CN1154794A - High-killing-rate anti-microorganism compound - Google Patents
High-killing-rate anti-microorganism compound Download PDFInfo
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- CN1154794A CN1154794A CN 96121944 CN96121944A CN1154794A CN 1154794 A CN1154794 A CN 1154794A CN 96121944 CN96121944 CN 96121944 CN 96121944 A CN96121944 A CN 96121944A CN 1154794 A CN1154794 A CN 1154794A
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Abstract
A method for restraining bacterium or algae growing by a compound using formula I or II in an industry place is disclosed. An antimicrobial compound and a mixture containing the antimicrobial compound for restraining bacterium or algae growing in an industry place are also disclosed.
Description
The present invention relates to be used to control or suppress the application of the Antimicrobe compound of growth of microorganism.Especially relate to of the application of dithiazole compound as Antimicrobe compound.
Antimicrobe compound is used to control the microorganism of wide spectrum on a large scale in multiple occasion.
The DE Pat.2848221A that transfers Bayer AG discloses 1,2, and 3-dithiazole compound and they are used for the application of medicine as Antimicrobe compound.This invention is unexposed or advise that this compound is used for control or inhibition bacterium or algal grown under industrial occasions.US 4059590 (Moore) discloses a class 4-halogen-5-aryl-1,2, and 3-dithiazole compound and they are as the application of weedicide and fungicide, but unexposed or advise that this compound is used under industrial occasions control or suppresses bacterium or algal grown.
The problem of many Antimicrobe compounds is that the slow and/or compound of their microbicidels remains in the environment.Recently people generally are concerned about adsorbable organic halogen in environment.Need not remain in the environment, the content of halogen of reduction is arranged and the Antimicrobe compound of quick sterilization power is arranged.
The present invention includes a kind of method, be included in the Antimicrobe compound of effective dose at least a among industrial site introduction-type I or the II at industrial site inhibition bacterium or algal grown,
Wherein X and Y independently are selected from Cl, Br and I,
, O, S or N-R; The phenyl of R=phenyl, replacement, benzyl, methyl or ethyl; R
1=(C
1-C
8) alkyl; R
2And R
3Independently be selected from H and (C
1-C
8) alkyl.
Another aspect of the present invention the Antimicrobe compound of formula II is provided and further comprise water and/or can with the composition of the miscible organic solvent of water.
Compound according to formula I and II is useful at many industrial sites.The industrial site that is fit to comprises that for example timber, coating, binder, caulk compound, putty, latex, paper pulp, fabric, leather, plastics, cardboard, lubricant, soap, cosmetics, washing agent, household products, cooling tower, air washer, paper pulp and paper are handled water, metal working fluid, graining paste, photograph developing liquid and fuel.Preferred industrial site is that cooling tower, air washer, paper pulp and paper are handled water and graining paste.
Compound according to formula I and II is well known to those skilled in the art at the consumption that industrial site suppresses bacterium and algal grown.Based on the typical consumption in protected place from 0.1 to 2000ppm.Preferred Antimicrobe compound consumption is from 0.1 to 300ppm, preferred especially 1-25ppm.
The phenyl that replaces is meant the phenyl that one or more hydrogen are replaced by other substituting group.The substituent example that is fit to comprises (C
1-C
3) alkyl, (C
1-C
3) alkoxyl, hydroxyl, nitro, halogen, cyano group and (C
1-C
3) alkylthio group.
Comprising as Antimicrobe compound as used herein that bactericide and algicide and antimicrobial acivity are believed to comprise eliminates simultaneously and suppresses or prevent microorganism such as bacterium and algae grows in the industrial site.
Be used for preferred Antimicrobe compound of the present invention and comprise for example 4-chloro-5H-1,2,3-dithiazole-5-ketone; 5-(p-nitrophenyl imido)-4-chloro-1,2,3-dithiazole and 5-(2-chlorobenzene imido)-4-chloro-1,2,3-dithiazole.
According to the method for U.S.4508908 (Virgilio) general description, pass through quaternization preparation formula II compound with suitable alkylating reagent and corresponding 4-halogen dithiazole ketone.Preferred the most active alkylating reagent such as dimethyl suflfate, dithyl sulfate, methyl fluorosulfonate, chlordene metaantimmonic acid trimethyl oxygen, fluoboric acid triethyl group oxygen, trifluoromethanesulfonic acid n-pro-pyl or n-octyl ester, hexafluorophosphoric acid trimethyl oxygen, trifluoromethanesulfonic acid methyl esters, trifluoromethanesulfonic acid allyl ester or the like.Quaterisation is undertaken by reacting at 20-100 ℃ of 4-halogen dithiazole ketone and alkylating reagent.This reaction can neat reactants be carried out or carry out in the presence of such as toluene, hexane or xylene solvent.Formula II compound can be used the means known in the art purifying.
Performance at microbicide known in the art can be improved by uniting with one or more other microbicides.Like this, other known microbicide can be united with microbicide of the present invention valuably.Can be valuably comprise with the microbicide of microbicide associating of the present invention-but be not limited to-5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2,2-two bromo-3-nitrilo-propionamides, bromo-chloro-dimethyl hydantoin, methylene-two-thiocyanates, glutaraldehyde, quaternary ammonium compound, 2-n-octyl-3-isothiazolone, 4,5-two chloro-2-n-octyl-3-isothiazolones, iodopropargyl butylcarbamate, 1,2-two bromo-2, the 4-dicyanobutane, 2-sulphur cyanogen methyl-thio-benzothiazole, the tetrachloro isophthalonitrile, 5-bromo-5-nitro-1, the 3-diox, 2-bromo-2-nitro propane diols, N, N '-dimethyl hydroxyl-5,5 '-dimethyl hydantoin, 1,2-benzisothiazole-3-ketone and 4,5-trimethylene-2-methyl-3-isothiazolone.With 5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2, it is preferred that 2-two bromo-3-nitrilo-propionamides, bromo-chloro-dimethyl hydantoin, methylene-two-thiocyanates, glutaraldehyde, quaternary ammonium compound and their mixture and microbicide of the present invention are united.
The following example further specifies various aspects of the present invention, but not in office where face limits the scope of the invention.Embodiment 1 4-chloro-5H-1,2, the preparation of 3-dithiazole-5-ketone
With with prepare 4-chloro-5H-1 in the same procedure described in the DE 2848221 A1 embodiment 2,2,3-dithiazole-5-ketone.Embodiment 2 5-(p-nitrophenyl imido)-4-chloro-1,2, the preparation of 3-dithiazole
With with prepare 5-(p-nitrophenyl imido)-4-chloro-1,2,3-dithiazole in the same procedure described in the DE 2848221 A1 embodiment 4.Embodiment 3 5-(2-chlorobenzene imido)-4-chloro-1,2, the preparation of 3-dithiazole
With with prepare 5-(2-chlorobenzene imido)-4-chloro-1,2,3-dithiazole in the same procedure described in the DE 2848221 A1 embodiment 4.Embodiment 4 anti-microbial test data
Antimicrobial acivity spectrum and anion surfactant are measured in minimal inhibitory concentration (MIC) test the influence of Antimicrobe compound antimicrobial acivity of the present invention.MIC passes through a kind of compound at basic salt medium (Minimal Salts Media, M9G), tryptic soy clear soup (Trypticase Soy Broth, TSB) or tryptic soy clear soup (Trypticase Soy Broth) add in the anion surfactant (TSB+AOS) and measure in two times of serial dilution agent.The stock solution or the dispersion liquid that are used in the typical concentration for preparing in 5: 3: 2 acetone, methyl alcohol and the water solvent solution and are the test compound of 1%wt are tested.The stock solution of one volume is assigned to and makes initial experimental concentration of initial stage in the medium is the 500ppm compound.
When being ready to do experiment, except first container, each container of dilution series contains the soybean clear soup of isopyknic no compound.The soybean clear soup that contains the test compound that initial concentration is arranged of two volumes in first container.Half soybean clear soup in first container is transferred to second container.Half of gained volume shifts out and is transferred to the 3rd container from second container after mixing.Whole circulation fully repeats, and obtains that a series of concentration are respectively 500,250,125,63,31,16,8 and 4,2,1,0.5,0.25ppm.
Each container is inoculated with the cell suspending liquid of suitable test organism then.Test organism and source thereof mark in the following Table 1.
The female R+H 156 of the dark red enzymes of table 1 biogenetic derivation Escherichia coli ATCC 11229 (from the separation of emulsions of polluting) Pseudomonas aeruginosa ATCC 15442 aspergillus niger ATCC 6275 bacteriums soybean clear soup, mould growing in a period of time with under to the temperature that is fit to by the test sample on the agar slant, algae is the green alga and the bluish-green bacterium mixture of growing in medium.When finish vegetative period,, shake soybean clear soup cell is disperseed for bacterium.
For fungi, by pipette, extract water to the inclined-plane and move spore with asepsis ring and collect spore.Make cell/spore suspension standardization by control incubation time, temperature and dilution volume.Suspension is used to inoculate the container that contains the clear soup compound then.
The temperature incubation that container is being fit to then.Behind the incubation, inspecting containers is to determine growth/not growth.Minimal inhibitory concentration (MIC) is defined as the minimum compound concentration that obtains complete inhibition test biological growth.The result of MIC test represents in the following Table 2.
Table 2
The MIC of 5 pairs of algae of MIC (ppm) esherichia coli Pseudomonas aeruginosa aspergillus niger rhodothece rubra Escherichia coli compound M9G TSB TSB TSB TSB TSBA 1 19＞300 125 75 7.5 300 2 250 500 500 50 50 500 3 32 500 500 50 50 500 embodiment
MIC to algae uses the method identical with afore-mentioned test to determine that different is that the storing solution volume that is assigned in the medium enough makes initial experimental concentration of initial stage reach the 25ppm compound.Table 3 is listed in test organism and its source.The result of MIC test represents in table 4.
Table 3
Biogenetic derivation (UTEX#) Chlorella pyrenoidosa 1230Scenedesmus quadricauda 614 spray Anabaenas (Anabaena flos-aquae) 426Phormidium luridum var olivace 584
Table 4
Minimal inhibitory concentration (ppm) Compound C hlorella Scenedesmus Anabaena Phormidium4-chloro-5H-1,2,3-dithiazole-5-ketone 3.9 3.9 3.9 7.8
From these data 4-chloro-5 H-1 as can be seen, 2,3-dithiazole-5-ketone suppresses algal grown at floor level.Embodiment 6 kills speed
The speed of killing of The compounds of this invention is being measured according to synthetic cooling tower water (" the SCW ") lining of the following step.
The TSB medium in the 2L flask, adds the 1L deionized water by weighing 30g TSB, and shaking flasks is dissolved fully and prepared up to TSB.Medium was 121 ℃ of autoclavings 20 minutes then.
Nutrient reserve liquid prepares in the 2L flask by the following material of weighing: 5.28g ammonium nitrate, 2.08g anhydrous phosphoric acid potassium, 4.62g glucose, 21.50g sodium carbonate and 20.10g potassium sulphate.Water transfers to 1L with cumulative volume.Solution filtration sterilization and in room storage.
Rigid stock solution prepares in the 2L flask by the following material of weighing: 59.36g calcium chloride (two hydrations), 45.02g magnesium chloride (six hydrations), 0.18g iron chloride (six hydrations) and 0.24g ethylenediamine tetra-acetic acid.Water transfers to 1L with cumulative volume.Solution filtration sterilization and in room storage.
Erosion/scale inhibitor the stock solution that concentrates prepares in the 2L flask by the following material of weighing: the 238.5g deionized water; 125.0g 45%wt potassium hydroxide aqueous solution; 23.0g 49.5-51%wt tolytriazole sodium water solution; 63.5g the 2-phosphono-1 of the approximate 50%wt of 42-44%wt aquation acrylate copolymer and 50.0g; 2, the 4-butane tricarboxylic acids aqueous solution.Shaking flasks is dissolved up to all liq, then solution filtration sterilization and in room storage.
Erosion/scale inhibitor the stock solution that should concentrate is used for cumulative volume being transferred to 1L and shaking preparation a kind of erosion/scale inhibitor stock solution by add erosion/scale inhibitor stock solution, the water that 9.20ml concentrates in the 2L flask, the erosion of gained/scale inhibitor stock solution filtration sterilization and in room storage.
SCW prepares in the 2L flask by adding 900ml deionized water and 10.88ml nutrient reserve liquid (pH10-13).PH is turned down pH6, adds the adaptable stock solution of 10.88ml then.After this add 10.88ml erosion/scale inhibitor stock solution.PH is transferred to 8.5 and with deionized water final volume is transferred to 1L then.Final solution filtration sterilization and in room storage.
The synthetic cooling water (" ESCW ") that concentrates makes separately by adding glucose and yeast extract, and final concentration is that 3000mg/L and 1000mg/L prepare.
The stock culture of underproof bacterium prepares by using the ring-type culture inoculation TSB agar plate from freezing bacterium stock culture.Each is dull and stereotyped only with a kind of bacterium line.Dull and stereotyped then 30 ℃ of overnight incubation, sealing, and be placed in the refrigerator up to needs (up to one month).Following biology is used for generating stocks medium.Pseudomonas aeruginosa ATCC15442 enteritis Klebsiella ATCC13883 clostridium perfringen ATCC13048
Inoculum is by being prepared from the freezing ESCW that stocks the 50ml of bacterial clump of media transfer to the 125ml conical flask with oese.This flask is placed on that (30 ℃) spend the night on the shaking machine of heating, then culture is transferred at 660nm place 0.3 ODU (" OD "), obtains 108 colony-forming units (" CFU ")/ml.If desired, adjust inoculum density by adding SCW.In case the inoculum of every kind of bacteria culture media is transferred to the 0.3OD at the 660nm place, three kinds of mixed three kinds of test bacterial inoculums that obtain mixing in 1: 1: 1 of culture.
The stock solution of the Antimicrobe compound of every kind of test is prepared into the solution of the DMSO of 1%wt.The Antimicrobe compound of test is 4-chloro-5H-1,2, and 3-dithiazole-5-ketone (" invention ") and a kind of known commerce Antimicrobe compound methylene two thiocyanates (" contrast ").
Test specimen is prepared as follows.In the conical flask of the 125ml of eight mark 1-8, each adds the SCW of 49.5ml.Sample 1 has only SCW, is blank sample.The bacterial inoculum mixture that in sample 2-8, adds 0.5ml.Sample 2 has only SCW and inoculum, is the sample that is untreated.Sample 3-8 allocates The compounds of this invention or control compounds into.Before the preparation, the volume of preparation shifted out in each flask make final volume remain on 50ml.Sample 3-5 is mixed with 1,5 and the 4-chloro-5H-1 of 10ppm, 2 respectively, 3-dithiazole-5-ketone.Sample 6-8 is mixed with 1,5 and 10ppm methylene two thiocyanates respectively.All take out the 2ml equal portions as the zero-time point from the blank sample and the sample that is untreated.Then all samples is placed on 35 ℃ the oscillator.
1,3, took out the equal portions of each sample in 6,24 and 48 hours.Each equal portions is used to contain the inoculation of the microtiter plate of TSB, with ten times of serial dilutions.Each plate was cultivated 48 hours at 30 ℃.Each board test growth then.The hole count that shows growth is transfused to computer program, calculates the most probable number (" MPN ") of CFU/ml.The 3 logarithm reduction-conducts of CFU/ml contrast-think fast kill rate with the sample that is untreated after six hours.Data are as follows.
Being untreated in 0 hour 1 hour 3 hours 6 hours 24 hours 1 blank＜1.11＜1.11＜1.11＜1.11＜1.112 of the logarithm sample Antimicrobe compound of the MPN of CFU/ml, 6.76 6.26 8.064 invention (5ppm)-3.49＜1.11, sample 6.26 6.67 6.76 7.81 7.493 invention (1ppm)-6.76＜1.11 4.065 invention (10ppm)-2.06＜1.11＜1.11 2.066 contrast (1ppm)-6.67 6.49 5.76 4.497 contrast 6.76 5.49＜1.118 contrast (10ppm)-6.44 6.49 5.26＜1.11, (5ppm)-6.26
These data show 5 and the 4-chloro-5H-1 of 10ppm, 2,3-dithiazole-5-ketone at 1 hour effectively, and a kind of known commodity Antimicrobe compound methylene two thiocyanates of 10ppm are up to 24 hours just effectively.
Claims (5)
1. one kind is suppressed the method for bacterium or algal grown at industrial site, and be included in industrial site and introduce and at least aly among the formula I of effective dose or the II kill, do not have the Antimicrobe compound that environment retains fast,
Wherein X and Y independently are selected from Cl, Br and I;
, O, S or N-R; The phenyl of R=phenyl, replacement, benzyl, methyl or ethyl;
R
1=(C
1-C
8) alkyl;
R
2And R
3Independently be selected from H and (C
1-C
8) alkyl.
2. according to the process of claim 1 wherein that the described effective dose of described Antimicrobe compound is 0.1-300ppm based on the gross weight of described industrial site.
3. according to the process of claim 1 wherein that described industrial site is to select: timber, coating, binder, caulk compound, putty, latex, paper pulp, fabric, leather, plastics, cardboard, lubricant, soap, cosmetics, washing agent, household products, industrial colling, metal working fluid, graining paste, photograph developing liquid and fuel from following group.
4. according to the Antimicrobe compound of formula II.
5. composition comprises Antimicrobe compound and water and/or water-miscible organic solvent according to formula II.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96121944 CN1154794A (en) | 1995-11-03 | 1996-10-31 | High-killing-rate anti-microorganism compound |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US006,244 | 1995-11-03 | ||
| US729,991 | 1996-10-11 | ||
| CN 96121944 CN1154794A (en) | 1995-11-03 | 1996-10-31 | High-killing-rate anti-microorganism compound |
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| Publication Number | Publication Date |
|---|---|
| CN1154794A true CN1154794A (en) | 1997-07-23 |
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ID=5127028
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|---|---|---|---|
| CN 96121944 Pending CN1154794A (en) | 1995-11-03 | 1996-10-31 | High-killing-rate anti-microorganism compound |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104920387A (en) * | 2015-05-25 | 2015-09-23 | 华中师范大学 | Application of thiadiazole compound in inhibiting growth of algae and activity of enzyme and algicide for inhibiting growth of algae |
-
1996
- 1996-10-31 CN CN 96121944 patent/CN1154794A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104920387A (en) * | 2015-05-25 | 2015-09-23 | 华中师范大学 | Application of thiadiazole compound in inhibiting growth of algae and activity of enzyme and algicide for inhibiting growth of algae |
| CN104920387B (en) * | 2015-05-25 | 2017-04-05 | 华中师范大学 | Application of the thiadiazole compound in the activity of algal grown and enzyme is suppressed and the algicide for suppressing algal grown |
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