CN1191073A - Dihaloformaldoxime carbamates as antimicrobial agents - Google Patents
Dihaloformaldoxime carbamates as antimicrobial agents Download PDFInfo
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- CN1191073A CN1191073A CN97117634A CN97117634A CN1191073A CN 1191073 A CN1191073 A CN 1191073A CN 97117634 A CN97117634 A CN 97117634A CN 97117634 A CN97117634 A CN 97117634A CN 1191073 A CN1191073 A CN 1191073A
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- 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
- A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
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- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
- A01N33/18—Nitro compounds
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The present invention discloses a method for resisting microorganism growing at the place which is invaded by the microorganism. The method comprises introducing at least one kind of formaldoxime carbamate dihalide with effective quantity for resisting the microorganism at the place.
Description
The present invention relates to a kind of method that suppresses growth of microorganism.The invention particularly relates to the purposes of some dihalo-formaldoxime carbamates as antimicrobial.
Antimicrobial by commercialization with microbial growth in prevention of water cooling tower, metal working fluid system, paint and other place.Present obtainable antimicrobial comprises the mixture of 5-chloro-2-methyl-3-isothiazolone (isothiazolone) and 2-methyl-3-isothiazolone.Although these isothiazolones are very effective aspect the prophylaxis of microbial growth, they are to cause death at a slow speed, and unstable under certain conditions.Nitrate is the effective stabilizer of 3-isothiazolone, but usually required salinity can cause such as the cohesion of latex and salt gather such problem in closed system.Therefore need to continue such antimicrobial: they be stable, salt content is not high, consumption is low, can cause death fast, with back degraded and safety when in environment, using rapidly.
US3,553,264 (Addor) disclose some dihalo-formaldoxime carbamates, its preparation method and they purposes as herbicide after seedling, and this patent is also enlightened the purposes of this class dihalo-formaldoxime carbamate as the intermediate of preparation insecticide.The purposes of this compounds as antimicrobial both do not enlightened, do not advised yet to this patent.
The invention provides a kind of method that suppresses microorganism in the place growth that is subjected to microbiological attack, this method comprises: at least a antimicrobial from antimicrobial effective dose to described place that introduce, this class antimicrobial consumption that wherein is employed is low, can cause death fast, with back degraded rapidly, and safety when in environment, using, this class antimicrobial belongs to following formula:
Wherein: X, Y are selected from Br, Cl or I separately; And R=(C
1-C
8) aryl of alkyl, aryl or replacement.
The term of using in this manual " antimicrobial " had both referred to suppress the compound (preservative) of growth of microorganism in given system, also refer to reduce the compound (disinfectant) of microorganism concn.Term " antimicrobial acivity " is meant the activity of antimicrobial elimination, inhibition or prophylaxis of microbial growth.Term " microorganism " is meant but is not limited to microorganism as fungi, bacterium and algae.Use following abbreviation in this specification: the L=liter; The mL=milliliter; The g=gram; The mol=mole; The mmol=mM; The wt%=percetage by weight; The mp=fusing point.This class antimicrobial can effectively resist including, but not limited to the microorganism of fungi, bacterium and algae.Except as otherwise noted, the scope of regulation should think to comprise end points.
The compound that is used as antimicrobial among the present invention is those compounds of above-mentioned formula (I).Preferred compound of the present invention is that wherein X and Y are those compounds of the above-mentioned formula (I) of bromine.The particularly preferred compound of the present invention comprises the compound in being listed in the table below:
The compound number compound name
1 N-methyl-dibromo formaldoxime carbamate
2 N-(2-chloroethyl)-dibromo formaldoxime carbamate
3 N-(4-chlorphenyl)-dibromo formaldoxime carbamate
4 N-(2,4 dichloro benzene base)-dibromo formaldoxime carbamate
5 N-ethyl-dibromo formaldoxime carbamate
6 N-(normal-butyl)-dibromo formaldoxime carbamate
7 N-(n-octyl)-dibromo formaldoxime carbamate
8 N-(n-hexyl)-dibromo formaldoxime carbamate
9 N-(4-aminomethyl phenyl)-dibromo formaldoxime carbamate
" alkyl " in this specification is meant straight or branched (C
1-C
12) alkyl, and " aryl of replacement " is meant the aryl after one or more hydrogen is replaced by other substituting group.The example of suitable substituents comprises: (C
1-C
3) alkyl, (C
1-C
3) alkoxyl, hydroxyl, nitro, halogen, cyano group, (C
1-C
3) alkylthio group and sulfydryl.The example of the phenyl that replaces comprises: 4-aminomethyl phenyl, 2-chlorphenyl, 3-chlorphenyl, 4-chlorphenyl, 2-methoxyphenyl and 4-methoxyphenyl.
Among the present invention, the carbamate of dibromo formaldoxime is normally synthetic like this: under 0-25 ℃ temperature, in the carrene that has as the catalyzer of dibutyl tin laurate, handle the dibromo formaldoxime with isocyanic acid alkyl or aryl ester.Reaction time was depended on the reactivity of isocyanates between 2～48 hours.For example, the synthetic available following reaction scheme of N-butyl dibromo formaldoxime carbamate is described:
The preparation of initiation material dibromo formaldoxime and dichloroindophenol sodium is known in the literature.For example, the synthetic of dibromo formaldoxime can be referring to Tetrahedron Letters, 25:487 (1984).It is for referencial use that the document is incorporated this paper into, the preparation of this article enlightenment dihalo-formaldoxime.
Antimicrobial of the present invention can be used to suppress microbial growth, is undertaken by the place of microbiological attack by one or more described reagent of antimicrobial effective dose are introduced.Suitable place is including, but not limited to cooling tower; Gas cleaner; Boiler; The mineral slurry; Wastewater treatment; The fountain of Gong viewing and admiring; Osmosis filtration; Ultrafiltration; Water ballast; Evaporative condenser; Heat exchanger; Paper pulp and paper conversion liquid; Plastics; Emulsion and dispersion liquid; Paint; Latex; Coating is as varnish; Building product such as putty, caulking agent and sealant; Building adhesive such as ceramic binder, carpet backing adhesive and laminating adhesive; Industrial or daily adhesive; Photographic chemical; Printed liquid; Household article such as bathroom disinfectant or sanitizer; Cosmetics; Shampoo; Soap; Detergent; Industrial disinfectant or sanitizer be as the cold sterilization agent, the hard surface disinfectant; Floor wax; The laundry washings; Metal working fluid; Transfer device lubricating oil; Hydraulic fluid; Leather and leather and fur products; Textile; Textile; Timber and wooden article such as plywood, particle board, compressive plate, the beam of lamination, the stranded plate of orientation (oriented strandboard), hardboard and flakeboard; PETROLEUM PROCESSING liquid; Fuel; Oil field liquid such as priming petock, tomography liquid (fracture fluids) and drilling mud; The agricultural assistant agent is anticorrosion; Surfactant is anticorrosion; Medical Devices; The diagnostic reagent preservation; Food preservation such as plastics or the papery packaging material for food; Various ponds; And spas.There is cooling tower in preferred place; Gas cleaner; Boiler; The mineral slurry; Wastewater treatment; The fountain of Gong viewing and admiring; Osmosis filtration; Ultrafiltration; Water ballast; Evaporative condenser; Heat exchanger; Paper pulp and paper conversion liquid; Plastics; Emulsion and dispersion liquid; Paint; Latex; And coating.
Suppress suitable consumption growth of microorganism, antimicrobial of the present invention and decide, but generally be 0.05～10, between the 000ppm based on described shielded place volume on shielded place.Preferred consumption is 0.1～5000ppm.For example, as cooling tower or paper pulp and this class place of paper conversion liquid, need 0.1～250ppm compound of the present invention to suppress growth of microorganism.In cooling tower or paper pulp and paper conversion liquid, preferably use 0.1～50ppm.Other place such as building product, oil field liquid or emulsion need 0.5～5000ppm compound of the present invention suppressing growth of microorganism, and as disinfectant or sanitizer the place may be up to 10,000ppm.
People in the present technique know, the effect of antimicrobial can be strengthened by combining with one or more other antimicrobial.So antimicrobial that can other is known combines valuably with antimicrobial of the present invention.Compound of the present invention can combine with following compounds: di-2-ethylhexylphosphine oxide (thiocyanates); Isothiazolone, as 2-(n-octyl)-4-isothiazoline-3-ketone, 4,5-two chloro-2-(n-octyl)-4-isothiazoline-3-ketone, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone, 1,2-benzisothiazole-3-ketone and 2-methyl-4,5-trimethylene-4-isothiazoline-3-ketone; Carbamate, as 3-iodine propargyl-N-butyl carbamate, tolimidazole-2-aminocarbamic acid ester, imidazolidinyl urea, diazolidinylurea, N '-(3, the 4-dichlorophenyl)-N, N-dimethyl urea, 3,4,4 '-trichloro-symmetrical diphenyl urea, dimethyldithiocarbamate and ethylenebis aminodithioformic acid disodium; Heterocyclic compound, as 2-pyridine thiol-1-zinc oxide, 2-pyridine thiol-1-sodium oxide molybdena, 10,10 '-oxo two phenoxy group arsines, N-trichloro-methylthio phthalimide, 5-oxygen-3,4-two chloro-1, the 2-dithiol, 3-bromo-1-chloro-5, the 5-dimethyl hydantoin, 4,4-dimethyl-1,3-dihydroxymethyl hydantoins, 2-(thiocyanomethylthio) benzothiazole, 2-methyl mercapto-uncle's 4-fourth amino-6-cyclopropylamino-S-triazine, the iodine PVP(polyvinyl pyrrolidone), 3,5-dimethyl-1H-pyrazoles-1-methyl alcohol, 1-(2-ethoxy)-2-octadecyl imidazoline, 4-(2-nitro butyl)-morpholine, triazine, N, N '-di-2-ethylhexylphosphine oxide (5-methyl isophthalic acid, the 3-oxazolidine), 2,2 '-oxo two (4,4,6-trimethyl-1,3,2-two oxa-borine alkane (dioxaborinane), 2,2 '-(1-methyl propylidene dioxy) two-(4-ethyl-1,3,2-two oxa-borine alkane), hexahydro-1,3,5-three (2-ethoxy)-S-triazine, 4,4-Er Jia Ji oxazolidine, 3,4,4-San Jia Ji oxazolidine, 4,4 '-(2-ethyl-nitro propylidene) dimorpholine, 2-methyl mercapto-uncle's 4-fourth amino-6-cyclopropylamino-S-triazine, 2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine, α-(2-(4-chlorphenyl) ethyl)-α-(1, the 1-dimethyl ethyl)-1H-1,2,4-triazolyl-(1)-ethanol, 1-((2-(2 ', 4 '-dichlorophenyl)-4-propyl group-1,3-dioxolane-2-base-methyl)-1H-1,2, the 4-triazole, DDAC, copper-oxine, (2-(2 for 1-, the 4-dichlorophenyl)-1,3-dioxolane-2-base-methyl)-1H-1,2, the 4-triazole, 2-(4-thiazolyl)-benzimidazole, 3,5-dimethyl-1,3,5-thiadiazine-2-thioketones, 2-chloro-4, two (ethylamino)-1 of 6-, 3, the 5-triazine, 2-chloro-4-ethylamino-uncle's 6-fourth amino-1,3, the 5-triazine, 1-(3-chlorallyl)-3,5,7-three azepines-1-nitrogen chlorination adamantane, copper naphthenate, 5-hydroxyl methoxy-1-azepine-3,7-two oxabicyclos (3.3.0) octane, 5-methylol-1-azepine-3,7-two oxabicyclos (3,3,0) octane, 7-ethyl-1,5-two oxa-s-3-azabicyclooctane, hexadecylpyridinium chloride, 3-bromo-1-chloro-5-dimethyl-5-ethyl hydantoins dodecyl-two (aminoethyl)-glycine, with poly-(the methylene oxygen ethyl) methyl isophthalic acid-azepine-3 of 5-hydroxyl, 7-two oxabicyclos (3.3.0) octane; Oxidant is as hydrogen peroxide, TBHP, cumene peroxide, clorox or calcium, sodium hypobromite or calcium, DCCA, TCCA (Trichloroisocyanuric acid), Peracetic acid, ozone, chlorine, bromine, chlorine dioxide, peroxidating one sulfone potassium (potassium peroxymonosulfone), percarbonate, sodium perborate, romamines and bromine chloride; Carboxylic acid and derivative thereof, as (E, E)-2,4-hexadienoic acid, benzoic acid, sodium propionate or calcium, disodium EDTA and sodium hydroxy methyl glycinate, the benzyl ester of 4-the hydroxybenzoic acid, (C of 4-hydroxybenzoic acid
1-C
4) Arrcostab, (the C of 4-hydroxybenzoic acid sodium salt
1-C
4) Arrcostab, the dimethylformamide of ready denier oil acid and 2,2-two bromo-3-nitrilo-propionamides; Alkohol and amine is as 1-(alkyl amino)-3-amino-propane, 2-bromo-2-nitro-1, ammediol; Phenoxetol; Benzylalcohol, n-2-methylol ethylaminoethanol, 2-hydroxypropyl amino methanol, 2-hydroxypropyl methane thiosulfonates, right-nitrophenol and 4-chloro-3, the 5-xylenol; Ammonium and phosphonium salt are as positive zephiran, hexadecyltrimethylammonium chloride, DDAC, poly-(hexylidene biguanides) hydrochloride, poly-(oxygen ethene (dimethylimino) ethylidene (dimethylimino) ethylene chlorination thing), alkyl dimethyl dichlorobenzyl ammonium chloride, dodine hydrochloride, 2-(sulfenyl in the last of the ten Heavenly stems) ethamine hydrochloride, quaternary ammonium compound, four (methylol) phosphonium chloride, four (methylol) sulphur acid Phosphonium; Aldehyde, ketone and formaldehyde releaser, as 1,5-glutaraldehyde, 1,2-benzene dicarboxylic aldehyde, formaldehyde, 2-bromo-4 '-hydroxy acetophenone, three (methylol) nitromethane and 5-bromo-5-nitro-1, the 3-diox; Halogenated aromatic compound, as 2,4,5,6-daconil M, 2,4,4 '-three chloro-2 '-hydroxy diphenyl ether, 2,2 '-dihydroxy-5,5 '-two chloro-diphenyl methanes and 1,6-two (4 '-the chlorphenyl biguanides)-hexane; The halogenated aliphatic compound, as 1,2-two bromo-2,4-dicyanobutane, diiodomethyl-right-tolyl sulfone, dibromo nitroethane, chlordene dimethyl sulfone; Alkene such as β-bromo-beta-nitrostyrene, 1,4-two (bromine oxethyl)-2-butylene, terpenes and tawny daylily alkene; Inorganic compound is as bismuth, copper, silver, copper-amine complex, nitric acid one bronze medal, borate, zinc oxide, sodium bromide, ammonium bromide, eight boric acid disodium tetrahydrates, tributyltin oxide and chromatize copper arsenate; Enzyme is as cellulase, α-Dian Fenmei, protease, polysaccharase, fructan-hydrolying enzyme; And surfactant, as alkyl aryl ester, polyethoxy alcohol, polyethoxy ether, phosphate, sulfonate, alpha-sulfonated fatty family raw material, thio succinate and DBSA.
Combine with antimicrobial of the present invention, preferred known antimicrobial has: di-2-ethylhexylphosphine oxide (thiocyanates), 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone, 2-n-octyl-4-isothiazoline-3-ketone, 4,5-two chloro-2-n-octyls-4-isothiazoline-3-ketone, 1, the 2-benzisothiazole-3-ketone, 2-pyridine thiol-1-zinc oxide, 2-pyridine thiol-1-sodium oxide molybdena, N '-(3, the 4-dichlorophenyl)-N, the N-dimethyl urea, 3-iodine propargyl-N-butyl carbamate, 10,10 '-oxo two phenoxy group arsines, 2-(thiocyanomethylthio) benzothiazole, 3-bromo-1-chloro-5, the 5-dimethyl hydantoin, 2,2-two bromo-3-nitrilo-propionamides, 1, the 5-glutaraldehyde, with 2-bromo-2-nitro-1, ammediol.
Compound of the present invention also can combine application with microbial control non-chemically, these methods for example: ultraviolet light; Ionizing radiation; Copper electrode; Silver electrode; With enzyme such as cellulase, α-Dian Fenmei, protease, polysaccharase and fructan-hydrolying enzyme.
If a kind of antimicrobial of the present invention is combined with second kind of antimicrobial, then first kind of antimicrobial is 99: 1～1: 99 to the weight ratio of second kind of antimicrobial; Preferably 75: 25～25: 75.Suppress or prevent growth of microorganism antimicrobial total amount essential, combination, be generally 0.05～10,000ppm based on the volume in described protected place.
Antimicrobial of the present invention can be introduced directly into place to be protected or can be used as prescription and add.Antimicrobial of the present invention can be formulated into multiple liquid or solid prescription.Particular type of used prescription (being solid or liquid) and composition will depend on the character of the prescription of place to be protected and development.For example, when worrying the danger of splashing or needing sustained release, then solid for mulation is preferred.If in a period of time prescription is metered into the place, then liquid formulations is preferred.Solid for mulation is particularly useful in as the place of cooling tower, latex and plastics.Liquid formulations is particularly useful in as paint, cosmetics, household cleaners and water treatment applications place.
Usually, antimicrobial of the present invention can be mixed with liquid form by antimicrobial is dissolved in carrier.Suitable carriers comprises water, organic solvent or its mixture.Any organic solvent needs only and last application adapts and the combating microorganisms agent does not produce destabilization, is exactly suitable.Appropriate organic solvent includes but not limited to: aliphatic series and aromatic hydrocarbon, as the mixture of dimethylbenzene, various alkylbenzenes; Halogenated aliphatic and aromatic hydrocarbon are as dichloroethylene and monochloro-benzene; Alcohol is as monobasic, binary and polyalcohol; Aldehyde; Ketone is as acetone, butanone and methyl iso-butyl ketone (MIBK); Ether; Glycol ether; The acetate glycol ether; At least the saturated and unsaturated fatty acid that has 4 carbon atoms; Ester is as ethyl acetate, butyl acetate, glycol ester and phthalic acid ester; And phenol.Preferred organic has glycol ether; The acetate glycol ether; Aliphatic series and aromatic hydrocarbon; And alcohol.
The water prescription of antimicrobial of the present invention can be prepared to dispersion, as polymeric dispersions; Emulsion; The emulsification concentrate; Micro emulsion; With the microemulsified concentrate.Dispersion, emulsion and micro emulsion can have oily continuous phase or water continuous phase.Water prescription generally contains 0.001～50wt% antimicrobial of the present invention, up to the surfactant of the organic solvent of 99wt%, 0.5～55wt%, up to the assistant agent of 15wt% with up to the water of 95wt%.Suitable surfactant has anionic species, as alkyl lauryl sulfonate and fatty alcohol ethoxylate sulfuric ester; Cationic; The nonionic class is as ethylene oxide-propylene oxide copolymer; With the both sexes class.Be applicable to that assistant agent in the water prescription generally comprises but is not limited to: thickener, antifreezing agent and defoamer.
The suitable solid for mulation of antimicrobial of the present invention includes but not limited to: polymeric sealant, those as preparing by interface condensation, cohesion, in-situ polymerization and physical method; Inclusion complex is as clathrate; Liposome; Substrate mixture is as particle, dispersible granules and wettable powder; And ion exchange resin.Polymeric sealant can be prepared to has nucleocapsid structure or overall structure.The suitable polymers sealant includes but not limited to: polyureas, polyamide, polyester, melocol, melamine-formaldehyde, polyacrylic acid and ester thereof, P-F and acetoacetic ester.
Inclusion complex can prepare by antimicrobial of the present invention is mixed host molecule.Suitable host molecule includes but not limited to: alpha-cyclodextrin; Beta-schardinger dextrin-; Gamma-cyclodextrin; Cyclodextrine derivatives is as methyl-beta-schardinger dextrin-; Crown ether; Urea; Quinhydrones; Dichloro-benzenes; The hydroxyl benzophenone; With 1,1,2,2-four (4-hydroxyphenyl) ethane.Inclusion complex can be used as solid composite, is absorbed on the solid carrier or is scattered in the non-active solvent.Inclusion complex is applicable to the application facet of water treatment, metal working fluid and paint.
Liposome can prepare by being dissolved in suitable solvent such as the chloroform with antimicrobial of the present invention with as the lipid of phosphatide.Remove and desolvate, add buffer, stir the particle that said composition gets required size.Liposome can be a multilayer, individual layer, or particle big or little.Liposome is applicable to based on the paint of solvent and cosmetics.
Substrate mixture can prepare by antimicrobial of the present invention is adsorbed on the solid carrier, wherein add suitable additive so as to make particle, can moisten the temperature powder and dispersible particle.These substrate mixtures can directly be used or available any conventional method further is processed into piller, small pieces or bulk.Particle generally contains 1～60wt% antimicrobial of the present invention; 30～98wt% absorbent carrier, as diatomite, water-soluble solid, magnetic particle, or forge inorganic matter such as silica, titanium dioxide and the zinc oxide of system; And 1～10wt% assistant agent.Wettable powder generally contains 1～60wt% antimicrobial of the present invention; 1～5wt% wetting agent; 1～20wt% dispersant; 10～95wt% adsorptive support, as forge the inorganic matter or the potter's clay of system; With assistant agent up to 10wt%.Dispersible particle generally contains 1～60wt% antimicrobial of the present invention; 30～95wt% adsorptive support, as forge the inorganic matter or the potter's clay of system; 5～40wt% dispersant; Surfactant up to 10wt%; With assistant agent up to 15wt%.Dispersible particle can further be extruded, dry and be processed into particle.
Provide following embodiment with further elaboration each side of the present invention, but which be not want to limit scope of the present invention aspect.
The preparation of embodiment 1:N-(normal-butyl)-dibromo formaldoxime carbamate
In ice bath and under the nitrogen protection, (11.8g adds 6.9g n-butyl isocyanate (0.058mol) in carrene 0.058mol) (20ml) solution, then add catalytic amount (8) dibutyl tin laurate toward the dibromo formaldoxime under magnetic agitation.At room temperature further stir this reactant mixture and reach 16 hours.Use then dilute sodium bicarbonate solution (2 * 50ml), water (5 * 25ml) and salt solution (50ml) wash this mixture.With organic layer MgSO
4Filter dry back.The filtrate vacuum concentration is got the 14.9g yellow oil.Also use hexane by column chromatography with silica gel: ethyl acetate (9: 1) wash-out, get purer yellow oil, be 12.1g (productive rate 69%).
To C
6H
10Br
2N
2O
2Results of elemental analyses as follows: calculated value: C=23.86%; H=3.34%; N=9.28%; Br=52.92%.Measured value: C=24.07%; H=3.47%; N=9.31%; Br=52.85%.
The preparation of embodiment 2:N-(4-aminomethyl phenyl)-dibromo formaldoxime carbamate
In ice bath and under the nitrogen protection, (2g, (1.6g is 12mmol) with the dibutyl tin laurate (5) of catalytic amount to add 4-aminomethyl phenyl isocyanates in carrene 9.86mmol) (20ml) solution toward the dibromo formaldoxime under magnetic agitation.At room temperature stir this reactant mixture and reach 16 hours.(3 * 50ml) and this reactant mixture of salt water washing, organic layer is at MgSO for water then
4Filter last dry back.The filtrate vacuum concentration is got crude product, by column chromatography with silica gel and use hexane: ethyl acetate (8: 1) wash-out and this crude product of purifying gets beige solid is 1.7g (productive rate 51%) mp=120-124 ℃.
To C
9H
8Br
2N
2O
2Results of elemental analyses as follows: calculated value: C=32.10%; H=2.40%; N=8.34%; Br=47.57%.Measured value: C=33.76%; H=2.35%; N=8.55%; Br=50.12%.
Embodiment 3: effect
In minimal inhibitory concentration (MIC) test, measured the influence of antimicrobial acivity spectrum and anionic surfactant to the antimicrobial acivity of useful in the present invention antimicrobial.MIC
sBe to measure by the compound in minimum salt culture medium (M9G), casein tryptose enzymolysis thing soybean fermented liquid (TSB) or casein tryptose enzymolysis thing soybean fermented liquid and the anionic surfactant (TSBA) being carried out two times of continuous rare continuous backs of releasing.Compound is at aspergillus niger (Aspergillus niger), rhodothece rubra (Rhodotorula rubra), Escherichia coli (Escherichia coli) and pseudomonas aeruginosa (Pseudomonas aeruginosa) and tested.The MIC result of the test is as follows:
Table 1
| Compound | Escherichia coli M9G | Escherichia coli TSB | Pseudomonas aeruginosa TSB | Aspergillus niger TSB | Rhodothece rubra TSB | Escherichia coli TSBA |
| 3 6 7 8 9 | ＜4 ＜4 ＜4 ＜4 ＜4 | ?63 ?250 ?63 ?63 ?32 | 63 63 ＞500 125 16 | ＞50 ＞50 50 ＞50 ＜0.8 | ??＞50 ??＞50 ??12.5 ??25 ??3.2 | ?63 ?63 ?125 ?32 ?32 |
The above results shows, and is effective especially aspect the microorganism of compound 3,6,7,8 and 9 in the control place.
Embodiment 4: fatality rate
Measured the fatality rate of all cpds of the present invention as follows.
The solution for preparing 5% alpha-alkene sulfonate (AOS): take by weighing 5g40%AOS and place the 100ml flask, add the 35ml deionized water and sway this solution.Then this solution is filtered sterilization.
The preparation of casein tryptose enzymolysis thing soybean fermented liquid (TSB) medium: take by weighing 30gTSB and place the 2L flask, add the 1L deionized water, and it is dissolved fully until TSB to sway this flask.Then this is cultivated based on 121 ℃ of following autoclavings 20 minutes.
The preparation of the solution of TSB+0.05%AOS: in the 250ml flask that fills the aseptic TSB of 100ml, add the aseptic 5%AOS of 1ml, then sway this solution.
The preparation of nutrition stock solution: take by weighing following material and place the 2L flask: 5.28g ammonium nitrate, 2.08g anhydrous phosphoric acid potassium, 4.62g glucose, 21.50g sodium carbonate and 40.20g potassium sulphate.Water is regulated cumulative volume to 1L, and it is dissolved entirely until solids to sway flask then.Then this solution being filtered the sterilization back deposits under room temperature.
The preparation of rigid stock (hardness stock): take by weighing following material and place the 2L flask: 59.36g calcium chloride (dihydrate), 45.02g magnesium chloride (hexahydrate), 0.18g iron chloride (hexahydrate), 0.06g copper chloride (dihydrate) and 0.24g sodium ethylene diamine tetracetate.Water is regulated cumulative volume to 1L.This solution is filtered sterilization back room temperature to be deposited.
The preparation of dense corrosion/pot trowel used for plastering inhibitor stock: take by weighing following material and place the 2L flask: the aqueous solution of the potassium hydroxide aqueous solution of 238.5g deionized water, 125.0g 45wt%, 23.0g 50wt% tolyl-triazole sodium, the 63.5g 42-44wt% acrylic polymer aqueous solution and the about 50wt%2-phosphono-1 of 50.0g; 2, the tricarboxylic aqueous solution of 4-butane.It is dissolved entirely until solids to sway this flask, then this solution is filtered sterilization back room temperature and deposits.
Utilize this dense corrosion/pot trowel used for plastering inhibitor liquid storage preparation corrosion/pot trowel used for plastering inhibitor liquid storage: in this dense corrosion of 9.20ml/pot trowel used for plastering inhibitor liquid storage adding 2L flask, the water adjusted volume is to 1L and sway again.Gained corrosion/pot trowel used for plastering inhibitor liquid storage is filtered sterilization back room temperature to be deposited.
The preparation of synthetic cooling water (" SCW "): 900ml deionized water and 10.88ml nutrition stock solution (pH10-13) are added in the 2L flask.PH is adjusted downward to pH6, adds the rigid stock of 10.88ml then.Then add 10.88ml corrosion/pot trowel used for plastering inhibitor liquid storage, regulate pH to 8 again, regulate final volume to 1L with deionized water.This final solution is filtered sterilization back room temperature to be deposited.
The preparation of inoculum: with 2 TSB agar slants of culture inoculation of a full ring from freezing stock culture.Under 30 ℃ with this slant culture 2 days.Wash cell on each inclined-plane with the aseptic phosphate buffer of 15ml (pH7.2).0.2OD when cell concentration is transferred to 600nm is (corresponding to about 1-2 * 10
8Individual bacterium/ml).This work stock (working stocks) is stored under 4 ℃ and is no more than 4-6 week.If also need the work stock after 6 weeks, then should prepare new stock.Utilize following organism to produce stock culture:
ATCC
Pseudomonas aeruginosa 15442
Friedlander (Klebsiella pneumonia) 13883
Clostridium perfringen (Enterobacter aerogenes) 13048
Carry out the test of fatality rate as follows: the aseptic SCW of 150 μ l is allocated in the 96 hole microtiter plates, in addition 150 μ l is added in first round.Adding from 1% or the testing compound of lower stock to provide the required initial concentration of 250ppm or 150ppm.Utilize one 12 passage pipettor to carry out two times of serial dilutions.Mixture with 1.5 μ l active redundancy cultures adopted 96 pin Dynatech at 1: 1: 1 under the ratio
The MIC2000 inoculator is inoculated simultaneously to all holes.Such 10
6The ultimate density of individual cell/ml.The plate of inoculating is deposited under room temperature.In the time of 4 and 24 hours, adopt this 96 pin inoculator to reclaim living cells in each hole by 1.5 μ l being changed over to 150 μ l TSB+0.05%AOS.To reclaim plate cultivated 48 hours down at 30 ℃.Record reclaims growth (+) and the not growth (-) in the plate, and concentration and time that the cell of indication inoculation reduces by two orders of magnitude at least, the result is as follows:
Table 2
| Valid density (ppm) | ||
| Compound | 4 hours | 24 hours |
| 3 6 8 9 | ????8 ????16 ????＜4 ????125 | ????＜4 ????16 ????＜4 ????8 |
The above results shows: compound 3,6,8 and 9 has the ability that causes death fast in synthetic cooling water; And these compounds are effective when hanging down consumption.
Claims (10)
1. one kind is suppressed the method that microorganism grows in the place that is subjected to microbiological attack, this method comprises: at least a antimicrobial from antimicrobial effective dose to described place that introduce, this class antimicrobial consumption that wherein is employed is low, can cause death fast, with back degraded rapidly, and safety when in environment, using, this class antimicrobial belongs to following formula:
Wherein: X, Y are selected from Br, Cl or I separately; And R=(C
1-C
8) aryl of alkyl, aryl or replacement.
2. the process of claim 1 wherein X=Y=Br.
3. the method for claim 2, wherein said antimicrobial is selected from: N-methyl-dibromo formaldoxime carbamate; N-(2-chloroethyl)-dibromo formaldoxime carbamate; N-(4-chlorphenyl)-dibromo formaldoxime carbamate; N-(2,4 dichloro benzene base)-dibromo formaldoxime carbamate; N-ethyl-dibromo formaldoxime carbamate; N-(normal-butyl)-dibromo formaldoxime carbamate; N-(n-octyl)-dibromo formaldoxime carbamate; N-(n-hexyl)-dibromo formaldoxime carbamate; And N-(4-aminomethyl phenyl)-dibromo formaldoxime carbamate.
4. the process of claim 1 wherein that described place is selected from cooling tower, gas cleaner, boiler, the mineral slurry, wastewater treatment, the fountain of Gong viewing and admiring, osmosis filtration, ultrafiltration, water ballast, evaporative condenser, heat exchanger, paper pulp and paper conversion liquid, plastics, emulsion and dispersion liquid, paint, latex, coating, wood stain, building product, building adhesive, industrial or daily adhesive, photographic chemical, printed liquid, household article, cosmetics, shampoo, soap, detergent, industrial disinfectant or sanitizer, floor wax, the laundry rinsing liquid, metal working fluid, transfer device lubricating oil, hydraulic fluid, leather and leather and fur products, textile, textile, timber and wooden article, PETROLEUM PROCESSING liquid, fuel, oil field liquid, the surfactant preservation, Medical Devices, the diagnostic reagent preservation, food preservation, various ponds and whirlpool.
5. the process of claim 1 wherein that described antimicrobial effective dose is 0.05～10 based on the volume in described place, 000ppm.
6. the method for claim 5, wherein said antimicrobial effective dose is 0.1～5000ppm based on the volume in described place.
7. the process of claim 1 wherein:
(a) described place is selected from cooling tower, gas cleaner, boiler, mineral slurry, wastewater treatment, the fountain of Gong viewing and admiring, osmosis filtration, ultrafiltration, water ballast, evaporative condenser, heat exchanger, paper pulp and paper conversion liquid, plastics, emulsion and dispersion liquid, paint, latex and coating;
(b) described antimicrobial effective dose is 0.1～5000ppm; With
(c) described antimicrobial is selected from: N-methyl-dibromo formaldoxime carbamate; N-(2-chloroethyl)-dibromo formaldoxime carbamate; N-(4-chlorphenyl)-dibromo formaldoxime carbamate; N-(2,4 dichloro benzene base)-dibromo formaldoxime carbamate; N-ethyl-dibromo formaldoxime carbamate; N-(normal-butyl)-two bromo-formaldoxime carbamate; N-(n-octyl)-dibromo formaldoxime carbamate; N-(n-hexyl)-dibromo formaldoxime carbamate; And N-(4-aminomethyl phenyl)-dibromo formaldoxime carbamate.
8. the method for claim 1, it further comprises the second kind of antimicrobial that is selected from following material: di-2-ethylhexylphosphine oxide (thiocyanates); Isothiazolone; Carbamate; Heterocyclic compound; Oxidant; Carboxylic acid and derivative thereof; Alkohol and amine; An is with phosphonium salt; Aldehyde, ketone and formaldehyde releaser; Halogenated aromatic compound; The halogenated aliphatic compound; Alkene; Inorganic compound; Enzyme; And surfactant.
9. the method for claim 8, wherein said second kind of antimicrobial is selected from: 5-chloro-2-methyl-4-isothiazoline-3-ketone; 2-methyl-4-isothiazoline-3-ketone; 2-n-octyl-4-isothiazoline-3-ketone; 4,5-two chloro-2-n-octyls-4-isothiazoline-3-ketone; 1, the 2-benzisothiazole-3-ketone; 2-pyridine thiol-1-zinc oxide; 2-pyridine thiol-1-sodium oxide molybdena; N '-(3, the 4-dichlorophenyl)-N, the N-dimethyl urea; 3-iodine propargyl-N-butyl carbamate; 10,10 '-oxo two phenoxy group arsines; 2-(thiocyanogen methyl mercapto) benzothiazole; 3-bromo-1-chloro-5, the 5-dimethyl hydantoin; 2,2-two bromo-3-nitrilo-propionamides; 1, the 5-glutaraldehyde; With 2-bromo-2-nitro-1, ammediol.
10. antimicrobial compositions, it comprises:
(a) antimicrobial of formula (I):
Wherein: X, Y are selected from bromine, chlorine or iodine separately; And R=(C
1-C
8) alkyl, aryl or replacement aryl and
(b) be selected from second kind of antimicrobial of following material: di-2-ethylhexylphosphine oxide (thiocyanates); Isothiazolone; Carbamate; Heterocyclic compound; Oxidant; Carboxylic acid and derivative thereof; Alkohol and amine; An is with phosphonium salt; Aldehyde, ketone and formaldehyde releaser; Halogenated aromatic compound; The halogenated aliphatic compound; Alkene; Inorganic compound; Enzyme; And surfactant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2437996P | 1996-08-14 | 1996-08-14 | |
| US024,379 | 1996-08-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1191073A true CN1191073A (en) | 1998-08-26 |
Family
ID=21820285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97117634A Pending CN1191073A (en) | 1996-08-14 | 1997-08-13 | Dihaloformaldoxime carbamates as antimicrobial agents |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH10279409A (en) |
| KR (1) | KR19980018695A (en) |
| CN (1) | CN1191073A (en) |
| BR (1) | BR9704364A (en) |
| PL (1) | PL321621A1 (en) |
| SG (1) | SG53039A1 (en) |
| SK (1) | SK109397A3 (en) |
| ZA (1) | ZA977083B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102599157A (en) * | 2010-12-27 | 2012-07-25 | 罗门哈斯公司 | Stabilized microbicidal composition |
| CN101326915B (en) * | 2007-06-21 | 2012-09-05 | 罗门哈斯公司 | Microbicidal composition |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3649136B2 (en) * | 2001-02-22 | 2005-05-18 | 栗田工業株式会社 | Slime control method in neutral papermaking process |
| TWI305554B (en) * | 2004-08-11 | 2009-01-21 | Formosa Taffeta Co Ltd | Yarns and fabrics having long-lasting mosquito repellent or antibacterial effect and their preparation |
| KR101230109B1 (en) * | 2006-01-25 | 2013-02-05 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Air filter having antimicrobial property |
| CN104397055A (en) * | 2014-10-19 | 2015-03-11 | 无棣华信石油技术服务有限公司 | Oilfield compound type bactericide and preparation method thereof |
-
1997
- 1997-08-08 ZA ZA9707083A patent/ZA977083B/en unknown
- 1997-08-08 SK SK1093-97A patent/SK109397A3/en unknown
- 1997-08-12 SG SG1997002917A patent/SG53039A1/en unknown
- 1997-08-13 CN CN97117634A patent/CN1191073A/en active Pending
- 1997-08-14 JP JP9231879A patent/JPH10279409A/en not_active Withdrawn
- 1997-08-14 PL PL97321621A patent/PL321621A1/en unknown
- 1997-08-14 KR KR1019970038877A patent/KR19980018695A/en not_active Application Discontinuation
- 1997-08-14 BR BR9704364A patent/BR9704364A/en active Search and Examination
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101326915B (en) * | 2007-06-21 | 2012-09-05 | 罗门哈斯公司 | Microbicidal composition |
| CN102599157A (en) * | 2010-12-27 | 2012-07-25 | 罗门哈斯公司 | Stabilized microbicidal composition |
Also Published As
| Publication number | Publication date |
|---|---|
| SG53039A1 (en) | 1998-09-28 |
| ZA977083B (en) | 1998-04-14 |
| JPH10279409A (en) | 1998-10-20 |
| BR9704364A (en) | 1999-05-11 |
| PL321621A1 (en) | 1998-02-16 |
| SK109397A3 (en) | 1998-06-03 |
| MX9706052A (en) | 1998-07-31 |
| KR19980018695A (en) | 1998-06-05 |
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