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WO1998031228A1 - Agents antimicrobiens/imputrescibilisants industriels, agents algicides et antiparasites contenant des n-quinoxalylanilines - Google Patents

Agents antimicrobiens/imputrescibilisants industriels, agents algicides et antiparasites contenant des 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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WO
WIPO (PCT)
Prior art keywords
cfs
quinoxalyl
group
quinoxalylaniline
atom
Prior art date
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PCT/JP1998/000208
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English (en)
Japanese (ja)
Inventor
Shinichi Igarashi
Mitsugu Futagawa
Original Assignee
Nissan Chemical Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Industries, Ltd. filed Critical Nissan Chemical Industries, Ltd.
Priority to CA002278244A priority Critical patent/CA2278244A1/fr
Priority to NZ336826A priority patent/NZ336826A/en
Priority to AU55747/98A priority patent/AU5574798A/en
Publication of WO1998031228A1 publication Critical patent/WO1998031228A1/fr

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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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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne des agents antimicrobiens/imputrescibilisants industriels, et des agents algicides et antiparasites contenant des N-quinoxalylanilines représentés par la formule générale (1). Dans cette formule, R1 et R2 sont indépendamment chacun H, halogéno, CF¿3?, C1-5 alkyl, C1-5 alcoxy ou NO2; R?3¿ est H, halogéno ou C¿1-5? alkyl; R?4¿ est H, C¿1-5? alkyl, C2-6 alcényl, C2-6 alkynyl, C2-6 alkylcarbonyl, C1-5 alkylsulfonyl ou C1-5 alkylsulfényl éventuellement substitué; X et Y sont chacun indépendamment NO2, CF3 ou halogéno; Z est H, halogéno, C1-5 alcoxy ou phénoxy éventuellement halogéné, nitré ou hydroxylée; m et n valent chacun indépendamment 0 ou 1 à condition que m et n ne valent pas 1 en même temps; et j et k valent chacun indépendamment 0, 1, 2 ou 3 à condition que j + k n'excède pas 3.
PCT/JP1998/000208 1997-01-21 1998-01-21 Agents antimicrobiens/imputrescibilisants industriels, agents algicides et antiparasites contenant des n-quinoxalylanilines WO1998031228A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002278244A CA2278244A1 (fr) 1997-01-21 1998-01-21 Agents antimicrobiens/imputrescibilisants industriels, agents algicides et antiparasites contenant des n-quinoxalylanilines
NZ336826A NZ336826A (en) 1997-01-21 1998-01-21 Industrial antimicrobial/mildew-proofing agents, algicides and antifouling agents containing N-quinoxalylanilines
AU55747/98A AU5574798A (en) 1997-01-21 1998-01-21 Industrial antimicrobial/mildew-proofing agents, algicides and antifouling agents containing n-quinoxalylanilines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP852097 1997-01-21
JP9/8520 1997-01-21

Publications (1)

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WO1998031228A1 true WO1998031228A1 (fr) 1998-07-23

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PCT/JP1998/000208 WO1998031228A1 (fr) 1997-01-21 1998-01-21 Agents antimicrobiens/imputrescibilisants industriels, agents algicides et antiparasites contenant des n-quinoxalylanilines

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AU (1) AU5574798A (fr)
CA (1) CA2278244A1 (fr)
NZ (1) NZ336826A (fr)
WO (1) WO1998031228A1 (fr)

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WO2000031050A1 (fr) * 1998-11-24 2000-06-02 Aventis Pharmaceuticals Products Inc. Composes de quinoline et quinoxaline
WO2006108224A1 (fr) * 2005-04-11 2006-10-19 Murdoch University Composés antiparasitaires
EA007807B1 (ru) * 1997-05-28 2007-02-27 Авентис Фармасьютикалз Инк. Стентовое устройство, содержащее соединения хинолина и хиноксалина, способ лечения рестеноза
KR100784291B1 (ko) * 1998-11-24 2007-12-11 아벤티스 파마슈티칼스 인크. 퀴놀린 및 퀴녹살린 화합물이 혼입된 중합체성 피복물을 갖는 스텐트 장치
KR100784289B1 (ko) * 1998-11-24 2007-12-12 아벤티스 파마슈티칼스 인크. 퀴놀린 및 퀴녹살린 화합물이 혼입된 중합체성 코팅을 갖는 스텐트 장치

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CN106573000B (zh) * 2014-07-07 2020-02-07 陈昆锋 作为抗癌药物的芳基胺取代的喹喔啉

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA007807B1 (ru) * 1997-05-28 2007-02-27 Авентис Фармасьютикалз Инк. Стентовое устройство, содержащее соединения хинолина и хиноксалина, способ лечения рестеноза
WO2000031050A1 (fr) * 1998-11-24 2000-06-02 Aventis Pharmaceuticals Products Inc. Composes de quinoline et quinoxaline
KR100784291B1 (ko) * 1998-11-24 2007-12-11 아벤티스 파마슈티칼스 인크. 퀴놀린 및 퀴녹살린 화합물이 혼입된 중합체성 피복물을 갖는 스텐트 장치
KR100784289B1 (ko) * 1998-11-24 2007-12-12 아벤티스 파마슈티칼스 인크. 퀴놀린 및 퀴녹살린 화합물이 혼입된 중합체성 코팅을 갖는 스텐트 장치
CN100390155C (zh) * 1998-11-24 2008-05-28 阿温蒂斯药物公司 喹啉和喹喔啉化合物
WO2006108224A1 (fr) * 2005-04-11 2006-10-19 Murdoch University Composés antiparasitaires
EP1871743A4 (fr) * 2005-04-11 2009-12-30 Univ Murdoch Composés antiparasitaires

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CA2278244A1 (fr) 1998-07-23
NZ336826A (en) 2000-06-23
AU5574798A (en) 1998-08-07

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