoxalylanilines of the present invention can be usually produced, for example, by the following method (a), (b) or (c) with reference to JP-A-60-97964.
  • Z 1 , Z 2 and Z 3 in the following formula are included in Z in the above “ ⁇ formula (1).
  • R 1 , R 2 , R 8 , X, Y, m, n, j and k are the same as those described above, and Ha 1 is a halogen atom such as a chlorine atom or a fluorine atom; 1 is a hydrogen atom, a hydrogen atom or a halogen atom.
  • Examples of the acid acceptor used for ⁇ J include alkali metal moxides, compounds, hydrides, hydrides or alkali: hydroxides and refractory compounds, and preferably potassium hydroxide, hydrogen And sodium chloride.
  • the above is preferably in an aprotic electrode such as dimethylformamide, dimethylsulfoxide, sulfolane, tetrahydrofuran, dioxane, etc., and a suitable S, e.g. Perform by stirring for 4 hours.
  • an aprotic electrode such as dimethylformamide, dimethylsulfoxide, sulfolane, tetrahydrofuran, dioxane, etc.
  • a suitable S e.g. Perform by stirring for 4 hours.
  • ⁇ 2 represents a chlorine atom, a halogen atom of a bromine atom ⁇ , RR 2 , R 3 , X, Y, m, n, j and k are the same as described above, and Z 8 is It can be substituted with an alkoxy group or a phenoxy group which may be substituted with a halogen atom, a nitro group or a hydroxyl group.
  • the acid acceptor used for this Si core is the same as that which can be used in the method of self (a), and the most frequently used solvents are methanol and ethanol in addition to the aprotic polar solvent of the self Alcohols such as tetrachloride, chloroform, m-dichlorobenzene, etc.
  • reaction time is 0.5 to 2 4 hours Mel.
  • R 4 is an alkylalkenyl group, alkynyl 3 ⁇ 4 ⁇ alkylcarbonyl
  • R 4 represents an alkyl alkenyl alkynyl alkyl carbonyl alkyl sulfonyl group or a alkyl sulfenyl group which may be substituted with a nitrogen atom
  • R 1 , R 2 , R 8 , X, Y , Z, m, n, j and k are the same as described above
  • Ha1 represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom.
  • Examples of the acid acceptor used in this step include tertiary amines, pyridines, and the like in addition to those described in the method of t (a), and hydrogenation is preferable for alkylation, alkenyl alkyne and alkynylation.
  • Sodium is suitable, and triethylamine or pyridine is also suitable.
  • the above ass is defined as the aprotic polar female medium obtained by the method of Ami (a), as well as carbon halides such as tetrachloride, chloroform, m-dichloro ⁇ benzene, or benzene.
  • the reaction is performed in a solvent such as aromatic carbon such as benzene, toluene, or xylene.
  • the reaction temperature is generally 130 to 150 ° C, and the reaction time is 0.5 to 24 hours.
  • the target compound obtained by the methods (a), (b) and (c) can be obtained as a pure product by recrystallization in an appropriate solvent, purification by column chromatography and the like.
  • the quinoxalyl anilines used as the active ingredient in the present invention may be used in the present invention, and the industrial antibacterial and antifungal agent, the paint agent and the biofouling inhibitor of the present invention are used.
  • other known antibacterial agents for industrial use such as anti-capi agents, agents or biofouling preventives can be further contained and used as a mixture.
  • Acid hypochlorite quaternary ammonium compound, arylisothiocyanate, 2-amino-3,4-chloro-1,4-naphthoquinone, ethylenebisbisthiothionate, 2- ⁇ -octyl-3-isothiazolone, glutaraldehyde, 5 —Chloro-2— ⁇ —decyl-1-3-isothiazolone, 5-chloro ⁇ —2,4-difluoro-6-methoxyisophthalonitrile, 2-chloro-1-4-methylamino-1 (5-isopropylamino s-triazine, 5 —Chloro-2-methyl-3-isothiazolone, 2,3-dichloro-1,4-naphthoquinone, jodomethyl- ⁇ -tolylsulfone, ⁇ , ⁇ -dimethyl ⁇ , 1-phenyl— ⁇ , 1 (fluorodichloromethylthio)
  • N-quinoxalylaniline used as the active ingredient in the present invention is composed of a single compound or a mixture of several types of N-quinoxalylanilines. It may be.
  • N-quinoxalyl anilines used as the active ingredient in the present invention may be added to the system for use alone or as a mixture of the active ingredient and a suitable carrier or solvent. Alternatively, it may be formulated as an aqueous emulsion or dispersion.
  • the formulation of the industrial antibacterial and antifungal agent, the algicide and the anti-biofouling agent of the present invention can be generally used in the field of industrial antibacterial, antifungal and algicidal agents.
  • N-quinoxalylanilines are mixed with appropriate carriers and auxiliary agents, such as surfactants, binders, and stabilizers, and mixed, and then wettable powders, emulsions, sols (flowable) Agent) and other suitable dosage forms.
  • the upper limit of the concentration of the active ingredient, N-quinoxalylaniline is limited as long as wettable powders, emulsions, solutions, sols, and other appropriate preparations can be prepared. However, it is incorporated in an amount of 1 to 90% by weight, preferably 3 to 40% by weight based on the weight of these preparations.
  • any solid or liquid can be used as long as it is commonly used for industrial antibacterial and antifungal agents and algicides, and it is not limited to a specific one.
  • solid carriers include mineral powders such as kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, white lime, slaked lime, silica sand, ammonium sulfate, urea, etc., or vegetable Powders, for example, soybean powder, (1), crystalline cellulose, etc., alumina, silicates, sugar polymerization, highly dispersible silicic acid, waxes and the like.
  • mineral powders such as kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, white lime, slaked lime, silica sand, ammonium sulfate, urea, etc.
  • vegetable Powders for example, soybean powder, (1), crystalline cellulose, etc., alumina, silicates, sugar polymerization, highly dispersible silicic acid, waxes
  • liquid carriers examples include water, alcohols, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc., aromatic carbons, for example, benzene, toluene, Xylene, ethylbenzene, benzene, cumene, methylnaphthalene, etc., or nitrogenated carbon dioxide, such as chloroform, dicole, methane, ethylene di- ⁇ -lide, etc., ethers, such as ethyl ether, dioxane, etc.
  • alcohols for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc.
  • aromatic carbons for example, benzene, toluene, Xylene, ethylbenzene, benzene, cumene, methylnaphthalene,
  • Ketones such as tetrahydrofuran, etc., for example, acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc., esters, for example, ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, nitrile, etc.
  • sulfoxides such as dimethyl sulfoxide
  • alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.
  • amines such as Liquefied amines
  • aliphatic and cycloaliphatic hydrogens such as ⁇ -hexane, cyclohexane, etc.
  • industrial gasoline petroleum ether, solvent naphtha, etc.
  • petroleum fractions paraffins, kerosene, , Etc.
  • surfactants are incorporated for the purpose of emulsification, dispersion, solubilization, wetting, foaming, spreading, and the like.
  • examples of such a surfactant include the following, but are not limited thereto.
  • non-ionic surfactants include polyoxetylene alkyl ether, polyoxetylene alkyl ester, polyoxetylene sorbitan alkyl ester, and sorbitan alkyl ester.
  • anionic surfactants include alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate and lauryl sulfate.
  • examples of the cationic surfactant include alkylamines (laurylamine, stearyltrimethylammonium ⁇ -lide, alkyldimethylbenzylammonium ⁇ -lide, etc.), and the like.
  • amphoteric surfactant include carboxylic acid (betaine type) sulfate, and the like.
  • polyvinyl alcohol PVA
  • carboxymethylcellulose CMC
  • gum arabic polyvinyl acetate
  • gelatin casein
  • sodium alginate sodium alginate
  • tragacanth gum guar gum
  • xanthan gum hide ⁇ -xypropylcellulose Thickeners and various auxiliaries
  • UV-absorbing stabilizers such as ID ⁇ IJ can be used.
  • the industrial antibacterial and antifungal agents and algicides of the present invention containing N-quinoxalylanilines as an active ingredient can be used for the following applications.
  • Biofouling prevention containing N-quinoxalylaniline as an active ingredient ll ⁇ includes fishing nets, ship bottoms, buoys and other underwater facilities, sea structures, thermal power plants, and condensate from nuclear power plants Shell cooling water system, chemical industry heat exchange Cooling water ⁇ ⁇ 7 routes, underwater structures such as dam attachments, and mussels such as mussels, fusippo, oysters, hydramushi, hydra, selbra, squirts, mosquitoes and snails to reservoirs etc. It can be used delicately to prevent the adhesion of harmful underwater organisms such as ⁇ , ⁇ and ⁇ .
  • Compound 6-Compound 20 was synthesized in the same manner as in Synthesis Example 1-Synthesis Example 5 and shown in Table 4.
  • Clay 7 3 The above mixture was uniformly mixed and pulverized to obtain a wettable powder containing 20% of active ingredient.
  • the formulated industrial antibacterial and antifungal agents and algicides of the present invention can be obtained by diluting various preparations as they are or by diluting them with an appropriate organic solvent, in various industrial raw materials or products.
  • the method of adding or mixing to the surface of various industrial raw materials or products, or the method of spraying or spraying various industrial raw materials or products on the surface of the industrial antibacterial * antifungal agent and diluent of the present invention It can be used by various methods in accordance with the conventional methods of using industrial antibacterial and antifungal agents and algicides, including the method of immersion. Not limited.
  • the industrial antibacterial agent of the present invention a preparation of an antifungal agent, an algicide and a biofouling inhibitor ii ⁇ lj, is outlined in the application field of biofouling prevention.
  • the N-quinoxallar used as an active ingredient in the present invention Nilins are used after being prepared in the form of paints, solutions, emulsions and the like. For the preparation of these paints, solutions, emulsions, etc., it is possible to adopt the commonly used formula.
  • the underwater biofouling prevention of the present invention is used in the form of an antifouling paint, for example, N-quinoxalylaniline as an active ingredient is blended with a film-forming agent to prepare
  • an antifouling paint for example, N-quinoxalylaniline as an active ingredient is blended with a film-forming agent to prepare
  • oil varnish As a coating film forming agent, oil varnish, synthetic resin, artificial rubber and the like are used.
  • a solvent, a pigment, or the like may be used according to the requirements.
  • the concentration of the active ingredient, N-quinoxalylaniline has no upper limit as long as ⁇ m can be formed, but 1 to 50% by weight based on the weight of the antifouling paint, Preferably, it is blended at a ratio of 5 to 20% by weight.
  • VYHH Vinyl synthetic resin, manufactured by UCC 7
  • the anti-biological adhesion in water of the present invention is used in the form of a solution, for example, a solution in which ⁇ -quinoxalylaniline, which is an effective component, is dissolved in a solvent together with a film-forming agent is prepared. «Adhesion of aquatic organisms by applying to fishing nets, fixed fishing nets, etc. Can be prevented.
  • Synthetic resin, artificial rubber, natural fiber and the like are used for the transformation of the coating film, and xylene, toluene, cumene, methylethylketone, methylisobutylketone, and acetone are used as the solvent.
  • an additive such as a plasticizer may be used according to the requirements.
  • the concentration of the active ingredient, N-quinoxalylaniline has no upper limit as long as a solution can be formed. It is blended at a rate of ⁇ 30%.
  • the emulsion is usually prepared.
  • the desired emulsion can be prepared by adding a surfactant to a solution of N-quinoxalylaniline, which is the active ingredient, in accordance with the “ ⁇ method” used in the preparation of the emulsion.
  • a surfactant to a solution of N-quinoxalylaniline, which is the active ingredient, in accordance with the “ ⁇ method” used in the preparation of the emulsion.
  • the prepared emulsion can be kneaded into a raw material such as a net or a fixed net used in the ocean or water, for example, a polymer resin or the like.
  • the active ingredient N-quinoxalylaniline
  • the active ingredient has no upper limit as long as the emulsion can be formed. It is blended at a ratio of 30.
  • the emulsion of the present invention can be used by adding it to water, storage water, etc. in order to prevent the underwater organisms from adhering to the water in the 7i pipeline or the reservoir for cooling water. Best form to do
  • Bacillus subtilis (Bacillus subtilis) consisted of 125 ml of Bouillon agar medium, 6.6 ml of test bacteria, and Trichophyton mentagrophytes. mentagrophytes) was added to 31.3 ml of the test bacterium to 125 ml of the sub-aperture agar medium, and the mixture was stirred with care so as not to mix with each other, and allowed to flow evenly on the plate to solidify. Next, a certain amount of the compound of the present invention was weighed and diluted with acetone to a predetermined concentration.
  • the prepared sample containing the compound of the present invention at a fixed concentration was impregnated into a paper disk, spread on a filter paper, air-dried, and placed at regular intervals on a plate on which each test bacterium was flowed.
  • Bacillus subtilis was cultured at 37 ° C for 1 and Trichophyton mentagrophytes was cultured for 28 and 3 at a constant temperature incubator.
  • Each ffill: Measured the diameter of the circle and determined the activity » was done.
  • Table 5 shows the results obtained when using a sample having a concentration of 10 ppm. However, the symbols in the table mean the following.
  • a dilution series (20,000, 10 000, 5000, 2500, 1250, 626, 313, 156, 78, 39 mg / 1) of the compound of the present invention was prepared using dimethyl sulfoxide.
  • Sensitive Medium 1 For bacteria, add Sensitive Medium 1
  • 0.5 ml was added to each 9.5 ml of potato dextrose agar medium (Kyosui Pharmaceutical), mixed and poured into a petri dish to form a solidified plate.
  • the concentrations of the compound of the present invention in the agar medium are 1000, 500, 250, 125, 62.5, 31.3, 15.6, 7.8, 3.9, and 2.0 mgZ1, respectively.
  • the inverting bacteria is a bouillon (Nissui Pharmaceutical Co., Ltd.) 37 C ⁇ Culturing for 20 hours.
  • the fungi were cultured on a potato dextrose agar medium (Kisui Pharmaceutical Co., Ltd.) for 10 weeks, and then a suspension of 10 6 CFU / m 1 was prepared.
  • the suspension of the test bacterium was streaked onto a drug-mixed agar plate using a platinum loop, and cultured for 18 to 20 hours at 37 ⁇ 1 C for bacteria and 27 to 7 for fungi.
  • the concentration that could not be seen was defined as the minimum development M degree (IC).
  • a dilution series (20,000, 10 000, 5000, 2500, 1250, 626, 313, 156, 78, 39 mg / 1) of the compound of the present invention was prepared using dimethyl sulfoxide. For this, 0.5 ml was added to each 9.5 ml of a potato dext ⁇ -agar agar medium (Kyosui Pharmaceutical), and 0.5 ml was added and mixed. Into a solidified plate. The concentrations of the compound of the present invention in the agar medium are 1000, 500, 250, 125, 62.5, 31.3, 15.6, 7.8, 3.9 and 2.0 mg / l, respectively. The inoculated bacteria were broth for sensitivity measurement (Nissui Pharmaceutical).
  • a solution of the compound of the present invention having a concentration of 200 OmgZl was prepared using dimethyl sulfoxide, and 1 ml of the sample solution was diluted with 19 ml of sterile tap water to prepare a solution having a concentration of 1 OmgZl.
  • the proliferation rate was determined by measuring the number of cells using a hemocytometer.
  • the growth inhibition rate was calculated from the comparison with the untreated group.
  • the cells were collected by centrifugation, and then methanol was added to disrupt the cells, and chlorophyll was extracted.
  • the growth rate was determined by measuring the amount of chlorophyll from the absorbance using a photometer. The growth inhibition rate was calculated by comparison with the untreated plot.
  • a zone to which only acetone was applied was provided as a blank, and a zone to which 0 mg of copper sulfate was applied was provided as a comparative agent.
  • adhesion control effect was determined in comparison with copper sulfate used as a comparative drug.
  • N-quinoxalylanilines represented by formula (1) are highly safe, exhibit a wide spectrum at low doses, and are suitable for industrial antibacterial, antifungal, algicide and biofouling prevention. Useful as

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Abstract

Industrial antimicrobial/mildew-proofing agents, algicides and antifouling agents containing N-quinoxalylanilines represented by general formula (1), wherein R?1 and R2¿ independently represent each H, halogeno, CF¿3?, C1-5 alkyl, C1-5 alkoxy or NO2; R?3¿ represents H, halogeno or C¿1-5? alkyl; R?4¿ represents H, C¿1-5? alkyl, C2-6 alkenyl, C2-6 alkynyl, C2-6 alkylcarbonyl, C1-5 alkylsulfonyl or optionally halogenated C1-5 alkylsulfenyl; X and Y independently represent each NO2, CF3 or halogeno; Z represents H, halogeno, C1-5 alkoxy or optionally halogenated, nitrated or hydroxylated phenoxy; m and n independently represent each 0 or 1 provided that m and n are not 1 at the same time; and j and k independently represent each 0, 1, 2 or 3, provided that j + k is not more than 3.

Description

明 細 書  Specification
N—キノキザリルァニリン類を含有する工業用抗菌 '抗カピ 、 殺藻剤及び生物 付着防 . 技術分野 Industrial antibacterials containing N-quinoxalylanilins, anti-capi, algicides and biofouling.
本発明は、 ェ讓品の抗菌 ·抗カビ剤及び殺藻剤、 ェ ¾ 品の製造過程で使用 する抗菌 ·抗カビ剤、 剤及び貝類等の有害な水中生物の付着を防止するため の水中生物付着防止剤に関する。 背景技術 '  The present invention relates to an antibacterial and antifungal agent and an algicidal agent for a product, and an antibacterial and antifungal agent used in the manufacturing process of the product and water for preventing harmful aquatic organisms such as shellfish from adhering. It relates to a biofouling inhibitor. Background technology ''
工業用抗菌 ·抗カビ剤及び殺藻剤は、 種々の工業製品及び工業施設での細菌、 真菌及び の生育及び増殖による様々な弊害を除去するために用いられる。 従来、 これらの工業用抗菌.抗カビ剤及び驢剤としては、 有機窒素系化合物、 有機窒素ィォゥ系化合物、 有機ハロゲン系化合物、 含窒素脂肪族ポリマ一及び重 金属配位化合物等が使用されている。  Industrial antibacterial and antifungal agents and algicides are used to eliminate various adverse effects caused by the growth and proliferation of bacteria, fungi, and fungi in various industrial products and facilities. Conventionally, as these industrial antibacterial and antifungal and antifungal agents, organic nitrogen compounds, organic nitrogen compounds, organic halogen compounds, nitrogen-containing aliphatic polymers and heavy metal coordination compounds have been used. I have.
生物付着防 il ^は、 漁網、 船舶の船底、 ブイ等の海中に置かれる設備、 海洋構 築物、 火力又は原子力発漸の徹器冷却水系、 化学工業の熱交換器糊用水の 路、 水中構築物或いは貯水池等に、 貝類等の有害な水中生物が付着するのを 防止するために用いられる。  Biofouling prevention il ^ is used for equipment installed in the sea, such as fishing nets, ship bottoms, buoys, etc., marine structures, thermal or nuclear power generation cooling water systems, chemical industry heat exchanger glue water paths, underwater It is used to prevent harmful aquatic organisms such as shellfish from attaching to structures or reservoirs.
これらの水中生物が^ 9に付着すれば、 網目が詰まり、 海水の の低下に 伴つて難魚の発育が阻害され、 魚病の多発を招く。  If these aquatic organisms attach to ^ 9, the mesh will be clogged and the development of hard-to-fish will be hindered by the decrease in seawater, resulting in frequent occurrence of fish diseases.
船舶へのこれら水中生物の付着は、 流体抵抗の増加を引き起こし、 その結果、 航行速度の低下、 消費燃料の増加さらに船底の清掃のための費用、 運行休止によ る費用等の損失を招く。 海洋設備、 海洋及び水中構築物においては、 水中生物の付着による重量増加及 び取扱い操作の著しい不便さを生じ、 玲冰路への付着は、 熱伝導度の低下を引き 起こすとともに、 路が閉塞したり、 ¾7j量が減少する等の問題を生じる。 従来、 これらの海水及び淡水水中生物の付着髓を防止するため、 ピストリブ チルスズォキシド等の有機スズ化合物、 硫酸銅及び亜酸ィ 等の銅化合物等を含 有する防汚塗料が使用されている。 The adhesion of these aquatic organisms to ships causes an increase in fluid resistance, resulting in a decrease in navigation speed, an increase in fuel consumption, and a loss of costs for cleaning the bottom of the ship and costs due to suspension of operation. In marine facilities, marine and underwater structures, the increase in weight and the inconvenience of handling operations due to the attachment of aquatic organisms cause the attachment to Ling Bing Road to cause a decrease in thermal conductivity and block the road. And the amount of ¾7j decreases. In the past, antifouling paints containing organic tin compounds such as pistrov tyl sulphoxide and copper compounds such as copper sulphate and nitrous acid have been used in order to prevent the attachment of living organisms to seawater and freshwater water.
特開昭 6 0 - 9 7 9 6 4号^には、 N—キノキザリルァニリン系化合物、 そ の製造法及び農園芸用殺菌、 &, 殺ダニ剤としての用途が開示されている。 しかし、 該 記載の化合物には、 工業用抗菌.抗カピ 、 殺藻剤及び生物付 着防 ljとしての用途の記載はない。 上述の有機窒素系化合物、 有機窒素ィォゥ系化合物、 有機ハ αゲン系化^)、 含窒素脂肪族ポリマ一及び重金属配位化合物等は、 刺激性があり労安法上問題に なる薬剤、 使用薬量が多く環境保護の観点から問題になる薬剤、 ホルマリン或い はハロゲンを遊離し、 人体への影響及び環境汚染が懸念される薬剤及び重金属に よる環謝染が懸念される薬剤を含んでおり、 工業用抗菌，抗カビ剤及び殺藻剤 全体が、 好ましい薬剤のみで構成されているとは言えない。  Japanese Patent Application Laid-Open No. 60-97764 discloses an N-quinoxalylaniline-based compound, a method for producing the compound, a disinfectant for agricultural and horticultural use, and a use as an acaricide. However, there is no description of the use of the compounds described as industrial antibacterials, anti-capi, algicides, and biofouling inhibitors. The above-mentioned organic nitrogen-based compounds, organic nitrogen-based compounds, organic halogenated compounds ^), nitrogen-containing aliphatic polymers, heavy metal coordination compounds, etc., are irritating agents and pose problems in the Labor Safety Act. Includes drugs that are large in dose and pose a problem from the viewpoint of environmental protection, drugs that release formalin or halogen, and that are likely to affect the human body and contaminate the environment, and drugs that are likely to cause ring contamination by heavy metals. Therefore, it cannot be said that the entirety of industrial antibacterial, antifungal and algicidal agents is composed of only preferable chemicals.
また、 生物付着防 としての上述の有機スズ化合物は、 水中生物の付着防止 には有効であるものの、 毒性が強く、 特に魚貝類の体内蓄積が著しく、 環謝染 を進行させるため現在規制の対象となっている。  Although the above-mentioned organotin compounds as an anti-fouling agent are effective in preventing the adhesion of aquatic organisms, they are highly toxic, and especially remarkably accumulate in fish and shellfish in the body. It has become.
例えば、 米国においては有機スズ防汚塗料規制法（1 9 8 7年） によって、 6 5フィート以下の船舶への有機スズ船舶塗料の使用が禁止され、 英国においては 食品環境保護 （ 1 9 8 7年） によってトリプチルスズ含有防汚剤は、 2 5メ ―トル以下の船舶および海洋農業への使用が禁止されている。  For example, in the United States, the Organotin Antifouling Paint Regulations Act (1987) banned the use of organotin marine paints on ships less than 65 feet, and in the UK, food environmental protection (19987) The use of antifouling agents containing triptyltin in ships and marine agriculture below 25 meters has been banned.
又、 日本においては化審法（ 1 9 9 0年） によってトリプチルスズォキシドが 第 1種特定ィ 物質に、 トリフェニルスズ化合物およびトリプチルスズ化合物が 第 2種特定ィ！^物質に指定され、 漁網用に関しては使用が禁止されている。 In Japan, triptyl suloxide has been approved by the Chemical Substances Control Law (1990). Triphenyltin compounds and triptyltin compounds are classified as Class 1 substances. ^ Specified as a substance and its use is prohibited for fishing nets.
更に、 トリプチルスズ系の船底塗料の使用抑制の措置（運!^通達、 1 9 9 0 年） もとられている。  Furthermore, measures have been taken to curb the use of triptyltin-based bottom paints (Luck! Notification, 1990).
±ίΕの銅化 は、 ¾7路及び船底部用の防汚謝に広く使用されてはいるが、 スズ化^！と同様重鍋である銅を含有しているため、 «の ^^染が懸念さ れ、 好ましい水中生物付着制御剤とは言えない。  ± ίΕ copper is widely used for anti-fouling for ¾7 road and ship bottom, but tinned ^! As it contains copper, which is a heavy pot, it is not a preferred agent for controlling the adhesion of underwater organisms due to concerns about ^^ staining.
本発明に用レ、られる化^!は上言 制法に記載されておらず、 また f ^に は N—キノキザリルァニリン類が工業用抗菌 ·抗カピ 、 ^^剤及び生物付着防 ΐί \として有効であることは何ら記載されていなレ、。 発明の開示  The chemical formula used in the present invention is not described in the above law, and f ^ is an industrial antibacterial / anti-capi, a ^^ agent and a biofouling preventive for N-quinoxalylaniline.レ There is no mention that it is valid as \. Disclosure of the invention
本発明者らは、 上!^題を解決するため鋭 ¾ ^討の結果、 Ν—キノキザリルァ 二リン類が、 安^ ¾が高く、 かっ^^染防止の から低薬量で幅広いスぺク トラムを発現する、 実用性の高い工業用抗菌，抗カピ 、 ^^剤及び生物付着防 ih^Jとなることを見出し、 本発明を した。  The present inventors have conducted intensive studies to solve the above problem, and as a result, have found that Ν-quinoxalyl diamines have a high level of safety and a low dose of a wide range of drugs due to their ability to prevent dyeing. The present invention has been found to be ih ^ J, which is a highly practical industrial antibacterial, anti-capi, ^^ agent and biofouling inhibitor which expresses a tram.
即ち、 本発明は、 ( 1 ) ：  That is, the present invention provides (1):
Figure imgf000005_0001
Figure imgf000005_0001
(式中、 R 1 及び R2 は、 それぞ 虫立に水素原子、 ハロゲン原子、 トリフルォ αメチル 原 «[ 1— 5のアルキル基、 原 1— 5のアルコキシ基 またはニトロ基を、 R 3 は水素原子、 ハロゲン原子または麟原 1—5のァ ルキル基を、 R4 は水素原子、 ¾¾原¾ 1 ー 5のアルキル基、 原 2— 6のアルケニル基、 原子数 2 - 6のアルキニル基、 原 2— 6のアル キルカルボニル基、 原 1 一 5のアルキルスルホニル基またはハロゲン原 子で置換されてもよい歸原 H— 5のアルキルスルフエニル基を、 X及び Y は、 それぞれ独立にニトロ基、 トリフルォロメチノレ基またはハロゲン原子を、 Z は水素原子、 ハ πゲン原子、 Κ¾原 1— 5のアルコキシ基またはハロゲン原 子、 ニトロ基または水酸基で置換されてもよいフヱノキシ基を表す。 但し、 m及 び nはそれぞれ独立に 0または 1を表すが、 m及び nは同時に 1を表すことはな い。 また、 j及び kはそれぞれ独立に 0、 1、 2または 3を表し、 j + kは常に 3以下を表す。 ) (Wherein, R 1 and R 2 are each a hydrogen atom, a halogen atom, a trifluoro α-methyl atom «[an alkyl group of 1-5, an alkoxy group of an atom 1-5 Or a nitro group, R 3 represents a hydrogen atom, a halogen atom or an alkyl group of Linbara 1-5, and R 4 represents a hydrogen atom, an alkyl group 1-5, an alkenyl group 2-6 An alkylsulfenyl group of the formula H-2, which may be substituted with an alkynyl group of the formulas 2-6, an alkylcarbonyl group of the formula 2-6, an alkylsulfonyl group of the formula 15 or a halogen atom, And Y are each independently substituted with a nitro group, a trifluoromethylol group or a halogen atom, and Z is substituted with a hydrogen atom, a π-gen atom, an alkoxy group or a halogen atom of nitrogen 1-5, a nitro group or a hydroxyl group. Represents a phenoxy group which may be substituted. However, m and n each independently represent 0 or 1, but m and n do not represent 1 at the same time. J and k each independently represent 0, 1, 2 or 3, and j + k always represents 3 or less. )
で表される N—キノキザリルァニリン類を含有することを特徴とする工業用抗菌 •抗カビ剤、 剤及び生物付着防止剤に閧するものである。 Industrial antibacterials, antifungal agents, agents and biofouling inhibitors characterized by containing N-quinoxalylanilines represented by the formula:
式（I ) において示される各置換基を具体的に説明する。  Each substituent represented by the formula (I) will be specifically described.
ハロゲン原子としては、 フッ素、 塩素、 臭素及びヨウ素が挙げられる。  Halogen atoms include fluorine, chlorine, bromine and iodine.
原 1—5のアルキル基としては、 メチル、 ェチル、 n-プロピル、 i-プ 口ピル、 n-ブチル、 i-ブチル、 S-ブチル、 t-ブチル、 1-ペンチル、 2-ペンチル、 3-ペンチル、 i-ペンチル、 neo-ペンチル、 t-ペンチル、 シクロプロピル、 1-メチ ルシクロプ πピル、 2-メチルシクロプロピル、'シクロブチル、 シク πペンチル等 が挙げられる。  The alkyl groups of the original 1-5 include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, S-butyl, t-butyl, 1-pentyl, 2-pentyl, 3-pentyl Pentyl, i-pentyl, neo-pentyl, t-pentyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 'cyclobutyl, cyclopipentyl and the like.
難原 2— 6のアルケニル基としては、 ェテニル、 1-プロぺニル、 2-プロ ぺニル、 1-メチルビニル、 1-ブテニル、 2-ブテニル、 3-ブテニル、 1-メチル -1 -プ ロぺニル、 1-メチル -2-プ σぺニル、 2-メチル -2-プ口ぺニル、 1 -ェチル- 2 -ビニル、 1-ペンテニル、 2-ペンテニル、 3-ペンテニル、 4-ペンテニル、 1, 2-ジメチル- 1 - プロぺニル、 1， 2 -ジメチル -2-プロぺニル、 1-ェチル -1-プ πぺニル、 1-ェチル -2- プ πぺニル、 1-メチル -1-ブテニル、 1-メチル- 2-ブテニル、 2-メチル- 1-ブテニル、 1 - i-プロピルビュル、 2， 4-ペンタジェニル、 1-へキセニル、 2-へキセニル、 3-へ キセニル、 4-へキセニル、 5-へキセニル、 2, 4-へキサジェニル、 1-メチル -1-ぺ ンテニル等が举げられる。 Examples of the alkenyl group of Regen 2-6 include ethenyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl. Phenyl, 1-methyl-2-propyl succinyl, 2-methyl-2-butanol, 1-ethyl-2-vinyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 , 2-Dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propyl pidinyl, 1-ethyl-2- Pi 、 nil, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-1-butenyl, 1-i-propylbutyl, 2,4-pentagenenyl, 1-hexenyl, 2-to Examples include xenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 2,4-hexenyl, 1-methyl-1-pentenyl, and the like.
驟原 2— 6のアルキニル基としては、 ェチニル、 1-プロビュル、 2-プロ ピニル、 1 -プチニル、 2-ブチュル、 3 -プチニル、 1-ペンチニル、 2-ペンチニル、 3-ペンチニル、 4-ペンチニル、 1-へキシニル、 2-へキシニル、 3-へキシニル、 4- へキシニル、 5-へキシニル等か '挙げられる。  The alkynyl group of the sake brewer 2-6 includes ethynyl, 1-propyl, 2-propynyl, 1-butynyl, 2-butul, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl and the like.
原 1 一 5のアルコキシ基としては、 メトキシ、 エトキシ、 II-プロポキ シ、 i-プロボキシ、 II-ブトキシ、 i-ブトキシ、 s-ブトキシ、 t-ブトキシ、 ペンチ ルォキシ が挙げられる。  Examples of the original alkoxy group include methoxy, ethoxy, II-propoxy, i-propoxy, II-butoxy, i-butoxy, s-butoxy, t-butoxy and pentoxy.
^^原子数 2— 6のアルキルカルボニル基としては、 メチルカルボニル、 ェチ ルカルポニル、 n-プロピルカルボニル、 i-プ αピルカルボニル、 η-プチルカルポ ニル、 i-ブチルカルボニル、 S-ブチルカルボニル、 t-ブチルカルポニル、 1-ペン チルカルボニル、 2-ペンチルカルポニル、 3-ペンチルカルボニル、 i-ペンチルカ ルポニル、 neo-ペンチルカルポニル、 t-ペンチルカルボニル、 シクロプ αピル力 ルポニル、 1-メチルシクロプロピルカルボニル、 2-メチルシクロプロピルカルボ ニル、 シクロブチルカルボニル、 シクロペンチルカルボニル等が挙げられる。  ^^ Alkylcarbonyl groups having 2 to 6 atoms include methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, i-α-pyrcarbonyl, η-butylcarbonyl, i-butylcarbonyl, S-butylcarbonyl, t-butylcarbonyl Butylcarbonyl, 1-pentylcarbonyl, 2-pentylcarbonyl, 3-pentylcarbonyl, i-pentylcarbonyl, neo-pentylcarbonyl, t-pentylcarbonyl, cyclopropyl α-pill force luponyl, 1-methylcyclopropylcarbonyl, 2-methyl Cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl and the like can be mentioned.
原子数 1— 5のアルキルスルホニル基としては、 メチルスルホニル、 ェチ ルスルホニル、 η-プロピルスルホニル、 i-プロピルスルホニル、 n-ブチルスルホ ニル、 i-ブチルスルホニル、 s-ブチルスルホニル、 t-ブチルスルホニル、 1-ペン チルスルホニル、 2-ペンチルスルホニル、 3-ペンチルスルホニル、 i-ペンチルス ルホニル、 neo-ペンチルスルホニル、 t-ペンチルスルホニル、 シクロプロピルス ルホニル、 1-メチルシク αプロピルスルホニル、 2-メチルシクロプロピルスルホ ニル、 シクロプチルスルホニル、 シク αペンチルスルホニル等か'举げられる。 ^^原子数 1 - 5のアルキルスルフェニル基としては、 メチルスルフエニル、 ェチルスルフヱニル、 n-プロピルスルフヱニル、 i-プ πピルスルフヱニル、 n-ブ チルスルフヱニル、 i-ブチルスルフヱニル、 s-ブチルスルフエ二ル、 t-ブチルス ルフ： Lニル、 1-ペンチルスルフヱニル、 2-ペンチルスルフヱニル、 3-ペンチルス ルフヱニル、 i-ペンチルスルフヱニル、 neo-ペンチルスルフヱニル、 t-ペンチル スルフヱニル、 シクロプロピルスルフエニル、 1-メチルシク σプロピルスルフエ ニル、 2-メチルシクロプロピルスルフヱニル、 シクロプチルスルフエニル、 シク 口ペンチルスルフヱニル等が挙げられる。 本発明の工業用抗菌，抗カビ剤、 藤剤及び生物付着防 は、 上記""^式 (1)で表される Ν—キノキザリルァニリン類を有効成分として含んでいればよ い。 Examples of the alkylsulfonyl group having 1 to 5 atoms include methylsulfonyl, ethylsulfonyl, η-propylsulfonyl, i-propylsulfonyl, n-butylsulfonyl, i-butylsulfonyl, s-butylsulfonyl, t-butylsulfonyl, 1-pentylsulfonyl, 2-pentylsulfonyl, 3-pentylsulfonyl, i-pentylsulfonyl, neo-pentylsulfonyl, t-pentylsulfonyl, cyclopropylsulfonyl, 1-methylcycl α-propylsulfonyl, 2-methylcyclopropylsulfonyl , Cyclobutylsulfonyl, cyclopentylsulfonyl, etc. ^^ Examples of the alkylsulfenyl group having 1 to 5 atoms include methylsulfenyl, ethylsulfenyl, n-propylsulfenyl, i-pipisulfulfenyl, n-butylsulfenyl, and i-butylsulfur Benzyl, s-butylsulfurenyl, t-butylsulfur: Lnil, 1-pentylsulfuryl, 2-pentylsulfuryl, 3-pentylsulfuryl, i-pentylsulfuryl, neo-pentylsulfur Examples include phenyl, t-pentyl sulfenyl, cyclopropylsulfenyl, 1-methylcyclopropyl sulfenyl, 2-methylcyclopropylsulfenyl, cyclobutylsulfenyl, and cyclopentylsulfenyl. Can be The industrial antibacterial, antifungal, antimicrobial and anti-biofouling agents of the present invention may contain the キ -quinoxalylaniline represented by the above-mentioned formula (1) as an active ingredient.
本発明の工業用抗菌 ·抗カビ剤、 剤及び生物付着防 Ιί^«の有効成分に含ま れる好ましい化合物を、 以下の第 1表から第 3表に列記するが、 本発明に用いら れる化合物はこれらに限定されるものではない。  Preferred compounds contained in the industrial antibacterial and antifungal agents, agents and biofouling-preventing active ingredients of the present invention are listed in Tables 1 to 3 below, and the compounds used in the present invention Is not limited to these.
但し、 表中の記号は以下の意味を表す。  However, the symbols in the table have the following meanings.
Me： メチル基、 E t ：ェチル基、 CO e：ァセチル基、 COE t ：ェチル カルボニル基、 S02 Me： メタンスルホニル基、 Me〇： メトキシ基、 ΕΐΟ ：ェトキシ基、 n-Pr 0：ノルマルプロポキシ基、 m-HO-PhO： メタヒ ドロキシフ Xノキシ ¾o Me: methyl group, E t: Echiru group, CO e: Asechiru group, COE t: Echiru carbonyl group, S0 2 Me: methanesulfonyl group, Me_〇: methoxy, EiO: Etokishi group, n-Pr 0: normal propoxy Group, m-HO-PhO: metahydroxyx X-noxy ¾o
Figure imgf000009_0001
Figure imgf000009_0001
ベンゼン環上置換基 Substituent on benzene ring
x\ 3 τ> 4 ィ liZ. L ) 4 I^Z. 0 I^A x \ 3 τ> 4 liZ.L) 4 I ^ Z. 0 I ^ A
U U
Γ1 Π η 1 U2 u Γ1 Π η 1 U2 u
rl WU2 n し 3 rl WU2 n then 3
U u u U u u
Π π π Π n 2 n NO 2 Π π π Π n 2 n NO 2
u υ u  u υ u
3
Figure imgf000009_0002
Three
Figure imgf000009_0002
u π u π η し Γ 3 u u π u π η Γ u 3 u
n IU2 u  n IU2 u
n し I13 u η U η Γし丄 1 し！13 n I I 1 3 u η U η Γ 丄 1 ！! 1 3
μ π π n ΜΛ2 VC L し ί* 3
Figure imgf000009_0003
μ π π n ΜΛ2 VC L ί * 3
Figure imgf000009_0003
Η η η 11 U η し J u  Η η η 11 U η then J u
し！13 Π I U2S! 1 3 Π I U2
11 U η Η 11 l V2 DI し TJ 11 U η Η 11 l V2 DI then TJ
Γ 3 Π WU2 丄 Η1 Η 11 Up ι レ 1 Πし Γ73。 u  Γ 3 Π WU2 丄 Η 1 Η 11 Up ι レ 1 Π Γ 73. u
n I 2  n I 2
2
Figure imgf000009_0004
Two
Figure imgf000009_0004
Η C1 Η Ν02 CI CF3 H NO 2Η C1 Η Ν0 2 CI CF 3 H NO 2
Η Η Η Ν02 F CF3 H NO 2Η Η Η Ν0 2 F CF 3 H NO 2
F Η Η NO 2 H Ν02 H CFsF Η Η NO 2 H Ν0 2 H CFs
F Η Η Η H . Ν02 H NO 2F Η Η Η H. Ν0 2 H NO 2
F Η Η Η H Ν02 H CFa
Figure imgf000009_0005
F Η Η Η H Ν0 2 H CFa
Figure imgf000009_0005
F Η Η C1 H Ν02 H CIF Η Η C1 H Ν0 2 H CI
F Η Η Ν02 H CF3 H NO 2F Η Η Ν0 2 H CF 3 H NO 2
F Η Η NO 2 H Η H NO 2F Η Η NO 2 H Η H NO 2
F Η Η CF3 H NO 2 H CF3 F Η Η CF 3 H NO 2 H CF 3
F Η Η NO 2 CI CF3 H NO 2F Η Η NO 2 CI CF 3 H NO 2
F Η Η NO 2 OEt CF3 H NO 2 F Η Η NO 2 OEt CF 3 H NO 2
F Η Η NO 2 OPh-OH-m CF3 H N02 F Η Η NO 2 OPh-OH-m CF 3 H N0 2
F Η Η H CI CF3 H NO 2 第 1表 feeさ ぺンゼン環上置換基 F Η Η H CI CF 3 H NO 2 Table 1 Substituents on the benzene ring
R 1 R3 R4 2位 3位 (Z) 4位 5位 6位 R 1 R 3 R 4 2nd 3rd (Z) 4th 5th 6th
F H H NO 2 OPr-n CF3 H NO 2FHH NO 2 OPr-n CF 3 H NO 2
F H H NO 2 Br CFs H NO 2F H H NO 2 Br CFs H NO 2
F H Me NO 2 CI CFs H NO 2F H Me NO 2 CI CFs H NO 2
F H COMe N02 CI CFs H NO 2FH COMe N0 2 CI CFs H NO 2
F H SO 2 Me NO 2 CI CFs H NO 2F H SO 2 Me NO 2 CI CFs H NO 2
F H SCC NO 2 CI CF3 H NO 2FH SCC NO 2 CI CF 3 H NO 2
F H COEt NO 2 CI CF3 H NO 2FH COEt NO 2 CI CF 3 H NO 2
F Me H N02 CI CFs H NO 2F Me H N0 2 CI CFs H NO 2
F Et H NO 2 CI CFs H NO 2F Et H NO 2 CI CFs H NO 2
F CI H NO 2 H H H NO 2
Figure imgf000010_0001
F CI H NO 2 HHH NO 2
Figure imgf000010_0001
C1 H H H H NO 2 H NO 2
Figure imgf000010_0002
C1 HHHH NO 2 H NO 2
Figure imgf000010_0002
C1 H H CI H NO 2 H CI C1 H H CI H NO 2 H CI
C1 H H NO 2 H CF3 H NO 2
Figure imgf000010_0003
C1 HH NO 2 H CF 3 H NO 2
Figure imgf000010_0003
C1 H H CF3 H NO 2 H CFs
Figure imgf000010_0004
C1 HH CF 3 H NO 2 H CFs
Figure imgf000010_0004
C1 H H NO 2 OPh-OH-m CF3 H NO 2
Figure imgf000010_0005
C1 HH NO 2 OPh-OH-m CF 3 H NO 2
Figure imgf000010_0005
C1 H H NO 2 OPr-n CF3 H NO 2C1 HH NO 2 OPr-n CF 3 H NO 2
C1 H H NO 2 Br CFs H NO 2
Figure imgf000010_0006
C1 HH NO 2 Br CFs H NO 2
Figure imgf000010_0006
C1 H SO 2 Me NO 2 CI CF3 H NO 2C1 H SO 2 Me NO 2 CI CF 3 H NO 2
C1 H SCCh NO 2 CI CFs H NO 2
Figure imgf000010_0007
C1 H SCCh NO 2 CI CFs H NO 2
Figure imgf000010_0007
C1 Me H NO 2 CI CFs H NO 2 C1 Me H NO 2 CI CFs H NO 2
C1 Et H NO 2 CI CFs H NO 2C1 Et H NO 2 CI CFs H NO 2
C1 CI H NO 2 H H H NO 2C1 CI H NO 2 H H H NO 2
C1 H H NO 2 F CF3 H NO 2C1 HH NO 2 F CF 3 H NO 2
Br H H NO 2 CI CF3 H NO 2Br HH NO 2 CI CF 3 H NO 2
Br H H NO 2 OEt CFs H NO 2 第 1表続き ベンゼン環 _上置換基 Br HH NO 2 OEt CFs H NO 2 Table 1 continued Benzene ring _ upper substituent
R1 R3 R4 2位 3位 (Z) 4位 5位 6位R 1 R 3 R 4 2nd 3rd (Z) 4th 5th 6th
Br Me H NO 2 CI CFa H NO 2
Figure imgf000011_0001
Br Me H NO 2 CI CFa H NO 2
Figure imgf000011_0001
CF3 H H NO 2 H NO 2 H CF3 CF 3 HH NO 2 H NO 2 H CF 3
CFa H H H H NO 2 H NO 2CFa H H H H NO 2 H NO 2
CF3 H H H H NO 2 H CF3 CF 3 HHHH NO 2 H CF 3
CF3 H H NO 2 H NO 2 H NO 2CF 3 HH NO 2 H NO 2 H NO 2
CF3 H H NO 2 H CFa H NO 2
Figure imgf000011_0002
CF 3 HH NO 2 H CFa H NO 2
Figure imgf000011_0002
CF3 H H NO 2 CI CF3 H NO 2CF 3 HH NO 2 CI CF 3 H NO 2
CF3 H H NO 2 OEt CF3 H NO 2
Figure imgf000011_0003
CF 3 HH NO 2 OEt CF 3 H NO 2
Figure imgf000011_0003
CF3 H H NO 2 Br CF3 H NO 2CF 3 HH NO 2 Br CF 3 H NO 2
CF3 H Me NO 2 CI CF3 H NO 2CF 3 H Me NO 2 CI CF 3 H NO 2
CF3 Me H NO 2 CI CF3 H NO 2CF 3 Me H NO 2 CI CF 3 H NO 2
CF3 Et H NO 2 CI CFs H NO 2
Figure imgf000011_0004
CF 3 Et H NO 2 CI CFs H NO 2
Figure imgf000011_0004
CF3 H H NO 2 F CF3 H NO 2CF 3 HH NO 2 F CF 3 H NO 2
H H CH2=CHCH2 NO 2 H N02 H CFs
Figure imgf000011_0005
HH CH 2 = CHCH 2 NO 2 H N0 2 H CFs
Figure imgf000011_0005
H H CH2=CHCH2 H H NO 2 H CFsHH CH 2 = CHCH 2 HH NO 2 H CFs
H H CH≡CCH2 NO 2 H NO 2 H NO 2HH CH≡CCH 2 NO 2 H NO 2 H NO 2
H H CH2 =CHCH2 NO 2 CI CF3 H NO 2HH CH 2 = CHCH2 NO 2 CI CF 3 H NO 2
H H CHョ CCH2 NO 2 OEt CF3 H NO 2HH CH CCH 2 NO 2 OEt CF 3 H NO 2
H H CH≡CCH2 NO 2 CI CFs H NO 2HH CH≡CCH 2 NO 2 CI CFs H NO 2
H Me CH2 =CHCH2 NO 2 CI CFs H NO 2H Me CH 2 = CHCH 2 NO 2 CI CFs H NO 2
H Et CHョ CCH2 NO 2 CI CF3 H NO 2H Et CH ョ CCH 2 NO 2 CI CF 3 H NO 2
H CI CH2=CHCH2 NO 2 CI CF3 H NO 2H CI CH 2 = CHCH 2 NO 2 CI CF 3 H NO 2
H H CH≡CCH2 NO 2 F CFs H NO 2
Figure imgf000011_0006
HH CH≡CCH 2 NO 2 F CFs H NO 2
Figure imgf000011_0006
F H CH2=CHCH2 H H NO 2 H CF3 FH CH 2 = CHCH 2 HH NO 2 H CF 3
F H CH≡CCH2 NO 2 H N02 H NO 2FH CH≡CCH 2 NO 2 H N0 2 H NO 2
F H CH2=CHCH2 NO 2 CI CFa H NO 2FH CH 2 = CHCH 2 NO 2 CI CFa H NO 2
F H CH≡CCH2 NO 2 OEt CF3 H NO 2FH CH≡CCH 2 NO 2 OEt CF 3 H NO 2
F H CH≡CCH2 NO 2 CI CF3 H NO 2 第 1 さ FH CH≡CCH 2 NO 2 CI CF 3 H NO 2 First
ベンゼン環上置換基  Substituent on benzene ring
R 1 R 3 R4 2位 3位 (Z) 4位 5位 6位R 1 R 3 R 4 2nd 3rd (Z) 4th 5th 6th
F Me CH2— CHCH2 NO 2 CI CF3 H NO 2 F Me CH2— CHCH2 NO 2 CI CF 3 H NO 2
F Et CH≡CCH2 NO2 CI CF3 H NO 2F Et CH≡CCH 2 NO2 CI CF 3 H NO 2
F CI CH2— CHCH2 NO2 CI CF3 H NO2F CI CH2— CHCH2 NO2 CI CF 3 H NO2
F H CH≡CCH2 NO 2 F CF3 H NO 2FH CH≡CCH 2 NO 2 F CF 3 H NO 2
C1 H CH2 = CHCH2 NO 2 H NO 2 H CFsC1 H CH2 = CHCH2 NO 2 H NO 2 H CFs
C1 H CH≡CCH2 H H NO 2 H NO 2
Figure imgf000012_0001
C1 H CH≡CCH 2 HH NO 2 H NO 2
Figure imgf000012_0001
C1 H CH≡CCH2 NO z H NO 2 H NO 2C1 H CH≡CCH 2 NO z H NO 2 H NO 2
C1 H CH 2― CHCH 2 NO2 CI CFa H NO 2C1 H CH 2 ― CHCH 2 NO2 CI CFa H NO 2
C1 H CH≡CCH2 NO 2 OEt CFs H NO 2C1 H CH≡CCH 2 NO 2 OEt CFs H NO 2
C1 H CH≡CCH2 NO 2 CI CF3 H NO 2C1 H CH≡CCH 2 NO 2 CI CF 3 H NO 2
C1 Me CH2― CHCH 2 NO 2 CI CFa H NO 2C1 Me CH2 ― CHCH 2 NO 2 CI CFa H NO 2
C1 Et CH≡CCH2 NO 2 CI H NO 2C1 Et CH≡CCH 2 NO 2 CI H NO 2
C1 CI CH2— CHCH 2 NO 2 CI CFs H NO 2C1 CI CH2— CHCH 2 NO 2 CI CFs H NO 2
C1 H CH≡CCH2 NO 2 F CFa H NO 2C1 H CH≡CCH 2 NO 2 F CFa H NO 2
Br H CH2=CHCH2 NO 2 H NO 2 H CFsBr H CH 2 = CHCH 2 NO 2 H NO 2 H CFs
Br H CH≡CCH2 H H NO 2 H NO 2 Br H CH≡CCH 2 HH NO 2 H NO 2
Br H CH2=CHCH2 H H NO 2 H CFsBr H CH 2 = CHCH 2 HH NO 2 H CFs
Br H CH≡CCH2 NO 2 H NO 2 H NO 2Br H CH≡CCH 2 NO 2 H NO 2 H NO 2
Br H CH2― CHCH 2 NO2 CI CF3 H NO 2 Br H CH2- CHCH 2 NO2 CI CF 3 H NO 2
Br H CHョ CCH2 NO2 OEt CFa H NO 2Br H CH CCH 2 NO2 OEt CFa H NO 2
Br H CH≡CCH2 NO2 CI CF3 H NO 2Br H CH≡CCH 2 NO2 CI CF 3 H NO 2
I H CH2— CHCH 2 NO2 CI CFa H NO 2 IH CH2— CHCH 2 NO2 CI CFa H NO 2
I H CH≡CCH2 NO 2 OEt CF3 H NO 2IH CH≡CCH 2 NO 2 OEt CF 3 H NO 2
CF3 H CH2 = CHCH 2 NO2 H NO 2 H CF3 CF 3 H CH2 = CHCH 2 NO2 H NO 2 H CF 3
CF3 H CH≡CCH2 H H NO 2 H NO 2CF 3 H CH≡CCH 2 HH NO 2 H NO 2
CF3 H CH2=CHCH2 H H NO 2 H CF3 CF 3 H CH 2 = CHCH 2 HH NO 2 H CF 3
CF3 H CH≡CCH2 NO 2 H NO 2 H NO 2
Figure imgf000012_0002
CF 3 H CH≡CCH 2 NO 2 H NO 2 H NO 2
Figure imgf000012_0002
CFs H CH≡CCH2 NO 2 OEt CF3 H NO 2CFs H CH≡CCH 2 NO 2 OEt CF 3 H NO 2
CFa H CH≡CCH2 NO 2 CI CFs H NO 2CFa H CH≡CCH 2 NO 2 CI CFs H NO 2
Me H H NO 2 H NO 2 H CF3 Me HH NO 2 H NO 2 H CF 3
Me H H H H NO 2 H NO 2Me H H H H NO 2 H NO 2
Me H H H H NO 2 H CFsMe H H H H NO 2 H CFs
Me H H NO 2 H NO 2 H NO 2
Figure imgf000012_0003
第 1繊き Me HH NO 2 H NO 2 H NO 2
Figure imgf000012_0003
1st fiber
^ンゼン環上置換基 ^ Substituent on the ring
R1 R3 R4 2位 3位 (Z) 4位 5位 R 1 R 3 R 4 2nd 3rd (Z) 4th 5th
Me H H N02 OEt CF3 H NO 2Me HH N0 2 OEt CF 3 H NO 2
Me Me H NO 2 CI CF3 H NO 2
Figure imgf000013_0001
Me Me H NO 2 CI CF 3 H NO 2
Figure imgf000013_0001
Me CI H NO 2 CI CFs H NO 2
Figure imgf000013_0002
Me CI H NO 2 CI CFs H NO 2
Figure imgf000013_0002
Me H Me NO 2 CI CFs H NO 2
Figure imgf000013_0003
Me H Me NO 2 CI CFs H NO 2
Figure imgf000013_0003
Me H SO 2 Me NO 2 CI CFs H NO 2 Me H SO 2 Me NO 2 CI CFs H NO 2
Me H SCC NO 2 CI CFa H NO 2Me H SCC NO 2 CI CFa H NO 2
Me H CH2 =CHCH2 NO 2 H NO 2 H CFsMe H CH2 = CHCH 2 NO 2 H NO 2 H CFs
Me H CH≡CCH2 H H NO 2 H NO 2Me H CH≡CCH 2 HH NO 2 H NO 2
Me H CH2 =CHCH2 H H NO 2 H CFaMe H CH 2 = CHCH 2 HH NO 2 H CFa
Me H CH≡CCH2 NO 2 H NO 2 H NO 2Me H CH≡CCH 2 NO 2 H NO 2 H NO 2
Me H CH2 ~ CHCH 2 NO 2 CI CF3 H NO 2Me H CH2 ~ CHCH 2 NO 2 CI CF 3 H NO 2
Me H CH≡CCH2 NO 2 OEt CF3 H NO 2Me H CH≡CCH 2 NO 2 OEt CF 3 H NO 2
Me H CH≡CCH2 NO 2 CI CFa H NO 2
Figure imgf000013_0004
Me H CH≡CCH 2 NO 2 CI CFa H NO 2
Figure imgf000013_0004
MeO H H H H NO 2 H NO 2 MeO H H H H NO 2 H NO 2
MeO H H H H NO 2 H CF3 MeO HHHH NO 2 H CF 3
MeO H H NO 2 H NO 2 H NO 2
Figure imgf000013_0005
MeO HH NO 2 H NO 2 H NO 2
Figure imgf000013_0005
MeO H H NO 2 OEt CFs H NO 2 MeO H H NO 2 OEt CFs H NO 2
MeO Me H NO 2 CI CFs H NO 2
Figure imgf000013_0006
MeO Me H NO 2 CI CFs H NO 2
Figure imgf000013_0006
MeO H COMe NO 2 CI CFs H NO 2 MeO H COMe NO 2 CI CFs H NO 2
MeO H SO 2 Me NO 2 CI CFs H NO 2
Figure imgf000013_0007
MeO H SO 2 Me NO 2 CI CFs H NO 2
Figure imgf000013_0007
MeO H CH2— CHCH 2 NO 2 H NO 2 H CFs MeO H CH2— CHCH 2 NO 2 H NO 2 H CFs
MeO H CH≡CCH2 H H NO 2 H NO 2MeO H CH≡CCH 2 HH NO 2 H NO 2
MeO H CH2 ~ CHCH 2 H H NO 2 H CFsMeO H CH2 ~ CHCH 2 H H NO 2 H CFs
MeO H CH≡CCH2 NO 2 H NO 2 H NO 2MeO H CH≡CCH 2 NO 2 H NO 2 H NO 2
MeO H CH2― CHCH 2 NO 2 CI CF3 H NO 2MeO H CH2- CHCH 2 NO 2 CI CF 3 H NO 2
MeO H CH≡CCH2 NO 2 OEt CF3 H NO 2 第 1表続き ベンゼン環上鼂換基 MeO H CH≡CCH 2 NO 2 OEt CF 3 H NO 2 Continuing from Table 1 Exchange group on benzene ring
R1 R3 R4 2位 3位 （Z) 4位 5位 6位 eO H CH≡CCH2 NO 2 CI CFs H NO 2R 1 R 3 R 4 2nd 3rd (Z) 4th 5th 6th eO H CH≡CCH 2 NO 2 CI CFs H NO 2
NO 2 H H N02 CI CFs H NO 2NO 2 HH N0 2 CI CFs H NO 2
NO 2 H H NO 2 OEt CFs H NO 2NO 2 H H NO 2 OEt CFs H NO 2
NO 2 Me H NO 2 CI CF3 H NO 2 NO 2 Me H NO 2 CI CF 3 H NO 2
NO 2 Et H NO 2 CI CFs H NO 2
Figure imgf000014_0001
NO 2 Et H NO 2 CI CFs H NO 2
Figure imgf000014_0001
NO 2 H COMe NO 2 CI CF3 H NO 2NO 2 H COMe NO 2 CI CF 3 H NO 2
U UU U
I U2 Π U2M6 I U2 し 1 If 3 Π I U2I U2 Π U2M6 I U2 1 1 If 3 Π I U2
TI err l „ II TI err l „II
Π しし 13 I U2 し 1 し f 3 Π  Π 13 13 I U2 1 1 f f 3 Π
NO 2 H CH 2 " CHCH 2 NO 2 H NO 2 H CF3 NO 2 H CH 2 "CHCH 2 NO 2 H NO 2 H CF3
NO 2 H CH≡CCH2 H H NO 2 H NO 2NO 2 H CH≡CCH 2 HH NO 2 H NO 2
NO 2 H CH 2 = CHCH 2 H H NO2 H CF3 NO 2 H CH 2 = CHCH 2 HH NO2 H CF 3
NO 2 H CHョ CCH2 NO 2 H NO 2 H NO 2NO 2 H CH CCH 2 NO 2 H NO 2 H NO 2
NO 2 H CH 2= CHCH 2 NO 2 CI CF3 H NO 2NO 2 H CH 2 = CHCH 2 NO 2 CI CF 3 H NO 2
NO 2 H CH≡CCH2 NO 2 OEt CF3 H NO 2NO 2 H CH≡CCH 2 NO 2 OEt CF 3 H NO 2
NO 2 H CHョ CCH2 NO 2 CI CF3 H NO 2 NO 2 H CH CCH 2 NO 2 CI CF 3 H NO 2
第 2表 Table 2
Figure imgf000015_0001
Figure imgf000015_0001
ベンゼン環上置換基 Substituent on benzene ring
R 2 R 3 R 4 2位 3位 （Z ) 4位 5位 6位 R 2 R 3 R 4 2nd 3rd (Z) 4th 5th 6th
H H NO 2 H NO 2 H CF-H H NO 2 H NO 2 H CF-
H H H H NO 2 H NO'H H H H NO 2 H NO '
F H H H H NO 2 H CFF H H H H NO 2 H CF
H H NO 2 H NO 2 H NOH H NO 2 H NO 2 H NO
H H CI H NO 2 H ClH H CI H NO 2 H Cl
H H NO 2 H CF3 H NOHH NO 2 H CF 3 H NO
H H NO 2 H H H NOH H NO 2 H H H NO
F H H CFs H NO 2 H CFF H H CFs H NO 2 H CF
F H H NO 2 CI CFs H NO
Figure imgf000015_0002
FHH NO 2 CI CFs H NO
Figure imgf000015_0002
F H H NO 2 OPh-OH-m CFs H NO F H H NO 2 OPh-OH-m CFs H NO
F H H H CI CFa H NOF H H H CI CFa H NO
1? u n u n NO, Γ H NO1? U n u n NO, Γ H NO
F H H NO 2 Br CFs H NOF H H NO 2 Br CFs H NO
F H Me N02 CI CF3 H NO
Figure imgf000015_0003
FH Me N0 2 CI CF 3 H NO
Figure imgf000015_0003
F H SOsMe NO 2 CI CFa H NOFH SOsMe NO 2 CI CFa H NO
F H SCC NO 2 ci - CF3 H NOFH SCC NO 2 ci-CF 3 H NO
F H COEt NO 2 CI CFa H NOF H COEt NO 2 CI CFa H NO
F Me H NO 2 CI CFa H NO
Figure imgf000015_0004
F Me H NO 2 CI CFa H NO
Figure imgf000015_0004
F CI H NO 2 H H H NO F CI H NO 2 H H H NO
F H H NO 2 F CFs H NOF H H NO 2 F CFs H NO
C1 H H NO 2 H NO 2 H CFC1 H H NO 2 H NO 2 H CF
C1 H H H H NO 2 H NOC1 H H H H NO 2 H NO
C1 H H H H NO 2 H CFC1 HHHH NO 2 H CF
C1 H H NO 2 H NO 2 H NOC1 H H NO 2 H NO 2 H NO
C1 H H CI H NO 2 H Cl 第 2¾ ^き C1 HH CI H NO 2 H Cl 2nd ^ ^
ベンゼン環上鼂換基  Exchange group on benzene ring
1\ 2 3 4 2位 3位 ( Z ) 4位 5位 6位 1 \ 2 3 4 2nd 3rd (Z) 4th 5th 6th
C1 H H NO 2 H CFs H NO 2C1 H H NO 2 H CFs H NO 2
C1 H H NO 2 H H H NO 2
Figure imgf000016_0001
C1 HH NO 2 HHH NO 2
Figure imgf000016_0001
C1 H H NO 2 CI CF3 H NO 2C1 HH NO 2 CI CF 3 H NO 2
C1 H H NO 2 OEt CF3 H NO 2C1 HH NO 2 OEt CF 3 H NO 2
C1 H H NO 2 OPh-OH-m CF3 H NO 2C1 HH NO 2 OPh-OH-m CF 3 H NO 2
C1 H H H CI CF3 H NO 2
Figure imgf000016_0002
C1 HHH CI CF 3 H NO 2
Figure imgf000016_0002
C1 H S02Me NO 2 CI CFs H NO 2 C1 H S0 2 Me NO 2 CI CFs H NO 2
Figure imgf000016_0003
Figure imgf000016_0003
C1 H H NO 2 F CFs H NO 2 C1 H H NO 2 F CFs H NO 2
Br H H NO 2 CI CFs H NO 2Br H H NO 2 CI CFs H NO 2
Br H H NO 2 OEt CF3 H NO 2
Figure imgf000016_0004
Br HH NO 2 OEt CF 3 H NO 2
Figure imgf000016_0004
I H H NO 2 CI CFs H NO 2 I H H NO 2 CI CFs H NO 2
CF3 H H NO 2 H NO 2 H CF3
Figure imgf000016_0005
CF 3 HH NO 2 H NO 2 H CF 3
Figure imgf000016_0005
CF3 H H NO 2 H ' NO 2 H NO 2CF 3 HH NO 2 H 'NO 2 H NO 2
CF3 H H NO 2 H CFs H NO 2CF 3 HH NO 2 H CFs H NO 2
CF3 H H NO 2 H H H NO 2CF 3 HH NO 2 HHH NO 2
CF3 H H CFs H NO 2 H CFsCF 3 HH CFs H NO 2 H CFs
CFs H H NO 2 CI CFs H NO 2CFs H H NO 2 CI CFs H NO 2
CF3 H H NO 2 OEt CFs H N02
Figure imgf000016_0006
CF 3 HH NO 2 OEt CFs H N0 2
Figure imgf000016_0006
CF3 H H NO 2 Br CF3 H NO 2CF 3 HH NO 2 Br CF 3 H NO 2
CF3 H Me NO 2 CI CFs H NO 2CF 3 H Me NO 2 CI CFs H NO 2
CF3 Me H NO 2 CI CFa H NO 2CF 3 Me H NO 2 CI CFa H NO 2
CF3 Et H NO 2 CI CFs H NO 2CF 3 Et H NO 2 CI CFs H NO 2
CF3 CI H NO 2 CI CFs H NO 2 第 2 き CF 3 CI H NO 2 CI CFs H NO 2 Second
ベンゼン環上置換基  Substituent on benzene ring
R 2 R 3 R 4 2位 3位 ( Z ) 4位 5位 6位
Figure imgf000017_0001
R 2 R 3 R 4 2nd 3rd (Z) 4th 5th 6th
Figure imgf000017_0001
Me H - H NO 2 H NO 2 H CF3 Me H-H NO 2 H NO 2 H CF 3
Me H H H H NO 2 H NO 2 Me H H H H NO 2 H NO 2
3  Three
Figure imgf000017_0002
Figure imgf000017_0002
Me H Me NO 2 CI CFs H NO 2 Me H Me NO 2 CI CFs H NO 2
Me H COMe NO 2 CI H NO 2Me H COMe NO 2 CI H NO 2
Me H SO 2 Me NO 2 CI CFa H NO 2Me H SO 2 Me NO 2 CI CFa H NO 2
Me H SCC NO 2 CI CFa H NO 2Me H SCC NO 2 CI CFa H NO 2
Me H COEt NO 2 CI CFs H NO 2
Figure imgf000017_0003
Me H COEt NO 2 CI CFs H NO 2
Figure imgf000017_0003
Me Et H NO 2 CI CFs H NO 2 Me Et H NO 2 CI CFs H NO 2
Me CI H NO 2 H H H NO 2Me CI H NO 2 H H H NO 2
Me H H NO 2 F CFa H NO 2Me H H NO 2 F CFa H NO 2
MeO H H NO 2 H NO 2 H CFsMeO H H NO 2 H NO 2 H CFs
MeO H H H H NO 2 H NO 2
Figure imgf000017_0004
MeO HHHH NO 2 H NO 2
Figure imgf000017_0004
MeO H H CI H NO 2 H し 1 MeO H H CI H NO 2 H 1
MeO H H NO 2 H CFs H NO 2MeO H H NO 2 H CFs H NO 2
MeO H H NO 2 H H H NO 2
Figure imgf000017_0005
MeO HH NO 2 HHH NO 2
Figure imgf000017_0005
MeO H H NO 2 CI CFs H NO 2MeO HH NO 2 CI CFs H NO 2
MeO H H NO 2 OEt CF3 H NO 2MeO HH NO 2 OEt CF 3 H NO 2
MeO H H NO 2 OPh-OH-m CFs H NO 2MeO HH NO 2 OPh-OH-m CFs H NO 2
MeO H H H C I CFs H NO 2MeO H H H C I CFs H NO 2
MeO H H NO 2 OPr-n CFs H NO 2 第 2織き
Figure imgf000018_0001
MeO HH NO 2 OPr-n CFs H NO 2 2nd weave
Figure imgf000018_0001
MeO Η Η NO 2 Br CF3 H NO 2 eO Η Me NO 2 CI CFs H NO 2
Figure imgf000018_0002
MeO Η Η NO 2 Br CF 3 H NO 2 eO Η Me NO 2 CI CFs H NO 2
Figure imgf000018_0002
MeO Η SO 2 Me NO 2 ci CF3 H NO 2MeO Η SO 2 Me NO 2 ci CF 3 H NO 2
MeO Η sec NO 2 CI CF3 H NO 2MeO Η sec NO 2 CI CF 3 H NO 2
MeO Η COEt NO 2 CI CFs H NO 2MeO Η COEt NO 2 CI CFs H NO 2
Hl / Μρ H NO 2 ci CF3 H NO
Figure imgf000018_0003
Hl / Μρ H NO 2 ci CF 3 H NO
Figure imgf000018_0003
Γ 1] H NO 2 H H H NO Γ 1] H NO 2 H H H NO
MPO Η H NO 2 F CFs H NOMPO Η H NO 2 F CFs H NO
Vi 2 Η 11 H NO 2 H NO 2 H CF
Figure imgf000018_0004
Vi 2 Η 11 H NO 2 H NO 2 H CF
Figure imgf000018_0004
U  U
1 W 2 π u n H 1 H NO 1 W 2 π u n H 1 H NO
1 U2 U η n H 11 H H NO1 U2 U η n H 11 H H NO
1 VJ2 υ η U n し Γ 3 H 11 Μ IiΠ 2 H 1 VJ2 υ η U n Γ 3 H 11 Μ IiΠ 2 H
1 U2 u π u n し 1 し Γ 3 NO riU2
Figure imgf000018_0005
レ Γ 3 H 11 NO1 U2 u π un then 1 Γ 3 NO riU2
Figure imgf000018_0005
レ H 3 H 11 NO
U U
1 U2 Π u n U n し 1 rしp Γ 3„ H 11 NO 1 U2 Π u n U n then 1 r then p Γ 3 „H 11 NO
UU
I U2 π u n DI し Γ 3 u Π l wnVI U2 π u n DI Γ 3 u Π l wnV
U π ale し 1 し Γ 3 n ΜΠリU π ale then 1 Γ 3 n
UU
I U2 6 n i 2 Πレ 1 し Γ 3 u n ΜΠ u し Γ 11 r I U2 6 n i 2 Π 1 3 u n ΜΠ u Γ 11 r
I U2 HL  I U2 HL
Γし 11
Figure imgf000018_0006
Pashi 11
Figure imgf000018_0006
u  u
1 U2 Π u Π Γ レ Γ 3 u π NO τ?  1 U2 Π u Π Γ レ Γ 3 u π NO τ?
Γ η rしu Π2^―― ΓしΗ ΠΓしΗ Π2 l U2 し 1 レ Γ 3 H 11 Ν liΩv υ  Η η r し u Π2 ^ ―― Γ Η ΠΓ Η l2 l U2 1 1 Γ H 3 H 11 Ν liΩv υ
Γ π し Π―しし Π2 リ H/し し！13 11 N 1，Oリ Γ π Π Π Π 2 Π H / H! 1 3 11 N 1, O
ΜΛ U ΜΛ U
Γ Π LH =しし H2 WU2 し し! ^ Λ Π Π LH = Shi H2 WU2 Shi! ^ Λ
3 n I U 3 n I U
F Me CH2=CHCH2 N02 CI CFs H NO
Figure imgf000018_0007
F Me CH 2 = CHCH 2 N02 CI CFs H NO
Figure imgf000018_0007
F Η CH≡CCH2 NO 2 F CF3 H NOF Η CH≡CCH 2 NO 2 F CF 3 H NO
C1 Η CH2=CHCH2 NO2 CI CFs H NOC1 Η CH 2 = CHCH 2 NO2 CI CFs H NO
C1 Η CH≡CCH2 NO2 OEt CFs H NO C1 Η CH≡CCH 2 NO2 OEt CFs H NO
C
Figure imgf000018_0008
1 Me し Π2 NO2 CI CF3 H NO 第 2雄き C
Figure imgf000018_0008
1 Me Π2 NO2 CI CF 3 H NO Second male
ベンゼン環上置換基  Substituent on benzene ring
R2 R3 R4 2位 3位 (Z) 4位 5位 6位R 2 R 3 R 4 2nd 3rd (Z) 4th 5th 6th
C1 CI CH2 == CHCH 2 NO 2 CI CF3 H NO 2 C1 CI CH2 == CHCH 2 NO 2 CI CF 3 H NO 2
C1 H - CH≡CCH2 NO 2 F CFs H NO 2C1 H-CH≡CCH 2 NO 2 F CFs H NO 2
Br H CH2— CHCH 2 NO 2 CI CF3 H NO 2Br H CH2— CHCH 2 NO 2 CI CF 3 H NO 2
Br H CH≡CCH2 NO 2 OEt CF3 H NO 2Br H CH≡CCH 2 NO 2 OEt CF 3 H NO 2
Br H CH≡CCH2 NO 2 CI CFa H NO 2Br H CH≡CCH 2 NO 2 CI CFa H NO 2
I H CH2 = CHCH2 NO 2 CI CF3 H NO 2IH CH 2 = CHCH 2 NO 2 CI CF 3 H NO 2
I H CH≡CCH2 NO 2 OEt CF3 H NO 2IH CH≡CCH 2 NO 2 OEt CF 3 H NO 2
I H CH≡CCH2 NO 2 CI CF3 H NO 2IH CH≡CCH 2 NO 2 CI CF 3 H NO 2
CFs H し M2——し ϋし M2 NO 2 CI CF3 H NO 2CFs H then M2 —— M2 NO 2 CI CF 3 H NO 2
CFs H CH≡CCH2 NO 2 OEt CF3 H NO 2CFs H CH≡CCH 2 NO 2 OEt CF 3 H NO 2
CF3 H CH≡CCH2 NO 2 CI CF3 H NO 2CF 3 H CH≡CCH 2 NO 2 CI CF 3 H NO 2
CF3 Me CH2 = CHCH 2 NO 2 CI CFs H NO 2CF 3 Me CH2 = CHCH 2 NO 2 CI CFs H NO 2
CF3 CI CH2 = CHCH 2 NO 2 CI CFa H NO 2CF 3 CI CH2 = CHCH 2 NO 2 CI CFa H NO 2
CFa H CH≡CCH2 NO 2 F CFa H NO:CFa H CH≡CCH 2 NO 2 F CFa H NO:
Me H CH2 = CHCH 2 NO 2 CI CFa H NO:Me H CH2 = CHCH 2 NO 2 CI CFa H NO:
Me H CH≡CCH2 NO 2 OEt CFs H NO;Me H CH≡CCH 2 NO 2 OEt CFs H NO;
Me H CH≡CCH2 NO 2 CI CFs H NO;Me H CH≡CCH 2 NO 2 CI CFs H NO;
Me Me CH 2 = CHCH 2 NO 2 CI CFs H NO;Me Me CH 2 = CHCH 2 NO 2 CI CFs H NO;
Me CI CH 2— CHCH 2 NO 2 CI CFa H NO.
Figure imgf000019_0001
Me CI CH 2— CHCH 2 NO 2 CI CFa H NO.
Figure imgf000019_0001
MeO H CH≡CCH2 NO 2 OEt CF3 H NOMeO H CH≡CCH 2 NO 2 OEt CF3 H NO
MeO H CH≡CCH2 NO 2 CI CF3 H NOMeO H CH≡CCH 2 NO 2 CI CF3 H NO
MeO Me CH2 =CHCH2 NO 2 CI CFa H NOMeO Me CH 2 = CHCH 2 NO 2 CI CFa H NO
MeO CI CH2— CHCH 2 NO 2 CI CFa H NOMeO CI CH2— CHCH 2 NO 2 CI CFa H NO
MeO H CH≡CCH2 NO2 F CFs H NOMeO H CH≡CCH 2 NO2 F CFs H NO
NO 2 H CH2 = CHCH 2 NO 2 CI CF3 H NONO 2 H CH2 = CHCH 2 NO 2 CI CF3 H NO
NO 2 H CHョ CCH2 NO2 OEt CF3 H NONO 2 H CH CCH 2 NO2 OEt CF 3 H NO
NO 2 H CH≡CCH2 NO 2 CI CFa H NONO 2 H CH≡CCH 2 NO 2 CI CFa H NO
NO 2 Me CH2 =CHCH2 NO 2 CI CFa H NONO 2 Me CH 2 = CHCH 2 NO 2 CI CFa H NO
NO 2 CI CH 2 = CHCH 2 NO 2 CI CF3 H NONO 2 CI CH 2 = CHCH 2 NO 2 CI CF 3 H NO
NO 2 H CH≡CCH2 NO 2 F CFa H NO NO 2 H CH≡CCH 2 NO 2 F CFa H NO
Figure imgf000020_0001
Figure imgf000020_0001
ベンゼン環上電換基 Exchange group on benzene ring
R 1 R2 R3 R4 2位 3位 （Z) 4位 5位 6位 R 1 R 2 R 3 R 4 2nd 3rd (Z) 4th 5th 6th
F F H H NO 2 H NO 2 H CF3 FFHH NO 2 H NO 2 H CF 3
F F H H H H NO 2 H NO 2F F H H H H NO 2 H NO 2
F F H H H H NO 2 H CF3 FFHHHH NO 2 H CF 3
F F H H N02 H NO 2 H NO 2
Figure imgf000020_0002
FFHH N0 2 H NO 2 H NO 2
Figure imgf000020_0002
F F Et H NO 2 CI CF3 H NO 2 FF Et H NO 2 CI CF 3 H NO 2
Figure imgf000020_0003
Figure imgf000020_0003
F F H SCC 13 NO 2 CI CFs H NO 2FFH SCC 1 3 NO 2 CI CFs H NO 2
F F H CH2=CHCH2 NO 2 CI CFa H NO 2FFH CH 2 = CHCH 2 NO 2 CI CFa H NO 2
F F H CHョ CCH2 NO 2 OEt CF3 H NO 2FFH CH CCH 2 NO 2 OEt CF 3 H NO 2
F F H CH≡CCH2 NO 2 CI CF3 H NO 2
Figure imgf000020_0004
FFH CH≡CCH 2 NO 2 CI CF 3 H NO 2
Figure imgf000020_0004
C1 C1 H H H H NO 2 H NO 2 C1 C1 H H H H NO 2 H NO 2
C1 C1 H H H H NO 2 H CF3
Figure imgf000020_0005
C1 C1 HHHH NO 2 H CF 3
Figure imgf000020_0005
C1 C1 H H NO 2 CI CFa H NO 2 C1 C1 H H NO 2 CI CFa H NO 2
C1 C1 H H NO 2 OEt CF3 H NO 2C1 C1 HH NO 2 OEt CF 3 H NO 2
C1 C1 Me H NO 2 CI CF3 H NO 2C1 C1 Me H NO 2 CI CF 3 H NO 2
C1 C1 Et H NO 2 CI CF3 H NO 2C1 C1 Et H NO 2 CI CF 3 H NO 2
C1 C1 CI H NO 2 CI CF3 H NO 2
Figure imgf000020_0006
C1 C1 CI H NO 2 CI CF 3 H NO 2
Figure imgf000020_0006
C1 C1 H Me NO 2 CI CF3 H NO 2 第 3難き ベンゼン環上置換某 C1 C1 H Me NO 2 CI CF 3 H NO 2 Third difficult substitution on the benzene ring
R 1 R2 R3 R4 2位 3位 （Z) 4位 5位 6位R 1 R 2 R 3 R 4 2nd 3rd (Z) 4th 5th 6th
C1 CI H COMe NO 2 CI CFa H NO 2 C1 CI H COMe NO 2 CI CFa H NO 2
C1 CI H SO 2 Me NO 2 CI CFa H NO 2
Figure imgf000021_0001
C1 CI H SO 2 Me NO 2 CI CFa H NO 2
Figure imgf000021_0001
C1 CI H CH≡CCH2 NO 2 OEt CF3 H NO 2 C1 CI H CH≡CCH2 NO 2 OEt CF3 H NO 2
CI CI H CH≡CCH2 NO 2 CI CF3 H NO 2 CI CI H CH≡CCH2 NO 2 CI CF 3 H NO 2
CI NO 2 H Η NO 2 H NO 2 H CF3 CI NO 2 H Η NO 2 H NO 2 H CF 3
CI NO 2 H ，， CI NO 2 H ,,
2
Figure imgf000021_0002
Two
Figure imgf000021_0002
CI NO 2 H Η NO 2 H NO 2 H NO 2 CI NO 2 H Η NO 2 H NO 2 H NO 2
CI NO a H Η NO 2 CI CFa H NO 2 CI NO a H Η NO 2 CI CFa H NO 2
CI NO 2 H Η NO 2 OEt CF3 H NO 2CI NO 2 H Η NO 2 OEt CF 3 H NO 2
CI NO 2 Me Η NO 2 CI CF3 H NO 2CI NO 2 Me Η NO 2 CI CF 3 H NO 2
CI NO 2 Et Η NO 2 CI CFs H NO 2
Figure imgf000021_0003
CI NO 2 Et Η NO 2 CI CFs H NO 2
Figure imgf000021_0003
CI NO 2 H Η NO 2 F CF3 H NO 2CI NO 2 H Η NO 2 F CF 3 H NO 2
CI NO 2 H Me NO 2 CI CF3 H NO 2CI NO 2 H Me NO 2 CI CF 3 H NO 2
CI NO 2 H COMe NO 2 CI CF3 H NO 2CI NO 2 H COMe NO 2 CI CF 3 H NO 2
CI NO 2 H SO 2 Me NO 2 CI CF3 H NO 2 CI NO 2 H SO 2 Me NO 2 CI CF 3 H NO 2
CI NO 2 H SCC NO 2 CI CFs H NO 2CI NO 2 H SCC NO 2 CI CFs H NO 2
CI NO 2 H CH2=CHCH2 NO 2 CI CFs H NO 2CI NO 2 H CH 2 = CHCH 2 NO 2 CI CFs H NO 2
CI NO 2 H CHョ CCH2 NO 2 OEt CF3 H NO 2CI NO 2 H CH CCH 2 NO 2 OEt CF 3 H NO 2
CI NO 2 H CH≡CCH2 NO 2 CI CFs H NO 2
Figure imgf000021_0004
CI NO 2 H CH≡CCH 2 NO 2 CI CFs H NO 2
Figure imgf000021_0004
Me CI H H H . H NO 2 H CF3 Me CI HHH. H NO 2 H CF 3
Me CI H H NO 2 H NO 2 H NO 2 Me CI HH NO 2 H NO 2 H NO 2
Me CI H H NO 2 CI CF3 H NO 2
Figure imgf000021_0005
Me CI HH NO 2 CI CF 3 H NO 2
Figure imgf000021_0005
Me CI Me H NO 2 CI CFs H NO 2 Me CI Me H NO 2 CI CFs H NO 2
Me CI Et H NO 2 CI CFa H NO 2Me CI Et H NO 2 CI CFa H NO 2
Me CI CI H NO 2 CI CFs H N02 Me CI CI H NO 2 CI CFs H N0 2
Me CI H H NO 2 F CFa H NO 2
Figure imgf000021_0006
Me CI HH NO 2 F CFa H NO 2
Figure imgf000021_0006
Me CI H COMe NO 2 CI CFa H NO 2 Me CI H COMe NO 2 CI CFa H NO 2
Me CI H SO 2 Me NO 2 CI CFs H NO 2 第 3表 さ Me CI H SO 2 Me NO 2 CI CFs H NO 2 Table 3
ベンゼン環上置換基  Substituent on benzene ring
r> 1 2 3 P ο / 1 ( 7  r> 1 2 3 P ο / 1 (7
K Δ, } 0 >L D  K Δ,} 0> L D
Me CI H scc NO 2 C1 CF3 H NO 2 Me CI H scc NO 2 C1 CF3 H NO 2
Me CI . H CH2二 CHCH2 NO 2 C1 CF3 H NO 2Me CI .H CH2 two CHCH2 NO 2 C1 CF3 H NO 2
Me CI H CH≡CCH2 NO 2 OEt CF3 H N02Me CI H CH≡CCH 2 NO 2 OEt CF 3 H N02
Me CI H CH≡CCH2 NO 2 C1 CF3 H N02Me CI H CH≡CCH 2 NO 2 C1 CF 3 H N02
NO H H Η liU 2 u Π し Γ 3
Figure imgf000022_0001
NO HH Η liU 2 u Π Γ Γ 3
Figure imgf000022_0001
NO? H H H Η i \J 2 n し Γ 3
Figure imgf000022_0002
NO? HHH Η i \ J 2 n then Γ 3
Figure imgf000022_0002
V\J 2 H 1 H1 IH 2 广し Γ 3 u  V \ J 2 H 1 H1 IH 2 广 3 u
Π ΜΛ Π ΜΛ
IVlcW Up 丄 1 ΝΠ。 uIVlcW Up 丄 1 ΝΠ. u
2
Figure imgf000022_0003
2Two
Figure imgf000022_0003
Two
Ν lΠV 2 し I u n 1 U2 uΝ lΠV 2 then I u n 1 U2 u
Figure imgf000022_0004
Figure imgf000022_0004
MeO N02 H Me Νθ2 CI CF3 H NO 2 MeO N02 H Me Νθ2 CI CF3 H NO 2
MeO N02 H COMe Ν02 CI CF3 H NO 2MeO N02 H COMe Ν02 CI CF3 H NO 2
MeO N02 H S02Me Ν02 CI CF3 H NO2 MeO N02 H S0 2 Me Ν02 CI CF3 H NO2
MeO N02 H SCC Ν02 CI CF3 H NO 2MeO N02 H SCC Ν0 2 CI CF3 H NO 2
MeO NO 2 H CH2
Figure imgf000022_0005
Ν02 CI CFs H NO 2MeO NO 2 H CH2
Figure imgf000022_0005
Ν0 2 CI CFs H NO 2
MeO N02 H CH≡CCH2 Ν02 OEt CF3 H NO 2MeO N02 H CH≡CCH 2 Ν0 2 OEt CF3 H NO 2
MeO NO 2 H CH≡CCH2 Ν02 CI CFs H NO 2 MeO NO 2 H CH≡CCH 2 Ν0 2 CI CFs H NO 2
本発明の N—キノキザリルァニリン類は、 特開昭 60 - 97964号 を参 考に通常、 例えば下記の （a)、 (b)又は（c)の方法により製造できる。 但し、 下 式中の Z1 、 Z2 及び Z3 は、 前記"^式（1)中の Zに包含さ The N-quinoxalylanilines of the present invention can be usually produced, for example, by the following method (a), (b) or (c) with reference to JP-A-60-97964. However, Z 1 , Z 2 and Z 3 in the following formula are included in Z in the above “^ formula (1).
(a) Z1 が水素原子、 ハロゲン原子の場合； (a) when Z 1 is a hydrogen atom or a halogen atom;
Figure imgf000023_0001
Figure imgf000023_0001
上言 Β ίΕ¾ϊにおいて R 1、 R2、 R8、 X、 Y、 m、 n、 j及び kは前述と同 じであり、 H a 1は塩素原子又は弗素原子などのハロゲン原子であり、 Z 1 は水 素原子又はノ、口ゲン原子である。 In the above formula, R 1 , R 2 , R 8 , X, Y, m, n, j and k are the same as those described above, and Ha 1 is a halogen atom such as a chlorine atom or a fluorine atom; 1 is a hydrogen atom, a hydrogen atom or a halogen atom.
この^ J に用いる酸受容体としては、 例えばアルカリ^ の m化物、 化 物、 素化物、 水素化物又はアルカリ: の水酸化物、 難化物などが 举げられるが、 望ましくは水酸化カリウム、 水素化ナトリウムなどである。  Examples of the acid acceptor used for ^ J include alkali metal moxides, compounds, hydrides, hydrides or alkali: hydroxides and refractory compounds, and preferably potassium hydroxide, hydrogen And sodium chloride.
上 は好ましくは、 ジメチルホルムアミド、 ジメチルスルホキシド、 スル ホラン、 テトラヒド口フラン、 ジォキサンなどの非プロトン性極¾ ^中で、 適 当な S、 例えば— 5 0〜1 0 0でで 0. 5〜2 4時問攪拌することにより行う。  The above is preferably in an aprotic electrode such as dimethylformamide, dimethylsulfoxide, sulfolane, tetrahydrofuran, dioxane, etc., and a suitable S, e.g. Perform by stirring for 4 hours.
(b) Z3 がアルコキシ基又はハロゲン原子、 ニトロ基又は; ^基で置換され てもよぃフヱノキシ基の場合； (b) when Z 3 is an alkoxy group or a halogen atom, a nitro group or a phenoxy group which may be substituted with a ^ group;
Figure imgf000023_0002
上 11¾£¾；において、 Ζ2は塩素原子、 臭素原^^のハロゲン原子を表し、 R R2、 R3、 X、 Y、 m、 n、 jおよび kは前述と同じであり、 Z 8 はアルコキ シ基又はハロゲン原子、 ニトロ基又は水酸基で置換されてもよいフヱノキシ基で める。 この Si芯に用いる酸受容体は、 ίίΙ己 ( a) の方法で用いることのできるものと 同一で、 よく使用される溶媒は、 請己の非プロトン性極 ½^媒の他にメタノール、 エタノールなどのアルコール類、 四塩ィ ^、 クロ πホルム、 m—ジクロ口ベン ゼンなどのハロゲン化炭ィ b7j素などが举げられる。
Figure imgf000023_0002
In the above 11¾ £ ¾, Ζ 2 represents a chlorine atom, a halogen atom of a bromine atom ^^, RR 2 , R 3 , X, Y, m, n, j and k are the same as described above, and Z 8 is It can be substituted with an alkoxy group or a phenoxy group which may be substituted with a halogen atom, a nitro group or a hydroxyl group. The acid acceptor used for this Si core is the same as that which can be used in the method of self (a), and the most frequently used solvents are methanol and ethanol in addition to the aprotic polar solvent of the self Alcohols such as tetrachloride, chloroform, m-dichlorobenzene, etc.
は、 一般に一 3 0で〜 1 5 O eCであり、 反応時間は 0. 5〜2 4時間 める。 Are generally one 3 0 ~ 1 5 O e C , the reaction time is 0.5 to 2 4 hours Mel.
( c ) R4 がアルキル アルケニル基、 アルキニル ¾^ アルキルカルボニル(c) R 4 is an alkylalkenyl group, alkynyl ¾ ^ alkylcarbonyl
¾^ ァルキルスルホニル基又はハロゲン原子で置換されてもよレヽアルキルスルフ ェニル基の場合； ¾ ^ alkylsulfenyl group or a peralkylsulfenyl group which may be substituted with a halogen atom;
Figure imgf000024_0001
上記反応において、 R4 はアルキル アルケニル アルキニル アルキ ルカルポ二ル ァルキルスルホニル基又はノヽ口ゲン原子で置換されてもよぃァ ルキルスルフエ二ル基を表し、 R 1、 R2、 R8、 X、 Y、 Z、 m、 n、 j及び kは前述と同じであり、 H a 1は塩素原子、 臭素原子又はヨウ素原子等のハロゲ ン原子を表す。
Figure imgf000024_0001
In the above reaction, R 4 represents an alkyl alkenyl alkynyl alkyl carbonyl alkyl sulfonyl group or a alkyl sulfenyl group which may be substituted with a nitrogen atom, and R 1 , R 2 , R 8 , X, Y , Z, m, n, j and k are the same as described above, and Ha1 represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom.
この跡に用いる酸受容体としては、 t (a) の方法で挙げたものの他に 3 級ァミン類、 ピリジン類などが挙げられるが、 望ましくはアルキル化、 アルケニ ルイ b¾びアルキニル化には水素化ナトリゥムが、 その他にはトリェチルァミン又 はピリジンが適している。  Examples of the acid acceptor used in this step include tertiary amines, pyridines, and the like in addition to those described in the method of t (a), and hydrogenation is preferable for alkylation, alkenyl alkyne and alkynylation. Sodium is suitable, and triethylamine or pyridine is also suitable.
上言 assは、 爾己（a) の方法で举げた非プロトン性極雌媒の他に四塩ィ 素、 クロ口ホルム、 m—ジクロ σベンゼンなどのハロゲン化炭ィ 素、 又はベン ゼン、 トルエン、 キシレンなどの芳香族炭ィ 7素などの溶媒中で行なわれる。 反応温度は、 一般に一 30で〜 1 50 °Cであり、 反応時間は 0. 5〜 24時間で める。 The above ass is defined as the aprotic polar female medium obtained by the method of Ami (a), as well as carbon halides such as tetrachloride, chloroform, m-dichloroσbenzene, or benzene. The reaction is performed in a solvent such as aromatic carbon such as benzene, toluene, or xylene. The reaction temperature is generally 130 to 150 ° C, and the reaction time is 0.5 to 24 hours.
(a) 、 （b) および （c) の方法で得られた目的化合物は、 適当な溶媒で再 結晶、 カラムク σマトグラフィーなどで精製して純品として得られる。  The target compound obtained by the methods (a), (b) and (c) can be obtained as a pure product by recrystallization in an appropriate solvent, purification by column chromatography and the like.
本発明にぉレ、て有効成分として使用する Ν—キノキザリルァニリン類は で 使用してもよく、 また本発明の工業用抗菌 ·抗カビ剤、 画剤及び生物付着防止 剤を使用する場合、 により、 他の公知の工業用抗菌'抗カピ剤、 剤又は 生物付着防!^をさらに含有させ、 混合剤として使用することができる。  The quinoxalyl anilines used as the active ingredient in the present invention may be used in the present invention, and the industrial antibacterial and antifungal agent, the paint agent and the biofouling inhibitor of the present invention are used. In some cases, other known antibacterial agents for industrial use, such as anti-capi agents, agents or biofouling preventives can be further contained and used as a mixture.
以下に代表例を列記するが、 これらに限定されるものではない。  Representative examples are listed below, but are not limited thereto.
亜酸ィ 、 4級アンモニゥム化合物、 ァリルイソチオシァネート、 2—ァミノ — 3—クロ口一 1, 4一ナフトキノン、 エチレン一ビス一チオシァネート、 2— η—ォクチルー 3—イソチアゾロン、 グルタルアルデヒド、 5—クロロー 2— η —デシル一 3—イソチアゾロン、 5—クロ π— 2, 4—ジフルオロー 6—メトキ シイソフタロニトリル、 2—クロ口一 4—メチルァミノ一（5—イソプロピルアミ ノー s—トリアジン、 5—クロロー 2—メチルー 3—イソチアゾロン、 2, 3 - ジクロロー 1, 4一ナフトキノン、 ジョ一ドメチルー ρ—トリルスルホン、 Ν, Ν—ジメチルー Ν， 一フエニル— Ν， 一 （フルォロジクロロメチルチオ） スルフ アミ ド、 Ν- (3, 4—ジクロロフエニル） 一 Ν， 一メチルゥレア、 Ν, Ν—ジ メチル一 N' - (3, 4—ジクロロフエニル） ゥレア、 ジンクジメチルジチォカ —バメート、 2, 6—ジクロ α— 3， 5—ジシァノ一 4—フエ二ルビリジン、 2, 4ージクロ口一 6— (0—クロロア二リノ） 一 s—トリアジン、 4, 5—ジクロ 口一 2— (4—クロ口ベンジル） 一 3—イソチアゾロン、 4, 5—ジクロロ一 2 ― (4—クロ口フエニル） 一 3—^ Γソチアゾロン、 4, 5 -ジクロロ一 2— η— へキシル— 3—イソチアゾロン、 4, 5—ジクロ π— 2— 11—ォクチルー 3 Γ ソチアゾロン、 1、 2—ジブ口モー 2、 4 一ジシァノブタン、 2 , 2—ジブロ乇 —3—二トリ口プロピオンアミ ド、 2—チオシァノメチルチオべンゾチアゾ一ル， 2 - ( 4—チアゾリル） ベンズイミダゾ一ル、 チアベンダゾ一ル、 テトラフルォ 口イソフタロニトリル、 2 , 3 , 5 , 6—テトラクロ口— 4— (メチルスルホニ ル） ピリジン、 テトラフェニルボランピリジン塩、 テトラメチルチウラムジスル フィ ド、 テトラェチルチウラムジスルフィ ド、 テトライソプ αピルチウラムジス ルフィ ド、 テトラ— η—ブチルチウラムジスルフィ ド、 テトラクロ口イソフタ口 二トリル、 テトラクロ口フタロニトリル、 C u— 1 0 %N i固溶合金、 N—トリ クロロメチルチオテトラヒドロフタルイミ ド、 N—トリクロロメチルチオフタル イミ ド、 2 , 3 , 6 —トリクロロー 4 一プロピルスルホ二ルビリジン、 N— ( 2 , 4 , 6—トリクロ口フエニル） マレイミ ド、 4 , 5 —トリメチレン一 2—メチル —3—イソチアゾロン、 2—ピリジンチオール— 1 —ォキシド 塩、 2 , 3 , 3—トリョードアリルアルコール、 N— (フルォロジクロ πメチルチオ） フタル イミ ド、 ビスジメチルジチ才力ルバモイルジンクエチレンビスジチォカーバメ一 ト、 N—フエネチルジクロロマレイミ ド、 2—ブロモ一 2—ニト σプロノ、。ンジォ —ル、 5 —ブロモ— 5 —ニトロ一 1， 3—ジォキサン、 ブロモクロロジメチルヒ ダントイン、 Ν—ベンジルジクロロマレイミ ド、 1 , 2—べンズイソチアゾリン 一 3 —オン、 2— （メトキシカルボニルァミノ） ベンズイミダゾ一ル、 4—メチ ルー 5 —クロ口— 2— η—ォクチルー 3 —イソチアゾロン、 2—メチルチオ一 4 一 t —ブチルアミノー 6 —シクロプロピルアミノー s —トリアジン、 N— 2—メ チルー 6—ェチルフヱニルジクロロマレイミ ド、 2—メチル— 3 —イソチアゾ π ン、 メチレン—ビス—チオシァネート、 3 —ョ—ドー 2—プロピニルプチルカ一 バメート、 ョードプロパルギルブチルカ一バメート。 Acid hypochlorite, quaternary ammonium compound, arylisothiocyanate, 2-amino-3,4-chloro-1,4-naphthoquinone, ethylenebisbisthiothionate, 2-η-octyl-3-isothiazolone, glutaraldehyde, 5 —Chloro-2— η —decyl-1-3-isothiazolone, 5-chloro π—2,4-difluoro-6-methoxyisophthalonitrile, 2-chloro-1-4-methylamino-1 (5-isopropylamino s-triazine, 5 —Chloro-2-methyl-3-isothiazolone, 2,3-dichloro-1,4-naphthoquinone, jodomethyl-ρ-tolylsulfone, Ν, Ν-dimethyl ー, 1-phenyl—Ν, 1 (fluorodichloromethylthio) sulfamido 、, Ν- (3,4-dichlorophenyl) mono-, mono-methyl-rea, Ν, Ν-di-methyl-N '-(3,4-dichlorophenyl) ゥA, Zinc dimethyl dithioca-bamate, 2,6-dichloro α-3,5-dicyano-4-phenylphenyline, 2,4 diclo-mouth 6- (0-chloroanilino) -1-s-triazine, 4 , 5-dichloro mouth 1 2- (4-chloro benzyl) 1-3-isothiazolone, 4,5-dichloro-1- 2-(4-chlorophenyl) 1 3- ^ Γsothiazolone, 4, 5-dichloro-1 2- η—Hexyl—3-isothiazolone, 4,5-dichloro π—2—11—octyl-3 Sothiazolone, 1,2-dibutene 2,4,1-dicyanobutane, 2,2-dibromo-3,2-tripropionamide, 2-thiocyanomethylthiobenzothiothiazole, 2- (4-thiazolyl) benz Imidazole, thiabendazole, tetrafluoro-mouth isophthalonitrile, 2,3,5,6-tetrachloro- mouth 4- (methylsulfonyl) pyridine, tetraphenylboranepyridine salt, tetramethylthiuram disulfide, tetraethyl Thiuram disulfide, Tetraisop α-Pyrthiuram disulfide, Tetra-η-butylthiuram disulfide, Tetrachloride isophthalate nitrile, Tetrachloride phthalonitrile, Cu-10% Ni solid solution alloy, N-Tri Chloromethylthiotetrahydrophthalimid, N-trichloromethylthiophthalimide, 2, 3, 6- Chloro-4 monopropylsulfonyl pyridine, N— (2,4,6-trichloromethyl) maleimide, 4,5—trimethylene-1 2-methyl-3-isothiazolone, 2-pyridinethiol-1-oxide salt, 2, 3,3-Triode allyl alcohol, N- (Fluorodichloro π-methylthio) phthalimide, Bisdimethyldithirubumoyl zinc ethylene bisdithiocarbamate, N-Phenethyldichloromaleimide, 2- Bromo-2-Nitto σ-prono. N-Diol, 5-bromo-5-nitro-1,3-dioxane, bromochlorodimethylhydantoin, ベ ン ジ ル -benzyldichloromaleimide, 1,2-benzisothiazoline-13-one, 2- (methoxycarbonyla Mino) benzimidazole, 4-methyl-5-chloro-5-η-octyl-3-isothiazolone, 2-methylthio-41-t-butylamino-6-cyclopropylamino-s-triazine, N-2-methyl 6-Ethylphenyldichloromaleimide, 2-Methyl-3-isothiazopine, Methylene-bis-thiocyanate, 3-Fedo-2-propynylbutyric carbamate, and Eodopropargyl butyl carbamate.
更に、 本発明において有効成分として使用する N—キノキザリルァニリン類は 単一の化合物或レ、は数種類の N—キノキザリルァニリン類の混合物から構成され ていてもよい。 Further, the N-quinoxalylaniline used as the active ingredient in the present invention is composed of a single compound or a mixture of several types of N-quinoxalylanilines. It may be.
本発明において有効成分として使用する N—キノキザリルァニリン類は単独で の使用用途のシステムに添加されてもよいし、 又は、 存効成分と颜ならば 適切な担体または溶剤からなる混合物として、 又は、 水性乳濁物または分散物と して配合されてもよい。  The N-quinoxalyl anilines used as the active ingredient in the present invention may be added to the system for use alone or as a mixture of the active ingredient and a suitable carrier or solvent. Alternatively, it may be formulated as an aqueous emulsion or dispersion.
本発明の工業用抗菌 ·抗カビ剤、 殺藻剤及び生物付着防止剤の製剤を、 工業用 抗菌，抗カビ剤及び殺藻剤の用途分野で概説すると、 本発明において有効成分と して使用する N—キノキザリルァニリン類は、 適当な担体及び補助剤、 例えば界 面活性剤、 結合剤、 安定剤などと配合して混合し、 常法によって水和剤、 乳剤、 ゾル剤 （フロアブル剤）及びその他の適当な剤形に製剤化して使用される。  The formulation of the industrial antibacterial and antifungal agent, the algicide and the anti-biofouling agent of the present invention can be generally used in the field of industrial antibacterial, antifungal and algicidal agents. N-quinoxalylanilines are mixed with appropriate carriers and auxiliary agents, such as surfactants, binders, and stabilizers, and mixed, and then wettable powders, emulsions, sols (flowable) Agent) and other suitable dosage forms.
これらの製剤を調製する場合には、 有効成分である N—キノキザリルァニリン 類は水和剤、 乳剤、 液剤、 ゾル剤及びその他の適当な製剤が調製できる限りにお いて濃度に上限はないが、 これら製剤の重量に対し、 1— 9 0重量％、 好ましく は 3— 4 0重量％の割合で配合される。  When preparing these preparations, the upper limit of the concentration of the active ingredient, N-quinoxalylaniline, is limited as long as wettable powders, emulsions, solutions, sols, and other appropriate preparations can be prepared. However, it is incorporated in an amount of 1 to 90% by weight, preferably 3 to 40% by weight based on the weight of these preparations.
使用できる担体としては、 工業用抗菌 ·抗カビ剤及び殺藻剤に常用されるもの であれば固体又は液体のいずれも使用でき、 特定のものに限定されるものではな い。  As a carrier that can be used, any solid or liquid can be used as long as it is commonly used for industrial antibacterial and antifungal agents and algicides, and it is not limited to a specific one.
固体担体の例としては、 鉱物質粉末、 例えばカオリン、 ベントナイト、 クレー、 モンモリ□ナイト、 珪藻土、 雲母、 バーミキユラィト、 石膏、 炭酸カルシウム、 ホワイト力一ボン、 消石灰、 珪砂、 硫安、 尿素等、 又は植物性粉末、 例 えば大豆粉、 ■、 結晶セルロース等、 アルミナ、 珪酸塩、 糖重合 高分散性 珪酸、 ワックス類、 等が挙げられる。  Examples of solid carriers include mineral powders such as kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, white lime, slaked lime, silica sand, ammonium sulfate, urea, etc., or vegetable Powders, for example, soybean powder, (1), crystalline cellulose, etc., alumina, silicates, sugar polymerization, highly dispersible silicic acid, waxes and the like.
液体担体の例としては、 水、 アルコール類、 例えばメチルアルコール、 ェチル アルコール、 n—プロピルアルコール、 イソプロピルアルコール、 エチレングリ コール、 ベンジルアルコール等、 芳香族炭ィ b ]素類、 例えばベンゼン、 トルエン、 キシレン、 ェチルベンゼン、 ク Π口ベンゼン、 クメン、 メチルナフタレン等、 又 はノヽロゲン化炭ィ J素類、 例えばクロ口ホルム、 ジク口口メタン、 エチレンジク αリ ド等、 エーテル類、 例えばェチルエーテル、 ジォキサン、 テトラヒドロフラ ン等、 ケトン類、 例えばアセトン、 メチルェチルケトン、 シクロへキサノン、 メ チルイソプチルケトン等、 エステル類、 例えば酢酸ェチル、 酢酸プチル、 ェチレ ングリコールァセテ一ト、 酢酸ァミル等、 二トリル類、 例えぱァセトニトリル、 プロピオ二トリル、 アクリロニトリル等、 スルホキシド類、 例えばジメチルスル ホキシド等、 アルコールエーテル類、 例えばエチレングリコールモノメチルェ一 テル、 エチレングリコールモノェチルエーテル等、 アミン類、 例えばトリェチル アミン等、 並びに脂肪族及び脂環端化水素類、 例えば η—へキサン、 シクロへ キサン等、 きらに工業用ガソリン （石油エーテル、 ソルベントナフサ等） 及び石 油留分（パラフィン類、 灯油、 軽油等） 、 等が挙げられる。 Examples of liquid carriers include water, alcohols, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc., aromatic carbons, for example, benzene, toluene, Xylene, ethylbenzene, benzene, cumene, methylnaphthalene, etc., or nitrogenated carbon dioxide, such as chloroform, dicole, methane, ethylene di-α-lide, etc., ethers, such as ethyl ether, dioxane, etc. Ketones such as tetrahydrofuran, etc., for example, acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc., esters, for example, ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, nitrile, etc. , Such as acetonitrile, propionitrile, acrylonitrile, etc., sulfoxides, such as dimethyl sulfoxide, alcohol ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc., amines, such as Liquefied amines, and aliphatic and cycloaliphatic hydrogens such as η-hexane, cyclohexane, etc., and industrial gasoline (petroleum ether, solvent naphtha, etc.) and petroleum fractions (paraffins, kerosene, , Etc.).
乳剤、 7i和剤、 ゾル剤 （フ αアプル剤） 等の製剤の場合には、 乳化、 分散、 可 溶化、 湿潤、 発泡、 拡展等の目的で界面活性剤が配合される。 このような界面活 性剤としては、 次に示されるものが挙げられるが、 これらのもののみに限定され るものではない。  In the case of preparations such as emulsions, 7i admixtures, and sols (α-apples), surfactants are incorporated for the purpose of emulsification, dispersion, solubilization, wetting, foaming, spreading, and the like. Examples of such a surfactant include the following, but are not limited thereto.
非ィォン型界面活性剤の例としては、 ポリォキシェチレンアルキルエーテル、 ポリォキシェチレンァルキルエステル、 ポリォキシェチレンソルビタンアルキル エステル及びソルビタンアルキルエステル、 等が挙げられる。  Examples of non-ionic surfactants include polyoxetylene alkyl ether, polyoxetylene alkyl ester, polyoxetylene sorbitan alkyl ester, and sorbitan alkyl ester.
陰イオン型界面活性剤の例としては、 アルキルベンゼンスルホネート、 アルキ ルスルホサクシネート、 アルキルサルフ 一ト、 ポリオキシエチレンアルキルサ ルフヱ一ト、 ァリ一ルスルホネート及びラウリルサルフェート、 等が挙げられる。 陽イオン型界面活性剤の例としては、 アルキルアミン類 （ラウリルァミン、 ス テアリルトリメチルァンモニゥムク σリ ド及びアルキルジメチルベンジルァンモ 二ゥムク σリ ド等） 、 等が挙げられる。 両性型界面活性剤の例としては、 カルボン酸（ベタイン型）硫酸エステル、 等 が举げられる。 Examples of anionic surfactants include alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate and lauryl sulfate. Examples of the cationic surfactant include alkylamines (laurylamine, stearyltrimethylammonium σ-lide, alkyldimethylbenzylammonium σ-lide, etc.), and the like. Examples of the amphoteric surfactant include carboxylic acid (betaine type) sulfate, and the like.
また、 これらの他に、 ポリビニルアルコール （PVA) 、 カルボキシメチルセ ルロース （CMC) 、 アラビアゴム、 ポリビニルアセテート、 ゼラチン、 カゼィ ン、 アルギン酸ソ一ダ、 トラガカントゴム、 グァガム、 ザンサンガム及びヒド α キシプロピルセルロース等の増粘剤及び各種補助剤を配合することができる。 さらに に応じて酸化防！]^、 紫外線吸 ID^IJ等のような安定化剤を適 fiinえ ることができる。  In addition to these, polyvinyl alcohol (PVA), carboxymethylcellulose (CMC), gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, tragacanth gum, guar gum, xanthan gum and hide α-xypropylcellulose Thickeners and various auxiliaries can be included. Further oxidation protection according to! ] ^, UV-absorbing stabilizers such as ID ^ IJ can be used.
本発明の、 N—キノキザリルァニリン類を有効成分として含む、 工業用抗菌' 抗カビ剤、 殺藻剤としては、 以下の用途に用いることができる。  The industrial antibacterial and antifungal agents and algicides of the present invention containing N-quinoxalylanilines as an active ingredient can be used for the following applications.
水性の塗料、 接着材、 ラテックス、 アクリル等のェマルジヨン製品、 デンプン、 顔料、 炭酸カルシウム等のスラリー製品及びジョイントセメントの中の細菌、 真 菌及び藻類の生長抑制；建材（建築建材、 土木建材等） の木材の防腐；切削油の 防腐；界面活性剤の防力ビ；工場の製造設備及びビル空調等における冷却塔、 パ ルプ及び «工場等の殺菌及びスライム生成防止； «及び皮革への噴霧または 浸潰処理による抗菌 ·抗カビ処理；塗料皿 特に外装塗料の塗料 が風雨に 曝されている間に発生する細菌 ·真菌及び による攻撃からの防御；塩化ビニ ル、 ポリウレタン、 ポリエチレン、 ポリプロピレン、 シリコン、 変性シリコン、 ナイロン、 エポキシ等の樹脂から成る内装'外装材（住宅用、 ,施設用）、建 材（建築建材、 土木建材等） 、 家電製品、 家庭用雑貨、 スポーツ用品等の抗菌 · 抗カビ及び殺藻；サトウキビ及びテンサイ糖の製造装置へのスライム堆積の防護 ；エア一ウォッシャー、 スクラツバ一システム及び工業用淡水供給システムにお ける微生物蓄積及び堆積の防止；食品工場等の衛生環境保持；製造設備の洗浄時, 下水処理場、 し尿処理場等の消臭殺菌；油田切削油、 泥水中及び二次石油回収プ ロセスにおける微生物汚染及び堆積の防止；紙被覆材及び被覆加工における細菌 及び真菌の生育防止；化粧品及びトイレタリ一製品の微生物汚染の防止；プール 等での藻 »長抑制；農業用配合物、 電着システム、 診断及び薬剤製品、 医療機 器等の微生物汚染の防止；写真処理における微生物蓄積の防止。 Waterborne paints, adhesives, latex, emulsion products such as acrylics, starch, pigments, slurry products such as calcium carbonate, and control of the growth of bacteria, fungi and algae in joint cement; building materials (building materials, civil engineering materials, etc.) Preservation of wood in wood; Preservation of cutting oil; Surfactant of surfactants; Sterilization and prevention of slime formation in cooling towers, pulp and «factory etc. in factory manufacturing equipment and building air conditioning, etc .;« and spraying on leather Antibacterial and antifungal treatment by immersion treatment; paint dishes, especially bacteria that occur while the paint of exterior paint is exposed to the weather; protection from fungal and bacterial attack; vinyl chloride, polyurethane, polyethylene, polypropylene, silicone, Interior / exterior materials (for housing,, facilities) and building materials (building materials, civil engineering materials) made of modified silicone, nylon, epoxy, etc. Materials), antibacterial and antifungal and algicidal products of household appliances, household goods and sports equipment; protection of slime deposits on sugarcane and sugar beet sugar production equipment; air-washers, scrubber systems and industrial freshwater supply systems Prevention of accumulation and accumulation of microorganisms in food processing; Maintenance of sanitary conditions in food factories, etc .; Cleaning of manufacturing facilities, deodorization and sterilization of sewage treatment plants and human waste treatment plants; Oilfield cutting oil, muddy water and secondary oil recovery processes Of microbial contamination and sedimentation in paper; bacteria in paper coating and coating processing Prevention of bacterial and fungal growth; prevention of microbial contamination of cosmetics and toiletry products; prevention of algae in pools, etc .; Prevent microbial accumulation in photographic processing.
N—キノキザリルァニリン類を有効成分として含む、 生物付着防 ll ^としては、 漁網、 船舶の船底、 ブイ等の海中に ヽれる設備、 海 m築物、 火力又は原子力 発電所の復水器冷却水系、 化学工業の熱交 冷却用水の ¾7路、 ダムの付属設 備等の水中構築物及び貯水池等へのムラサキイガイ、 フジッポ、 カキ、 ヒドロム シ、 ヒドラ、 セルブラ、 ホヤ、 コケムシ及びタニシ等の貝繊びにァォサ、 ァォ ノリ及びシォミ ドロ等の^ 等の有害な水中生物の付着防止等に用いることがで さる。  Biofouling prevention containing N-quinoxalylaniline as an active ingredient ll ^ includes fishing nets, ship bottoms, buoys and other underwater facilities, sea structures, thermal power plants, and condensate from nuclear power plants Shell cooling water system, chemical industry heat exchange Cooling water 水 の 7 routes, underwater structures such as dam attachments, and mussels such as mussels, fusippo, oysters, hydramushi, hydra, selbra, squirts, mosquitoes and snails to reservoirs etc. It can be used delicately to prevent the adhesion of harmful underwater organisms such as サ, ァ and シ.
次に N—キノキザリルァニリン類の合成例を示すが、 本発明に用いられる化合 物は、 これらに限定されるものではなレ、。  Next, synthesis examples of N-quinoxalylanilines are shown, but the compounds used in the present invention are not limited to these.
合成例 1 Synthesis example 1
N-(6-クロ口- 2-キノキザリル) -2, 6-ジニトロ- 3 -クロ口- 4-トリフルォロメチル ァニリン （化合物 1 )  N- (6-chloro-2-quinoxalyl) -2,6-dinitro-3-cyclo--4-trifluoromethylaniline (Compound 1)
(1) 2-ァミノ- 6- クロ口キノキザリンの合成  (1) Synthesis of 2-amino-6-cycloquinoxaline
2 1のォ一トクレーブに 2， 6-ジク π πキノキザリン 1 5 O gと 2 8 %のアンモ ニァ水 5 0 O m lを入れ 1 2 0でで 2 4時間加熱した。 放冷後得られた結晶物を 水洗乾燥し、 エタノールで再結晶して 2-ァミノ- 6-クロ口キノキザリン 8 6 g (m p 2 1 7〜2 2 0で） の淡褐色結晶を得た。  In a 21 autoclave, 2,6-dic ππ quinoxaline 15 Og and 28% ammonia water 50 Oml were added and heated at 120 for 24 hours. After allowing to cool, the obtained crystal was washed with water and dried, and recrystallized from ethanol to obtain 86 g (at mp 21 to 220) of light brown crystals of 2-amino-6-chloroquinoxalin.
(2)化合物 1の合成  (2) Synthesis of compound 1
ΙίίΕ(Ι)の反応で得られた 2-ァミノ -6-クロ口キノキザリン 5 gをジメチルホル ムアミ ド 5 O m 1に溶解し、 撹梓しながら— 3 (TCに冷却した。 粉末状の水酸化 カリウム 3. 7 gを添加し、 2，4-ジクロロ- ¾ 5-ジニト αベンゾトリフルォライ ド 8. 5 gをジメチルホルムアミ ド 1 5 m lに溶解した溶液を加えた。 徐々に室 温まで加温して 2 4時間撹拌した。 反応液を水中に投入し希塩酸で酸性にした後、 生成物をベンゼンにて抽出した。 ベンゼン層を水洗、 硫酸ナトリウムで乾；^、 溶媒留去して黄 fe^晶を得た。 この結晶をシリカゲルカラムクロマトグラフィー5 g of 2-amino-6-chloroquinoxalin obtained in the reaction of の (Ι) was dissolved in 5 Om 1 of dimethylformamide, and cooled under stirring to -3 (cooled to TC. 3.7 g of potassium was added, and a solution of 8.5 g of 2,4-dichloro-¾5-dinitα-benzotrifluoride dissolved in 15 ml of dimethylformamide was added. The mixture was warmed to warm and stirred for 24 hours. After the reaction solution was poured into water and acidified with diluted hydrochloric acid, the product was extracted with benzene. The benzene layer was washed with water and dried over sodium sulfate; ^, the solvent was distilled off to obtain yellow fe ^ crystals. The crystals are subjected to silica gel column chromatography.
(溶離液：ベンゼン/^酸ェチル = 4 / 1 ) にて精製し、 N- (6-クロ口- 2-キノキ ザリル) - 2» 6-ジニトロ- 3-クロ口- 4-トリフルォロメチルァ二リン 8. 1 g (m p(Eluent: benzene / ethyl ester = 4/1) and purified by N- (6-chloro-2-quinoxalyl) -2 »6-dinitro-3-chloro-4-4-trifluoromethyl 8.2 g (mp
1 8 2 - 1 8 7 °C) を得た。 合成例 2 1 82-1 87 ° C). Synthesis example 2
N-(6-クロ口- 2-キノキザリル)- 2， 6-ジニトロ- 3-ェトキシ- 4-トリフルォロメチ ルァニリン （化合物 2 )  N- (6-chloro-2-quinoxalyl) -2,6-dinitro-3-ethoxy-4- trifluoromethylaniline (Compound 2)
エタノール 1 5 m 1に水素化ナトリウム 4 gを加え、 水素ガスの発生がな くなるまで充分撹拌した後、 合成例 1で得られた N-(6-クロ口- 2-キノキザリル） -2， 6-ジニトロ- 3-クロ π-4-トリフルォロメチルァ二リン 2 gをジメチルスルホキ シド 2 0 m 1に溶解した溶液を加え、 8 0でにて 3時間撹拌した。 放冷後、 跡 液を水中に投入し、 希塩酸で酸性にした後、 生成物をベンゼンにて抽出した。 ベ ンゼン層を水洗、 硫酸ナトリウムで乾燥後、 溶媒留去して黄 晶を得た。 この 結晶をシリカゲルカラムクロマトグラフィー （溶離液：クロ口ホルム） にて精製 し、 N-(6-クロ口- 2-キノキザリル)- 2, 6-ジニトロ- 3-ェトキシ -4-トリフルォロメ チルァ二リン 1 . 1 g (m p 1 5 0〜： L 5 5 °C) を得た。 合成例 3  4 g of sodium hydride was added to 15 ml of ethanol, and the mixture was sufficiently stirred until hydrogen gas was no longer generated. Then, N- (6-chloro-2--2-quinoxalyl) obtained in Synthesis Example 1 was obtained. A solution of 2 g of 6-dinitro-3-chloro π-4-trifluoromethylaniline dissolved in 20 ml of dimethyl sulfoxide was added, and the mixture was stirred at 80 for 3 hours. After cooling, the trace liquid was poured into water, acidified with dilute hydrochloric acid, and the product was extracted with benzene. After washing the benzene layer with water and drying over sodium sulfate, the solvent was distilled off to obtain yellow crystals. The crystals were purified by silica gel column chromatography (eluent: chloroform-form) to give N- (6-chloro-2-quinoxalyl) -2,6-dinitro-3-ethoxy-4-trifluoromethylaniline. 1 g (mp 150-: L 55 ° C) was obtained. Synthesis example 3
N-(6-クロ口- 2-キノキザリル)- 2, 4-ジニト口- 6-トリフルォロメチルァ二リン （ 化合物 3 )  N- (6-chloro-2-quinoxalyl) -2,4-dinitto-6-trifluoromethyladiline (Compound 3)
2-ァミノ- 6-クロ口キノキザリン 1 gをジメチルホルムアミ ド 1 5 m lに溶解 し、 撹拌しながら— 3 0 に冷却した。 粉末状の水酸化力リウム 0. 8 gを添加 し、 2-クロ口- ¾5 -ジニトロべンゾトリフルオライド 1. 5 gをジメチルホルム アミド 5mlに溶解した溶液を加えた。 徐々に室温まで加温して 3時間撹拌した。 1 g of 2-amino-6-quinoxalin was dissolved in 15 ml of dimethylformamide and cooled to −30 with stirring. 0.8 g of powdered potassium hydroxide added Then, a solution prepared by dissolving 1.5 g of 2-chloro--5-dinitrobenzotrifluoride in 5 ml of dimethylformamide was added. The mixture was gradually warmed to room temperature and stirred for 3 hours.
液を水中に投入し、 希塩酸で酸性にし、 析出した黄 晶を濾取した。 得ら れた結晶を水洗後乾燥させ、 シリカゲル力ラムクロマトグラフィー （溶離液：ク ロロホルム/^酸ェチル =5/1) にて精製し、 N- (6-クロ口- 2-キノキザリル )-2» 4-ジニト α-6-トリフルォロメチルァ二リン 9 g (m ρ 90〜 93。C) を得 The solution was poured into water, made acidic with diluted hydrochloric acid, and the precipitated yellow crystals were collected by filtration. The obtained crystals are washed with water, dried and purified by silica gel column chromatography (eluent: chloroform / ethyl ester = 5/1) to give N- (6-chloro-2-quinoxalyl) -2. »9 g (m ρ 90-93.C) of 4-dinit α-6-trifluoromethylaniline
/ 0 合成例 4 / 0 Synthesis example 4
N-(6-クロ口 - 2-キノキザリル) -2, 4， 6-トリニトロァニリン （化合物 4 )  N- (6-chloro-2-quinoxalyl) -2,4,6-trinitroaniline (compound 4)
2 -ァミノ- 6-クロ口キノキザリン 1 gをジメチルホルムアミ ド 1 5mlに溶解 し、 撹拌しながら— 50でに冷却した。 粉末状の水酸化力リウム 0. 8 gを添加 し、 2，4，6-トリニトロフルォロべンゼン1. 3 gをジメチルホルムアミ ド 5m 1に溶解した溶液を加えた。徐々に室温まで加温して 1 0時間撹拌した。 液 を水中に投入し、 希塩酸で酸性にし、 析出した黄 晶を濾取した。 得られた結 晶を水洗後、 乾燥させ、 シリカゲルカラムクロマトグラフィー （溶離液：ベンゼ ン Z酢酸ェチル = /1) にて精製し、 N-(6-ク口口- 2-キノキザリル) -2， 4， 6-ト リニトロア二リン 0. 9 g (mp 120~1 30°C) を得た。 合成例 5  1-g of 2-amino-6-cloquinoxalin was dissolved in 15 ml of dimethylformamide, and cooled to -50 with stirring. 0.8 g of powdered lithium hydroxide was added, and a solution of 1.3 g of 2,4,6-trinitrofluorobenzene in 5 ml of dimethylformamide was added. The mixture was gradually warmed to room temperature and stirred for 10 hours. The solution was poured into water, acidified with dilute hydrochloric acid, and the precipitated yellow crystals were collected by filtration. The obtained crystals are washed with water, dried, and purified by silica gel column chromatography (eluent: benzene Z-ethyl acetate = / 1) to give N- (6-kuguchi-2-quinoxalyl) -2, 0.9 g of 4,6-trinitroaniline (mp 120 to 130 ° C) was obtained. Synthesis example 5
N-ァセチル -N-(6-クロロ- 2-キノキザリル) -2， 6-ジニトロ- 3 -クロ口- 4-トリフル ォロメチルァ二リン （化合物 5 )  N-Acetyl-N- (6-chloro-2-quinoxazalyl) -2,6-dinitro-3-chloro-1,4-trifluoromethyladiline (Compound 5)
合成例 1で得られた N- (6-クロロ- 2-キノキザリル) -2, 6-ジニト口- 3-ク口口- 4 -トリフルォロメチルァニリン 1 gをベンゼン 20mlに溶解し、 トリエチルァミ ン 0. 4 gを加えた。 この混合液に塩化ァセチル 0. 3 gを加え、 室温にて 6時 間撹拌した。生成した^ を濾別し、 濾液を希塩酸及び水で洗浄した後、 乾燥、 溶媒留去して黄 明のガラス状物質を得た。 このガラス状物質をシリ力ゲル力 ラムクロマトグラフィー （溶離液：ベンゼン/ m酸ェチル =4/1) にて精製し、 N-ァセチル -N-(6-クロ口- 2-キノキザリル） -2， 6-ジニトロ- 3-クロ口- 4-トリフルォ ロメチルァ二リン 0. 8 g (ガラス状） を得た。 合成例 6 -合成例 20 Dissolve 1 g of N- (6-chloro-2-quinoxalyl) -2,6-dinitto-3-kuguchi-4-4-trifluoromethylaniline obtained in Synthesis Example 1 in 20 ml of benzene and add triethylamido. 0.4 g was added. 0.3 g of acetyl chloride was added to the mixture, and the mixture was stirred at room temperature for 6 hours. While stirring. The formed solid was filtered off, and the filtrate was washed with dilute hydrochloric acid and water, dried and evaporated to obtain a yellowish glassy substance. This glassy substance was purified by silica gel chromatography (eluent: benzene / ethyl acetate = 4/1) to give N-acetyl-N- (6-chloro-2-quinoxalyl) -2, 0.8 g (glassy) of 6-dinitro-3-chloro-4--4-trifluoromethylaniline was obtained. Synthesis Example 6-Synthesis Example 20
合成例 1―合成例 5と同様の方法により化合物 6 -化合物 20を合成し第 4表 に した。 Compound 6-Compound 20 was synthesized in the same manner as in Synthesis Example 1-Synthesis Example 5 and shown in Table 4.
第 4表 Table 4
Figure imgf000034_0001
化合物 ベンゼン環上置換基 物 性
Figure imgf000034_0001
Compound Substituent on benzene ring
No. R 1 R 3 R 4 2位 3位 ( Z ) 4位 5位 6位 mp ( "U No.R 1 R 3 R 4 2nd 3rd (Z) 4th 5th 6th mp ("U
6 H H H NO 2 C1 CF3 H NO 2 89- 906 HHH NO 2 C1 CF 3 H NO 2 89- 90
7 H CH3 H NO 2 C1 CFs H NO 2 183-1857 H CH 3 H NO 2 C1 CFs H NO 2 183-185
8 CF3 H H NO 2 C1 CF3 H NO 2 163-1658 CF 3 HH NO 2 C1 CF 3 H NO 2 163-165
9 CFs H H NO 2 OEt CF3 H NO 2 164-1669 CFs HH NO 2 OEt CF 3 H NO 2 164-166
10 CI H H NO 2 H CF3 H NO 2 182-18610 CI HH NO 2 H CF 3 H NO 2 182-186
11 CI H H NO 2 OPh-OH- m CFs H NO 2 234-24211 CI HH NO 2 OPh-OH- m CFs H NO 2 234-242
12 H H H NO 2 H NO 2 H CF3 100-10512 HHH NO 2 H NO 2 H CF 3 100-105
13 CI H H H CI CFs H NO 2 226-22713 CI H H H CI CFs H NO 2 226-227
14 CI H H H H NO 2 H NO 2 232-23514 CI H H H H NO 2 H NO 2 232-235
15 CI H H H H NO 2 H CFs 215-22015 CI H H H H NO 2 H CFs 215-220
16 CI H H CI H NO 2 H CI ガラス状16 CI H H CI H NO 2 H CI Glassy
17 H CI H NO 2 CI CFs H NO 2 173-17417 H CI H NO 2 CI CFs H NO 2 173-174
18 CI H CH3 NO 2 CI CF3 H NO 2 ガラス状18 CI H CH 3 NO 2 CI CF 3 H NO 2 Glassy
19 CI H SO2 CH 3 NO 2 CI CF3 H NO 2 ガラス状19 CI H SO2 CH 3 NO 2 CI CF 3 H NO 2 Glassy
20 CI H sec" NO2 CI CF3 H NO 2 ガラス状 本発明の N—キノキザリルァニリン類を工業用抗菌 ·抗カヒ J及び 剤とし て用いる場合の処方例を化合物 1及び 3を用い示すが、 有効成分の配合割合、 担 体及び補助剤の種類また添加量等はこれらに限定されるものではない。 20 CI H sec "NO2 CI CF 3 HNO2 glassy Formulation examples when the N-quinoxalylanilines of the present invention are used as industrial antibacterial and antifungal agents and agents are shown using compounds 1 and 3. However, the compounding ratio of the active ingredient, and the types and amounts of the carrier and the auxiliary agent are not limited to these.
Figure imgf000034_0002
化合物 1 化合物 3 処方例 1 (乳剤）
Figure imgf000034_0002
Compound 1 Compound 3 Formulation Example 1 (emulsion)
成分 重量％  Ingredient weight%
化合物 1 5  Compound 1 5
ジメチルスルホキシド 8 5  Dimethyl sulfoxide 8 5
メチルイソプチルケトン 5  Methyl isobutyl ketone 5
ソルポール 8 0 O A 5  Solpol 8 0 O A 5
(東邦化学社製乳化剤） 上記を混合溶解して有効成分 5 %を含む乳剤を得た £ It was obtained (Toho Chemical Co., Ltd. emulsifier) emulsion containing 5% active ingredient were mixed and dissolved the £
処方例 2 (水和剤） Formulation Example 2 (Wettable powder)
成分  Ingredient
化合物 3 2 0  Compound 3 2 0
ラウリルサルフエ一ト 7  Lauryl Sulfate 7
クレー 7 3 上記を均一に混合粉砕して有効成分 2 0 %を含む水和剤を得た  Clay 7 3 The above mixture was uniformly mixed and pulverized to obtain a wettable powder containing 20% of active ingredient.
処方例 3 (フロアブル剤） Formulation Example 3 (Floable agent)
成分 重量％  Ingredient weight%
化合物 1 2 0  Compound 1 2 0
ラウリルサルフヱ一ト 2  Lauryl Sulfate 2
ザンサンガム 2  Xanthan gum 2
ヒドロキシプ σピルセルロース 1  Hydroxyl σ pill cellulose 1
蒸留水 7 5 上記をボールミルに入れ 1 2時間粉砕混合して有効成分 2 0 %を含むフロ ァブル剤を得た。 製剤化された本発明の工業用抗菌 ·抗カビ剤及び殺藻剤は、 各種の製剤をその まま、 又は^しくは適当な有機溶媒で希釈して、 各種の工業用原材料中にまた は製品中に添加混合する方法、 各種の工業用原材料や製品の表面に塗布または噴 霧する方法または各種の工業用原材料や製品を本発明の工業用抗菌 *抗カビ剤及 び 剤の希釈液中に浸漬する方法、 等を含め、 これまでに" «的に行われてき た工業用抗菌 ·抗カビ剤及び殺藻剤の使用方法に従って各種の方法により使用で きるが、 いずれの特定の方法のみに限定されるものではなレ、。 Distilled water 75 The above was placed in a ball mill and ground and mixed for 12 hours to obtain a flowable agent containing 20% of the active ingredient. The formulated industrial antibacterial and antifungal agents and algicides of the present invention can be obtained by diluting various preparations as they are or by diluting them with an appropriate organic solvent, in various industrial raw materials or products. The method of adding or mixing to the surface of various industrial raw materials or products, or the method of spraying or spraying various industrial raw materials or products on the surface of the industrial antibacterial * antifungal agent and diluent of the present invention It can be used by various methods in accordance with the conventional methods of using industrial antibacterial and antifungal agents and algicides, including the method of immersion. Not limited.
本発明の工業用抗菌 '抗カビ剤、 殺藻剤及び生物付着防 ii^ljの製剤を、 生物付 着防 の用途分野で概説すると、 本発明において有効成分として使用する N— キノキザリルァニリン類は、 塗料、 溶液、 乳剤等の形態に調製して使用される。 これら塗料、 溶液、 乳剤等の調製には通常実施される"^的処方を採用するこ とがでさる。  The industrial antibacterial agent of the present invention, a preparation of an antifungal agent, an algicide and a biofouling inhibitor ii ^ lj, is outlined in the application field of biofouling prevention. The N-quinoxallar used as an active ingredient in the present invention Nilins are used after being prepared in the form of paints, solutions, emulsions and the like. For the preparation of these paints, solutions, emulsions, etc., it is possible to adopt the commonly used formula.
本発明の水中生物付着防 を防汚塗料の形態で使用する場合には、 例えば有 効成分である N—キノキザリルァニリン類を塗膜形成剤に配合して,を調製し、 船舶の船底、 海灘築物、 冷却用 ¾7j管路或いは水中構築物等に塗布することに よつて水中生物の付着繁殖を防止することができる。  When the underwater biofouling prevention of the present invention is used in the form of an antifouling paint, for example, N-quinoxalylaniline as an active ingredient is blended with a film-forming agent to prepare By applying to the bottom of a ship, a seaside structure, a cooling 7j pipeline, or an underwater structure, the adhesion and propagation of aquatic organisms can be prevented.
塗膜形成剤としては、 油ワニス、 合成樹脂、 人造ゴム等が用いられる。  As a coating film forming agent, oil varnish, synthetic resin, artificial rubber and the like are used.
更に、 に応じて溶剤、 顔料等を使用しても差し支えない。  Further, a solvent, a pigment, or the like may be used according to the requirements.
塗料を調製する場合には、 有効成分である N—キノキザリルァニリン類は^ m が形成できる限りにおいて濃度に上限はないが、 防汚塗料の重量に対し、 1〜5 0重量％、 好ましくは 5〜2 0重量％の割合で配合される。  When preparing a paint, the concentration of the active ingredient, N-quinoxalylaniline, has no upper limit as long as ^ m can be formed, but 1 to 50% by weight based on the weight of the antifouling paint, Preferably, it is blended at a ratio of 5 to 20% by weight.
本発明の水中生物付着防 It ^を防汚塗料として用レヽる場合の処方例を示す。 処方例 4 An example of the formulation in the case of using the underwater organism adhesion prevention It ^ of the present invention as an antifouling paint is shown. Prescription example 4
成分  Ingredient
化合物 1 8  Compound 1 8
VYHH (ビニル系合成樹脂、 UCC社製） 7  VYHH (vinyl synthetic resin, manufactured by UCC) 7
ロジン 7  Rosin 7
リン酸トリクレジル 3  Tricresyl phosphate 3
タルク 2 ϋ  Talc 2 ϋ
硫酸バリウム 1 5  Barium sulfate 1 5
弁柄 1 ϋ  Red stalk 1
キシレン 20  Xylene 20
メチルイソプチルケトン 1 0  Methyl isobutyl ketone 1 0
1 00  1 00
処方例 5 Prescription example 5
成分 重量％ 化合物 3 5  Ingredient wt% Compound 3 5
CR- 1 0 (塩化ゴム樹脂、 旭電化社製） 13  CR-10 (chlorinated rubber resin, manufactured by Asahi Denka) 13
20  20
タルク 20  Talc 20
可塑剤 2  Plasticizer 2
弁柄 1 0  Red petals 1 0
キシレン 30  Xylene 30
1 00  1 00
本発明の水中生物付着防! ^を溶液の形態で使用する場合には、 例えば有効成 分である Ν—キノキザリルァニリン類を塗膜形成剤と共に溶媒に溶解した溶液を 調製して、 «漁網、 定置漁網等に塗布することによって水中生物の付着,を 防止することができる。 In the case where the anti-biological adhesion in water of the present invention is used in the form of a solution, for example, a solution in which 有効 -quinoxalylaniline, which is an effective component, is dissolved in a solvent together with a film-forming agent is prepared. «Adhesion of aquatic organisms by applying to fishing nets, fixed fishing nets, etc. Can be prevented.
塗膜形翻としては、 合成樹脂、 人造ゴム、 天纖脂等が用いられ、 溶媒とし ては、 キシレン、 トルエン、 クメン、 メチルェチルケトン、 メチルイソプチルケ トン及びァセトン等が用いられる。  Synthetic resin, artificial rubber, natural fiber and the like are used for the transformation of the coating film, and xylene, toluene, cumene, methylethylketone, methylisobutylketone, and acetone are used as the solvent.
更に に応じて添加剤、 例えば可塑剤等を使用しても差し支えない。 溶液を調製する場合には、 有効成分である N -キノキザリルァニリン類は溶液 が形成できる限りにおいて濃度に上限はないが、 溶液の重量に対し、 1〜5 0重 量 、 好ましくは 5〜3 0 %の割合で配合される。  Further, an additive such as a plasticizer may be used according to the requirements. When a solution is prepared, the concentration of the active ingredient, N-quinoxalylaniline, has no upper limit as long as a solution can be formed. It is blended at a rate of ~ 30%.
本発明の水中生物付着防 を防汚剤溶液として用いる場合の処方例を示す。 処方例 6  An example of a formulation in the case where the anti-biological matter in water of the present invention is used as an antifouling agent solution is shown. Prescription example 6
成分  Ingredient
化合物 1 1 5  Compound 1 1 5
アクリル樹脂（5 0 %キシレン液〉 5 0  Acrylic resin (50% xylene liquid) 50
キシレン 3 5  Xylene 3 5
1 0 0  1 0 0
処方例 7 Prescription example 7
成分  Ingredient
化合物 3 1 0  Compound 3 1 0
アクリル樹脂 ( 5 0 %キシレン液） 0  Acrylic resin (50% xylene liquid) 0
ジ第 3級ノニルペンタスルフィッド 5  Di-tertiary nonyl pentasulfide 5
流動パラフィン 5  Liquid paraffin 5
キシレン 4 0  Xylene 4 0
1 0 0  1 0 0
本発明の水中生物付着防 lh¾を乳剤の形態で使用する場合には、 通常乳剤を調 製する際の"^的方法に従い、 有効成分である N—キノキザリルァニリン類の溶 液に界面活性剤を添加し、 所望の乳剤を調製することができ、 用いる界面活測 の種類に特に限定はない。 When the underwater organism-fouling inhibitor lh¾ of the present invention is used in the form of an emulsion, the emulsion is usually prepared. The desired emulsion can be prepared by adding a surfactant to a solution of N-quinoxalylaniline, which is the active ingredient, in accordance with the “^ method” used in the preparation of the emulsion. There is no particular limitation.
調製した乳剤は、 海洋又は水中で使用する^»網、 定置網等の原料素材、 例 えば高分子樹脂等に練り込んで用いることができる。  The prepared emulsion can be kneaded into a raw material such as a net or a fixed net used in the ocean or water, for example, a polymer resin or the like.
乳剤を調製する場合には、 有効成分である N—キノキザリルァニリン類は乳剤 が形成できる限りにおいて に上限はないが、 乳剤の籠に対し、 1— 5 0重 量 、 好ましくは 3— 3 0 の割合で配合される。  When an emulsion is prepared, the active ingredient, N-quinoxalylaniline, has no upper limit as long as the emulsion can be formed. It is blended at a ratio of 30.
又、 本発明の上纖 は乳剤は、 冷却用水の ¾7i管路或いは貯水池等におけ る水中生物の付着灘を防止するため、 用水、 貯水等に添加して用いることもで さる 0 発明を実施するための最良の形態  In addition, the emulsion of the present invention can be used by adding it to water, storage water, etc. in order to prevent the underwater organisms from adhering to the water in the 7i pipeline or the reservoir for cooling water. Best form to do
以下、 本発明について、 更に具体的かつ詳細に上記化合物 1、 3及び化合物 4、 7、 9を用い実施例で説明するが、 本発明はこれらに限定されるものではない。  Hereinafter, the present invention will be described more specifically and in detail with reference to Examples using Compounds 1, 3 and Compounds 4, 7, and 9, but the present invention is not limited thereto.
Figure imgf000039_0001
Figure imgf000039_0001
纖例 1 (抗菌.抗カビ活 Fiber Example 1 (Antibacterial and antifungal activity
バチルス サブチリス (Bacillus subtilis)はブイョン寒天培地 1 2 5 m 1に 対して検定菌 6. 6 m 1、 トリコフィトン メンタグロフィテス （Trichophyton mentagrophytes) はサブ口一寒天培地 125mlに対して検定菌 31. 3 m 1を 添加し、 各々? たないように注意しながら攪拌しプレートに均一に流し固化さ せた。 次に、 本発明の化合物を一定量秤量し、 アセトンにて所定の濃度に希釈し た。 調製した本発明の化合物を一定濃度含む試料をペーパーディスク （paper di sk) にしみ込ませ濾紙上に広げて風乾後、 各々の検定菌を流したプレート上に等 間隔に置いた。 バチルス サブチリス (Bacillus subtilis)は 37°Cで 1曰、 ト リコフィ トン メンタグロフィテス (Trichophyton mentagrophytes)は 28でで 3曰間恒温器で培養し、 各々の ffill:円の直径を測定し、 活性 »を行った。 10 Oppm濃度の試料を用いた場合の結果を第 5表に示した。 但し、 表中の記号は 以下を意味する。 Bacillus subtilis (Bacillus subtilis) consisted of 125 ml of Bouillon agar medium, 6.6 ml of test bacteria, and Trichophyton mentagrophytes. mentagrophytes) was added to 31.3 ml of the test bacterium to 125 ml of the sub-aperture agar medium, and the mixture was stirred with care so as not to mix with each other, and allowed to flow evenly on the plate to solidify. Next, a certain amount of the compound of the present invention was weighed and diluted with acetone to a predetermined concentration. The prepared sample containing the compound of the present invention at a fixed concentration was impregnated into a paper disk, spread on a filter paper, air-dried, and placed at regular intervals on a plate on which each test bacterium was flowed. Bacillus subtilis was cultured at 37 ° C for 1 and Trichophyton mentagrophytes was cultured for 28 and 3 at a constant temperature incubator. Each ffill: Measured the diameter of the circle and determined the activity » Was done. Table 5 shows the results obtained when using a sample having a concentration of 10 ppm. However, the symbols in the table mean the following.
A バチルス サブチリス (Bacillus subtilis)  A Bacillus subtilis
B トリコフィ トン メンタグロフィテス (Trichophyton mentagrophytes) B Trichophyton mentagrophytes
+ P lh円 （A； 10〜13mm、 B； 10〜2 Omm)が觀される。 + P lh circle (A; 10-13 mm, B; 10-2 Omm) is observed.
M:円が されない。  M: There is no circle.
第 5表  Table 5
化合物 判定  Compound judgment
No.  No.
A B  A B
1 +  1 +
3 +  3 +
4 + +  4 ++
7 + 実施例 2 (抗菌.抗カビ活性  7 + Example 2 (antibacterial and antifungal activity
本発明の化合物をジメチルスルホキシドを用いて、 希釈列 （20000、 10 000、 5000、 2500、 1250、 626、 313、 156、 78、 39 mg/1)を調製した。 これを細菌については感 用培地一 N (曰水製薬） を 用い、 真菌についてはポテトデキストロース寒天培地（曰水製薬） の各 9. 5m 1に 0. 5mlを添加混合し、 シャーレに流して固化平板とした。 寒天培地の本 発明の化合物の濃度は、 各々 1000、 500、 250、 125、 62. 5、 3 1. 3、 15. 6、 7. 8、 3. 9、 2. 0 m gZ 1になる。 接翻菌は感 測定用ブイヨン （日水製薬） で 37。Cヽ 20時間培養した。 また、 真菌はポテト デキストロース寒天培地（曰水製薬） で 10曰間培養した後、 それぞれ 106CF U/m 1の懸濁液を調製した。 試験菌懸濁液を白金耳を用いて薬剤混合寒天平板 に画線塗布し、 細菌については 37 ± 1 Cで 18— 20時間、 真菌については 2 7でで 7曰間培養し、 それぞれ発育の見られない濃度をもって最小発育 M 度 ( I C) とした。 結果を第 6表及び第 7表に示した。 但し、 表中の記号は以下 を意味する。 A dilution series (20,000, 10 000, 5000, 2500, 1250, 626, 313, 156, 78, 39 mg / 1) of the compound of the present invention was prepared using dimethyl sulfoxide. For bacteria, add Sensitive Medium 1 For fungi, 0.5 ml was added to each 9.5 ml of potato dextrose agar medium (Kyosui Pharmaceutical), mixed and poured into a petri dish to form a solidified plate. The concentrations of the compound of the present invention in the agar medium are 1000, 500, 250, 125, 62.5, 31.3, 15.6, 7.8, 3.9, and 2.0 mgZ1, respectively. The inverting bacteria is a bouillon (Nissui Pharmaceutical Co., Ltd.) 37 C ヽ Culturing for 20 hours. The fungi were cultured on a potato dextrose agar medium (Kisui Pharmaceutical Co., Ltd.) for 10 weeks, and then a suspension of 10 6 CFU / m 1 was prepared. The suspension of the test bacterium was streaked onto a drug-mixed agar plate using a platinum loop, and cultured for 18 to 20 hours at 37 ± 1 C for bacteria and 27 to 7 for fungi. The concentration that could not be seen was defined as the minimum development M degree (IC). The results are shown in Tables 6 and 7. However, the symbols in the table mean the following.
A：バチルス サブチリス (Bacillus subtilis)  A: Bacillus subtilis
B： トリコフィ トン メンタグ πフィテス (Trichophyton mentagrophytes) B: Trichophyton mentagrophytes
C :スタフイロコッカス ァゥレウス (Staphylococcus aureus) C: Staphylococcus aureus
D：ェシヱリツチア コリ （Escherichia coli)  D: Escherichia coli
E：シュ一ドモナス エルギノ一ザ (Pseudomonas aeruginosa)  E: Pseudomonas aeruginosa
F：ァスペルギス ニガ一 （Aspergillus niger)  F: Aspergillus niger
G :ぺニシリュウム フニク πサム (Penicillium funiculosum)  G: Penicillium funiculosum
H :キャンディダ アルビカンス （Candida albicans)  H: Candida albicans
第 6表 細菌に対する M I C測定結果（m g/ 1 )  Table 6 Results of MIC measurement for bacteria (mg / 1)
化合物 議菌  Compound
No. A C D E  No. A C D E
1 < 2. 0 く 2. 0 31. 3 15. 6  1 <2.0 0 2. 0 31.3 15.6
3 < 2. 0 < 2. 0 15. 6 31. 3 第 7表 真菌に対する M I C測定結果（m gノ 1 ) 3 <2.0 <2. 0 15.6 31.3 Table 7 MIC measurement results for fungi (mg / l)
化合物 試験真菌  Compound test fungus
No. F G B H  No. F G B H
1 2. 0 ぐ 2. 0 15. 6 <2. 0  1 2. 0 2. 0 15.6 <2. 0
8 3. 9 3. 9 < 2. 0 15. 6 実施例 3 (抗菌，抗カビ活性 IHffi)  8 3. 9 3. 9 <2.0 15.6 Example 3 (antibacterial and antifungal activity IHffi)
本発明の化合物をジメチルスルホキシドを用いて、 希釈列 （20000、 10 000、 5000、 2500、 1250、 626、 313、 156、 78、 39 mg/1)を調製した。 これを細菌については感受性用培地一 N (曰水製薬） を 用い、 真菌についてはポテトデキスト σ—ス寒天培地（曰水製薬） の各 9. 5m 1に 0. 5mlを添加混合し、 シャ一レに流して固化平板とした。 寒天培地の本 発明の化合物の濃度は、 各々 1000、 500、 250、 125、 62. 5、 3 1. 3、 15. 6、 7. 8、 3. 9、 2. 0 m g/ 1になる。 接種細菌は感¾¾ 測定用ブイヨン （日水製薬） で 37。C、 20時間培養した。 また、 真菌はポテト デキストロース寒天培地（曰水製薬） で 10曰間培養した後に、 それぞれ 108 CFU/m 1の懸濁液を調製した。 菌懸濁液を白金耳を用いて薬剤混合寒天 平板に画線塗布し、 細菌については 37 ± 1てで 18— 20時間、 真菌について は 27でで 7曰間培養し、 それぞれ発育の見られない濃度をもって最小発育阻止 濃度（MI C) とした。 結果を第 8表及び第 9表に示した。 但し、 表中の記号は 以下を意味する。 A dilution series (20,000, 10 000, 5000, 2500, 1250, 626, 313, 156, 78, 39 mg / 1) of the compound of the present invention was prepared using dimethyl sulfoxide. For this, 0.5 ml was added to each 9.5 ml of a potato dext σ-agar agar medium (Kyosui Pharmaceutical), and 0.5 ml was added and mixed. Into a solidified plate. The concentrations of the compound of the present invention in the agar medium are 1000, 500, 250, 125, 62.5, 31.3, 15.6, 7.8, 3.9 and 2.0 mg / l, respectively. The inoculated bacteria were broth for sensitivity measurement (Nissui Pharmaceutical). C, and cultured for 20 hours. Moreover, fungi after 10曰間cultured in potato dextrose agar (曰水Pharmaceutical), suspension of each 10 8 CFU / m 1 was prepared. The bacterial suspension was streaked onto a drug-mixed agar plate using a platinum loop, and cultured for 18-20 hours at 37 ± 1 for bacteria and 7 to 27 at fungi for fungi. The minimum inhibitory concentration (MIC) was defined as the concentration that did not exist. The results are shown in Tables 8 and 9. However, the symbols in the table mean the following.
I ： ミクロコッカス ルテア （Micrococcus lutea)  I: Micrococcus lutea
J： コリネノ クテリユウム アクアティカム （Corynebgacterium aquaticum) J: Corynebgacterium aquaticum
K：アル力リゲネス ファェカリス (Alcali genes faecal is) K: Alcali genes faecal is
L：サルモネラ チイフィムリュウム （Salmonella typhymuriura)  L: Salmonella typhymuriura
M：ケトミユウム グロボサム （ etoraium globosura) N： リゾーノヽ。ス 才ひーゼ (Rhizo us oryzae) M: etoraium globosura N: Resono. Rhizo us oryzae
0： πド卜ノレラ ノレブラ (Rodotorula rubra)  0: π dotonorera norebra (Rodotorula rubra)
P：サッカロマイセス セルビシァェ (Saccharomyces cervisiaes) 第 8表 細菌に対する M I C測定結果（mgZl)  P: Saccharomyces cervisiaes Table 8 MIC measurement results for bacteria (mgZl)
化合物 ^^細菌  Compound ^^ bacteria
No. I J κ L  No. I J κ L
1 < 2. 0 < 2. 0 < 2. 0 > 1000 真菌に対する M I C測定結果 (mg/1)  1 <2.0 <2.0 <2.0> 1000 MIC measurement results for fungi (mg / 1)
化合物  Compound
No. N 0 P  No. N 0 P
1 <2. 0 > 500 <2. 0 > 500 実施例 4 (レジオネラ菌に対する殺菌効力 ffi)  1 <2.0> 500 <2.0> 500 Example 4 (Bactericidal efficacy against Legionella)
本発明の化合物をジメチルスルホキシドを用いて、 200 OmgZl濃度の溶 液を調製し、 その試料液 lmlを滅菌水道水 19mlで希釈して 1 O OmgZl 濃度の溶液を調製した。 この本発明の化合物を含む試料溶液 2 Omlに »菌液 A solution of the compound of the present invention having a concentration of 200 OmgZl was prepared using dimethyl sulfoxide, and 1 ml of the sample solution was diluted with 19 ml of sterile tap water to prepare a solution having a concentration of 1 OmgZl. In 2 Oml of the sample solution containing the compound of the present invention »
[レジオネラ ニューモフイラ （Legionella pneumophila)， 3. 1 x 108個 Z ml] を 0. lml接種した。 30°Cで 24時間接触作用させ、 作用後の生菌数 を測定した。結果を第 10表に示した。 0.1 ml of [Legionella pneumophila, 3.1 × 10 8 Z ml] was inoculated. The cells were contacted at 30 ° C for 24 hours, and the number of viable bacteria after the action was measured. The results are shown in Table 10.
第 1 0表  Table 10
化合物 No. 24時間後の生菌数/ m 1 Compound No. Viable bacteria count after 24 hours / m 1
1 < 10 1 <10
3 < 10  3 <10
対照翻水道水） 1. 2X 1 0 実施例 5 (淡^^に対する増殖阻害活性 I») 対数増殖期にある淡水緑藻 (Selenastrum capricornutum) 1 05個 / m 1を含 む培地に、 各々一定量の本発明の化合物を溶解し、 培地中の本発明化合物の濃度 が各々 500 ppb、 5 O ppbである試料を調製し、 23 ± 1。C、 24時間連 謹明条件で静驟養した。 Contrasting tap water) 1.2 X 10 Example 5 (growth inhibitory activity against light ^^ I ») Freshwater green alga (Selenastrum capricornutum) 1 0 5 cells / m 1 and including medium in the logarithmic growth phase, respectively to dissolve the amount of a compound of the present invention, each concentration of the compound of the present invention in the medium 500 ppb, 5 Prepare a sample that is O ppb, 23 ± 1. C, 24 hours a day.
72時間後に血球計数装置を用レ、て細胞数を測定することにより増殖率を求め た。 増殖阻害率は、 無処理区との比較から算出した。  After 72 hours, the proliferation rate was determined by measuring the number of cells using a hemocytometer. The growth inhibition rate was calculated from the comparison with the untreated group.
結果を第 1 1表に示した。  The results are shown in Table 11 below.
第 1 1表  Table 11
化合物 増殖阻害率 (%)  Compound growth inhibition rate (%)
No.  No.
500 ρ p b 50 ρ ρ b  500 ρ p b 50 ρ ρ b
1 89 33  1 89 33
3 95 69  3 95 69
4 93 34  4 93 34
7 59 1 7  7 59 1 7
9 82 9 実施例 6 (海；†¾藻に対する増殖阻害活性 fM)  9 82 9 Example 6 (sea; growth inhibitory activity against algae fM)
対数増 ¾19にある海水珪藻 (Nitzschia closterium) 1 05個 / m 1を含む培 地に、 各々一定量の本発明の化合物を溶解し、 培地中の本発明化合物の濃度が各 々 500 ppb、 5 O ppbである試料を調製し、 23 ± 1。C、 24時間連 « 明条件で静«養した。 The culture ground containing seawater diatom (Nitzschia closterium) 1 0 5 cells / m 1 in the logarithmic increase ¾19, respectively to dissolve the amount of a compound of the present invention, the concentration of the compound of the present invention in the medium each 500 ppb, Prepare a sample that is 5 O ppb, 23 ± 1. C, rested for 24 hours under light conditions.
72時間後に細胞を遠心分離することにより集めた後、 メタノールを添加して 細胞を破砕し、 クロロフィルを抽出した。  After 72 hours, the cells were collected by centrifugation, and then methanol was added to disrupt the cells, and chlorophyll was extracted.
光度計を用いて吸光度からクロロフィル量を測定し、 増殖率を求めた。 増 殖阻害率は、 無処理区との比較から算出した。  The growth rate was determined by measuring the amount of chlorophyll from the absorbance using a photometer. The growth inhibition rate was calculated by comparison with the untreated plot.
結果を第 12表に示した。 第 1 2表 The results are shown in Table 12. Table 12
化合物 増殖阻害率 {%)  Compound growth inhibition rate (%)
N o . 5 0 0 ρ p b 5 0 ρ p b No. 5 0 0 ρ p b 5 0 ρ p b
1 1 0 0 9 8 1 1 0 0 9 8
3 9 6 9 8  3 9 6 9 8
4 8 9 4 3  4 8 9 4 3
7 1 0 0 0  7 1 0 0 0
9 1 0 0 2 8 実施例 7 (生物付着防止活性議  9 10 0 2 8 Example 7 (Biofouling prevention activity
2. 8 m gの化合物 1をアセトン約 1 m 1に完全に溶解し、 纖紙上に描かれ た直径 4 c mのゾーン内に、 それぞれのサンプル溶液を均一に塗布した。  2. 8 mg of Compound 1 was completely dissolved in about 1 ml of acetone, and each sample solution was uniformly applied in a 4 cm diameter zone drawn on fiber paper.
ブランクとしてアセトンのみを塗布したゾーン、 比較薬剤として、 硫酸銅 0 m gを塗布したゾーンを設けた。  A zone to which only acetone was applied was provided as a blank, and a zone to which 0 mg of copper sulfate was applied was provided as a comparative agent.
乾燥後、 殻長が 2— 2. 5 c m前後のムラサキイガイをスぺ一サ一としてゴム 片を用い、 それぞれのゾーンの外周に 4個体づっ接着した。 調整した試験板を、 海水が流入する水槽中に浸潰し、 喑所で3時間静置した。 水槽中から纖板を上 げ、 ムラサキイガイ足糸の付着位置と本数を計測した。 同様の方法にて、 2. 6 11^及び1 . 3 m gの化合物 3を用い試験を実施した。 After drying, mussels having a shell length of about 2 to 2.5 cm were adhered to the outer periphery of each zone using rubber pieces as a splicer. The prepared test plate was immersed in a water tank into which seawater flows, and allowed to stand at a place for 3 hours. The fiber board was lifted from the water tank, and the attachment position and number of mussels were measured. In a similar manner, tests were performed using 2.611 ^ and 1.3 mg of compound 3.
比較薬剤として用いた硫酸銅との対比で、 付着制御効果 （付着忌避活性） を求 めた。  The adhesion control effect (adhesion repellent activity) was determined in comparison with copper sulfate used as a comparative drug.
付着忌避活性の評価法は、 伊奈和夫、 衛藤英男著 「ムラサキイガイを用いた海 洋付着生物の付着忌避物質の検纖」 （化学と生物、 第 2 8巻（第 2号） 、 1 3 2〜1 3 8頁（1 9 9 0年） に従った。  The evaluation method of the adhesion repellent activity is described in Kazuo Ina and Hideo Eto, “Testing of Adhesion Repellents for Marine Adherent Organisms by Using Mussels” (Chemistry and Biology, Vol. 28 (No. 2), 132- 138 pages (1990).
結果を第 1 3表に示した。 第 1 3表 The results are shown in Table 13. Table 13
有効成分 薬量 (m ) 判定  Active ingredient dose (m) Judgment
化合物 1 2. 8 + +  Compound 1 2.8 + +
化合物 3 2. 6 + +  Compound 3 2.6 + +
1 . 3 + +  1.3 +++
比較薬剤 （硫酸銅） 1 . 0 + +  Comparative drug (copper sulfate) 1.0 + +
0. 5 +  0.5 +
ブランク 一 尚、 表中の記号は下記の意味を表す。  Blank I The symbols in the table represent the following meanings.
+ +：ゾーン内に全く付着せず、 強レ、忌避効果が認められる。  + +: Does not adhere to the zone at all.
+：ゾーン内への付着も観測されるが、 大部分はゾーン外に付着し、 忌避効果が認められる。  +: Adhesion inside the zone is also observed, but most adhere outside the zone, and a repellent effect is observed.
-：ゾーン内外に同程度に付着し、 忌避効果が認められない。 産 の利用可能性  -: Attached to the same extent inside and outside the zone, no repelling effect is observed. Availability
"^式 ( 1 ) で表される N—キノキザリルァニリン類は、 安全性が高く、 低薬 量で幅広いスペクトラムを発現し、 工業用抗菌，抗カビ剤、 殺藻剤及び生物付着 防 として有用である。  "^ The N-quinoxalylanilines represented by formula (1) are highly safe, exhibit a wide spectrum at low doses, and are suitable for industrial antibacterial, antifungal, algicide and biofouling prevention. Useful as

Claims

請 求 の 範 囲 似 ( 1 ) Similar to the scope of the request (1)
Figure imgf000047_0001
Figure imgf000047_0001
(式中、 R 1 及び R2 は、 それぞ: に水素原子、 ハロゲン原子、 トリフルォ ロメチル 原 1— 5のアルキル 原"？ — 5のアルコキシ基 またはニトロ基を、 R 3 は水素原子、 ノ、 σゲン原子または驟原 ¾U— 5のァ ルキル基を、 R4 は水素原子、 ¾原子数 1—5のアルキル基、 原子敷 2—(Wherein, R 1 and R 2 are each a hydrogen atom, a halogen atom, a trifluoromethyl atom 1-5 alkyl atom "? — 5 alkoxy or nitro group, and R 3 is a hydrogen atom, σ-gen atom or syrup ¾U-5 alkyl group, R 4 is hydrogen atom, ¾alkyl group with 1-5 atoms, atomic layer 2—
6のアルケニル基、 ^ ^ 2― 6のアルキニル 原子数 2― 6のアル キルカルボニル基、 原子数 1 一 5のアルキルスルホニル基またはノヽロゲン原 子で置換されてもよい壓原" ¾ 1—5のアルキルスルフエニル基を、 X及び Y は、 それぞ ¾ϋにニトロ トリフルォロメチル基またはハロゲン原子を、 ζ は水素原子、 ノ、ロゲン原子、 難原 1—5のアルコキシ基またはハロゲン原 子、 ニトロ基または水酸基で置換されてもよいフヱノキシ基を表す。但し、 m及 び nはそれぞれ独立に 0または 1を表すが、 m及び nは同時に 1を表すことはな い。 また、 j及び kはそれぞ ^S:に 0、 1、 2または 3を表し、 j +kは常に 3以下を表す。 ） 6 alkenyl groups, ^ ^ 2-6 alkynyl, 2-6 alkylcarbonyl groups, 15-alkylsulfonyl groups or a pressure source which may be substituted with a nitrogen atom "¾1-5 X and Y are each ¾ϋ a nitrotrifluoromethyl group or a halogen atom, and ζ is a hydrogen atom, a hydrogen atom, a logen atom, an alkoxy group or a halogen atom of Refractory 1-5. Represents a phenoxy group which may be substituted with a nitro group or a hydroxyl group, provided that m and n each independently represent 0 or 1, but m and n do not represent 1 at the same time. k represents 0, 1, 2 or 3 in ^ S :, and j + k always represents 3 or less.
で表される N—キノキザリルァニリン類を含有することを■とする工業用抗菌 •抗カビ剤。 An industrial antibacterial agent containing an N-quinoxalylaniline represented by the following formula:
2. m及び nが 0である請求項 1記載の N—キノキザリルァニリン類を含有 することを特徴とする工業用抗菌，抗カビ剤。 2. The compound according to claim 1, wherein m and n are 0. An industrial antibacterial and antifungal agent characterized by the following:
3. mが 1で、 nが 0である請求項 1記載の N—キノキザリルァニリン類を 含有することを特徴とする工業用抗菌 ·抗カビ剤。  3. An industrial antibacterial and antifungal agent comprising the N-quinoxalylaniline according to claim 1, wherein m is 1 and n is 0.
4. mが 0で、 nが 1である請求項 1記載の N—キノキザリルァニリン類を 含有することを特徴とする工業用抗菌 ·抗カピ 0 4. The industrial antibacterial and anti-capi 0 containing N-quinoxalyl anilines according to claim 1, wherein m is 0 and n is 1.
5. R 2が水素原子である請求項 2記載の N—キノキザリルァニリン類を含有 することを特徴とする工業用抗菌，抗カピ 。 5. An industrial antibacterial and anticapi containing the N-quinoxalylaniline according to claim 2 , wherein R2 is a hydrogen atom.
6. R 1が水素原子である請求項 2記載の N—キノキザリルァニリン類を含有 することを特徴とする工業用抗菌 ·抗カピ 。 6. An industrial antibacterial and anti-capi containing the N-quinoxalylanilines according to claim 2, wherein R 1 is a hydrogen atom.
7. 請求項 1記載の N—キノキザリルァニリン類を含有することを薩とす る殺藻剤。  7. An algicide characterized by containing the N-quinoxalyl aniline according to claim 1.
8. 請求項 2記載の N—キノキザリルァニリン類を含有することを特徴とす る殺藻剤。  8. An algicide comprising the N-quinoxalylaniline according to claim 2.
9. 請求項 3記載の N—キノキザリルァニリン類を含有することを特徴とす る殺藻剤。  9. An algicide comprising the N-quinoxalylaniline according to claim 3.
1 0. 請求項 4記載の N—キノキザリルァニリン類を含有することを特徴と する 剤。  10. An agent comprising the N-quinoxalyl aniline according to claim 4.
1 1 . 請求項 5記載の N—キノキザリルァニリン類を含有することを ®と する 剤。  11. An agent comprising the N-quinoxalylaniline according to claim 5.
1 2. 請求項 6記載の N—キノキザリルァニリン類を含有することを特徴と する 剤。  1 2. An agent comprising the N-quinoxalyl aniline according to claim 6.
1 3. 請求項 1記載の N—キノキザリルァニリン類を含有することを と する生物付着防!^。  1 3. Biofouling prevention comprising the N-quinoxalyl aniline described in claim 1! ^.
1 4 . 請求項 2記載の N—キノキザリルァニリン類を含有することを特徴と する生物付着防 «J0 14. An anti-biofouling agent comprising the N-quinoxalyl aniline according to claim 2 «J 0
1 5 . 請求項 3記載の N—キノキザリルァニリン類を含有することを特徴と する生物付着防 。 15. A biofouling preventive, comprising the N-quinoxalylaniline according to claim 3.
1 6 . 請求項 4記載の N—キノキザリルァニリン類を含有することを特徴と する生物付着防！^。  16. Biofouling prevention, characterized by containing the N-quinoxalylaniline according to claim 4! ^.
1 7. 請求項 5記載の N—キノキザリルァニリン類を含有することを鐘と する生物付着防 i Wo  1 7. Biofouling prevention containing the N-quinoxalyl aniline described in claim 5 as a bell i Wo
1 8. 請求項 6記載の N—キノキザリルァニリン類を含有することを特徴と する生物付着防！^。  1 8. Biofouling prevention characterized by containing the N-quinoxalyl aniline according to claim 6! ^.
PCT/JP1998/000208 1997-01-21 1998-01-21 Industrial antimicrobial/mildew-proofing agents, algicides and antifouling agents containing n-quinoxalylanilines WO1998031228A1 (en)

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