CN104910208A - Quaternary phosphonium salt type N-halamine antibacterial agent and preparation method thereof - Google Patents
Quaternary phosphonium salt type N-halamine antibacterial agent and preparation method thereof Download PDFInfo
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- 0 C*P(C)C(C1CCCCC1)=CCCN(C(C(C)(C)N1)=O)C1=O Chemical compound C*P(C)C(C1CCCCC1)=CCCN(C(C(C)(C)N1)=O)C1=O 0.000 description 1
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Abstract
The invention discloses a small molecule quaternary phosphonium salt type N-halamine antibacterial agent and a preparation method thereof. The antibacterial agent is prepared by integrating a quaternary phosphonium salt group and a N-halamine group into a single molecule by chemical covalent bond, solves the problem of poor hydrophily of N-halamine molecules, and retains the respective advantages of two antibacterial agents including N-halamine and quaternary phosphonium salt unit respectively, the antibacterial agent is good in sterilization effect, cost is low, technological process is simple, and the small molecule quaternary phosphonium salt type N-halamine antibacterial agent is suitable for medical treatment and public health, food safety, environmental protection, and many other fields.
Description
Technical field
The present invention relates to antibacterial agent, be related specifically to one class season phosphonium salt type halogen amine antibacterial moleucles and preparation method thereof, belong to antimicrobial technology field.
Background technology
Along with epoch and scientific and technological progress, the requirement of people to environment and health is also more and more higher.Antiseptic-germicide, as a kind of effective means resisting pathogenic bacterium, virus, has been widely used in all many-sides such as health care, food-processing, clothes processing, environmental improvement.
Antiseptic-germicide refers to that a class can be killed microorganism or be suppressed the chemical substance of microbial growth, to the effect that bacterium, fungi, spore etc. all have certain deactivation or suppress it to grow.Its function is divided into antibacterial and sterilization two kinds, and antibacterial being delays to hinder microbial growth, and sterilization is directly kills microorganism.Above two kinds of functions with target bacterial classification, working concentration, mutually transform from the different of the conditions such as bacterium duration of contact, temperature, humidity, can there is no tight lattice and define.
The huge number that antiseptic-germicide comprises, is broadly divided into inorganic, organic, natural three major types.The advantage such as although mineral-type antiseptic-germicide has good heat resistance, persistence is strong, continuity is high and security is good, also there is shortcomings, as cupric ion easily makes material variable color, silver ions type antiseptic-germicide is expensive, and anti-mold effect is bad, and addition is larger.Above-mentioned shortcoming makes the development space of conventional inorganic class antiseptic-germicide comparatively narrow.Although natural antimicrobial agent has good biocompatibility, the shortcomings such as it exists, and raw material sources are limited, difficulty of processing large, high temperature easy in inactivation, greatly limit its range of application.Organic antiseptic-germicide comprises of a great variety, as guanidine class, phenols, halogen substiuted class, quaternary ammonium salt season phosphonium salt class etc., wherein much all there is the features such as cheaper starting materials is easy to get, easily preparation, germ-killing efficiency is high, effect is lasting, be it is found that just more and more and be used.
Season, phosphonium salt structure was similar to quaternary ammonium salt, but due to season phosphine ionic radius large compared with quaternary ammonium ion, so season phosphonium salt polarized action stronger, to the negative charge on Membranes surface, there is stronger sucking action, therefore its sterilization effect is better than quaternary ammonium salt.If but life-time service, microorganism drug resistance problems can be produced, also facilitate this kind of antimicrobial molecule secondary pollution problem in the environment simultaneously.
Halogen atom with positive charge in halogen amine molecule has strong oxidizing property, after contacting with thalline, and the series of receptors in meeting oxidation bacteria somatocyte, thus suppress metabolic process and the enzyme catalysis system of even destroying thalline, thus cause thalline dead.Owing to containing strong oxidizing property halogen atom in molecule, so halogen amine antiseptic-germicide generally can not make thalline produce resistance.
Summary of the invention
The object of the invention is to prepare a kind of antibacterial agent: adopt chemosynthesis strategy by halogen amine groups and season phosphonium salt group be incorporated in same small molecules, solve the water-soluble bad problem of halogen amine antiseptic-germicide on the one hand, obtain active higher antimicrobial molecule on the other hand; Another object of the present invention is to provide the preparation method of above-mentioned season phosphonium salt type halogen amine antiseptic-germicide.
Concrete technical scheme of the present invention is: one season phosphonium salt type halogen amine antiseptic-germicide provided by the invention, has following chemical structural formula:
Wherein, n is selected from the integer of 2 ~ 10, and A is selected from aliphatics three grades of base phosphines or aromatic series three grades of base phosphines.
Further, in technique scheme, described aliphatics three grades of base phosphines contain three C
1~ C
18alkyl chain and a phosphorus atom.
Further, in technique scheme, described aromatic series three grades of base phosphines contain three phenyl and a phosphorus atom.
Present invention also offers the preparation method of above-mentioned season phosphonium salt type halogen amine antiseptic-germicide, comprise the preparation of 3-(n-alkylhalide group)-5,5-dimethyl hydantion, the preparation of glycolylurea base season phosphonium salt, the ion-exchange of glycolylurea base season phosphonium salt and season phosphonium salt the several step of chlorination:
(1) synthesis of 3-(n-alkylhalide group)-5,5-dimethyl hydantion:
First by 5,5-dimethyl hydantion is dissolved in acetone, add salt of wormwood, reflux 0.5h, in mixture, add alkylene dihalide again, continue backflow 4 ~ 12h, be cooled to room temperature, concentrate under vacuum after removing inorganic salts and can obtain bromine alkylated hydantoin because of compound, pillar layer separation can further improve purity;
(2) season phosphonium salt synthesis:
By the bromine alkylated hydantoin of gained in (1) because compound is dissolved in appropriate acetonitrile, dissolve fully, add equimolar amount aliphatics three grades of base phosphines or aromatic series three grades of base phosphines, reflux 12 ~ 24h, be cooled to room temperature, except desolventizing can obtain bromination season phosphonium salt type hydantoin-based compound under vacuum condition;
(3) season phosphonium salt ion-exchange:
By the bromination season phosphonium salt type hydantoin-based compound NaOH of step (2) gained, NaCl solution pre-treatment, again described season phosphonium salt is mixed with saturated solution, cross chlorion type anionite-exchange resin, collect relative leacheate, concentrated under vacuum condition, chlorination season phosphonium salt type hydantoin-based compound can be obtained;
(4) season phosphonium salt chlorination:
The tertiary butanol aqueous solution (trimethyl carbinol: water=4:1) being 4:1 by chlorination season phosphonium salt type hydantoin-based compound volume ratio obtained in (3) dissolves completely, t-butyl hypochlorate is added under lucifuge condition, stir 12 ~ 24h under normal temperature lucifuge condition, namely obtain generalformulaⅰcompound by concentrated for reacted mixing solutions.
Further, in technique scheme, in step (1), the mol ratio of salt of wormwood and 5,5-dimethyl hydantion is 3 ~ 5:1.
Further, in technique scheme, in step (1), the mol ratio of alkylene dihalide and 5,5-dimethyl hydantion is 2 ~ 4:1.
Further, in technique scheme, in step (4), t-butyl hypochlorate and chlorination season phosphonium salt type hydantoin-based compound mol ratio be 3 ~ 5:1.
Further, in technique scheme, described in step (1), alkylene dihalide structural formula is X
1-(CH
2) n-X
1, wherein X
1be selected from I, Br or Cl, n is selected from the integer of 2 ~ 10.
Invention beneficial effect
Although Halamine antibacterial agent sterilization speed is exceedingly fast, halogen amine compound is generally by acid amides chlorination or bromination, therefore its wetting ability is poorer than acid amides, thus limits its use range.This kind novel season phosphonium salt type halogen amine antiseptic-germicide both efficiently solved the water-soluble bad problem of traditional halogen amine antiseptic-germicide, remain again that halogen amine anti-type antiseptic-germicide sterilization speed is fast, renewable, has a broad antifungal spectrum, not easily produce the advantages such as resistance.
Specific embodiment
Further illustrate feature of the present invention below by embodiment, but the protection domain of this patent does not limit by embodiment.
Embodiment 1
First 5,5-dimethyl hydantion 4g (being about 31.2mmol) is added in 500mL single port flask, then add 200mL acetone, flask is placed in oil bath preheating.After dissolution of solid, add about 17g K
2cO
3(being about 123.2mmol), add 40 ~ 50mL acetone, in reactor, add 1,3-dibromopropane 18.9g (being about 9.6mL, 93.7mmol) after backflow 0.5h, continue heated overnight at reflux.With the washing for several times of 100mL moisture, after reacted mixture removing inorganic salt impurities, except desolventizing under vacuum condition, obtain crude product, pillar layer separation can further improve its purity, and productive rate is about 85%, and product structure is shown below:
First 3.0g (being about 12.1mmol) compound 1 is dissolved in about 50mL acetonitrile, in reactor, passes into N
2discharged by air, then in reactor, inject tributylphosphine 1.6g (being about 2mL, 8.0mmol) with syringe, reflux is about stopped reaction after 48h, then concentratedly under vacuum removes desolventizing, then through column chromatography purified product.This reaction yield is greater than 95%, and product structure is shown below:
What this experiment used is 201 × 7 type anionite-exchange resin, before ion-exchange, first will carry out pre-treatment to resin.Treatment process is: first use saturated aqueous common salt, gets the twice that its volume approximates processed resin volume, soaks 18 ~ 20h then filtering salt solution, clean by rinsed with deionized water, until discharge water not to be with yellow; Then 4 ~ 8h is soaked, filtering acid solution with 5%HCl, by rinsed with deionized water to neutral; Use 2% ~ 4%NaOH solution soaking, 4 ~ 8h again, filtering alkali lye, by rinsed with deionized water to neutral stand-by.Be Cl with saturated aqueous common salt by the anionresin in resin
-, then with deionized water, resin wash is extremely neutral, then compound 2 is dissolved in water a small amount of as far as possible, slow transit through anionite-exchange resin, obtain chlorion type tributyl season phosphonium salt using after the water Ex-all of solvent under vacuum condition, its structure is as follows:
First 2.0g compound 3 (being about 5.0mmol) is dissolved in 20mL tertiary butanol aqueous solution (volume ratio of the trimethyl carbinol and water is 4:1), drip t-butyl hypochlorate 2.2g and (be about 2.3mL, 19.8mmol), under normal temperature, lucifuge stirring is spent the night.Remove solvent and unnecessary t-butyl hypochlorate by concentrated under vacuum for reaction solution, season according to claim 1 phosphonium salt type halogen amine antiseptic-germicide can be obtained.Its productive rate is greater than 95%, and nuclear-magnetism characterization data is:
1H NMR(D
2O,500MHz,δ)3.60(t,J＝6.75Hz,2H),2.05-2.14(m,8H), 1.77-1.87(m,2H),1.27–1.49(m,12H),1.40(s,6H),0.82(t,J＝7.25Hz,9H)；
13C NMR(D
2O,126MHz,δ)177.0,155.6,66.4,39.8,23.3,22.7,21.0,19.7,17.7,15.7,12.6.
Structure is shown below:
Embodiment 2
5,5-dimethyl hydantion 3.2g (being about 25.3mmol) is dissolved in about 200mL acetone, in complete backward reactor to be dissolved, adds K
2cO
313.8g (being about 101.2mmol), adds 1,12-dibromo-dodecane 24.9g (being about 75.9mmol) after reflux 0.5h in reactor, stopped reaction after the about 24h that continues to reflux.After removing inorganic salt impurities, concentrated except desolventizing under vacuum, after column chromatography is purified compound 17, its productive rate is more than 70%, and structure is shown below:
2.5g compound 5 (being about 6.7mmol) is dissolved in 40mL acetonitrile.To be dissolved completely after, in reactor, pass into N
2by complete for air emptying.Tributylphosphine 1.2g (being about 1.5mL, 6.0mmol) is injected again, stopped reaction after continuation reflux 48h in reactor.Reaction solution is concentrated except desolventizing under vacuum, and purify through column chromatography and can obtain compound 6, its productive rate is greater than 80%, and structure is shown below:
Compound 7 obtains after ion-exchange for compound 6, and its structure is shown below:
Compound 7
1.5g (being about 2.8mmol) compound 7 is dissolved in 15mL tertiary butanol aqueous solution (volume ratio of the trimethyl carbinol and water is 4:1), drip t-butyl hypochlorate 1.2g in complete backward reactor to be dissolved and (be about 1.3mL, 11.2mmol), stopped reaction after stir about 24h under normal temperature lucifuge condition, concentration of reaction solution under vacuum condition, compound 8 is obtained except after desolventizing and unnecessary t-butyl hypochlorate, this reaction yield is greater than 95%, and nuclear-magnetism characterization data is:
1H NMR(D
2O,500MHz,δ)3.44(t,J＝6.75Hz,2H),2.05-2.17(m,8H),1.12-1.56(m,32H),1.37(s,6H),0.85(t,J＝7.25Hz,9H)；
13C NMR(D
2O,126MHz,δ)175.6,155.0,66.0,39.5,30.3,29.7,29.3,29.3,29.0,28.5,27.6,26.3,23.5,23.0,21.6,21.1,21.0,18.2,17.8,12.9.
Product structure is shown below:
Antibacterial test:
Sterilization experiment is with 0.57 × 10
6cFU intestinal bacteria ATCC 25922 is target bacterial classification, prepare with aforesaid method season phosphonium salt type halogen amine antiseptic-germicide and the solution (active chlorine content is 20ppm) of compound 4 it is killed, result is within 5min, and intestinal bacteria ATCC 25922 is all killed.And the compound 9 reported only can kill the intestinal bacteria of 90.6% under similarity condition in 5min.
Then with 1.66 × 10
6cFU intestinal bacteria ATCC 25922 is target bacterial classification, with the solution that active chlorine content is 20ppm compared for different carbon chain lengths season phosphonium salt type halogen amine antiseptic-germicide sterilization effect.Found that compound 4 kills the intestinal bacteria of 95.96% in 5min, and compound 8 kills the intestinal bacteria of 99.33% in same time.Proved by sterilization experiment, the season of synthesized different carbon chain lengths is in phosphonium salt type halogen amine antiseptic-germicide, best with compound 8 sterilization effect.
Claims (8)
1. season a phosphonium salt type halogen amine antiseptic-germicide, it is characterized in that there is formula I structure:
Wherein, n is selected from the integer of 2 ~ 10, and A is selected from aliphatics three grades of base phosphines or aromatic series three grades of base phosphines.
2. season according to claim 1 phosphonium salt type halogen amine antiseptic-germicide, it is characterized in that described aliphatics three grades of base phosphines contain three C
1~ C
18alkyl chain and a phosphorus atom.
3. season according to claim 1 phosphonium salt type halogen amine antiseptic-germicide, it is characterized in that described aromatic series three grades of base phosphines contain three phenyl and a phosphorus atom.
4. as claimed in claim 1 season phosphonium salt type halogen amine antiseptic-germicide preparation method, it is characterized in that comprising the following steps:
(1) synthesis of 3-(n-alkylhalide group)-5,5-dimethyl hydantion:
First by 5,5-dimethyl hydantion is dissolved in acetone, add salt of wormwood, reflux 0.5h, in mixture, add alkylene dihalide again, continue backflow 4 ~ 12h, be cooled to room temperature, concentrate under vacuum after removing inorganic salts and can obtain bromine alkylated hydantoin because of compound, pillar layer separation can further improve purity;
(2) season phosphonium salt synthesis:
By the bromine alkylated hydantoin of gained in (1) because compound is dissolved in appropriate acetonitrile, dissolve fully, add equimolar amount aliphatics three grades of base phosphines or aromatic series three grades of base phosphines, reflux 12 ~ 24h, be cooled to room temperature, except desolventizing can obtain bromination season phosphonium salt type hydantoin-based compound under vacuum condition;
(3) season phosphonium salt ion-exchange:
By the bromination season phosphonium salt type hydantoin-based compound NaOH of step (2) gained, NaCl solution pre-treatment, again described season phosphonium salt is mixed with saturated solution, cross chlorion type anionite-exchange resin, collect relative leacheate, concentrated under vacuum condition, chlorination season phosphonium salt type hydantoin-based compound can be obtained;
(4) season phosphonium salt chlorination:
The tertiary butanol aqueous solution being 4:1 by chlorination season phosphonium salt type hydantoin-based compound volume ratio obtained in (3) dissolves completely, t-butyl hypochlorate is added under lucifuge condition, stir 12 ~ 24h under normal temperature lucifuge condition, namely obtain generalformulaⅰcompound by concentrated for reacted mixing solutions.
5. preparation method according to claim 4, is characterized in that: in step (1), and the mol ratio of salt of wormwood and 5,5-dimethyl hydantion is 3 ~ 5:1.
6. preparation method according to claim 4, is characterized in that: in step (1), and the mol ratio of alkylene dihalide and 5,5-dimethyl hydantion is 2 ~ 4:1.
7. preparation method according to claim 4, is characterized in that: in step (4), t-butyl hypochlorate and chlorination season phosphonium salt type hydantoin-based compound mol ratio be 3 ~ 5:1.
8. preparation method according to claim 4, is characterized in that: described in step (1), alkylene dihalide structural formula is X
1-(CH
2) n-X
1, wherein X
1be selected from I, Br or Cl, n is selected from the integer of 2 ~ 10.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106220569B (en) * | 2016-08-05 | 2018-07-13 | 大连理工大学 | A kind of quaternary halogen amine antibacterial precursor, preparation and the application process immobilized for inactive surfaces |
| CN108752279A (en) * | 2018-07-18 | 2018-11-06 | 大连理工大学 | A kind of sulfonium salt type chloramines antiseptic and its synthetic method |
| CN109248334A (en) * | 2018-08-31 | 2019-01-22 | 湖南博隽生物医药有限公司 | A kind of surgical sewing thread antibacterial agent and preparation method thereof |
| CN110372533A (en) * | 2019-07-20 | 2019-10-25 | 大连理工大学 | A kind of linear chloramines antibacterial agent of cationic and its synthetic method |
| CN112110957A (en) * | 2020-09-20 | 2020-12-22 | 天津理工大学 | Preparation method and application of perylene-containing quaternary phosphonium salt and antibacterial filter column thereof |
| CN112970761A (en) * | 2021-02-03 | 2021-06-18 | 长春工业大学 | Quaternized halamine modified graphene oxide antibacterial nanoparticles and preparation method thereof |
| CN113136270A (en) * | 2021-04-19 | 2021-07-20 | 安徽达尔美生物科技有限公司 | Plant type antibacterial cleaning agent and production process thereof |
| AU2017327753B2 (en) * | 2016-09-13 | 2022-03-10 | Duluxgroup (Australia) Pty Ltd | Antimicrobial compounds or precursors thereof comprising one or more cationic centers and a coating-incorporation group |
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| WO2013173905A1 (en) * | 2012-05-17 | 2013-11-28 | University Of Manitoba | Biocidal compounds and methods for using same |
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| WO2013173905A1 (en) * | 2012-05-17 | 2013-11-28 | University Of Manitoba | Biocidal compounds and methods for using same |
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| CN106220569B (en) * | 2016-08-05 | 2018-07-13 | 大连理工大学 | A kind of quaternary halogen amine antibacterial precursor, preparation and the application process immobilized for inactive surfaces |
| AU2017327753B2 (en) * | 2016-09-13 | 2022-03-10 | Duluxgroup (Australia) Pty Ltd | Antimicrobial compounds or precursors thereof comprising one or more cationic centers and a coating-incorporation group |
| CN108752279A (en) * | 2018-07-18 | 2018-11-06 | 大连理工大学 | A kind of sulfonium salt type chloramines antiseptic and its synthetic method |
| CN109248334A (en) * | 2018-08-31 | 2019-01-22 | 湖南博隽生物医药有限公司 | A kind of surgical sewing thread antibacterial agent and preparation method thereof |
| CN110372533A (en) * | 2019-07-20 | 2019-10-25 | 大连理工大学 | A kind of linear chloramines antibacterial agent of cationic and its synthetic method |
| CN110372533B (en) * | 2019-07-20 | 2021-06-15 | 大连理工大学 | Cationic linear chloramine antibacterial agent and synthetic method thereof |
| CN112110957A (en) * | 2020-09-20 | 2020-12-22 | 天津理工大学 | Preparation method and application of perylene-containing quaternary phosphonium salt and antibacterial filter column thereof |
| CN112110957B (en) * | 2020-09-20 | 2023-07-28 | 天津理工大学 | Preparation method and application of perylene-containing quaternary phosphonium salt and antibacterial filter column thereof |
| CN112970761A (en) * | 2021-02-03 | 2021-06-18 | 长春工业大学 | Quaternized halamine modified graphene oxide antibacterial nanoparticles and preparation method thereof |
| CN113136270A (en) * | 2021-04-19 | 2021-07-20 | 安徽达尔美生物科技有限公司 | Plant type antibacterial cleaning agent and production process thereof |
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