CN105900979A - Preparation method of multi-quaternary ammonium salt fungicide - Google Patents
Preparation method of multi-quaternary ammonium salt fungicide Download PDFInfo
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- CN105900979A CN105900979A CN201610328458.9A CN201610328458A CN105900979A CN 105900979 A CN105900979 A CN 105900979A CN 201610328458 A CN201610328458 A CN 201610328458A CN 105900979 A CN105900979 A CN 105900979A
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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
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
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- C07—ORGANIC CHEMISTRY
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
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Abstract
The invention relates to a preparation method of a multi-quaternary ammonium salt fungicide. The preparation method comprises the following steps: halogenating polylol: mixing the polylol and a halogenating reagent in a solvent 1 at room temperature; after stirring for 0.5-1 hour, heating to a reflowing temperature of the solvent 1 and stirring for 3-4 hours; cooling to room temperature; washing with an alkali solution and separating the solution for three times; recycling an organic layer; drying and distilling to remove the solvent 1, so as to obtain polybasic haloalkane; synthesizing multi-quaternary ammonium salt: mixing tertiary amine and a solvent 2; after the tertiary amine is completely dissolved, adding the polybasic haloalkane by three times; heating to the reflowing temprature of the solvent 2 and reacting for 3-6 hours under the condition that the solvent 2 reflows; and removing a reflowing condensation device and distilling to remove the solvent 2 so as to obtain the multi-quaternary ammonium salt fungicide. The preparation method of the multi-quaternary ammonium salt fungicide has the advantages that the types of the quaternary ammonium salt fungicide are expanded so that the prepared product has good sterilization effect and a similar complicated synthesis process of polymerized quaternary ammonium salt is also avoided.
Description
Technical field
The present invention relates to a kind of antibacterial, particularly relate to the preparation method of a kind of multi-quaternary ammonium salt antibacterial.
Background technology
Quaternary ammonium compound is that a class antibacterial activity is high, applies effective antibacterial.As far back as the relevant report just having quaternary ammonium salt bactericide at the beginning of last century.Its bactericidal action stems from the negative electricity that in molecule, the azonia of quaternary ammonium group can be carried with the acidic phospholipid in biological cell membrane and interacts, once the two combines, the hydrophobic tail base of quaternary ammonium salt will be embedded into the inside of anti-bacterial hydrophobic film, effectively squeezes into the film surface of antibacterial.When quaternary ammonium salt concentration is higher, quaternary ammonium salt will destroy the structure of bacterial cell membrane.Meanwhile, quaternary ammonium salt can also destroy the albumen on bacterial cell membrane and enzyme.Being acted on by these, quaternary ammonium salt is had an effect with bacterial cell membrane, destroys the integrity of cell membrane, so that intracellular matter flows out, causes bacterial cell death, reaches the effect of sterilization.
At present the quaternary ammonium salt bactericide of exploitation as contained by it quaternary ammonium salt chain number be divided into strand quaternary ammonium salt bactericide, double-chain quaternary ammonium salt antibacterial and polymeric quaternary bactericide.The antibiotic property of strand quaternary ammonium salt bactericide depends critically upon the hydrophobicity of cell surface, owing to the hydrophobicity of bacterial cell surface is with the hydrogen ion concentration of local environment, i.e. the acid-base value of system, change and change.Therefore, the change of the Acidity of Aikalinity of sterilization system can affect the anti-microbial property of strand quaternary ammonium salt bactericide.Generally, strand quaternary ammonium salt bactericide only the most just can show high antibiotic property.Double-chain quaternary ammonium salt is except the sterilization mechanism of strand quaternary ammonium salt bactericide, it is also possible to RNA and the synthesis of protein.Additionally, the molecule charge intensity of double-chain quaternary ammonium salt antibacterial and molecular polarity are both greater than strand quaternary ammonium salt, it is easier to carry out adsorption reaction, so double-chain quaternary ammonium salt has higher bactericidal property with the electric charge of cell surface.With small molecule quaternary ammonium salt except that quaternary ammonium salt molecule after producing high-molecular, relative molecular mass increases, and positive charge density improves.Owing to microbial cell surface is electronegative, and the phospholipid that is contained within of cell membrane and the hydrolysis of some memebrane proteins are the most electronegative.Therefore, polymeric quaternary ammonium salts contributes to adsorbing thalline and being combined with cell membrane, thus reaches the effect of sterilization.Along with, the use of quaternary ammonium salt bactericide, antibacterial shows increasing Drug resistance.The preparation of polymeric quaternary ammonium salts simultaneously needs to introduce polymerization technique, and its preparation method is complex.Therefore, novel quaternary ammonium salt bactericide is developed extremely urgent.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides the preparation method of a kind of multi-quaternary ammonium salt antibacterial, it is therefore an objective to simplify production technology, the kind of extension quaternary ammonium salt bactericide, improve the using effect of quaternary ammonium salt bactericide.
For reaching above-mentioned purpose, the preparation method of the present invention a kind of multi-quaternary ammonium salt antibacterial, be made up of following step: the halo of polyhydric alcohol: by polyhydric alcohol and halogenating agent in solvent 1 in mixed at room temperature, after stirring 0.5-1 hour, it is warming up to after the reflux temperature of solvent 1 is stirred for 3-4 hour, be cooled to room temperature, with aqueous slkali washing, separatory three times, reclaim organic layer, after being dried and solvent 1 being distilled off, obtain polynary alkyl halide；
The synthesis of multi-quaternary ammonium salt: mixed with solvent 2 by tertiary amine, after tertiary amine is completely dissolved, adds polynary alkyl halide in three times, it is heated to the reflux temperature of solvent 2, reacts 3-6 hour in the case of solvent 2 refluxes, remove reflux condensate device, solvent 2 distillation is walked, obtains multi-quaternary ammonium salt antibacterial.
Described polyhydric alcohol is glycerol, trimethylolpropane and tetramethylolmethane.
Described halogenating agent is thionyl chloride, hydrogen bromide or phosphorus oxychloride.
Described alkali is sodium hydroxide, potassium hydroxide or sodium carbonate.
In the halogenating reaction of described polyhydric alcohol, the mol ratio of polyhydric alcohol and halogenating agent according to: using glycerol and during trimethylolpropane, the mol ratio of polyhydric alcohol and halogenating agent is 1:3.1-1:3.5；When using tetramethylolmethane, the mol ratio of polyhydric alcohol and halogenating agent is 1:4.1-1:4.5.
Described solvent 1 is toluene, normal heptane or normal octane, its addition and reactant equal-volume.
Described tertiary amine chemical constitution: CnH2n+1—N(CH3)2, wherein, n=4-18.
Described solvent 2 is ethanol, propanol or butanol, its addition and reactant equal-volume.
Advantages of the present invention effect: extend the kind of quaternary ammonium salt bactericide, is a novel quaternary ammonium salt bactericide of class.In its preparation process, employing the common polyhydric alcohol such as glycerol, raw material sources are wide, low price.Meanwhile, the preparation method of multi-quaternary ammonium salt is easy, on the premise of the product ensureing preparation has good bactericidal effect, it is to avoid the complicated synthesis technique of polymeric quaternary ammonium salts.The multi-quaternary ammonium salt antibacterial of preparation can be used for each field such as sewage disposal, medical facilities sterilization.
Detailed description of the invention
Below the present invention is described in detail in, but the protection domain of invention is not limited by embodiment.
Embodiment 1
The halo of polyhydric alcohol: 1 mole of glycerin and 3.2 moles of thionyl chlorides are mixed at room temperature with isopyknic toluene, after stirring 0.5 hour, it is warming up to after refluxing toluene temperature is stirred for 4 hours, it is cooled to room temperature, with sodium hydroxide solution washing, separatory three times, reclaim organic layer, after being dried and toluene being distilled off, obtain polynary alkyl halide；
The synthesis of multi-quaternary ammonium salt: by N, N-dimethyl butylamine mixes with ethanol equal-volume, treat N, after N-dimethyl butylamine is completely dissolved, add polynary alkyl halide in three times, be heated to alcohol reflux temperature, react 6 hours in the case of alcohol reflux, remove reflux condensate device, ethanol distillation is walked, obtain multi-quaternary ammonium salt antibacterial.
Embodiment 2
The halo of polyhydric alcohol: 1 mole of trimethylol propane and 3.5 mole hydrogen are mixed at room temperature with isopyknic normal heptane, after stirring 0.5 hour, it is warming up to after normal heptane reflux temperature is stirred for 3 hours, it is cooled to room temperature, with potassium hydroxide solution washing, separatory three times, reclaim organic layer, after being dried and normal heptane being distilled off, obtain polynary alkyl halide；
The synthesis of multi-quaternary ammonium salt: by N, N-dimethylamylamine mixes with ethanol equal-volume, treat N, after N-dimethyl butylamine is completely dissolved, add polynary alkyl halide in three times, be heated to alcohol reflux temperature, react 3 hours in the case of alcohol reflux, remove reflux condensate device, ethanol distillation is walked, obtain multi-quaternary ammonium salt antibacterial.
Embodiment 3
The halo of polyhydric alcohol: 1 mole of trimethylol propane and 3.1 mole hydrogen are mixed at room temperature with isopyknic normal octane, after stirring 0.7 hour, it is warming up to after normal octane reflux temperature is stirred for 3.5 hours, it is cooled to room temperature, with sodium carbonate liquor washing, separatory three times, reclaim organic layer, after being dried and normal octane being distilled off, obtain polynary alkyl halide；
The synthesis of multi-quaternary ammonium salt: by N, N-dimethyl amine mixes with ethanol equal-volume, treat N, after N-dimethyl butylamine is completely dissolved, add polynary alkyl halide in three times, be heated to alcohol reflux temperature, react 4 hours in the case of alcohol reflux, remove reflux condensate device, ethanol distillation is walked, obtain multi-quaternary ammonium salt antibacterial.
Embodiment 4
The halo of polyhydric alcohol: 1 mole of pentaerythritol and 4.1 moles of phosphorus oxychloride are mixed at room temperature with isopyknic toluene, after stirring 0.8 hour, it is warming up to after refluxing toluene temperature is stirred for 3.2 hours, it is cooled to room temperature, with sodium hydroxide solution washing, separatory three times, reclaim organic layer, after being dried and toluene being distilled off, obtain polynary alkyl halide；
The synthesis of multi-quaternary ammonium salt: by N, N-dimethyl heptyl amice mixes with ethanol equal-volume, treat N, after N-dimethyl butylamine is completely dissolved, add polynary alkyl halide in three times, be heated to alcohol reflux temperature, react 5 hours in the case of alcohol reflux, remove reflux condensate device, ethanol distillation is walked, obtain multi-quaternary ammonium salt antibacterial.
Embodiment 5
The halo of polyhydric alcohol: 1 mole of glycerin and 4.5 moles of thionyl chlorides are mixed at room temperature with isopyknic toluene, after stirring 1 hour, it is warming up to after refluxing toluene temperature is stirred for 3 hours, it is cooled to room temperature, with sodium hydroxide solution washing, separatory three times, reclaim organic layer, after being dried and toluene being distilled off, obtain polynary alkyl halide；
The synthesis of multi-quaternary ammonium salt: by N, N-dimethyl octylame mixes with propanol equal-volume, treat N, after N-dimethyl butylamine is completely dissolved, add polynary alkyl halide in three times, be heated to propanol reflux temperature, react 5 hours in the case of propanol refluxes, remove reflux condensate device, propanol distillation is walked, obtains multi-quaternary ammonium salt antibacterial.
Embodiment 6
The halo of polyhydric alcohol: 1 mole of glycerin and 4.3 moles of thionyl chlorides are mixed at room temperature with isopyknic toluene, after stirring 1 hour, it is warming up to after refluxing toluene temperature is stirred for 4 hours, it is cooled to room temperature, with sodium hydroxide solution washing, separatory three times, reclaim organic layer, after being dried and toluene being distilled off, obtain polynary alkyl halide；
The synthesis of multi-quaternary ammonium salt: by N, N-dimethyl nonyl amine mixes with butanol equal-volume, treat N, after N-dimethyl butylamine is completely dissolved, add polynary alkyl halide in three times, be heated to butanol reflux temperature, react 5 hours in the case of butanol refluxes, remove reflux condensate device, butanol distillation is walked, obtains multi-quaternary ammonium salt antibacterial.
Embodiment 7
Tertiary amine in embodiment 1 is N, N-dimethyl certain herbaceous plants with big flowers amine.The other the same as in Example 1.
Embodiment 8
Tertiary amine in embodiment 2 is N, N-dimethyl undecylamine.The other the same as in Example 2.
Embodiment 9
Tertiary amine in embodiment 3 is N, N-dimethyl lauryl amine.The other the same as in Example 3.
Embodiment 10
Tertiary amine in embodiment 4 is N, N-dimethyl tridecyl amine.The other the same as in Example 4.
Embodiment 11
Tertiary amine in embodiment 5 is N, N-dimethyl tetradecy lamine.The other the same as in Example 5.
Embodiment 12
Tertiary amine in embodiment 6 is N, N-dimethyl pentadecyl amine.Other is with embodiment 6.
Embodiment 13
Tertiary amine in embodiment 1 is N, N-dimethyl cetylamine.The other the same as in Example 1.
Embodiment 14
Tertiary amine in embodiment 2 is N, N-dimethyl heptadecyl-amine.The other the same as in Example 2.
Embodiment 15
Tertiary amine in embodiment 3 is N, Dymanthine.The other the same as in Example 3.
Claims (8)
1. the preparation method of a multi-quaternary ammonium salt antibacterial, it is characterized in that being made up of following step: the halo of polyhydric alcohol: by polyhydric alcohol and halogenating agent in solvent 1 in mixed at room temperature, after stirring 0.5-1 hour, it is warming up to after the reflux temperature of solvent 1 is stirred for 3-4 hour, it is cooled to room temperature, with aqueous slkali washing, separatory three times, reclaim organic layer, after being dried and solvent 1 being distilled off, obtain polynary alkyl halide；
The synthesis of multi-quaternary ammonium salt: mixed with solvent 2 by tertiary amine, after tertiary amine is completely dissolved, adds polynary alkyl halide in three times, it is heated to the reflux temperature of solvent 2, reacts 3-6 hour in the case of solvent 2 refluxes, remove reflux condensate device, solvent 2 distillation is walked, obtains multi-quaternary ammonium salt antibacterial.
The preparation method of a kind of multi-quaternary ammonium salt antibacterial the most according to claim 1, it is characterised in that described polyhydric alcohol is glycerol, trimethylolpropane and tetramethylolmethane.
The preparation method of a kind of multi-quaternary ammonium salt antibacterial the most according to claim 1, it is characterised in that described halogenating agent is thionyl chloride, hydrogen bromide or phosphorus oxychloride.
The preparation method of a kind of multi-quaternary ammonium salt antibacterial the most according to claim 1, it is characterised in that described alkali is sodium hydroxide, potassium hydroxide or sodium carbonate.
The preparation method of a kind of multi-quaternary ammonium salt antibacterial the most according to claim 1, it is characterized in that in the halogenating reaction of described polyhydric alcohol, the mol ratio of polyhydric alcohol and halogenating agent according to: using glycerol and during trimethylolpropane, the mol ratio of polyhydric alcohol and halogenating agent is 1:3.1-1:3.5；When using tetramethylolmethane, the mol ratio of polyhydric alcohol and halogenating agent is 1:4.1-1:4.5.
The preparation method of a kind of multi-quaternary ammonium salt antibacterial the most according to claim 1, it is characterised in that described solvent 1 is toluene, normal heptane or normal octane, its addition and reactant equal-volume.
The preparation method of a kind of multi-quaternary ammonium salt antibacterial the most according to claim 1, it is characterised in that described tertiary amine chemical constitution: CnH2n+1—N(CH3)2, wherein, n=4-18.
The preparation method of a kind of multi-quaternary ammonium salt antibacterial the most according to claim 1, it is characterised in that described solvent 2 is ethanol, propanol or butanol, its addition and reactant equal-volume.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111955474A (en) * | 2020-09-15 | 2020-11-20 | 郑州德融科技有限公司 | Bactericide for fracturing and production process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194974A (en) * | 1997-03-27 | 1998-10-07 | 武汉挪亚科技有限公司 | Process for synthesis of n-dodecyl trimethyl ammonium chloride |
| CN102952023A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Star-shaped hydrate anti-agglomerant and its preparation method |
| CN103191671A (en) * | 2013-04-17 | 2013-07-10 | 重庆理工大学 | Trimeric quaternary ammonium salt type cationic surface active agent and preparation method thereof |
| CN104086436A (en) * | 2014-07-14 | 2014-10-08 | 山东省泰和水处理有限公司 | Synthetic method of star-shaped tetra-quaternary ammonium salt |
-
2016
- 2016-05-18 CN CN201610328458.9A patent/CN105900979A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194974A (en) * | 1997-03-27 | 1998-10-07 | 武汉挪亚科技有限公司 | Process for synthesis of n-dodecyl trimethyl ammonium chloride |
| CN102952023A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Star-shaped hydrate anti-agglomerant and its preparation method |
| CN103191671A (en) * | 2013-04-17 | 2013-07-10 | 重庆理工大学 | Trimeric quaternary ammonium salt type cationic surface active agent and preparation method thereof |
| CN104086436A (en) * | 2014-07-14 | 2014-10-08 | 山东省泰和水处理有限公司 | Synthetic method of star-shaped tetra-quaternary ammonium salt |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111955474A (en) * | 2020-09-15 | 2020-11-20 | 郑州德融科技有限公司 | Bactericide for fracturing and production process thereof |
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Application publication date: 20160831 |