WO1998039289A1 - Urea derivatives, and industrial antibacterial and antifungal agents, algaecides and antiperiphytic agents containing the same - Google Patents
Urea derivatives, and industrial antibacterial and antifungal agents, algaecides and antiperiphytic agents containing the same Download PDFInfo
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- WO1998039289A1 WO1998039289A1 PCT/JP1998/000855 JP9800855W WO9839289A1 WO 1998039289 A1 WO1998039289 A1 WO 1998039289A1 JP 9800855 W JP9800855 W JP 9800855W WO 9839289 A1 WO9839289 A1 WO 9839289A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- 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<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
-
- 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<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C275/32—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms
- C07C275/34—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms having nitrogen atoms of urea groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C275/36—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms having nitrogen atoms of urea groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with at least one of the oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. N-aryloxyphenylureas
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/64—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups singly-bound to oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/38—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atom of at least one amino group being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfones
- C07C317/42—Y being a hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
Definitions
- the present invention relates to antibacterial and antifungal agents and algicides for industrial products, antibacterial agents used in the manufacturing process of industrial products and aquatic organisms for preventing the adhesion of harmful aquatic organisms such as algicides and shellfish. Adhesion prevention. Background art
- Anti-capi and bulking agents include organic nitrogen compounds, organic nitrogen compounds, and organic halogenated compounds ⁇ ! Nitrogen-containing fat polymers and heavy metal coordination compounds are used.
- Biofouling prevention ih ⁇ fishing nets, ship bottoms, buoys, and other underwater facilities, thigh structures, thermal or nuclear power cooling water systems, chemical industry heat exchanger cooling water mm, underwater structures Or it is used to prevent harmful aquatic organisms such as heads from attaching to reservoirs.
- No. 63900 (9 2) discloses diphenyl ether type and diphenyl sulfone type ⁇ rea induction, its ⁇ t method and herbicides.
- g and German Patent Publication DE 3 2 3 8 0 7 9 ⁇ include benzothiazolyloxyphenyl-rea and benzoxazolyloxyphenyl-rea derivatives and their t methods. And herbicides are disclosed.
- the above-mentioned organic nitrogen-based compounds, organic nitrogen-based compounds, organic halogen-based compounds, nitrogen-containing fats, polymers, and heavy ⁇ Ji coordination compounds are irritating drugs that pose a problem in the Labor Safety Act, However, there are many drugs that may cause problems from the viewpoint of protection, such as drugs that release formalin or halogen, and that may affect the human body and cause cm staining. Industrial antibacterial and anti-capi and fillers cannot be said to consist entirely of preferred agents.
- organotin compounds as biofouling inhibitors are effective in preventing the aquatic organisms from fouling, but are highly toxic, and especially remarkably accumulate in fish heads. ing.
- triptylsuzuoxide was designated as a first-class specified substance by the I ⁇ method (1990), and triphenylsuccinide and triptyltin compounds were designated as a second-class specified chemical. Use is forbidden.
- the copper compound of ⁇ is widely used for antifouling for roads and ship bottoms, it contains copper which is heavy like ⁇ tin, so there is a concern that ⁇ It can not be said that it is underwater organism adhesion control.
- composition is effective as a fiber or a biofouling agent. Disclosure of the invention
- the present inventors have conducted intensive studies in order to solve the above problem, and as a result, it has been found that ⁇ rea induction is high in price, and since it is effective in preventing brown spots, it exhibits a broad spectrum with a low dose and is highly practical.
- the present invention has been found to be an industrial antibacterial 'anti-kahi ⁇ , ⁇ agent and biofouling prevention II ⁇ , and has made the present invention.
- the present invention provides-, (1):
- W represents an oxygen atom or SO 2
- R 1 represents a C 3 alkyl group
- R 2 Represents a C w alkyl group or a C 8 alkoxy group
- R 1 represents a hydrogen atom, a halogen atom, a cyano group or a C 8 alkyl group (the alkyl group may be optionally substituted with a fluorine atom).
- p is 0, 1, 2 or 3
- Ar is " ⁇ (2):
- X 1 and Upsilon 1 are each d-6 alkyl group (the alkyl group may be optionally substituted with fluorine atom), d-6 alkoxy group (the alkoxy group is a fluorine atom Optionally substituted) or a halogen atom, and 1 and m each represent: 0 to 5 and 1 + m always represents 5 or less.
- X 2 and Y 2 are each a ⁇ ⁇ 8 alkyl group (the alkyl group may be optionally substituted with a fluorine atom), a d-3 alkoxy group (the alkoxy group is a fluorine atom A nitro group or a halogen atom, z represents a ⁇ or ⁇ atom, and n and 0 represent w: 0 to 0 respectively.
- the present invention relates to industrial antibacterials, anti-capitifiers, Wk agents and anti-biofouling agents which contain ⁇ rare compounds represented by the formula [1].
- nj is normal
- ij is iso
- sj is secondary
- rtj plays the character
- r neo j plays the neo.
- the C physician 8 alkyl group methyl, Echiru, n- propyl, i- flop ⁇ pills, cyclopropyl, and the like.
- the ds alkyl group includes methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, S-butyl, t-butyl, ⁇ -pentyl, 2-pentyl, 3-pentyl, i -Pentyl, neo-pentyl, t-pentyl, cyclopentyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and the like.
- Examples of the alkoxy group include methoxy, ethoxyquin, n-propoxy, i-propoxy, cyclopropoxy and the like.
- d- 5 alkoxy groups 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-methylcyclopipropoxy, 2-methylcyclopropoxy, cyclobutoxy, cyclopentyloxy and the like.
- Halogen atoms include fluorine, chlorine, bromine and iodine.
- Preferred compounds of the present invention include the following compounds.
- urea derivative represented by (1) is contained as an active ingredient.
- the urea of the present invention ⁇ I, jorlock. Patents EP 36390, JP-A-58-216175, and German Patent DE 3238079, etc. are usually used, for example, in the form of ®S (a), (b), (c) and (d). can do.
- Ar, R 1 , R 2 , R 8 and p in the lower ESJS ⁇ ; are the same as described above, and Ha 1 represents a chlorine atom, a bromine atom or a halogen atom of iodine source ⁇ .
- the acid acceptor to be used includes, for example, alkali hydroxides, oxides, hydrides, hydrides or hydroxides of alkaline earths, and the like. , Potassium, sodium hydride and the like.
- the as is preferably dimethylformamide, dimethylsulfoxide, acetate Nitrile, tetrahydrofuran, Jiokisan, acetone, an aprotic polar solvent such as methyl E chill ketone proceeds by ⁇ suitable temperature, for example 2 to 2 4 hours in one 2 0 1 5 0 e C.
- examples of the acid acceptor used for the condensation with nitrophenols include alkali hydroxides, hydrides, omm, ⁇ hydrides, hydroxides of alkaline earths, and fiberized products.
- sodium hydroxide, oxidized realm, difficult realm, hydrogenated sodium and the like are used.
- the book is preferably prepared in an aprotic polar medium such as dimethylformamide, dimethylsulfoxide, sulfolane, acetonitrile, tetrahydrofuran, dioxane, acetone, methylethylketone, or the like, in a suitable medium, for example, in the form of 210 180.
- the reaction proceeds by stirring for 224 hours.
- Reduction of the nitro group usually proceeds by hydrogenation (catalytic reduction) in the presence of a fiber such as Pd-C or Raney Ni.
- This hydrogenation proceeds by using a suitable solvent such as tetrahydrofuran,, ethyl, dioxane or the like, for example, by stirring for 0.5 (TC for 0.524 hours).
- a suitable solvent such as tetrahydrofuran,, ethyl, dioxane or the like, for example, by stirring for 0.5 (TC for 0.524 hours).
- Examples of the acid acceptor used for the condensation with sorbamoyl halide include alkali gold Hydroxides, carbonates, carbonates, hydrides or hydroxides of alkaline earth metals, tertiary amines, pyridines, etc., preferably potassium carbonate, nitrogen oxides, etc. Sodium, triethylamine, pyridine and the like.
- the book is preferably a non-protonic solvent such as dimethylformamide, acetonitrile, tetrahydrofuran, dioxane, acetone, methylethylketone, etc .; halogenated carbon such as chloroform, m-dichlorobenzene, etc .; Using a solvent such as aromatic benzene, toluene, xylene, etc. 7jc element or the like, a suitable solvent, for example, ⁇ 20 to 100. Proceed by stirring with C for 0.5-24 hours.
- a non-protonic solvent such as dimethylformamide, acetonitrile, tetrahydrofuran, dioxane, acetone, methylethylketone, etc .
- halogenated carbon such as chloroform, m-dichlorobenzene, etc .
- a suitable solvent for example, ⁇ 20 to 100. Proceed by stirring with C for 0.5-24 hours.
- the acid acceptor used for the condensation with thiophenols includes, for example, alkali metal hydroxides, carbonates, carbonized ⁇ ⁇ , hydrides or alkali hydroxides, and fluorides.
- alkali metal hydroxides carbonates, carbonized ⁇ ⁇ , hydrides or alkali hydroxides, and fluorides.
- the book is preferably prepared in an aprotic polar medium such as dimethylformamide, dimethylsulfoxide, sulfolane, acetonitrile, tetrahydrofuran, dioxane, acetone, methylethylketone, etc. in a suitable iS, e.g. Proceed by stirring for 2 to 24 hours.
- an aprotic polar medium such as dimethylformamide, dimethylsulfoxide, sulfolane, acetonitrile, tetrahydrofuran, dioxane, acetone, methylethylketone, etc.
- a suitable iS e.g. Proceed by stirring for 2 to 24 hours.
- Oxidation of a thiol group to a sulfone group is usually carried out with m-chloroperbenzoic acid, (Peroxy acid +,), etc. ⁇
- examples of the acid acceptor used for the condensation with nitrobenzenethiols include, for example, an alkali metal hydroxide, a compound, a mamm, a hydride or an alkaline earth hydroxide, a compound, and the like.
- Preferable examples include a hydroxide hydroxide, a difficult lithium, and a sodium hydride.
- the present s is preferably used in an aprotic polar medium such as dimethylformamide, dimethylsulfoxide, acetotrinole, tetrahydrofuran, dioxane, acetone, methylethylketone, etc. in a suitable aprotic medium, for example, Proceed by stirring at 0-150 for 2-24 hours.
- an aprotic polar medium such as dimethylformamide, dimethylsulfoxide, acetotrinole, tetrahydrofuran, dioxane, acetone, methylethylketone, etc.
- the target compound obtained in the formulas (a), (b), (c) and (d) can be obtained as a pure product by recrystallization with an appropriate solvent, purification by column chromatography, etc. Monkey
- the urea derivative used as an active ingredient in the present invention may be used as an active ingredient.
- the industrial antibacterial agent / anti-capi agent, the agent and the biofouling inhibitor ih ⁇ of the present invention may further contain anti-capi, a ⁇ agent or an anti-biofouling agent, and can be used as a mixture.
- Image H quaternary ammonium compound, arylisothiocyanate, 2-amino-3,4-chloro-1,4-naphthoquinone, ethylene-bis-thiocyanate, 2-n-octyl-3-isothiazolone, glutaraldehyde, 5-alpha-low 2-n-decyl-3-isothiazolone, 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile, 2-chloro-1-methylamino-6-isopropyl pyramino s-triazine, 5 —Chloro-2-methyl-3-y, thiazolone, 2,3-dichloro-1,4-naphthoquinone, jodomethyl— ⁇ -tolylsulfone, ⁇ , ⁇ —dimethyl-N '—Feneru N'-(fluoro Dichloromethylthio) sulfamide, ⁇
- the perylene derivative used as an active ingredient in the present invention may be composed of a single compound or a mixture of several kinds of perylene derivatives.
- urea as an active ingredient in the present invention May be added to the system, or may be formulated as a mixture of a suitable carrier or solvent if the amount is less than 7 minutes, or as a 7j emulsion or dispersion.
- the formulation of the industrial antibacterial, antifungal, algicidal and biofouling inhibitor of the present invention is outlined in the field of application of industrial antibacterial, antifungal and bulking agents.
- the urea shoes may be mixed and mixed with suitable carriers and auxiliary agents, such as surfactants, binders, irons, and the like, in a conventional manner; l-emulsions, emulsions, sols (flowables) and other suitable It is used after being formulated into a dosage form.
- any solid or liquid can be used as long as it is commonly used for industrial antibacterial agents and antifungal agents, and it is not limited to a specific one.
- solid bodies include mineral powders such as kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate; K ash, white carbon, slaked lime, ammonium sulfate, urea, etc., or plants Powders, for example, soybean powder, coconut, crystalline cellulose, etc., alumina, silicate, sugar-polymerized highly dispersible, waxes and the like.
- mineral powders such as kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate; K ash, white carbon, slaked lime, ammonium sulfate, urea, etc.
- Powders for example, soybean powder, coconut, crystalline cellulose, etc., alumina, silicate, sugar-polymerized highly dispersible, waxes and the like.
- liquid carriers examples include water, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc., aromatics such as benzene, toluene, xylene, ethylbenzene, Benzene, cumene, methylnaphthalene, etc., or carbon halides 7j, such as chloroform, dichloromethane, ethylene dichloride Mouth lids, ethers, such as ethyl ether, dioxane, tetrahydrofuran, etc., ketones, such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc., esters, such as ethyl acetate,, butyl, ethyle Glycotriacetate, Okiamyl, etc., nitrinoles, such as
- 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 (such as laurylamine, stearyltrimethylammonium chloride and alkyldimethylbenzylammonium chloride).
- amphoteric surfactant examples include carboxylic acid (betaine type) sulfate, and the like.
- carboxylic acid betaine type
- PVA polypinyl alcohol
- CMC carboxymethyl cellulose
- gum arabic polyvinyl acetate
- gelatin casein
- sodium alginate sodium alginate
- tragacanth gum guar gum
- xanthan gum hydroxypropyl
- a thickener such as cellulose and various auxiliaries can be blended.
- ⁇ antioxidant according to, 0 qs & [pi e Rukoto monkey in a stabilizer such as an ultraviolet absorption TOJ
- the industrial antibacterial anti-capillary agent of the present invention containing a rare agent as an active ingredient can be used for the following applications.
- Anti-biofouling which contains urea as an active ingredient, can be used in the sea, such as fishing nets, ship bottoms, buoys, etc., marine structures, or cooling water systems from nuclear power plants. Cooling water ⁇ 7j roads, underwater structures such as auxiliary equipment for dams, and mussels such as mussels, fujibo, oysters, hydramushi, hydra, selbra, sea squirrels, mosses, and snails, etc. It can be used to prevent harmful underwater organisms such as ⁇ .
- step S pyridine was distilled off under water, and 50 ml of water was added to the residue, followed by stirring. The obtained crystals were filtered and washed with n-hexane to obtain 2.10 g of Dani ⁇ II o
- Formulation examples when the urea derivative of the present invention is used as an industrial antibacterial / anti-capi and ⁇ agent are shown using the compound of the present invention, but the compounding ratio of the active ingredient, and the type and amount of the carrier and the auxiliary agent, etc. It is not limited to
- the formulated industrial antibacterial, anti-capi ⁇ j and bulking agents of the present invention can be used in various industrial raw materials or products by using various preparations as they are or in a suitable organic solvent. Or mixing or spraying on the surface of various industrial raw materials or products, or adding various industrial raw materials or products to the industrial antibacterial, anti-capi and diluent solutions of the present invention. It can be used by various methods in accordance with the industrial antibacterial and antifungal and algicidal methods that have been practiced so far, including the method of immersion, etc. It is not limited.
- the industrial antibacterial and anti-capillary bulking agent and the preparation for preventing biofouling of the present invention are summarized in the field of application of biofouling prevention li ⁇ lj.
- the urea derivative used as an active ingredient in the present invention is a solution, It is prepared and used in the form of an emulsion or the like.
- the underwater biofouling inhibitor of the present invention is used in the form of an antifouling paint, for example, an active ingredient, a urea derivative, is mixed with a ⁇ -shaped idiot to prepare a thigh, and the bottom of a ship, a marine structure, The 7jc pipeline or layer is applied to underwater structures, etc. It is possible to prevent adhesion of things ⁇ !
- oil varnish As a forming agent, oil varnish, synthetic resin, artificial rubber and the like are used.
- pigments and the like may be used.
- the concentration of the active ingredient, urea derivative has no upper limit as long as it can be formed, but i ⁇ 5 om &%, preferably 5 ⁇ 20 with respect to the weight of the antifouling paint. It is blended at a rate of S4%.
- a formulation example in the case of using the underwater organism adhesion prevention of the present invention as an antifouling is shown by using the present invention, but is not limited thereto.
- VYHH (vinyl synthetic resin, V C CV) 7
- the underwater biofouling prevention ih ⁇ of the present invention is used in the form of a solution, for example, a solution prepared by dissolving the active ingredient urea derivative ⁇ : in a solvent together with a ⁇ !
- a solution prepared by dissolving the active ingredient urea derivative ⁇ : in a solvent together with a ⁇ ! By applying to a net or the like, it is possible to prevent underwater organisms from adhering.
- synthetic male synthetic male, artificial rubber, natural fineness and the like are used, and as a bandit, xylene, toluene, cumene, methyl ethyl ketone, methyl isobutyl ketone, and acetone are used.
- an additive such as ⁇ r, etc. may be used according to.
- concentration of urea derivative, which is an active ingredient there is no upper limit to the concentration of urea derivative, which is an active ingredient, as long as a solution can be formed, but it is mixed at a ratio of 1 to 5, preferably 5 to 30% with respect to the Sfi of the solution. Is done.
- a surfactant is usually added to a solution of urea as an active ingredient according to a standard method for preparing an emulsion to prepare a desired emulsion. It can be prepared and the type of surfactant used is not particularly limited.
- the emulsion thus prepared can be kneaded with raw materials such as a net used in the ocean or water, and a fixed net, for example, kneaded with a resin or the like.
- the concentration of the active ingredient, urea derivative has no upper limit as long as the emulsion can be formed, but it is 1 to 50% by weight, preferably 3 to 30% by weight based on the weight of the emulsion. It is blended in a ratio.
- the solution or emulsion of the present invention can also be used by adding it to service water, water storage, or the like, in order to prevent adherence of aquatic organisms in a 7j pipeline or a reservoir.
- 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 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.
- each dissolving amount of a compound of the present invention, to prepare a concentration of the present compound in the medium are each 500 ppb, 5 Opp b
- the temperature is 20 ⁇ 2 for freshwater silica and the temperature is 23 ⁇ 2 ° C for the other cells, and the culture is shaken at 100 rpm for 24 hours under continuous light.
- the proliferation rate was determined by measuring the total cell volume using a hemocytometer.
- the growth inhibition rate was calculated by comparison with the untreated group.
- a zone to which only acetone was applied was provided as a blank, and a zone to which Omg and 0.5 mg of copper sulfate was applied was provided as a comparative agent.
- a mussel (Mytilus edulis) having a shell length of about 2 to 2.5 cm was used as a spacer, and four pieces were adhered to the outer periphery of each zone.
- the prepared was immersed in an aquarium bathing in seawater or ⁇ ⁇ , and ⁇ ⁇ was raised from the 0 aquarium which was allowed to stand at the place for 3 hours, and the adhesion position of the mussel mussels was measured.
- tests were conducted using Compounds 2 to 5, Compound 8 and Compounds 11 to 15, and the adhesion control effect (adhesion repellent activity) was determined by comparison with copper sulfate used as a comparative drug.
- the urea derivative represented by (1) has high tt, exhibits a wide spectrum at a low dose, and is useful as an antibacterial agent for industrial use, as an anti-capillary agent, and as a biofouling preventive.
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Abstract
Description
明 細 書 ゥレア誘^:及び当該化合物を含有する工業用抗菌 ·抗カピ 、 ^^剤及び生物 付着防 技術分野 Specifi cations ^ Rare compounds: and industrial antibacterial, anti-capi, ^^ agents and biofouling prevention technology containing the compound
本発明は、 工業製品の抗菌 ·抗カビ剤及び殺藻剤、 工業製品の製造過程で使用 する抗菌 ·抗カピ 、 殺藻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 il ^に関する。 背景技術 The present invention relates to antibacterial and antifungal agents and algicides for industrial products, antibacterial agents used in the manufacturing process of industrial products and aquatic organisms for preventing the adhesion of harmful aquatic organisms such as algicides and shellfish. Adhesion prevention. Background art
工業用抗菌 ·抗カピ 及び纖剤は、 種々のェ纖品及びェ難設での細菌、 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。 赚、 これらの工業用抗菌.抗カピ 及び纏剤としては、 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^！、 含窒素脂脑ポリマ—及び重 金属配位化合物等が使用されている。 Industrial antibacterial, anti-capi and fiber agents are used to remove various adverse effects due to the growth and proliferation of bacteria, fungi and varieties in various textile products and difficulties.赚, These industrial antibacterial. Anti-capi and bulking agents include organic nitrogen compounds, organic nitrogen compounds, and organic halogenated compounds ^! Nitrogen-containing fat polymers and heavy metal coordination compounds are used.
生物付着防 ih^は、 漁網、 船舶の船底、 ブイ等の海中に置かれる設備、 海腿 築物、 火力又は原子力発 の餘器冷却水系、 化学工業の熱交換器冷却用水の mm, 水中構築物或いは貯水池等に、 頭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 ih ^: fishing nets, ship bottoms, buoys, and other underwater facilities, thigh structures, thermal or nuclear power cooling water systems, chemical industry heat exchanger cooling water mm, underwater structures Or it is used to prevent harmful aquatic organisms such as heads from attaching to reservoirs.
これらの水中生物か ¾m ^に付着すれば、 網目が詰まり、 海水の腿の低下に 伴って難魚の発育が阻害され、 魚病の多発を招く。 If these aquatic organisms adhere to ¾m ^, the mesh will be clogged, and the growth of hard-to-fish will be hindered as the thighs of the seawater drop, leading to 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 S*増加及 び取扱い操作の著しい不便さを生じ、 路への付着は、 導度の低下を引き 起こすとともに、 ¾7j路が閉塞したり、 ¾ 量が減少する等の問題を生じる。 鄉、 これらの海水及び淡水水中生物の付着灘を防止するため、 ピストリブ チルスズォキシド等の有機スズ化合物、 硫酸銅及び亜酸化銅等の銅化合物等を含 有する防汚^^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, S * increases due to the attachment of aquatic organisms and significant inconvenience in handling operations, and attachment to roads causes a decrease in conductivity and blocks roads This causes problems such as a decrease in the amount. In order to prevent the seawater and freshwater aquatic organisms from adhering to the sea, antifouling containing organic tin compounds such as pistrov tyl sulphoxide and copper compounds such as copper sulfate and cuprous oxide is used.
本発明のゥレア誘 に類似する先行技術としては、 ョ一口ツバ公開特許第 3 As prior art similar to the perylene induction of the present invention, Japanese Patent Publication No.
6 3 9 0号 （Α 2 ) に、 ジフエニルエーテル型及びジフエニルスルホン型の ゥレア誘導 その^ t法及び除草剤が開示されており、 特開昭 5 8— 2 1 6 1No. 63900 (9 2) discloses diphenyl ether type and diphenyl sulfone type ゥ rea induction, its ^ t method and herbicides.
7 5号^ |g及びドイツ特許公報 D E 3 2 3 8 0 7 9号^には、 ベンゾチアゾリ ルォキシフヱニルゥレア誘 及びべンゾォキサゾリルォキシフヱニルゥレア誘 その^ t法及び除草剤が開示されている。 上述の有機窒素系化合物、 有機窒素ィォゥ系化合物、 有機ハロゲン系化合物、 含窒素脂瞧ポリマ一及び重^ Ji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 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 cm 染が懸念される薬剤及び重鍋に よる^ t染が懸念される薬剤を含んでおり、 工業用抗菌 ·抗カピ 及び纏剤 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。 No. 7 5 ^ | g and German Patent Publication DE 3 2 3 8 0 7 9 ^ include benzothiazolyloxyphenyl-rea and benzoxazolyloxyphenyl-rea derivatives and their t methods. And herbicides are disclosed. The above-mentioned organic nitrogen-based compounds, organic nitrogen-based compounds, organic halogen-based compounds, nitrogen-containing fats, polymers, and heavy ^ Ji coordination compounds are irritating drugs that pose a problem in the Labor Safety Act, However, there are many drugs that may cause problems from the viewpoint of protection, such as drugs that release formalin or halogen, and that may affect the human body and cause cm staining. Industrial antibacterial and anti-capi and fillers cannot be said to consist entirely of preferred agents.
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、 特に魚頭の体内蓄積が著しく、 mm を進行させるため現在規制の対象となっている。 In addition, the above-mentioned organotin compounds as biofouling inhibitors are effective in preventing the aquatic organisms from fouling, but are highly toxic, and especially remarkably accumulate in fish heads. ing.
例えば、 米国においては有機スズ防汚塗難制法（1 9 8 7年） によって、 6 5フィ一ト以下の船舶への有機スズ船舶 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 JP For example, in the United States, the Organotin Antifouling and Paint Restriction Act (11987) banned the use of organotin vessels on vessels less than 65 feet, and in the UK, food environmental protection (199) 8 7) The antifouling agent containing triptyl tin was JP
一トル以下の船舶および海洋農業への が禁止されている。 Prohibition on vessels under 1 torr and marine agriculture is prohibited.
又、 日本においてはィ I ^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 物質に、 トリフェニルスズィ匕合物およびトリプチルスズ化合物が 第 2種特定化学物質に指定され、 漁網用に関しては使用が禁止されている。 In Japan, triptylsuzuoxide was designated as a first-class specified substance by the I ^ method (1990), and triphenylsuccinide and triptyltin compounds were designated as a second-class specified chemical. Use is forbidden.
更に、 トリプチルス：^の船底謝の使用抑制の措置（運 通達、 1 9 9 0 年） もとられている。 In addition, measures have been taken to limit the use of triptyls: ^ in the bottom of the ship (Notification, 1990).
^の銅化合物は、 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^ である銅を含有しているため、 の^ §染が懸念さ t 好ましい水中生物付着制麵とは言えない。 Although the copper compound of ^ is widely used for antifouling for roads and ship bottoms, it contains copper which is heavy like ^ tin, so there is a concern that ^ It can not be said that it is underwater organism adhesion control.
本発明に用レ、られる化^!は上 制法に記載されておらず、 また una に は本発明化^は含まれるものではなく、 本発明のゥレア誘^が: c抗菌 · 抗カヒ^、 纖剤及び生物付着防 として有効であることは何ら記載されてい ない。 発明の開示 The use of the present invention is not described in the law, and una does not include the use of the present invention. No mention is made that the composition is effective as a fiber or a biofouling agent. Disclosure of the invention
本発明者らは、 上 題を解決するため鋭 討の結果、 ゥレア誘^が、 安 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'抗カヒ^、 ^^剤及び生物付着防 II ^となること を見出し、 本発明を した。 The present inventors have conducted intensive studies in order to solve the above problem, and as a result, it has been found that ゥ rea induction is high in price, and since it is effective in preventing brown spots, it exhibits a broad spectrum with a low dose and is highly practical. The present invention has been found to be an industrial antibacterial 'anti-kahi ^, ^^ agent and biofouling prevention II ^, and has made the present invention.
即ち、 本発明は、 -- , ( 1 ) ： That is, the present invention provides-, (1):
[式中、 Wは酸素原子又は S O 2を意味し、 R 1 は Cい 3アルキル基を意味し、 R2 は C wアルキル基又は Cい 8アルコキシ基を し、 R1 は水素原子、 ハロゲン 原子、 シァノ基又は Cい 8ァルキル基（該アルキル基はフッ素原子で任意に置換さ れていてもよい） を意味し、 pは 0、 1、 2又は 3を表し、 Arは"^ ( 2 ) ： [Wherein, W represents an oxygen atom or SO 2, R 1 represents a C 3 alkyl group, R 2 Represents a C w alkyl group or a C 8 alkoxy group, and R 1 represents a hydrogen atom, a halogen atom, a cyano group or a C 8 alkyl group (the alkyl group may be optionally substituted with a fluorine atom). Where p is 0, 1, 2 or 3, and Ar is "^ (2):
(式中、 X 1及び Υ 1は、 それぞれ に d-6アルキル基（該アルキル基はフッ 素原子で任意に置換されていてもよい）、 d-6アルコキシ基（該アルコキシ基は フッ素原子で任意に置換されていてもよい）又はハロゲン原子を し、 1及び mは、 それぞ： に 0から 5の撤を表し、 1 +mは常に 5以下を表す。 } を 麟するか又は"^ ( 3 ) ： (Wherein, X 1 and Upsilon 1 are each d-6 alkyl group (the alkyl group may be optionally substituted with fluorine atom), d-6 alkoxy group (the alkoxy group is a fluorine atom Optionally substituted) or a halogen atom, and 1 and m each represent: 0 to 5 and 1 + m always represents 5 or less. (3):
{式中、 X2及び Y2は、 それぞ に〇ぃ8アルキル基（該アルキル基はフッ 素原子で任意に置換されていてもよい）、 d- 3アルコキシ基（該アルコキシ基は フッ素原子で任意に置換されていてもよい）、 ニトロ基又はハロゲン原子を し、 zは瞧原子又はィォゥ原子を し、 n及び 0は、 それぞ w:に 0から{Wherein, X 2 and Y 2 are each a 〇 ぃ8 alkyl group (the alkyl group may be optionally substituted with a fluorine atom), a d-3 alkoxy group (the alkoxy group is a fluorine atom A nitro group or a halogen atom, z represents a 瞧 or ゥ atom, and n and 0 represent w: 0 to 0 respectively.
4の^:を表し、 n + oは常に 4以下を表す。 } を意味する。 ]で表されるゥレア 誘 及び当該化^を含有することを mとする工業用抗菌，抗カピ刻、 Wk 剤及び生物付着防止剤に関するものである。 4 represents ^ :, and n + o always represents 4 or less. } Means The present invention relates to industrial antibacterials, anti-capitifiers, Wk agents and anti-biofouling agents which contain ゥ rare compounds represented by the formula [1].
( 1 ) において示される各置 m¾を具体的に説明する。 Each position m¾ shown in (1) will be specifically described.
尚、 本明細書中 「nj はノルマルを、 「ij はイソを、 「sj はセカンダリーを、 rtj はタ一シャリ一を、 rneoj はネオを する。 In this specification, "nj is normal," ij is iso, "sj is secondary, rtj plays the character and r neo j plays the neo.
Cい 8アルキル基としては、 メチル、 ェチル、 n-プロピル、 i-プ αピル、 シクロ プロピル等が挙げられる。 The C physician 8 alkyl group, methyl, Echiru, n- propyl, i- flop α pills, cyclopropyl, and the like.
d- sアルキル基としては、 メチル、 ェチル、 n-プロピル、 i-プロピル、 n -プチ ル、 i-ブチル、 S-ブチル、 t-ブチル、 π-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、 シク口プ αピル、 1-メチルシクロプロピ ル、 2-メチルシクロプロピル、 シクロブチル、 シクロペンチル等が挙げられる。 アルコキシ基としては、 メトキシ、 エトキン、 n-プロボキシ、 i-プロポキ シ、 シクロプロボキシ等が挙げられる。 The ds alkyl group includes methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, S-butyl, t-butyl, π-pentyl, 2-pentyl, 3-pentyl, i -Pentyl, neo-pentyl, t-pentyl, cyclopentyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and the like. Examples of the alkoxy group include methoxy, ethoxyquin, n-propoxy, i-propoxy, cyclopropoxy and the like.
d-5アルコキシ基としては、 メトキシ、 エトキシ、 n-プロボキシ、 i -プロボキ シ、 n-ブトキシ、 i-ブトキシ、 S-ブトキシ、 t-ブトキシ、 n-ペンチルォキシ、 2- ペンチルォキシ、 3-ペンチルォキシ、 i-ペンチルォキシ、 neo-ペンチルォキシ、 t-ペンチルォキシ、 シクロプロボキシ、 1-メチルシク πプロボキシ、 2-メチルシ クロプロボキシ、 シクロブトキシ、 シクロペンチルォキシ等が挙げられる。 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。 d- 5 alkoxy groups 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-methylcyclopipropoxy, 2-methylcyclopropoxy, cyclobutoxy, cyclopentyloxy and the like. Halogen atoms include fluorine, chlorine, bromine and iodine.
本発明の好ましい化合物としては、 以下に举げる化合物が挙げられる。 Preferred compounds of the present invention include the following compounds.
(I) (I)
Wか 原子である""^ ( 1 ) で表されるウレァ誘 。 Urea invitation represented by W or the atom "" ^ (1).
(I I) (I I)
Wが S 02随原子である"^ ( 1 ) で表されるウレァ誘 Urea induction represented by "^ (1), where W is the S 0 2 atom
(I II) (I II)
pが 1である上記 (〖)記載のゥレア誘 ゥ rare induction according to the above (〖) wherein p is 1
(IV) (IV)
Pが 2である上記 (I)記載のゥレア誘 (V) ゥ rare induction according to the above (I) wherein P is 2 (V)
pが oである上記 (〖)記載のゥレア誘 ゥ rare induction according to the above (〖) wherein p is o
(VI) (VI)
ρが 0である上記 (I I)記載のゥレア誘 ゥ rare induction according to the above (II) wherein ρ is 0
(VII) (VII)
ρが 1である上言己 (II)言己載のウレァ誘^。 本発明の工業用抗菌 .抗カピ 、 纏剤及び生物付着防 は、 上記"^ 上 is 1 (II) Urea invitation ^ The industrial antibacterial anti-capi, bulking agent and biofouling preventive of the present invention are as described above with "^
( 1 ) で表されるゥレア誘導体を有効成分として含んでいればよい。 It is sufficient that the urea derivative represented by (1) is contained as an active ingredient.
本発明の工業用抗菌 ·抗カピ 、 ^^剤及び生物付着防 it Jの有効成分に含ま れる化合物の具体例を、 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^!はこれらに限定されるものではない。 Specific examples of the compounds contained in the active ingredients of the industrial antibacterial anti-capi, ^^ agent and the anti-biofouling it J of the present invention are listed in Tables 1 to 3 below. Is not limited to these.
但し、 "^ (1A)、 (IB) . (1C)、 (ID) . (IE) , ( 1 F)、 (1G)、 （1H)、 （11)、 （1J)、 （IK)及び（1L)で表されるゥ レア誘^は、 R 3が水素原子以外の場合に適用される。 However, "^ (1A), (IB). (1C), (ID). (IE), (1F), (1G), (1H), (11), (1J), (IK) and ( The) rare induction represented by 1L) is applied when R 3 is other than a hydrogen atom.
又、 表中の記号は以下の意味を表す。 The symbols in the table have the following meanings.
Me：メチル基、 MeO：メトキシ Me: methyl group, MeO: methoxy
第 1表 Table 1
位 3位 4位 5位 6位 R 3 u 4 u 3rd 4th 5th 6th R 3 u 4 u
n n Π n u n u Π n n Π n u n u Π
u u u u
π n Π Π n し 1 u n rl n H u H し J u π n Π Π n then 1 u n rl n H u H then J u
Π n u Π n u H し Π n u Π n u H
Me Π n u Π H Π u Me Π n u Π H Π u
Π Me Π u Π u Π Me Π u Π u
n Π n Π
H H Me H H HH H Me H H H
Me Π H H し 1Me Π H H then 1
H Me ri H Π し 1
Me H H H H CNMe H H H H CN
H Me H H H CNH Me H H H CN
H H Me H H CNH H Me H H CN
Me H H H H CFsMe H H H H CFs
H Me H H H CFaH Me H H H CFa
H H Me H H CFsH H Me H H CFs
H Me Me H H HH Me Me H H H
Me H Me H H HMe H Me H H H
Me H H Me H HMe H H Me H H
MeU rl H H H H r r MeU rl H H H H r r
H MeU H H H H H MeU H H H H
H H MeU H H HH H MeU H H H
MeU o MeU o
Π rl Π Π し 1 rl MeU u n n n L i rj rj _Π Π rl Π Π 1 1 rl MeU u n n n L i rj rj _Π
Π Π MeU u Π n し 1 Π Π MeU u Π n then 1
MeU Π Π Π Π LN n eu Π n n しMeU Π Π Π Π LN n eu Π n n
Π rl Meu u rl rl し
H MeO H H H CF3 H MeO HHH CF 3
H H MeO H H CFsH H MeO H H CFs
H MeO MeO H H HH MeO MeO H H H
MeO H MeO H H HMeO H MeO H H H
MeO H H MeO H HMeO H H MeO H H
CFa H H H H H さ CFa HHHHH Sa
ベンゼン環上の置換基 1 .7¾ 7 V 1 \ 位 3位 4位 5位 6位 R3 Substituents on the benzene ring 1 .7¾ 7 V 1 \ position 3 of 4 of 5 of 6 of R 3
U u u Π CF3 H Π Π ΠU uu Π CF 3 H Π Π Π
U Π H CFs u n u n TJ U Π H CFs u n u n TJ
Π Π
し Γ 3 H H u u Γ H 3 H H u u
f n し i f n then i
U Π CFa H u u U Π CFa H u u
Π n し 1 Π n then 1
U Π H CFa u U Π H CFa u
Π n し i Π n then i
It43 H H u π n し IN u It 4 3 HH u π n then IN u
Π CF3 H u Π CF 3 Hu
Π n IN u π H CFa u n Π し し 3 H H n u Π L 3 Π n IN u π H CFa u n Π 3 H H n u Π L 3
Η CFa H Π n し i* 3 Π H CFs ri Π し 3 し 3ϋ H H H H HΗ CFa H Π n shi i * 3 Π H CFs ri Π shi 3 shi 3ϋ H H H H H
Π CFsO H Π rl H n H CFsO H H Π し 1< 3ϋ H H Π Π Π CFsO H Π rl H n H CFsO H H Π 1 <3ϋ H H Π Π
Π CFaO H U Π CFaO H U
Π n し 1 Π n then 1
Π H CFsO u u Π し i し 3D H H n u n しΠ H CFsO u u i i 3D H H n u n
Π CFsO H Π n し INΠ CFsO H Π n
Π H CFsO Π rl IN し Ρ 3D H H u Π u Π し!13CF H CFsO Π rl IN Ρ Ρ 3D HH u Π u Π !! 1 3
Π CF30 H u Π n し 3Π CF 3 0 H u Π n then 3
Π H CFsO u Π u n し 3 し HI* 2V H H u Π u n u ΠΠ H CFsO u Π u n 3 3 HI * 2V H H u Π u n u Π
U U
π CHF20 H U π CHF 20 HU
n n n
し HI* 2U H H u n n し i u n CHF2O H u n n し i HI * 2U H Hun n then i u n CHF2O H u n n then i
位 3位 4位 5位 6位 R 3 u n u Π V_ l丄丄 2 H H I i Γ rし 11 u Π u n H丄 1 H丄 1 H u 3rd 4th 5th 6th R 3 unu Π V_ l 丄 丄 2 HHI i Γ r shi 11 u Π un H 丄 1 H 丄 1 H u
n し i n U Π n Π u n then i n U Π n Π u
n u Π rし 11 U n H H u u n u Π r then 11 U n H H u u
し 1 Π Π n n nし 1 u U u u Then 1 Π Π n n n then 1 u U u u
し JL Π Π n r n し 11 u u r 1 u Π u Then JL Π Π n r n then 11 u u r 1 u Π u
Π し 1 Π pしi n i u u u し 1 1 Π p i i n i u u u
し i n Π Π Π し u J Shi i n Π Π し shi u J
n し 1 u u T n then 1 u u T
n n Π し IN u TJ n n IN IN IN u TJ
n n し u n Π し IN n n then u n IN IN
IJ u u TJ IJ u u TJ
し i n n Π し！1 3 n し 1 u u u Inn Π 1 3 n then 1 uuu
Π n Π し！1 3Π n Π 1 3
H Γ 1 H Γ 1
n し i u LI n then i u LI
n Π し I1 3 u u u し 1 し i Π n Π Π u u u U し 1 n し i n Π Π u TJ u n Π I I 1 3 uuu 1 1 i i Π n Π Π uuu U 1 1 n in in Π Π u TJ u
し 1 n Π し JL Π Π 1 n し Π JL Π
IJ u し i u r IJ u then i u r
n n H 1 n n H 1
n し i Π u u u u n し i し i Π Π Π u u n u u u r n Π Π Π u τ? u n then i Π u u u u n then i then i Π Π Π u u n u u u r n Π Π Π u τ? u
n r n u Π u Π U Π u u u u n n Γ n Π n n r n u Π u Π U Π u u u u n n Γ n Π n
T? u T? U
r n u n n Π し 1 u n r u n I nJ H n し 1 u Π u Π r u n u Π し 1 r n u n n Π 1 1 u n r u n I nJ H n 1 1 u Π u Π r u n u Π 1 1
u Π u Π H n U n ΓしΜ u Π u Π H n U n Γ
I ΠJ Γ Γ u n u n U n しI ΠJ Γ Γ u n u n U n
H H Γ u u H H Γ u u
H Π し IN H IN
F H H H H CF3 FHHHH CF 3
H F H H H CF3 HFHHH CF 3
H H F H H CF3 HHFHH CF 3
F F H H H HF F H H H H
H F F H H HH F F H H H
F F H F F HF F H F F H
F F F F F H ¾cさ ベンゼン環上の置換基 (X1,及び Y1 FFFFFH Substituents on the benzene ring (X 1 and Y 1
位 3
H CI F H H HH CI F H H H
H F CI H H HH F CI H H H
H Me MeO H H HH Me MeO H H H
H rし 1 l H H HH r 1 l H H H
H F MeO H H HH F MeO H H H
Me H H MeO H HMe H H MeO H H
H Me CFsO H H HH Me CFsO H H H
H Me CF3 H H HH Me CF 3 HHH
H Me CI H H HH Me CI H H H
F F Me F F HF F Me F F H
F F MeO F F H FF MeO FFH
第 2表 Table 2
\ L \ L
H H H H Me MeH H H H Me Me
H H H H Me MeOH H H H Me MeO
Me H H H Me MeMe H H H Me Me
H Me H H Me MeH Me H H Me Me
H H Me H Me MeH H Me H Me Me
H H H Me Me MeH H H Me Me Me
Me H H H Me MeOMe H H H Me MeO
H Me H H Me MeOH Me H H Me MeO
H H Me H Me MeOH H Me H Me MeO
H H H Me Me MeOH H H Me Me MeO
MeO H H H Me MeMeO H H H Me Me
H MeO H H Me MeH MeO H H Me Me
H H MeO H Me MeH H MeO H Me Me
H H H MeO Me MeH H H MeO Me Me
MeO H H H Me MeOMeO H H H Me MeO
H MeO H H Me MeOH MeO H H Me MeO
H H MeO H Me MeOH H MeO H Me MeO
H H H MeO Me MeOH H H MeO Me MeO
CF3 H H H Me MeCF 3 HHH Me Me
H CF3 H H Me MeH CF 3 HH Me Me
H H CFs H Me MeH H CFs H Me Me
H H H CF3 Me MeHHH CF 3 Me Me
CF3 H H H Me MeOCF 3 HHH Me MeO
H CF3 H H Me MeOH CF 3 HH Me MeO
H H CFa H Me MeO ¾¾¾さ ts合へテロ環上の置換基 ： (X2 n及び Y 2。） HH CFa H Me MeO Substituents on the hetero ring of length ts: (X 2 n and Y 2 )
4位 5位 6位 7位 R 1 R 2 4th 5th 6th 7th R 1 R 2
H H H CF3 Me MeOHHH CF 3 Me MeO
CF30 H H H Me MeCF 3 0 HHH Me Me
H CFaO H H Me MeH CFaO H H Me Me
H H CFsO H Me Me
CFaO H H H Me MeO
H H CFsO H Me MeO H H CFsO H Me MeO
H H H CFaO Me MeOH H H CFaO Me MeO
CHF20 H H H Me Me CHF 2 0 HHH Me Me
H H NO 2 H Me Me
NO 2 H H H Me MeO NO 2 H H H Me MeO
H NO 2 H H Me MeOH NO 2 H H Me MeO
H H NO 2 H Me MeO
F H H H Me Me F H H H Me Me
H F H H Me MeH F H H Me Me
H H F H Me MeH H F H Me Me
H H 1 H 1 r H H 1 H 1 r
F H H H Me MeO F H H H Me MeO
H F H H Me MeOH F H H Me MeO
H H F H Me MeOH H F H Me MeO
H H H F Me MeOH H H F Me MeO
CI H H H Me Me 表続き f巨 5へテロ環上の置換基 ： (X2 n及び Y2。) CI HHH Me Me Table continued f Substituents on the 5 heterocycles: (X 2 n and Y 2 )
4位 5位 6位 7位 R 1 R2 4th 5th 6th 7th R 1 R 2
H C1 H H Me MeH C1 H H Me Me
H H CI H Me MeH H CI H Me Me
H H H CI Me MeH H H CI Me Me
C1 H H H Me MeOC1 H H H Me MeO
H C1 H H Me MeOH C1 H H Me MeO
H H CI H Me ' MeOH H CI H Me 'MeO
H H H CI Me MeOH H H CI Me MeO
Me H Me H Me MeMe H Me H Me Me
H Me Me H Me MeH Me Me H Me Me
Me H MeO H Me MeMe H MeO H Me Me
MeO H Me H Me MeMeO H Me H Me Me
Me H CI H Me MeMe H CI H Me Me
CI H Me H Me MeCI H Me H Me Me
MeO H CI H Me MeMeO H CI H Me Me
MeO H NO 2 Me Me MeMeO H NO 2 Me Me Me
H C1 CI H Me MeH C1 CI H Me Me
H F CI H Me MeH F CI H Me Me
H C1 F H Me MeH C1 F H Me Me
H CFsO Me H Me MeH CFsO Me H Me Me
H CFsO CI H Me MeH CFsO CI H Me Me
H CF3 Me H Me MeH CF 3 Me H Me Me
H CFs F H Me MeH CFs F H Me Me
Me H Me H Me MeOMe H Me H Me MeO
H Me Me H Me MeOH Me Me H Me MeO
Me H MeO H Me MeOMe H MeO H Me MeO
MeO H Me H Me MeOMeO H Me H Me MeO
Me H CI H Me MeOMe H CI H Me MeO
CI H Me H Me MeOCI H Me H Me MeO
MeO H CI H Me MeO
H CI CI H Me MeO H CI CI H Me MeO
H F CI H Me MeOH F CI H Me MeO
H CI F H Me MeOH CI F H Me MeO
H CF30 Me H Me MeO 続き 縮合へテロ環上の置換基 （X2 n及び Y2。） H CF 30 Me H Me MeO Continuing Substituents on the fused heterocycle (X 2 n and Y 2 )
位 5位 6位 7位 R 1 R2 Rank 5 Rank 6 Rank 7 R 1 R 2
Η CFsO CI H Me MeOΗ CFsO CI H Me MeO
Η CFs Me H Me MeOΗ CFs Me H Me MeO
Η CF3 F H Me MeO Η CF 3 FH Me MeO
第 3表 Table 3
4位 5位 6位 7位 R 1 R 2 4th 5th 6th 7th R 1 R 2
Η H H H Me MeΗ H H H Me Me
Η H H H Me MeO Me H H H Me MeΗ H H H Me MeO Me H H H Me Me
H Me H H Me MeH Me H H Me Me
H H Me H Me MeH H Me H Me Me
H H H Me Me Me Me H H H Me MeOH H H Me Me Me Me H H H Me MeO
H Me H H Me MeOH Me H H Me MeO
H H Me H Me MeOH H Me H Me MeO
H H H Me Me MeO eO H H H Me MeH H H Me Me MeO eO H H H Me Me
H MeO H H Me MeH MeO H H Me Me
H H MeO H Me MeH H MeO H Me Me
H H H MeO Me Me MeO H H H Me MeOH H H MeO Me Me MeO H H H Me MeO
H MeO H H Me MeOH MeO H H Me MeO
H H MeO H Me MeOH H MeO H Me MeO
H H H MeO Me MeO CF3 H H H Me MeHHH MeO Me MeO CF 3 HHH Me Me
H CFs H H Me MeH CFs H H Me Me
H H CF3 H Me MeHH CF 3 H Me Me
H H H CF3 Me Me CF3 H H H Me MeOHHH CF 3 Me Me CF 3 HHH Me MeO
H CF3 H H Me MeO 表続き 縮合へテロ環上の置換基 （X2 n及び Y2。） H CF 3 HH Me MeO Table continued Substituents on the fused heterocycle (X 2 n and Y 2 )
4位 5位 6位 7位 R 1 R 4th 5th 6th 7th R 1 R
Η H H Me MeO Η H H CF3 Me MeOΗ HH Me MeO Η HH CF 3 Me MeO
CF30 H H H Me Me H CFsO H H Me Me
H H H CFsO Me Me H H H CFsO Me Me
CF30 H H H Me MeO H CFaO H H Me MeO H H CFaO H Me MeO CF 3 0 HHH Me MeO H CFaO HH Me MeO HH CFaO H Me MeO
H CHF20 H H Me MeO
H NO 2 H H Me Me H NO 2 H H Me Me
H H NO 2 H Me MeH H NO 2 H Me Me
H H H NO 2 Me Me NO 2 H H H Me MeOH H H NO 2 Me Me NO 2 H H H Me MeO
H NO 2 H H Me MeOH NO 2 HH Me MeO
H H NO 2 H Me MeOH H NO 2 H Me MeO
H H H NO 2 Me MeOH H H NO 2 Me MeO
F H H H Me MeF H H H Me Me
H F H H Me MeH F H H Me Me
H H F H Me MeH H F H Me Me
H H H F Me MeH H H F Me Me
F H H H Me MeOF H H H Me MeO
H F H H Me MeOH F H H Me MeO
H H F H Me MeOH H F H Me MeO
H H H F Me MeO 表; 15Cさ 縮合へテロ環上の置換基 - は; 及び Y2。） HHHF Me MeO Table; 15C substituents on the fused heterocycle-are; and Y 2 . )
4位 5位 6位 7位 R 1 R 2 4th 5th 6th 7th R 1 R 2
CI H H H Me MeCI H H H Me Me
H CI H H Me MeH CI H H Me Me
H H CI H Me MeH H CI H Me Me
H H H CI Me MeH H H CI Me Me
C1 H H H Me MeOC1 H H H Me MeO
H CI H H Me MeOH CI H H Me MeO
H H CI H Me MeOH H CI H Me MeO
H H H CI Me MeOH H H CI Me MeO
Me H Me H Me MeMe H Me H Me Me
H Me Me H Me MeH Me Me H Me Me
Me H MeO H Me MeMe H MeO H Me Me
MeO H Me H Me MeMeO H Me H Me Me
Me H CI H Me MeMe H CI H Me Me
CI H Me H Me MeCI H Me H Me Me
MeO H CI H Me MeMeO H CI H Me Me
MeO H N02 Me Me MeMeO H N0 2 Me Me Me
H CI CI H Me MeH CI CI H Me Me
H F CI H Me MeH F CI H Me Me
H CI F H Me MeH CI F H Me Me
H CFsO Me H Me MeH CFsO Me H Me Me
H CFsO CI H Me MeH CFsO CI H Me Me
H CF3 Me H Me MeH CF 3 Me H Me Me
H CFa F H Me MeH CFa F H Me Me
Me H Me H Me MeOMe H Me H Me MeO
H Me Me H Me MeOH Me Me H Me MeO
Me H MeO H Me MeOMe H MeO H Me MeO
MeO H Me H Me MeOMeO H Me H Me MeO
Me H CI H Me MeOMe H CI H Me MeO
CI H Me H Me MeOCI H Me H Me MeO
MeO H CI H Me MeOMeO H CI H Me MeO
MeO H NO Me Me MeOMeO H NO Me Me MeO
H CI CI H Me MeOH CI CI H Me MeO
H F CI H Me MeOH F CI H Me MeO
H CI F H Me MeO 表続き 縮合へテロ環上の置換基 （X2 n及び Y2。） H CI FH Me MeO Table continued Substituents on the fused heterocycle (X 2 n and Y 2 )
4位 5位 6位 7位 R 1 R2 4th 5th 6th 7th R 1 R 2
Η CFaO Me H Me MeOΗ CFaO Me H Me MeO
Η CF30 CI H Me MeOΗ CF 30 CI H Me MeO
Η CF3 Me H Me MeOΗ CF 3 Me H Me MeO
Η CF3 F H Me MeO Η CF 3 FH Me MeO
本発明のウレァ化^ Iは、 ョーロック、。特許 EP 36390号 、 特開昭 58 -216175号^ ¾びドイツ特許 DE 3238079号 等を に、通 常例えば ®S¾ (a)、 （b)、 （c)及び（d)の方麟により^ tすること ができる。 The urea of the present invention ^ I, jorlock. Patents EP 36390, JP-A-58-216175, and German Patent DE 3238079, etc. are usually used, for example, in the form of ®S (a), (b), (c) and (d). can do.
但し、 下 ESJS^;中の Ar、 R1 、 R2、 R8及び p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^^のハロゲン原子を表す。However, Ar, R 1 , R 2 , R 8 and p in the lower ESJS ^; are the same as described above, and Ha 1 represents a chlorine atom, a bromine atom or a halogen atom of iodine source ^^.
ί£¾ (a) ί £ ¾ (a)
(a)において、 用いる酸受容体としては、 例えばアルカリ の水酸 化物、 化物、 素化物、 水素化物或いはアルカリ土類^の水酸化物、 離化物等が挙げられるが、 好ましくは水酸化力リゥム、 碰カリゥム、 水素化 ナトリウム等が挙げられる。 In (a), the acid acceptor to be used includes, for example, alkali hydroxides, oxides, hydrides, hydrides or hydroxides of alkaline earths, and the like. , Potassium, sodium hydride and the like.
本 as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、 ァセト 二トリル、 テトラヒドロフラン、 ジォキサン、 アセトン、 メチルェチルケトン等 の非プロトン性極性溶媒中で、 適当な温度、 例えば一 2 0 1 5 0 eCで 2~ 2 4 時間攫拌することにより進行する。 The as is preferably dimethylformamide, dimethylsulfoxide, acetate Nitrile, tetrahydrofuran, Jiokisan, acetone, an aprotic polar solvent such as methyl E chill ketone proceeds by攫拌suitable temperature, for example 2 to 2 4 hours in one 2 0 1 5 0 e C.
(b) (b)
(b) において、 ニトロフエノール類との縮合に用いる酸受容体として は、例えばアルカリ^ の水酸化物、 赚化物、 omm, τ素化物或いは アル力リ土^ の水酸化物、纖化物等が举げられるが、 好ましくは水酸化ナ トリゥ厶、 化力リゥム、 難力リゥム、 水素化ナトリゥム等が举げられる。 本 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、 ァセトニトリル、 テトラヒドロフラン、 ジォキサン、 アセトン、 メチルェ チルケトン等の非プロトン性極 ¾ ^媒中で、 適当な ί¾ 、 例えば一 2 0 1 8 0 でで 2 2 4時間撐拌することにより進行する。 In (b), examples of the acid acceptor used for the condensation with nitrophenols include alkali hydroxides, hydrides, omm, τ hydrides, hydroxides of alkaline earths, and fiberized products. Preferably, sodium hydroxide, oxidized realm, difficult realm, hydrogenated sodium and the like are used. The book is preferably prepared in an aprotic polar medium such as dimethylformamide, dimethylsulfoxide, sulfolane, acetonitrile, tetrahydrofuran, dioxane, acetone, methylethylketone, or the like, in a suitable medium, for example, in the form of 210 180. The reaction proceeds by stirring for 224 hours.
二ト口基の還元は、 通常 P d一 C或いはラネー N i等の纖存在下、 水素添加 (接触還元） により進行する。 Reduction of the nitro group usually proceeds by hydrogenation (catalytic reduction) in the presence of a fiber such as Pd-C or Raney Ni.
本水素添加 は、 テトラヒドロフラン、 ,ェチル、 ジォキサン等の を 用い、 適当な 、 例えば 0 5 (TCで 0. 5 2 4時間撹拌することにより進 行する。 This hydrogenation proceeds by using a suitable solvent such as tetrahydrofuran,, ethyl, dioxane or the like, for example, by stirring for 0.5 (TC for 0.524 hours).
力ルバモイルハライドとの縮合に用いる酸受容体としては、 例えばアルカリ金 属の水酸化物、 炭酸化物、 炭^素化物、 水素化物或いはアルカリ土類金属の水 酸化物、 化物、 3級ァミン類、 ピリジン類等が挙げられるが、 好ましくは炭 酸カリウム、 素ィ匕ナトリウム、 トリェチルァミン、 ピリジン等が挙げられる。 本 は、 好ましくはジメチルホルムアミド、 ァセトニトリル、 テトラヒドロ フラン、 ジォキサン、 アセトン、 メチルェチルケトン等の非プロトン性極 ¾ ^媒、 クロ口ホルム、 m—ジクロ口ベンゼン等のハロゲン化炭ィ 7j素、 或いはベンゼン、 トルエン、 キシレン等の芳香^^ィ 7jc素等の溶媒を用い、 適当な ί«、 例えば— 2 0〜1 0 0。Cで 0. 5〜2 4時間撹拌することにより進行する。 Examples of the acid acceptor used for the condensation with sorbamoyl halide include alkali gold Hydroxides, carbonates, carbonates, hydrides or hydroxides of alkaline earth metals, tertiary amines, pyridines, etc., preferably potassium carbonate, nitrogen oxides, etc. Sodium, triethylamine, pyridine and the like. The book is preferably a non-protonic solvent such as dimethylformamide, acetonitrile, tetrahydrofuran, dioxane, acetone, methylethylketone, etc .; halogenated carbon such as chloroform, m-dichlorobenzene, etc .; Using a solvent such as aromatic benzene, toluene, xylene, etc. 7jc element or the like, a suitable solvent, for example, −20 to 100. Proceed by stirring with C for 0.5-24 hours.
HJS¾ ( c ) HJS¾ (c)
( c ) において、 チオフエノ一ル類との縮合に用いる酸受容体としては、 例えばアルカリ金属の水酸化物、 炭酸化物、 炭 ^τ素化物、 水素化物或いはアル カリ の水酸化物、 ^化物等が挙げられるが、 好ましくは水酸化ナトリ ゥム、 水酸化カリウム、 難カリウム、 水素化ナトリウム等が举げられる。 In (c), the acid acceptor used for the condensation with thiophenols includes, for example, alkali metal hydroxides, carbonates, carbonized ^ τ, hydrides or alkali hydroxides, and fluorides. However, preferred are sodium hydroxide, potassium hydroxide, difficult potassium, sodium hydride and the like.
本 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、 ァセトニトリル、 テトラヒドロフラン、 ジォキサン、 アセトン、 メチルェ チルケトン等の非プロトン性極 ¾ ^媒中で、 適当な iS 、 例えば一 2 0〜1 8 0 でで 2〜2 4時間撹拌することにより進行する。 The book is preferably prepared in an aprotic polar medium such as dimethylformamide, dimethylsulfoxide, sulfolane, acetonitrile, tetrahydrofuran, dioxane, acetone, methylethylketone, etc. in a suitable iS, e.g. Proceed by stirring for 2 to 24 hours.
チォェ一テル基のスルホン基への酸ィ匕は、 通常 m—クロ口過安息香酸、 過, (過酸ィ bi素 +,)等を用い容易に行うことができる < Oxidation of a thiol group to a sulfone group is usually carried out with m-chloroperbenzoic acid, (Peroxy acid +,), etc. <
(d) (d)
Ar Ar
( d) において、 ニトロベンゼンチオール類との縮合に用いる酸受容体 としては、 例えばアルカリ^ mの水酸化物、 化物、 mamm, 水素化物 或いはアルカリ土^ の水酸化物、 化物等が挙げられるが、 好ましくは水 酸化力リゥム、 難力リウム、 水素化ナトリゥム等が挙げられる。 In (d), examples of the acid acceptor used for the condensation with nitrobenzenethiols include, for example, an alkali metal hydroxide, a compound, a mamm, a hydride or an alkaline earth hydroxide, a compound, and the like. Preferable examples include a hydroxide hydroxide, a difficult lithium, and a sodium hydride.
本 ®s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、 ァセト 二トリノレ、 テトラヒド口フラン、 ジォキサン、 アセトン、 メチルェチルケトン等 の非プロトン性極 ¾ ^媒中で、 適当な S 、 例えば— 2 0〜 1 5 0でで 2〜 2 4 時間撹拌することにより進行する。 The present s is preferably used in an aprotic polar medium such as dimethylformamide, dimethylsulfoxide, acetotrinole, tetrahydrofuran, dioxane, acetone, methylethylketone, etc. in a suitable aprotic medium, for example, Proceed by stirring at 0-150 for 2-24 hours.
合成した二ト口ベンゼンチォエーテル類の二ト口基の還元及びチォェ一テル基 のスルホン基への酸化は、 (b)及び SJS¾ ( c )記載の方法と同様の方 法により行うことができる。 The reduction of the nitro group of the synthesized benzene thioethers and the oxidation of the thioether group to the sulfone group can be carried out in the same manner as described in (b) and SJS¾ (c). .
又、 力ルバモイルハライド類との縮合は (b)記載の方法と同様の方法 により行うことができる。 Condensation with carbamoyl halides is carried out in the same manner as described in (b). Can be performed.
(a)、 （b)、 （c)及び （d)の方麟で得られた目的化合物は、 適当な 溶媒で再結晶、 カラムクロマトグラフィ一等の手段で精製して純品として得るこ とがでさる。 The target compound obtained in the formulas (a), (b), (c) and (d) can be obtained as a pure product by recrystallization with an appropriate solvent, purification by column chromatography, etc. Monkey
本発明において有効成分として使用するゥレア誘導体は で使用してもよく、 また本発明の工業用抗菌 ·抗カピ 、 剤及び生物付着防 ih^を使用する場合、 により、 他の公知の工業用抗菌.抗カピ 、 ^^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 urea derivative used as an active ingredient in the present invention may be used as an active ingredient. In addition, when the industrial antibacterial agent / anti-capi agent, the agent and the biofouling inhibitor ih ^ of the present invention are used, It may further contain anti-capi, a ^^ agent or an anti-biofouling agent, and can be 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.
画ィ H、 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—ナフトキノン、 エチレン一ビス—チオシァネート、 2— n—才クチルー 3—イソチアゾロン、 グルタルアルデヒド、 5—ク αロー 2— n 一デシルー 3—イソチアゾロン、 5—クロロー 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— 6—イソプ口ピルアミ ノー s—トリアジン、 5—クロロー 2—メチルー 3—ィ、ンチアゾロン、 2, 3 - ジクロロ— 1, 4一ナフトキノン、 ジョ一ドメチル— ρ—トリルスルホン、 Ν， Ν—ジメチルー N' —フエ二ルー N' - (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 N' —メチルゥレア、 Ν, Ν—ジ メチル一 N' — (3, 4ージクロ口フエニル） ゥレア、 ジンクジメチルジチォカ ーバメート、 2, 6—ジクロロ一 3, 5—ジシァノ一 4—フエ二ルビリジン、 2, 4ージクロロー 6— （0—クロロア二リノ） 一 s—トリアジン、 4, 5—ジクロ π- 2 - (4—クロ口ベンジル） 一 3—イソチアゾロン、 4, 5—ジクロロー 2 ― (4—クロ αフエニル） 一 3—イソチアゾロン、 4, 5—ジクロ口一 2— η— へキシル— 3—イソチアゾロン、 4, 5—ジクロロ— 2— η—ォクチルー 3—ィ 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—ジブロモ 一 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ブール、Image H, quaternary ammonium compound, arylisothiocyanate, 2-amino-3,4-chloro-1,4-naphthoquinone, ethylene-bis-thiocyanate, 2-n-octyl-3-isothiazolone, glutaraldehyde, 5-alpha-low 2-n-decyl-3-isothiazolone, 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile, 2-chloro-1-methylamino-6-isopropyl pyramino s-triazine, 5 —Chloro-2-methyl-3-y, thiazolone, 2,3-dichloro-1,4-naphthoquinone, jodomethyl— ρ-tolylsulfone, Ν, Ν—dimethyl-N '—Feneru N'-(fluoro Dichloromethylthio) sulfamide, Ν— (3,4-dichlorophenyl) -N'-methylperyl, Ν, Ν—dimethyl-1-N '— (3,4-dichlorophenyl) peryl, Dimethyldithiocarbamate, 2,6-dichloro-1,3,5-dicyan-4-phenylviridine, 2,4-dichloro-6- (0-chloroanilino) -1-s-triazine, 4,5-dichloroπ- 2- (4-chlorobenzyl) -1,3-isothiazolone, 4,5-dichloro-2- (4-chloroalphaphenyl) -1,3-isothiazolone, 4,5-dichloro-1,2-η-hexyl-3-isothiazolone , 4, 5-dichloro-2-η-octyl-3-isothiazolone, 1,2-dibutone 2,4-dishanbutane, 2,2-dibromo 1--3-tripropionamide, 2-thiocyanomethylthiobenzothiabul,
2— （4 一チアゾリル） ベンズイミダゾール、 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 一 （メチルスルホニ ル） ピリジン、 テトラフヱ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、 テトラエチルチウラムジスルフィ ド、 テトライソプロピルチウラムジス ルフィ ド、 テトラー η—ブチルチウラムジスルフィ ド、 テトラク π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 —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 一 3—イソチアゾロン、 2—ピリジンチォ一ルー 1ーォキシド 塩、 2 , 3 ,2- (4-thiazolyl) benzimidazole, thiabendazole, tetrafluoro-mouth isophthalonitrile, 2,3,5,6-tetraclo-mouth- 4- (methylsulfonyl) pyridine, tetraphenylboranepyridine salt, tetramethylthiuram Disulfide, Tetraethylthiuram disulfide, Tetraisopropylthiuram disulfide, Tetra-η-butylthiuram disulfide, Tetrac π-open isophthalate nitrile, Tetraclo-phthalone nitrile, Cu-10% Ni solid solution alloy , N-trichloromethylthiotetrahydrophthalimid, N-trichloromethylthiophthalimide, 2,3,6-trichloro-4-propylsulfonylviridine, N- (2,4,6-trichloromethylphenyl) maleide, 4 , 5 — Trimethylene-1 2-methyl-1 3-isothiazolone 2 Pirijinchio one Roux 1 Okishido salt, 2, 3,
3—トリヨ一ドアリルアルコール、 N— (フルォ πジクロロメチルチオ） フタル イミ ド、 ビスジメチルジチォカルバモイルジンクエチレンビスジチォ力一バメー ト、 N—フエネチルジクロロマレイミ ド、 2—プロモー 2—ニトロプロパンジォ ール、 5 —ブロモ一 5 —ニトロ一 1 , 3 —ジォキサン、 ブロモク σロジメチルヒ ダントイン、 Ν—べンジルジク πロマレイミ ド、 1 , 2 -ベ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） ベンズイミダゾール、 4ーメチ ルー 5 —クロロー 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 一プチルァミノ一 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 —ェチルフエニルジクロロマレイミ ド、 2—メチルー 3 —イソチアゾロ ン、 メチレン—ビス一チオシァネート、 3—ョードー 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。 3-triiodoallyl alcohol, N- (fluoro π-dichloromethylthio) phthalimide, bisdimethyldithiocarbamoyl zinc ethylene bisdithioate, N-phenethyldichloromaleimide, 2-promo 2- Nitropropanediol, 5-Bromo-5-Nitro-1,3-dioxane, Bromo σ-dimethyl dimethyl dantoin, N-benzyldi-pi-romaleimide, 1,2-Benzisothiazoline-13-one, 2- (Methoxycarbonyl Amino) benzimidazole, 4-methyl-5-chloro-2-η-octyl-3-isothiazolone, 2-methylthio-14-t-butylamino-16-cyclopropylamino-s-triazine, N-2-methyl-6 Tylphenyldichloromaleimide, 2-methyl-3-isothiazolone, methylene-bis Shianeto, 3-Yodo 2-propynyl Petit Luke one Bameto, ® over de propargyl butyl mosquitoes one Bameto.
更に、 本発明において有効成分として使用するゥレア誘導体は単一の化合物或 レ、は数種類のゥレァ誘 の混合物から構成されていてもよい。 Further, the perylene derivative used as an active ingredient in the present invention may be composed of a single compound or a mixture of several kinds of perylene derivatives.
本発明において有効成分として使用するウレァ誘 は で の使用用途 のシステムに添加されてもよいし、 又は、 ^^分と ならば適切な担体また は溶剤からなる混^)として、 又は、 7j性乳濁物または分散物として配合されて もよい。 Use of urea as an active ingredient in the present invention May be added to the system, or may be formulated as a mixture of a suitable carrier or solvent if the amount is less than 7 minutes, or as a 7j 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，抗カビ剤及び纏剤の用途分野で概説すると、 本発明において有効成分と して使用するウレァ誘靴は、 適当な担体及び補助剤、 例えば界面活性剤、 結合 剤、 安 などと配合して混合し、 常法によって; l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, antifungal, algicidal and biofouling inhibitor of the present invention is outlined in the field of application of industrial antibacterial, antifungal and bulking agents. The urea shoes may be mixed and mixed with suitable carriers and auxiliary agents, such as surfactants, binders, irons, and the like, in a conventional manner; l-emulsions, emulsions, sols (flowables) and other suitable It is used after being formulated into a dosage form.
これらの製剤を調製する場合には、 有効成分であるウレァ誘離は水和剤、 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 SSに対し、 1— 9 0重量％、 好ましくは 3— 4 0 When preparing these preparations, there is no upper limit on the concentration of the active ingredient, urea, as long as wettable powders, emulsions, solutions, sols, and other appropriate preparations can be prepared. 1 to 90% by weight, preferably 3 to 40% of SS
%の割合で配合される。 %.
使用できる担体としては、 工業用抗菌 '抗カビ剤及び^^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 0 As a carrier that can be used, any solid or liquid can be used as long as it is commonly used for industrial antibacterial agents and antifungal agents, and it is not limited to a specific one.
固術旦体の例としては、 鉱物質粉末、 例えばカオリン、 ベントナイト、 クレー、 モンモリロナイト、 珪藻土、 雲母、 バーミキユラィト、 石膏、 炭酸カルシウム、 ； K灰、 ホワイトカーボン、 消石灰、 m 硫安、 尿素等、 又は植物性粉末、 例 えば大豆粉、 猶&、結晶セルロース等、 アルミナ、 珪酸塩、 糖重合^ 高分散性 、 ワックス類、 等が挙げられる。 Examples of solid bodies include mineral powders such as kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate; K ash, white carbon, slaked lime, ammonium sulfate, urea, etc., or plants Powders, for example, soybean powder, coconut, crystalline cellulose, etc., alumina, silicate, sugar-polymerized highly dispersible, 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 π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 素類、 例えばベンゼン、 トルエン、 キシレン、 ェチルベンゼン、 クロ口ベンゼン、 クメン、 メチルナフタレン等、 又 はハロゲン化炭ィ 7j素類、 例えばクロ口ホルム、 ジクロロメタン、 エチレンジク 口リ 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、 ,プチル、 ェチレ ングリコールァセテ一ト、 隱ァミル等、 二トリノレ類、 例えばァセトニトリル、 プロピオ二トリル、 ァクリロ二トリノレ等、 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エー 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^ ¾び脂環 ¾ ^ 素類、 例えば n—へキサン、 シクロへ キサン等、 さ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 iOT 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 such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc., aromatics such as benzene, toluene, xylene, ethylbenzene, Benzene, cumene, methylnaphthalene, etc., or carbon halides 7j, such as chloroform, dichloromethane, ethylene dichloride Mouth lids, ethers, such as ethyl ether, dioxane, tetrahydrofuran, etc., ketones, such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc., esters, such as ethyl acetate,, butyl, ethyle Glycotriacetate, Okiamyl, etc., nitrinoles, such as acetonitrile, propionitrile, acrylonitrile, etc., sulfoxides, such as dimethyl sulfoxide, alcohol ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethylene Amines, such as tyl ether, for example, triethylamine, etc., and fatty acids, such as n-hexane and cyclohexane, and industrial gasoline (petroleum ether, solvent naphtha, etc.) and iOT Oil fractions (paraffins, kerosene, gas oil, etc.), and the like.
乳剤、 水和剤、 ゾル剤 （フロアブル剤） 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, wettable powders, and sols (flowables), 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、 アルキルサルフェート、 ポリオキシエチレンアルキルサ ルフェート、 ァリ一ルスルホネート及びラウリルサルフヱ一ト、 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アンモニゥムクロリ ド及びアルキルジメチルベンジルアンモ ニゥムクロリ ド等） 、 等が挙げられる。 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 (such as laurylamine, stearyltrimethylammonium chloride and alkyldimethylbenzylammonium chloride).
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 が挙げられる。 また、 これらの他に、 ポリピニルアルコール （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ロ 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^^に応じて酸化防止剤、 紫外線吸 TOJ等のような安定化剤を適量 &Πえ ることがでさる 0 Examples of the amphoteric surfactant include carboxylic acid (betaine type) sulfate, and the like. In addition to these, polypinyl alcohol (PVA), carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, tragacanth gum, guar gum, xanthan gum and hydroxypropyl A thickener such as cellulose and various auxiliaries can be blended. Further ^^ antioxidant according to, 0 qs & [pi e Rukoto monkey in a stabilizer such as an ultraviolet absorption TOJ
本発明の、 ゥレア誘^を有効成分として含む、 工業用抗菌'抗カピ 、 k 剤としては、 以下の用途に用いることができる。 The industrial antibacterial anti-capillary agent of the present invention containing a rare agent as an active ingredient can be used for the following applications.
水性の塗料、 材、 ラテックス、 アクリル等のェマルジヨン製品、 デンプン、 »k 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^ の生長抑制； m m , 土木建材等） の 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 »5ェ場等の殺菌及びスライム生成防止；纖及び皮革への噴霧または 浸漬処理による抗菌 ·抗カビ処理； ^& . 特に外^^の^ H¾I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、 エポキシ等の棚 から成る内装 ·外装材（住宅用、 隨施設用）、 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 ；サトウキビ及びテンサイ糖の 装置へのスライム堆積の, Waterborne paints, materials, latex, emulsion products such as acrylics, starches, slurry products such as »k calcium carbonate and growth control of bacteria, fungi and ^ in joint cement; mm, preservation of civil engineering materials, etc .; Preservation of cutting oil; surface active agent of surfactant; disinfection of cooling towers, pulp and »5 places in factory manufacturing facilities and building air conditioning etc. and prevention of slime generation; by spraying or dipping on fiber and leather Antibacterial and antifungal treatment; ^ &. Protection from attack by bacteria, fungi and ^, especially when ^ H¾I outside is exposed to the elements; vinyl chloride, polyurethane, polyethylene, polypropylene, silicone, Interior and exterior materials consisting of shelves made of modified silicone, nylon, epoxy, etc. (for homes and other facilities), building materials (building materials, civil engineering materials, etc.), home appliances, household goods Antibacterial, antifungal and such as sporting goods; slime deposition to the device of cane and beet sugar,
；エアーウォッシャー、 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；∞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 ^^長抑制；農業用配合物、 電着システム、 診断及び薬剤製品、 mm 器等の 物汚染の防止；写真処理における 物 の防 iho Prevention of accumulation and accumulation of microorganisms in air washers, scrubber systems, and industrial freshwater supply systems; maintenance of sanitary conditions in food factories, etc .; deodorization and sterilization of sewage treatment plants, human waste treatment plants, etc. when washing equipment; Prevent microbial contamination and sedimentation in oilfield cutting oil, 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; ^^ length control; agricultural formulations, electrodeposition systems, diagnostic and pharmaceutical products, mm Prevention of contamination of equipment such as vessels;
ウレァ誘 を有効成分として含む、 生物付着防 としては、漁網、 の 船底、 ブイ等の海中に動ヽれる設備、 海 築物、 又は原子力発 の 器冷却水系、 イ^：ェ業の熱交 m¾冷却用水の ¾7j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、 フジッボ、 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^ κ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きる。 Anti-biofouling, which contains urea as an active ingredient, can be used in the sea, such as fishing nets, ship bottoms, buoys, etc., marine structures, or cooling water systems from nuclear power plants. Cooling water 貝 7j roads, underwater structures such as auxiliary equipment for dams, and mussels such as mussels, fujibo, oysters, hydramushi, hydra, selbra, sea squirrels, mosses, and snails, etc. It can be used to prevent harmful underwater organisms such as ^.
次にウレァ誘雜の合成例を示すが、 本発明に用いられる化^)は、 これらに ^されるものではない。 Next, synthetic examples of urea attraction will be described, but the compound used in the present invention is not limited thereto.
合成例 1 (化^ IIの合成） Synthesis Example 1 (Synthesis of Chemical ^ II)
化合物 1 Compound 1
4— (2—メチルベンゼンスルホニル） ァニリン 2. 47gを無水ピリジン 2 Omlに溶解し、 0〜5°Cで N, N—ジメチルカルバモイルク口ライド 1. 29 gを加え、 室温で 24時間攪拌した。 Dissolve 2.47 g of 4- (2-methylbenzenesulfonyl) aniline in 2 Oml of anhydrous pyridine, add 1.29 g of N, N-dimethylcarbamoyl chloride at 0-5 ° C, and stir at room temperature for 24 hours .
S)»了後、 赃下ピリジンを留去し、 残渣に水 50mlを加え撹拌した。 得られた結晶を濾過し、 n—へキサンで洗净し、 匕^ IIを 2. 10 g得た o After completing step S), pyridine was distilled off under water, and 50 ml of water was added to the residue, followed by stirring. The obtained crystals were filtered and washed with n-hexane to obtain 2.10 g of Dani ^ II o
酰 69. 0〜72. 0°C 酰 69.0 ~ 72.0 ° C
合成例 2 (化合物 8の合成） N一 Me Synthesis Example 2 (Synthesis of Compound 8) N-one Me
3し " /ノ 3 "
化合物 8 Compound 8
3- (4一トリフルォロメチルフエノキシ） ァニリン 1. O gを無水ピリジン 10mlに溶解し、 0〜5でで N, N—ジメチルカルバ乇イルク口ライド 0. 5 2 gを加え、 室温で 24時間攪拌した。 3- (4-Trifluoromethylphenoxy) aniline 1. Dissolve Og in 10 ml of anhydrous pyridine, add 0.52 g of N, N-dimethylcarbadiyl chloride at 0-5 and add room temperature For 24 hours.
終了後、 账下ピリジンを留去し、 残渣に水 20mlを加え撹拌した。 得られた結晶を濾過し、 n—へキサンで洗浄し、 乾燥後、 化^ 8を 0. 98 g得た o After completion, pyridine was distilled off under water, and 20 ml of water was added to the residue, followed by stirring. The obtained crystals were filtered, washed with n-hexane, and dried to obtain 0.98 g of compound 8
1 19. 0〜1 19. 5°C 1 19.0 to 1 19.5 ° C
合成例 3〜1 0 (化^) 2〜7及び化合物 9〜10) Synthesis Examples 3-10 (Chemical Formula) 2-7 and Compounds 9-10)
化合物 2 化合物 3 Compound 2 Compound 3
化合物 6 化合物 7 Compound 6 Compound 7
O O O O
/λ-(:¾)2θ 人 .Me Me- (C / λ- (: ¾) 2θ person .Me Me- (C
N 、す )2OH N人-.. MeN, s ) 2 OH N people-.. Me
H H H H
F,C OMe F, C OMe
化合物 9 化合物 1 o Compound 9 Compound 1 o
合成例 1及び合成例 2と同様の操作により化合物 2〜 7及び化合物 9〜 1 0を 合成した。 Compounds 2 to 7 and 9 to 10 were synthesized in the same manner as in Synthesis Examples 1 and 2.
化^ 12 (油状物質） Chemically ^ 12 (oily substance)
化^) 3 (固形物質） ^) 3 (solid substance)
化^ 14 (固形物質） Chemical compound 14 (solid substance)
化^) 5 議 1 34. 0-1 36. 0°C) 5) 1 34. 0-1 36.0 ° C)
化 6 (固形物質） Chemical formula 6 (solid substance)
化 ^¾!7 (固形物質） o Nl 化 (油状物質） ^ ¾! 7 (solid) o Nl (oil)
化^ 11 0 麵 1 22, 0-1 24. 0°C) ^ 11 0 麵 1 22, 0-1 24.0 ° C)
合成例 1 1 (化合物 1 3の合成） Synthesis Example 1 1 (Synthesis of Compound 13)
化合物 1 3 N, N—ジメチルー N' — （4ーヒドロキシフエニル）尿素し 80 g (0. 01モル） 、 2—クロロメチルチアゾール 1. 84g (0. 01モル）及び無水 カリウム 1. 38g (0. 01モル） を乾燥ァセトニトリノレ 30 m 1に加え 、 攪拌しながら徐々に加熱し、 還流 態で 8時間 を行った。 Compound 1 3 N, N-dimethyl-N '-(4-hydroxyphenyl) urea 80 g (0.01 mol), 2-chloromethylthiazole 1.84 g (0.01 mol) and anhydrous potassium 1.38 g (0.01 mol) Mol) was added to 30 ml of dried acetonitrile, and the mixture was gradually heated with stirring and refluxed for 8 hours.
終了後、 JEE下溶媒を留去し、 乾固させ、 残渣にクロ口ホルム 200ml 及び水 100mlを加えて、 攪拌した後、 水層を分離し、 溶媒を留去した。 得られた残渣をシリカゲルクロマトグラフィー （溶出液：クロ口ホルム） で分 離、 精製し、 ■を濃縮乾固することにより、 N, N—ジメチル一 N' - [4- After completion, the solvent was distilled off under JEE and evaporated to dryness. To the residue were added 200 ml of chloroform and 100 ml of water. After stirring, the aqueous layer was separated and the solvent was distilled off. The obtained residue is separated and purified by silica gel chromatography (eluent: black form) and concentrated to dryness to give N, N-dimethyl-1-N '-[4-
(2—べンゾチアゾリルメトキシ） フエニル]尿素（化^ 13) 2. 06g (収 率 60%)を得た。2.06 g (yield 60%) of (2-benzothiazolylmethoxy) phenyl] urea (C ^ 13) was obtained.
ll^l 58. 0-162°C 合成例 12-22 (ィ匕^ II 1-12及び化^ II -22) ll ^ l 58. 0-162 ° C Synthesis Example 12-22 (Idani ^ II 1-12 and Chemical ^ II-22)
化合物 1 1 化合物 1 2
化合物 1 4 化合物 1 5
化合物 1 6 化合物 1 7
化合物 1 8 化合物 1 9 Compound 1 8 Compound 1 9
化合物 2 0 化合物 2 1
化合物 2 2 Compound 2 2
合成例 1 1と同様の操作により化^ II 1〜12及び化^ 14〜22を合成 した。 Compounds II 1 to 12 and Compounds 14 to 22 were synthesized by the same operation as in Synthesis Example 11.
化^ 11 1 145. 0〜146. 0で） ^ 11 1 145.0-146.0)
化^) 12 瞧 127. 0〜130. 0°C) ^) 12 瞧 127.0-130.0 ° C)
ィ匕^ II 4 謹 153. 0〜155. O'C) 匕 匕 ^ II 4. 153. 0 ~ 155. O'C)
化 ^#115 議 152. 0〜155. 0eC) ^ # 115 par.152.0 ~ 155.0 e C)
化^) 16 瞧 161. 0〜1 63. O'C) ^) 16 瞧 161.0-1 63. O'C)
ィ匕^ II 7 02. 0〜105. 0。C) I-Dai ^ II 7 02. 0-105.0. C)
化合物 1 8 謹 1 66. 0〜170. 0eC) 化^ II 9 謹 1 23. 0〜1 26. 0°C) Compound 1 8謹1 66. 0~170. 0 e C) (Chemical ^ II 9 lucky 1 23.0-12.6.0 ° C)
化^ 120 瞧 1 25. 0-1 27. 0°C) ^ 120 瞧 1 25. 0-1 27.0 ° C)
化^ 121 謹 99. 0〜1 00. 0。C) Chemistry ^ 121 Graceful 99.0 ~ 10.00. C)
化合物 22 (油状物質） Compound 22 (oil)
本発明のゥレア誘 を工業用抗菌 ·抗カピ 及び^^剤として用いる場合の 処方例を本発明化合物を用い示すが、 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レ Formulation examples when the urea derivative of the present invention is used as an industrial antibacterial / anti-capi and ^^ agent are shown using the compound of the present invention, but the compounding ratio of the active ingredient, and the type and amount of the carrier and the auxiliary agent, etc. It is not limited to
処方例 1 (乳剤） Formulation Example 1 (emulsion)
成分 Λ% Ingredient Λ%
本発明化^! 5 Invented ^! 5
ジメチルスルホキシド 85 Dimethyl sulfoxide 85
メチルイソプチルケトン 5 Methyl isobutyl ketone 5
ソルポール 80 OA 5 Solpol 80 OA 5
(東邦化学 乳化剤） (Toho Chemical emulsifier)
1 00 1 00
上記を混合溶解して有効成分 5 %を含む乳剤を得た。 By mixing and dissolving the above, an emulsion containing 5% of the active ingredient was obtained.
処方例 2 (水和剤） Formulation Example 2 (Wettable powder)
成分 Λ% Ingredient Λ%
本発明化合物 20 Compound of the present invention 20
ラウリルサルフヱ一ト 7 Lauryl Sulfate 7
クレー 73 Clay 73
1 00 1 00
上記を均一に混合粉砕して有効成分 20%を含む；! KfP剤を得た < 処方例 3 (フロアブル剤） The above mixture was uniformly mixed and crushed to contain 20% of active ingredient;! KfP agent was obtained < Formulation Example 3 (Floable agent)
成分 Ingredient
本発明化合物 2 0 Compound 20 of the present invention
ラウリルサルフエ一ト 2 Lauryl Sulfate 2
ザンサンガム 2 Xanthan gum 2
ヒドロキシプ αピルセルロース 1 Hydroxy α-pill cellulose 1
蒸留水 7 5 Distilled water 7 5
1 0 0 1 0 0
上記をボ一ルミルに入れ 1 2時間粉砕混合して有効成分 2 0 %を含むフロ アプル剤を得た。 The above was placed in a ball mill and pulverized and mixed for 12 hours to obtain a flooring agent containing 20% of the active ingredient.
製剤化された本発明の工業用抗菌，抗カピ^ j及び纏剤は、 各種の製剤をその まま、 又は 7姥しくは適当な有機溶媒で 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 ·抗カピ 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い。 The formulated industrial antibacterial, anti-capi ^ j and bulking agents of the present invention can be used in various industrial raw materials or products by using various preparations as they are or in a suitable organic solvent. Or mixing or spraying on the surface of various industrial raw materials or products, or adding various industrial raw materials or products to the industrial antibacterial, anti-capi and diluent solutions of the present invention. It can be used by various methods in accordance with the industrial antibacterial and antifungal and algicidal methods that have been practiced so far, including the method of immersion, etc. It is not limited.
本発明の工業用抗菌 ·抗カピ^ 纏剤及び生物付着防 の製剤を、 生物付 着防 li^lj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ウレ ァ誘導体は、 、 溶液、 乳剤等の形態に調製して使用される。 The industrial antibacterial and anti-capillary bulking agent and the preparation for preventing biofouling of the present invention are summarized in the field of application of biofouling prevention li ^ lj.The urea derivative used as an active ingredient in the present invention is a solution, It is prepared and used in the form of an emulsion or the like.
これら,、 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。 In preparing these solutions, emulsions, and the like, it is possible to employ typical formulations which are usually performed.
本発明の水中生物付着防止剤を防汚塗料の形態で使用する場合には、 例えば有 効成分であるウレァ誘導体を瞧形翩に配合して腿を調製し、船舶の船底、 海 築物、 用 ¾7jc管路或レヽ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^!を防止することができる。 When the underwater biofouling inhibitor of the present invention is used in the form of an antifouling paint, for example, an active ingredient, a urea derivative, is mixed with a 翩 -shaped idiot to prepare a thigh, and the bottom of a ship, a marine structure, The 7jc pipeline or layer is applied to underwater structures, etc. It is possible to prevent adhesion of things ^!
形成剤としては、 油ワニス、 合 s¾tfl旨、 人造ゴム等が用いられる。 As a forming agent, oil varnish, synthetic resin, artificial rubber and the like are used.
更に、 機に応じて翻、 顔料等を使用しても差し支えない。 Furthermore, depending on the machine, pigments and the like may be used.
,を調製する場合には、 有効成分であるウレァ誘 は 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、 i〜5 o m&%, 好ま しくは 5〜2 0 S4%の割合で配合される。 , The concentration of the active ingredient, urea derivative, has no upper limit as long as it can be formed, but i ~ 5 om &%, preferably 5 ~ 20 with respect to the weight of the antifouling paint. It is blended at a rate of S4%.
本発明の水中生物付着防 を防汚,として用いる場合の処方例を本発明化 を用い示すが、 これらに限定されるものではない。 A formulation example in the case of using the underwater organism adhesion prevention of the present invention as an antifouling is shown by using the present invention, but is not limited thereto.
処方例 4 Prescription example 4
成分 籠％ 本発明化合物 8 Ingredient Cage% Compound of the present invention 8
VYHH (ビニル系合成樹脂、 V C CV ) 7 VYHH (vinyl synthetic resin, V C CV) 7
ロジン 7 Rosin 7
リン酸トリクレシル 3 Tricresyl phosphate 3
タルク 2 0 Talc 2 0
硫酸バリウム 1 5 Barium sulfate 1 5
弁柄 1 0 Red petals 1 0
キシレン 2 0 Xylene 2 0
メチルイソプチルケトン 1 0 Methyl isobutyl ketone 1 0
1 0 0 1 0 0
処方例 5 Prescription example 5
成分 Ingredient
本発明化合物 5 Compound 5 of the present invention
C R - 1 0 (塩ィ匕ゴム樹] 5旨、 m 1 3 C R-10 (Shiidai rubber tree) 5 meaning, m 1 3
2 0 タルク 2 0 2 0 Talc 2 0
可讓 2 Allowable 2
弁柄 1 0 Red petals 1 0
キシレン 3 0 Xylene 3 0
1 0 0 1 0 0
本発明の水中生物付着防 ih^を溶液の形態で使用する場合には、 例えば有効成 分であるウレァ誘^:を^!形成剤と共に溶媒に溶解した溶液を調製して、 漁網、 定 e¾¾網等に塗布することによつて水中生物の付着,を防止することが できる。 When the underwater biofouling prevention ih ^ of the present invention is used in the form of a solution, for example, a solution prepared by dissolving the active ingredient urea derivative ^: in a solvent together with a ^! By applying to a net or the like, it is possible to prevent underwater organisms from adhering.
賺形成剤としては、 合雄旨、 人造ゴム、 天細旨等が用いられ、 匪とし 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。 As a part forming agent, synthetic male, artificial rubber, natural fineness and the like are used, and as a bandit, xylene, toluene, cumene, methyl ethyl ketone, methyl isobutyl ketone, and acetone are used.
更に、 に応じて添加剤、 例えは^ r顯等を使用しても差し支えない。 溶液を調製する場合には、 有効成分であるウレァ誘 ·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 Sfiに対し、 1〜5 好ましく は 5〜3 0 %の割合で配合される。 Further, an additive such as ^ r, etc. may be used according to. When preparing a solution, there is no upper limit to the concentration of urea derivative, which is an active ingredient, as long as a solution can be formed, but it is mixed at a ratio of 1 to 5, preferably 5 to 30% with respect to the Sfi of the solution. Is done.
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本発明 化合物を用い示すが、 これらに限定されるものではない。 Formulation examples using the compound of the present invention in the case of using the anti-biological matter in water of the present invention as an antifouling agent solution are shown, but the present invention is not limited thereto.
処方例 6 Prescription example 6
成分 m % Ingredient m%
本発明化合物 1 5 Compound 15 of the present invention
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 処方例 7 1 0 0 Prescription example 7
成分 Λ% Ingredient Λ%
本発明化^! 1 0 Invented ^! 1 0
アクリル樹脂（5 0 %キシレン液） 4 0 Acrylic resin (50% xylene liquid) 40
ジ第 3級ノニルペンタスルフィ、ジ ド 5 Di-tertiary nonyl pentasulfy, Zide 5
¾S&パラフィン 5 ¾S & 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 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、 有効成分であるウレァ誘 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、 用いる界面活性剤の種類に特に限 定はない。 When the underwater biofouling preventive composition of the present invention is used in the form of an emulsion, a surfactant is usually added to a solution of urea as an active ingredient according to a standard method for preparing an emulsion to prepare a desired emulsion. It can be prepared and the type of surfactant used is not particularly limited.
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 えば髙 樹脂等に練り で用いることができる。 The emulsion thus prepared can be kneaded with raw materials such as a net used in the ocean or water, and a fixed net, for example, kneaded with a resin or the like.
乳剤を調製する場合には、 有効成分であるウレァ誘 は乳剤が形成できる限 りにおいて濃度に上限はないが、 乳剤の重量に対し、 1 - 5 0 %、 好ましく は 3— 3 0重量％の割合で配合される。 When an emulsion is prepared, the concentration of the active ingredient, urea derivative, has no upper limit as long as the emulsion can be formed, but it is 1 to 50% by weight, preferably 3 to 30% by weight based on the weight of the emulsion. It is blended in a ratio.
又、 本発明の上記溶液又は乳剤は、 御用水の ¾7j管路或いは貯水池等におけ る水中生物の付着 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。 発明を実施するための最良の形態 The solution or emulsion of the present invention can also be used by adding it to service water, water storage, or the like, in order to prevent adherence of aquatic organisms in a 7j pipeline or a reservoir. BEST MODE FOR CARRYING OUT THE INVENTION
以下、 本発明について、 更に具体的且つ詳細に上記化合物 1〜2 2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 to 22. However, the present invention is not limited thereto.
m i (淡 ^ ^に対する増殖阻害活性 H ffi) 対数増 にある淡 7jC¾ (セレナストルムカプリコルヌタム， Selenastrum capricornutum ) 1 0 6個 Zm l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 5 0 0 p p b、 5 O p p bである試料を調製し、 2 3 ± 1で、 2 4時間 明餅で静§¾養した。 mi (light growth inhibition activity H ffi against ^ ^) Pale 7jC¾ in the exponential increase (Serena strike Lum Capri Korunu Tam, Selenastrum capricornutum) 1 0 medium containing six Zm l, respectively dissolving an amount of a compound of the present invention, each concentration of the compound of the present invention in the medium Samples of 500 ppb and 5 O ppb were prepared and cultivated at 23 ± 1 for 24 hours with rice cake.
7 2時間後に血球計数装置を用い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 4表に示した。 The results are shown in Table 4.
第 4表 Table 4
化合物 増殖阻害率 {%) Compound growth inhibition rate (%)
N o. 5 0 0 ρ p b 5 0 ρ ρ B No. 5 0 0 ρ pb 5 0 ρ ρ B
1 9 6 3 5 1 9 6 3 5
2 9 7 9 6 2 9 7 9 6
3 9 5 4 9 3 9 5 4 9
4 9 4 2 3 4 9 4 2 3
5 9 5 8 2 5 9 5 8 2
6 9 8 9 7 6 9 8 9 7
7 9 7 7 1 7 9 7 7 1
8 9 7 9 6 8 9 7 9 6
9 9 7 9 7 9 9 7 9 7
1 0 9 7 8 2 1 0 9 7 8 2
1 1 9 7 9 4 1 1 9 7 9 4
1 2 9 7 8 6 1 2 9 7 8 6
1 3 9 4 1 7 1 3 9 4 1 7
1 4 8 6 1 1 1 4 8 6 1 1
1 5 9 6 6 6 1 5 9 6 6 6
1 6 9 5 3 2 17 97 63 1 6 9 5 3 2 17 97 63
18 96 72 18 96 72
19 97 81 19 97 81
20 93 22 20 93 22
21 96 32 21 96 32
22 96 45 実施例 2 (海 7j¾藻に対する増殖阻害活性 22 96 45 Example 2 (Proliferation inhibitory activity against sea 7j¾ algae
対数増画にある海 7]¾藻（二?チアクロステリゥム， Nitzschia closterium) 1 0 δ個 /ml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 500ppb、 50 p p bである試料を調製し、 23 ± 1で、 24時間 明餅で静¾¾養した。 The sea in logarithmic enrichment 7] A certain amount of each compound of the present invention is dissolved in a medium containing 10 δ / ml of algae (Nitzschia closterium), and the present invention in the medium is dissolved. Samples in which the concentrations of the compounds were 500 ppb and 50 ppb, respectively, were prepared, and they were refrigerated at 23 ± 1 for 24 hours with rice cake.
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 細胞を破枠し、 クロロフィルを抽出した。 After 72 hours, the cells were collected by centrifugation, then methanol was added to break 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 5表に示した。 The results are shown in Table 5.
第 5表 Table 5
増殖阻害率 %) (Growth inhibition rate%)
No. 500 ρ p b Β"0 ρ ρ 5" No. 500 ρ p b Β "0 ρ ρ 5"
1 64 22 1 64 22
2 96 92 2 96 92
3 88 40 3 88 40
4 91 18 4 91 18
5 89 58 5 89 58
6 95 92 92 39 6 95 92 92 39
8 93 90 8 93 90
9 96 90 9 96 90
10 91 5 10 91 5
1 1 66 49 1 1 66 49
12 84 58 12 84 58
13 76 62 13 76 62
14 73 0 14 73 0
15 90 88 15 90 88
16 95 75 16 95 75
17 89 37 17 89 37
18 90 85 18 90 85
19 93 85 19 93 85
20 81 0 20 81 0
21 90 48 21 90 48
22 87 0 実施例 3 (淡水^ に対する増殖阻害活 22 87 0 Example 3 (growth inhibitory activity against freshwater
対数増翻にある淡水麵 1 05個 Zm 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 500ppb、 5 Opp bである を調製し、 淡水珪^ ϋにおいては 20±2で、 他の麵においては 23±2°Cの温度で、 24時間連 β明 で 100 r pmの振とう培養を行つ In medium containing fresh noodles 1 0 5 Zm 1 in the logarithmic increase transliteration, each dissolving amount of a compound of the present invention, to prepare a concentration of the present compound in the medium are each 500 ppb, 5 Opp b The temperature is 20 ± 2 for freshwater silica and the temperature is 23 ± 2 ° C for the other cells, and the culture is shaken at 100 rpm for 24 hours under continuous light.
72及び 168時間後に血球計数装置を用いて総細胞容積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 and 168 hours, the proliferation rate was determined by measuring the total cell volume using a hemocytometer. The growth inhibition rate was calculated by comparison with the untreated group.
結果を第 6表〜第 1 1表に示した。 但し、 表中の記号は以下を意味する。 The results are shown in Tables 6 to 11. However, the symbols in the table mean the following.
A：淡 T l^ (ク πレラ ビレノイド-サ， Chlorella pyrenoidosa) A: Light T l ^ (Chπella pyrenoidosa)
B：淡水藍藻類（ミク nシス ΐイス ルギ /-ザ， Microcystis aeruginosa) B: Freshwater blue-green algae (Micron cisis algae / -The, Microcystis aeruginosa)
C：淡 麵（ダ仃トマ工 π Diatoma elongatum) C: Tan 麵 (Datoma Engineering π Diatoma elongatum)
D： ¾fe ^^ (セネ xムス八フニカス， Scenedesmus Dannonicus) D: ¾fe ^^ (Sene x Muss Hachifunikas, Scenedesmus Dannonicus)
E：淡 T ^ (了ンキス iデスムスフ了ルカタス， Ankistrodesmus falcatus) E: Light T ^ (Ronkisu idesmushururukatas, Ankistrodesmus falcatus)
F：淡 7_ ^S (クラミドモナス レインハ-ディ， Chlamydomonas reinhardii) F: light 7_ ^ S (Chlamydomonas reinhardii)
第 6表 （ Aに対する活性） Table 6 (Activity for A)
増殖阻害率 {%) 化合物 0 Ο ρρΈ 5 O ppb Growth inhibition rate (%) Compound 0 Ο ρρΈ 5 O ppb
No. 72hr I60hr 72hr rNo. 72hr I60hr 72hr r
2 6 4 6 5 3 4 02 6 4 6 5 3 4 0
1 3 6 5 0 3 0 01 3 6 5 0 3 0 0
1 5 7 2 8 0 5 0 7 第 7表 （Bに対する活性） 15 7 2 8 0 5 0 7 Table 7 (Activity against B)
増殖阻害率 (%) 化合物 "5 0 0卯 F 5 O pb Proliferation inhibition rate (%) Compound "500 F5 O pb
No. 72 r 168hr 72hr 168hrNo. 72 r 168hr 72hr 168hr
2 5 9 9 1 2 2 02 5 9 9 1 2 2 0
8 6 4 9 4 4 5 98 6 4 9 4 4 5 9
1 3 4 8 7 9 0 1 31 3 4 8 7 9 0 1 3
1 5 7 2 9 6 5 7 8 4 第 8表 （Cに対する活性） 1 5 7 2 9 6 5 7 8 4 Table 8 (Activity for C)
増殖阻害率 {%) Growth inhibition rate (%)
50 Oppb 5 O pb50 Oppb 5 O pb
No. 72hr 馳 r 72hr 16No. 72hr r 72hr 16
2 81 95 58 872 81 95 58 87
1 3 71 98 3 1 661 3 71 98 3 1 66
1 5 83 96 55 9 1 第 9表 （Dに対する活性） 1 5 83 96 55 9 1 Table 9 (Activity against D)
増殖阻害率（％) 化合物 500 ppb 5 O pb Growth inhibition rate (%) Compound 500 ppb 5 O pb
No. 72hr 168hr 72hr 馳 rNo. 72hr 168hr 72hr
2 76 96 82 932 76 96 82 93
8 95 97 94 968 95 97 94 96
1 0 95 97 78 641 0 95 97 78 64
1 3 88 82 1 6 01 3 88 82 1 6 0
1 5 82 94 83 931 5 82 94 83 93
1 7 89 96 53 52 第 1 0表 （Eに対する活性） 1 7 89 96 53 52 Table 10 (Activity against E)
増殖阻害率 (%) 化^) "B 0 ODpb 5 Oppb No. 72hr l¾8hr 72fir 168hr Growth inhibition rate (%) ^) "B 0 ODpb 5 Oppb No. 72hr l¾8hr 72fir 168hr
1 3 93 93 98 99 第 1 1表 （Fに対する活性） 1 3 93 93 98 99 Table 11 (Activity against F)
増殖阻害率 {%) Growth inhibition rate (%)
500 ppb ― 5 O pb―500 ppb ― 5 O pb ―
No. 72hr ~~ I r "72R? I FNo. 72hr ~~ I r "72R? IF
1 3 99 98 96 93 例 4 (生物付着防止活性謹 1 3 99 98 96 93 Example 4
2. Omgの化合物 1をアセトン約 1 m 1に完全に溶解し、 に描かれ た直径 4 cmのゾーン内に、 サンプル溶液を均一に塗布した。 2. Omg of Compound 1 was completely dissolved in about 1 ml of acetone, and the sample solution was uniformly applied in a 4 cm diameter zone indicated by.
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、 硫酸銅し Omg及び 0. 5mg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 Omg and 0.5 mg of copper sulfate was applied was provided as a comparative agent.
乾燥後、 殻長が 2— 2. 5 cm前後のムラサキイガイ (Mytilus edulis) をス ぺーサ一としてゴム片を用 、、 それぞれのゾ一ンの外周に 4個体づっ接着した。 調製した を、 海水か ¾λする水槽中に浸潰し、 喑所で 3時間静置した 0水 槽中から^ ^を上げ、 ムラサキイガイ足糸の付着位置と » [を計測した。 同様 の方法にて、 化合物 2〜5、 化合物 8及び化合物 1 1〜15を用い試験を実施し 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。 After drying, a mussel (Mytilus edulis) having a shell length of about 2 to 2.5 cm was used as a spacer, and four pieces were adhered to the outer periphery of each zone. The prepared was immersed in an aquarium bathing in seawater or ^ λ, and ^ ^ was raised from the 0 aquarium which was allowed to stand at the place for 3 hours, and the adhesion position of the mussel mussels was measured. In the same manner, tests were conducted using Compounds 2 to 5, Compound 8 and Compounds 11 to 15, and the adhesion control effect (adhesion repellent activity) was determined by comparison with copper sulfate used as a comparative drug.
付着^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翻質の検纖」 （ィ と生物、 第 28巻（第 2号）、 13 2〜1 38頁（1990年） に従った。 The evaluation method of adhesion ^ activity is described in Kazuo Ina and Hideo Eto, "A study of the adhesion repellent of marine marine organisms using mussels" (I and Biology, Vol. 28 (No. 2), 132-1) Page 38 (1990).
結果を第 12表に示した。 The results are shown in Table 12.
第 12表 Table 12
有効成分 薬量 (mg) 判定 Active ingredient Dose (mg) Judgment
化^ II 2. 0 + + ^^ II 2.0 + +
化合物 2 2. 4 + + Compound 2 2.4 + +
1. 2 + + 1.2 + +
0. 6 + 0.6 +
化合物 3 1. 8 + + Compound 3 1.8 + +
0. 9 + + 化合物 4 1. 8 + 0.9 +++ Compound 4 1.8 +
化合物 5 2. 4 + + Compound 5 2.4 + +
1. 2 + + 1.2 + +
i -^ z 2. 0 + + i-^ z 2.0 + +
化合物 13 2. 1 + + Compound 13 2.1 + +
1. 1 + 1. 1 +
化合物 1 2. 1 + Compound 1 2.1 +
化合物 15 2. 4 + + Compound 15 2.4 + +
1. 2 + 1.2 +
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、 強い忌 効果が認められる。 + +: Does not adhere at all in the zone, and a strong repellent effect is observed.
+：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 効果が認められる。 +: Adhesion inside the zone is also observed, but most adhere outside the zone, and repellent effects are observed.
一：ゾーン内外に同 に付着し、 忌 効果が認められない。 産 ^±の利用可能性 1: The same adheres inside and outside the zone, and no repellent effect is observed. Availability ^ ±
(1)で表されるウレァ誘 は、 安 ^ttが高く、 低薬量で幅広いスぺ クトラムを発現し、 工業用抗菌'抗カピ 、 剤及び生物付着防 として有 用である。 The urea derivative represented by (1) has high tt, exhibits a wide spectrum at a low dose, and is useful as an antibacterial agent for industrial use, as an anti-capillary agent, and as a biofouling preventive.
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU61188/98A AU6118898A (en) | 1997-03-03 | 1998-03-02 | Urea derivatives, and industrial antibacterial and antifungal agents, algaecidesand antiperiphytic agents containing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4783497 | 1997-03-03 | ||
| JP9/47834 | 1997-03-03 | ||
| JP5017497 | 1997-03-05 | ||
| JP9/50174 | 1997-03-05 |
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| WO1998039289A1 true WO1998039289A1 (en) | 1998-09-11 |
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ID=26388027
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP1998/000855 Ceased WO1998039289A1 (en) | 1997-03-03 | 1998-03-02 | Urea derivatives, and industrial antibacterial and antifungal agents, algaecides and antiperiphytic agents containing the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010126456A (en) * | 2008-11-26 | 2010-06-10 | Sumika Enviro-Science Co Ltd | Wood preservation composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010126456A (en) * | 2008-11-26 | 2010-06-10 | Sumika Enviro-Science Co Ltd | Wood preservation composition |
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| Publication number | Publication date |
|---|---|
| AU6118898A (en) | 1998-09-22 |
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