WO1999062335A1 - Derive de phenylhydrazine, agent antibacterien et antifongique, algicide industriel et agent de prevention de la fixation d'organismes, comprenant ledit derive - Google Patents

Derive de phenylhydrazine, agent antibacterien et antifongique, algicide industriel et agent de prevention de la fixation d'organismes, comprenant ledit derive Download PDF

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Publication number
WO1999062335A1
WO1999062335A1 PCT/JP1999/002934 JP9902934W WO9962335A1 WO 1999062335 A1 WO1999062335 A1 WO 1999062335A1 JP 9902934 W JP9902934 W JP 9902934W WO 9962335 A1 WO9962335 A1 WO 9962335A1
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group
atom
carbon atoms
compound
methyl
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PCT/JP1999/002934
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English (en)
Japanese (ja)
Inventor
Shinichi Igarashi
Taito Nishino
Toshiaki Takeyama
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Nissan Chemical Industries, Ltd.
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Priority to AU40581/99A priority Critical patent/AU4058199A/en
Publication of WO1999062335A1 publication Critical patent/WO1999062335A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals
    • 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 ring carbon atoms

Definitions

  • the present invention relates to antibacterial and antifungal agents and algicides for industrial products, antibacterial and antifungal agents used in the manufacturing process of industrial products, and water for preventing the attachment of harmful aquatic organisms such as algicides and shellfish. It relates to a biofouling inhibitor. Background art
  • Industrial antibacterial and antifungal agents and algicides are used to eliminate various adverse effects of the growth and growth of bacteria, fungi and algae on 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.
  • Anti-fouling agents can be found in underwater equipment such as fishing nets, ship bottoms, buoys, marine structures, condenser cooling water systems for thermal or nuclear power plants, heat exchanger cooling water intake channels for the chemical industry, It is used to prevent harmful aquatic organisms such as shellfish from attaching to underwater structures or reservoirs.
  • the phenylhydrazine derivative having a virazole ring of the present invention is a novel compound, and is completely different from the compound described in this publication in the bonding position on the pyrazole ring.
  • organotin compounds as biofouling inhibitors are effective in preventing the fouling of aquatic organisms, but they are highly toxic, and they cause significant accumulation of fish and shellfish in the body. Is currently being regulated.
  • triptyl sulphoxide is designated as a Class 1 specified chemical substance by the Chemical Substances Control Law (1990), and triphenyltin compounds and tripriptyl tin compounds are designated as a Class 2 specified chemical substance. Use is prohibited.
  • the above-mentioned copper compounds are widely used in antifouling paints for intake channels and ship bottoms, but contain copper, which is a heavy metal like tin compounds. It cannot be said to be a biofouling control agent in water. Disclosure of the invention
  • the inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that phenylhydrazine derivatives have a high safety and a wide spectrum with a low dose from the viewpoint of preventing environmental pollution.
  • the present invention was found to be a highly industrial antibacterial and antifungal agent, an algicide and a biofouling inhibitor, and completed the present invention.
  • the present invention provides a compound represented by the following general formula (1):
  • X and ⁇ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom, and a carbon atom of 1 Or 5 carbon atoms substituted with a halogen atom
  • W is
  • X 1 and Y 1 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom, Represents an alkoxy group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms substituted with a halogen atom or a ditro group, and m and n each independently represent 0 or 1.
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group of 5 C 1 -C substituted with an alkyl group or a halogen atom having 1 to 5 carbon atoms
  • R 3 Represents an alkyl group having 1 to 3 carbon atoms.
  • X and Y each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom, and a carbon atom of 1 Or 5 carbon atoms substituted with a halogen atom
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a carbon atom substituted with an alkyl group having 1 to 5 carbon atoms or a halogen atom
  • R 3 represents an alkyl group having 1 to 5 atoms
  • R 3 represents an alkyl group having 1 to 3 carbon atoms.
  • n means normal, “i” means iso, “s” means secondary, “t” means unique, and “neo” means neo.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • alkyl group having 1 to 3 carbon atoms examples include methyl group, ethyl group, n-propyl group, i-propyl and cyclopropyl.
  • Alkyl groups having 1 to 5 carbon atoms include, in addition to these, , N-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, i-pentyl, neo-pentyl, t- Examples include a pentyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclobutyl group and a cyclopentyl group.
  • alkoxy group having 1 to 5 carbon atoms examples include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, S-butoxy, t-butoxy, n -Pentyloxy, 2-pentyloxy, 3-pentyloxy, i-pentyloxy, neo-pentyloxy, t-pentyloxy, cyclopropoxy, trimethylcyclopropoxy, 2-methylcyclopropoxy, cyclobutoxy and And a cyclopentyloxy group.
  • alkyl group having 1 to 5 carbon atoms substituted with a halogen atom examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, sec-butyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, i-pentyl, neo-pentyl, t-pentyl, 1-methylcyclopropyl, 2- Fluorine, chlorine, bromine and / or methylcyclopropyl, cyclobutyl and cyclopentyl groups Mono-, di-, tri- and polysubstituted by iodine atoms are included.
  • alkoxy group having 1 to 5 carbon atoms substituted with a halogen atom examples include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, i-pentyloxy, neo-pentyloxy, t-pentyloxy, cyclopropoxy, 1-methylcyclopropoxy, 2-methylcyclopropoxy And mono-, di-, tri- and poly-substituted groups of a fluorine atom, a chlorine atom, a bromine atom and a Z or iodine atom of the group, cyclobutoxy group and cyclopentoxy group.
  • Preferred as X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-group.
  • Preferred as X 1 and Y 1 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, t-butyl group, n-pentyl group, trifluoromethyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group, trifluoromethoxy group Or a nitro group.
  • Desirable R 1 and R 2 each independently include a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group.
  • Preferred R 3 includes a methyl group, an ethyl group, an n-propyl group and an i-propyl group.
  • the industrial antibacterial / antifungal agent, algicide and biofouling inhibitor of the present invention may contain the phenylhydrazine derivative represented by the above general formula (1) as an active ingredient. Preferred embodiments of the present invention are described below.
  • An industrial antibacterial and antifungal agent characterized by containing a phenylhydrazine derivative represented by the formula (1).
  • X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t —Butyl, n-pentyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, n-pentyloxy, trifluoromethoxy
  • X 1 and Y 1 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, t-butyl group,
  • X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a methoxy group or a nitro group
  • X 1 and Y 1 are each independently A hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a t-butyl group or a methoxy group, and the hydrazine derivative according to the embodiment (2), wherein R 3 is a methyl group.
  • Industrial antibacterial agent. Drag agent.
  • a biofouling inhibitor containing a phenylhydrazine derivative represented by the formula (1) A biofouling inhibitor containing a phenylhydrazine derivative represented by the formula (1).
  • X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a methoxy group or a nitro group, and R 3 is a methyl group.
  • Preferred compounds contained in the active ingredients of the industrial antibacterial and antifungal agents, algicides and biofouling inhibitors of the present invention are listed in Tables 1 and 2 below, and the compounds used in the present invention Is not limited to these.
  • Me methyl group
  • Et ethyl group
  • Pr—n normal propyl group
  • Pr—i isopropyl group
  • Bu_n normal butyl group
  • Bu—t Yuichi Sharybutyl group
  • P en—n normal pentyl group
  • OM e methoxy group
  • 0Et ethoxy group
  • 0Pr_n normal propoxy group
  • 0Bu—n normal butoxy group.
  • HH OMe HH CI CI Me The phenylhydrazine derivative of the present invention is disclosed in International Patent Publication No.WO96 / 38419, Japanese Patent Publication No. 491-111061, and Japanese Patent Application Laid-Open No. 2-2955962. It can be produced with reference to Japanese Patent Application Laid-Open No. Hei 2-3030157, Doit Patent DE38021075 and European Patent EP640479.
  • the phenylhydrazine derivative represented by the general formula (2) can be produced by the following method. That is, a pyrazolecarboxylic acid (a) is converted into a carboxylic acid halide (b) according to a conventional method, and then reacted with various phenylhydrazines (c) to obtain a compound of the present invention represented by the general formula (2). Can be manufactured.
  • X, Y, R 1 , R 2 and R 3 represent the same meaning as described above, and ⁇ represents a halogen atom such as a chlorine atom or a bromine atom.
  • halogenation step of the pyrazole carboxylic acids (a) it is possible to directly add thionyl halide, halogenidine, oxyhalogenated phosphorus, phosgene, etc., but usually in an inert solvent such as chloroform, benzene, and toluene. It is better to carry out at 0 to 120 ° C or the reflux temperature of the solvent.
  • the step of producing the compound of the present invention represented by the general formula (2) can be performed in a suitable inert solvent.
  • the solvent include aromatic hydrocarbons such as toluene, xylene and chlorobenzene, halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane, ethers such as diisopropyl ether, tetrahydrofuran and dioxane, and acetonitrile and the like.
  • examples thereof include polar solvents such as nitriles, dimethyl sulfoxide, and dimethylformamide.
  • an organic base eg, pyridine, triethylamine
  • an inorganic base eg, carbon dioxide, hydroxide, sodium hydride
  • the reaction temperature is usually preferably from 0 to 50 ° C.
  • the compound of the present invention represented by the general formula (2) of the obtained crude product can be used as it is.
  • recrystallization, solvent washing, column chromatography or the like can be usually applied.
  • the phenylhydrazine derivative used as an active ingredient in the present invention may be used alone, or when the industrial antibacterial / antifungal agent, algicide and biofouling inhibitor of the present invention are used. If necessary, other known industrial antibacterial and antifungal agents, algicides or biofouling inhibitors can be further contained and used as a mixture.
  • N-decyl-N-isononyl- ⁇ , ⁇ -dimethylammonium chloride poly [oxy- Quaternary ammonium compounds such as 1,2-ethanediyl (dimethylimino) -1,2-ethanediyl (dimethylimino) -1,2-ethanediyl dichloride];
  • Aldehyde compounds such as glutaraldehyde
  • N-nitrogen-based compounds such as bromochlorodimethylhydantoin and trichloromouth isocyanuric acid
  • Guanide-based compounds such as poly (hexamethylene biguanide) hydrochloride; zinc dimethyldithiolate zinc rubamate, getyldithi zinc dirubinate zincate, dibutyruditi zinc zinc rubamate, ethyl benzyldithilate zinc salt
  • Zinc acid salt ethylene bisdithiol zinc salt, propylene bisdithiol zinc salt, bis (dimethyldithiol rubamoyl) ethylene bisdithiol zinc salt, ethylene bisdithiol zinc manganese acid, dimethyldithionate zinc Dithiocarbamate-based metal compounds such as nickel rubamate, nickel dibutyldithiocarbamate, dimethyldithiophene copper rubamate, and dimethyldithiocarbamate iron;
  • Copper-based metal powders such as copper powder and copper-nickel alloy powder
  • Copper compounds such as cuprous oxide, cuprous thiocyanate (copper rhodan), basic copper carbonate, copper pyrophosphate, copper naphthenate, copper abietic acid, and copper oxyquinoline;
  • Pyrithion-based metal compounds such as zinc salt of 2-pyridinethiol-1-oxide and copper salt of 2-pyridinthiol-toxide;
  • 2-mercaptobenzothiazole 2- (thiocyanomethylthio) benzothiazol, 2- (thiocyanomethylsulfonyl) benzothiazol, 2-thiothianoethylthio-1 4-cyclobenzotothiazole, 2-thiocyanopropyl Benzothiazole-based compounds such as thio-5,7-dichlorobenzothiazole and 2-thiothianomethylthio-1,4,5,6,7-tetrachloro benzothiazole;
  • Ditolyl compounds such as tetrafluoroisophthalonitrile, tetrachloroisophthalonitrile, 5-chloro-1,2,4-difluoro-6-methoxyisophthalonitrile, 2,4,5,6—tetrachloroisophthalonitrile ;
  • Quinone compounds such as 2,3-dichloro-1,4-naphthoquinone, 2-amino-3-chloro-1,4-naphthoquinone, 2,3-dicyanone 1,4 dithiaanthraquinone;
  • N-trichloromethylthiotetrahydrofurophthalimide N-1,1,2,2—tetrachloroethylthiotetrahydrofurimidate
  • N-trichloromethylthiophthalimid N-fluorodichloromethylthiophthalimid Amide, N, N-dimethylamino N'-phenyl N '-(fluorodichloromethylthio) sulfamide, trichloromethylthiomethanesulfone p-chloroanilide, N— (1,1,2,2 —Tetrachloro-2-fluoroethylthio) methanesulfonylanilide, N-fluorodichloromethylthio-1-N—3-chlorophenyl-1-N′-dimethylurea, N—fluorodichloromethylthio-N—3, 4-N-Methylurine, N-Fluoro-N-methylthio-N-Tris
  • Alkyl phenyl phosphate compounds such as tris (octylphenyl) phosphate, tris (nonylphenyl) phosphate, tris (dinonylphenyl) phosphate, and tris (mono and di-mixed nonylphenyl) phosphate;
  • phenylhydrazine derivative used as an active ingredient in the present invention may be composed of a single compound or a mixture of several types of phenylhydrazine derivatives.
  • the phenylhydrazine derivative used as an active ingredient in the present invention may be added alone to the above-mentioned use application system, or as a mixture comprising the active ingredient and, if necessary, an appropriate carrier or solvent, or It may be formulated as an aqueous emulsion or dispersion.
  • the formulation of the industrial antibacterial and antifungal agent, the algicide and the biofouling inhibitor of the present invention can be used as an active ingredient in the present invention when outlined in the field of application of the industrial antibacterial and antifungal agent and the algicide.
  • the phenylhydrazine derivative is mixed with a suitable carrier and auxiliary agent, for example, a surfactant, a binder, a stabilizer, etc., and mixed, and then wettable powders, emulsions, sols (floatables), etc. And used in an appropriate dosage form.
  • 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 are mineral powders such as lime ore, bentonite, clay, montmorilloite, diatomaceous earth, mica, vermicillaite, gypsum, calcium carbonate, phosphate lime, white limestone, slaked lime, silica sand, Examples include ammonium sulfate, urea, etc., or vegetable powders, for example, soybean powder, starch, crystalline cellulose, etc., alumina, silicates, sugar polymers, highly dispersible silicic acids, waxes, etc.
  • liquid carriers examples include water, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc., aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, Chlorobenzene, cumene, methylnaphthalene, etc.
  • alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc.
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, Chlorobenzene, cumene, methylnaphthalene, etc.
  • halogenated hydrocarbons for example, chloroform, dichloromethane, ethylene dichloride, etc.
  • ethers for example, ethyl ether, dioxane, tetrahydrofuran, etc.
  • ketones for example, acetone, methylethyl ketone, cyclohexanone, methylisobutyl.
  • sulfoxides For example, dimethyl sulfoxide, alcohol ethers, for example, ethylene
  • 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.
  • nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, and sorbitan alkyl ester.
  • anionic surface active agents alkylbenzene Natick DOO, alkyl Rusuru Hosah succinates, alkyl monkey sulfates, polyoxyethylene alkyl Sa Rufuwe DOO, ⁇ Li one Rusuruhone preparative and Raurirusarufuwe one preparative, and the like
  • cationic surfactant examples include alkylamines (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, etc.), and the like.
  • amphoteric surfactant examples include carboxylic acid (betaine type) sulfate, and the like.
  • polyvinyl alcohol PVA
  • carboxymethyl cellulose CMC
  • gum arabic polyvinyl acetate
  • gelatin case , Alginate, tragacanth gum, guar gum, xanthan gum, hydroxypropylcellulose and other thickeners and various adjuvants.
  • a suitable amount of a stabilizer such as an antioxidant or an ultraviolet absorber can be added.
  • the industrial antibacterial and antifungal agents and algicides of the present invention containing a phenylhydrazine derivative as an active ingredient can be used for the following applications.
  • Building materials building materials (building materials, civil engineering materials, etc.), antibacterial and antifungal and algicidal products for home appliances, household goods, sports goods, etc .; protection of slime deposits on sugarcane and sugar beet sugar manufacturing equipment; air cleaner Prevention of accumulation and accumulation of microorganisms in scrubber systems and industrial freshwater supply systems; maintenance of sanitary conditions in food factories; deodorization and sterilization of sewage treatment plants, human waste treatment plants, etc. when washing production facilities; Prevent microbial contamination and sedimentation in muddy water and secondary oil recovery processes; Prevent the growth of bacteria and fungi in paper coatings and coatings; Prevent microbial contamination in cosmetics and toiletry products Control algae growth in pools, etc. Prevention of microbial contamination of agricultural formulations, electrodeposition systems, diagnostic and pharmaceutical products, medical equipment, etc .; prevention of microbial accumulation in photographic processing.
  • An anti-fouling agent containing a phenylhydrazine derivative as an active ingredient such as fishing nets, the bottom of ships, buoys and other submarine equipment, marine structures, condenser cooling water systems for thermal or nuclear power plants, and heat from the chemical industry Water mussels, mussels, oysters, hydrmes for underwater structures such as water intake channels for exchanger cooling water and auxiliary equipment for dams, and reservoirs It can be used to prevent the adhesion of harmful aquatic organisms such as shellfish such as seaweed, hydra, selbra, sea squirt, bryophytes and snails, and algae such as azaa, honori and shimidro.
  • harmful aquatic organisms such as shellfish such as seaweed, hydra, selbra, sea squirt, bryophytes and snails
  • algae such as azaa, honori and shimidro.
  • Formulation examples when the phenylhydrazine derivative of the present invention is used as an industrial antibacterial and antifungal agent and an algicide are shown using the compound of the present invention.
  • the compounding ratio of the active ingredient, the type and amount of the carrier and the auxiliary agent are shown. Are not limited to these.
  • the above mixture was placed in a ball mill and pulverized and mixed for 12 hours to obtain a flooring 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 water or an appropriate organic solvent, and then preparing them in various industrial raw materials or products. To the surface of various industrial raw materials and products, or to spray various industrial raw materials and products in the diluent of the industrial antibacterial, antifungal and algicidal agents of the present invention. It can be used by various methods in accordance with the generally used methods of industrial antibacterial and antifungal agents and algicides, including the method of immersion in water, etc. It is not limited.
  • Formulations of the industrial antibacterial and antifungal agents, algicides and biofouling inhibitors of the present invention are outlined in the field of application of biofouling inhibitors.
  • the phenylhydrazine derivative used as an active ingredient in the present invention is a paint , Solutions, emulsions and the like.
  • general recipes usually used can be adopted for the preparation of these paints, solutions, emulsions and the like.
  • a paint is prepared by blending a phenylhydrazine derivative, which is an active ingredient, with a film-forming agent, and is used to prepare a ship bottom, marine By applying it to a structure, a cooling water intake pipe or an underwater structure, it is possible to prevent the adhesion and propagation of underwater organisms.
  • 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 as necessary.
  • concentration of the phenylhydrazine derivative as an active ingredient as long as a coating film can be formed, but 1 to 50% by weight, preferably 5 to 50% by weight based on the weight of the antifouling paint. It is blended at a ratio of 20% by weight.
  • VYHH Vinyl synthetic resin, manufactured by UCC 7
  • the underwater biofouling inhibitor of the present invention is used in the form of a solution, for example, a solution in which a phenylhydrazine derivative, which is an effective component, is dissolved in a solvent together with a film-forming agent is prepared, and the solution is used for aquaculture nets and stationary. By applying it to fishing nets and the like, it is possible to prevent the adhesion and propagation of aquatic organisms.
  • Synthetic resins, artificial rubbers, natural resins and the like are used as the film forming agent, and xylene, toluene, cumene, methylethylketone, methylisobutylketone, acetate and the like are used as the solvent.
  • an additive such as a plasticizer may be used if necessary.
  • concentration of the funinylhydrazine derivative, which is an active ingredient as long as a solution can be formed, but 1 to 50% by weight, preferably 5 to 30% by weight of the solution is used. It is blended in a ratio.
  • Formulation examples when the underwater biofouling inhibitor of the present invention is used as an antifoulant solution are shown using the compounds of the present invention, but are not limited thereto.
  • a surfactant is usually added to a solution of the phenylhydrazine derivative as an active ingredient according to the general method for preparing an emulsion, and Can be prepared, and there is no particular limitation on the type of surfactant used.
  • the prepared emulsion can be used by kneading it into raw materials such as aquaculture nets and fixed nets used in the ocean or water, for example, polymer resins and the like.
  • the concentration of the phenylhydrazine derivative as an active ingredient has no upper limit as long as the emulsion can be formed.
  • the concentration is 1 to 50% by weight, preferably 3 to 30% by weight based on the weight of the emulsion. In the proportion of
  • the above-mentioned solution or emulsion of the present invention can also be used by adding to water or water storage in order to prevent adherent propagation of aquatic organisms in a cooling water intake pipe or a reservoir.
  • the compound of the present invention was diluted with dimethyl sulfoxide in a series of dilutions (200 0 0, 1 0 0 0 0 0, 5 0 0 0, 2 5 0 0, 1 2 5 0, 6 2 6, 3 1 3, 1 5, 7, 8, 39, 20, 20, 10, 2.5 mgZl) were prepared.
  • Sensitivity Medium 1N Nasui Pharmaceutical
  • Potato dextrose agar medium Nasui Pharmaceutical
  • the concentration of the compound of the present invention in the agar medium was 100, 500, 250, 125, 125, respectively. 62.5, 31.3, 15.6, 7.8, 3.9, 2.0, 1.0, 0.5, 0.25, 0.125 mg / l .
  • the inoculated bacteria were cultured at 37 ° C for 20 hours in broth for sensitivity measurement (Nissui Pharmaceutical), and the fungi were cultured in potato dextrose agar medium (Nissui Pharmaceutical) for 10 days. A suspension of 10 S CFU / ml was prepared.
  • the suspension of the test bacterium was streaked using a platinum loop on a drug-mixed agar plate.
  • the bacterium was incubated at 37 ⁇ 1 ° C for 18 to 20 hours, and the fungus was 27. After culturing at C for 7 days, the concentration at which no growth was observed was defined as the minimum inhibitory concentration (MIC).
  • MIC minimum inhibitory concentration
  • the compounds of the present invention were diluted with dimethylsulfoxide in a dilution series 56, 78, 39 mg / 1) were prepared.
  • Sensitivity Medium 1N (Nissui Pharmaceutical)
  • Potato Dextrose Agar Medium (Nissui Pharmaceutical)
  • the concentration of the compound of the present invention in the agar medium was 100,500,250,125,62.5,31.3,15.6,7.8,3. 9, 2. O mg / 1.
  • the inoculated bacteria were cultured at 37 ° C for 20 hours in a broth for sensitivity measurement (Nissui Pharmaceutical), and the fungi were cultured for 10 days on a potato dextrose agar medium (Nissui Pharmaceutical).
  • the suspension of the test bacteria 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 7 days at 27 ° C for fungi.
  • the concentration at which no growth was observed was defined as the minimum inhibitory concentration (MIC).
  • the compound of the present invention was made into a solution having a concentration of 200 mg / l using dimethyl sulfoxide, and 1 ml of the solution was diluted with 19 ml of sterilized tap water to prepare a solution having a concentration of 100 mg / l.
  • the sample solution 2 0 m 1 in the test bacterial solution was 0. 1 ml inoculated (legionella New ⁇ Huy La (Legionella pneumophila), 3. 1 x 1 0 8 or Zm 1).
  • a fixed amount of the compound of the present invention was dissolved in a medium containing 10 V m1 of freshwater green algae (Selenastrum capricornutum) in the logarithmic growth phase, and the concentration of the compound of the present invention in the medium was 50%. Samples of 0 ppb and 50 ppb were prepared, and were incubated at 23 ⁇ 1 ° C for 24 hours under continuous lighting conditions.
  • the proliferation rate was determined by measuring the number of cells using a hemocytometer.
  • the growth inhibition rate was calculated by comparison with the untreated group.
  • the cells were collected by centrifugation, and methanol was added to disrupt the cells and chlorophyll was extracted. The amount of chlorophyll was measured from the absorbance using a spectrophotometer to determine the growth rate.
  • the growth inhibition rate was calculated by comparison with the untreated group.
  • A Freshwater green algae (Chlorella pyrenoidosa)
  • B Freshwater cyanobacteria (Microcystis aeruginosa)
  • C Freshwater diatom (Diatoma elongatum, Matoma elongatum)
  • the compound of the present invention was completely dissolved in 1 ml of acetone and applied uniformly in a 4 cm diameter zone drawn on a test plate.
  • a zone to which only acetone was applied was provided as a blank, and a zone to which 1.0 mg and 0.5 mg of copper sulfate were applied as comparative agents was provided.
  • blue mussels Mytilus edulis
  • the prepared test plate was immersed in a water tank into which seawater flows, and allowed to stand in a dark place for 3 hours.
  • the adhesion control effect was determined in comparison with copper sulfate used as a comparative drug.
  • the phenylhydrazine derivative represented by the general formula (1) is highly safe, exhibits a wide spectrum at a low dose, and is an industrial antibacterial agent, an antifungal agent, an algicide, and a biofouling inhibitor. Useful as an agent.

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Abstract

L'invention concerne un agent antibactérien et antimycotique industriel, un algicide et un agent empêchant la fixation de certains organismes, agents caractérisés en ce qu'ils comprennent un dérivé de phénylhydrazine représenté par la formule générale (1), dans laquelle X et Y représentent indépendamment H, un halogène, un groupe alkyle C1-5, un groupe alkyle C1-5 à substitution halogène, un groupe alcoxy C1-5, un groupe alcoxy C1-5 à substitution halogène ou un groupe nitro ; et W représente la formule (1-1) dans laquelle X1 et Y1 sont, indépendamment, tels que définis respectivement pour X et Y, m et n représentent indépendamment 0 ou 1, ou la formule (1-2) dans laquelle R1 et R2 représentent indépendamment H, un halogène, un groupe alkyle C¿1-5? ou un groupe alkyle C1-5 à substitution halogène et R?3¿ représente un groupe alkyle.
PCT/JP1999/002934 1998-06-02 1999-06-02 Derive de phenylhydrazine, agent antibacterien et antifongique, algicide industriel et agent de prevention de la fixation d'organismes, comprenant ledit derive WO1999062335A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU40581/99A AU4058199A (en) 1998-06-02 1999-06-02 Phenylhydrazine derivative, and commercial antibacterial and antimycotic agent, algicide and agent for preventing attachment of organism comprising the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP10/152585 1998-06-02
JP15258598 1998-06-02
JP15258698 1998-06-02
JP10/152586 1998-06-02

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WO1999062335A1 true WO1999062335A1 (fr) 1999-12-09

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Cited By (7)

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CN103179857A (zh) * 2010-08-20 2013-06-26 陶氏益农公司 包括腙衍生物和铜的协同杀藻组合物
WO2015060613A1 (fr) 2013-10-21 2015-04-30 Daewoong Pharmaceutical Co., Ltd. Nouveau dérivé oxodihydropyridinecarbohydrazide antifongique
JPWO2018025966A1 (ja) * 2016-08-04 2019-06-06 株式会社ブリヂストン ゴム組成物、タイヤ、添加剤及びヒドラジド化合物
KR101991276B1 (ko) * 2018-01-19 2019-06-21 전남대학교산학협력단 신규 균주 페니실리움 아쿠아티쿰 및 이를 이용한 퇴행성 뇌질환 치료제
US10351661B2 (en) 2015-12-10 2019-07-16 Ppg Industries Ohio, Inc. Method for producing an aminimide
US10377928B2 (en) 2015-12-10 2019-08-13 Ppg Industries Ohio, Inc. Structural adhesive compositions
CN111377869A (zh) * 2018-12-27 2020-07-07 南京农业大学 一种二卤代吡唑甲醛的卤代苯腙类化合物、制备方法及其应用

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JPS63152355A (ja) * 1986-08-04 1988-06-24 Meiji Seika Kaisha Ltd Ｎ′−（フルオロフエニル）ベンゾヒドラジド誘導体および非医療用殺微生物剤
JPH02300157A (ja) * 1989-05-11 1990-12-12 Tosoh Corp ベンジルカーバゼート誘導体及びそれを含有する農園用殺菌剤
JPH04327508A (ja) * 1991-04-23 1992-11-17 Tosoh Corp 工業用殺菌剤
WO1996038419A1 (fr) * 1995-05-31 1996-12-05 Nissan Chemical Industries, Ltd. Derives de 5-pyrazolecarboxamide et agent de lutte contre les maladies des plantes

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JPS56158768A (en) * 1980-05-09 1981-12-07 Nissan Chem Ind Ltd Substituted pyrazole derivative and industrial antimicrobial and antifungal agent containing the same
JPS63152355A (ja) * 1986-08-04 1988-06-24 Meiji Seika Kaisha Ltd Ｎ′−（フルオロフエニル）ベンゾヒドラジド誘導体および非医療用殺微生物剤
JPH02300157A (ja) * 1989-05-11 1990-12-12 Tosoh Corp ベンジルカーバゼート誘導体及びそれを含有する農園用殺菌剤
JPH04327508A (ja) * 1991-04-23 1992-11-17 Tosoh Corp 工業用殺菌剤
WO1996038419A1 (fr) * 1995-05-31 1996-12-05 Nissan Chemical Industries, Ltd. Derives de 5-pyrazolecarboxamide et agent de lutte contre les maladies des plantes

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103179857A (zh) * 2010-08-20 2013-06-26 陶氏益农公司 包括腙衍生物和铜的协同杀藻组合物
EP2605653A1 (fr) * 2010-08-20 2013-06-26 Dow AgroSciences LLC Compositions algicides synergiques comprenant des dérivés d'hydrazone et du cuivre
EP2605653A4 (fr) * 2010-08-20 2014-01-08 Dow Agrosciences Llc Compositions algicides synergiques comprenant des dérivés d'hydrazone et du cuivre
US8906829B2 (en) 2010-08-20 2014-12-09 Dow Agrosciences Llc Synergistic algicidal compositions including hydrazone derivatives and copper
EP3060549A4 (fr) * 2013-10-21 2017-06-21 Daewoong Pharmaceutical Co., Ltd. Nouveau dérivé oxodihydropyridinecarbohydrazide antifongique
KR20150046456A (ko) * 2013-10-21 2015-04-30 주식회사 대웅제약 신규한 항진균성 옥소다이하이드로피리딘카보하이드라자이드 유도체
JP2016535017A (ja) * 2013-10-21 2016-11-10 デウン ファーマシューティカル カンパニー リミテッド 新規な抗真菌性オキソジヒドロピリジンカルボヒドラジド誘導体
US9617216B2 (en) 2013-10-21 2017-04-11 Daewoong Pharmaceutical Co., Ltd. Antifungal oxodihydropyridinecarbohydrazide derivative
WO2015060613A1 (fr) 2013-10-21 2015-04-30 Daewoong Pharmaceutical Co., Ltd. Nouveau dérivé oxodihydropyridinecarbohydrazide antifongique
KR102076820B1 (ko) 2013-10-21 2020-02-13 주식회사 대웅테라퓨틱스 신규한 항진균성 옥소다이하이드로피리딘카보하이드라자이드 유도체
US10351661B2 (en) 2015-12-10 2019-07-16 Ppg Industries Ohio, Inc. Method for producing an aminimide
US10377928B2 (en) 2015-12-10 2019-08-13 Ppg Industries Ohio, Inc. Structural adhesive compositions
US11518844B2 (en) 2015-12-10 2022-12-06 Ppg Industries Ohio, Inc. Method for producing an aminimide
US11674062B2 (en) 2015-12-10 2023-06-13 Ppg Industries Ohio, Inc. Structural adhesive compositions
JPWO2018025966A1 (ja) * 2016-08-04 2019-06-06 株式会社ブリヂストン ゴム組成物、タイヤ、添加剤及びヒドラジド化合物
JP7146636B2 (ja) 2016-08-04 2022-10-04 株式会社ブリヂストン ゴム組成物、タイヤ、添加剤及びヒドラジド化合物
KR101991276B1 (ko) * 2018-01-19 2019-06-21 전남대학교산학협력단 신규 균주 페니실리움 아쿠아티쿰 및 이를 이용한 퇴행성 뇌질환 치료제
CN111377869A (zh) * 2018-12-27 2020-07-07 南京农业大学 一种二卤代吡唑甲醛的卤代苯腙类化合物、制备方法及其应用
CN111377869B (zh) * 2018-12-27 2023-02-17 南京农业大学 一种二卤代吡唑甲醛的卤代苯腙类化合物、制备方法及其应用

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